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EMPA20070485

UNIVERSITY OF ABERDEEN DEPARTMENT OF CHEMISTRY

Thermodynamics of Cement Hydration


by Thomas Matschei Dipl.-Ing., Bauhaus University Weimar

A Thesis presented for the degree of Doctor of Philosophy at the University of Aberdeen

Aberdeen, 06 December 2007

Declaration

This Thesis is submitted to the University of Aberdeen for the degree of Doctor of Philosophy. It is a record of the research carried out by the author, under the supervision of Professor F.P. Glasser. It has not been submitted for any previous degree or award, and is believed to be wholly original, except where due acknowledgement is made.

Thomas Matschei Aberdeen, December 2007

Abstract

Abstract
The application of thermodynamic methods to cement science is not new. About 80 years ago, Bogue wrote a series of equations describing the relationship between clinker raw meal chemical composition and the mineralogy of the finished clinker. These enabled the amounts of minerals to be calculated from a bulk chemical composition. Fundamental to the equations was a precise description of the high temperature equilibrium achieved during clinkering. Bogue admitted four oxide components into the calculation; lime, alumina, silica and ferric oxide and assumed that equilibrium was attained (or very nearly attained) during clinkering. This approach, which is, with modifications, still a widely used tool to quantify cement clinkering, was one of the main motivations of this work. Thus the overall aim of this Thesis is to provide a generic toolkit, which enables the quantification of cement hydration. The use of thermodynamic methods in cement hydration was often doubted, as the water-cement system was considered to be too complex. Furthermore metastable features occur, e.g. C-S-H, which lead to the conclusion cement hydration is a non-equilibrium process. Nevertheless pioneering works, by Damidot and Glasser, as well as from other groups e.g. Reardon et al. and Berner et al. prove that cement hydration follows the basic principles of physical chemistry by minimisation of the free energy of an isochemical system. Hence these studies demonstrated the usefulness of thermodynamic equilibrium models in cement hydration. However the success and the accuracy of these predictions are strongly linked to a reliable thermodynamic database, including the standard state properties of the aqueous species and the cement hydrates. Whereas the thermodynamic properties of the aqueous ions are well described in the literature, the dataset for cement hydrates is incomplete or inconsistent, or both. Thus the main goal of this Thesis was to develop a consistent thermodynamic database, which enables the assessment of the constitution of hydrated Portland cements. Because hydrated concretes are exposed to different service temperatures, data were obtained in the range ~1C to 99C. The database is developed for commonly-encountered cement substances including C-S-H, Ca(OH)2, selected AFm, AFt and hydrogarnet compositions as well as solid solutions. Literature data were critically assessed and completed with own experiments. The tabulated thermodynamic properties were derived by a harmonisation of the available data. The new database enables the hydrate mineralogy to be calculated from the bulk chemical composition of the system: most solid assemblages, the persistence of C-S-H and failure to nucleate siliceous hydrogarnet apart, correspond closely to equilibrium. This realisation means that hydrate assemblages can be controlled. The development of a thermodynamic approach also enables a fresh look at how mineralogical changes occur as a function of cement composition as well as in response to environmentally-conditioned reactions. According to a literature review the constitution of the AFm phase in Portland cement is very sensitive with respect to its chemical environment. Except for limited replacement of sulfate by hydroxide, AFm phases do not form solid solutions and, from the mineralogical standpoint, behave as separate phases. Therefore, in dependence of the bulk chemical composition, many hydrated cements will contain mixtures of AFm phases rather than a single AFm solid solution. Relative to previous databases, sulfate-AFm is shown to have a definite range of stability at 25C thus removing long-standing disagreement with theory about its persistence in hydrated cement pastes. Carbonate is shown to interact strongly with AFm and displaces OH- and SO42- at species activities

Abstract

commonly-encountered in cement systems across a broad range of temperatures 50C. Many of the predicted reactions were confirmed by focussed experiments and literature studies. Possible anion substitutions in the AFt phase were investigated. Non-ideal thermodynamic models for SO4-CO3-AFt and ettringite-thaumasite solid solutions were derived from solubility experiments. Whereas at 25C only minor anion substitution is likely, low temperatures tend to stabilise carbonate substituted AFt phases. Possible pathways of thaumasite formation were developed. It was concluded that there is no single route of thaumasite formation, but several pathways for thaumasite formation may occur simultaneously. Limestone, mainly consisting of calcite, is a permitted additive to Portland cements up to a 5 wt.-% limit under EN 197. The final chapter, on the impact of calcite addition upon cement hydration, enables a quantitative approach to its interaction with cement phases and prediction of space filling properties of pastes. The distribution of sulfate in AFt and AFm is much affected by the presence of carbonate. In the presence of portlandite the stabilisation of carboaluminate results in changes of the amounts of both portlandite and AFt: specimen calculations are presented to quantify these changes. Calculations of the specific volume of solids as a function of calcite addition suggest that the space filling ability of the paste is optimised when the calcite content is adjusted to maximise the AFt content. Additional calculations show how sulfate and carbonate distribution are affected by temperature. Carboaluminates become increasingly unstable at elevated temperatures, 50C, whereas carbonate substitution in AFt is favoured at low temperatures in the presence of calcite. The resulting consequences of thermal cycles on the space filling properties of hydrated cements are discussed.

Keywords: thermodynamics, thermodynamic data, modelling, cement hydration, AFm, AFt, sulfate, carbonate

Acknowledgement

Acknowledgement
Several people contributed to the successful completion of this Thesis, to whom I am grateful and indebted: Professor Fred Glasser for his excellent supervision of this project during my time in Aberdeen. I am most grateful for the advice and support he gave me throughout the duration of this Thesis. I enjoyed our long-lasting, motivating and academically stimulating discussions, mainly related to cement -surely one of the most fascinating manmade materials of this world-, but also to several other aspects of daily life. Dr. Barbara Lothenbach, EMPA Dbendorf, my Thesis co-supervisor, for invaluable assistance with questions about thermodynamic modelling and guidance with GEMS-PSI. Her enthusiasm contributed to the completion of the database and related applications. My industrial advisors, Dr. Ellis Gartner, Lafarge Central Research, France, and Dr. Duncan Herfort, Aalborg Portland Group, Denmark, for stimulating discussions and guidance during this work. Nanocem, a research network of European cement producers and academic institutions, for funding this work and for giving me the opportunity to present and discuss the results at several intern meetings as well as at international conferences. Special thanks to Professor Karen Scrivener, representing members of Nanocem and the Nanocem steering-committee, for valuable discussions and helpful critics during the preparation of publications related to this Thesis. I would like to thank Marie-Alix Dalang-Secrtan for her help with administration throughout this project and for assistance with the preparation of the Workshop Thermodynamic Modelling. Dr. Dmitrii Kulik, PSI, Switzerland, for troubleshooting and assistance with GEMS-PSI and for helpful advice during the preparation of the thermodynamic database. In that respect I would also like to thank Dr. John Gisby, NPL, UK, for his comments. The staff of the Chemistry Department, University of Aberdeen, for technical assistance. I would like to thank Professor Jrg Feldmann and his TESLA-team for invaluable guidance and introduction in analytical methods for civil engineers as well as for giving me the opportunity to participate in various group meetings. Thanks to Professor Donald Macphee for inspiring discussions about cement science, especially with respect to thaumasite formation. I enjoyed the refreshing discussions with the recently formed cement-group as well as with my colleagues from office G 85. The staff at EMPA Dbendorf, for great technical and intellectual support during my stay in Switzerland. I would like to thank my examiners, Professor Denis Damidot, Ecole des Mines de Douai, France, and Professor Donald Macphee, University of Aberdeen, for critically reviewing this work.

Finally, special thanks go to

Kristina, for her infinite patience with this cement guy

my friends, whose support I appreciated throughout the years

ein besonderes Dankeschn gebhrt meiner Familie in Deutschland, insbesondere meinen Eltern, Grosseltern, sowie allen Verwandten, die mich ber Jahre hinweg trotz mancher privater Rckschlge uneigenntzig mit viel Geduld und Aufmunterung untersttzt und einen entscheidenden Anteil am erfolgreichen Abschluss dieser Arbeit haben .

Table of contents

Abstract

.............................................................................................................................3

Acknowledgement................................................................................................................5 1. 2. 3.
3.1. 3.2. 3.3. 3.4. 3.5. 3.5.1 3.5.2 3.5.3 3.5.4 3.5.5

Introduction..............................................................................................................10 Status of database development..............................................................................11 Analytical methods...................................................................................................12


Preparation of samples .......................................................................................................... 12 X-ray diffraction.................................................................................................................... 12 Thermal analysis ................................................................................................................... 12 Microscopic examinations..................................................................................................... 13 Analysis of solutions ............................................................................................................. 13 Calcium, aluminium and sodium........................................................................................... 13 Sulfate ............................................................................................................................... 13 Silicon ............................................................................................................................... 14 Carbon ............................................................................................................................... 14 Measurement of pH............................................................................................................... 14

4.
4.1. 4.1.1 4.1.2 4.1.3 4.2. 4.3. 4.3.1 4.3.2 4.3.3 4.3.4 4.4. 4.4.1 4.4.2 4.4.3 4.4.4 4.5. 4.5.1 4.5.2 4.5.3 4.6.

Development of a thermodynamic database for cement hydrates ......................15


Synthesis of relevant cement hydrates .................................................................................. 15 Hydrogarnet........................................................................................................................... 15 AFm phases ........................................................................................................................... 16 AFt phases ............................................................................................................................. 17 Solubility determinations ...................................................................................................... 18 Methods used to derive and manipulate thermodynamic data .............................................. 19 Software and standard databases........................................................................................... 19 Estimation of heat capacity ................................................................................................... 19 Solubility based estimation of standard molar thermodynamic properties ........................... 21 Thermodynamics of solid solutions and the use of Lippmann phase diagrams .................... 23 Results ................................................................................................................................... 27 Hydrogarnet........................................................................................................................... 27 AFm phases ........................................................................................................................... 30 AFt phases ............................................................................................................................. 41 C-S-H ............................................................................................................................... 44 Discussion ............................................................................................................................. 46 Data accuracy ........................................................................................................................ 46 Relations between equilibrium and kinetics.......................................................................... 48 Applications of the database.................................................................................................. 49 Concluding remarks .............................................................................................................. 52

Table of contents

5.
5.1. 5.1.1 5.1.2 5.1.3 5.2.

The AFm phase in Portland cement.......................................................................53


Literature review ................................................................................................................... 53 General remarks on the structure and formation of AFm phases .......................................... 53 Stability of AFm phases ........................................................................................................ 54 Solid solutions between AFm phases.................................................................................... 56 Preparation of solid solutions ................................................................................................ 61

5.1.4 Summary and conclusions from the literature....................................................................... 59 5.3. Formation of AFm phases and AFm solid solutions ............................................................. 62 5.3.1 Monosulfoaluminate-hydroxy-AFm solid solutions ............................................................. 62 5.3.2 Monosulfoaluminate-monocarboaluminate........................................................................... 73 5.3.3 Monocarboaluminate-hydroxy-AFm..................................................................................... 74 5.4. Ternary phase relations between sulfate-, carbonate- and hydroxy-AFm............................. 75 5.4.1 Metastable phase assemblages at 25C ................................................................................. 75 5.4.2 Stable phase assemblages at 25C......................................................................................... 76 5.5. 5.5.1 5.5.2 5.5.3 5.6. Discussion of the results........................................................................................................ 78 Extent of solid solution ......................................................................................................... 78 Transformation mechanisms ................................................................................................. 79 Solubility data and its interpretation ..................................................................................... 79 Conclusions ........................................................................................................................... 80

6.
6.1.

The AFt phase in Portland cement.........................................................................82


State of the art of science ...................................................................................................... 82

6.1.1 General remarks on the structure and composition of AFt.................................................... 82 6.1.2 Solid solutions between AFt phases...................................................................................... 83 6.1.3 The formation of thaumasite and related solid solutions....................................................... 84 6.2. Solid solutions between sulfate- and carbonate-AFt ............................................................. 87 6.2.1 Synthesis of solid solutions and investigations of the solid phase ........................................ 87 6.2.2 Thermodynamic modelling of the solid solution formation.................................................. 88 6.3. 6.3.1 6.3.2 6.3.3 6.3.4 6.4. Investigations on thaumasite ................................................................................................. 92 The need for investigations ................................................................................................... 92 Synthesis of thaumasite ......................................................................................................... 92 The temperature-dependent stability of thaumasite in aqueous solutions............................. 94 Solid solution formation between ettringite and thaumasite ............................................... 100 Formation of thaumasite and ettringite solid solutions in hydrated cements ...................... 104

6.4.1 Carbonate substitution in SO4-AFt at 25C......................................................................... 104 6.4.2 Phase assemblages including thaumasite and related solid solutions.................................. 106 6.5. Discussion ........................................................................................................................... 112 6.5.1 Interpretation of phase diagrams ......................................................................................... 112 6.5.2 Formation of AFt solid solutions......................................................................................... 112 6.5.3 Pathways of thaumasite formation ...................................................................................... 114

Table of contents

7.

The influence of limestone addition on cement hydration .................................116

7.1. Literature review ................................................................................................................. 116 7.1.1 Limestone addition to Portland cement............................................................................... 116 7.1.2 Influence of temperature on the mineralogy of hydrated (limestone blended) Portland cement: 25C and above...................................................................................................... 118 7.2. Implications of limestone addition to cement hydration ..................................................... 121 7.2.1 Experiments on the role of carbonate and sulfate on C3A hydration .................................. 121 7.2.2 Phase relations between AFt-AFm phases relevant to Portland cements at 25C............... 124 7.2.3 7.2.4 7.2.5 7.2.6 7.3. Reactive vs. filler calcite .............................................................................................. 128 Quantification of phases...................................................................................................... 131 Space filling by cement paste solids.................................................................................... 133 Composition of the aqueous phase...................................................................................... 135 Applicability to Portland cement systems ........................................................................... 136

7.3.1 Experimental validation of phase changes .......................................................................... 136 7.3.2 Space filling vs. engineering properties .............................................................................. 139 7.4. 7.4.1 7.4.2 7.4.3 7.4.4 7.5. 7.5.1 7.5.2 7.5.3 7.5.4 The role of temperature on Portland cement hydration....................................................... 142 Thermally induced mineralogy changes.............................................................................. 142 Space filling vs. temperature ............................................................................................... 148 Experimental verification of thermally induced phase changes.......................................... 151 Summary ............................................................................................................................. 160 Discussion ........................................................................................................................... 161 Limitations of the methodology and of the database........................................................... 161 Kinetic factors: availability of sulfate, carbonate and alumina in the course of hydration . 166 Volume changes .................................................................................................................. 168 Thermally induced phase changes....................................................................................... 169

8.
8.1. 8.2.

Summary and conclusions.....................................................................................171


Thermodynamic quantification of cement hydration .......................................................... 171 Implications for cement hydration ...................................................................................... 172

References.........................................................................................................................174 Abbreviations ...................................................................................................................187


Nomenclature in cement chemistry................................................................................................ 187 Abbreviations used in calculations................................................................................................. 187 Other abbreviations ........................................................................................................................ 188

Figures and Tables...........................................................................................................189


Figures Tables ...................................................................................................................................... 189 ...................................................................................................................................... 194

Appendix .........................................................................................................................195

Introduction

10

1. Introduction
One of the unsolved problems in the application of Portland cement is to quantify the performance lifetimes of concrete constructions. The problem affects nuclear waste containments and, increasingly, long-lived infrastructure developments where quantification has failed to keep pace with the expectation of stakeholders. Although a wealth of empirical evidence on the performance of historic concretes information on their formulation is available, emplacement and exposure history is often incomplete and, moreover, the nature of cements supplied today will almost certainly have changed since the original construction. Empirical studies and historic examples have however yielded much useful qualitative information on the aggressivity of various service environments. Numerous tests and test methods have been used as indicators of durability but they do not yield generic conclusions and their predictive capabilities are limited. As a consequence, designers of long-lived constructions have at present to rely on received wisdom, as interpreted by experts and incorporated into codes of practice. The changing nature of cements is also of concern. Cement producers are under pressure to lower the specific energy requirements of cement production and reduce gaseous emissions. These goals are presently addressed by a combination of methods; partly by optimisation of process technology, including the use of alternative fuels and raw materials (the effect of which are beyond the scope of this study), and partly by reliance on supplementary cement materials to lessen the need for energyrich cement. Although the use of supplementary materials is generally regarded as beneficial in terms of strength and durability as, for example highlighted by developments in cement and concrete standards, long term performance is not fully understood. Supplementary materials presently in use include industrial by-products such as slag, fly ash, silica fume, etc. as well as natural materials, e.g. ground limestone, natural pozzolanic and semi-synthetic pozzolans such as metakaolin. Each of these materials has a complex but distinctive chemistry, mineralogy and granulometry. Moreover, each type of material ranges in composition and performance. Studies of their behaviour in blended cements under controlled conditions are confined to selected compositions and short term (1-5 years) laboratory measurements, perhaps supplemented by observations on actual constructions, for which conditions may not be well controlled. The complexity of blended cement systems and the wide-ranging nature of supplementary cementing materials have meant that guesses -sometimes well informed- have to be made at the outset about what aspects of behaviour should be studied. But the number and complexity of the resulting systems are such that results are often confined to measurement of a few of the many parameters affecting performance. Arguably the most serious question arising from the results of empirical testing is how to extend or extrapolate the results to other compositions and formulations, or to conditions other than those measured, or both. At present one cannot address these issues, except qualitatively. If quantification of performance is to be achieved, a new paradigm is needed and a key to the development of a successful paradigm must be to concentrate on generic approaches. Thermodynamics provides a consistent framework for the analysis of complex systems. Given an adequate database to support calculations, its strength lies in its generic nature; user-defined compositions and conditions can be selected for calculation. This realisation is not new although previous attempts to apply thermodynamics have had only limited success.

Introduction

11

From an industrial point of view it could be argued that thermodynamic approaches to cement durability are too theoretical and the calculations too difficult to perform. However, the latter is no longer true: geochemists, faced by similar problems of treating complex systems, have developed and validated computer-based protocols capable of being implemented on a PC. Thus reliable protocols are available, many of which are in the public domain. Furthermore these protocols often couple to other modules, for example, enabling mass to be conserved in the course of reaction while maintaining a system of balanced equations. Selected physical properties can also be calculated, for example by enabling the specific volumes occupied by the constituent solid phases of mixtures to be tabulated. Thermodynamics is most readily applied to isochemical systems, i.e., to systems having a constant composition, whereas many cement deterioration reactions involve transport of species into or out of the matrix (or both). But computer-based calculations also enable more complex conditions to be imposed on the system. It is not argued that the primary output achieved by application of thermodynamic methods necessarily enables the durability and performance of cements and concretes to be quantified. But it is believed that, in the search for quantification, a sound quantitative understanding of cement paste mineralogy and of the ability to calculate features and processes arising from the interaction of cement with potentially aggressive agents introduced from the environment, with additional possibilities for calculating physical functions and the introduction of kinetic variables, constitutes a great step forward. Other necessary links to develop integrated models of cement performance will be anticipated in the discussion.

2. Status of database development


After years of development, Babushkin et al. published the first reasonably comprehensive compilation of thermodynamic data for cement substances. Their book [12] also gives numerous application examples but, as these are pre-computer, the examples selected for calculation tend to be rather simplistic and at first sight, do not afford significant advance over empirical conclusions. However a serious problem is that referenced data in this compilation have proved difficult if not impossible to trace to source. Other databases adding to our knowledge of cement substances have been produced subsequently, e.g., by Atkins et al. [9][10][21], Damidot [44], Reardon [158][159], Lothenbach and Winnefeld [125] by the Lawrence Livermore National Laboratory [38] and by ANDRA, the French National Agency for Radioactive Waste Management [30]. Studies of phase equilibria, cited subsequently in the text, have also added data on the thermodynamic properties of specific substances. Experimental studies have shown that temperature is an important parameter with respect to the formation of phase assemblages in the course of cement hydration. Pioneering calculations by Damidot et al. [43][44][45][46][47][48][49] disclosed that thermodynamics enables to understand phase transitions due to temperature changes as well as due to changes of the chemical composition. Returning to the present state of development of performance-based thermodynamic models, calculation is handicapped by lack of a consistent database applicable to a wide range of temperature and cement compositions. Thus the aim of this work was to make progress towards the development of a database which is sufficiently reliable and inclusive to sustain and support calculations as well as experiments.

Analytical methods

12

3. Analytical methods
A programme of the acquisition of thermodynamic data was undertaken. This involved synthesis, characterisation, analysis and data integration. New data were obtained through synthesis of phase pure substances with subsequent solubility measurements. Focussed experiments were designed to substantiate calculated results in the course of application of the database.

3.1. Preparation of samples


Cement hydrates are generally very sensitive to decomposition by carbonation. Therefore many syntheses and solubility experiments must be performed under N2-atmosphere to minimise access of atmospheric CO2. Generally, if not stated otherwise, the synthesised solids, aged and stored in inert HDPE or PTFE ware, have been vacuum-filtered with Whatman #540 filter paper and washed several times with ultra pure degassed water to remove alkalis, if present. Subsequently the solids were dried over saturated CaCl2 solution at 37% r.h. for 2 weeks. Immediately before X-ray analysis a light disaggregation of the dried solids was necessary, using an agate mortar, to obtain a homogeneous powder. Solutions were obtained by filtration of 15 ml aliquots (30 ml for carbon determination) of the excess solution through a 0.22 m alkali-resistant MF-millipore membrane syringe filter unit. Part of the solution (10 ml) was acidified with 1 ml 0.1 M HCl for cation analysis; the remainder was used to measure pH and determine anions, e.g. sulfate or carbonate. Solutions awaiting analysis were stored briefly in polypropylene (PP) centrifuge tubes.

3.2. X-ray diffraction


Mineralogical examination of the dried solid was made by X-ray diffractometry (XRD) using a PANALYTICAL XPERT PRO diffractometer with CuK-radiation at room temperature, ~25C; the angular scan was between 5-80 2 with a step size of 0.02 and a count time of 1 s per step. To characterise products of the temperature-dependent reactions in cementitious systems (chapter 7) a BRUKER D8 ADVANCE powder diffractometer was used for X-ray analysis. XRD-data of the samples have been collected using CuK radiation at room temperature, ~25C. The angular range was set between 5-40 2 with a step size of 0.04 and a count time of 2 s per step. Powder samples were filled sideways to the sample holder to minimise preferred orientation effects, particularly important for samples containing platy crystals, e.g. AFm and/or portlandite.

3.3. Thermal analysis


A simultaneous TGA-SDTA apparatus TGA/SDTA 851 by METTLER-TOLEDO INC. was used for thermal analysis. Simultaneous TGA/SDTA collects complex thermo- and differential-thermogravimetric weight changes (TGA and DTG) as well as thermal effects (DTA) during heating of the sample. In the current investigations thermal analysis was used to determine the state of hydration of the investigated solids. Furthermore significant weight losses during thermal decomposition may be used for identification and distinction of the solids in phase mixtures. The observed temperature range was between 30C to 980C; the rate of heating was 10C/min. All measurements were done in N2-atmosphere.

Analytical methods

13

3.4. Microscopic examinations


An environmental scanning electron microscope (ESEM) FEI XL 30 was used for microscopic observations. In contrast to ordinary SEMs, no additional sample preparation, e.g. coating, was necessary and samples could be investigated in a defined gas atmosphere. Thus the possibilities of experimental artefact formation, e.g. changes of morphology due to coating and dehydration, were reduced. In the current work the GSE (gaseous secondary electron) or BSE (back scatter electron) detectors were used for observations in a low vacuum water vapour atmosphere (pressure: ~1 Torr). The acceleration voltage was 10 to 25 kV depending on the investigated sample.

3.5. Analysis of solutions 3.5.1 Calcium, aluminium and sodium


Aqueous calcium, aluminium and sodium were analysed by atomic absorption spectrometry using a VARIAN SPECTRAA 10 flame AAS. A nitrous oxide / acetylene flame was used for calcium and aluminium and an air / acetylene flame for sodium. Calcium was measured at a wavelength of 422.7 nm. Aluminium was determined at a wavelength of 309.3 nm whereas sodium was analysed at 589 nm. Standards were prepared from 1000 mg/l TITRISOL (VWR chemicals). A linear calibration curve for calcium was obtained in the range from 0 - 5 mg Ca2+/l and for sodium from 0 - 2.5 mg Na+/l; 2500 mg K+/l, as analytical grade KCl, was added to suppress ionisation. Due to minor sodium impurities in KCl the analytical limit of detection of sodium was ~0.5 mg Na+/l. For calcium and sodium analysis samples were diluted with 2500 mg K+/l solution to suppress ionisation prior to analysis. Aluminium was usually measured in undiluted samples; no further suppressing agents were added. Standards for aqueous aluminium calibration were prepared in the range between 0-100 mg Al3+/l. High calcium concentrations (~400 mg Ca2+/l) may interfere with aluminium determinations. To evaluate this matrix effect, a standard of 40 mg Al3+/l was diluted by a factor of 2 with a saturated Ca(OH)2-solution (initial concentration 850 mg Ca2+/l). The subsequently measured Al3+ concentration, 17.4 mg/l, was slightly lower than the theoretical reference value of 20 mg/l. A sensitivity analysis has shown that the analytical errors from this slight depression do not significantly affect the subsequent thermodynamic calculations.

3.5.2 Sulfate
Aqueous sulfate concentrations were determined by ion chromatography with a DIONEX DX-120 IC. An ion exchange analytical column IONPAC AS 4A 4mm equipped with a guard column was fitted for sulfate analysis. The analyte was injected into a 25 l sample loop; the applied pressure was set between 1000-1100 psi (67-74 bars). The eluent used was 1.8 mM Na2CO3 / l.7 mM NaHCO3. The eluent conductivity was suppressed by an ASRS Ultra self regenerating suppressor with deionised water (> 18 M cm) regenerant. The chromatograph had a linear calibration in the range 0-10 mg SO42-/l and standards were prepared from 1000 mg SO42-/l TITRISOL solution. The achieved detection limit was ~0.25 mg SO42-/l at a background activity of ~14 S. Due to low SO42concentrations, most measurements were taken on undiluted samples and the mean value of three independent analyses used to minimise the analytical error.

Analytical methods

14

3.5.3 Silicon
A spectrophotometric method based on the molybdenum blue method was adopted to determine the silicon concentration: Ramachandran and Gupta [156]. A CAMSPEC 301 spectrophotometer was used for the measurements. The optimum wavelength for silicon determination was 810 nm. Standards were prepared from 1000 mg Si4+/l TITRISOL solution. A linear calibration was achieved in the range from 0 to 5 mg Si4+/l.

3.5.4 Carbon
Carbon was analysed using a LABTOC Analyser by PPM. Ultra-violet-promoted persulphate oxidation is used to determine the contamination of dissolved organics present in the sample. The content of total inorganic carbon (TIC) was determined as difference from the concentrations of total carbon (TC) and total organic carbon (TOC) present in the solution. TC was first determined as the sum of TIC- and TOC-content. In a second step, TOC was determined from the catalytically oxidised CO2. Inorganic carbonates were automatically removed by sample pre-treatment using an acid sparge. A sample with reagent was then injected in to the reaction vessel, the vessel being continuously sparged by a carrier gas (typically nitrogen), to liberate any CO2 gas generated through oxidation. The resulting evolved CO2 is delivered to an infrared detection system. The CO2 plot is integrated and compared against a calibration curve to determine the reportable value. The detection limit for a reliable TIC measurement using this method is ~ 1 mg/l; problems arose due to the low concentrations of TIC in the solutions. In most cases the concentrations of carbon in solution were lower than the limit of detection. Thus it was decided to estimate the values with the help of thermodynamic calculations based on assumed equilibria with phases with known thermodynamic properties, e.g. calcite.

3.5.5 Measurement of pH
The pH was measured by a METTLER TOLEDO system equipped with a combination pH electrode INLAB 413 for simultaneous determination of pH and temperature of the solution. The pH-meter was calibrated with a 3-point calibration with pH 4.01, 7.00 and 9.21 buffers (at 25C). Additionally calibration was checked with a saturated Ca(OH)2 solution (pH~12.48 at 25C) as an external buffer. The pH was automatically corrected by the pH-meter for the measured temperature. To minimise carbonation effects, the pH was measured immediately after filtration of the sample solutions.

Development of a thermodynamic database for cement hydrates

15

4. Development of a thermodynamic database for cement hydrates


A thermodynamic database will include many substances for which standard compilations already provide adequate data: it is not necessary to start totally afresh. For example, the thermodynamic properties of water and of many aqueous ions and complexes are well known. Database development focussing on cements is therefore mainly concerned with the properties of solids that are abundant in cements but uncommon or absent in nature. Thus a comprehensive database can be compiled by focussing on relatively few substances.

4.1. Synthesis of relevant cement hydrates


The synthesis of the relevant cement hydrates required several solid precursors. These were made from analytical grade (AR) reagents. C3A was prepared from a 3:1 molar ratio of CaCO3 and Al2O3. The Al2O3 had a high fineness, dmax < 10 m, to enhance its reactivity. To eliminate adsorbed water, the Al2O3 and the CaCO3 were dried previously at 950C or 100C overnight, respectively. The starting materials were mixed to a homogeneous paste with water in an agate mortar. A sufficient viscosity was necessary to avoid segregation. Afterwards the mixture was dried for 2 hours at 50C. Then it was placed in a platinum crucible and heated to 950C in a muffle furnace to decarbonate the CaCO3. After 4 hours the temperature was increased to 1400C for another 6 hours. Then the sintered material was cooled down, ground to a fineness < 75 m and reheated to 1400C for 6-10 hours. This procedure was repeated at least four times. Afterwards the material was checked for purity by XRD. No significant impurities e.g. free lime, CaO, were found following the described procedure. Lime, CaO, was obtained from decarbonation of analytical grade CaCO3 at 900C overnight. The purity was checked by XRD and showed no impurities. Due to its sensitivity to hydration and carbonation only freshly prepared CaO was used. Anhydrite, CaSO4, was used as sulfate source in the experiments. It was prepared by dehydration of gypsum in a muffle furnace at 750C for 5 hours.

4.1.1 Hydrogarnet
Hydrogarnet is usually defined in the cement literature as the silicon-free composition Ca3Al2(OH)12. However silicon is a main constituent of Portland and blended Portland cements and the existence of solid solution between katoite, Ca3Al2(OH)12, and grossularite, Ca3Al2Si3O12, is well-known both in the laboratory and from natural occurrences. Siliceous hydrogarnet thus impacts significantly on silicon distribution in cements. To enable thermodynamic calculations, two different compositions were synthesised. Ca3Al2(OH)12 was prepared by mixing previously synthesised C3A with boiling water and subsequent ageing at 105C in sealed PTFE bottles for 7 days. A siliceous composition was also prepared with the target composition Ca3Al2SiO4(OH)8, starting from stoichiometric amounts of CaO, Na2Si2O52H2O, NaAlO2 and water. A slurry of Na2Si2O52H2O and NaAlO2 was prepared with an appropriate amount of water. In a separate operation, CaO was suspended in boiling ultra pure water and the slurry containing mixed Na2Si2O52H2O, NaAlO2 added. Subsequently the preparation was aged for 4 weeks with periodic agitation at 105C in sealed PTFE bottles until filtration.

Development of a thermodynamic database for cement hydrates

16

3 Garnet silicon content [mol]

grossular (C3 AS3; PDF 1-74-1087 ) hibbschite (C3 AS2.3 D1.4; PDF 1-84-2016 )

2
hibbschite (C3 AS2 H2; PDF
31-250 )

hibbschite (C3 AS2 H2; PDF 1-73-1654 )

sil. hydrogarnet (C3 AS1.25 H3.5; PDF 45-1447 )

1
sil. hydrogarnet (C3 AS0.8 H4.4 ) C3 AH6
(PDF 24-217)

0 11.8

11.9

12

12.1

12.2

12.3

12.4

12.5

12.6

Unit cell size []

Fig. 4.1: Estimation of the silicon-content of siliceous hydrogarnet; data marked PDF are from the Powder Diffraction File. Data not marked were obtained in the course of the title study (solid compounds). The composition of the synthesised solid solution (open diamond) is estimated by fitting to the curve shown by a dashed line.

A literature review showed that the synthesis and characterisation of siliceous hydrogarnet is more complicated than the silicon-free variant. Jappy, et al. [95] synthesised hydrogrossular solid solutions Ca3Al2(SiO4)3-x(OH)4x and encountered two different hydrogarnet phases in most preparations. A miscibility gap was postulated to exist at low silica substitutions. However in the title study, one synthesis yielded a single hydrogarnet phase. According to subsequent XRD analysis this solid solution had a lower silicon-content than the target composition, Ca3Al2SiO4(OH)8. Its silicon-content was estimated assuming a linear relation of the unit cell lattice parameter between C3AH6 (a0~12.58 , PDF 24-217) and grossular, Ca3Al2(SiO4)3 (a0~11.85 , PDF 39-368). The unit cell size of the synthetic (a0 = ~12.39 ) was calculated by refining its XRD-pattern by least squares minimisation on 14 reflections with the software CELREF using silicon, a0= 5.4308 as an internal standard (see Fig. 4.1). Accordingly, its formula was corrected to Ca3Al2(SiO4)0.8(OH)8.8. The XRD-pattern also contained reflections attributed to C-S-H and most of the missing silica and part of the alumina are believed to be present as minor C-S-H impurity.

4.1.2 AFm phases


Although the stability relations of the AFm phases are known to be sensitive to temperature, few relevant data are available. To enable an estimation of thermodynamic data, the following preparation route yielded suitable material. Monosulfoaluminate, Ca4Al2(SO4)(OH)126H2O, becomes more stable at temperatures > ~40C. So a 1:1 molar mixture of C3A and CaSO4 was suspended at 100C in initially ultra pure water and thereafter kept at 85C for 7 days to synthesise phase pure monosulfoaluminate. Monocarboaluminate, Ca4Al2(CO3)(OH)125H2O, was prepared by mixing C3A and CaCO3 in a 1:1 molar ratio with previously degassed ultra pure water at 25C and stored with agitation in HDPE-bottles for 14 days until filtration at 25C. A second source of monocarboaluminate was prepared by mixing stoichiometric amounts of CaO, CaCO3 and gibbsite (Al(OH)3) with a 0.1 M KOH solution. The suspension was agitated periodically and stored at 50C for 4 weeks, with subsequent washing.

Development of a thermodynamic database for cement hydrates

17

Hemicarboaluminate, Ca4Al2(CO3)0.5(OH)135.5H2O, was made by addition of C3A, CaCO3 and CaO in stoichiometric quantities to previously degassed ultra pure water at 25C and stored in HDPE-bottles to achieve a successful synthesis. The mixture was aged with stirring for 14 days before filtration. C4AHx, Ca4Al2(OH)14xH2O, was synthesised according to the method of Atkins et al. [9]. C3A was mixed with CaO in a 1:1 molar ratio at 5C using degassed ultra pure water (w/s ~ 10). Afterwards the preparation was stirred for 72 hours and periodically agitated, still at 5C. After 3 weeks at 5C the solid was vacuum filtered under N2-atmosphere. Several methods for the preparation of strtlingite, Ca2Al2SiO2(OH)103H2O are described in the literature (e.g. sol-gel, preparation from glasses, etc.). These routes were pursued but the best preparations were obtained by starting from a stoichiometric mix of CaO, Na2Si2O52H2O, NaAlO2 and water (w/s ~ 10) at 25C. First, all chemicals were separately suspended in ultra pure water at 25C. The slurry containing sodium aluminate solution was added to the previously prepared portlandite solution with stirring. Finally the sodium silicate solution was added and the resulting suspension stirred for 4 weeks at 25C prior to filtration. HDPE-bottles were used in all stages of the preparation. Unlike other cement hydrates, which are uniformly white, the strtlingite preparation had a pale bluish colour.

4.1.3 AFt phases


The preparation and determination of the solubility of SO4-AFt, ettringite, has been the subject of numerous investigations [8][9][147][192]. The literature data show generally good agreement and it was therefore concentrated on its less well characterised carbonate analogue, CO3-AFt or tricarboaluminate, Ca6Al2(CO3)3(OH)1226H2O, which was synthesised using a modification of the method of Carlson and Berman [36] by precipitation from a stoichiometric mixture of CaO, NaAlO2 and Na2CO3 in a 10% w/v sucrose solution. The previously-prepared slurries of sodium aluminate and sodium carbonate were added to the sucrose-portlandite mixture (total w/s ~ 10), stirred for 3 days and periodically agitated at 25C until filtration after ~ 2 weeks.

Development of a thermodynamic database for cement hydrates

18

4.2. Solubility determinations


Solubility determinations were made at various temperatures between 5C and 105C. Two series of reaction mixtures were prepared to derive solubility data for katoite, Ca3Al2(OH)12. In the experiment from undersaturation, previously synthesised dry Ca3Al2(OH)12 powder was redispersed in water (water/solid-ratio ~ 30) at 25C and then stored in HDPE-bottles (at temperatures < 70C) or PTFE-bottles (at temperatures 70C) isothermally at well-spaced intervals between 5C to 105C prior to analysis. In a second series, a slurry of Ca3Al2(OH)12, prepared from C3A as described at 105C, was divided into several samples with the aid of a syringe. The sample bottles (HDPE or PTFE) were then filled with boiled water, sealed under N2-atmosphere and slowly cooled to the desired temperature and held for ~ 4 weeks prior to analysis. The water/solid massratio of the second set of samples was deliberately set to ~ 1000 to enable direct comparison with the results of Wells et al. [193], which were also obtained at this ratio. Experiments were conducted from both super- and undersaturation for monosulfoaluminate, monocarboaluminate and hemicarboaluminate at temperatures between 5C and 110C. Stoichiometric mixtures of C3A with either CaSO4 or CaO and CaCO3 (see paragraph 4.1) were used at various temperatures in experiments from supersaturation (water/solid-ratio ~ 30). Solubilities from undersaturation were determined by redispersing previously synthesised and characterised single phase solids in ultra pure degassed water (water/solid-ratio ~ 30). The samples were analysed after 4 - 6 weeks reaction time in both cases. Additionally a second dataset for hemicarboaluminate at 25C was generated by reaction of monocarboaluminate with synthetic C4AH13 (previously prepared at 5C) at a 1:1 molar ratio (water/solid-ratio ~ 30): complete reaction at 25C required ~ 3 weeks. The synthesis of siliceous hydrogarnet, strtlingite and the second source of monocarboaluminate required the addition of alkalis and synthesis was thus achieved at high aqueous pH. Most of the alkalis could be removed by flushing the filtrates several times with ultra pure degassed water prior to drying. Residual alkali contents are commented subsequently. Solubilities determined from undersaturation were obtained by redispersing powders of each mineral in ultra pure, degassed water (water/solid-ratio ~ 30) and undertaking analyses at well-spaced time intervals.

Development of a thermodynamic database for cement hydrates

19

4.3. Methods used to derive and manipulate thermodynamic data 4.3.1 Software and standard databases
Chemical thermodynamic modelling consists of calculating the chemical speciation (i.e. amounts or concentrations of chemical components in all phases present in equilibrium state) from total bulk composition of the system and thermodynamic data for components. In the GEM (Gibbs free energy minimisation) method and GEMS-PSI code [109], the total Gibbs energy of the system is minimised at given temperature and pressure; accordingly, for each component, the standard molar Gibbs energy at the temperature of interest must be provided. Calculations require a database of thermodynamic properties of components (substances), a correct statement of the problem, and a solver of chemical equilibria. In this work GEMS-PSI [109] was used - a software package including a GEM solver, a built-in thermodynamic database [93] and a graphical user interface for easy extension of the thermodynamic database to user-defined projects. This was convenient because not all cement minerals are included in standard databases such as Nagra-PSI [93] supplied within GEMS-PSI package. This database was initially designed in logK format for application to codes that use law of mass action algorithms at standard conditions (1bar and 25C); to include it in GEMS, the logK values were converted into standard molar Gibbs energies and merged with the slop98.dat database [96][172], which was originally developed for the SUPCRT92 code [96]. For aqueous species, this dataset is based on the HKF (Helgeson-Kirkham-Flowers) equation of state which can be used to calculate temperature and pressure corrections up to 1000C and 5 kbar; the necessary parameters for aqueous species relevant for cementitious systems are given in [172][179] and are summarised in Table A.1. The heat capacity coefficients needed for temperature corrections for most of the minerals in the GEMS databases are also given in the slop98.dat dataset. The database, included in the current software package, GEMS version 2.2, is documented in [184] and is in the public domain [93][96][172]. Raw data for minerals obtained in the title study have been converted into standard molar thermodynamic properties and added to the GEMS-PSI database in order to perform modelling calculations. Temperature corrections for thermodynamic properties of condensed substances (e.g. minerals) used in GEMS are based on the well known standard integration of the heat capacity function (e.g. [143]) as discussed below.

4.3.2 Estimation of heat capacity


The heat capacity function for solids (at constant pressure) was calculated according to Eq. 4.1 where a0, a1, a2 and a3 are empirically derived, temperature independent parameters characteristic of each solid.
Cp o = a 0 + a 1 T + a 2 T 2 + a 3 T 0.5

(4.1)

The heat capacities can be measured experimentally or, as was done here, estimated by using a reference reaction with a solid having a known heat capacity and similar structure. As shown by Helgeson et al. [89], this principle was successfully applied to estimate the heat capacity of silicate minerals by formulating a reaction involving a structurally-related mineral of known heat capacity. Gu et al. [86] used a similar approach to predict equilibrium constants for reactions related to aqueous species. Nevertheless, Helgeson et al. [89] pointed out that this method has limitations due to the differing thermodynamic properties of water, variously bound loosely as hydrate water or structurally, as OH-groups. To minimise errors associated with the varying strengths of bonding for water, care was taken to formulate reference reactions so as not to involve free water as a substituent in reactions unless appropriate to do so. Table 4.1 shows the coefficients to determine the heat capacity of reference solids to estimate heat capacity data of the relevant cement hydrates.

Development of a thermodynamic database for cement hydrates


Table 4.1: Standard molar thermodynamic properties of cement hydrates at 25C, 1 bar
Phase log KS0 f G 0
[kJ/mol]

20

f H 0

S0

a0 hydrogarnet

a1
2

a2

a3
0.5

VII

Ref

[kJ/mol] [J/(molK] [J/(molK)] [J/(molK )]

[JK/mol] [J/(molK )] [cm3/mol]

C3AH6 C3AS0.8H4.4

-20.84 -29.87

-5010.1 -5368.0

-5540 -5855

419 369

292I 109 AFt

0.561I 0.631

0 -1.95e+06

0 2560

150 143

t.s. t.s.

C6AsH32 C6AcH32

-44.90 -15205.9 -46.50 -14565.7

-17535 -16792

1900 1858

1939 I 2042 AFm

0.789 I 0.558

0 -7.78e+06

0 0

707 650

[123]
t.s.

C4AsH12 C4AcH11 C4Ac0.5H12 C4AH13 C2AH8 C2ASH8 jennite-type (C1.67SH2.1) tobermorite type (C0.83SH1.3) water (H2O) CAH10 SiO2 (amorph)

-29.26 -31.47 -29.13 -25.40 -13.56 -19.70

-7778.5 -7337.5 -7336.0 -7326.6 -4812.8 -5705.1

-8750 -8250 -8270 -8300 -5433 -6360

821 657 713 708 438 546

594 I 618 664 711 392 438 C-S-H

1.168 I 0.982 1.014 1.047 0.714 0.749

0 -2.59e+06 -1.30e+06 0 0 -1.13e+06

0 0 -800 -1600 -800 -800

309 262 285 274 184 216

t.s. t.s. t.s. t.s. t.s. t.s.

-13.17 -8.0

-2480.8 -1744.4

-2723 -1916

140 80

210 85

0.120 0.160

-3.07e+06 0

0 0

78III 59III

[123] [123]

supplementary data -237.2 -7.50 -4622.4 -848.9 -1797.8 -1322.1 -897.0 -604.0 -1129.2 -1151.0 -286 -5320 -903 -2023 -1435 -985 -635 -1207 -1289 70 501 41 194 107 83 39 93 70 75 151 47 91 70 187 49 105 36 clinker phases C3S -C2S C3A C4AF -2784.3 -2193.2 -3382.3 -4786.5 -2931 -2308 -3561 -5080 169 128 205 326 209 152 261 374 0.036 0.037 0.019 0.073 -4.25e+06 -3.03e+06 -5.06e+06 0 0 0 0 0 73 52 89 130 [12] [12] [12] [12] 0 1.113 0.034 0.318 0.099 -0.022 0.004 0.022 0.191 0 0 -1.13e+06 0 0 0 -6.53e+05 -2.59e+06 0 0 3200 0 0 0 -1600 0 0 0 18 194 29 IV 75 46 33
IV IV IV

[93]
t.s.

[104] [93] [93] [93] [93] [93] [93]

gypsum (CaSO42H2O) anhydrite (CaSO4) portlandite (Ca(OH)2) lime (CaO) calcite (CaCO3) gibbsite (Al(OH)3)

17 IV 37 32
IV IV

t.s. - data obtained in title study Isee Ederova et al. [57] IIcalculated from unit cell parameters given in Taylor [180] if not stated otherwise IIIsee Lothenbach et al. [123] IV see GEMS-PSI-dataset [93][184]

Development of a thermodynamic database for cement hydrates


Table 4.2: Reference reactions used to estimate unknown heat capacities of cement minerals Phase
Siliceous hydrogarnet Monocarboaluminate Hemicarboaluminate Hydroxy-AFm C2AH8 CAH10 Strtlingite Tricarboaluminate

21

Formula and reference reaction


Ca3Al2(SiO4)0.8(OH)8.8 + 1.6 Ca(OH)2 Ca3Al2(OH)12 + 0.8SiO2 + 1.6CaO Ca4Al2(CO3)(OH)125H2O + 0.5CaSO42H2O + 0.5CaSO4 Ca4Al2(SO4)(OH)126H2O + CaCO3 Ca4Al2(CO3)0.5(OH)135.5H2O + 0.25CaSO42H2O + 0.75CaSO4 Ca4Al2(SO4)(OH)126H2O + 0.5CaCO3 + 0.5Ca(OH)2 Ca4Al2(OH)146H2O + CaSO4 Ca4Al2(SO4)(OH)126H2O + Ca(OH)2 2Ca2Al2(OH)103H2O + CaSO4 Ca4Al2(SO4)(OH)126H2O + Ca(OH)2 + 2Al(OH)3 CaAl2(OH)82H2O + CaSO4 + 2Ca(OH)2 Ca4Al2(SO4)(OH)126H2O 2Ca2Al2SiO2(OH)103H2O + CaSO4 Ca4Al2(SO4)(OH)126H2O + 2SiO2 + Ca(OH)2 + 2Al(OH)3 Ca6Al2(CO3)3(OH)1226H2O + 3CaSO4 Ca6Al2(SO4)3(OH)1226H2O + 3CaCO3

The coefficients of the heat capacity function (Eq. 4.1) of the relevant cement hydrates were calculated according to reference reactions given in Table 4.2. Experimentally-determined heat capacities by Ederova and Satava [57] and data from the built-in GEMS database [93][184] were used as the basis for the estimation of the unknown coefficients (see Table 4.1). Analogue structures were used in the calculations, e.g. for unknown AFm phases monosulfoaluminate was used as the model. Assuming the reference reaction Eq. 4.2; Eq. 4.3 shows the principle way of calculating the necessary coefficient, an,A, for component A with the aid of the known coefficients an,B and an,C with y moles of component B and z moles of component C.

A yB + zC an,A = yan,B + zan,C

(4.2) (4.3)

Table 4.1 summarises the resulting coefficients and estimated standard heat capacities at 25C and 1 bar pressure calculated from Eq. 4.1.

4.3.3 Solubility based estimation of standard molar thermodynamic properties


Explanation of the basic principles of the formulation, calculation and manipulation of solubility products is given in textbooks [143]. In this Thesis, activity coefficients of the relevant species were calculated using the extended Debye-Hckel Eq. 4.4:
log i = Azi 2 I 1 + Bi I + bI

(4.4)

where i is the activity coefficient of ion i, A and B are Debye-Hckel solvent parameters dependent on the dielectric constant of water and temperature, zi is the ionic charge, i is a parameter dependent on the size of ion, i, taken from [93][184]; b is a semi-empirical parameter (~0.064 at 25C) and I is the effective ionic strength. Aqueous ion activities and speciation were calculated using the GEMS database appropriate to the particular calculation. Finally, temperature-dependent solubility products were calculated from the activities obtained according to the dissolution reactions in Table 4.3.

Development of a thermodynamic database for cement hydrates


Table 4.3: Dissolution reactions used to calculate solubility products Mineral
C3AH6 Siliceous hydrogarnet Monosulfoaluminate Monocarboaluminate Hemicarboaluminate C4AH13 C2AH8 CAH10 Strtlingite

22

Dissolution reaction
Ca3Al2(OH)12 3Ca2+ +2AlO2- + 4OH- + 4H2O Ca3Al2(SiO4)0.8(OH)8.8 3Ca2+ +2AlO2- + 0.8HSiO3-+ 3.2OH- + 2.4H2O Ca4Al2(SO4)(OH)126H2O 4Ca2+ +2AlO2- + SO42- + 4OH- + 10H2O Ca4Al2(CO3)(OH)125H2O 4Ca2+ +2AlO2- + CO32- + 4OH- + 9H2O Ca4Al2(CO3)0.5(OH)135.5H2O 4Ca2+ +2AlO2- + 0.5CO32- + 5OH- + 9.5H2O Ca4Al2(OH)146H2O 4Ca2+ +2AlO2- + 6OH- + 10H2O Ca2Al2(OH)103H2O 2Ca2+ +2AlO2- + 2OH- + 7H2O CaAl2(OH)86H2O Ca2+ +2AlO2- + 10H2O Ca2Al2SiO2(OH)103H2O 2Ca2+ +2AlO2- + HSiO3-+ OH- +7H2O Ca6Al2(SO4)3(OH)1226H2O 6Ca2+ +2AlO2- + 3SO42- + 4OH- + 30H2O Ca1.67SiO2(OH)3.330.43H2O 1.67Ca2+ + HSiO3-+ 2.33OH- + 0.43H2O Ca0.83SiO2(OH)1.670.5H2O 0.83Ca2+ + HSiO3-+ 0.67OH- + 0.5H2O

Tricarboaluminate (CO3-AFt) Ca6Al2(CO3)3(OH)1226H2O 6Ca2+ +2AlO2- + 3CO32- + 4OH- + 30H2O Ettringite (SO4-AFt) Jennite-type C-S-H Tobermorite-type C-S-H

The Gibbs energy of reaction rG0T at temperature T was computed using Eq. 4.5:
rG0 T = RT ln K T

(4.5)

where R = 8.31451 J/(molK) is the universal gas constant and KT is a thermodynamic equilibrium constant (=equilibrium solubility product) at a given temperature. From the solubility products calculated at each temperature, the standard molar thermodynamic properties of each solid were computed with the help of GEMS-PSI using the built-in three-term temperature extrapolation [106][108] to obtain a temperature-dependent logK function, which was fitted to the previously calculated solubility products. This function was estimated using Eq. 4.6 and the relationships shown in Eqns. 4.6 to 4.12.
log K T = A 0 + A 2 T 1 + A 3 ln T

(4.6)

and

A0 =

0.4343 0 r S0 T0 r Cp T 0 (1 + ln T0 ) R
0.4343 0 ( r H 0 T0 r Cp T T0 ) 0 R

(4.7) (4.8) (4.9)

A2 =

A3 =

0.4343 r Cp 0T0 R
0

0 0 r S0 T = r S T0 + r Cp T ln

T T0

(4.10) (4.11) (4.12)

0 0 rH0 T = r H T 0 + r Cp T 0 (T T0 ) 0 0 rG0 T = r H T T r S T

Development of a thermodynamic database for cement hydrates

23

The heat capacity effect of reaction, rCp0T = rCp0T0 = ao, was assumed to be constant over the temperature range 0-100C. Two parameters were adjusted to obtain a best visual fit to the experimental data: 1) rG0T at the reference state (25C and 1 bar pressure) was estimated according to Eq. 4.5 using the experimentally-derived solubility product at 25C. 2.) rH0T at the reference state was estimated to obtain the best visual fit between extrapolated solubility products according to Eq. 4.6 and calculated solubility products from experimentallyderived solubilities. rS0T was subsequently calculated using Eq. 4.12. Then the related standard molar thermodynamic properties were calculated according to dissolution reactions given in Table 4.3 using standard state properties of the aqueous species Table A.1 and the earlier estimated parameters rG0T, rH0T and rS0T. Combined with previously estimated Cp(T) coefficients (Table 4.1) and the known HKF parameters of the aqueous species, the individual temperature dependency of Cp(T) was subsequently calculated for each hydrate phase. Thus, in a final step, the solubility products were recalculated by GEMS using built-in parts of the SUPCRT92 program [96] to derive temperaturedependent values. Differences arising between the first approach, using the three-term temperature extrapolation with assumed constant rCp0T, and the second calculation, taking into account temperature-dependent heat capacity coefficients according to Table 4.1 and using values from the GEMS standard database [93][184], are marginal and lie within limits of other errors over the temperature range 0 to ~100C [106]. To check the internal consistency of the thermodynamic database, the experimentally-derived solubility data were predicted using the derived thermodynamic database and the observed phase assemblages. This seems like a circular argument and indeed is not intended to prove that the data are correct, only to demonstrate that internal self-consistency was achieved. Generally the best agreement between recalculated and experimental solubility data of AFm, AFt and hydrogarnet phases was observed by suppressing the formation of gibbsite in the computations. The experimentally-derived solubility data for each phase are also listed in the appendix A of this Thesis, leaving the reader free to perform other calculations, if desired.

4.3.4 Thermodynamics of solid solutions and the use of Lippmann phase diagrams
Solid solutions are frequently encountered in cementitious systems. The molar Gibbs free energy Gss of a solution between different end members i can be calculated according to Eq. 4.13:

G ss =

X G
i f i

0 i

+ G M

(4.13) (4.14) (4.15) (4.16)

G M = G id + G ex = RT ( X i ln K i ln K ss )

G id = RT

ln X i ln i

G ex = RT

Development of a thermodynamic database for cement hydrates

24

The first term of Eq. 4.13 describes the free energy of a mechanical mixture of the end members i of the solid solution and is calculated using the mole fraction Xi = ni/ni (ni is the mole amount of the end member i; Xi = 1) and fGi0 - the standard molar Gibbs energy of formation of end member i. The second term of Eq. 4.13 expresses the molar Gibbs energy of mixing, GM for a given composition of the solid solution series and is computed according to Eq. 4.14 as the sum of the Gibbs energy of mixing of an ideal solid solution, Gid, and the excess Gibbs energy of mixing, Gex, for the solid solution. Gid is calculated as described in Eq. 4.15 (with R, the universal gas constant, and T as the temperature of interest). The excess Gibbs energy of mixing, Gex, is only needed to compute thermodynamic properties of non-ideal solid solutions and can be calculated according to Eq. 4.16, where i is the activity coefficient of the end member i. In the case of an ideal solid solution, all i equal 1 and thus Gex = 0. In the title study, an ideal solid solution model (Gex = 0) was used to describe the thermodynamic properties of single phase calcium-silicatehydrate (C-S-H). A more detailed explanation of this solid solution model can be found in [104]. As shown in Eq. 4.14, GM can be calculated independently, from the deviation of a linear function of the sum of the partial solubility products Ki of the end members i of the solid solution and the actually calculated solubility product Kss of the solid solution at stoichiometric saturation as described by Glynn [80]. Several cementitious phases form non-ideal solid solutions, but only over a limited range of compositions. Hence, miscibility gaps will be observed. In the case of non-ideal mixing the Gibbs energy of the solid solution, Gss, is calculated with Eq. 4.13 and the activity coefficients i 1 and the excess Gibbs energy of mixing, Gex, of a binary solid solution are calculated according to Eq. 4.17:

G ex = RT (X 1 ln 1 + X 2 ln 2 )

(4.17)

where X1= n1/(n1+n2) and X2 = n2/(n1+n2) (n1 and n2 are the amounts of end members; X1+X2=1). The GEMS-PSI code has several built-in functions for non-ideal solid solutions [105]. In this Thesis, a semi-empirical model first suggested by Guggenheim and later developed by Redlich and Kister [80][81][82] was used to estimate the excess Gibbs free energy function of non-ideal binary solid solutions (Eq. 4.18):

G ex = X 1 X 2 RT (a 0 + a 1 ( X 1 X 2 ) + a 2 ( X 1 X 2 ) 2 + ...)

(4.18)

The empirical interaction parameters a0, a1, are dimensionless. As shown by Glynn [81], knowledge of two fitting parameters a0 and a1 is sufficient to estimate the excess Gibbs energy function with reasonable accuracy. The activity coefficients i of the end members i can be derived by fitting a0 and a1 to Eq. 4.18 and estimated according to Eqns. 4.19 and 4.20:

ln 1 = X 2 [a 0 + a 1 (3X 1 X 2 )]
2

(4.19) (4.20)

ln 2 = X 1 [a 0 a 1 (3X 2 X 1 )]
2

In the title study, the software MBSSAS [81] was used to derive the fitting parameters a0 and a1 based on experimentally-observed compositional boundaries of the miscibility gap in the binary solid solution series. A detailed description of MBSSAS is given in [81]: Kersten [101] applied a similar approach to estimate thermodynamic data for C-S-H.

Development of a thermodynamic database for cement hydrates

25

Lippmann phase diagrams


Lippmann [120][121][122] developed a mathematical algorithm to construct phase diagrams to display all possible equilibrium states of a binary solid solution B1-xCxA and its related aqueous phase composition. The diagrams are based on the law of mass action equilibrium according to Eqns. 4.21 and 4.22 ([81][82]):

[ B + ][ A ] = K BA X BA BA

(4.21) (4.22)

[ C + ][ A ] = K CA X CA CA

where [A-], [B+], [C+] are the aqueous activities of the ionic species A-, B+ and C+; KBA and KCA are the solubility products of the end members BA and CA of the binary solid solution series; XBA and XCA are the mole fractions of BA and CA in the solid and BA and CA are the activity coefficients of the BA and CA members of the solid solution series; BA and CA are calculated according to Eqns. 4.19 and 4.20 respectively, with X1 = XBA and X2 = XCA. To enable the construction of this phase diagram Lippmann [121] introduced the total solubility product as sum of Eqns. 4.23 and 4.24 and it is expressed as follows:

or

= [A ]([B + ] + [C + ])

(4.23)

eq , sd

= K BA X BA BA + K CA X CA CA

(4.24)

Eq. 4.24 is used to derive the solidus curve of a Lippmann diagram in dependence of the solidphase composition of the solid solution series. To enable a complete description of the binary solid solution aqueous solution (SSAS) system a mathematical function needs to be derived to relate the aqueous composition to the total solubility product . Thus Lippmann [121] derived the solutus-equation according Eq. 4.25:

eq , sl

X C,aq X B,aq =1 K + K CA CA BA BA

(4.25)

where XB,aq and XC,aq are the aqueous activity fractions [82][121] of the substitutable species B+ and C+ calculated according to Eqns. 4.26 and 4.27: X B , aq =
X C,aq =

[ B+ ] K X = BA BA BA + + [ B ] + [C ] eq , sd

(4.26)

K X [C + ] = CA CA CA + + [ B ] + [C ] eq,sd

(4.27)

As stated by Glynn [81] the activity coefficients BA and CA are dependent on the solid-phase composition (compare with Eqns. 4.19 and 4.20) and therefore are not a function of the aqueous phase composition except in the case of an ideal solid solution with BA = CA = 1.

Development of a thermodynamic database for cement hydrates

26

To enable the construction of a Lippmann phase diagram the dimensionless parameters a0 and a1 have to be derived to calculate the activity coefficients BA and CA according to Eqns. 4.19 and 4.20. Glynn [81] developed the software MBSSAS which uses the previously described mathematical relations to calculate thermodynamic equilibrium states of binary SSAS systems and to construct Lippmann phase diagrams. In dependence of the input parameters, MBSSAS is able to calculate the fitting parameters a0 and a1 or computes the location of miscibility gaps if the fitting parameters are estimated. In cement science MBSSAS was applied by Kersten [101] to estimate thermodynamic data for C-S-H. Further information about the software and possible applications are given in [80][81][82][101][105]. In the current work MBSSAS was used to calculate the fitting parameters based on experimentallyestimated compositional boundaries of the miscibility gap in different binary solid solution series. Lippmann diagrams were used to refine the parameters a0 and a1 to experimentally-derived solubility data. A more detailed description and an example of the use of Lippmann phase diagrams will be given in chapter 5.3.1.

Development of a thermodynamic database for cement hydrates

27

4.4. Results
Table 4.1 (chapter 4.3.2) summarises all thermodynamic data obtained in this study as well as thermodynamic data of supplementary phases needed to estimate the data of the cement hydrates. The following paragraphs explain in detail the determination of standard molar thermodynamic properties of the individual cement hydrates.

4.4.1 Hydrogarnet C3AH6, Ca3Al2(OH)12


As shown in Fig. 4.2, no significant changes of mineralogy occurred in the temperature range from 25C to 105C amongst the solid samples commencing from undersaturation: C3AH6 was the only crystalline phase detected by XRD. However at 5C small amounts of C2AH8 and monocarboaluminate were present. Whereas the formation of monocarboaluminate is an artefact, probably due to CO2 contamination of the sample during preparation, formation of C2AH8 seems to be favoured at low temperatures. Table A.2 (appendix A) shows the results of the solubility experiments for C3AH6; the solubilities of calcium and aluminium remain little-changed over the range studied. Thus the observed decrease of pH with rising temperature results mainly from the temperaturedependent change of the ion product of water. The mean aqueous ratios of Ca:Al, ~ 3 : 2, indicate congruent dissolution; comparable solubilities derived from super- and undersaturation are very similar. No significant solubility changes occurred between 28 and 84 days, suggesting that a steady state was reached within 28 days. Fig. 4.3 shows the evolution of calculated solubility products using solubility data from different sources including those obtained in the title study. In the low temperature range, from 0C to 50C, considerable data scatter is obvious. Although apparently comparable experimental conditions were used, older solubility data published by Wells et al. [155][193] and by DAns et al. [51][52] differ significantly from those obtained in the title study. Possible reasons for the disagreement with Wells et al. are discussed in chapter 4.5. On the other hand, the solubility products calculated from other available literature sources [8][9][32][35][139][162] agree well with the dataset within analytical accuracies.
all main peaks hydrogarnet (C3AH 6) M c - M onocarboaluminate

Intensity 500 counts

105 degC 25 degC


C2 AH8

Mc 10 12 14 16 18 20 22

Mc 24 26 28 30 32

5 degC

[2 Cuk ]
Fig. 4.2: Comparison of XRD-patterns of C3AH6 following annealing at 5C, 25C and 105C (approach from undersaturation)

Development of a thermodynamic database for cement hydrates


C 3 AH 6
4) -21 -22 -23 -24 0 20 5) 6) 8) 7) Concentration [mmol/l] 1) 3) 2) 5) 5) 8) 10 8 calcium 6 4 aluminium 2 0 120 0 20 40 60 80 Temperature [C]

28

Calc. solubility product log Ksp

-20

7) 1) Carlson 1958 5) Atkins 1991

2) Roberts 1969 6) D'Ans 1953 3) Butler 1958 7) Wells 1943 4) Nacken 1934 8) Peppler 1954

40 60 80 Temperature [C]

100

100

Fig. 4.3: Calculated solubility products of C3AH6 from solubility experiments (lines show calculated results as best fit)

Fig. 4.4: Recalculated solubility data for hydrogarnet, C3AH6, based on fitted thermodynamic data from Fig. 4.3 (markers show experimental values from the title study; lines show calculated results; formation of gibbsite suppressed in calculations.)

The resulting standard molar thermodynamic properties of C3AH6 are summarised in Table 4.1. The data agree well with those reported by Babushkin et al. [12] (fG0 = -5014.1 kJ/mol, fH0 = -5548 kJ/mol) as well as with experimentally-determined fH0 by Berman [23] (fH0 ~ -5561 kJ/mol) and Schnitz et al. [168] ( fH0 ~ -5551.5 kJ/mol): all lie within the expected range of analytical errors. Fig. 4.4 shows the recalculated temperature-dependence of calcium and aluminium solubilities from C3AH6 redispersed in pure water using the experimental conditions described in paragraph 4.3.3. The calculated data show good agreement with averaged measured concentrations. Consideration of other solubility data (see Fig. 4.3), especially values at lower temperatures, results in slightly lower concentrations compared to the data obtained in this Thesis. Hydrogarnet was predicted as the only stable CaO-Al2O3-H2O solid at this composition over the temperature range from 5 to 100C at 1 bar pressure.

Siliceous hydrogarnet, Ca3Al2(SiO4)0.8(OH)8.8


As shown in Fig. 4.5, phase pure siliceous hydrogarnet could not be synthesised using the procedure described in 4.1.1. Small amounts of a C-S-H phase, coprecipitated during the initial synthesis of siliceous hydrogarnet, persisted at all temperatures between 5C to 85C despite three dispersions in the course of solubility experiments. As noted in section 4.1.1, it is likely that the siliceous hydrogarnet had a lower silicon-content than the target. Thus provisional solubility products were calculated using the composition estimated from XRD data, Ca3Al2(SiO4)0.8(OH)8.8. Table A.3 shows provisional solubility data for the siliceous hydrogarnet. Comparison with the C3AH6 data shows that silica substitution leads to a significant reduction of solubility, indicating stabilisation of the hydrogarnet phase by silica substitution. The calculated solubility products of siliceous hydrogarnet are considerably lower than those of C3AH6.

Development of a thermodynamic database for cement hydrates

29

Hg

Hg - Siliceous Hydrogarnet C-S-H - Calcium-Silicate-Hydrate

Hg Hg

Hg

Hg

C-S-H

85 degC Intensity 250 counts 55 degC 25 degC


C-S-H C-S-H C-S-H

5 degC 16 18 20 22 24 26 28 30 32 34 [2 Cuk ]

14

Fig. 4.5: Comparison of XRD-patterns of siliceous hydrogarnet following ageing at temperatures in the range 5C - 85C (approach from undersaturation)

As shown in Table A.3, small amounts of sodium were also present in the aqueous solution. The amount of sodium in the solution diminished with each extraction and successive redispersion, suggesting that the sodium is mainly adsorbed in the C-S-H hydrate phase and is probably not structurally incorporated in the garnet-structured hydrate. C-S-H -present as impurity- is known to bind sodium weakly [92] and the equilibrium with dissolved sodium also influences the pH of the solution. Nevertheless, concentrations of other relevant ions remained generally constant. Thus the apparent decrease of the solubility product with each new extraction at a given temperature is mainly attributed to a lowered hydroxide activity due to decreasing aqueous sodium concentrations. Fig. 4.6 shows a comparison of experimentally-derived, temperature-dependent solubility products for siliceous hydrogarnet, Ca3Al2(SiO4)0.8(OH)8.8. The fitted values are calculated from the data in Table 4.1. There is a lack of consistent data for siliceous hydrogarnet; the only previous solubility data for siliceous hydrogarnet were published by Atkins et al. for 25C [9] and by Jappy et al. [95] for 95C. These investigations [9][95] apparently used preparations with two coexisting hydrogarnet phases and it is not therefore possible to compare these data directly with those obtained in the title study. Nevertheless the solubility trends given for siliceous hydrogarnets with high silica contents [9][95] generally agree with those of the title study; the greater the substitution of silica in hydrogarnet, the lower the solubility. A comparison of experimentally-derived solubilities of C3AS0.8H4.4 with modelled values is demonstrated in Fig. 4.7, to prove the solubility experiments. Small concentrations of sodium were determined in the solubility experiments and, to enable a direct relation with the experimental values, 0.4 mmol sodium/kg water were arbitrarily added to the model solution to simulate the impact of sodium on C3AS0.8H4.4 solubility. While the aluminium concentrations are slightly overestimated by calculation, data for calcium and silicon show good agreement with the averaged measured solubilities. C3AS0.8H4.4 is computed to be the only stable solid at this composition between 5 to 100C.

Development of a thermodynamic database for cement hydrates


C 3 AS 0.8 H 4.4

30

Calc. solubility product logKsp

-28 Concentration [mmol/l] -29 -30 -31


1)

1 0.8

2) 1)

calcium 0.6 0.4 aluminium 0.2 silicon 0 0 20 40 60 Temperature [C] 80 100

-32 0 20

1) Atkins 1991 2) Jappy 1991 40 60 Temperature [C] 80 100

Fig. 4.6: Calculated solubility products of siliceous Fig. 4.7:Recalculated solubility data for siliceous hydrogarnet, C3AS0.8H4.4, from solubility experiments hydrogarnet, C3AS0.8H4.4, based on fitted thermody(lines show best fit to the calculated results) namic data from Fig. 4.6 (markers show experimental values from this study; lines show calculated trends; formation of gibbsite suppressed in calculations.)

4.4.2 AFm phases Monosulfoaluminate, Ca4Al2(SO4)(OH)126H2O


Monosulfoaluminate preparations give apparently single phase preparations with relatively coarse hexagonal plate morphology (see Fig. 4.8 a). As shown in Fig. 4.9, monosulfoaluminate was the dominant phase at all temperatures. However after redispersion at 5C, 25C and 50C, small amounts of ettringite developed (see Fig. 4.8 b). Additionally, small amounts of hemicarboaluminate were formed in several samples indicating minor CO2 contamination during sample preparation and treatment. No mineralogical changes were observed in a sample stored at 25C for 26 months. Despite the supposed metastability of monosulfoaluminate with respect to hydrogarnet and ettringite, C3AH6 was generally absent except at 5C; see below.

(a)

(b)

ettringite

Fig. 4.8: ESEM micrographs of synthetic monosulfoaluminate a) after synthesis at 85C and b) after 4 weeks redispersion in deionised water at 25C

Development of a thermodynamic database for cement hydrates

31

Ms

M s - M onosulfoaluminate AFt - Ettringite Hc - Hemicarboaluminate

Ms Ms
5000 counts

Ms

90C
AFt
AFt

Intensity

AFt AFt
AFt

70C 50C Hc 25C


24

AFt Hc
10 12 14

16

18

20

22

5C

[2 Cuk ]

Fig. 4.9: Comparison of XRD-patterns of monosulfoaluminate after ageing at temperatures in the range 5C - 90C (approach from undersaturation)

Temperature-dependent solubility data for monosulfoaluminate are compiled in Table A.4 Calcium and aluminium concentrations remained relatively constant over the temperature range investigated. Although the aqueous ratio of Ca : Al (~ 4: 1.3 - 1.9) is close to congruency the Ca : SO4 ratio (~ 500) differs significantly from congruent dissolution behaviour at ~25C. This incongruent solubility behaviour was reported by Atkins et al. [9], whose solubility data at 25C agree very well with those of the title study. Nevertheless, with rising temperatures, the dissolution of monosulfoaluminate approaches congruency; sulfate concentrations increase significantly between 25 and 70C. At higher temperatures, 70C, monosulfoaluminate dissolves congruently. An exception to the lack of C3AH6 formation is the experiment at 5C, with approach from supersaturation. Significant amounts of C3AH6 formed and solubility values derived from this experiment differ significantly from other supposedly comparable data. Therefore this data set was not used in this study but is recorded in Table A.4. Although the application of the solubility product concept to phases showing incongruent dissolution is problematical, solubility products were nevertheless calculated according to Table 4.3. The averaged temperature-dependent solubility products were used to estimate the standard molar thermodynamic properties of monosulfoaluminate. A comparison between the fitted solubility product curve and calculated values from other data sources [8][9][97][99][196][197] shows good agreement within the range of possible analytical errors, Fig. 4.10. Only the solubility product calculated from solubility data by DAns et al. [51] is significantly higher than the fit. The estimated data from the title study (fG0 ~ -7778.5 kJ/mol, fH0 ~ -8750 kJ/mol, S0 ~ 821 J/molK) agree well with the dataset published by Babushkin et al. [12] (fG0 ~ -7779 kJ/mol, fH0 ~ -8772 kJ/mol, S0 ~ 747 J/molK) and reasonably well with data obtained by Satava [165] (fG0 ~ -7732 kJ/mol, fH0 ~ -8712 kJ/mol, S0 ~ 791 J/molK); estimated values for fH0 are slightly less than experimental data from dissolution calorimetry reported by Berman [24] (fH0 ~ -8786 kJ/mol).

Development of a thermodynamic database for cement hydrates

32

To test the consistency of the derived dataset, experimental solubility data were recalculated using standard thermodynamic properties of the phases given in Table 4.1; Fig. 4.11 shows that calculated and experimental values exhibit very good agreement in the temperature range between 25 and 100C. Only values obtained at 5C from analyses from undersaturation differ significantly from the trend lines. It is interesting to note that, as indicated in Fig. 4.11, monosulfoaluminate is predicted to appear as a stable phase at temperatures > 5C in the system CaO-Al2O3-CaSO4-H2O using the revised values for hydrogarnet, C3AH6. Small amounts of AFt are predicted at temperatures ~ 70C, and AFt formation was indeed observed in experiments. This indicates that coprecipitation of AFt and monosulfoaluminate lowers total Gibbs energy of the system and is energetically favourable. Formation of small amounts of AFt has been reported by several authors who tried to synthesise monosulfoaluminate at ~25C by adding stoichiometric amounts of calcium, aluminium and sulfate [9][51][99]. Nevertheless, and in agreement with own calculations, formation of hydrogarnet was not observed. According to calculations by Damidot et al. [46][47] monosulfoaluminate is metastable with respect to a mixture of C3AH6 and ettringite at temperatures < ~40C. These calculations used thermodynamic data derived from C3AH6 solubilities given by Wells et al. [193]. But according to the title study, monosulfoaluminate will be stable at and below room temperature. The calculations indicate a lower thermal stability limit of SO4-AFm at ~55C. Monosulfoaluminate is predicted to decompose to a mixture of C3AH6 and ettringite at <5C (not shown in Fig. 4.11 due to prevailing inaccuracies in the thermodynamic data). Additionally, at temperatures < ~ 10C, C2AH8 and CAH10 are close to saturation.
-28 1) -29 2) 3) 4) 6) 3) Concentration [mmol/l] 3) 6 4 aluminium 2 0 0 20 40 60 80 100 Temperature [C] sulfate calcium C 4 AsH 12 + AFt 8 C 4 AsH 12

Calc. solubility product log Ksp

-30

5)

-31 0 20

1) D'Ans 1953 4)Zhang 2000 2) Jones 1944 5)Zhang 1980 3) Atkins 1991 6)Kalousek 1941

40 60 Temperature [C]

80

100

Fig. 4.10: Calculated solubility products of monosulfoaluminate from solubility experiments (line shows calculated best fit)

Fig. 4.11: Recalculated solubility data for nominally monosulfoaluminate based on fitted thermodynamic data from Fig. 4.10 (markers show experimental values from the title study; lines show calculated results; formation of gibbsite suppressed in calculations.)

Development of a thermodynamic database for cement hydrates

33

Monocarboaluminate, Ca4Al2(CO3)(OH)125H2O
Fig. 4.12 shows that the XRD-pattern of monocarboaluminate remained unchanged at temperatures 70C, confirming its persistence. Monocarboaluminate and small amounts of calcite were observed as crystalline phases after 6 weeks storage at 70C. As shown in Fig. 4.12, monocarboaluminate decomposes to a mixture of C3AH6 and CaCO3 at temperatures 90C. But weak X-ray reflections of monocarboaluminate persisted and are interpreted as indicating that equilibrium may not have been reached in these samples.
M c - M onocarboaluminate C3AH 6 - Hydrogarnet Cc - Calcite

10000 counts

Mc

C3AH 6

Mc

Mc

Cc

110 C

Intensity

90C 70C 50C


12 14 16 18 20 22 24 26 28 30

10

5C

[2 Cuk ]

Fig. 4.12: Comparison of XRD-patterns of monocarboaluminate after annealing at temperatures in the range 5C - 110C (approach from undersaturation)

Until recently, solubility data for monocarboaluminate were only available at 25C [49][91][141]. Thus an important target of this study was to extend the known dataset to other temperatures: these data are given in Table A.5. Monocarboaluminate is incongruently soluble: the estimated aqueous calcium : carbonate ratios (Ca2+ : CO32- > 300) differ greatly from congruency. Carbonate concentrations were always below the detection limit of the analytical technique (< ~0.1 mmol/l CO32-). Thus a direct determination of aqueous carbonate was not possible. Other authors report the same analytical problems [49][91][141]. To enable calculation of solubility products, carbonate concentrations were computed assuming a saturation of the supernatant with respect to calcite. Small amounts of calcite were found as a supernumerary phase in all analyses. However, although this does not necessarily confirm that calcite is in equilibrium with the solution, this approach has given good agreement between experimental and calculated data. A comparison of the solubility product from the title study with other values calculated from solubility data [36][49][91], demonstrates good data consistency for monocarboaluminate at 25C (Fig. 4.13). Only the equilibrium constants computed from solubility data by Zhang [196] and Nishikawa [141] are slightly lower than those of the title study. As shown in Table A.5 and Fig. 4.14, calcium and aluminium concentrations increase regularly to about 90C; the 110C value apparently decreases slightly. Calculated solubility curves based on the new dataset (Table 4.1) reproduce well the experimentally-determined values. In agreement with the XRD analysis, (Fig. 4.12), monocarboaluminate is predicted to decompose at temperatures > ~85C to mixtures of C3AH6 and calcite. Kuzel and Baier [114] investigated the hydration of calcium aluminate cements in the presence of calcium carbonate at elevated temperatures and found similar results, suggesting that the solid phase assemblage of gibbsite-monocarboaluminate is stable up to 90 5C.

Development of a thermodynamic database for cement hydrates

34
C 3 AH 6 + calcite

monocarboaluminate + calcite Calc. solubility product logKsp -30 Concentration [mmol/l] 8 6 calcium 4

-31

1) 2) 3) 4) 5) 0 20
1) Hobbs 2001 4) Nishikawa 1992 2) Damidot 1994 5) Zhang 1980 3) Carlson 1960

-32

aluminium 2 0 0 20 40 60 carbonate 80 100 120

-33

40

60

80

100

Temperature [C]

Temperature [C]

Fig. 4.13: Calculated solubility products of monocarboaluminate from solubility experiments (line shows calculated best fit)

Fig. 4.14: Recalculated solubility data for monocarboaluminate based on fitted thermodynamic data from Fig. 4.13; (markers show experimental values from the title study, lines show calculated fit). Predicted solid phases are shown at the top. Formation of gibbsite suppressed in calculations.

Hemicarboaluminate, Ca4Al2(CO3)0.5(OH)135.5H2O
Although its existence has been known since the 1960s [163][169], hemicarboaluminate is one of the least well characterised AFm phases. Damidot et al. [49] published the first thermodynamic data for this compound showing it to be incompatible with calcite. Despite its suggested lack of importance in real systems saturated with respect to calcite [79], investigations by Kuzel et al. [113][117] and recent calculations in this Thesis (chapter 7) predict that hemicarboaluminate will be encountered in OPC with very low carbonate contents (i.e. virtually carbonate-free cements). Until recently, no temperature-dependent data for the stability of hemicarboaluminate were available.
Mc
Hc - Hemicarboaluminate M c - M onocarboaluminate C3AH 6 - Hydrogarnet P - Portlandite

Mc Hc
10000 counts C3AH 6

Hc

Hc

Mc

C3AH 6 Mc Hc M c Mc

85C 50C

Mc Intensity
Hc Mc

Hc

40C 25C

5C 10 12 14 16 18 20 22 24 [2 CuK ]
Fig. 4.15: Comparison of XRD-patterns of hemicarboaluminate after ageing at temperatures in the range 5C - 85C (approach from undersaturation)

Development of a thermodynamic database for cement hydrates

35

As shown in Fig. 4.15, the intensities of the XRD-reflections of hemicarboaluminate decrease regularly over the temperature range between 5C and 40C while at the same time, those of C3AH6 and monocarboaluminate increase in intensity in the range 5 to 40C. But hemicarboaluminate was absent at both 50C and 85C and the phase constitution was instead dominated by the coexistence of monocarboaluminate, C3AH6 and portlandite. Solubilities of hemicarboaluminate were obtained from super- and undersaturated solutions; the results are shown in Table A.6. The resulting calculated solubility products, Table A.6, were used to fit the standard thermodynamic properties of the compound (Fig. 4.16 and Table 4.1). The amounts of dissolved carbonate were always below the detection limit of the analytical technique but in this instance, carbonate concentrations could not be calculated by assuming calcite saturation because hemicarboaluminate is not stable in the presence of calcite. But, since XRD-investigations showed hemicarboaluminate to be compatible with monocarboaluminate, saturation with respect to the latter was assumed and used to fix the carbonate concentration. Hemicarboaluminate solubilities are strongly incongruent. As can be seen in Fig. 4.17, calcium concentrations increase with rising temperatures to ~50C, at and above which hemicarboaluminate is predicted to be unstable. The derived solubility products from this study agree reasonably well with values calculated from solubility data by Hobbs [91] (using carbonate concentrations estimated by assuming monocarboaluminate saturation) and by Damidot et al. [49]. Hemicarboaluminate decomposes progressively with increasing temperatures. As calculated, (Fig. 4.18), and in agreement with XRD-analyses (Fig. 4.15), the amount of hemicarboaluminate decreases regularly with increasing temperatures while increasing proportions of C3AH6 and monocarboaluminate develop. It is tentatively concluded that the upper thermal stability limit of hemicarboaluminate is 45 5C.
monocarb. + calcite + hemicarb. + monocarb. portlandite + portlandite + C 3 AH 6 C 3 AH 6 + C 3 AH 6

Calc. solubility product log Ksp

-28 Concentration [mmol/l] 1)

-29

2) -30 1) 1) Hobbs 2001 2) Damidot 1994 40 60

-31 0 20

18 16 14 12 10 8 6 4 2 0 0

calcium

aluminium 20

carbonate

40

60

80

100

Temperature [C]

Temperature [C]

Fig. 4.16: Calculated solubility products of hemicarboaluminate from solubility experiments (line shows calculated best fit)

Fig. 4.17: Recalculated solubility data for hemicarboaluminate based on fitted thermodynamic data from Fig. 4.16 (markers show experimental values from the title study, lines show calculated fits). Predicted solid phases are shown at the top.

Development of a thermodynamic database for cement hydrates

36

m onocarb.+ hem icarb. + m onocarb. + C 3 AH 6 C 3 AH 6 + portlandite

C 3 AH 6 + portlandite+ calcite

2 1.5 solids [g]


hem icarb.

1
m onocarb.

0.5 0 0 20
C 3 AH 6 portlandite

calcite

40

60

80

100

Temperature [C]

Fig. 4.18: Calculated mass balance of initially hemicarboaluminate (2g hemicarb. reacted in 60 g water at selected temperatures between 1C - 99C). Predicted solid phases are shown at the top. Note the discontinuities at ~50C and 80C resulting from phase changes.

C4AH13-C2AH8, Ca4Al2(OH)146H2O - Ca2Al2(OH)103H2O


The system CaO-Al2O3-H2O has been much studied at different temperatures generating numerous solubility data. The main datasets at or below ambient temperature are those of DAns [52] (20C), Wells [193] (21C), Faurie-Mounier [61] (20C), Butler [32] (5C) and Carlson [35] (1C). Depending on the initial bulk Ca/Al ratio, two different hexagonal C-A-H phases were observed: C2AH8 was the main C-A-H phase at Ca/Al ratios ~ 1 whereas C4AHx dominated at high Ca/Al ratios, 2. The solubility data from different literature sources were used to calculate temperature-dependent solubility products of C4AH13, C2AH8 and CAH10 (Fig. 4.19 and Fig. 4.20). The data trends are relatively consistent comparing 5C and 25C. Additional data for C4AH13 obtained in the course of the title study are listed in Table A.7.
-24 Calc. solubility product log Ksp -25 -26 -27 -28 0 6) 9) 2) 3) 1) 4) 7) 8) Calc. solubility product log Ksp -12

5)

-13 4) 5) -14 2) 3) 1) -15 0 20 5)

6)

1) Carlson 1958 4) D'Ans 1953 7) Zhang 2000 2) Roberts 1969 5) Wells 1943 8) Atkins 1991 3) Butler 1958 6) Hobbs 2001 9) Peppler1954

1) Carlson1958 4) D'Ans 1953 2) Roberts1969 5) Wells 1943 3) Butler 1958 6) Peppler1954

20

40

60

40

60

Temperature [C]

Temperature [C]

Fig. 4.19: Calculated solubility products of C4AH13 (left) and C2AH8 (right) from literature solubility data (lines show calculated best fit)

Development of a thermodynamic database for cement hydrates

37

Calc. solubility product log Ksp

-5 -6 -7 -8 -9 0 20 40 60 Temperature [C] 1) 2) 3)

4)

1) 2) 3) 4)

Carlson 1958 Roberts 1969 Butler 1958 P ercival 1958

Fig. 4.20: Calculated solubility products of CAH10 from literature solubility data (line shows calculated best fit)

The stability of C4AHx relative to mixtures of portlandite and C3AH6 is in dispute. Broadly the literature offers two interpretations; citations [61][52][193] report that C4AHx decomposes rapidly to mixtures of C3AH6 and portlandite at and above 20 - 25C. On the other hand, Carlson [35], Roberts [162], Seligman and Greening [170] and van Aardt and Visser [1] report the opposite: C3AH6 and portlandite react with formation of C4AHx, at low temperatures, 1 - 5C. Furthermore Butler and Taylor [32] and Carlson [35] show the apparent stable formation of CAH10 at low Ca/Al ratios and temperatures 5C. Butler and Taylor report that CAH10 is a stable phase in the system CaO-Al2O3-H2O and thus C2AH8 should decompose to a mixture of CAH10 and C4AH13 at low temperatures. However subsequent investigations by Percival and Taylor [145] have led to the conclusion that CAH10 is not stable at temperatures above 21C. Only Peppler and Wells [155] gave solubility data for C4AH13 at higher temperatures, > 25C. Analysis of the phase composition showed increasing amounts of C3AH6 formed upon prolonged ageing at temperatures 50C, which indicates decomposition of C4AH13 and C2AH8 at elevated temperatures. However the early-age values of C2AH8 and C4AH13, before the onset of significant decomposition, are close to the values reported here. DAns [52] observed the same stability trend for prolonged ageing at 25C. Hobbs [91] showed significant differences between solubility data obtained from undersaturation (aged ~ 515 d) and supersaturation (aged ~170 d). Major differences in the aluminium concentration caused large deviations between the solubility products calculated from under- and supersaturation. Nevertheless, relative to the many sources of data, there is generally good agreement between the various solubility datasets. The fitted value of C4AH13 for fH0 (-8302 kJ/mol) agrees reasonably with the calculated data by Babushkin et al. [12] (fH0 ~ 8318 kJ/mol). But fG0of C4AH13 (-7326.6 kJ/mol) is significantly higher than was calculated by Babushkin et al. (fG0 ~ -7347.8 kJ/mol). The data for C2AH8 (fG0 ~ -4813 kJ/mol, fH0 ~ -5432 kJ/mol) are in very good agreement with Babushkin et al. [12] (fG0 ~ - 4818 kJ/mol, fH0 ~ -5436 kJ/mol). The estimated values for CAH10 (fG0 ~ -4622 kJ/mol, fH0 ~ -5320 kJ/mol) agree very well with the calculated data by Babushkin et al. [12]: (fG0 ~ -4618 kJ/mol, fH0 ~ -5320 kJ/mol).

Development of a thermodynamic database for cement hydrates


a) 5C
a) C2AH 8
Carlson 1958 Roberts 1968 Butler 1958

38

8 Aluminium [mmol/l] 6 4

10 Aluminium [mmol/l] 8 6

b) 25C
C2AH 8 a')
D'Ans 1953 Wells 1943 Percival 1959 Faurie 1966

d') CAH 10 4 2 0 0 f')


Al(OH) 3

d) CAH 10 2
Al(OH) 3 C3 AH 6

b) C4AH 13 e) 10 15

g') b') C4AH 13


C3 AH6

Ca(OH) 2

f) 0

h) c) 20

e')

Ca(OH) 2 c')

10 Calcium [mmol/l]

15

c)

20

Calcium [mmol/l]

Fig. 4.21: Solubility relations between C2AH8, C4AH13 and CAH10 in the system CaO-Al2O3-H2O at 5C (left) and 25C (right) (markers show experimental values, solid lines show calculated results). The relevant aqueous compositions are given in Table 4.4).

The solubility relations between C2AH8, C4AH13 and CAH10 are shown in Fig. 4.21 together with the calculated solubilities of gibbsite and hydrogarnet. Using the estimated thermodynamic data (Table 4.1), experimental solubility values can be recalculated and are found to agree well with the experimental data. As noted previously, C4AH13 decomposes to a mixture of C3AH6 and portlandite with time at 25C. Thus the metastability of C4AHx phases with respect to C3AH6 has to be suppressed to enable recalculation of the solubility values, shown in Fig. 4.21. The trend lines illustrate the recalculated solubilities of the C-A-H phases using thermodynamic data from the title study. As shown by a dashed line, C2AH8 (Fig. 4.21 (a), curve a-b, is metastable with respect to CAH10 and C4AH13 at 5C. Metastable and stable aqueous invariant points from Fig. 4.21 are listed in Table 4.4, note that C4AH13 is predicted to decompose to C3AH6 and portlandite at 25C, but is computed to be stable at 5C, indicating an upper limit of thermal stability for C4AH13 at ~10C.
Table 4.4: Metastable and stable invariant points in the system CaO-Al2O3-H2O at 5 and 25C Temperature Point Coexisting solids Ca Al
[C] [Fig. 4.21] [mmol/l] [mmol/l]

pH

metastable invariant points (this study)


5 25 25 25 5 5 5 25 25 25 25 20 25 25 25 25
1)

b b c g e h c e c

CAH10 and C4AH131) C2AH8 and C4AH131)


2)

9.84 10.80 19.38 9.82 8.51 18.71 21.15 8.03 19.37 [46] [49] [52] [46] [49] [52] [11] 5.35 5.60 5.63 20.95 21.95 20.93 17.44

1.10 2.52 0.18 3.03 0.68 0.07 0.04 1.09 0.09 0.357 0.340 0.245 0.007 0.0075 0.032 0.150

12.93 12.19 12.48 12.14 12.88 13.22 13.27 12.10 12.48 11.96 11.97 --12.52 12.52 -----

C4AH13 and Ca(OH)2 (portlandite) CAH10 and C2AH81)

stable invariant points (this study)


C3AH6 and Al(OH)3 (gibbsite) C4AH13 and C3AH6 C4AH13 and Ca(OH)2 (portlandite) C3AH6 and Al(OH)3 (gibbsite) C3AH6 and Ca(OH)2 (portlandite)

stable invariant points (literature)


C3AH6 and Al(OH)3 (gibbsite) C3AH6 and Al(OH)3 (gibbsite) C3AH6 and Al(OH)3 (gibbsite) C3AH6 and Ca(OH)2 (portlandite) C3AH6 and Ca(OH)2 (portlandite) C3AH6 and Ca(OH)2 (portlandite) C3AH6 and Ca(OH)2 (portlandite)
2)

metastable with respect to C3AH6 and gibbsite metastable with respect to C3AH6 and portlandite

Development of a thermodynamic database for cement hydrates

39

Strtlingite, Ca2Al2SiO2(OH)103H2O
The XRD-reflections of the strtlingite preparation (Fig. 4.22) are broadened and the intensities are relatively weak, indicating poor crystallinity, although the position and relative intensities of all reflections agree with the pattern calculated from structural data by Kuzel [111] and by Rinaldi et al. [161]. According to Kwan et al. [119], who used a method similar to that of this Thesis to synthesise strtlingite, the reflection at ~29.5 2 (CuK radiation) may be attributed to C-S-H impurity. Furthermore this reflection overlaps with the main reflections of calcite. In this work, the peak intensities did not change over the temperature range studied, but slight contamination of the samples with respect to calcite cannot be excluded. After several dispersions, a slight decrease of the intensities of the XRD-reflections of strtlingite was observed compared to the fresh sample.
Str
Str - Strtlingite C-S-H - Calcium-Silicate-Hydrate Cc - Calcite

Str Str
C-S-H, Cc

Str Str Str Str 85C


250 counts

55C 25C 5C

Intensity 6

10

12

14

16

18

20

22

24

26

28

30

32

[2 Cuk ]

Fig. 4.22: Comparison of XRD-patterns of nominally strtlingite after ageing at temperatures in the range 5C - 85C (approach from undersaturation)

In agreement with published data by Kuzel [111] the thermal analysis pattern of strtlingite (Fig. 4.23) showed three endothermic peaks (a minor peak at ~120C and main peaks at ~165C and 220C). The total water content of the sample used in the title study, after drying over saturated CaCl2 solution at 37% r.h., is 32.4 wt.-%, close to the theoretical value (34.4 wt.-% for Ca2Al2SiO2(OH)103H2O) and in good agreement with values obtained on natural strtlingite (32.5 wt.-%) by Rinaldi [161]. As C-S-H has a lower percentage water content than strtlingite at 37% r.h. [180], it is believed that at most only a small amount of C-S-H can be present (< 10 - 15%); had more C-S-H been present, the total weight loss of the sample would have been significantly reduced due to dilution by C-S-H. Fig. 4.23 shows the foil-like morphology of synthetic strtlingite. No distinction between strtlingite and possible contaminants (C-S-H, or calcite, or mixtures thereof) was possible because of their morphological similarities. Solubilities of the synthetic strtlingite samples have been obtained in the range from 5 to 85C and are listed in Table A.8. In one series of experiments, significant amounts of sodium were found to be present in the solution, indicating insufficient washing of the synthesised solids before redispersion. However electron microprobe analysis of the solids did not show significant incorporation of sodium into the structure and data obtained from this preparation were admitted to solubility product calculations; the resulting values are in good agreement with those obtained from preparations known to be sodium-free.

Development of a thermodynamic database for cement hydrates

40

100 relative weight [wt.-%] 95 90 85 80 75 70 65 0 200 400 600 800 1000 Temperature [C]

DTG-curve

TG-curve

Fig. 4.23: ESEM image of strtlingite (left) and corresponding TG-and DTG-curves (right)

The averaged isothermal solubility products, used to estimate the enthalpy of reaction, are given in Fig. 4.24. It is noteworthy that, although only few solubility data for strtlingite are available, the differences between solubility products calculated from the literature [8][9][34][154][189] are small; they agree well with own results at 25C, even though different procedures had been used to synthesise strtlingite. The resulting thermodynamic data are compiled in Table 4.1. In agreement with results by Atkins et al. [9], it was found that the number of redispersions significantly influences the solubility of synthetic strtlingite. Calcium and aluminium concentrations generally decrease with increasing cycles of redispersion, whereas the silicon concentration increases. According to Atkins et al. [9], synthetic strtlingite tends to decompose with increasing redispersions to a C-A-S-H gel the presence of which alters the solubilities significantly. Accordingly, the maximum number of redispersions was limited in the title study to two. As shown in Fig. 4.25 and Table A.8, experimentally-derived solubilities of calcium and aluminium from strtlingite tend to increase with increasing temperature, whereas the silicon concentrations remain relatively constant. With the help of the fitted thermodynamic data (Table 4.1), solubility data were also recalculated to assess the impact of residual sodium, assuming an arbitrary aqueous concentration of 2 mmol sodium/kg H2O.
-18 Concentration [mmol/l] 2.4 2.0 1.6 1.2 0.8 0.4 0.0 100 0 20 40 60 Temperature [C] 80 100 silicon aluminium calcium

C 2 ASH 8

Calc. solubility product log Ksp

-19 1) -20 1) 2) 3) 4)
1) 2) 3) 4) Quillin 1994 T urriziani 1964 Atkins 1991 Carlson 1964

-21 0 20

40 60 Temperature [C]

80

Fig. 4.24: Calculated solubility products of strtlingite from solubility experiments (line shows calculated best fit)

Fig. 4.25: Recalculated solubility data for strtlingite based on fitted thermodynamic data from Fig. 4.24 (markers show experimental values from this study, lines show calculated fit). Predicted solid phases are shown at the top. Formation of gibbsite suppressed in calculations.

Development of a thermodynamic database for cement hydrates

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Although the solubility measurements agree well with the values by Atkins et al. [9], recalculation did not reproduce the experimental data. A computation of the solubility data in the presence of CS-H, believed to be present as an impurity, using the solid solution model described by Kulik et al. [104] and by Lothenbach et al. [123], resulted in great differences compared to the experimental values. However if a slight excess of calcium and aluminium (bulk amounts of CaO and Al2O3 ~1wt.-% higher than initially admitted to calculation) were artificially added, this was sufficient to reconcile calculation and experiment. Reasons for this behaviour are not clear: the water content of the Na2Si2O52H2O reactant needs to be checked. On the other hand, it is not clear how to treat the contaminants thermodynamically as long as uncertainties remain about their exact amount and composition and further investigations are needed to solve this problem. Only few studies dealt with the formation of strtlingite and related phase assemblages. The possibility of the existence of other aluminate-silicate-containing phases and/or related solid solutions has to be considered in future studies. However the consistency between the literature data and those obtained in the title study should encourage the user to treat these data as useful but not definitive.

4.4.3 AFt phases SO4-AFt, Ca6Al2(SO4)3(OH)1226H2O


Solubility data by Perkins and Palmer [147] for SO4-AFt were fitted by Lothenbach et al. [123] in the range from 5C to 75C using the software GEMS and the same thermodynamic database as in this Thesis; these data were adopted. Heat capacity coefficients were obtained experimentally from calorimetric heat capacities by Ederova [57]: the derived standard molar thermodynamic properties of SO4-AFt are listed in Table 4.1.
Calc. solubility products log Ksp -37 -39 -41 -43 -45 -47 -49 0 20 40 60 80 100 Temperature [C]

3)

3)

1) 1)

2) 3) 1)

1) Macphee 2004 2) Reardon 1994 3) Atkins 1991

Fig. 4.26: Calculated solubility product of ettringite according to solubility experiments by Perkins & Palmer [147] and other literature sources (line shows calculated fit)

Fig. 4.26 shows a comparison of calculated solubility products based on the fitted standard thermodynamic properties of SO4-AFt with solubility products calculated from experimental solubilities of SO4-AFt at different temperatures and from different literature sources [8][9][127] [147][192]. As shown in Fig. 4.26, the values generally agree within limits of analytical errors: fG0 (-15205.9 kJ/mol) and fH0 (-17535 kJ/mol) are consistent with values calculated by Babushkin et al. [12] (fG0 ~ -15205.7 kJ/mol and fH0 ~ -17578 kJ/mol) and those extrapolated by Perkins et al. [147] (fG0 ~ -15211 kJ/mol and fH0 ~ -17550 kJ/mol). fH0 is in good accord with calorimetrically-derived values of Berman [25]: fH0 ~ -17543 kJ/mol.

Development of a thermodynamic database for cement hydrates

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CO3-AFt, Ca6Al2(CO3)3(OH)1226H2O
The existence of a carbonate analogue of SO4-AFt was first described by Carlson and Berman [36]. However, as shown in [36] and subsequently confirmed by Pllmann et al. [152], synthesis of CO3AFt has only been achieved in a solution containing sucrose as well as sodium carbonate. This leads to a strong increase of the solubility of calcium in conjunction with high carbonate concentrations. Other synthesis methods under conditions likely to occur in cementitious system were unsuccessful and gave mixtures of monocarboaluminate and calcite, suggesting that CO3-AFt is metastable with respect to CO3-AFm in Portland cement pastes. This contention was later proved by Damidot et al. [49] who published the first thermodynamic data for CO3-AFt.
800 600 400 200 0 5 10 15 20 25 30 35 40 [2 ] CuK calcite

Intensity [cps]

Fig. 4.27: XRD-pattern (left) and scanning electron micrograph (right) of CO3-AFt used for solubility determinations.

A fresh set of solubility experiments was initiated to determine the solubility of CO3-AFt made using the sucrose method at 25C, as described in section 4.1.3. Fig. 4.27 shows the XRD-pattern of the dry CO3-AFt powder and its typical needle-like morphology. Mixtures of previously dried CO3-AFt with ultra pure water were aged up to 9 months at 25C. Despite the supposed metastability of CO3-AFt with respect to CO3-AFm, no obvious mineralogical changes were observed: CO3-AFt continued to coexist with small amounts of calcite. The solubility data of successive extractions are given in Table A.9. Although solubility data for CO3-AFt have only been determined at 25C the temperaturedependent behaviour of CO3-AFt can be estimated using the Helgeson approach [89]. Data can be approximated for other temperatures by formulating a reference reaction with compounds of similar structure and known entropies. The reference reaction for CO3-AFt is listed in Table 4.2. With the known entropies of anhydrite and calcite and the previously estimated value for ettringite (see Table 4.1) the standard absolute molar entropy of CO3-AFt was estimated assuming S0r = 0. Subsequently fH0 was calculated using the Gibbs-Helmholtz relation (Eq. 4.12), the known standard state entropies of the elements [109] and fG0. In the literature only one value for fH0 was found for CO3-AFt [12]; fH0 ~ -16217 kJ/mol for the 30 H2O hydrate (which corresponds to ~ -16789 kJ/mol for the 32 H2O hydrate) in very good agreement with the estimated value (fH0 ~ -16792 kJ/mol) for the formula with 32 H2O. The resulting estimated standard molar thermodynamic data of CO3-AFt are summarised in Table 4.1. The computed composition of the aqueous phase in equilibrium with CO3-AFt and calcite at 25C showed good agreement with the averaged solubility data for CO3-AFt (Table A.9).

Development of a thermodynamic database for cement hydrates

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Calc. solubility products log Ksp

-40 -42 -44 -46 -48 -50 -52 0 20 40 60 80 100 Temperature [C]
1) Damidot 1994

230
1)
C3 A + CaCO3 + 11H 2 O --> C4 AcH11

210 [kJ/mol] - G
0 r

190 170 150 0 20 40 60 Temperature [C] 80 100


C3 A + 3CaCO3 + 32H2 O --> C6 Ac3 H32

Fig. 4.28: Calculated solubility product of CO3-AFt from solubility experiments. The solid diamond shows the single value experimentally-determined in the title study. The solid line shows the calculated solubility product: see text and estimated thermodynamic data

Fig. 4.29: Free energy plot of CO3-AFt and monocarboaluminate

As noted, although CO3-AFt is metastable with respect to monocarboaluminate at ~25C, free energy plots are a useful instrument to derive data about relative stabilities of phases as a function of temperature. Fig. 4.29 compares free energy plots for the formation of monocarboaluminate and CO3-AFt from C3A and calcite over the temperature range 1 to 99C. As expected, monocarboaluminate is thermodynamically more stable than CO3-AFt between 1 to 99C. But with decreasing temperatures CO3-AFt is increasingly stabilised and is close to being more stable than monocarboaluminate at 1C. Due to lack of experimental data and uncertainties in the estimation of thermodynamic parameters, the present state of the data must be regarded as provisional. Nevertheless low temperatures tend to stabilise CO3-AFt and substitution of SO42- by CO32- in the ettringite structure is clearly favoured at low temperatures, < 25C. Thaumasite is another compound containing essential carbonate and having an AFt type structure. In contrast to CO3-AFt and SO4-AFt, aluminium is replaced by silicon in the thaumasite structure. According to the literature [2][40], and in contrast to CO3-AFt, thaumasite has a stability range in the cement system and is preferably formed at low temperatures, < 10C. This is in agreement with own calculations, where it was shown that CO3-containing AFt structures are stabilised at low temperatures. Furthermore Macphee and Barnett [127] and others [103][126][185] have shown that SO4-AFt forms solid solutions with thaumasite. Macphee and Barnett [127] published solubility data for the solid solutions but not for the thaumasite end member. Bellmann [20] obtained solubility data for natural thaumasite, but only at 8C. Thus until recently no complete thermodynamic dataset for thaumasite was available. In the course of this work a new dataset was prepared to (i) predict the temperature-dependent stability of thaumasite and (ii) to enable the modelling of the solid solution behaviour between thaumasite and SO4-AFt (see chapter 6).

Development of a thermodynamic database for cement hydrates

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4.4.4 C-S-H
C-S-H (calcium-silicate-hydrate) is the main phase of hydrated Portland and blended cements and is responsible for strength development and hydraulic behaviour. Its composition is normally defined by its calcium/silica ratio. Several authors derived solubilities from synthetic C-S-H [14][66][72][85][164][178][181][191] and the overall picture is consistent. The maximum Ca/Si ratio of C-S-H in hydrated cement pastes is variously claimed to lie between 1.5 and 1.9 in portlandite saturated systems and, due to phase rule restrictions, C-S-H in Portland cements and blended cements which contain excess portlandite, will have as a first approximation a nearly constant composition ~1.5-1.9 CaOSiO2nH2O, where n is largely dependent on the humidity of the hydrated cement paste. Several thermodynamic models [26][71][73][77][101][104][142][158] have been developed to describe the solubility properties of C-S-H.

10 Silicon [mmol/l] 1
calculated

0.1 0.01 0.001 0.0 5.0 10.0 15.0 20.0 Calcium [mmol/l]

Flint/Wells 1934 Roller/Ervine 1941 Greenberg/Chang 1965 Fuji/Kondo 1981 Suzuki et al. 1985 Atkins et al. 1991 Barbarulo 2002 Walker 2003

Fig. 4.30: Comparison of recalculated solubility of C-S-H at 25C (solid line) with experimental values from literature (markers) at temperatures between 20C - 30C (see references)

According to Kulik and Kersten [104] an ideal solid solution model is sufficient to describe the solubility behaviour of C-S-H, as solid solution is continuous and no miscibility gaps at relevant Ca/Si-ratios are reported. Tobermorite-type C-S-H (Ca/Si=0.83), a jennite-type C-S-H (Ca/Si=1.67) and amorphous silica were used as end members of two different solid solution series, as defined by Lothenbach et al. [123], who gave a detailed description of the derivation of thermodynamic data for the C-S-H end members; related data were compiled in Table 4.1. As shown in Fig. 4.30, the recalculated solubility of C-S-H agrees reasonably well with literature values. According to Kulik and Kersten [104] one solid solution (tobermorite-jennite) describes the Ca/Si range 0.83 (Ca/Si)C-S-H 1.67 while a second solid solution (amorphous silica - tobermorite) is used to describe the range 0 (Ca/Si)C-S-H 0.83. However, according to investigations by Greenberg et al. [85] and Suzuki et al. [178], and as described by Taylor [180], C-S-H gel coexists with a silica species with low calcium content and a composition close to amorphous silica at initial Ca/Si ratios below ~ 0.6 - 0.85, indicating either a miscibility gap in the second solid solution series or that it has a sharp cut-off at a critical Ca/Si ratio. Therefore the user has to decide which model to apply but, in agreement with the literature, it is recommended to use a model with one solid solution having tobermorite- and jennite-type C-S-H as end members. This allows a coexistence of

Development of a thermodynamic database for cement hydrates

45

amorphous silica and C-S-H (Ca/Si = 0.83) at low initial bulk Ca/Si ratios < 0.83, and also enables unambiguous calculation of the range of Ca/Si ratios of most interest to cement paste to be encompassed. These conclusions are supported by recent calculations by Kulik [107]. The C-S-H phase may sorb sulfate, alumina and alkalis. At present, these chemical variants are not included into a thermodynamic model. However, Hong et al. [92] give distribution coefficients of the sorption of alkalis into C-S-H, which can be used to estimate the amount of sorbed alkalis in C-S-H in dependence of the alkali concentration of the pore solution of the hydrated cement paste. Similarly, the amount of sorbed sulfate can be approximated. Corresponding temperaturedependent values for the adsorption of sulfate to C-S-H are given in [15][54][130][160]. Richardson and Groves [160] also describe aluminium for silica substitution in the C-S-H structure. The amount of substituted aluminium increases with decreasing Ca/Si ratios and can be estimated using the relations described in [160].

Development of a thermodynamic database for cement hydrates

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4.5. Discussion 4.5.1 Data accuracy


The data for individual substances vary in quality. The reasons for this have been developed in the text but it is still difficult to establish error limits. Firstly, the quality of synthesis is variable: it is difficult if not impossible to establish the absolute phase purity of the preparations. Only the use of single crystals would enable a high confidence in the absolute purity of the preparations used. Secondly, the substances themselves vary in crystallinity with as yet unknown consequences to the numerical values of the data derived from their use. An example is strtlingite, X-ray patterns of which always exhibit line broadening associated with low crystallinity, small crystallite size and internal disorder, perhaps with respect to the stacking of successive layers: no attempt was made to deconvolute the causes of line broadening or the impact of crystallinity on thermodynamic properties. But it could be argued that the AFm phase, particularly strtlingite occurring in commercial cements, also exhibits disorder and thus the synthetic product is representative of real strtlingite. The results, expressed in tables and diagrams, comprise a working set of data for subsequent calculations. It is not claimed that the database is perfect and indeed have noted the shortcomings of particular datasets as appropriate. In a very few cases where data are incomplete, there is also noted work in progress. It is the authors hope that, as the use of thermodynamic methods becomes routine, others will add to and improve the accuracy of the compilation. A general source of experimental uncertainty concerns the analytical data. Some of the very low concentrations, e.g. the aluminium concentrations of C3AH6 in equilibrium with portlandite, have numerical values close to the limit of accurate analysis. Carbonate concentrations generally had to be estimated assuming equilibrium with other carbonate phases whose thermodynamic properties were known, e.g., calcite. However, as shown in this work, the solubility data generally pass two tests: of self-replication; that is when used as inputs for calculations they reproduce reliably the input data, usually in the form of solubilities, and second, that they are derived from approach to equilibrium from both oversaturation and undersaturation. This latter test, while not infallible, is generally regarded as substantive proof of the attainment of equilibrium. Moreover the data presented are broadly comparable with those for other substances recorded in the literature. Care was taken to assess all main solubility investigations recorded in the accessible literature. However, as many of the investigations go back to the 1930s, when analytical techniques were often not advanced sufficiently to analyse low concentrations of species, these add another source of uncertainty. Impurities present in solutions can significantly influence the solubility data. For example a large data scatter was observed for the solubilities of hydrogarnet, C3AH6. The older datasets by Wells et al. [193] and Peppler et al. [155], used to derive thermodynamic values in previous databases, differ significantly from data obtained in the course of the title study. Wells et al. [193] and Peppler et al. [155] used glass flasks in the course of the solubility determinations. Thus it is likely that silicon was dissolved in the course of the experiment. As shown in section 4.4.1, silicon can be bound in the hydrogarnet structure and the resulting siliceous hydrogarnet, Ca3Al2(SiO4)3-x(OH)4x, will be significantly stabilised by silica and have lower solubility than the silica-free composition. Atkins et al. [7], who determined solubilities of C3AH6 assemblages, confirmed this hypothesis. In the silica-free samples the solubility product of C3AH6 at 25C was close to the values obtained in the title study whereas in assemblages containing silicates, e.g. C-S-H and strtlingite, the

Development of a thermodynamic database for cement hydrates

47

solubility products attributed to hydrogarnet were significantly lowered. Indeed, Wells and coworkers recognised significant silica substitution was occurring in the structure of ferric and aluminous hydrogarnets arising from dissolved silica [65] although no specific statement about the role of silicon impurities was made in their study of C3AH6 solubility. Furthermore it is generally known that CO2 interacts strongly with the cement hydrates. Thus, while care was taken in the title study to avoid CO2-contamination by using a N2-atmosphere, traces of carbonate were invariably present. Another source of uncertainty is the fitting procedure of the experimental data used to derive standard molar thermodynamic data. Kulik [106] gives an overview concerning uncertainties of temperature extrapolations of thermodynamic data. Thermodynamic data of the title study were fitted by a three-term temperature extrapolation and this method is believed to be more reliable than other commonly-used temperature extrapolations [106]. As demonstrated in Fig. 4.31 solubility products estimated with the widely used integrated Vant Hoff method show significantly larger deviations from the experimentally-derived values at elevated temperatures. The difference between extrapolated temperature-dependent solubility products of the hydrates using the threeterm extrapolation and solubility products, calculated from the fitted standard thermodynamic properties and the estimated heat capacity coefficients according to section 4.3.2, are generally small over the temperature range 0 to 99C (Fig. 4.31).
-28 Van't Hoff extrap olation -29 -30 -31
1)

Calc. solubility product log Ksp

Cp(T) integration
2) 1)

three term temp erature extrapolation 1) Atkins 1991 2) Jap py 1991 40 60 Temperature [C] 80 100

-32 0 20

Fig. 4.31: Comparison of solubility products calculated from the three-term temperature extrapolation (solid black line) and integrated Vant Hoff extrapolation (dashed black line) with values calculated from standard Cp(T) integration and experimentally-derived solubility products of siliceous hydrogarnet (markers)

Development of a thermodynamic database for cement hydrates

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4.5.2 Relations between equilibrium and kinetics


In the course of preparing this study, there were numerous comments that, while equilibrium is studied, kinetics is ignored. This comment contains an element of truth: it is not possible to advance both topics given constraints on resources. But kinetics is not ignored. For example in the system CaO-SiO2-H2O, the stable phases tobermorite and jennite are suppressed in favour of metastable C-S-H: C-S-H is assigned a definite set of thermodynamic properties and is allowed to participate in reactions with other phases, including some that are thermodynamically stable under the conditions of the calculation. This was done in the knowledge that the C-S-H phase is persistent. While accepting that the kinetics are important, relatively little progress has been made in their quantification. A thermodynamic approach is immediately successful in showing why this is so. Reactions can be divided into two types: internal, in which overall composition does not change (isochemical) and externally-induced, where cement solids react with their service environment. The latter class of reactions are intrinsically more difficult to quantify because the bulk composition of solids changes in the course of reaction. But thermodynamics immediately shows that, in seeking to understand the diffusion of a single species into (or out of) cement, it is in fact necessary to constantly recalculate mass balances: diffusion of a single species in isolation is insufficient to account for the overall reactions. A thermodynamic approach, which automatically tabulates mass balances, provides a mass balance template for subsequent kinetic studies and usefully highlights the underlying mechanisms and their probable importance. The experimental studies give direct information on reaction kinetics. Many examples are given in the text of reactions which occur relatively rapidly (hours to days) while others occur slowly or not at all. An example of slow reactions is the stability of siliceous hydrogarnet at low temperatures and at low carbonate and sulfate activities (see paragraph below). There also exists a third class of reactions: those predicted to occur but where observation and experiment are inadequate to determine whether or not the relevant prediction is confirmed. It is thus suggested that the kinetics are best approached in conjunction with thermodynamic equilibrium calculations rather than as a separate exercise: the driving forces responsible for change have a thermodynamic basis and, moreover, comparison of calculation and experiment shows that with few exceptions, the principal of local equilibrium is maintained, or nearly so, in the course of environmentally-conditioned reactions. Many of the verification experiments performed in the course of this thesis and in other supporting studies disclose that reaction occurs relatively rapidly. Of course the experimental conditions were selected to facilitate reaction, as for example, by using high water/solid-ratios. Nevertheless further work may disclose that phase changes in cement mineralogy driven by temperature changes occur relatively rapidly. It is of course a well-known generalisation that reaction rates become more rapid at higher temperatures, but perhaps surprisingly, some mineralogical conversion reactions were found to proceed rapidly (days or weeks) at 5C. Thus while kinetics are important, much evidence indicates that, with the notable exception of C-S-H, the internal constitution of hydrated Portland cements tends to approach a thermodynamic equilibrium.

Development of a thermodynamic database for cement hydrates

49

4.5.3 Applications of the database


Inspection of data tables does not directly reveal relationships between chemistry and mineralogy and its variation with temperature to see the effects, much thermodynamic modelling calculations are needed. But five features stand out. Firstly, the assemblage of portlandite and C-S-H dominate the products of cement hydration. With few exceptions -thaumasite being an important one-, these phases persist in most of the assemblages and are rather insensitive in composition to the presence or absence of other phases and, although the C-S-H phase can vary widely in its Ca/Si ratio, its ratio is effectively fixed at or near its highest attainable value (1.5 - 1.9) in the presence of portlandite. Secondly, the minor phases of hydrated Portland cement (AFm, AFt,...) are very variable in composition and structure. By not forming complete solid solution even within a structural family, the nature of the minor solids remains very sensitive to changes in bulk composition and temperature: note for example, the chemical-mineralogical complexity of the AFm and AFt families. Thirdly the temperature dependence of the nature of the stable phases is quite remarkable and will be explored in a subsequent chapter (see sections 6 and 7), following additional calculations. Fourthly, changes between assemblages, particularly in respect of the minor phases, require mass transport and structural reconstitution. This creates a series of buffering reactions within the cement paste matrix. For example internal buffering systems exist for hydroxyl, sulfate and carbonate: while the first of these is relatively well-known, the existence of buffers for other species and the consequences of buffering with respect to alteration has been less well recognised. The workings of these buffer systems and their interactions, as well as their consequences to environmentally-conditioned reactions of cement systems, will undoubtedly assist the future development of chemical/ mineralogical models of cement performance. Finally, the database derived in this Thesis redefines the stability of sulfoaluminate hydrates and shows that sulfate interacts strongly with carbonate. The undoubted persistence of sulfate-AFm amongst the hydration products of commercial cements has long been at variance with its supposed instability at < 40C: it has been necessary to attribute its persistence to metastability. However, this work shows monosulfoaluminate hydrate to be more stable than hitherto supposed, with a lower limit of thermal stability at ~55C in the system CaO-Al2O3-CaSO4-H2O. This revision immediately resolves a long-standing conflict. However the importance of treating sulfate in conjunction with carbonate is emphasised and the sharp temperature dependence of sulfate-carbonate phase relations is highlighted. Albert, et al. [4], have recently suggested that calcium monosulfoaluminate was preserved to lower temperatures, <40C, by the reduced activity of water in hydrated cement paste. While they direct attention to an important factor, it is not in fact necessary to invoke special conditions to explain the stability of sulfate-AFm according to the revised data. However, it is agreed with these authors about the importance of extending knowledge of cement hydration to regimes characterised by having reduced water activities, as for example may occur in alkali-activated systems or in normal compositions at low w/s-ratios. The relative thermodynamic stabilities of the cement hydrates are very sensitive to their chemical environment. Care has to be taken that the calculated temperature-dependent stability regions for each mineral depend on the total chemical composition of the system and cannot be extrapolated to more complex chemical environments, such as those in commercial cement. Two examples will be discussed briefly:

Development of a thermodynamic database for cement hydrates

50

The influence of sulfate and carbonate on the stability of hydrate phases containing calcium and aluminium
Fig. 4.32 a) shows the temperature-dependent free energy plots of the reaction of tricalcium aluminate (C3A) and gypsum with water in dependence of the presence of carbonate. Until recently it was believed that the assemblage ettringite + C3AH6 was more stable than monosulfoaluminate [46]. However, applying the dataset of the title study as shown in Fig. 4.32 a), for a carbonate-free system with an initial molar bulk ratio SO3/Al2O3 = 1, reactions (2) and (3) show that monosulfoaluminate (C4AsH12) is calculated to be more stable (rG0 of reaction (2) < rG0 of reaction (3)) than a mixture of ettringite (C6AsH32) and C3AH6 at temperatures > ~5C: see Fig. 4.32 a). This is in agreement with own investigations, which have shown that monosulfoaluminate forms and persists at 25C for more than 20 months. However the stable hydration products change significantly if carbonate is introduced. According to reaction (1), gypsum will react with part of the alumina to form ettringite whereas the remaining alumina reacts with calcite to form monocarboaluminate. Thus the addition of calcite leads indirectly to the low temperature stabilisation of ettringite.
a) system CaO-Al2O3-CaSO4-CaCO3-H2O
250 240 [kJ/mol] 230 220 210 200 190 0 10 20
(3) C3 A + CaSO4 .2H 2 O +~12.67H2 O --> ~0.33 C6 As3 H32 + ~0.67 C3 AH6 (1) C3 A + CaCO3 + CaSO4 .2H2 O +16H 2 O -->~0.33 C6 As3 H 32 +~0.67C4 AcH11 +~0.33CaCO3

b) system CaO-Al2O3-CaCO3-H2O
230
(4) C3 A + CaCO3 + 11H 2 O --> C4 AcH11

220 [kJ/mol] - G
0 r

(2) C3 A + CaSO4 .2H2 O +10H 2 O

210 200 Point B 190 180 0 10 20 30 40 50 60 70 80 Temperature [C] 90 100

Point A

--> C4 AsH 12

- G

X
(5) C3 A + CaCO3 + 6H2 O --> C3 AH 6 + CaCO 3

30

40 50 60 70 Temperature [C]

80

90 100

Fig. 4.32: Influence of sulfate and carbonate on the relative stabilities of aluminate hydrates.

On the other hand, as shown in Fig. 4.32 b), monocarboaluminate is predicted to be stable up to 85C (reaction (4)) and C3AH6 and calcite will be formed at higher temperatures, >85C, according to reaction (5) (see Point B Fig. 4.32 b)). In agreement with the investigations of the title study (see chapter 4.4.2), as well as observations by Kuzel and Baier [114], this upper stability temperature (~85 to 90C) is valid in the sulfate-free system CaO-Al2O3-CaCO3-H2O. However from these investigations one cannot conclude that monocarboaluminate will be stable up to 85C in a sulfatecontaining environment, e.g. in Portland cement. In a sulfate-containing system, monocarboaluminate will only be stable up to 50C and monosulfoaluminate will form instead according to reaction (2) at higher temperatures; see Point A of Fig. 4.32 a). This means that the reported upper stability temperature of monocarboaluminate will decrease significantly in hydrated Portland cement because sulfate is normally present. Several other aspects of the data will require to be investigated. Arguably, the most important concerns the potential for phase changes in cement pastes at low temperatures. Low temperatures, in the range 0 - 20C, increasingly stabilise carbonate substitution into the ettringite phase. This potential substitution could enable formation of ettringite without need for additional sulfate and

Development of a thermodynamic database for cement hydrates

51

may help explain why enhanced ettringite formation appears to be a precursor to thaumasite: reaction proceeds in two stages by replacement of sulfate in ettringite by carbonate followed by silicate replacement of aluminate, with conversion of carbonate-AFt to thaumasite.

The influence of silica on the stability of hydrate phases containing calcium and aluminium
Silica is one of the main constituents of Portland cements. Fig. 4.33 a) shows free energy plots of the reaction of C3A, with gypsum and water. As noted, in the silica-free system CaO-Al2O3-CaSO4H2O, with an initial molar bulk SO3/Al2O3 ratio = 1, monosulfoaluminate is more stable than the phase assemblage of ettringite (C6AsH32) and C3AH6 at temperatures > ~5C (reactions (2) and (3), Fig. 4.33 a). But if silicon is added to the system, according to reaction (1) the phase assemblage of C6AsH32 and C3AS0.8H4.4, which represent a member of the solid solution series Ca3Al2(SiO4)3-x(OH)4x, has a lower Gibbs free energy of reaction and is therefore thermodynamically more stable than monosulfoaluminate (reaction (2)) at temperatures from 1 to 99C. In the system CaO-Al2O3-CaCO3-H2O, addition of silicon causes an analogous thermodynamic stabilisation of the hydrogarnet phase (Fig. 4.33 b)). Whereas in the silicon-free system, monocarboaluminate is calculated to be more stable than the assemblage of C3AH6 and calcite at temperatures below ~85C, if silica is added according to reaction (4), C3AS0.8H4.4 and calcite become more stable than monocarboaluminate. Thus calcite is predicted to be an essentially inert material in the system CaO-Al2O3-CaCO3-SiO2-H2O at all temperatures, 1-99C.
a) system CaO-Al2O3-CaSO4-SiO2-H2O
280 260 - G r [kJ/mol] 240 220 200 180 0 10
(3) C3 A + CaSO4 .2H2 O +12.666H2 O -->0.33 C6 As3 H32 + 0.67C3 AH6 (1) C3 A + CaSO4 .2H2 O + 0.533 SiO2 +11.6H2 O --> 0.33C6 As3 H32 + 067C3 AS0.8 H4.4

b) system CaO-Al2O3-CaCO3-SiO2-H2O
280 260 [kJ/mol] 240 220 200 180 160
90 100
(6) C3 A + CaCO 3 +6H2 O --> C3 AH6 + CaCO 3 (5) C3 A + CaCO 3 +11H 2 O --> C4 AcH11 (4) C3 A + CaCO 3 + 0.8 SiO 2 +4.4H2 O --> C3 AS0.8 H4.4 + CaCO3

(2) C3 A + CaSO4 .2H2 O +10H2 O --> C4 AsH12

20

30 40 50 60 70 Temperature [C]

80

- G

10 20 30 40 50 60 70 80 90 100 Temperature [C]

Fig. 4.33: Influence of silicon on the relative stabilities of aluminate hydrates.

Probably due to kinetic reasons, siliceous hydrogarnet is rarely observed in hydrated Portland cement at room temperature. Numerous researchers have shown that AFm phases are abundant reaction products of Portland cements. In agreement with experimental results, sulfate- and carbonate-AFm phases are observed as persistent phases in Portland cement. It is not possible to extrapolate stability regions obtained from simplified model systems with two or three components directly to complex chemical systems, e.g. to commercial Portland cement, with numerous components present. However, with the knowledge of the thermodynamic properties of all potential reaction products and a suitable software, it is possible to undertake the additional calculations necessary to predict and quantify the phase assemblages. On the other hand, as shown above, the database cannot be used as a black-box approach and fundamental knowledge about the processes of cement hydration, including knowledge of reaction pathways and

Development of a thermodynamic database for cement hydrates

52

metastable vs. stable phase assemblages -the latter based on experimental observations- is necessary to ensure that the calculations are appropriate.

4.6. Concluding remarks


A short review of the obtained dataset showed that the composition of the AFm phase varies with chemical environments. The stability of the different AFm phases is temperature-dependent. Furthermore the stability of the AFm phases with respect to other cement hydrates, e.g. AFt and hydrogarnet needs to be investigated. Thus an extensive work programme was set up to investigate the AFm and AFt phase assemblages in Portland cement. Using the presently available thermodynamic data it is assumed that C-S-H and portlandite, the main constituents of Portland cement, do not interfere with AFm and AFt phases, except with respect to sulfate sorption and aluminium substitution in C-S-H, and in the formation of thaumasite. In the case of thaumasite formation, a correction has been applied (see section 6.3) to accommodate this. Systematic investigations, presented in subsequent chapters of this work, dealt with the following aspects: Investigation of AFm phase assemblages in Portland cement. The possibility of solid solution formation between AFm phases in the system CaO-Al2O3-CaSO4-CaCO3-H2O at 25C and the impact on Portland cement hydration was investigated. Generic paradigms to the distribution of sulfate and carbonate in dependence of the chemical composition of Portland cement were developed. The formation of solid solutions between SO4-AFt, CO3-AFt and thaumasite was examined. Another important scope of this work was to investigate the impact of calcite (limestone) additions on the hydration of Portland cement. By calculating specific volume changes, the investigations are closely linked to mechanical and physical properties of the hydrated cement paste. The influence of elevated temperatures in the range 5C to 85C on phase assemblages in hydrated Portland cement containing limestone was subject of investigation.

The AFm phase in Portland cement

53

5. The AFm phase in Portland cement


5.1. Literature review 5.1.1 General remarks on the structure and formation of AFm phases
The AFm (Al2O3-Fe2O3-mono) phases are amongst the most important hydrate phases in Portland cement systems. AFm phases, grown from aqueous solution generally form platy, hexagonal crystals with a good (0001) cleavage. AFm phases have the formula [Ca2(Al,Fe)(OH)6]XxH2O where X equals an exchangeable singly charged or half of a doubly charged, anion. The principal structure of AFm phases was first described by Buttler et al. [33] who investigated its naturally occurring analogue, hydrocalumite, C3AxCaCl2yCa(OH)2zCaCO3nH2O with x+y+z=1. Generally the unit cells of the AFm phases can be described as hexagonal with a = 0.57 - 0.59 nm. The layer thickness is dependent on the size of the X anion and the interlayer water content. The interlayer water content, and thus the layer thickness, decreases upon stepwise dehydration. Derived from a brucite-like layer structure, AFm phases have principal layers comprising Ca2+ ions with a regular substitution of (Al3+, Fe3+) for Ca2+. This positively charged main layer has the composition [Ca2(Al,Fe)(OH)62H2O]+. Allmann [5] published an advanced and later refined [6] structure model for monosulfoaluminate Ca4Al2(SO4)(OH)126H2O (Figs. 5.1 and 5.2). The monosulfoaluminate-hydrate crystallises in a hexagonal structure with the spacegroup R3. According to Allmanns investigations, the Al3+ ions are octahedrally coordinated by six OH- -ions. Two thirds of the interlayer water molecules are bound to calcium. Due to a shift of the Ca-atoms of +/- 0.57 out of the centre of the (OH)6-octahedra towards an additional OH-- group in the interlayer, the coordination of Ca2+-ions is effectively sevenfold. Alternating with the principal layers, negatively charged interlayers with the composition [SO42-3H2O]- balance the charges of the main layers and form hydrogen bridges between main layer and interlayer. The SO42- anions and one third of the interlayer water molecules are disordered: the remaining water molecules fill the spaces in the interlayer. Thus part of the water molecules are not integrated as hydrogen bridges into the crystal structure of the AFm phases. These non-bonded water molecules can be reversibly removed from the compound depending on the relative humidity of the environment. Due to this behaviour, different water contents can be observed for AFm phases. The transition between different hydration states, e.g. C4AH19 and C4AH13, is discontinuous.

[Ca2Al(OH)6]+ [SO42-3H2O][Ca2Al(OH)6]+ [SO42-3H2O]-

Fig. 5.1: Brucite-like [Ca2Al(OH)6]+main layer projected onto the c-axis according to Allmann [6]

Fig. 5.2: Structure of according to Allmann [6]

monosulfoaluminate

The AFm phase in Portland cement

54

Different anions can be integrated into the AFm interlayer with the general composition [XmH2O]- where X denotes a singly-charged e.g. OH-, or half of a doubly charged anion, e.g. SO42-. The most important anions present in hydrating OPC and blended cements are OH-, SO42and CO32-, to form hydroxy-AFm C4AHx, monosulfoaluminate C4AsHx and monocarboaluminate C4AcHx respectively [180]. Anions like Cl-, CrO42- and SeO42- can be bound in the crystal structure of AFm phases [19][112][146] but are not included in the scope of this investigation. Pllmann [149] also shows that organic anions e.g. carboxylic acid groups can be incorporated into an AFmlike structure although the layer spacing is vastly increased to accommodate the organic chains. In the presence of amorphous silica or silica-containing blends, e.g. blast furnace slags or metakaolin, the formation of C2ASH8, strtlingite, or gehlenite hydrate, is observed [199]. The crystal data [111] of strtlingite show it to be an AFm phase with an aluminosilicate anion in the interlayer. Due to changing hydration state in response to the relative humidity of the environment, a careful interpretation of experimental results with regard to the initial hydration state is necessary. To enable phase analysis without carbonation, e.g. by X-ray diffraction, the solid may need to be dried and, as a consequence, the water content of the interlayer may be affected. For example, C4AHx is likely to reduce its water content from x = 19 to x = 13 water molecules at relative humidity < 88% and 20C [180]. As many experiments were carried out at relative humidity < 100% the initial hydration state of C4AHx is often referred to x = 13 and therefore an artificially low water content may be observed. On the other hand, the high ionic strength of the pore solution of hydrated OPC decreases the activity of water and favours a lower hydration state of the AFm phase [79]. Thus care is required to preserve the initial hydration state during subsequent analysis of the solid; if this is not possible any changes of the hydration state during the analysis should be recorded. The ability to form solid solutions is dependent on mechanism as well as upon the thermodynamics. It is well known that AFm phase compositions are sensitive to anion exchanges with their environment and formation of solid solutions between AFm end members cannot be neglected. One of the most important AFm phases in hydrated OPC is monosulfoaluminate, with stoichiometric composition C4AsHx. But several investigations describe formation of solid solutions between monosulfoaluminate and other AFm phases in hydrated OPC, e.g. hydroxy-AFm, C4AHx, or monocarboaluminate, C4AcHx.

5.1.2 Stability of AFm phases


The absolute stability of selected AFm compositions is shown in Table 5.1. The Table needs to be used in conjunction with supplementary information. For example, cements normally contribute a high hydroxyl content to the mix water so OH- is invariably present at high concentrations. Most modern cements contain sulfate, added as calcium sulfate, to control set times. But in the cement environment sulfate is sparingly soluble and carbonate even less soluble at high pH. Hence these species, carbonate and sulfate, have low aqueous concentrations, but nevertheless compete for anion sites in AFm structures. Carbonate sources include i) alkali sulfates condensed onto clinker in the course of cooling or from added clinker kiln dust; these sulfates are in fact solid solutions with carbonate partly replacing sulfate [18] ii) carbonates gained by reaction with the atmosphere iii) carbonate added as a permitted extender, normally in the form of interground calcite and iv) carbonate present as impurity in gypsum. Damidot [49] showed that with rising carbonate activity, hydroxy-AFm was replaced, first by hemicarboaluminate and then by monocarboaluminate. As the carbonate content of the AFm solid increased stepwise, its stability at 25C also increased.

The AFm phase in Portland cement


Table 5.1: Thermodynamic stabilities of selected AFm phases at 25C Distinctive Formula Designation Stability at 25C and 1 Anion bar
OHC3ACa(OH)2xH2O hydroxy-AFm Unstable - decomposes to hydrogarnet C3AH6, and portlandite Stable - but not many thermodynamic data available; unstable in contact with calcite stable Calculated to be stable above 40C - at lower temperatures decomposes to AFt, C3AH6 and gibbsite stable at 25C [AlSi(OH)8]ClC2ASH8 C3ACaCl2xH2O gehlenite hydrate, strtlingite Friedel`s salt stable Stable, but not described in this work. Mainly occurs as an alteration product of cement paste in chloriderich environments

55

Reference

[193]

OH-; CO32-

C3ACa[(OH)(CO3)0.5]xH2O hemicarboaluminate

[49]

CO32SO42-

C3ACaCO3xH2O C3ACaSO4xH2O

monocarboaluminate monosulfoaluminate

[49] [47]

This study [48] [45]

This pattern of stability means that, in addition to taking into account the bulk chemistry of cements, one must also note that some AFm compositions are metastable under all conditions and are prone to decomposition or reaction while others have a definite range of stability under conditions relevant to the internal environment achieved in commercial cements. The impact of small amounts of carbonate on the nature and stability of the AFm phase is noteworthy; Table 5.2 shows selected composition data for AFm phases, from which it can be seen that ideal hemicarboaluminate and monocarboaluminate contain only 3.9 and 7.7 wt.-% CO2 respectively.
Table 5.2: Sulfate- and carbonate-contents of minerals relevant to Portland cement
Mineral Formula Carbonate content CO2 [wt.-%] Sulfate content SO3 [wt.-%]

Gypsum Ettringite

CaSO42H2O Ca6Al2(SO4)3(OH)1226H2O

44.0 7.7 3.9

46.5 19.1 12.9 -

Monosulfoaluminate Ca4Al2(SO4)(OH)126H2O Calcite CaCO3

Monocarboaluminate Ca4Al2(CO3)(OH)125H2O Hemicarboaluminate Ca4Al2(CO3)0.5(OH)135.5H2O

The AFm phase in Portland cement

56

5.1.3 Solid solutions between AFm phases Solid solutions between monosulfoaluminate and hydroxy-AFm
The literature reveals considerable divergence of interpretation concerning the existence and extent of solid solution between OH- and SO4-AFm phases, arguably the most important pair with respect to the constitution of fresh, carbonate-free Portland cements. Jones [97] published results of an investigation of the system CaO-Al2O3-CaSO4-H2O at 25C. Microscopic examination of the hexagonal calciumsulfoaluminate hydrates showed changing refractive indices of the solid phases with changing initial CaSO4/Al2O3 ratios. Therefore it was concluded that a complete solid solution series exists between monosulfoaluminate and hydroxyAFm. DAns and Eick [51] found similar results in their microscopic examination of the quaternary CaOAl2O3-CaSO4-H2O at 20C. They concluded the existence of complete miscibility between both end members, C4AsHx and C4AHx. Turriziani [190] synthesised a solid solution series between C4AsHx and C4AHx following the method used by DAns and Eick [51], with changing molar CaSO4/Al2O3 ratios between 0.22 to 1.0 and higher. The microscopic studies of samples cured for 30 days apparently confirmed the results of DAns and Eick [51] showing complete miscibility between end members. But in contrast to the optical properties, the X-ray data showed two immiscible phases with patterns similar to those of mixtures of sulfate- and hydroxy-AFm. A direct comparison to the results from Jones [97] and DAns and Eick [51] cannot be made as X-ray data were not obtained in DAns and Eicks studies, but Turrizianis data are internally inconsistent. Roberts [163] published a detailed examination of the formation of AFm solid solutions. A solid solution series between C4AsHx and C4AHx was prepared by adding increasing amounts of gypsum to a suspension of C4AHx and water. After ageing the mixture for at least 7 days, the subsequent Xray investigation showed a shift of the d-space of the main basal reflection of the solid solution d0001 from ~ 9.0 to 8.77 with decreasing molar CaSO4/Al2O3 ratios from 1 to 0.5. At CaSO4/Al2O3 ratios 0.5 two phases were observed: the limiting solid solution with a d-spacing of 8.77 and C4AH19. Thus it was believed that there is a miscibility gap occurred between C4AHx and a limiting solid solution, having the approximate composition C4ASO3xH2O. Seligmann [169] synthesised a similar C4AsHx-C4AHx solid solution series by hydration of C3A with varying amounts of Ca(OH)2 and CaSO42H2O. In comparison with Roberts work, a limiting solid solution composition of C4A3/5 SO3xH2O was reported. Pllmann [150] confirmed Roberts results. A C4AsHx-C4AHx solid solution series was prepared, as described above, by hydration of C3A or CA with Ca(OH)2 and CaSO42H2O for 8 months. A miscibility gap between CaSO4/Al2O3 ratios from 0 to 0.5 was concluded from least square refinements of X-ray patterns of the aged precipitates. The limiting solid solution with, a d0001 value of 8.76 , had the approximate composition C4ASO3xH2O and was termed hemisulfate. Furthermore it was shown that there is a strong temperature dependence of the extent of solid solution between C4AsHx and C4AHx. The width of the miscibility gap increased at 60C to include ratios between 0 to 0.8. However, at temperatures 45C, C4AH19 was not stable and decomposed slowly to a mixture of C3AH6 and Ca(OH)2 in compositions within the supposed miscibility gap. At

The AFm phase in Portland cement

57

80C no miscibility of C4AsHx and C4AHx was observed. The X-ray analysis of the precipitates showed a mixture of C4AsHx with C3AH6 and Ca(OH)2. More recently, Zhang [197] synthesised solid solutions between sulfate- and hydroxy-AFm according to Pllmanns method, by mixing stoichiometric amounts of CA, Ca(OH)2 and CaSO42H2O. Solids and solutions were analysed after ageing for ~16 months at 25C. The XRDpattern showed, in contrast to the results from Pllmann and Roberts, C4AsHx and C4AHx occurring as two immiscible phases. Furthermore ettringite, C6As3H32, was found in sulfate-rich compositions and C3AH6 and Ca(OH)2 at the hydroxide-rich end of the notional solid solution series. Additionally the author measured the conductivity of the mother liquor of the solid solution with CaSO4/Al2O3 ratios of 1 and 0.5. After a reasonable time (100-200days) for equilibration the conductance of the solution was still decreasing and had not stabilised by the end of the investigations, after ~ 260 d. This behaviour was interpreted as arising from an ongoing phase transformation. Therefore the authors supposed that initially solid solutions formed but that these decomposed in the course of the experiments. But, due to missing phase analyses in the first stages of the experiment, this could not be proved. Glasser et al. [79] prepared solid solutions between sulfate- and hydroxy-AFm by mechanical mixing of C4AH13 and sulfate-AFm and by mixing appropriate quantities of C3A, Ca(OH)2 and CaSO42H2O. The samples were stored 9 months at 5C and then analysed by analytical electron microscopy. A plot of the sulfate content of all analysed samples showed two population clusters, one in the range of 0-20 mol% sulfate and the other between 45-90 mol% sulfate. The results were interpreted as indicating incomplete solid solution between hydroxy- and sulfate-AFm end members: the hydroxy-AFm phase showed a mean sulfate content of 6 mol% and the sulfate-AFm phase had a mean composition of ~75-90 mol% sulfate. The substantial scatter of the analysis data was ascribed either to an intergrowth of sulfate- and hydroxy-type-AFm, or to equilibrium not having been obtained despite 9 months reaction time, or both. Kapralik and Hanic [100] investigated the hydration products of sulfoaluminate clinker, C4A3s, with increasing addition of CaO. The mixtures were prepared with a water/solid-ratio of 10:1 and stored at 25C for 18 days. X-ray patterns showed a compound with similar crystallographic properties (d0001 ~ 8.79 ) to those of the limiting solid solution C4ASO3xH2O reported by Pllmann and Roberts. Furthermore, a second hydrate with a d0001 value of ~10.52 was found and attributed to a higher hydrated form of the solid solution. Stark et al. [176] investigated the hydration of OPC at different temperatures and showed the formation of a tetracalciumsulfoaluminate hydrate solid solution. Additionally to AFm solid solutions, ettringite, portlandite and C-S-H were observed after 24 hours hydration. Due to the variance of the electron microprobe analysis an exact quantification of the amount of substituted sulfate in AFm was not possible. Further investigations at 62C indicated no AFm solid solution formation; monosulfoaluminate and hydrogarnet, C3AH6, were observed among other hydration products: ettringite, portlandite and hydrotalcite. At 5C C4AHx was the only AFm phase detected in hydrated OPC after 21 d. Thus the solid solution between C4AsHx and C4AHx will be formed over a limited temperature range from 5 to 65C.

The AFm phase in Portland cement

58

The studies thus far described were made at self-generated pH values, typically close to 12. However Kalousek [99] has studied AFm reactions with added alkali. These may well be relevant to real cements in which the aqueous ratio OH/SO4 is affected by readily soluble alkalis. It was shown that significant substitution of sulfate by hydroxyl occurred in the presence of alkalis, effectively NaOH. For example, the sulfate content of the monosulfoaluminate-like phase decreased from 1 mol SO3 when no additional alkalis were present, to 0.22 mol in ~ 0.6 N NaOH-solution. Aqueous calcium concentrations decreased while aluminium and sulfate concentrations increased with rising aqueous alkali contents. As the amount of NaOH increased, analysis of the solids showed a nearly constant sulfate content of 0.66 mol, corresponding to the composition C4As0.66Hx in the range between 0.15 N NaOH to 0.27 N NaOH. A further increase of the NaOH concentration, to 0.6 N NaOH, led to a reduction of the total sulfate in the solid phase to 0.22 mol SO42-. Kalousek [99] concluded that complete solid solution occurred between monosulfoaluminate and hydroxyAFm. But the corresponding XRD-patterns showed a rapid decrease of the d0001 values from 8.9 for 1 mol SO3, i.e. monosulfoaluminate, to ~8.0 - 8.2 at ~ 0.5 - 0.6 mol SO3 in the solid phase: no further decrease was observed, despite rising aqueous alkali concentrations. These values might be an indication of a miscibility gap at low sulfate contents, less than ~0.5 - 0.6 mol SO3 in the solid phase, although no second phase was identified. But the solids were investigated after only 48 hours of equilibration; their X-ray peaks were very broad: the solids were probably poorly crystallised and the accuracy of measuring d0001 correspondingly poor. Furthermore, Kalousek [99] worked with highly concentrated NaOH-solution. Dosch [55] showed the existence of the U-phase, a sodium substituted AFm phase, which may precipitate at high sodium concentrations. The separate identity of the U-phase - not known to Kalousek [99] at the time - may therefore affect the interpretation of these data.

AFm phases and related solid solutions in carbonate-containing systems


According to EN 197, CEM I may contain up to 5% minor constituents; including limestone. Furthermore other types of blended cements containing up to 35 % CaCO3 are permitted by EN 197. Therefore carbonate-containing systems are important and have to be considered in hydrate phase assemblages, even in the absence of external carbonation. The most important carbonate-containing AFm phase is monocarboaluminate, C4AcHx. It is found as a reaction product of the hydration of C3A with CaCO3. The structure is similar to that of monosulfoaluminate; it is fully ordered and is composed of positively charged [Ca4Al2(OH)12]2+ main layers and negatively charged [CO35H2O]2- interlayers. The Al3+ and Ca2+ ions are six- and sevenfold coordinated, respectively, by oxygen atoms. The planar CO32- groups are directly connected to the main layers and are tilted by 21.8 from the plane of the layers [68]. Investigations of possible solid solution formation between monocarboaluminate and hydroxy-AFm by Roberts [163] showed no solid solution. However at CaCO3/Al2O3 ratios < 1, a second compound with a d0001 value of ~8.2 , was found as an additional reaction product. According to its composition this hydrate was termed hemicarboaluminate, C4Ac0.5H11. The X-ray patterns of the solids showed a mixture of mono- and hemicarboaluminate up to CaCO3/Al2O3 ratios of 0.5; the amount of hemicarboaluminate increased until at a CaCO3/Al2O3 ratios of 0.5 only this hydrate occurred. At CaCO3/Al2O3 ratios <0.5, the amount of hemicarboaluminate again diminished and C4AHx was present as an additional compound. Due to its fixed composition over a wide range of CaCO3/Al2O3 ratios, hemicarboaluminate should be referred to as a distinct compound. Furthermore, Roberts showed that the so-called -C4AH13 with a d0001 value of ~8.2 , first described by Wells et al. [193] as a polymorph of C4AH13, is probably hemicarboaluminate.

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59

Later works by Fischer [63] verified Roberts results. Dosch et al. [56] obtained similar results but the stoichiometrically calculated composition of the 8.2 hydrate was given as C4Ac0.25H12. The discrepancy between Roberts and Doschs results may be explained by additional carbonation occurring during storage or X-ray examination, resulting in a subsequently higher CO3 content in the system than initially calculated. Thermodynamic calculations by Damidot et al. [49] showed that hemicarboaluminate is only persistent below the self-generated carbonate activities of calcite. Thus the formation of hemicarboaluminate becomes unlikely in real systems where CaCO3 is present; the activity of carbonate is sufficient to stabilise monocarboaluminate. Experimental results by Pllmann [148] show that there is probably no solid solution between the monocarboaluminate and the monosulfoaluminate end member. Both hydrates coexisted with unchanged X-ray patterns over a range from 0<SO4/CO3<1 (molar ratio). Hemicarboaluminate was formed as an additional AFm phase. Kuzel et al. [117] investigated the hydration of C3A in the presence of Ca(OH)2, CaCO3 and CaSO42H2O. At a molar composition C3A:CaO:CaSO4:CaCO3 = 1:1:1:2/3 the final hydration products consisted of ettringite, monocarboaluminate and portlandite after 720 h hydration. If the amount of CaCO3 was reduced to C3A:CaO:CaSO4:CaCO3=1:1:1:1/3, ettringite, hemicarboaluminate, small amounts of monocarboaluminate and portlandite were found as reaction products. Further reduction of the CaCO3 content, in connection with a reduced sulfate content to a molar composition of C3A:CaO:CaSO4:CaCO3=1:1:1/2:1/4, led to the formation of a mixture of monosulfoaluminate, hemicarboaluminate and portlandite. Monocarboaluminate was not observed as reaction product. Finally, if the sulfate content was diminished to C3A:CaO:CaSO4:CaCO3=1:1:1/4:1/4, the limiting solid solution between monosulfoaluminate and hydroxy-AFm as well as hemicarboaluminate and portlandite occurred; formation of solid solutions between carbonate- and sulfate-AFm were not observed. It is therefore probable that monocarboaluminate and monosulfoaluminate will not occur together in real systems, as even very low CO2 contents are apparently sufficient to suppress formation of monosulfoaluminate in cements.

5.1.4 Summary and conclusions from the literature


There has been a tendency to regard the constituents of a hydrated cement paste as consisting of four main hydrate phases; Ca(OH)2, C-S-H, AFt and AFm. This simplification, in which the AFm phase is regarded as a single phase with chemical variants, is perhaps satisfactory for a broad-brush approach, but does not conform to reality and is too simplistic to develop for a quantitative model of cement paste. However, the number and constitution of the AFm family of phases is subject to a range of partially conflicting conclusions. It is noted that the internal inconsistencies in interpretation of the evidence contained in some papers and, if the evidence is reinterpreted it is found that: The cation chemistry of AFm phases of cement and blended cement is relatively simple; the divalent ion is overwhelmingly calcium and the trivalent ion, aluminium.

The AFm phase in Portland cement

60

The hydration state of AFm is variable, but at the moderately high ionic potential, hydroxyl ion concentration and pH values, typical of Portland cement, a satisfactory representation of the formula unit is Ca4Al2(X)(OH)12.nH2O where x = 2 OH- or one divalent anion, e.g., CO32- or SO42- and n= 5-6 H20. With few exceptions, AFm phases do not form significant solid solutions. Thus the AFm phases are conveniently distinguished by means of a prefix, e.g., OH-AFm, SO4-AFm, CO3-AFm or in the case of hemicarboaluminate, OH/CO3-AFm. An exception has to be made for SO4-AFm which forms extensive solid solutions with OHAFm, extending to ~50 mol% replacement of sulfate. However, the resulting solid solutions may be labile and are not persistent over 1-3 year timescales at ~20C. The absolute order of thermodynamic stability of AFm variants at ~25C appears to be, in order of increased stability: OH-AFm < SO4-AFm < CO3-AFm

The anion constitution of AFm is sensitive to the chemistry of cement and responsive to interactions between cement and its service environment.

The AFm phase in Portland cement

61

5.2. Preparation of solid solutions


A focus of the current work was to determine if significant solid solution occurred between AFm end members. Phase relations in the following systems were considered as to be the most important for cement systems: Monosulfoaluminate - hydroxy-AFm Monosulfoaluminate - monocarboaluminate Monocarboaluminate - hydroxy-AFm

Two approaches have been applied to synthesise solid solutions (see Table C.1 - Table C.5 for exact amounts used in the experiments): i) by mechanical mixing of previously synthesised AFm end members (monosulfoaluminate, C4AsHx; monocarboaluminate, C4AcHx and hydroxy-AFm, C4AHx) ii) by precipitation from supersaturated solutions, formed by mixing appropriate amounts of previously synthesised C3A, CaO, CaSO4 or CaCO3, respectively, depending on the desired phase or phase assemblage. Approach i) was used to clarify whether reaction occurs, i.e. solid solution formation occurred spontaneously between the AFm phases; also, where reaction was complete, to derive solubility data. Approach ii) was applied to solubility determinations and derivation of thermodynamic data and to conduct experiments on the extent of solid solution formation between AFm phases. Additional solubility data commencing from undersaturation were obtained by redissolving the reaction products obtained from the mixed end member method. The AFm solid solution experiments were made at 25C. Water/solid-ratios were restricted to < 30 to reduce errors induced by incongruent dissolution. Solid and aqueous phases were analysed and prepared according to the experimental procedures described in chapter 3.

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62

5.3. Formation of AFm phases and AFm solid solutions 5.3.1 Monosulfoaluminate-hydroxy-AFm solid solutions Investigations of the solid phase
Because of divergent literature results, particular attention was paid to the interactions between monosulfoaluminate and hydroxy-AFm. Fig. 5.3 shows the XRD-patterns of powders of the monosulfoaluminate-hydroxy-AFm solid solutions, obtained from initially supersaturated solutions after 4 weeks of annealing. The AFm phase, as determined by XRD, generally corresponds to the 13 H2O variant but, as noted, even the gentlest drying could result in desiccation of the 19 H2O variant. The main aim was to avoid artefacts arising from carbonation; therefore no distinction was made between 13 and 19 H2O variants (or their anion-substituted forms) and the phase is simply reported as C4AHx. Up to a calculated substitution of 50 mol% SO42- by OH-, the observed pattern is dominated by a single solid solution with reflections close to those of monosulfoaluminate. However the position of the main basal reflection, 0001, shifts as a regular function of SO4/OH ratio. At initial molar SO4/(SO4+2OH)-ratios < 0.5 a second phase was detected by XRD. Its XRDpattern is similar to that of C4AH13 and is therefore associated with a hydroxy-AFm type phase. At SO4/(SO4+2OH) ~ 0.05 this hydroxy-AFm type phase became the only solid. Small amounts of C2AH8 were found in all mixtures within the range of 0.05 SO4/(SO4+2OH) 0.7. Minor AFt was also found in one preparation, that of the monosulfoaluminate end member. C3AH6 occurred in the preparation of the hydroxy-AFm end member, which indicates a tendency to partial decomposition of C4AHx in the absence of sulfate.

M H
C3AH 6

M, H

H - Hydroxy-AFm type ss M- Monosulfate type ss

0 hydroxy-AFm 0.05 0.20 0.40 SO 4/(SO 4+2OH)-ratio

1000 cps

0.50 0.60 0.80

Intensity

1.00 monosulfoaluminate 5 10 15 20 25 de gre e s 2 [ CuK ]


Fig. 5.3: XRD-pattern of selected solid solutions between monosulfoaluminate and hydroxy-AFm aged 28d

The AFm phase in Portland cement

63

The systematic peak shift of the main basal reflections of the monosulfoaluminate type phase is shown in Fig. 5.4. This and other evidence discloses that significant change occurs up to a solid molar SO4/(SO4+2OH) ratio of ~ 0.5; the interplanar distance for (0001) decreases from ~8.94 0.02 for pure monosulfoaluminate to ~8.79 0.02 for the limiting monosulfoaluminate type solid solution at SO4/(SO4+2OH) ~ 0.5. At SO4/(SO4+2OH) < 0.5 - 0.6, d0001 of the monosulfoaluminate type phase value did not change significantly. Instead a hydroxy-AFm phase with d0001 ~ 7.96 0.02 was detected at SO4/(SO4+2OH) ~ 0.4, increasing in amount as the sulfate ratio decreased. These two observations, taken in conjunction, confirm the presence of a miscibility gap between both end members. At a SO4/(SO4+2OH) ratio of 0.05 only one phase, with reflections similar to C4AH13, was observed. This might indicate limited sulfate incorporation into the hydroxy-AFm end member. Nevertheless, it is difficult to interpret the results with precision due to the prevailing detection limits; the limits shown are derived from solubility data, shown subsequently, and do not conflict with the XRD interpretation. As shown in Fig. 5.4, and in agreement with the data of Pllmann [150], no significant peak shift was observed within the hydroxy-AFm type phase. Therefore, and taking solubility data into account, its composition is assumed to be close to that of C4AH13 although limited (maximum 5 mol%) sulfate-AFm incorporation is not excluded. The XRD-investigation of the reaction products obtained from mixing previously synthesised monosulfoaluminate and hydroxy-AFm showed qualitatively similar results to those obtained from supersaturation. Thus mixtures of hydroxy- and sulfate-AFm spontaneously react with formation of solid solutions extending between monosulfoaluminate and SO4/(SO4+2OH) ~ 0.5. However the mixtures with high initial hydroxy-AFm contents (SO4/(SO4+2OH) 0.6) showed generally higher d0001 values relative to the solids obtained from mixed raw materials (see Fig. 5.4). The reason is probably partial initial carbonation of the C4AHx phase; a hemicarboaluminate type phase was observed instead of C4AHx at (SO4/(SO4+2OH) 0.6 (see Fig. B.1), leading to a lower content of reactive C4AHx. Therefore the real SO4/(SO4+2OH) ratio is probably higher than calculated.
9.00 8.95

supersaturation mixed endmembers Poellmann

[]
0001

8.90 8.85 8.80 8.75


SO4-AFm-type ss

interplanar spacings d

8.00 7.95 7.90 0 C4AH x

OH-AFm-type ss

0.2 0.4 0.6 0.8 1 calc. S O 4/(S O 4+2OH) ratio C4AsH 12

Fig. 5.4: Observed interplanar distances d0001 of monosulfoaluminate type solid solution (top) and hydroxy-AFm type solid solution (bottom)

The AFm phase in Portland cement

64

A0 []

C0 []

27.0 26.8 26.6 26.4 26.2 26.0 0 C4AH x 0.2 0.4 0.6 0.8 calc. S O 4/(S O 4+2OH) ratio

5.79 5.78

780.0 calc. cell volume [ ] 775.0 770.0 765.0 760.0 755.0 750.0 0 0.2 0.4 0.6 0.8 1 C4AsH 12 C4AH x calc. S O 4/(S O 4+2OH) ratio
3

lattice parameter

A0

5.76 5.75 5.74 1 C4AsH 12

Fig. 5.5: Refined lattice parameter for the monosulfoaluminate type phase with changing SO4/(SO4+2OH) ratio

lattice parameter

C0

5.77

Fig. 5.6: Calculated volume change for the monosulfoaluminate type phase with changing SO4/(SO4+2OH) ratio

Volume changes in the unit cell due to the solid solution formation were obtained using the software CELREF, to refine the obtained XRD-pattern by least squares minimisation. The calculated results (Fig. 5.5) show that the decrease of sulfate content tends to result in a decrease of the unit cell lattice parameters up to a nearly constant size at SO4/(SO4+2OH) < ~0.5 - 0.6. As shown in Fig. 5.6, the total volume of the unit cell decreased ~ 2.5 % with increasing replacement of sulfate by hydroxide. As no standard was used to calibrate measurements for experimental deviations of the 2 values, these results are best used to indicate trends of changing unit cell size with increasing sulfate substitution. ESEM micrographs of the monosulfoaluminate end member and its solid solutions, Fig. 5.7 (a) and (b) show well-crystallised hexagonal, platy crystals with diameters between 4 - 30 m. In agreement with XRD data, needle-like AFt prisms with lengths up to ~5 m were found randomly distributed in the monosulfoaluminate preparation, Fig. 5.7 (a). In contrast to the end member preparation, no ettringite was observed when ~10 mol% of the sulfate was substituted by hydroxide i.e., at a solid molar SO4/SO4+2OH ~ 0.9, Fig. 5.7 (b).

(a)

(b)

Fig. 5.7: ESEM micrographs of the monosulfoaluminate end member and ettringite (a) and the monosulfoaluminate type solid solution (~10 mol% of sulfate substituted by hydroxide) (b)

The AFm phase in Portland cement

65

Thermodynamic modelling of the solid solution formation


With the aid of the previously derived thermodynamic data of monosulfoaluminate and hydroxyAFm (Table 4.1) and the Redlich-Kister non-ideal solid solution model (chapter 4.3.4) it is possible to estimate the thermodynamic properties of the solid solution. The dissolution reaction for the non-ideal monosulfoaluminate-hydroxy-AFm solid solution series is shown in Eq. 5.1:
Ca 4 Al2 (SO 4 ) x (OH) 142 x 6H 2 O 4Ca 2+ + 2AlO2 + xSO4 + (6 - 2x)OH- + 10H2 O
2-

(5.1)

In agreement with own experimental data and literature data by Roberts [163] and Pllmann [150] ~ 50 mol% of sulfate in the monosulfoaluminate-phase can be replaced by hydroxide. However the data about sulfate substitution in the original hydroxy-AFm phase are not consistent. Pllmann found no sulfate substitution. However according to investigations in this Thesis the pure hydroxyAFm end member tends to decompose relatively rapidly; C3AH6 is observed in the XRD-pattern Fig. 5.3 and ESEM micrographs (Fig. 5.8) after 4 weeks of hydration. Furthermore calcium concentrations of the aqueous phase are significantly higher and approach portlandite saturation compared to the preparation at low sulfate contents at SO4/(SO4+2OH)=0.05 (see solubility data Table A.11). This indicates that minor sulfate substitution stabilises hydroxy-AFm. However this amount of sulfate is too small to be quantified by the experimental methods used in this work. Thus the existing miscibility gap of the solid solution series (according Eq. 5.1) is provisionally defined as x1 x 0.5. But, as described below, x1 can be estimated with the help of Lippmann diagrams.

Fig. 5.8: ESEM micrograph of cubic C3AH6 crystals on the surface of a crystal of the hydroxy-AFm end member

As shown by Glynn [80], Lippmann phase diagrams are a useful instrument to fit the dimensionless parameters a0 and a1, necessary to calculate the activity coefficients of the members of the solid solution series. According to the mathematical algorithm described in chapter 4.3.4 the total solubility product of the monosulfoaluminate-hydroxy-AFm solid solution series can be derived from the dissolution reactions (see Table 4.3) of monosulfoaluminate and hydroxy-AFm (Eq. 5.2; [ ] denote activities of the aqueous species):

[Ca 2 + ] 4[AlO2 ] 2[OH ] 4 [H 2 O]10 [SO 4 ] + [OH]2


-

(5.2)

Solubility data for the solid solution series need to be extracted to enable a calculation of the total solubility product. Solubilities (Table A.10) were obtained as described above from initially supersaturated and undersaturated solutions with respect to the solid solution series. As shown in Table A.10 and Fig. B.1 (see appendix B) the samples from undersaturation and mixed end members did partly carbonate, indicated by the presence of hemicarboaluminate. Thus only the

The AFm phase in Portland cement

66

apparently non-carbonated samples from supersaturation and samples from undersaturation and mixed end members with x 0.7 (see Eq. 5.1) were used in the following calculations. The geochemical software GEMS-PSI was applied to calculate the activities of the aqueous species, to allow a computation of a series of total solubility products of the monosulfoaluminate-hydroxyAFm solid solution series according Eq. 5.2. The data points thus obtained were included as experimentally-derived solidus points in a Lippmann diagram, Fig. 5.9. Subsequently a theoretical solidus was calculated using Eq. 4.24 with the previously determined solubility constants of the monosulfoaluminate and hydroxy-AFm end members (Table 4.1). The software MBSSAS was used to determine the non-dimensional parameters a0 and a1, necessary to calculate the activity coefficients i of the end members according to Eqns. 4.19 and 4.20. To obtain the best fit of the theoretical solidus curve with the experimental data points (black markers Fig. 5.9) the miscibility gap fractions need to be estimated. As mentioned above to simplify the estimation and in agreement with own experiments and observations by Roberts [163] and Pllmann [150] the upper end of the miscibility gap was assumed to be fixed at x = 0.5 according Eq. 5.1. Thus only the first parameter x1 was varied. As shown in Fig. 5.9 the best fit between experimentally-derived data-points and theoretically calculated solidus was obtained with the estimated miscibility gap fractions 0.03 x 0.5 (Eq. 5.1) and a0 =0.188 and a1=2.49. Lippmann diagrams are very sensitive against changes of the miscibility gap fractions. Thus this method of fitting the empirical parameters a0 and a1 in combination with a suitable software, e.g. MBSSAS, has proved to be very powerful owing to the sufficiency of experimental data.
C4AsxH13-x miscibility gap C4AsxH13-x(0.5 x1)

-24 -25 -26 log eq -27 -28 -29 -30 0

C4As0.03H12.97 + C4As0.5H12.5 mean eq,exp datapoints solidus

calc. GEM S a0 =0.188 a1 =2.49

solidus

solutus
datapoints solutus
calc. GEMS undersaturation supersaturat ion mixed end members

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1
C4 AsH12

C4 AH13

calc. SO 4/(SO 4+2OH) ratio or X SO 4 2- ,aq

Fig. 5.9: Lippmann diagram for the monosulfoaluminate-hydroxy-AFm system at 25C with a0=0.188 and a1=2.49 for miscibility gap fractions 0.03 x 0.5 (Eq. 5.1) (solid black lines represent theoretically calculated solidus and solutus in dependence of the SO4/(SO4+2OH)-ratio of the solid solutions. Dashed line including white markers shows calculated total solubility products in dependence of the molar SO4/(SO4+2OH)-ratio of the bulk composition with a0=0.188 and a1=2.49 (see text for explanation). Black markers are mean experimental points derived from solubility experiments (data given in Table A.10) in dependence of the molar SO4/(SO4+2OH)-ratio of the bulk composition)

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67

The deviations of the calculated data points using the inbuilt non-ideal solid solution model of GEMS-PSI (white markers, dashed line, Fig. 5.9) can be explained by differences in the solid SO4/(SO4+2OH)-ratio. The theoretical solidus of the Lippmann diagram (black solid line) is plotted as function of the theoretical solid solution composition; assuming that no other solids are present. However in the experiments as well as in the calculations using GEMS, AFt was calculated to be present at SO4/(SO4+2OH)-ratios 0.98 and C2AH8 was observed and calculated to be present at SO4/(SO4+2OH)-ratios 0.70. To enable a direct comparison between calculated and experimentally derived total solubility products, both values were plotted against the initially calculated molar SO4/(SO4+2OH)-ratio of the bulk composition. Thus the dashed line, Fig. 5.9, was used to fit the calculated total solubility products, including the a0 and a1 parameters, to the experimental values, as it was not possible to analyse accurately the composition of the solid solution. With the help of the previously determined fitting parameters a0 and a1 and the known activities of the sulfate and hydroxide-species, it is now possible to calculate the experimentally-derived solutus of the Lippmann diagram (Fig. 5.9) using Eq. 5.3:

X SO 2 ,aq X OH ,aq 4 1 = + eq,sl K C AsH C AsH K C AH C AH 4 13 4 13 4 12 4 12

(5.3)

where KC4AsH12 and KC4AH13 are the solubility products of the end members, C4AsH12 and C4AH13 are the activity coefficients of the end members and XSO42- , aq and XOH-, aq are the aqueous activity fractions of the substitutable species SO42- and OH- calculated using Eqns. 5.4 and 5.5 (where [ ] denote calculated activities of the aqueous species:
X SO 2 ,aq =
4 [SO 2 ] 4 2 [SO 4 ] + [OH ] 2

(5.4) (5.5)

X OH , aq =

[OH ] 2 [SO 2 ] + [OH ] 2 4

As shown in Fig. 5.9 experimentally-derived values (solutus markers, Fig. 5.9) agree well with the theoretically computed solutus using Eqns. 4.25-4.27. Originally Lippmann diagrams were used to express thermodynamic equilibrium states between the solid solution composition and the related aqueous phase. For example, one can determine the activity fractions of the sulfate and hydroxide species of the related aqueous phase by drawing a horizontal line from the solidus of the solid solution with known composition to the related solutus and read off the values for XSO4,aq on the abscissa. Thus, as shown above, Lippmann diagrams are a useful instrument to describe the thermodynamic behaviour of solid solutions and to derive missing parameters necessary to illustrate the thermodynamics of SSAS. However, due to existing uncertainties about the exact upper and lower limit of the miscibility gaps, the derived numerical values should be regarded as provisional because they are sensitive to changes of the compositional boundaries of the miscibility gap. Furthermore the sulfate concentration of many samples was below the limit of detection (< ~0.002 mmol SO42-/l). Thus sulfate concentrations had to be estimated by applying the non-ideal solid solution model at SO4/(SO4+2OH)-ratios 0.8 . However due to the supposedly very low values (<<0.002 mmolSO42-/l) this has only minor impact on the total solubility product of the solid solution.

The AFm phase in Portland cement

68

hydroxy-AFm type ss

miscibility gap

monosulfoaluminate type ss

1.0 0.5 0.0 G (kJ/mol) -0.5 -1.0 -1.5 -2.0 -2.5

lim .m onosulf.- and hydroxy-AFm type ss

Gex

GM Gid

0 0.1 C 4AH x

0.2

0.3

0.4

0.5

0.6

0.7

0.8

SO 4/(2OH+SO 4)-ratio

0.9 1 C 4AsH 12

Fig. 5.10: Gibbs energy of ideal mixing, Gid, excess Gibbs energy of mixing, Gex, and resulting molar Gibbs energy of mixing, GM, calculated from Eq.4.14 for the monosulfoaluminate-hydroxy-AFm solid solution series

With the help of the previously derived parameters a0 and a1, it is now possible to determine the changes of the (excess) Gibbs energies of mixing. Fig. 5.10 compares the functions of the Gibbs energy of ideal mixing, Gid, the estimated excess Gibbs energy of mixing Gex and the resulting estimated Gibbs energy of mixing of the monosulfoaluminate-hydroxy-AFm solid solution series, GM, according to Eqns. 4.14 - 4.16. The molar Gibbs energy of the solid solution can be estimated according to Eq. 4.13 as the sum of the partial Gibbs energies of monosulfoaluminate and hydroxyAFm and Gm. The best fit of the calculated solubilities of the monosulfoaluminate-hydroxy-AFm solid solution series, relative to experimental solubility data at 25C, was obtained with the assumed compositional boundaries of the miscibility gap and the resulting Guggenheim parameters (a0=0.188 and a1=2.49). As shown in Fig. 5.11, comparison between experimentally-derived solubility data using averaged values from super- and undersaturation and calculated solubilities of the monosulfoaluminate-hydroxy-AFm solid solution at 25C shows excellent agreement in the range 0.05 SO4/(2OH+SO4) 1, which accounts for the good internal consistency of the dataset. Only the solubility data for the pure hydroxy-AFm end member differ significantly from the calculated values. This behaviour can be explained by the metastability of C4AHx with respect to C3AH6 and portlandite. As this decomposition reaction of C4AHx was only observed in the sulfatefree preparation this might indicate the stabilisation of the hydroxy-AFm end member by substitution of small amounts of sulfate in the structure.

The AFm phase in Portland cement


a)
20 concentration [mmol/l] pH 15 Ca 10 5 0 0
C 4AHx

69
b)
12.5 concentration [mmol/l] 1.E+00 1.E-01 1.E-02
limit of detection

12.0 pH

SO4

2-

11.5 Al 11.0 0.2 0.4 0.6 0.8 1


C 4AsH12

1.E-03 1.E-04 1.E-05 0 0.2 0.4 0.6 0.8 1


C 4AsH12 C 4AHx calc. SO4 / (SO4 +2OH)-ratio

calc. SO4 / (SO4 +2OH)-ratio

Fig. 5.11:Comparison of calculated (lines) and mean experimental (markers) solubility data for the SO4AFm and OH-AFm solid solution series at 25C

Fig. 5.11 b) shows that the aqueous sulfate concentrations are generally very low and at SO4/(2OH+SO4) ratios 0.8 they lie below the analytical detection limit. Except for the hydroxyAFm end member the predicted phase assemblages agreed well with the experimental observations. In agreement with XRD-analysis, small amounts of AFt were predicted to coprecipitate at SO4/(2OH+SO4) ratios 0.98; also, traces of C2AH8 were both predicted and observed at SO4/(2OH+SO4) ratios 0.70.

Investigations to the long-term stability of the solid solution series


According to calculations of this Thesis (see Table 4.4), in agreement with experiments and observations by Wells et al. [193], DAns and Eick [52] and Faurie-Mounier [61], hydroxy-AFm is metastable with respect to a mixture of C3AH6 and portlandite at ~25C. Thus to enable a recalculation of solubility data and solid distribution the metastability of C4AH13 with respect to C3AH6 was suppressed in the previous computations. This is justified as no formation of C3AH6 was observed in the experiments with initial SO4/(SO4+2OH)-ratios > 0.05 aged for 28 days. On the other hand, Zhang [197] examined samples after prolonged ageing and suggested that initially formed solid solutions were probably unstable and decomposed to the end members:
In the sulfate-solid solution series, the enrichment of SO4 in hydrocalumite is likely achieved by disproportionating the initially formed complete solid solution into the OH- and SO4-rich phases.

In their work the aqueous solubility was analysed at intervals, and was still declining in the final interval measured, it was considered possible that solid solutions might have formed during the early stages of reaction but were not present at the end of the experiments after ~560 d, the only point in time at which samples were subject to X-ray examination. Thus the literature reveals considerable divergence of interpretation concerning the existence and extent of solid solution between OH- and SO4-AFm phases. Hence another aim of this work was to assess the long-term stability of the solid solution series. Thus the composition of aqueous and solid phases of the preparations from supersaturation, which showed no signs of initial carbonation, were analysed again after 1 year and 2 years ageing, respectively.

The AFm phase in Portland cement

70

M H
C3AH 6 P

M, H

H - Hydroxy-AFm type ss M - M onosulfate type ss P - Portlandite Hc- Hemicarboaluminate

0 0.05 0.20
1000 cps

hydroxy-AFm SO 4/(SO 4+2OH)-ratio

0.40
Hc

0.50 0.60 0.80

Intensity

AFt

AFt

1.00 monosulfoaluminate 20 25

10

15 degrees 2 [ CuK ]

Fig. 5.12: XRD-pattern of solid solutions between monosulfoaluminate and hydroxy-AFm aged 2 years

The composition of the solid phase of the OH-SO4-AFm solid solution series after prolonged ageing (2 years) is shown in Fig. 5.12. The XRD-pattern of the sulfate-containing preparations shows no apparent differences to the pattern obtained after 28 days, except that small amounts of hemicarboaluminate were found in the preparations at SO4/(SO4+2OH)-ratios of 0.4 and 0.5. It is interesting to note that the hydroxy-AFm end member is almost fully decomposed to a mixture of C3AH6 and portlandite, whereas in the preparation with a SO4/(SO4+2OH)-ratio = 0.05 only minor decomposition of the hydroxy-AFm-type solid solution occurred. However complete exsolution of the solid solution series, as found by Zhang [197], did not occur. But in contrast to the 28 d samples increasing amounts of C3AH6 were found with decreasing initial sulfate contents of the solid solution preparation (Fig. 5.13). Furthermore no C2AH8, which is metastable with respect to C3AH6 and Al(OH)3 (gibbsite) at 25C, was found after 2 years. However no crystalline aluminium hydroxide-phase was found by XRD. Thus either amorphous aluminium hydroxide has formed or part of the AFm solid solutions has reacted with C2AH8 to form C3AH6.

C3AH 6

Portlandite

0 0.05 0.20 0.40 0.50 0.70


AFt AFt

hydroxy-AFm
SO 4/ (SO 4 +2OH)-ratio

Intensity

100 cps

0.80 1.00 18.5

monosulfoaluminate

15.5

16.0

16.5

17.0

17.5

18.0

de gre e s 2 [ CuK ]

Fig. 5.13: Formation of C3AH6 in dependence of the initial molar bulk SO4/(SO4+2OH)-ratio of the solid solution preparations at 25C

The AFm phase in Portland cement


2 solid solutions with fixed com position 1 solid solution with changing com position

71
x ~ 0.76 ~0.76 x 1.0 x ~ 1.0

5 4 solids [g] 3 2 1 0 0

5 4 solids [g] 3 2 C3 AH6 1 portlandite 0 0


C 4AHx

C4 As 0.03 H12.97

C4 As xH13-x

C4 As xH13-x
(0.5 x 1.0)

C4 As 0.5 H12.5

C2 AH8 0.2 0.4 0.6 0.8

AFt 1
C 4AsH12

AFt 0.4 0.6 0.8 1


C 4AsH12

0.2

C 4AHx

calc. SO4 /(SO4 +2OH)-ratio

calc. SO4 /(SO4 +2OH)-ratio

Fig. 5.14: calculated thermodynamic metastable solid mass balance changes of the monosulfoaluminate-hydroxy-AFm solid solution series at 25C

Fig. 5.15: calculated thermodynamic stable solid mass balance changes of the monosulfoaluminatehydroxy-AFm solid solution series at 25C

Thermodynamic mass balance computations were used to assess the long-term stability of the AFm solid solutions. Figs. 5.14 and 5.15 show the calculated mass balance changes under the initial experimental conditions described in Table C.1. In Fig. 5.14 the metastability of C4AH13 and related solid solutions with respect to C3AH6 has been suppressed. The result of the calculation agrees well with the phases observed after 28 days of hydration (compare with Fig. 5.3). At SO4/(SO4+2OH)-ratios 0.5 a single solid solution with changing composition dominates the solid phases; at SO4/(SO4+2OH)-ratios 0.98 AFt was also predicted to occur. At SO4/(SO4+2OH)ratios < 0.5 two solid solutions with fixed composition and minor amounts of C2AH8 are predicted. Fig. 5.15 shows the computed stable phase assemblages taking hydrogarnet into account. According to calculations, the hydroxy-AFm solid solution, a part of the hydroxide-rich monosulfoaluminate-type solid solutions (with x < 0.76) and C2AH8 are not stable and will decompose to a mixture of C3AH6 and portlandite. Due to the decomposition reactions the monosulfoaluminate-type solid solutions are enriched in sulfate and the maximum sulfate substitution in AFm decreases to ~24 mol% (compare to ~ 50 mol% in the metastable state). In agreement with long-term experiments (Fig. 5.13), an increase of the amount C3AH6 is observed in the course of the transition from metastable to the thermodynamically stable phase assemblage. In contrast to the calculations no portlandite was found in the experiments, except in the preparation of the hydroxy-AFm end member, and the hydroxy-AFm type solid solution were still found at SO4/(SO4+2OH) 0.2, which indicates that the samples have not yet reached equilibrium.
[] 9.00 8.95 8.90 8.85 8.80 8.75 8.70 0 C 4AHx 0.2 0.4 0.6 0.8 calc. SO 4/(SO 4+2OH) ratio 1 C 4AsH12
4weeks 2years

interplanar spacings d

0001

Fig. 5.16: Changes of interplanar distances d0001 of monosulfoaluminate type solid solution with prolonged ageing up to 2 years at 25C

The AFm phase in Portland cement

72

A closer inspection of the peak-shift of the main basal reflection, 0001, of the XRD-pattern of the monosulfoaluminate-type solid solutions shows that the d-spacings of samples cured for 2 years tend to increase at initial molar bulk sulfate-ratios 0.4 SO4/(SO4+2OH) 0.7 (Fig. 5.16). This indicates an enrichment of sulfate in the solid solution samples. However it is interesting to note that the pattern of the sulfate-rich solid solutions at SO4/(SO4+2OH) 0.8 remain unchanged. According to the previous calculation the limiting solid solution, stable in the presence of hydrogarnet and portlandite, has a computed composition Ca4Al2(SO4)0.76(OH)12.486H2O. Thus, in broad agreement with the XRD-observations (Fig. 5.16), the hydroxide-rich monosulfoaluminate type solid solutions tend to decompose partly to form more sulfate-rich solid solutions. An exception is the preparation with an initial SO4/(SO4+2OH)-ratio = 0.2. After 2 years ageing, no significant change of the peak shift was found compared to the younger sample. In this sample the hydroxyAFm type solid solution was still observed, whereas this phase was absent at SO4/(SO4+2OH) = 0.4. As hydroxy-AFm solid solutions are less stable than the monosulfoaluminate-type solid solutions it is believed that this phase will probably decompose before the monosulfoaluminatetype solid solution decomposes. The observed phase changes should be reflected by changing solubilities of the related solid solution preparations (see Table A.11). And indeed, the total solubilities of the main elements did change significantly in the course of the experiment and approach the predicted stable composition, shown in Fig. 5.17 by solid black lines, with time. Thus calcium concentrations increase to reach portlandite saturation at about 20 mmol/l, whereas aluminium concentrations decreased significantly. Sulfate concentrations at SO4/(SO4+2OH) 0.8 are still below the limit of detection but are predicted to increase ~ 2 orders of magnitude with time. As shown in Fig. 5.18, the changes of the aqueous phase composition caused an increase of pH at SO4/(SO4+2OH) 0.8. By summarising the results one can conclude that solid solutions between hydroxy-AFm and monosulfoaluminate do form, but that hydroxy-AFm type solid solutions and part of the monosulfoaluminate solid solutions are metastable with respect to hydrogarnet (and portlandite). This results in partial decomposition of the initially formed solid solutions in conjunction with an enrichment of sulfate in the monosulfoaluminate-type solid solution with a maximum sulfate substitution of ~24 mol% at equilibrium with hydrogarnet and portlandite. However this process is quite slow and takes years to go to completion. However the total exsolution of the solid solutions to the hydroxy-AFm and monosulfoaluminate end members, as suggested by Zhang [197] was not observed, despite using a longer reaction period than Zhang.
20 concentration [mmol/l] 15 10 5 0 0
C 4AHx

concentration [mmol/l]

Ca

56 d 1 year 2 years

1.E+00 1.E-01 1.E-02

56 d

1year

2years

SO4
limit of detection

2-

1.E-03 1.E-04 1.E-05

A Al 0.2 0.4 0.6 0.8 1


C 4AsH12

0
C 4AHx

0.2

0.4

0.6

0.8

1
C 4AsH12

calc. SO4 /(SO4 +2OH)-ratio

calc. SO4 /(SO4 +2OH)-ratio

Fig. 5.17: Comparison of calculated (solid lines = stable phase assemblage including C3AH6; dashed lines metastable phase assemblage, formation of C3AH6 suppressed) and mean experimental (markers) solubility data for the SO4-AFm and OH-AFm solid solution series in dependence of the sample age at 25C

The AFm phase in Portland cement

73

12.75 12.50 pH 12.25 12.00 11.75 0


C 4AHx

56 d 1 year 2 years

0.2

0.4

0.6

0.8

1
C 4AsH12

calc. SO4 /(SO4 +2OH)-ratio

Fig. 5.18: Change of pH due to prolonged ageing of the solid solution preparations at 25C (markers = experimentally-measured; solid lines = calculated stable phase assemblage including C3AH6; dashed lines calculated metastable phase assemblage, formation of C3AH6 suppressed)

5.3.2 Monosulfoaluminate-monocarboaluminate
Pllmann [148] reports that extensive solid solution does not occur between the sulfate- and carbonate-AFm end members and an experimental check was made to confirm this conclusion. The mixed end member method was used: previously synthesised monocarboaluminate and monosulfoaluminate were mixed in a 1:1 molar ratio with degassed ultra pure water with a final water/solid-ratio of ~ 30. After 4 weeks the solids were analysed by XRD. As shown in Fig. 5.19 a), no significant peak shift, which would indicate changed anion population, was observed for either end member. The initial d0001 values remained unchanged at ~8.94 for monosulfoaluminate and ~7.6 for monocarboaluminate, respectively. In the absence of evidence for reaction, it is provisionally accepted that no extensive solid solution formation occurs between these two end members at 25C. AFt was found additionally to be present in small amounts.
a) no portlandite added; reacted 4 weeks at 25C b) excess portlandite added; reacted 5 and 10 days at 25C
1:1 molar mixture of both endmembers
P AFt Ms Hc Mc

1:1 molar mixture of both endmembers


Ms Mc Ms Ms Mc

Mc-

10 days
AFt

Intensity 1000 cps

AFt

monosulfoaluminate

Intensity 10 00 cps

Ms Hc AFt

monocarboaluminate

5 days

10

15 [2 CuKa]

20

25

10

15 [2 CuKa]

20

25

Fig. 5.19: Comparison of XRD-pattern of 1:1 molar mixtures of synthesised sulfate- and carbonate-AFm end members (Ms - monosulfoaluminate Mc - monocarboaluminate P - portlandite AFt - ettringite Hc hemicarboaluminate)

The AFm phase in Portland cement

74

The addition of portlandite to a mixture of monocarbo- and monosulfoaluminate resulted in the formation of hemicarboaluminate. As shown in Fig. 5.19 b), the intensities of the hemicarboaluminate basal reflection at ~8.2 increased with increasing reaction time in the presence of excess solid Ca(OH)2 at 25C.

5.3.3 Monocarboaluminate-hydroxy-AFm
Solids were prepared from supersaturation having molar carbonate ratios CO3/(CO3+2OH) of 1 (i.e., 100 mol% monocarboaluminate), 0.8, 0.5, 0.2 and 0 (i.e., 100 mol% hydroxy-AFm). Fig. B.2 (appendix B) shows the observed phase assemblages from XRD analysis of the solid phase at different carbonate : hydroxide ratios. The precipitation of a hemicarboaluminate-like phase was observed at ratios 0.2 < CO3/(CO3+2OH) < 0.8. However hemicarboaluminate was the only solid phase at one ratio, CO3/(CO3+2OH) ~ 0.5, suggesting a nearly ideal stoichiometric composition, Ca4Al2(CO3)0.5(OH)13xH2O.
interplanar spacings d0001 [] 8.30 8.10 7.90 7.70 7.50
hemicarboaluminate monocarboaluminate hydroxy-AFm hemicarb. Fischer et al.

0 C 4AHx

0.2

0.4 0.6 0.8 1 calc. CO 3/(CO 3+2OH) ratio C 4AcH11

Fig. 5.20: Comparison of d0001 spaces for C4AHx-C4AcH11 mixed solids at 25C

Comparison of the d0001 values of the main basal reflection of the crystalline solids agree well with those obtained by Fischer et al. [63] using silicon as internal standard. Accordingly the values for monocarboaluminate and hydroxy-AFm were used as internal standards with which to compare d0001 values for hemicarboaluminate. As shown in Fig. 5.20, the main basal reflection of hemicarboaluminate increased slightly, d0001 shifted from ~8.15 to ~8.25 with decreasing carbonate contents in the solids. The contention that this is caused by ion exchange, CO32- 2OH-, requires more systematic investigations; for present purposes, stoichiometry is assumed, but it is possible, indeed likely, that hemicarboaluminate has a short range of (2OH/CO3) ratios. Table 5.3 summarises the relationships between molar carbonate and hydroxide ratios in the solid and solid phase development. The partial breakdown of hydroxy-AFm is reflected by the appearance of the characteristic set of reflections for hydrogarnet in the X-ray pattern (Fig. B.2).
Table 5.3: Observed phase assemblages and their dependence of the initial solid carbonate ratio at 25C

molar CO3/(CO3+2OH) ratio

observed solid(s)1)

1.0 0.8 0.5 0.2 0


1)

monocarboaluminate monocarboaluminate, hemicarboaluminate hemicarboaluminate hemicarboaluminate, hydroxy-AFm, hydrogarnet (C3AH6) hydroxy-AFm, hydrogarnet (C3AH6)

due to prevailing detection limits the presence of traces of other solids cannot be excluded

The AFm phase in Portland cement

75

5.4. Ternary phase relations between sulfate-, carbonate- and hydroxy-AFm 5.4.1 Metastable phase assemblages at 25C
Fig. 5.21 shows the ternary AFm system consisting of sulfate-, hydroxy-, and carbonate-AFm, calculated for 25C with the aid of the thermodynamic data in Table 4.1 under consideration of partial solid solution formation between monosulfoaluminate and hydroxy-AFm. Fig. 5.21 is restricted to interactions between these three AFm phases; no other solid phases were admitted. The interactions and phase assemblages between these AFm phases were calculated with a total solid content of 1 mol AFm dispersed in 1 kg water, but are not expected to be sensitive to the relative masses of solid and aqueous phases except at high dilutions, such that incongruent dissolution affects the bulk composition of solids.

A
monosulfoaluminate (Ms)

A'
Ms-type ss

limiting Ms-type ss (~ C4 As 0.5 Hx)

B
miscibility gap (limiting Mstype ss + C4 AHx)

M s-type ss + Hc Ms + Hc

Ms(ss)+Mc

monosulfoaluminate + monocarboaluminate

M s + Hc + M c

limiting M s-ty pe ss + C4AH x+ Hc

C
C4 AHx

Hc + C4AH x

hemicarboaluminate (Hc)

Hc + M c

E
monocarboaluminate (Mc)

Fig. 5.21: Calculated metastable phase assemblages between different AFm phases at 25C. A possible range of stoichiometry of hemicarboaluminate and C4AHx is not shown. (Note: the region of two solid phases Ms type ss + Hc and Ms(ss) +Mc in which the monosulfoaluminate-type phase has a variable composition; the exact position of point A on A-B is strongly dependent from the chosen solid solution model)

Fig. 5.21 is best used as a tool to understand the possible interactions between these three AFm phases in response to changes in anion activities. However in the first set of calculations the metastability of hydroxy-AFm and related solid solutions with respect to C3AH6 and portlandite is suppressed to present a complete picture of possible interactions between hydroxy-, sulfate- and carbonate-AFm at early ages of hydration. A minor substitution of sulfate in the hydroxy-AFm end member is neglected in Fig. 5.21 as this has only insignificant impact on the shown phase diagram. A second set of calculation will show the influence of the metastability of hydroxy-AFm and related solid solutions on the phase assemblages. A significant substitution of sulfate due to the incorporation of hydroxide in monosulfoaluminate characterises region A-C-D, Fig. 5.21. The experimental results show that the sulfate content of the solid solution is variable in the two-phase region A-B-D; the limiting solid solution has a

The AFm phase in Portland cement

76

composition of ~ C4As0.5Hx. The solid solution composition remains fixed at ~ 50 mol% in region B-C-D. As Fig. 5.21 shows, the C4AHx type solid solution will only occur as a phase of essentially fixed composition together with the limiting monosulfoaluminate solid solution and hemicarboaluminate in region B-C-D. C4AHx cannot persist together with both ideal monosulfoaluminate and monocarboaluminate. In a carbonate-free system, C4AHx will react with monosulfoaluminate to form a solid solution according to Eq. 5.6 (with x+y = 1; y 0.5):
H 2O x(Ca 4 Al 2 (SO 4 )( OH )12 nH 2 O) + y (Ca 4 Al 2 (OH )14 nH 2 O) + (x + y)Ca 4 Al 2 (SO 4 ) x (OH )14 2 x nH 2 O

(5.6)

The addition of monocarboaluminate will initially cause hemicarboaluminate to form as a result of the reaction of monocarboaluminate with C4AHx according to Eq. 5.7:
+H 2O 0.5( C a 4 Al 2 (OH) 14 nH 2 O) + 0.5(Ca 4 Al 2 (CO 3 )( OH )12 nH 2 O) Ca 4 Al 2 (CO 3 ) 0.5 (OH )13 nH 2 O

(5.7)

The reaction of monocarboaluminate with C4AHx is generally thermodynamically preferred relative to formation of the monosulfoaluminate-C4AHx solid solution series. Thus, while C4AHx is still present, it will react first with monocarboaluminate to form hemicarboaluminate (Eq. 5.7); any remaining C4AHx will preferentially react with monosulfoaluminate to form a solid solution (Eq. 5.6). Moreover, in the presence of excess monocarboaluminate, all available C4AHx will preferentially react to form hemicarboaluminate; extensive solid solution formation between monosulfoaluminate and hydroxy-AFm will not be observed in the presence of monocarboaluminate. Therefore only minor hydroxide for sulfate substitution will be observed to occur in the monosulfoaluminate phase in the region A-D-E of Fig. 5.21, i.e., monosulfoaluminate will have close to its ideal composition (up to ~10 mol% calc. maximum sulfate substitution possible). Due to the reactions shown in Eqns. 5.6 and 5.7, C4AHx will not persist at higher activities of sulfate and/or carbonate, i.e., in the presence of ideal monosulfoaluminate and monocarboaluminate. According to the calculations based on the thermodynamic data compiled in this work, hemicarboaluminate is metastable in the shaded region A-A-E (Fig. 5.21) with respect to monocarboaluminate. Thus in region A-A-E monocarboaluminate is predicted to coexist with monosulfoaluminate-type solid solutions. However the exact position of point A is strongly dependent from the chosen solid solution model and deviations of the thermodynamic data of the related hydrate phases. But as shown in Fig. 5.21 region A-A-E is relatively small compared to other stability fields and does not affect the main conclusions depicted in Fig. 5.21. Pllmann et al. [151] reported that monosulfoaluminate-hydroxy-AFm solid solutions may interact with hemicarboaluminate forming limited ternary solid solutions including carbonate, sulfate and hydroxide ions. However no solubility data for these solid solutions are available. Therefore these ternary solid solutions cannot as yet be integrated into the dataset to assess their thermodynamic stability and relations with other hydrate phases.

5.4.2 Stable phase assemblages at 25C


As described earlier hydroxy-AFm type solid solutions and part of the monosulfoaluminate-type solid solutions are metastable with respect to hydrogarnet and portlandite and tend to slowly decompose to the latter with time. The resulting phase changes will mainly affect region A-C-D of the original metastable phase diagram Fig. 5.21. As a result of these phase changes Fig. 5.22 was developed to represent the stable phase relations between AFm phases and hydrogarnet at 25C. The size of region A-B-D, where monosulfoaluminate-type solid solutions coexists with

The AFm phase in Portland cement

77

hemicarboaluminate, decreased markedly (compared to Fig. 5.21), due to the metastability of monosulfoaluminate-type solid solutions with x ~0.76 (Eq. 5.1) with respect to a mixture of C3AH6, portlandite and the limiting monosulfoaluminate type solid solution with x ~0.76 (Eq 5.1) which coexists with hemicarboaluminate in region B-C-D. According to experiments described in this Thesis metastable phase assemblages, as shown in Fig. 5.21, are likely to form in the initial stage of hydration and tend to be persistent. The decomposition of these metastable phase assemblages is generally very slow, on the order of years. Thus to assess short-term-experiments < 1 year it is recommended to use the partly metastable phase relations shown in Fig. 5.21. An exemption is the hydroxy-AFm end member which tends to decompose fairly rapid in a sulfate free environment. However as experiments did show, its persistence is significantly improved due to apparently minor sulfate substitution in its structure.

A
monosulfoaluminate (Ms) Ms-type ss limiting Ms-type ss B (~ C4 As 0.76 Hx)
1)

A'

M stype ss + Hc1)
Ms(ss)+Mc 2)

monosulfoaluminate + monocarboaluminate
3)

limiting Ms-type ss + C3 AH6 + Ca(OH)2


M s + Hc + M c1) limiting M s-type ss + C3AH 6+ Ca(OH)2 + Hc

Hc + C3AH 6 + Ca(OH)2

C3 AH6 + Ca(OH)2

hemicarboaluminate (Hc)

Hc + M c1)

E
monocarboaluminate (Mc)

Fig. 5.22: Calculated stable phase assemblages between different AFm phases at 25C. A possible range of stoichiometry of hemicarboaluminate and C4AHx is not shown. (Note: the region of two solid phases Ms type ss + Hc and Ms(ss) +Mc in which the monosulfoaluminate-type phase has a variable composition; due to phase rule restrictions additionally traces of 1) C3AH6 2) gibbsite 3) gibbsite and AFt predicted in relevant stability fields; the exact position of point A on A-B is strongly dependent from the chosen solid solution model).

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78

5.5. Discussion of the results 5.5.1 Extent of solid solution


Perhaps surprisingly, AFm phases form only limited mutual solid solutions under conditions likely to be obtained in cement environments. Thus, for example, hydroxy- and carbonate-AFm phases are not directly miscible but instead form an ordered solid solution, i.e., a definite compound, ideally with the 1:1 ratio. Part of the reason for lack of miscibility is associated with the difficulty of generating high component activities of some species, e.g., carbonate. In normal cement environments the solubility of carbonate is invariably low, being limited by the solubility of carboaluminates and calcite. Where it is possible to achieve a relatively broad spectrum of component activities, as for example can be achieved for sulfate and, especially, hydroxide, significant ranges of solid solutions may form in response to the expanded range of species activities. It is shown that at self-generated aqueous concentrations of sulfate and hydroxide, solid solution extends from sulfate-AFm to approximately 50 mol% of a C4AHx end member. This limit is not invariably agreed in experimental studies [150][163][197]. In some cases, data pointing to complete solid solution contain internal conflict and the interpretation is thus suspect. It is nevertheless possible to envisage conditions, for example where precipitation of AFm occurs from highly supersaturated solution, or in the presence of cations interacting only weakly with solids but promoting high concentrations of hydroxyl, e.g., sodium or potassium hydroxides. But the results reported in this Thesis are probably applicable to normal OPC compositions, i.e., those with pH in the range conditioned by portlandite (~12.5 at 25C) and up to pH about one unit more. Besides need for conditions favouring formation of solid solutions, kinetics needs also to be considered; solid solutions of exotic compositions may form, but will they be stable or persistent? In this connection, it is worth recalling that C4AHx is not only metastable, it is also labile. Its labile behaviour is manifested by its comparatively rapid decomposition at ambient temperature to the more stable solid phases, hydrogarnet (C3AH6) and portlandite (Ca(OH)2). Sulfate-AFm preparations, on the other hand, while claimed to be thermodynamically metastable at <40C [46][47], are nevertheless persistent at 25C. Zhang [197] made preparations which might initially have contained AFm (sulfate/hydroxy) solid solutions but after prolonged ageing (560d at 25C) were found to have decomposed to mixtures of sulfate-AFm and other solids, e.g., C3AH6. According to own investigations and calculations reported in this Thesis monosulfoaluminate and part of the monosulfoaluminate-hydroxy-AFm solid solution series (up to ~24 mol% sulfate replacement possible) are thermodynamically stable at 25C. Experiments have shown that the hydroxide-substituted sulfate-AFm solid solutions are relatively persistent and, moreover, are observed to occur in real cements, it is important to include them in a phase development model. In this connection, it is noteworthy that it was possible rapidly to achieve hydroxide-substituted AFm by mechanically mixing the two solids, hydroxy- and sulfate-AFm, at 25C, suggesting that this associates good persistence within a range of solid solutions: partial OH- for SO42- substitution does not necessarily detract from the ability of these solid solutions to form and persist. As will be shown, a variety of mechanisms contribute to the ultimate decomposition of these phases.

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79

5.5.2 Transformation mechanisms


It has always been assumed that changes in the anion chemistry of an AFm phase occur by ion exchange. In this view, the [Ca2Al(OH)6]+ layers are relatively fixed, while water and chargebalancing anions in interstitial spaces are regarded as more mobile and hence exchangeable. Thus the chemistry of the interlayer ions adjusts itself to that of the pore fluid. So, for example, if a cement develops C4AHx but carbonate ions become slowly available, perhaps from dissolution of added calcite, a change in AFm composition will occur and it will proceed via ion exchange, first to hemicarboaluminate and eventually to monocarboaluminate. But the structures of the three phases differ in detail and, as shown, they do not form continuous solid solution. It is therefore difficult to envisage the transformation proceeding by other than by a reconstructive process; that is, one phase dissolves while another, differing in composition and structure, nucleates and crystallises. While transformation by ion exchange could permit the morphology and microstructure to persist throughout the conversion(s), nucleation and crystallisation are more likely to require a reconstitution of the microstructure. Putnis et al. [153] have recently described a novel mechanism for pseudomorphic replacement of one phase by another and this may have relevance for the mechanism of transformations amongst AFm phases driven by anion exchanges. The net result of this study is to create uncertainty concerning the actual mechanism of the transformation and consequently, the potential for changes in microstructure associated with transformations occurring amongst the AFm phase(s). More accurate structure determinations of individual AFm phases would be helpful to elucidate the actual mechanism of transformation: the structures may have a common plan, but differ significantly in detail and these details are important in the present context. It is not impossible to envisage the transformation between AFm phases occurring by ion exchange but with some simultaneous reordering and rearrangement within the [Ca2Al(OH)6]+ layers avoiding, or partly avoiding, need for a nucleation and crystallisation step, as described in [153]. However, the discontinuous nature of the AFm phase, requiring that it be treated as a series of discrete phase rather than a single solid solution must affect subsequent treatments of paste mineralogy.

5.5.3 Solubility data and its interpretation


Interest in the solubility of AFm phases centres on the solid solution series between sulfate- and hydroxy-AFm end members: these data are shown in Table A.10 and Table A.11. Special problems arise in determining the solubility of C4AHx at 25C because other hydration states, notably the 19 H2O state stable at > 88% r.h. and the 13 H2O state at < 88 % r.h. [180]. However the impact of lower r.h. parallels the behaviour of solutions with lowered water activities corresponding to the high ionic strengths observed in cement pore fluids [79]. Consequently, it is difficult reliably to perform solubility measurements on a single hydration state, although the author believes, solubility data reported here are obtained on C4AHx, with x close to 19, after allowing for other anionic substituents. But, the preparation for X-ray diffraction, done in a dry protective atmosphere to avoid carbonation, results in some dehydration of C4AHx with the result that the XRD-data actually relate to the 13 H2O state, or 13-x if some sulfate solid solution occurs. The extent of solid solution, as well as its persistence, may be influenced by the hydration state of C4AHx. Thus it is not surprising that solid solution would be incomplete between C4AsH12 or its highly hydrated form C4AsH14 and C4AH19. There is a shortage of direct and reliable information on AFm hydration states to progress this assessment. The possibility of using synchrotron radiation and examining AFm solids still in contact with solution offers hope that new data can be obtained to settle this question. The higher ionic potential of the aqueous phase of cements resulting from

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80

dissolution of alkalis, etc. may tend to favour the 13 H2O state [79] of the C4AHx phase or the 12 H2O state of monosulfoaluminate. Secondly, the lability of the C4AHx phase results in a difficult experimental choice: either prolong the time allowed for equilibration with an aqueous phase and risk decomposition to other solids, thereby influencing in solubility, or else use only brief equilibration times, thereby minimising decomposition, but perhaps failing to saturate the aqueous phase. C4AHx almost certainly takes into solid solution a small amount of sulfate. Lippmann diagrams are a useful instrument to estimate the extent of solid solution; accurate experimental data are a precondition. Best estimates of the extent of solid solution are on the order of max. 3% according to the derived best fit to the theoretical Lippmann diagram Fig. 5.9. This small sulfate content apparently causes a drastic lowering of calcium concentrations. However the lowering is not necessarily a consequence of solid solution; if it were, it would imply strong crystallochemical stabilisation by sulfate. Addition of a small amount of sulfate significantly reduces the labile nature of C4AHx. The solubility measurements, supposedly on C4AHx, may actually relate to a selfgenerated spurious invariant point of an aqueous solution coexisting with a mixture of phases; hydroxy-AFm solid solutions as well as the stable monosulfoaluminate type solid solutions and C2AH8. However decomposition has much less impact on the rest of the system and the solubility trends are consistent with a broad two (solid) phase gap and continuous solid solution ranging between initially about 50 mol% SO42- and the monosulfoaluminate end member. The miscibility gap is likely to be widened with time. However experiments have shown that decomposition of the labile solid solutions is slow: it is likely to be several years until the final equilibrium stage is reached.

5.6. Conclusions
A basic thermodynamic description of the AFm phase(s) necessitating collection of new data, and its coupling to experimental investigations, has enabled new insights into the relations between the most important AFm phases likely to occur in Portland cement: The principal findings are: AFm phases containing as principal anions OH-, SO42- and CO32- are incompletely miscible with each other. Thus several AFm phases may coexist in a matured cement paste at ~25C. An extensive solid solution with a miscibility gap may occur between monosulfoaluminate and C4AHx. The substitutable SO42- content, by OH- is ~ 50 mol% of the initial sulfate content of monosulfoaluminate but is likely to decrease with prolonged ageing (1-2 years) at 25C. Due to discrepancies in the literature, long term investigations and calculation were used to determine the thermodynamic stability of the solid solutions. According to the calculation, supported by experiments, hydroxy-AFm solid solutions and part of the monosulfoaluminate type solid solutions with ~24 mol% hydroxide substitution are thermodynamically metastable with respect to hydrogarnet, portlandite and sulfate-rich monosulfoaluminate type solid solutions (max. ~24 mol% hydroxide substitution). The amount of substitutable OH- in hydroxy-AFm due to incorporation of SO42- is small (5%). Thermodynamics and experiment agree in support of the above conclusions. However hydroxide-substituted sulfate-AFm have only a small driving force for decomposition at ~25C, as a consequence of which they are persistent.

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Carbonate and sulfate provide thermodynamic stabilisation for the AFm phase. Thus monocarboaluminate and part of the monosulfoaluminate-hydroxy-AFm solid solution series are stable at 25C. Hemicarboaluminate is a stable phase over a short range of carbonate activities at ~25C. This range, although short, coincides with commonly encountered conditions in cements, e.g. the presence of minor carbonate even in fresh clinker, and for this reason it should not be excluded from consideration in a mineralogical model for paste hydration.

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82

6. The AFt phase in Portland cement


6.1. State of the art of science 6.1.1 General remarks on the structure and composition of AFt
AFt (Al2O3-Fe2O3-tri) phases are a typical hydration product of commercial Portland cement. AFt phases belong mineralogically to the ettringite group of minerals with a general formula [Ca3(Al,Fe)(OH)612H2O]2X3xH2O, where X equals an exchangeable doubly charged anion or rather infrequently, two formula units of a singly charged anion. The term AFt was introduced by Smolczyk [173] to describe the ettringite-type hydration product of Portland and slag blended cements, due to minor compositional differences to the natural mineral ettringite, ideally Ca6Al2(SO4)3(OH)1226H2O. In the literature [180] it is generally agreed that the AFt phase, which is formed in the early hydration of most Portland cements, has a chemical composition which is close to ettringite, although the existence of AFt solid solutions has been described [16][127][152]. Moore and Taylor [134] [135] and Courtois et al. [39] published the first comprehensive studies on the crystal structure of ettringite based on XRD investigations. Recently Hartmann and Berliner [88] complemented the crystal structure of ettringite by determining the missing positions of the hydrogen atoms by time-of-flight neutron diffraction techniques. Gtz-Neunhffer and Neubauer [83] reported a refined structure model for ettringite based on XRD powder diffraction and previously published models. All structures agree basically with the model proposed by Moore and Taylor [135]: AFt phases exhibit a hexagonal prismatic column-based structure. The columns, with the empirical formula [Ca3(Al,Fe)(OH)612H2O]3+, run parallel to the prism c-axis and are composed of (Al,Fe)(OH)6 octahedra bound by OH- groups to CaO8 polyhedra. Each calcium atom is coordinated by four H2O molecules Fig. 6.1 a). As shown in Fig. 6.1 b) the columns are surrounded by channels containing sulfate and the remaining water. Per formula unit of ettringite, Ca6Al2(SO4)3(OH)1226H2O, the channels contain four sites, three are occupied by sulfate and one by two water molecules.

a)

b)
S Ca Al

b a c

Fig. 6.1: Crystal structure of ettringite. (a) part of a column (A=Al, C = Ca, H = O of an OH group, W = O of an H2O molecule; Hydrogen atoms omitted); (b) projection of the structure according Moore and Taylor [135] on (0001) (columns (big circles) channels (small circles) and unit cell (rhomboid) are indicated). Modified from Taylor [180]

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Beside sulfate, different anions, X, have been reported to be bound into the ettringite structure. The current study concentrated on compositions relevant to cement, despite the existence of more exotic AFt phases. Flint and Wells [67] observed the formation of a mixture of hexagonal platy AFm-like crystals with a composition of 3CaOAl2O3CaSiO312H2O and needle-like AFt crystals with a proposed composition 3CaOAl2O33CaSiO3xH2O (x in the range of 30 - 32) from a solution containing appropriate amounts of silica, calcium and aluminium. Furthermore the formation of hydrated hexacalcium aluminate with a composition 3CaOAl2O33Ca(OH)230H2O, made by mixing a limesucrose solution with calcium aluminate solution, was described. Carlson and Berman [36] and later Pllmann et al. [152] repeated successfully the synthesis of 3CaOAl2O33Ca(OH)230H2O according to the procedure given by Flint and Wells, but agreed that the compound is very sensitive to carbonation and converts with time to a carbonate analogue of ettringite with a composition 3CaOAl2O33CaCO332H2O. Carlson and Berman [36] synthesised this carbonate analogue of ettringite (tricarboaluminate, 3CaOAl2O33CaCO332H2O) using a sucrose solution and stoichiometric amounts of CaO, NaAlO2 and NH4HCO3. However tricarboaluminate could not be synthesised in the absence of sucrose; the formation of monocarboaluminate was observed instead. Hence it seems to be unlikely that tricarboaluminate will appear as a hydration product of Portland cement. Carlson and Berman [36] reinvestigated the silica-containing samples prepared by Flint and Wells [67] after ageing for more than 18 years. The XRD-pattern of these preparations showed a strong pattern similar to tricarboaluminate and diffuse signals corresponding to strtlingite and C-S-H. The solids lacked good morphology and were concluded to be poorly crystalline. The overall chemical composition of the solid was in agreement with the results earlier published by Flint and Wells [67]. However, in contrast to Flint and Wells, considerable amounts of CO2 (0.73 moles per mole of Al2O3) were found to be present in these samples, which suggests a formation of a solid solution between 3CaOAl2O33CaSiO3xH2O and 3CaOAl2O33CaCO332H2O.

6.1.2 Solid solutions between AFt phases


Carlson and Berman [36] investigated the possibility of solid solution formation between sulfateAFt and tricarboaluminate. In a first approach, the procedure to form sulfate-AFt was modified by partial replacement of calcium sulfate by calcium carbonate. This resulted in the formation of a mixture of sulfate-AFt and monocarboaluminate. In a second trial the lime-sucrose method was applied but half of the ammonium bicarbonate was replaced by ammonium sulfate. The XRDpattern showed the presence of two distinct AFt phases, one with reflections close to sulfate-AFt and the other close to tricarboaluminate. Thus Carlson and Berman concluded that if solid solution occurs, it is limited in extent. In contrast to Carlson and Berman [36], Pllmann [152] successfully applied the sucrose method to synthesise solid solutions between sulfate-AFt and its carbonate analogue by direct precipitation of the solids from a supersaturated lime-sucrose mixture by mixing solutions containing appropriate amounts of NaAlO2, Na2CO3 and Na2SO4. Lattice constants were refined by least square methods from the XRD-pattern of the solids. He found that almost 2/3 of the sulfate of AFt can be replaced by carbonate. However no sulfate substitution was found for the tricarboaluminate end member. Additional experiments demonstrated that ~50 mol% of the sulfate can be replaced by hydroxide, OH-, if sucrose solutions are used. Furthermore he showed that there is a continuous solid solution

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series between the hexacalcium aluminate hydrate, 3CaOAl2O33Ca(OH)230H2O, and tricarboaluminate. Barnett et al. [16] published an XRPD-fitting study of the solid solutions between sulfate-AFt and tricarboaluminate prepared according the procedures described by Pllmann et al. [152]. In agreement with Pllmann, only limited solid solution formation was found and about 2/3 of the sulfate could be replaced by carbonate in the original sulfate-AFt structure. In contrast to Pllmanns investigation significant amounts of carbonate were believed to be replaced by sulfate in the structure of tricarboaluminate, which resulted in a formation of a second solid solution series, though the determination of the chemical composition of the solid solution was not possible. Midgley and Rosaman [131] investigated the time-dependent phase evolution of hydrated Portland cement. They found a systematic decrease of the d0001 value of ettringite in conjunction with a shift of the normalised peak temperature in DTA investigations of ettringite to higher temperatures. Solid solutions between sulfate-AFt and hexacalcium aluminate hydrate (hydroxy-AFt) exhibit similar results: with increasing hydroxide substitution; the d0001 value decreased and the normalised peak temperature in the DTA experiments increased. Thus Midgley and Rosaman concluded a progressive substitution of sulfate by hydroxide in the AFt structure as it occurs in Portland cement with increasing reaction time. In solubility determinations Warren and Reardon [192] found significant deviations of the ettringite solubility product at pH values > 13 compared to the mean values obtained at lower hydroxide activities. A possible explanation is the substitution of OH- for SO42- in the ettringite structure at higher hydroxide activities. Recently Neubauer et al. [140] reported a significant decrease of the dimension of the c lattice constant of AFt in the early stages of hydration. It is believed that at the outset of hydration, a ironand carbonate-rich AFt formed which was metastable and converted with time to an aluminiumand sulfate-rich AFt. However as long as no detailed information about chemical changes of the ettringite composition during hydration are available, it is difficult to apply these results.

6.1.3 The formation of thaumasite and related solid solutions


The first known occurrence of thaumasite induced deterioration of concrete was reported by Erlin and Stark [59] in 1965. They showed the coexistence of thaumasite, Ca3Si(OH)6(SO4)(CO3)12H2O, with calcite, gypsum and brucite in the affected regions of a sewer pipe. In another pipe, thaumasite, ettringite, gypsum and traces of calcite were found below a seriously deteriorated zone. In 1975 van Aardt and Visser [2] found the formation of thaumasite in 1 year old autoclaved Portland cement mortar containing dolomitic aggregates exposed to sodium sulfate solutions at 5C. Growing concerns about reports of concrete deterioration resulting from thaumasite formation led to the formation of a Thaumasite Expert Group in the UK in 1998. Since that time, more cases of thaumasite formation have been reported worldwide and the number of scientific publications dealing with the thaumasite form of sulfate attack (TSA) has increased. As this chapter deals more with the thermodynamic stability of thaumasite and related solid solutions, a review of the literature was restricted to these aspects. General overviews about thaumasite formation in concrete are given in [183] and in a special issue of Cement and Concrete Composites edited by Macphee and Diamond [128].

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85

The structure of thaumasite


The structure of thaumasite is similar to the column- and channel-based structure of ettringite (Fig. 6.1); carbonate replaces part of the sulfate in the channel sites while silicon replaces aluminium in the columns (see [58]). Thus the coordination of silicon in thaumasite is sixfold, which is unusual in low pressure phases. Indeed thaumasite is the only known mineral with Si(OH)6 octahedra to be formed at low pressure and ambient temperatures.

Ca

Solid solution formation


The existence of solid solutions between SO4-ettringite and thaumasite in nature is known [103][138]. Murdoch and Chalmers [138] described an ettringite-like mineral with considerable amounts of SiO2 and CO2 and designated it as woodfordite, Ca6Al1.5(SO4,SiO3,CO3)3(OH)10.5 15H2O. The authors subsequently revised this claim on the grounds that woodfordite is not a new mineral but is closely related to ettringite and withdrew the name woodfordite [136][137]. Lukas [126] found the occurrence of ettringite-thaumasite solid solutions in deteriorated concrete in tunnels with similar crystallographic properties as described by Murdoch and Chalmers. Barnett et al. [17] synthesised several members of the solid solution series and showed that limited solid solution between both end members occurs and thus a miscibility gap in the solid solution series exists. Later several researchers identified thaumasite-ettringite solid solutions in concretes undergoing sulfate attack [28][31][185][102]. Thus the formation of solid solution between both minerals has to be considered as an important process in the progression of sulfate attack in concrete and Bensted [22] proposed the woodfordite-route as one possible step of the formation of thaumasite in concrete. Torres et al. [185] found ettringite-thaumasite solid solutions in cement paste undergoing sulfate attack. The extent of solid solution formation was discussed. Due to divergent outcomes of the XRD-peak fitting procedure compared to results given by Barnett et al. [17], it was concluded that the solid solution behaviour of ettringite and thaumasite is more complex than initially believed. The results indicated the presence of sulfate- and/or carbonate-rich ternary solid solutions between thaumasite, ettringite and possibly, tricarboaluminate.

The temperature-dependent stability of thaumasite and related solid solutions


It is generally believed that thaumasite preferentially forms in carbonate-containing service environments at temperatures below 15C. However Diamond [53] recently described thaumasite formation in California at temperatures well above 15C. Brown and Hooton [31] found thaumasite in concrete samples stored in MgSO4 and Na2SO4 solutions at 23C for 21 years. Macphee and Barnett [127] obtained solubility data of ettringite-thaumasite solid solutions in the temperature range between 5C - 30C; no apparent decomposition of thaumasite and related solid solutions occurred after 6 months storage at 30C, which suggests the persistence of thaumasite at temperatures at least up to ~30C. Blanco Varela et al. [28] studied the effect of cement C3A content, temperature and storage medium on the formation of thaumasite in precarbonated mortars. Thaumasite and thaumasite solid solutions formed at both 5C and 21C. The kinetics of formation is not only dependent on temperature but also on the chemistry of the aqueous phase. Samples stored at 5C in water formed thaumasite after 5 years, whereas the same samples stored at 21C in a 2% gypsum solution formed thaumasite after 16 months.

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86

Giampaolo [76] estimated the upper thermal stability limit of thaumasite to 605C from coupled dehydration and XRD experiments. In his experiments different batches of natural thaumasite were heated in an oven to 67, 77, 83 or 90C. After 240h at 67C no significant changes of the unit-cell parameters were detected, whereas thaumasite dehydrated completely to form amorphous phase(s) after 270h at 77C. Subsequent rehydration experiments at 18C and 60C of the dehydrated samples resulted in the formation of gypsum and calcite from the initially amorphous dehydration products. Giampaolo concluded that the dehydration of thaumasite is irreversible at the applied experimental temperatures.

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6.2. Solid solutions between sulfate- and carbonate-AFt 6.2.1 Synthesis of solid solutions and investigations of the solid phase
The literature review has shown that a limited solid solution formation between SO4- and CO3-AFt is likely. To address this aspect, of the possible occurrence of carbonate-AFt and carbonatecontaining AFt solid solutions in hydrated cement paste, experiments have been made on the synthesis and properties of sulfate- carbonate-AFt phases. First, carbonate-AFt was prepared using a modification of the method of Carlson and Berman [36] as described in chapter 4.1.3; sulfate-AFt was synthesised according to the method given by Atkins et al. [9]. In contrast to Pllmann et al. [152] and Barnet [16], who used a sucrose method with strongly supersaturated solutions with respect to the AFt solid solutions, in this Thesis the solid solutions were prepared by dispersing the previously synthesised SO4-AFt and CO3-AFt in different stoichiometric ratios in ultra pure water at 25C (w/s ~ 30). Ten physical mixtures of sulfate- and carbonate-AFt were prepared at wellspaced intervals and reacted at 25C for up to 84 days. Afterwards, to enable the derivation of a model to assess the thermodynamic stability of the SO4-CO3-AFt solid solution series with respect to other cement hydrates, the supernatants were analysed according the procedure described in chapter 3.1 and 3.5 and solids were analysed by XRD according to chapter 3.2.

SO4 -AFt CO3 -AFt

SO4 - CO3 AFt AFt

0.20 0.40
5000 counts

0.50 0.60 0.80

Intensity

1.00 SO 4 -AFt

10

12

14

16

[2 CuK ]
Fig. 6.2: XRD-patterns of selected SO4-CO3-AFt phase solid solutions at 25C

Selected X-ray diffraction patterns of preparations reacted for 84 days are shown in Fig. 6.2. Small amounts of calcite were found as an additional phase in all carbonate-containing preparations. Marks show the ideal positions of low 2 reflections for sulfate- and carbonate-AFt. The system is binary but miscibility between the two end members is incomplete: the presence of a two-phase region is indicated in the range 0 to 50 mol% sulfate-AFt, broadly in agreement with the findings of Pllmann et al. [152] and Barnett et al. [16], although the maximum sulfate substitution is slightly less than observed in [16][152]. The differences of the extent of miscibility between this study and results published in the literature probably arose from the different synthesis routes. In the mixed end member approach used in this study, the supersaturation of the solution with respect to the solid solutions is very small, whereas the degree of initial supersaturation is likely to be very high

SO 4/(SO 4 +CO 3 )-ratio [-]

0 CO 3 - AFt 0.05

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88

in the sucrose method used in both [16] and [152]. As a result of the changed conditions, a more extensive solid solution formation will be observed. However it is difficult to determine the real limits of miscibility as in the mixed end member approach it could be argued that kinetical restraints retard a solid solution formation while on the other side, in the sucrose preparations, initially formed metastable solid solutions might decompose with time to more stable phase assemblages. However this study has shown, in agreement with the literature, that solid solutions between SO4-AFt and CO3-AFt form spontaneously.

6.2.2 Thermodynamic modelling of the solid solution formation


As previously described in chapter 4.3.4 a binary non-ideal solid solution model was used to estimate the thermodynamic properties of the SO4-CO3-AFt solid solution series. The dissolution reaction of the solid solution series is given in Eq. 6.1:
Ca 6 Al 2 (SO 4 ) x (CO 3 ) 3 x (OH)12 26H 2 O 6Ca 2 + + 2AlO2 + xSO4 + (3 x)CO 3 + 4OH - + 30H 2 O (6.1)
22

To fix phase boundaries, X-ray diffraction data need to be considered together with solubility data obtained from the same compositions. The investigation of the solid phases has shown that there is a divergence between the phase boundaries estimated from solid state investigations in this study and values reported in the literature. Lippmann diagrams have been shown to be a useful tool to estimate the extent of miscibility in a binary solid solution system (see chapter 5.3) and to show the relation between the chemical compositions of the solid and aqueous phases. The solubility data obtained on the solid solution series are listed in Table A.12. The carbonate concentrations were always below the limit of detection and had to be estimated by assuming an equilibrium with calcite. Subsequently activities of the relevant ions were computed using GEMS and the appropriate solubility data. Thus it is now possible to calculate the total solubility product of the AFt solid solution series according to Eq. 6.2; [ ] denote activities of the aqueous species:

= [Ca

2+

] 6 [AlO2 ] 2 [OH ] 4 [H 2 O] 30 [SO 4 ] 3 + [CO 3 ]3


-

(6.2)

The solidus of the Lippmann phase diagram represents a series of total solubility products calculated from the aqueous phase composition in dependence of the changing chemical composition of the solid phase. As shown in chapter 5.3.1, Lippmann diagrams in conjunction with the software MBSSAS can be used to estimate the dimensionless Guggenheim parameters a0 and a1, which are necessary to calculate the activity coefficients of the sulfate and carbonate end members in dependence of the solid phase composition according to Eqns. 4.19 and 4.20. The theoretical total solubility product is then calculated with Eq. 4.24. To obtain realistic values of the miscibility gap boundaries, literature investigations as well as solubility and solid state investigations reported here have to be in agreement. Thus the miscibility gap boundaries should be in the range x1~0~0.15 x x2~1 ~1.5 according to Eq. 6.1. To harmonise the available literature data with results obtained in this study and to enable the estimation of x1, one end of the miscibility gap was fixed to x2 = 1.25, the mean value between previously reported results and data obtained in this study.

The AFt phase in Portland cement


C6AsxC(3-x)H32 (0 x 0.12)

89

miscibility gap C6Asxc(3-x)H32(1.25 x3)

-44.50 -45.00

C6As0.12c2.88H32 + C6As1.25c1.75H32

data points solidus

mean eq,exp calc. GEM S a0 =-0.823 a1 =2.82

solidus log eq -45.50 -46.00 solutus -46.50


data points solutus
calc. GEMS (log Ksp=-44.9) exp. mixed end members (log Ksp=-44.9) exp. mixed end members (log Ksp=-45.4) calc. for log Ksp(SO4-AFt)=-44.9

calc. for log K sp(SO4-AFt)=-45.4

-47.00 0.0 0.1 0.2 0.3 0.4 0.5


CO3 -AFt

0.6

0.7
2-

0.8

0.9

1.0

solid SO 4/(SO 4+CO 3) or X SO 4

SO 4 -AFt

Fig. 6.3: Lippmann diagram for the SO4-CO3-AFt solid solution series at 25C with a0=-0.823 and a1=2.82 for miscibility gap fractions 0.12 x 1.25 (Eq. 6.1) (solid black lines represent theoretically calculated solidus and solutus in dependence of the SO4/(SO4+CO3) ratio of the solid solutions; open symbols shows calculated solidus in dependence of the molar SO4/(SO4+CO3) ratio of the bulk composition with Log Ksp,SO4AFt=-44.9. Solid (black and grey) markers are mean experimental points derived from solubility experiments (data given in Table A.12) in dependence of the molar SO4/(SO4+CO3) ratio of the bulk composition). Dashed lines are theoretically calculated solidus and solutus for Log Ksp,SO4-AFt=-45.4.

To fix the second boundary x1 of the miscibility gap, the resulting experimental and theoretical solidus functions were plotted as a Lippmann diagram and the parameters a0 and a1 were calculated using the software MBSSAS and varying the x1 value of the miscibility gap in the presumed range 0 to 0.15. As shown in Fig. 6.3 the difference between the initial total solubility products of the end members is relatively small and lies within the range of the observed analytical error, especially at the sulfate-rich end of the solid solution series. Thus it is difficult to obtain a best fit for parameters a0 and a1 from the Lippmann diagram. The best qualitative agreement between experimental and theoretical solidus was obtained by setting the miscibility gap fractions to 0.12 x 1.25 with a0=-0.823 and a1=2.82. However, as shown in Fig. 6.3, theoretically calculated values for the solidus are apparently always higher than the experimental values. As the experimental values are consistently lower than calculated, a systematic error is assumed. The mean value of the solubility product of the pure SO4AFt end member, computed to be ~-45.4 in this study, is lower than the database entry for SO4AFt, -44.9, but, as shown in Fig. 4.26, lies well within the limits of analytical error for the database entry. A recalculation of the solidus assuming a corrected solubility product for the AFt end member to be -45.4, gives reasonable agreement between experimental and theoretical solidus, which suggests that the chosen non-ideal solid solution model with the parameters a0=-0.823 and a1=2.82 is qualitatively correct.

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To complement the Lippmann phase diagram (Fig. 6.3) and establish the relation between the constitution of the aqueous phase and the solid solution composition, the solutus function needs to be included. With the help of the previously determined fitting parameters a0 and a1 and the known activities of the sulfate- and carbonate-species, the experimental solutus can be calculated with Eq. 6.3:

X CO 2 ,aq X SO 2 ,aq 4 = + 1 eq,sl K C As H C As H K C Ac H 3 C Ac H 6 3 32 6 3 32 6 3 32 6 3 32

(6.3)

where KC6As3H32 and KC6Ac3H32 are the solubility products of the end members, C6As3H32 and C6Ac3H32 are the activity coefficients of the end members and XSO42- , aq and XCO32-, aq are the aqueous activity fractions of the substitutable species SO42- and CO32- calculated from Eqns. 6.4 and 6.5; [ ] denote calculated activities of the aqueous species:
X SO 2 ,aq =
4 3 [SO 2 ] 4 2 3 2 3 [SO 4 ] + [CO 3 ] 2 3 [CO 3 ] 2 3 [SO ] + [CO 3 ] 2 3 4

(6.4)

X CO2 ,aq =
3

(6.5)

As shown in Fig. 6.3, experimentally-derived values (triangular and cross markers) agree well with the theoretically computed solutus.
3.0 relative changes of the energy of mixing G m [kJ/mol] 2.0 1.0 0.0 -1.0 -2.0 -3.0 -4.0 -5.0 0 0.1 0.2 0.3 0.4 0.5 0.6 experimental calculated

calc. misc. gap


1)

1)

single datapoint

0.7 0.8

0.9

CO 3-AFt

molar bulk S O 4/(S O 4+CO 3)-ratio

S O 4-AFt

Fig. 6.4: Comparison between calculated and theoretical changes of the relative energy of mixing of the SO4-CO3-AFt solid solution series at 25C

Fig. 6.4 shows a comparison between the theoretically calculated and experimentally-derived relative energies of mixing in dependence of the solid solution composition. The relative energy changes are independent of the initial solubility product of the end members. The theoretical energy of mixing is calculated using Eq. 4.14 and the previously derived dimensionless Guggenheim parameters a0 and a1. The experimentally-derived values are calculated according to the following procedure: Independently of the existence of a miscibility gap, the solubility product of a solid solution at stoichiometric saturation Kss [81] can be calculated based on applying the law of mass action to the dissolution Eq. 6.1 for ettringite solid solutions (Eq. 6.6; [ ] denote species activities):
K ss = [Ca 2 + ] 6 [AlO 2 ] 2 [OH ] 4 [SO 4 ] x [CO 3 ] 3 x [H 2 O] 30
2 2

(6.6)

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91

The relative energy of mixing as a function of the molar bulk composition of the solid solution can be calculated according to Eq. 6.7:

G m = RT (

ln K i ln K ss )

(6.7)

To minimise the systematic error and discrepancies between the previously derived solubility constants, Ki is taken to be the experimentally-derived solubility constant and Xi the mole fraction of end member i. Thus the energy of mixing of the end members becomes zero by definition and only relative changes are compared. As shown in Fig. 6.4 the relative changes of the theoretical energy of mixing and the values derived from the experiments are in good agreement, which supports the applicability of the solid solution model and its accuracy. Both curves display a similar curvature and pass through a minimum between SO4/(SO4+CO3) ~0.6 to ~0.8, which corresponds to the maximum driving force of solid solution formation between the two end members. The mean experimental values at SO4/(SO4+CO3) = 0.7 to 0.9 are slightly lower than calculated but the deviations from the theoretical curve are within the analytical errors. With the known parameters a0 and a1 and the thermodynamic properties of the end members it is now possible to recalculate the solubility data of the SO4-CO3-AFt solid solution series. A comparison of calculated and experimental solubility data (Fig. 6.5) shows very good agreement. Solubilities in the region of two solid phases (0.04 SO4/(SO4+CO3) ~0.42) should be constant and this is in fact observed with the result that solubility curves for each species consist of two portions: a horizontal region of constant solubility, where solubility is constrained by phase rule considerations, and a curved segment characterised by decreasing pH as well as calcium and aluminium concentrations (Fig. 6.5 a)). A significant increase of the sulfate concentration occurs, almost three orders of magnitude as the composition approaches the sulfate end member of the ettringite solid solution series; note the use of a log concentration scale in Fig. 6.5 b).

a)
10 pH Concentration [mmol/l] 8 calcium 6 4 2 0 0 CO 3-AFt 0.2 0.4 0.6 0.8 1 S O 4-AFt calc. SO 4/(SO 4+CO 3)-ratio aluminium 11.6 11.4 11.2 11.0 pH 12.0

b)
1.E+01 Concentration [mmol/l] 1.E+00 sulfate 1.E-01 carbonate 1.E-02 1.E-03 0 CO 3-AFt 0.2 0.4 0.6 0.8 1 S O 4-AFt calc. SO 4/(SO 4+CO 3)-ratio

11.8

Fig. 6.5: Comparison of calculated (lines) and mean experimental (markers) solubilities for the SO4-AFt and CO3-AFt solid solution series at 25C (Note that the calculation is restricted to SO4-CO3-AFt solid solutions in equilibrium with small amounts of calcite, except in the preparation of the SO4-AFt end member)

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6.3. Investigations on thaumasite 6.3.1 The need for investigations


Juel et al. [98] developed a thermodynamic model to predict the stability of thaumasite. This model is based on phase rule and mass balance restrictions and gives useful information about the qualitative and quantitative composition of phase assemblages compatible -or incompatible- with thaumasite. Experimental work in support of this model was confined to 5C and both ettringite and thaumasite were assumed to have their ideal compositions. But Macphee and Barnett [127] published solubility data for ettringite-thaumasite solid solutions showing extensive solid solubility of thaumasite in ettringite and this Thesis supports their conclusions. To enable thermodynamic modelling of the solid solution formation it is necessary to know the thermodynamic properties of the pure end members of the solid solution series. Unfortunately, Macphee and Barnett [127] did not give solubilities for the thaumasite end member and it is thus difficult to estimate the thermodynamic properties of the solid solutions. However Bellmann [20] reports solubilities of natural thaumasite, but only at 8C. The preparations by Macphee and Barnett [127], disclosing the existing miscibility gap between ettringite and thaumasite, can be used to estimate the thermodynamic properties of thaumasite. Damidot et al. [44] used their data to derive a solubility constant for thaumasite at 25C at which temperature thaumasite was stable. Invariant points were calculated for phase assemblages including thaumasite in the system CaOAl2O3SiO2CaSO4CaCO3H2O. However limitations of the data meant that calculations were confined to 25C. Thus need arises to determine thermodynamic properties of the thaumasite end member and its temperature dependence in order to assess its stability and compatibility, especially in the range 0C to 30C.

6.3.2 Synthesis of thaumasite


A critical review of the literature shows that the synthesis of thaumasite is relatively difficult compared to other AFt phases, e.g. SO4-AFt or CO3-AFt. Thaumasite forms slowly and low temperatures are preferred. According to the literature [3][17][177] the best synthesis is obtained using a sucrose solution instead of water. In the current study, approximately 25g batches of thaumasite were synthesised using the sucrose method described by Barnett et al. [17]: typically 4.34 g of Na2Si2O52H2O, 4.23g of Na2CO3, 5.65 g of Na2SO4 and 6.70 g of freshly burnt CaO and ~ 440 ml of a 10% w/v sucrose solution were mixed according to the following procedure: 1. The CaO was dissolved in to the 10% w/v sucrose solution and cooled to 5C. 2. A slurry containing Na2Si2O52H2O, Na2CO3, Na2SO4 and 60g water was prepared and agitated for 10 min. 3. The sodium salt slurry was added to the lime-sucrose solution and stored for 6 weeks at 5C. To accelerate reaction the slurry was stirred continuously for 2 weeks and agitated regularly thereafter. 4. After 6 weeks the solid was vacuum-filtered with Whatman #540 filter paper and washed several times with ultra pure degassed water to remove alkalis and sucrose. Subsequently the solid was dried over saturated CaCl2 solution at 37% r.h. at 25C for 3 weeks and analysed by XRD using a PANALYTICAL XPERT PRO diffractometer; the operating parameters are described in chapter 3.2.

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93

CO3 -AFt Ca6 Al(OH)12 (CO3 )3 .26H2 O calcite

20000 counts

SO4 -AFt Ca 6 Al(OH)12 (SO4 )3 .26H2 O

Intensity

Thaumasite Ca3 Si(OH)6 CO3 SO4 .12H2 O calcite

10

15 [2 Cuk ]

20

25

30

Fig. 6.6: Comparison of the XRD-pattern of synthetic thaumasite with SO4-AFt and CO3-AFt

In contrast to Aguilera et al. [3] and Barnett et al. [17], who obtained impure thaumasite in phase mixtures, the XRD-pattern of the solid obtained in the title study showed the formation of nearly phase pure thaumasite after 6 weeks (Fig. 6.6); only traces of calcite were detected. Fig. 6.6 shows the similarity of the thaumasite pattern to those of SO4-AFt and CO3-AFt: all belong to the same AFt family. As indicated by a dashed line in Fig. 6.6, the position of main basal reflection of thaumasite (d100~9.53) is between those of comparable reflections of SO4-AFt (d100~9.72) and CO3-AFt (d100~9.38). This is in agreement with investigations by Barnett et al. [16], showing a decrease of the lattice parameters of the unit cell dimension with increasing carbonate substitution. ESEM micrographs of the solid, Fig. 6.7, show the typical needle-like morphology of minerals belonging to the AFt group. The thaumasite crystals have an average length of ~ 2-3 m and have an aspect ratio of typically ~ 15-20.
100
DT G

2.0E-03 differential weight loss [mg/K] 0.0E+00


~450C ~720C ~910C

90 relative weight [wt.-%] 80 70 60 50 40 0


133C TG

-2.0E-03 -4.0E-03 -6.0E-03 -8.0E-03 -1.0E-02 -1.2E-02 -1.4E-02

200

400 600 800 Temperature [C]

1000

Fig. 6.7: ESEM micrograph of synthetic thaumasite at 5C

Fig. 6.8: Thermal analysis (TG and DTG data) of synthetic thaumasite

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94

The TG and DTG curve of synthetic thaumasite Fig. 6.8 showed a 4 step-weight loss: The first step (DTG maximum at 133C) can be attributed to the loss of loosely bound water linking the columns (~37.3%). A second step (DTG maximum at ~450C) is likely due to the decomposition of OH-groups. The sum of both weight losses corresponds closely to the total amount of bound water; 44.3 wt.-% versus a theoretically calculated water content of 43.4 wt.-% using the formula Ca3Si(SO4)(CO3)(OH)612H2O. The third step, at 720C, is believed to be caused by a loss of carbon dioxide; the mass loss of ~7 wt.-% carbon dioxide, which agrees with the theoretical CO2 content (~7 wt.-%). The origin of the fourth step, a weight loss of ~3 wt.-% at ~910C, remains less clear. It could be that this is an additional peak due to the loss of CO2, which would however imply a higher carbonate content than theoretically calculated. Gtz-Neunhfer [84] found a similar peak at the thermal analysis of ettringite, synthesised by the sucrose method. However, this peak only occurred in N2-atmosphere. Gtz Neunhfer [84] suggested that small amounts of organic carbon, probably present as contamination due to insufficient washing, reduced parts of the SO42- to SO32which subsequently decomposed to SO2 (g) at ~ 900C. If the latter hypothesis is correct the binding of sucrose to the solid needs to be explained. If the sucrose is structural (which appears unlikely on crystallochemical grounds) it would result in significantly lower water contents of thaumasite. However as the water content is close to the theoretical value it is believed that small amounts of sucrose were probably adsorbed on the surface of the thaumasite samples 1.

6.3.3 The temperature-dependent stability of thaumasite in aqueous solutions Experimental


To assess the stability of thaumasite and derive solubility data, 0.5g of previously synthesised thaumasite was redispersed in 60 g ultra pure degassed water. Several preparations were stored 4 weeks at 1, 5, 25, 40, 55 and 70C in HDPE-bottles or PTFE bottles, respectively. Subsequently ~ 30ml of the aqueous phase were removed in a N2-atmosphere with a syringe and analysed as described in chapter 3.5. The remaining preparations were filled with ultra pure degassed water and two more sets of solubility data were obtained in 4 week cycles at 1, 5, 25, 40, 55 and 70C, according to the procedure described above. At the end of the experiment the remaining solids were dried over saturated CaCl2-solution at 37% r.h. and subsequently analysed by XRD using a PANALYTICAL XPERT PRO diffractometer according to chapter 3.2. Additionally the solubility of a natural thaumasite sample from Akschal/Kazakhstan, was determined to compare these data with the data obtained from synthetic thaumasite and previously reported data in the literature [20][44][127]. Samples intended for solubility determinations were gently ground by hand and sieve sized to 40m using an agate mortar and subsequently dispersed in ultra pure degassed water using a water/solid-ratio of ~100. The dispersions were stored for 180d at either 5C or 25C respectively. The aqueous phase was analysed as described above.

Investigation of the solid phases


Fig. 6.9 shows the temperature-dependent XRD-pattern of the solids after a series of 3 redispersions (after 84d) of the originally phase-pure thaumasite.

Balonis [13] confirms that rigorous washing of ettringite, synthesised by the sucrose method, eliminates these effects. It is likely that sucrose is strongly retained at the surface of thaumasite.

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95

Th

Th - Thaumasite Cc - Calcite C-S-H - Calcium silicate hydrate

Th
10000 counts

Th Th Th Th Th Th Cc

1C
Cc Cc -

5C 25C
C-S-H

Intensity

C-S-H C-S-H
Cc

Cc

40C

55C 70C 25 30

10

15

20 [2 Cuk ]

Fig. 6.9: XRD-pattern of synthetic thaumasite and related and related decomposition products upon redispersion at temperatures from 1 to 70C

Between 1 to 40C, the XRD-pattern showed thaumasite as main solid with traces of calcite. However at 55C, only small amounts of thaumasite remained but large quantities of calcite and C-S-H, indicated by the broad reflection at ~ 6.2 2, developed. Between 55C and 70C the intensity of the calcite reflection increased slightly while the C-S-H signal remained unchanged but the thaumasite signal disappeared. Thus at temperatures >40C the solubility of thaumasite increases significantly. In contrast to the needle-like thaumasite present between 1 to 40C (see Fig. 6.7) ESEM micrographs showed a mixture of poorly crystalline C-S-H and calcite, only small amounts of thaumasite were present at 55C (Fig. 6.10). Thaumasite was absent at 70C: C-S-H and calcite were the only solids present after 12 weeks annealing at 70C (Fig. 6.11). The C-S-H morphology at 70C is foil-like.

thaumasite

calcite C-S-H

Fig. 6.10: ESEM micrograph of partly decomposed synthetic thaumasite embedded in a matrix of C-S-H and calcite at 55C

Fig. 6.11: ESEM micrograph of C-S-H and calcite resulting from thaumasite decomposition at 70C

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96

a)
100 relative weight [wt.-%] 90 80 70 60 50 40 0 200 400 600 800 1000 Temperature [C] 1 - 40C 55C 70C

b)
2.0E-03 differential weight loss [mg/K] 0.0E+00 -2.0E-03 -4.0E-03 -6.0E-03 -8.0E-03 -1.0E-02 -1.2E-02 -1.4E-02 0 200 400 600 800 1000 Temperature [C] 1 - 40C 55C 55C 70C 1 - 40C 70C

Fig. 6.12: Thermal analysis (TG data left; DTG data right; heating rate 10K/min; N2-atmosphere) of synthetic thaumasite and related decomposition products following redispersions at temperatures from 1 to 70C.

The thermal analysis of the dried solids after 12 weeks annealing at temperatures between 1 to 70C is shown in Fig. 6.12. Up to 40C no differences were observed in the TG and DTG-patterns: the DTG pattern (Fig. 6.12 b) shows the typical peaks previously observed for synthetic thaumasite. The sample previously annealed at 55C showed a significant decrease of the area of the main peak of thaumasite dehydration at ~100C but the peak area at ~ 760C resulting from decarbonation of calcite increased significantly. The sample stored at 70C showed no thaumasite. A broad peak between ~90 to 140C indicates the typical slow dehydration of C-S-H. Furthermore the peak at 460C resulted from the decomposition of OH- groups of C-S-H. Due to absence of thaumasite and release of water, the relative amount of calcite increased, as evidenced by the increase of the calcite peak area at 760C. The peak at ~900C, typical of the samples which contained thaumasite, disappeared.

Thermodynamic modelling
To derive a consistent thermodynamic dataset for the temperature dependence of thaumasite solubility, data obtained from undersaturation are listed in Table A.13. Due to divergent literature results, solubility data of natural thaumasite after 180d equilibration at 5C and 25C, respectively, are given together with the solubilities of synthetic thaumasite. As noted in Table A.13, carbonate concentrations were always below the analytical limit of detection (~0.1mmol/l); the aqueous carbonate concentrations had to be estimated by assuming a saturated solution with respect to calcite. As before (paragraph 4.4.2), although the presence of calcite does not necessarily confirm that this phase is in equilibrium with the solution, this approach has given good agreement between experimental and calculated data. The theoretical principles of the solubility based estimation of thermodynamic properties of minerals are described in chapter 4.3.3. Based on the assumed dissolution reaction of thaumasite, Eq. 6.8, and the law of mass action, temperature-dependent solubility products of thaumasite were calculated according to Eq. 6.9:
Ca 3 Si(OH) 6 (SO 4 )(CO3 ) 12H 2 O 3Ca 2+ + HSiO3 + SO 4 + CO3 + OH + 14H 2 O [Ca 2+ ]3 [HSiO3 ] [SO 4 ] [CO3 ] [OH ] [H 2 O]14
2 2 2 2

(6.8) (6.9)

where [ ] denote aqueous species activities.

The AFt phase in Portland cement


Table 6.1: Standard molar thermodynamic properties of thaumasite at 25C
log KS01) C3SscH15
1)

97

fG
[kJ/mol]

fH
[kJ/mol]

S 897.5

a0 1030.54

a1 0.263

a2
[JK/mol]

a3
[J/(molK0.5)]

V
[cm3/mol]

2 [J/K/mol] [J/(molK)] [J/(molK )]

-24.75

-7564.5

-8700

-3.395e+06

3302)

according to Eq. 6.9 2)calculated from [58]

Activities of the aqueous species were calculated with the GEMS-PSI routine [109] using the extended Wateq-Debye-Hckel equation (Eq. 4.4). The standard thermodynamic properties of aqueous species used in the calculations are given in Table A.1. The experimentally-determined solubility products of each sample batch are listed in Table A.13: data cover the range 1C to 55C. Two solubility determinations of natural thaumasite are also shown. The standard molar thermodynamic properties of thaumasite were computed with the help of GEMS-PSI using a three-term temperature extrapolation to fit a theoretical temperaturedependent function of the solubility product to experimental values, as described in chapter 4.3.3. The resulting thermodynamic properties are summarised in Table 6.1. The derivation of the coefficients necessary to compute the heat capacity of thaumasite is described below. Fig. 6.13 compares solubility products on natural and synthetic thaumasite in the range 1C to 55C. All data were obtained monotropically, from undersaturation. The data obtained in the title study agree well, within limits of error, with those obtained by Macphee and Barnett [127], but differ from the data for natural thaumasite reported by Bellmann [20] at 8C. Experiments done in the course of the title study excluded atmospheric carbon dioxide, whereas the solubility determinations reported by Bellmann were made in the presence of air, and these conditions may lead to the decomposition of thaumasite [129]. As explained in chapter 4.3, and as a first approximation, the heat capacity effect of reaction was assumed to remain constant over the temperature range 1 to 60C by using the three-term temperature extrapolation. The heat capacity function for solids (at constant pressure) is usually calculated according to Eq. 4.1, where a0, a1, a2 and a3 are empirically derived. The heat capacities can be measured experimentally or, as was done here, estimated using a reference reaction with a solid having a known heat capacity and similar structure. As shown by Helgeson et al. [89], this principle was successfully applied to estimate the heat capacity of silicate minerals by formulating a reaction involving a structurally-related mineral of known heat capacity.
-22 Calc. solubility product log Ksp -23 -24 -25 -26 -27 -28 0 2) 10 20 1) 1)
1) Macphee and Barnett 2004 2) Bellmann 2004

synthetic thaumasite natural thaumasite 1)

30 40 Temperature [C]

50

60

Fig. 6.13: Calculated solubility products of synthetic and natural thaumasite samples from solubility experiments (lines show calculated best fits using a three-term temperature extrapolation (solid black line) and integrated Cp(T) integration (dashed line))

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98

Thus, with the knowledge of the temperature-dependent heat capacity function of the structurallyrelated ettringite and auxiliary data on other minerals given in Table 4.1, the coefficients necessary to calculate the heat capacity of thaumasite were estimated using Eq. 4.1 and the following reference reaction, Eq. 6.10:
2(Ca3Si(OH)6 (SO4 )(CO3 ) 12H2O) + 2Al(OH)3 + 1.5CaSO4 + CaO Ca 6 Al2 (SO4 )3 (OH)12 26H2O + 2CaCO3 + 2SiO2 + 0.5CaSO4 2H2O

(6.10)

As shown in Fig. 6.13, the resultant differences on the calculated solubility product, using the temperature-dependent heat capacity function instead of the constant value applied in the threeterm temperature extrapolation, are marginal in the temperature range 1C to 60C. With the standard thermodynamic properties of thaumasite, Table 6.1, and data for other relevant cement hydrates (Table 4.1) temperature-dependent solubility data of thaumasite were recalculated by applying the same conditions as used in the experiments (0.5g thaumasite in 60g water). The results are shown in Fig. 6.14.
Calc.+ Thaum asite + Calcite Th.+ Calc.+ C-S-H C-S-H Thaum asite + Calcite Th.+ Calc. + C-S-H

Calc.+ C-S-H

16 Concentration [mmol/l] 14 12 10 8 6 4 2 0

1.E+01 Concentration [mmol/l] 1.E+00 1.E-01 1.E-02 1.E-03 0 10 20 30 40 50 60 70 80 0 10 20 30 40 50 60 70 80 Temperature [C] Temperature [C]

silicon

calcium

sulfate

carbonate

Fig. 6.14: Recalculated solubility data for thaumasite based on fitted thermodynamic data (Table 6.1) and for other relevant cement hydrates (Table 4.1); (markers show experimental values of synthetic thaumasite obtained in this work, lines show calculated fit). Predicted solid phases are shown at the top.

As illustrated in Fig. 6.14, the calculated solubility data for thaumasite show generally good agreement with the experimentally-derived dataset. The dissolution of thaumasite is incongruent under all conditions of the solubility studies. Despite an underestimation of the calculated silicon concentrations at 1C and 5C, both datasets, experimental and calculated, generally agree, proving the internal consistency of the data. Especially in the temperature range from 1 to ~35C, where the solid phase assemblage consists mainly of thaumasite and traces of calcite, the differences between experimental calcium and sulfate concentrations are within analytical errors. In the temperature range 1C to ~ 35C concentrations of calcium, sulfate and silicon increase, whereas calculated carbonate concentrations showed a continuous decrease with increasing temperature. At temperatures > ~35C calcium and sulfate concentrations increase significantly, whereas silicon concentrations decrease due to the formation of C-S-H. Thaumasite is absent at temperatures above 70C. Under the chosen experimental conditions, no other sulfate-containing phase is formed. Thus all sulfate stays in solution 2 and sulfate concentration remains constant at temperatures 70C. It has to be noted that at temperatures ~ 70C the solution is almost saturated with respect to
2

except for minor sulfate sorbed in C-S-H.

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99

anhydrite, although the XRD analysis showed no formation of anhydrite or other sulfate phases (gypsum or hemihydrate). Fig. 6.15 shows the thermodynamically predicted mass balance changes under the previously described experimental conditions (0.5g thaumasite equilibrated in 60g water). Thaumasite and traces of calcite are the only solids encountered over the temperature range 1 to ~35C. At temperatures 35C thaumasite starts to decompose slowly with formation of C-S-H (Ca/Si~0.8 ~0.9) and calcite. At 68C thaumasite will have fully decomposed to a mixture of C-S-H (Ca/Si ~ 0.9) and calcite. The calculations confirm in principle the experimental observations: the XRDpattern of thaumasite did not change significantly between 1 to 40C, at 55C thaumasite (although only in small amounts) coexisted with C-S-H and calcite while at 70C thaumasite was fully decomposed to a mixture of C-S-H and calcite.
Thaumasite + Calcite Th.+ Calc.+ C-S-H Calc.+ C-S-H

Calc. relative amount of solids [wt.-%]

100.0 80.0 60.0 40.0 20.0 0.0 0 10 20

thaumasite

Ca/Si ~ 0.9

C-S-H
~0.8 Ca/Si ~ 0.9

calcite

30 40 50 Tempe rature [C]

60

70

80

Fig. 6.15: Calculated mass balance changes due to the decomposition of thaumasite with increasing temperatures (water/solid-ratio = 120)

It is important to note that, due to the increasing solubility of thaumasite with increasing temperature and its incongruent dissolution, the resulting relative mass balance changes are much influenced by the w/s-ratio used in the experiments. Thus thaumasite may be fully depleted at high w/s-ratios > 100, as were used in the solubility experiments at temperatures lower than 70C. This can lead to misinterpretations of the upper stability limit of thaumasite in aqueous solutions, which has to be defined as functions of both w/s-ratio and temperature. Thermodynamic calculations were used to estimate the upper thermal stability limit of thaumasite. Fig. 6.16 shows a comparison of free energy plots of reaction to form thaumasite (reaction (1), Fig. 6.16) or a mixture of anhydrite, C-S-H (Ca/Si=1.0), calcite and water (reaction (2)), by using the same phases consisting of lime, gypsum, amorphous silica and calcite (for thermodynamic data see Table 4.1). The two free energy curves intersect at 685C. As the free energy of reaction (1) is more negative than reaction (2), thaumasite is predicted to be a stable phase under the chosen conditions in the system CaO-SiO2-CaCO3-CaSO4-H2O at 68C. At temperatures 68C the free energy change reverses and thaumasite is predicted to decompose to the phase assemblage of anhydrite, C-S-H and calcite. The maximum stability temperature of thaumasite, 685C, is in good agreement with the experimentally-derived thermal stability limit by Giampaolo [76].

The AFt phase in Portland cement


Thaumasite stable Th. unstable 120
1) CaO+SiO2 +CaSO 4 .2H 2 O+CaCO3 +13H2 O --> C3 SscH15

100

(thaumasite)

110 - G0r [kJ/mol] 100 90 80 70 0 10 20 30 40 50 60 70 Te mpe rature [C] 80 90 100


2) CaO+SiO 2 +CaSO4 .2H 2 O+CaCO 3 --> CaO.SiO 2 .1.49H2 O+ CaSO 4 +CaCO 3 +0.51H2 O

3) CaO+SiO2 +CaSO 4 .2H2 O+CaCO3 +1.49H2 O --> CaO.SiO2 .1.49H2 O+ CaSO 4 .2H 2 O+CaCO 3

Fig. 6.16: Free energy-plot of the relative thermodynamic stability of thaumasite in the system CaO-SiO2CaCO3-H2O

Additionally Fig. 6.16 shows the free energy plot of the formation of the phase assemblage gypsum, C-S-H and calcite (reaction 3)). But at temperatures above ~ 50C, gypsum is thermodynamically metastable with respect to anhydrite and accordingly, gypsum is not predicted to be a stable decomposition product of thaumasite at elevated temperatures 68C.

6.3.4 Solid solution formation between ettringite and thaumasite


Until recently it was not possible to model this solid solution formation owing to i) a lack of a consistent temperature-dependent thermodynamic dataset for the thaumasite end member and ii) lack of solubility data for the solid solutions. However since Macphee and Barnett [127] published a solubility dataset for the members of the solid solution series at 5C, 15C and 30C, and since datasets for the thaumasite and ettringite end members were derived in this study, it is now possible to model the solid solution behaviour of thaumasite and ettringite. The calculations are based on the theory for non-ideal model binary solid solutions described in chapter 4.3.4. According to Macphee and Barnett [127] the dissolution reaction of the thaumasiteettringite solid solution series can be described, assuming a doubled molar unit of thaumasite (Ca6Si2(OH)12(SO4)2(CO3)224H2O), according to Eq. 6.11:
Ca 6 Al2 xSi 2 2 x (SO4 ) 2 + x (CO3 ) 2 2 x (OH)12 (24 + 2x )H 2 O 6Ca 2 + + 2xAlO2 + (2 2x )HSiO3 + (2 2x )CO3 + (2 + x)SO4 + (2 + 2x )OH + (28 + 2x )H 2 O
2 2

(6.11)

Macphee and Barnett [127] report the degree of aluminium substitution in thaumasite is very small. However, depending on temperature, up to ~50 mol% of the aluminium of the ettringite end member might be replaced by silicon (see Fig. 6.17). To enable thermodynamic modelling the limits of the miscibility gap need to be fixed; as suggested by Macphee and Barnett [127] these were placed at 0.025 x 0.5 in Eq. 6.11.

The AFt phase in Portland cement

101

miscibility gap applied in the calculations (1 nSioct 1.95)

30 Temperature [C] 25 20 15 10 5 0 0
SO4 -AFt C6 As 3 H32

1 phase
(SO4 -AFt - thaumasite solid solution)

thaumasite-ty pe p hase

immiscible region with 2 phases


(lim. SO 4-AFt-thaumasite-ss + thaumasite-typ e ss)

0.25

0.5

0.75

1 nSi oct

1.25

1.5

1.75

Thaumasite 2(C3 SscH15 )

Fig. 6.17: Temperature dependence of the phase relations between thaumasite and ettringite, SO4-AFt (according to Macphee and Barnett [127])

In the formal thermodynamic sense the thaumasite-ettringite solid solution series is not binary because a coupled substitution of silica and carbonate has to be considered in the original AFt structure. This becomes apparent by formulating a total solubility product, , of the solid solution series according to Lippmann [121] by adding the solubility product of ettringite (Eq. 6.12) and the doubled solubility product of thaumasite (Eq. 6.9) according to Eq. 6.13:
[Ca 2+ ] 6 [AlO2 ] 2 [SO 4 ]3 [OH ] 4 [H 2 O]30
2

(6.12)

[Ca ] [SO 4

2+ 6

2 2

X 44444 Y 444 644444 4 7 4 8 644 4 7 8 2 2 2 2 2 2 2 ] [OH ] [H 2 O] [AlO2 ] [SO 4 ][OH ] [H 2 O] + [HSiO3 ] [CO3 ] (6.13)
2 28

where [ ] denotes aqueous species activities Thus one limitation of the proposed binary model is, as shown by the two terms X and Y in parentheses (Eq. 6.13), that aluminium, sulfate and water have to be replaced simultaneously by silica and carbonate in the original ettringite structure and vice versa in the thaumasite structure. Thus for charge balance reasons a replacement of 1 mol aluminium requires the simultaneous substitution of 0.5 mol sulfate, 1 mol hydroxide and 1 mol water in the ettringite structure while incorporation of 1 mol silica requires a simultaneous substitution of 1 mol carbonate. It is questionable if in reality the phase boundaries of this simultaneous ion-substitution are rigidly fixed, as assumed in the model. To overcome this problem a ternary non-ideal solid solution model would have to be developed based on thaumasite, carbonate-AFt and sulfate-AFt. But due to the high complexity and unknown interactions between thaumasite and carbonate-AFt it is not been practicable to develop such a model for this Thesis; additional experimental would help to decide what priority should be attached to a higher-order solid solution model for AFt phases. The solid solution behaviour between thaumasite and ettringite has been modelled by using the known miscibility gap boundaries and the binary non-ideal solid solution model described above. Due to the assumed simultaneous multiple substitution of aluminium, sulfate, hydroxide and water or silica, carbonate and hydroxide (Eq. 6.13) the construction of a Lippmann phase diagram [121],

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102

which is restricted to a binary system with single ion substitution, seems not to be appropriate, although theoretically possible. The software MBSSAS [81] and the thermodynamic data of thaumasite (Table 6.1) and ettringite (Table 4.1) were used to derive the necessary Guggenheim parameters by applying the miscibility gap fractions (0.025 x 0.5; Eq. 6.11): the estimated parameters are a0 = -0.05 and a1 = 2.74 for these boundaries. By applying the above Guggenheim parameters, the energy of mixing at a given composition can be calculated according to Eqns. 4.13 - 4.20 (chapter 4.3.4). From the known energy of mixing, the related theoretical solubility product of the solid solution at a given composition can be computed by transforming Eq. 4.14. To enable a comparison between the calculated thermodynamic properties of the solid solution series to the experimentally-observed data given by Macphee and Barnett [127] a theoretical solubility product 3 of the solid solutions at stoichiometric saturation can be calculated with the solubility data given in [127] and GEMS-PSI. The calculation assumes a solid composition as given by Eq. 6.11 and is done based on the law of mass action of Eq. 6.11 according to Eq. 6.14; [ ] denote activities):
K ss = [Ca 2+ ]6 [AlO2 ] 2 x [HSiO3 ] 2 2 x [SO 4 ] 2+ x [CO3 ] 2 2 x [OH ] 2+ 2 x [H 2 O] 28+ 2 x
miscibility gap (0.5 Si/(Si+Al) 0.975)
2 2

(6.14)

theor. solubility product log K

-42.00 -44.00 -46.00 -48.00 -50.00 -52.00 -54.00 0


S O 4-AFt C 6As 3H32

ss

experim ental data Macphee and Barnett 2004

5C 15C 30C

0.2

0.4

0.6

0.8

1
Thaumasite 2(C 3S scH15)

molar bulk Si/(Si+Al) ratio of solid

Fig. 6.18: Comparison of theoretically calculated solubility products (solid lines denote single solid phase regions and dashed lines two solid phase regions), using the Guggenheim parameters a0 = -0.05 and a1 = 2.74) and experimentally-derived solubility products (calculated from solubility data by Macphee and Barnett [127]) for compositions of the thaumasite-ettringite solid solution series).

As the notation solubility product refers to a pure one-component phase the term theoretical solubility product is introduced. In agreement with Glynn [80] the theoretical solubility product used here refers to a solid composition which remains invariant owing to kinetic and compositional restrictions.

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Provided sufficient experimental data are available, the procedure described above enables a fit to the empirical Guggenheim parameters a0 and a1 without using a Lippmann diagram as described in [121]. However the experimentally-derived theoretical solubility products from data by Macphee and Barnett [127], Fig. 6.18, exhibit considerable scatter and only a small number of data are available, which makes it impossible to derive the parameters without additional information about the solid composition. But the experimental data shown in Fig. 6.18 agree in principle with the calculated data using the non-ideal solid solution model. It is noteworthy that despite two different solubility datasets for the end members and the solid solutions, a good agreement between predicted and observed data at three different temperatures was achieved. Only two data, for the ettringite end member and the data point at Si/(Si+Al)=0.8, both at 30C, differ significantly from the calculated values. All other values are within analytical error of less than one order of magnitude ( 0.9 log_k units). This i) shows a good consistency between both datasets and ii) underlines the accuracy of the temperature-dependent estimation of standard thermodynamic data of the end members. With the assumed model it is now possible to recalculate the solubility data of the solid solutions. An example is shown in Fig. 6.19 for 15C; although considerable dispersion of experimental points occur, calculated and experimental solubility agree in principle and show the same tendencies: carbonate and silicon exhibit the lowest concentrations followed by increasing amounts of aluminium, sulfate and calcium. In contrast to the SO4-CO3-AFt solid solution series (see Fig. 6.5), no significant changes of the aqueous calcium, sulfate and aluminium concentrations were predicted with changing composition. However the experimental solubility data show that the calcium concentrations decrease whereas silicon tends to increase with increasing silica and carbonate substitution as the thaumasite end member is approached. This is contradictory to the calculations which predicts the concentrations of all species to remain constant at compositions within the miscibility gap, 0.5 Si/(Si+Al) 0.975.
C6SA1-xs3-xc2xH32-2x C6A0.5Ss2.5cH31 + (0.975 x=Si/(Si+Al)1) C6S2.975A0.025s2.5cH3
(0.5 x=Si/(Si+Al)0.975)

C6SA1-xs3-xc2xH32-2x C6A1-xS2xs3-xc2xH32-2x
(0 x=Si/(Si+Al)0.5)

(0.975 x=Si/(Si+Al)1)

C6A1-xS2xs3-xc2xH32-2x

2 concentration [mmol/l] 1.6 1.2 0.8 0.4 0

(0 x=Si/(Si+Al)0.5)

C6A0.5Ss2.5cH31 + C6S2.975A0.025s2.5cH3
(0.5 x=Si/(Si+Al)0.975)

1 concentration [mmol/l]

calcium

0.1 silicon 0.01 carbonate 0.001

sulfate

aluminium 0.2 0.4 0.6 0.8 1 Thaumasite calc. molar Si/(Si+Al)-ratio 2(C 3S scH15)

0 S O 4-AFt C 6As 3H32

0 0.2 0.4 0.6 0.8 1 S O 4-AFt calc. molar Si/(Si+Al)-ratio Thaumasite 2(C 3S scH15) C 6As 3H32

Fig. 6.19: Comparison of calculated (lines) and experimental (single markers, taken from Macphee and Barnett [127]) solubility data for the ettringite-thaumasite solid solution series at 15C (Note that the calculation is restricted to ettringite-thaumasite solid solutions in equilibrium with small amounts of calcite, except for the SO4-AFt end member)

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While reasons for this disagreement are not clear, the Rietveld analysis of the preparations by Macphee and Barnett [17][127] showed increasing amounts of amorphous phase present towards the thaumasite-end of the solid solution series. The preparation may contain impurities and C-S-H is probably also present. The Ca/Si ratio of the C-S-H is likely to decrease with increasing silica substitution, which is consistent with decreasing calcium and increasing silicon concentrations, as experimentally observed (see Fig. 6.19).

6.4. Formation of thaumasite and ettringite solid solutions in hydrated cements


Damidot et al. [49] have shown that the formation of tricarboaluminate is not likely in cement paste due to the greater stability of monocarboaluminate. However the thermodynamic data used by Damidot et al. for CO3-AFt have been significantly revised and two non-ideal solid solutions i) between SO4-AFt and CO3-AFt and ii) between SO4-AFt and thaumasite were included in this study. Thus previous investigations and calculations raise the following question:
Is extensive carbonate and silica substitution in AFt likely to occur in commercial cement paste?

With the estimated thermodynamic properties of the ettringite-thaumasite and SO4-CO3-AFt solid solutions it is now possible to calculate the relevant hydrate phase assemblages including the extent of solid solution formation. Calculations were done by using GEMS-PSI (see chapter 4.3.1). The necessary thermodynamic data of relevant cement hydrates are given in Table 4.1 and Table 6.1. For practical reasons, the calculations were restricted to calcite saturated systems. This restriction is useful because either i) most cements are saturated in calcite by addition of calcite in the course of manufacture or ii), if not saturated during manufacture, they quickly become calcite saturated in the course of service. A second constraint is the suppression of siliceous hydrogarnet in the calculations: i) there are still uncertainties about the thermodynamic data and ii) according to data derived in this study, most of the AFm phases are metastable with respect to siliceous hydrogarnet in silica-containing systems. AFm phases, e.g. carboaluminates and monosulfoaluminate are commonly observed in hydrated cements to the exclusion or virtual exclusion of siliceous hydrogarnet. It seems therefore justified to suppress the formation of siliceous hydrogarnet as a first approximation to develop a consistent picture.

6.4.1 Carbonate substitution in SO4-AFt at 25C


As indicated in chapter 6.2.2, substitution of carbonate in AFt might lead to a stabilisation of AFt solid solutions. An experiment was done to test this hypothesis: C3A was mixed with Na2CO3 and CaSO4 (molar ratios C3A:Na2CO3:CaSO4 = 1 : 1.2 : 1.8) and excess portlandite to obtain a SO4CO3-AFt solid solution with a SO4/(SO4+CO3) ratio of 0.6. Na2CO3 was used to achieve high carbonate activities during the initial stages of reaction. In contrast to the synthesis procedure of CO3-AFt (chapter 4.1.3) deionised water (w/s ~ 30) was used instead of a sucrose solution to simulate similar conditions as encountered in cementitious systems. The mixture was reacted for 4 weeks in HDPE bottles. The solids were filtered and dried over saturated CaCl2-solution at ~37% r.h. and subsequently analysed by XRD using a PANALYTICAL XPERT PRO diffractometer; see chapter 3.2. As shown in Fig. 6.20 a phase mixture consisting of AFt with reflections close to SO4-AFt, monocarboaluminate, calcite and portlandite has formed instead of a single SO4-CO3-AFt solid solution. The formation of monocarboaluminate and calcite suggest that extensive carbonate substitution is unlikely in SO4-AFt in hydrated Portland cements at 25C.

The AFt phase in Portland cement


3500 3000 Intensity [counts] 2500 2000 1500 1000
AFt AFt AFt AFt P AFt AFt Mc AFt AFt AFt AFt Cc

105

AFt

Mc

AFt - SO 4-AFT M c - monocarboaluminate Cc - calcite P - portlandite

500 0 5 10 15 20 [2 Cuk ]

25

30

Fig. 6.20: XRD-pattern of a mixture of initially C3A, CaSO4, Na2CO3 (molar ratio 1 : 1.8 : 1.2) and excess Ca(OH)2 reacted 4 weeks in deionised water (w/s~30) at 25C

Subsequently the maximum possible carbonate substitution in SO4-AFt under conditions likely to occur in hydrated cement paste was calculated using GEMS-PSI. A theoretical composition of 1 mol Ca6Al2(SO4)x(CO3)3-xOH1226H2O (with 0 x 3) was equilibrated with 1.5 mol portlandite and 1kg H2O (pH buffered by portlandite to 12.48). The calculated mass balance changes are shown in Fig. 6.21. A maximum of 9 mol% substitution of sulfate by carbonate will occur under conditions, such that pH is buffered by portlandite and the carbonate activity is buffered by the coexistence of calcite and monocarboaluminate. The carbonate activity of the buffer pair is thus insufficient to stabilise carbonate-AFt and/or SO4-CO3-AFt solid solutions with a SO4/(SO4+CO3) ratio ~0.1, the composition of which is replaced by a mixture of phases: calcite, portlandite and monocarboaluminate. The carbonate solubility of carbonate-AFt is significantly higher than that of monocarboaluminate and calcite at the same pH and temperature; the thermodynamic calculations disclose that the carbonate activity generated by calcite and monocarboaluminate at the relevant pH, ~12.5, is insufficient to stabilise carbonate-AFt. Therefore the ettringite phase appearing at 25C in systems whose pH is buffered by portlandite, and where the maximum carbonate activity is conditioned by the presence of a physical excess of calcite and monocarboaluminate, is predicted to lie close to sulfate ettringite. Nevertheless, since some carbonate can substitute into ettringite, the maximum amount of ettringite is not limited by sulfate content.
2.5 AFt (ss) (~9 % CO 3 )+ calcite + monocarbonate+CH 2 amount of solids [mol] calcite 1.5 monocarboaluminate portlandite SO 4-AFt ss (~9% CO 3 )
22-

AFt (ss) + CH

0.5

0 0 0.1 CO 3-AFt 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 SO 4/(SO 4+CO 3)-ratio 1 SO 4-AFt

Fig. 6.21: Calculated stable assemblages in the SO4-CO3-AFt system buffered by excess portlandite at 25C

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6.4.2 Phase assemblages including thaumasite and related solid solutions


An increasing number of cases of the formation of thaumasite in concrete have been reported since the 1990s. Growing concerns about the stability of typical cement phase assemblages with respect to thaumasite have led to increased research activities in the field of thaumasite formation. Several publications [28][44][126][127][185] note the importance of the formation of thaumasite-ettringite solid solutions in the course of sulfate attack. Thus this study concentrates mainly on phase assemblages occurring in Portland and blended cements undergoing sulfate attack including the formation of thaumasite-ettringite solid solutions. To avoid duplication the reader is referred to Damidot et al. [44] who calculated stable phase assemblages including ettringite and thaumasite in equilibrium with an aqueous phase in the system CaO-Al2O3-SiO2-CaCO3-CaSO4-H2O at 25C. Possible pathways of the formation of thaumasite and ettringite-thaumasite solid solutions are discussed subsequently. To enable a graphical representation only phase assemblages relevant to Portland and blended cements were considered, which include at least one of the following silica-containing constituents: C-S-H, SiO2 (amorphous) and/or thaumasite. The calculations were restricted to calcite saturated systems as calcite is generally encountered in field studies and, in agreement with the restrictions in EN 197, many European Portland cements contain up to 5% limestone - itself mainly calcite. As correctly stated by Damidot et al. [44] a graphical representation of the system CaO-Al2O3SiO2-CaCO3-CaSO4-H2O is difficult due to its high dimensionality. However by applying the above-mentioned restrictions it is possible to construct a 3D phase diagram. As shown in Fig. 6.22, the most useful graphical representation of the system is achieved using the molalities of sulfate, hydroxide and aluminate as variables. In general hydroxide is a dependent variable in alkali-free systems (the role of Na, K is discussed later) and the solubility of the cement solids is allowed to control the hydroxide activity. Fig. 6.22 can be interpreted as follows. All the labelled assemblages contain calcite (solid) and an aqueous phase in addition to those shown on the figure. Considerable supplementary information is presented in Table 6.2. Some of the solids, notably C-S-H, ettringite and thaumasite have variable compositions and Table 6.2 also gives key data on solid solution compositions. The phase relations are sensitive to temperature. Thus a second diagram constructed for 5C is shown in Fig. 6.23. Fig. 6.22 shows the stability fields of relevant phase assemblages at 25C. The general sequence of phase formation does not differ significantly from that shown in [44] except that i) the formation of solid solutions between ettringite and thaumasite and ettringite and tricarboaluminate was taken into account and ii) that at higher silica activities, strtlingite will have a stability field; phase assemblages including siliceous hydrogarnet were not taken into account for the reasons mentioned above. C-S-H, although strictly not thermodynamically stable, has nevertheless been admitted into the calculation because of its well-known persistence in cement pastes. This does not present any difficulties with respect to calculations. Fig. 6.22 does not however enable calculation of the amount of phases present nor does the physical size of phase fields necessary represent their abundance or importance to the constitution of cement pastes.

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107

Fig. 6.22: 3D-representation of part of the system CaO-Al2O3-SiO2-CaCO3-CaSO4-H2O at 25C and 1bar total pressure (solubility surfaces representative for solids in equilibrium with excess calcite; see Table 6.2 for additional carbonate and silicon concentrations at relevant invariant points)

The results of calculation indicate two invariant points, one relevant to the phase constitution of ordinary Portland cement and the other to blended cements, containing sufficient slag or fly ash to react with portlandite; these are designated points I (with Ca(OH)2) and K (without Ca(OH)2) respectively. Because of their importance to the mineralogy of cement paste, the diagram is oriented so as to give prominence to these points. Table 6.2 shows the composition of the aqueous phase at these (and other) points from which it will be noted that the calcium solubility at point K is about an order of magnitude less, and the pH decreased by about 0.5 units, with respect to point I. Solids at both points I and K coexist with an AFt phase and in both cases, the phase is ettringitelike. However the calculations predict the formation of a SO4-CO3-AFt solid solution (~9 mol% CO3 substitution; AFt: Ca6Al2(SO4)2.73(CO3)0.27(OH)1226H2O) but no significant silica substitution in AFt in point I, which agrees with the predicted carbonate substitution for the silica-free system (Fig. 6.21). However a simultaneous silica and carbonate substitution, i.e., the formation of a thaumasite-ettringite solid solution with a substitution of 20% thaumasite, is calculated for point K, Fig. 6.22. The AFt phase at point K has a composition corresponding to Ca6Al1.6Si0.4(SO4)2.8 (CO3)0.4(OH)1225.6H2O. The increasing silica and carbonate substitution is ascribed to the increase in silica and carbonate activities between the two points. The increase in silica activity also affects the constitution of C-S-H: note that the Ca/Si molar ratio of C-S-H, ~1.6 at point I, decreases to ~1.25 at point K. Thus the calculations indicate that silica and carbonate substitution in AFt is more likely to occur i) in silica-rich blended cements, assuming an excess of calcite is present, or ii) in portlandite-depleted cements which have undergone leaching.

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Table 6.2: Composition of aqueous phase of selected stable phase assemblages and invariant points in the system CaO-Al2O3-SiO2-CaSO4-CaCO3-H2O at 1bar and 5 and 25C (sorted in order of decreasing OH molalities, excess calcite present)
Pt. Temp [C] A B I H G T S J C K L R D M Q E W N F X U O V P 25 5 25 5 25 5 25 5 25 5 25 5 25 5 5 25 5 25 5 25 5 25 5 25 5 25 5 25 5 25 5 25 5 25 5 25 5 25 5 25 5 25 5 25 25 pH [-] 12.48 13.27 12.48 13.27 12.48 13.27 12.48 13.27 12.47 13.27 12.43 13.24 12.43 13.24 12.95 12.06 12.68 12.06 12.69 11.80 12.66 11.51 12.38 11.42 12.21 11.42 12.21 10.23 10.61 9.84 10.33 9.84 10.33 9.79 10.33 9.02 9.47 9.02 9.47 8.56 8.46 8.56 8.46 8.46 8.46 34.44 39.05 34.44 39.05 34.42 39.05 34.38 39.05 34.38 39.04 31.62 36.69 31.62 36.69 18.45 12.86 9.60 12.85 9.85 6.96 8.21 3.50 4.32 2.88 3.10 2.75 3.20 0.190 0.077 0.073 0.042 0.073 0.042 0.065 0.041 0.011 0.006 0.011 0.006 0.004 6E-04 0.004 6E-04 0.003 0.003 19.37 21.17 19.37 21.17 19.39 21.17 19.55 21.18 19.53 21.18 30.69 30.66 30.69 30.66 9.75 6.99 5.28 7.01 5.28 3.89 4.88 2.28 2.61 1.71 1.86 1.84 1.87 15.74 14.19 1.21 0.965 1.2 0.96 1.68 1 0.32 0.26 0.32 0.26 15.73 14.27 15.73 14.27 15.72 15.72 OH Ca I AlI 0 0 0.0074 0.0015 0.0074 0.0015 2E-04 3E-04 0 0 0 0 3E-07 8E-09 0.013 0.130 0.085 0.130 0.085 0.140 0.110 0.268 0.205 0.220 0.140 0.210 0.140 0.015 0.004 0.048 0.018 0 0 0.043 0.017 0.007 0.002 0 0 0 0 0.003 3E-04 0 0.002 CO3 I 0.0065 0.0055 0.0065 0.0055 0.0065 0.0055 0.0065 0.0055 0.0065 0.0055 0.0065 0.0055 0.0065 0.0055 0.0060 0.0070 0.0065 0.0070 0.0065 0.008 0.007 0.009 0.008 0.009 0.009 0.009 0.009 0.008 0.007 0.023 0.021 0.023 0.021 0.021 0.021 0.280 0.250 0.280 0.250 0.055 0.13 0.055 0.133 0.068 0.068 SO4 I 0 0 0 0 0.024 0.004 0.18 0.01 0.18 0.01 12.47 10.56 12.47 10.56 0.005 0 0 0.028 0.004 0.084 0.006 0.270 0.019 0 0 0.160 0.008 15.62 14.18 0 0 0 0 0.580 0.054 0 0 0 0 15.62 14.18 15.62 14.18 15.63 15.63 Si I 0.0287 0.0392 0.0287 0.0392 0.0287 0.0392 0.0287 0.0392 0.0287 0.0392 4E-04 4E-05 4E-04 4E-05 0.110 0.098 0.166 0.098 0.166 0.145 0.113 0.095 0.054 0.240 0.200 0.240 0.196 0.004 3E-04 4.22 3.06 4.19 3.04 4.00 3.03 2.26 1.47 2.26 1.47 2.07 1.26 2.08 1.42 2.04 2.04 Ca/SiII [-] 1.57 1.59 1.57 1.59 1.57 1.59 1.57 1.59 1.57 1.59 --------1.37 1.25 1.10 1.25 1.10 1.00 ------0.86 0.85 0.86 0.86 ----0.83 0.83 0.83 0.83 0.83 0.83 --------------------Cc, CH, C-S-H Cc, CH, C-S-H Cc, CH, Mc, C-S-H Cc, CH, Mc, C-S-H Cc, CH, Mc, AFt(ss 9%CO3), C-S-H Cc, CH, Mc, AFt(ss33%CO3), C-S-H Cc, CH, AFt(ss), Th, C-S-H Cc, CH, AFt(ss), Th, C-S-H Cc, CH, Th, C-S-H Cc, CH, Th, C-S-H Cc, CH, Th., Gp Cc, CH, Th., Gp Cc, CH, AFt(ss), Th, Gp Cc, CH, AFt(ss), Th, Gp Cc, Mc, AFt(ss), Th, C-S-H Cc, Mc, Str, C-S-H Cc, Mc, Str, C-S-H Cc, Mc, Str, AFt (ss 20%Th), C-S-H Cc, Mc, Str, Th, C-S-H CC, Str, AFt(ss), Th, C-S-H Cc, Mc, Str, AFt(ss), Th Cc, Str, AFt(ss), Th, AH3 Cc, Str, AFt(ss), Th, AH3 Cc, Str, AH3, C-S-H Cc, Str, AH3, C-S-H Cc, Str, Th, AH3, C-S-H Cc, Str, Th, AH3, C-S-H Cc, AFT(ss), Th, AH3, Gp Cc, AFT(ss), Th, AH3, Gp Cc, AH3, C-S-H, SiO2(am) Cc, AH3, C-S-H, SiO2(am) Cc, C-S-H, SiO2(am) Cc, C-S-H, SiO2(am) Cc, Th, AH3, C-S-H, SiO2(am) Cc, Th, AH3, C-S-H, SiO2(am) Cc, AH3, SiO2(am) Cc, AH3, SiO2(am) Cc, SiO2(am) Cc, SiO2(am) Cc, Th, SiO2(am), Gp Cc, Th, SiO2(am), Gp Cc, Th, AH3, SiO2(am), Gp Cc, Th, AH3, SiO2(am), Gp Cc, SiO2(am), Gp Solids [mmol/kg]

Cc, AH3, SiO2(am), Gp I all molalities given as total concentrations independently from the individual speciation; II Ca/Si of C-S-H if present abbreviations: Cc - Calcite, CH - Portlandite, Mc - Monocarboaluminate, Str - Strtlingite, AFt(ss 8%Th) - ettringite-thaumasite solid solution with a calculated substitution of 8% Thaumasite, AFt(ss) - limiting ettringite-thaumasite solid solution with a calculated substitution of 50% Thaumasite (if Thaumasite is present), Th - Thaumasite (minor Al substitution possible), AH3 - gibbsite, Gp - Gypsum, SiO2(am) amorphous Silica, C-S-H - Calcium-Silicate-Hydrate

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109

In the current model, C-S-H is treated as an ideal solid solution between tobermorite and jennitetype end members (see chapter 4.4.4). The incorporation of other species into C-S-H is not automatically calculated in the present state of the database. Richardson and Groves [160] describe aluminium for silica substitution in the C-S-H structure. The amount of substituted aluminium increases with decreasing Ca/Si ratios and can be estimated using the relations described in [160]. To assess the chemical constitution of C-S-H in cement undergoing sulfate attack it is important to consider the sorption of sulfate to C-S-H; data for temperature-dependent values for the adsorption of sulfate to C-S-H can be found in [14][15][54][160]. Furthermore Hong and Glasser [92] provide data for the sorption of alkalis to C-S-H. Thus the chemical constitution of C-S-H can in principle be corrected with these data. As demonstrated in Fig. 6.22, AFt solid solutions are generally predicted to be stable at lower sulfate concentrations than are required for thaumasite precipitation. However it is interesting to note that this trend is reversed if the silica activity is further increased, e.g. in systems with C-S-H with a Ca/Si ratio <1 (between points L and N): thaumasite is predicted to form at lower sulfate concentrations than are needed to form ettringite solid solutions, which could markedly influence the pathway of thaumasite formation in relevant compositions. But in this context it has to be noted that, compared to Portland and blended Portland cements with lower silica activity, the threshold sulfate concentration to form thaumasite and/or AFt-thaumasite solid solutions (Points L and M) is up to 10 times higher. As shown in Fig. 6.22 and Table 6.2, the AFm chemistry is significantly affected by changing hydroxide, silica and carbonate activities. Whereas at portlandite and calcite saturated conditions monocarboaluminate dominates, strtlingite will form instead at increased silica activities. At 25C monocarboaluminate is predicted to coexist with C-S-H at Ca/Si ratios 1.25. Based on the currently available dataset, strtlingite is expected to coexist with C-S-H at ~0.9 Ca/Si 1.25. AFm phases become unstable if the sulfate activity is increased. As shown in Fig. 6.22 and in agreement with calculations by Damidot [43], strtlingite is predicted to persist to higher sulfate molalities than monocarboaluminate. This might be one possible explanation of the better performance of slag- or metakaolin-rich, strtlingite-containing cements to sulfate exposure. Thus in the region L-M-R of Fig. 6.22 it is interesting to note that strtlingite is predicted to coexist stably with thaumasite and calcite, whereas monocarboaluminate is incompatible with thaumasite at 25C. A further increase of the sulfate activity leads to an enrichment of silicate and carbonate in the AFt phase before the phase boundary (line H-L) is crossed and thaumasite coexists with the limiting AFt solid solution with 50 mol% thaumasite substitution (Ca6(Al,Si)(SO4)2.5(CO3)(OH)1225H2O). As demonstrated in Fig. 6.22 thaumasite is more stable than AFt solid solutions at low hydroxide activities (and increased carbonate and silica activities, see Table 6.2). For example at invariant point O the coexistence of thaumasite with gibbsite, amorphous silica, gypsum and calcite at pH ~8.56 is predicted, which indicates a high stability of thaumasite with respect to carbonation processes, whereas the AFt solid solution is only computed to be stable at pH 10.23 (point Q). The practical implications of Fig. 6.22 are that, at calcite saturation and even in the presence of excess calcite, thaumasite will not appear at equilibrium in either plain or blended Portland cements at 25C. As shown in Fig. 6.22 and Table 6.2, only minor carbonate substitution occurs in the AFt phase in hydrated Portland cements or limestone blended cements saturated with respect to calcite and portlandite. However in the presence of excess calcite the amount of AFt is less limited in blended cements by the available sulfate content, as increasing substitution by a thaumasite

The AFt phase in Portland cement

110

component, including silica and carbonate, becomes energetically possible. Moreover as will be explained in a subsequent section, temperatures <25C enhance the stability of substitutions in ettringite. Furthermore in most cases where C-S-H has a Ca/Si ratio 1, the silicate- and carbonaterich AFt solid solutions are precursors of the precipitation of thaumasite at 25C in cements undergoing sulfate attack. Fig. 6.23 shows the coexisting phase assemblages and invariant points of part of the system CaOAl2O3-SiO2-CaCO3-CaSO4-H2O at 5C. In comparison to Fig. 6.22 it is obvious that the stability fields of thaumasite shift significantly to lower sulfate concentrations. A comparison of the relevant invariant points is given in Table 6.2. Furthermore, the stability field of the ettringite-type AFt solid solutions coexisting with C-S-H in region H-I-J decreases due to the higher stability of thaumasite. Not surprisingly, therefore, the conditions required for thaumasite formation at 5C are attained with less alteration of the cement composition than at 25C.

Fig. 6.23: 3D-representation of part of the system CaO-Al2O3-SiO2-CaCO3-CaSO4-H2O at 5C and 1bar total pressure (solubility surfaces representative for solids in equilibrium with excess calcite; see Table 6.2 for additional carbonate and silicon concentrations at relevant invariant points)

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Carbonate substitution in the ettringite-type AFt phase is significantly increased at lower temperatures. For example the predicted carbonate substitution for point I, most relevant to ordinary Portland cements, increased from ~9 mol% at 25C (AFt composition: Ca6Al2(SO4)2.73(CO3)0.27(OH)1226H2O) to ~33 mol% at 5C (AFt composition: Ca6Al2(SO4)2(CO3) (OH)1226H2O). Another interesting feature of Fig. 6.23 is the predicted coexistence of monocarboaluminate with thaumasite in the region J-K-L which was an incompatible phase assemblage at 25C. In this context small errors in the thermodynamic data become important. The free energy difference between the two competing phase assemblages i) monocarboaluminate+thaumasite or ii) ettringite+monocarboaluminate is small (see Fig. B.3, appendix B). Minor changes in numerical values of the thermodynamic parameters will influence the predicted phase assemblages significantly. However it is difficult to experimentally prove the calculations. Mixtures of monocarboaluminate+thaumasite or ettringite+monocarboaluminate might not react, due to the small thermodynamic driving force of reaction as indicated in Fig. B.3 in the relevant temperature range (~7.57.5C). The calculations disclose no significant silica substitution in AFt at invariant points I at either temperature, 5 and 25C. This result should be regarded as trend rather than as fixed overall valid statement. For example a change of the fG0 of thaumasite of ~-1300 J/mol at 25C, involving a stabilisation of thaumasite, would change the result and predict a thaumasite-ettringite solid solution instead of SO4-CO3-AFt. This would imply simultaneous carbonate and silica substitution could occur at point I at both 5 and 25C. Another possibility, the formation of ternary solid solid solutions involving ettringite, thaumasite and tricarboaluminate, was not considered in the calculations but is of potential importance.

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6.5. Discussion 6.5.1 Interpretation of phase diagrams


In the interpretation of Fig. 6.22 and Fig. 6.23 phase boundaries have their usual significance: to cross a phase boundary, solids have to reconstitute and, to change the phase assemblage, considerable mass transport/ exchange must occur partially to reconstitute the solids: not only will the nature of the phases change, some appearing and others disappearing, but even those phases which persist may change in amount. Thus the relative size of the phase fields shown in Fig. 6.22 and Fig. 6.23 is not relevant to the importance of the assemblage. Instead, its importance depends on how much mass has to be transported to achieve change. This cannot be inferred directly from inspection of the Figures. However consideration of the mass balances with knowledge of the constitution of the phases generally discloses what has to change and how much mass is required to be transferred in order to drive a particular transformation.

6.5.2 Formation of AFt solid solutions


The composition of ettringite has long been known to permit novel substitutions, for example of borate for sulfate, as occurs in charlesite. But under conditions prevailing in normal Portland cements, the composition of the AFt phase has generally been regarded as being close to that of ettringite, Ca6Al2(SO4)3(OH)1226H2O. The present study is not complete with respect to the composition of AFt in cement but it does provide new information on carbonate and sulfate balances as well as on solid solutions between AFt and thaumasite. The composition of AFt at constant temperature is essentially fixed by four variables: the activities of sulfate, hydroxide, carbonate and silicate. However while the actual numerical values of these activities range widely; different types of control affect the parametric values. In the presence of portlandite the pH is essentially controlled by the solubility of portlandite. Thus hydroxide is an abundant aqueous species, which is present in relatively high concentrations. However carbonate concentrations in the aqueous phase are numerically much lower and, if one wants to preserve cement phases such as C-S-H, AFt and portlandite, their stabilities are limited by the solubility of calcite to ~ 0.007 mmol/kg carbonate at 25C because at higher carbonate activities, these phases are susceptible to carbonation. Likewise the sulfate ion concentrations are effectively buffered by the solubility of AFt and are on the order of 0.02 mmol/kg; Table 6.2 shows exact values for the relevant aqueous concentrations at the relevant invariant points. An important additional factor affecting phase composition is temperature. The calculated phase relations are very sensitive to relatively small temperature differences in the range 0- 25C. Thus if Fig. 6.22 and Fig. 6.23, together with Table 6.2, are compared, several trends become evident. First the range of stable ettringite-type AFt solid solutions enlarges rapidly with decreasing temperature with respect to the maximum possible amount of carbonate and silicate substitution. In particular, the stability of carbonate within the AFt structure is greatly enhanced at lower temperatures with the result that extensive solid solution formation towards the carbonate-AFt composition is more likely at low temperatures, e.g. at 5C. This solid solution is not however continuous, but can extend to a maximum of ~60 mol% carbonate end member in SO4-AFt, depending on the boundary conditions. This helps to explain the observation that a large increase in amount of ettringite seems to precede thaumasite formation; it is characteristically a low temperature feature, and carbonate can bulk out and reduce the amount of sulfate required for formation of an ettringitelike AFt phase.

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Table 6.3: Comparison of calculated activities for selected aqueous species relevant to point I, Fig. 6.22, in dependence of the alkali content of the aqueous phase at 25C (see Table 6.2 for aq. composition) activity
pt. solids
AFt(ss, 9%CO3), Mc, calcite, C-S-H, CH AFt(ss, 8%CO3), Mc, calcite, C-S-H, CH pH [OH ]
--

ratio
[SO4 ]
2-

[CO3 ]

2-

[OH]/[SO4]

[CO3]/[SO4]

I (no alkalis) I (500 mmol Na+/kg)

12.48 13.58

2.99E-02 3.60E-01

4.71E-07 6.91E-05

6.69E-06 1.11E-03

4476 323

0.070 0.062

While departures from the ideal ettringite composition were calculated not to exceed 10% at 25C, at 5C the solubilities of these other components in ettringite become too large to be ignored. The composition of AFt can be expressed in terms of four end members, ideal ettringite, the carbonate ettringite described by Carlson [36], hydroxy-substituted ettringite and ideal thaumasite. Note that in the first three cases, the mechanism can formally be defined in terms of simple isomorphous replacement, e.g., of sulfate by hydroxide or carbonate, but the replacement necessary to achieve thaumasite requires multiple substitutions. Although the relevant activities are well defined for the alkali-free system (Table 6.2), commercial cements also contain alkalis -sodium and potassium- which perturb these numerical values and must be taken into account to apply the data to commercial cements. The main part of the alkalis in Portland cement is associated to alkali sulfates. As most of the sulfate is removed in the early stages of hydration, the role of alkalis is, most simply and directly, to elevate pH and thereby increase the hydroxide concentration. Hong and Glasser [92] showed that some alkali is also absorbed into solids. Sulfate remaining in solution plays a secondary role in satisfying the charge balance on alkali. But, at constant temperature, and as the alkali concentration increases, the soluble sulfate concentration also increases. This elevation of sulfate is also accompanied by rising silicate and carbonate concentration although these increases are less marked. But the order of concentration of anions in pore fluid -all potentially available for substitution in AFt- remains [OH]>[SO4]> [SiO4] (or other appropriate silicate anion) > [CO3]. Thus at constant temperature, three factors govern the constitution of the AFt phase: i) the activity fractions of anion species ii) numerical values of the partition coefficient of anions between aqueous and solid for each relevant species and each relevant solid, iii) the possible occurrence of two AFt type phases and iv) the competition of other solids, e.g. AFm, often for the same anions. First, at the self-generated pH imposed by portlandite, the carbonate activity generated by carboaluminates and/or calcite, and the silicate activity generated by high Ca/Si ratio C-S-H, the AFt phase can be expected to have close to the ideal ettringite composition, with not more than about 9 mol% of sulfate anions replaced by carbonate at 25C, point I Fig. 6.22. Thaumasite is not stable under these conditions. Secondly, if alkalis are present such that the pH rises above the portlandite threshold, both aqueous [OH-] and [SO42-] activities in pore fluid increase. This relation is demonstrated in Table 6.3 for point I, Fig. 6.22 at 25C. However, perhaps unexpectedly, the activity ratio [OH]/[SO4] decreases, as shown in Table 6.3, which indicates that despite an increase of the hydroxide activity resulting from alkali addition as (Na,K)OH, not much sulfate will be replaced in the cement solids by OH with increasing alkali content. Thus OH- substitution is expected to be of minor importance in ettringite even in the presence of increasing hydroxide contents. A similar relation can be derived for the expected carbonate substitution. The [CO3]/[SO4]

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activity ratio decreases slightly with increasing alkali content. As a consequence, the maximum carbonate substitution in AFt at I decreases also slightly to 8% (Table 6.3). Finally, increasing the carbonate activity beyond that conditioned by the solubility of calcium carbonate is not practical without at the same time beginning to decompose the normal matrixforming phases, e.g., C-S-H. Thus while carbonate activity affects the formation of thaumasite, not much latitude exists for increasing carbonate activities in relatively unaltered cement, although this restriction is clearly removed during the later stages of alteration, for example after portlandite has been depleted. An important consequence of these considerations is that i) the composition of the AFt phase is likely to undergo reversible changes as functions of temperature and activity of potential anionic substituents, ii) the amount of AFt that can form is not necessarily limited by the sulfate content: other ions may substitute and thereby enhance AFt formation, especially at low temperatures and iii) as a result of the temperature dependence and composition of the constitution of AFt, and of other concomitant phase changes, the specific volume of the solids and the amount of bound water may exhibit significant changes over a narrow range of temperatures, 5C -25C, with marked increases expected to occur at low temperatures.

6.5.3 Pathways of thaumasite formation


Literature studies tend to distinguish between deterioration in cements arising from ettringite formation and those caused by thaumasite. The logic of this distinction needs to be explained. In the classic case, of the ettringite form of sulfate attack, the amount of ettringite is increased either (or both) by a temperature-dependent redistribution of sulfate (internal sulfate attack) and ingress of additional sulfate from the service environment. However the thaumasite form of sulfate attack (TSA) does not depend on sulfate alone: carbonate and silicate are required. As with enhanced ettringite formation, the sources of silica and sulfate could be internal or external, or both. Thus the required mass of species necessary to form thaumasite could arise from i) migration from the service environment of sulfate, carbonate and silicate, ii) leaching, iii) availability of one or more of sulfate, silicate and carbonate from aggregate, from fillers added to cement or from C-S-H, or iv) some combination of the above sources. Thermodynamic calculations do not reveal or distinguish between possible sources of sulfate, carbonate and silicate but they do suggest i) that, owing to the estimated theoretical stability of thaumasite at temperatures up to 40C and possibly as high as 68C, thaumasite formation is not necessarily and uniquely a low-temperature process and ii) that reactions involving the AFt phase are part of a continuum and that division into characteristic types, e.g., TSA, is operationally convenient but not fundamental. Fig. 6.22 and Fig. 6.23 show that, considering plain Portland cement, several pathways are possible for thaumasite formation; there is no single route to form thaumasite. These pathways were outlined in detail by Damidot et al. [44] and, while the present study provides additional fine detail regarding the influence of temperature and solid solution formation, the basics remain unaffected. Thus Fig. 6.22 and Fig. 6.23 do not show all the possible pathways of thaumasite formation because it is constructed for the special condition that calcite saturation is maintained. However from published descriptions of field occurrences of TSA [41][42] it appears that this condition obtains in the majority of cases (in some examples uncertainties remain because the necessary data are not given). So Fig. 6.22 and Fig. 6.23 probably illustrate the most commonly-encountered reaction pathways to thaumasite formation.

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Depending on the composition of the service environment, it would be possible to form thaumasite at both 5C and 25C either in the presence of portlandite and C-S-H (along G-H, Fig. 6.22 and Fig. 6.23) or if leaching and reaction removed free portlandite, by first forming a substituted AFt solid solution together with C-S- H (in region (H-I-K-L Fig. 6.22 or region H-I-J Fig. 6.23) and subsequently, mixtures of thaumasite with AFt. This route seems to be commonly encountered in field studies and has led to the belief that AFt is a necessary precursor to thaumasite. In the sense that AFt is a normal constituent of most cement, including cement not showing signs of alteration, this assertion is true. But as the diagrams show, i) a number of sequences are possible and ii) because of compositional variation in AFt, including partial substitution of sulfate by carbonate and aluminium by silicate, the amount of AFt phase may well increase significantly before thaumasite first appears. The extent of this increase will be more important at low temperatures and underlies the conclusion of several field studies, that often considerable amounts of AFt are reported in these samples. However as shown in Fig. 6.22 and Fig. 6.23 it is possible that zones evolve in the course of reaction in which progressive decalcification due to leaching occurs. These leached zones are likely to be located close to the surface exposed to the aggressive solution. The silica activity is relatively high due to the formation of C-S-H with low Ca/Si ratios 1 as a consequence of leaching. In these zones, thaumasite is predicted to form directly, without AFt, along the connection between points L-M-N at 25C and J-K-M-N at 5C. Thus the case study has shown that several pathways of thaumasite formation exist, rather than a single route, e.g. as suggested by Bensted [22]. It is likely that in most concretes exposed to sulfaterich environments zoned microstructures will evolve and, as a consequence, several pathways to thaumasite formation occur simultaneously as sequence of different local equilibria. The initial formation of AFt solid solutions is an essential precursor to form thaumasite in the calcium-rich core zones whereas in the decalcified near surface zones thaumasite may form directly. In conclusion, the thaumasite problem is undoubtedly complicated. But this is not because of any special properties of thaumasite itself, although its complex chemistry does increase the number of cement components required for its formation. All the evidence is that thaumasite forms normally, in response to the composition of cement and its interaction with its service environment. The physical chemical rules governing the formation of thaumasite are not different than for other cement phases. An ordinary Portland cement cured at ambient temperatures will never form quantities of either, or both, ettringite and thaumasite sufficient to cause subsequent physical expansion and cracking. But thermal cycling and chemical exchanges between cement paste and its service environment can cause problems.

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7. The influence of limestone addition on cement hydration


7.1. Literature review 7.1.1 Limestone addition to Portland cement
Cement manufacturers are under pressure to reduce costs and decrease emissions while at the same time, producing a quality product with high early strength and superior durability. Limestone is much used in this context as a partial replacement for cement and appears to be innocuous at least up to 5% replacement: it is a permitted additive under the EN 197 specification. The role of calcite, as inert filler or as a reactive admixture (or both), has been much studied in the literature. Thus numerous investigations exist, dealing with aspects of limestone addition. Many of the studies use high levels of calcite, such that most of the calcite acts as a filler. Therefore the literature review was limited to publications relevant to this study, using mainly lower additions, 1-10 wt.-%. The review is selective, and concentrates on what, from present knowledge, appear to be the salient publications.

Mineralogical changes
Following the discovery of monocarboaluminate by Bessey [27] and its successful synthesis by Carlson and Berman [36], there is little doubt about the reactivity of calcite in limestone blended Portland cements. However researchers argue about the extent of reaction and its consequences to Portland cement hydration. While Sprung and Siebel [175] concluded that only a small fraction of limestone is reactive, and therefore no effects on cement hydration will be expected, Seligman and Greening [169], Kuzel et al. [113][115][116][117] and others [29][37][166] observed significant changes in the mineralogy of hydrated Portland cements in the presence of carbonate or calcium carbonate, the main mineral component of limestone. Seligman and Greening [169] showed that the addition of 5% calcite to an originally carbonatefree Portland cement (44.5% C3S, 28.0% C2S, 12.2% C3A, 6.8% C4AF and 1.83% SO3, w/c=0.5) led to significant changes of the mineralogy of the hydrated cement paste. After 28d moist curing a monosulfoaluminate solid solution was detected in the carbonate-free control sample; ettringite peaks were absent in the XRD-pattern. However the calcite blended samples showed significant amounts of ettringite as well as monocarboaluminate after the same curing period. Hemicarboaluminate was found as an intermediate compound after 14d of hydration which converted to monocarboaluminate with time. The carbonate-free control sample was reinvestigated after 14 years of hydration. Monosulfoaluminate persisted as the main sulfoaluminate phase, but no formation of ettringite was observed. Kuzel [113] showed the influence of the carbonate content on the hydration products of OPC. Even low carbonate contents in OPC led to changes of the paste mineralogy. In nearly carbonate-free systems (<0.1 wt.-% CO2) the amount of initially formed ettringite diminished and a sulfate-type AFm was observed after 50 h hydration. In contrast, at only slightly higher CO2 contents of ~0.4 wt.-% CO2, more ettringite and less monosulfoaluminate were observed together with hemicarboaluminate. A further enhancement of the carbonate content to ~0.9 wt.-% CO2 led to the formation of mono- and hemicarboaluminate while the amount of initially formed ettringite persisted unchanged. Formation of monosulfoaluminate was not observed. Furthermore, Kuzel referred to the possibility of delayed ettringite formation if carbonate-free cement, previously hydrated for 310 days, was subsequently exposed to atmospheric CO2 in combination with

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sufficient humidity. It was shown that access of CO2 led to a transformation of sulfate-AFm to monocarboaluminate and the sulfate thus released initiated secondary ettringite formation. A shift of the hk0 reflections of ettringite was observed and could be a sign of partial replacement of sulfate anions in the AFt structure, presumably by carbonate. Bonavetti et al. [29] investigated the hydration of OPC blended with 20 wt.-% CaCO3. Ettringite and monocarboaluminate were detected after 3 days of hydration. After 28 days the amount of ettringite diminished and monosulfoaluminate coexisted with monocarboaluminate. In the course of hydration, monosulfoaluminate disappeared and monocarboaluminate and ettringite were found as apparently stable hydration products after 90 days. In agreement with thermodynamic calculations by Damidot et al. [49], hemicarboaluminate was not found in the presence of CaCO3. Sawicz and Heng [166] found that limestone prevents the conversion of AFt (ettringite) into monosulfoaluminate. Monocarboaluminate and hemicarboaluminate are formed instead of monosulfoaluminate. On the other hand, Ramachandran and Zhang [157] concluded, but only from thermal analysis experiments, that the conversion of ettringite to monosulfoaluminate is accelerated by the presence of CaCO3. Thus the literature reveals divergent opinions about the influence of limestone on the hydration of Portland cement.

Physical and mechanical properties


Ingram and Daugherty [94] review the many claims for the physical attributes of limestone. The opinions about possible benefits of the addition of limestone conflict. Studies by Bobrowski et al. (cited in [94]) indicate that the addition of 3-5% limestone does either improve, or has no effect on the engineering properties of limestone blended cement. On the other hand Adams and Race (cited in [94]) found that 2-5% addition of limestone significantly increased the 4d drying shrinkage of mortars. A cement with low C3A content was used in their experiments. Bedard and Bergeron (cited in [94]) found no negative influence of 4.1 and 2.3 % limestone addition to C3A-rich cement. Concretes cured at ambient temperatures had compressive strengths similar to the carbonate-free control sample at 1-56 d. Ingram and Daugherty concluded that the addition of up to 5% limestone has at worst no effect on the engineering properties of the cement, but at best, has a positive influence. Sprung and Siebel [175] investigated the strength development and freeze thaw resistance of different limestone blended cement concretes. They concluded that concretes made from cements blended with up to 20% limestone have similar performance compared to Portland cement-only concrete. Soroka and Setter [174] investigated the effect of different fillers on the compressive strength of blended cements. It was shown that limestone blended cement samples exhibited the largest gain in strength, compared to other pozzolanic fillers, including Rhine trass. A maximum strength increase was found at ~10% limestone substitution of the cement especially in the early age samples. Soroka and Setter argued that the strength increase is mainly due to an acceleration of cement hydration due to the availability of crystallisation nuclei provided by the fillers rather than being caused by a chemically induced strength gain due to the formation of carboaluminates.

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Tsivilis, et al. [186][187][188] published a series of papers to the effects of limestone addition on the engineering properties of Portland cements and concretes. They showed that addition of up to 10% limestone either increased or had no effect on the 1-28d compressive strength of hydrated mortars (w/c=0.5). Concrete investigations showed that up to 20% limestone addition led to a marginal decrease of compressive strength, while 35% limestone substitution caused a significant loss of compressive strength. In another study Tsivilis et al. [187] showed that limestone additions up to 15% did not significantly change the total porosity of concretes. Furthermore they showed a positive influence of increasing C3A contents on the total porosity and permeability of limestone blended cements. Catinaud [37] investigated the role of limestone on the leaching mechanisms of hydrated cement paste and paste containing C3S, C3A and gypsum blended with calcite (w/c=0.5) at 25C. An analysis of the porosity of the initial state of the samples before immersion in water for the leaching experiments showed an increase in porosity with increasing limestone addition (5, 10, 20 wt.-% CaCO3). However samples were vacuum dried for 3h at 105C before the porosity measurement. Initially portlandite, carboaluminate phases and AFt were present in the samples. No analysis was provided after drying at 105C, so the extent of drying damage, if any, is unknown. The literature review has shown that there are divergent opinions about possible benefits of the addition of limestone. Claims of decreased porosity and strength increases could not be proven, although the majority of the literature on limestone addition showed no severe reduction of the physical and mechanical properties if low amounts of limestone were added (<10%). The present study, including AFt- AFm phase relations, concentrates on the impacts of calcite on paste mineralogy. With help of space filling calculations and mineralogical maps in dependence of the composition of reactive cement fractions, a systematic investigation of the role of limestone has been used to provide better understanding of the quantitative aspects of cement hydration in the presence of calcite additions.

7.1.2 Influence of temperature on the mineralogy of hydrated (limestone blended) Portland cement: 25C and above
The literature about temperature-dependent changes on limestone blended cements is limited. Therefore the review was extended and takes Portland cements into account as well as delayed ettringite formation (DEF), a widely studied subject relevant to heat cured cements. Until recently no thermodynamic dataset was available to assess the temperature-dependent stability of carboaluminate phases, i.e. hemi- and monocarboaluminate. Fentiman [62] examined the hydration of carboaluminate cement (limestone blended high alumina cement) at different temperatures. In his work he showed that monocarboaluminate formed in cures at least up to 50C. At temperatures above 55C C3AH6 dominated the XRD-pattern, at least up to 7d hydration. Furthermore he reported an increase of the amounts of monocarboaluminate at the expense of C3AH6 and calcite on curing the carboaluminate cement paste up to 7d hydration at 65C and 70C, which is in dispute with his earlier findings (see [62]). Kuzel and Baier [114] investigated the hydration of calcium aluminate cements in the presence of calcite at different temperatures. They showed that monocarboaluminate is persistent up to 905C; at higher temperatures it converts to C3AH6 and calcite. Kuzel and Baier showed that the addition of -C2S led to an apparent stabilisation of the hydrogrossular phase, C3AS3-xH2x, due to the incorporation of silica in the structure. Monocarboaluminate, C3AS3-xH2x, gibbsite and calcite

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coexisted at least up to 6 months at 60C. However no siliceous hydrogarnet appeared in aluminate cement blended with powdered quartz or silica and cured at 25C or 60C. Sulfate was absent in the studies discussed above. Investigations of the hydration of sulfate resisting Portland cement containing small amounts of calcite at elevated temperatures by Lothenbach et al. [124] have shown that monocarboaluminate tends to convert to monosulfoaluminate at the expense of ettringite at temperatures ~50C. A similar reaction was shown by Ghorab et al. [75]. A mixture of ettringite and monocarboaluminate (mole ratios 1:1 and 10:1) decomposed in boiling water (~100C) to monosulfoaluminate, hydrogarnet and calcite. Provided sufficient sulfate is available (SO3/Al2O3 3), ettringite itself is stable up to ~1155C as experimentally shown by Zhou and Glasser [195] and Hall et al.[87]. This was confirmed in investigations by Shimada and Young [171] who have investigated the stability of ettringite in alkaline solutions at 80C. Ettringite persisted for 12h at 80C although the formation of the Uphase, a sodium substituted AFm phase, was found at initial sodium concentrations 0.25 N. Furthermore the coexistence of ettringite with C-S-H in alkaline solutions was investigated. A mixture of C3S and ettringite was heat treated for 12h in various concentrations of NaOH solutions. With rising NaOH concentrations, increasing amounts of monosulfoaluminate were observed. Ettringite peaks were absent in the XRD-pattern at 0.75 N. No formation of the U-phase was reported. However in contrast to the experiments made with pure ettringite, the ratio ettringite:solution was significantly increased from 1:2 to 1:8. The increasing amounts of alkalis resulted in a strong increase of the aqeuous sulfate concentration, especially at high temperatures, which could have caused the precipitation of monosulfoaluminate, as observed in the latter case. Thus the reformation of ettringite after cooling cannot only be attributed to an increased sulfate sorption to C-S-H. The influence of alkalis on DEF was shown by Wieker and Herr [194] and later confirmed by Famy and Kelham (both cited in [182]): increasing amounts of alkalis led to an increase of expansion of heat cured mortars, provided sufficient sulfate was available. The formation of monosulfoaluminate has been reported in heat cured samples mainly under the aspect of DEF. But why does monosulfoaluminate form at elevated temperatures and is converted to ettringite at lower temperatures? Calculations by Damidot and Glasser [46][47] showed that monosulfoaluminate is apparently metastable with respect to C3AH6 and AFt at 25C, becoming stable at temperatures above ~40C. This would be one possible explanation of the conversion of monosulfoaluminate to ettringite due to cooling of heat cured mortars. On the other hand, Paul and Glasser [144] reported the formation of a sulfate-substituted siliceous hydrogarnet due to prolonged heat curing of Portland cement paste for more than 8 years at 85C. No AFm or AFt phase was found in these samples and it was assumed that sulfate was substituted into hydrogarnet. A second explanation of the mechanisms of DEF is the increased sulfate sorption of C-S-H at increased temperatures which might cause a destabilisation of ettringite and force precipitation of monosulfoaluminate, which subsequently transforms back to ettringite due to slow desorption of sulfate from C-S-H at ambient temperatures, as discussed by Fu et al. [70] and Famy et al. [60]. In that respect the possibility of increased sulfate sorption on C-S-H due to increased amounts of alkalis has to be mentioned, as discussed by Glasser et al. [78]. Barbarulo [14][15] has reported increasing sulfate sorption in C-S-H with increasing temperatures and alkali contents.

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Kuzel and Strohbauch [118] provide a third theory to explain the conversion of monosulfoaluminate to ettringite at ambient temperatures as they showed that monosulfoaluminate present in initially carbonate-free cements will be transformed to ettringite and carboaluminate due to subsequent carbonation of the paste. A similar mechanism was described by Seligman and Greening [169]. The literature review has shown that there is a general lack of systematic studies on the influence of carbonate on the hydration of Portland cement at temperatures other than room temperature. Moreover carbonate would appear to interact with sulfate, so the role of carbonate cannot be studied in isolation. The upper thermal stability limit of carboaluminates could not be estimated due to a lack of thermodynamic data. No consistent conclusion of the influence of temperature on the stability of carboaluminates is possible based on literature reports. In hydrated Portland cements it is generally accepted that monosulfoaluminate does form at elevated temperatures and converts to ettringite due to cooling. But there are divergent opinions about the mechanisms of this process.

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7.2. Implications of limestone addition to cement hydration 7.2.1 Experiments on the role of carbonate and sulfate on C3A hydration
AFm and AFt phases are the main hydration products of the aluminate phases in Portland cement clinker (C3A and C4AF): they react with water and sulfate or, if available, carbonate. Studies of pure phases generally help to explain the hydration mechanisms. Kuzel and Pllmann [117] published probably the most extensive experimental study to the hydration of C3A in the presence of lime, calcium sulfate and calcium carbonate. Their main findings are summarised in chapter 5.1.3. Due to the existence of several literature studies on the hydration of C3A in the presence of sulfate and carbonate at room temperature it was decided to concentrate on two experimentals paths to confirm the literature studies: (i) investigation of the hydration of C3A with calcium sulfate in a carbonate-free system and (ii) investigation of the hydration of C3A with calcium sulfate in the presence of excess calcite. Excess portlandite (as free lime) was added to each experiments to buffer the pH of the aqueous phase to ~ 12.48 at 25C. Tricalcium aluminate, anhydrite and lime were freshly prepared according to the procedure described in chapter 4.1. Analytical grade calcium carbonate was used as carbonate source in respective experiments. Previously boiled and degassed ultra pure water (water/solid-ratio = 5) was used in all experiments. HDPE bottles served as storage containers for the samples. The reaction temperature was kept constant at ~25C. The samples were initially stirred for 7d using magnetic stirrers and regularly agitated afterwards. To avoid CO2-contaminations all experiments were carried out under N2-atmosphere. In the carbonate-free experiment (i) a mixture of C3A, CaSO4 and CaO in a 1:1:2 molar ratio were used as starting materials, whereas in experiment (ii) a molar composition C3A:CaSO4:CaCO3:CaO = 1:1:1:2 was hydrated. To assess the kinetic pathway of hydration, mineralogical changes in the samples were monitored qualitatively by XRD at selected points in time over 90d. Part of the suspension was removed using a syringe and vacuum filtered subsequently using G4 Pyrex glass filter funnels in N2-atmosphere. Hydration was stopped and remaining water removed by flushing the samples with acetone. The subsequent XRD analysis of the dry powder was done using a BRUKER D8 ADVANCE powder diffractometer. The instrumental setup is described in chapter 3.2. No attempts were made to scale the reported reaction times to commercial cement systems. Although realistic ratios of oxides were used, the kinetics are typical of suspensions, not pastes, Moreover it was not intended to produce powder size distributions typical of ground commercial clinker. Fig. 7.1 shows the mineralogical changes during hydration of C3A in the presence of sulfate (SO3/Al2O3=1) and absence of carbonate. As expected from the literature, ettringite formed as initial hydration product together with portlandite, which was invariably present. The amounts of AFt increased with increasing reaction time, while the amounts of anhydrite and C3A decreased. Anhydrite was fully consumed after ~14d of hydration which corresponds to a maximum amount of AFt present. Once all anhydrite has been consumed, AFt starts to convert to monosulfoaluminate due to reaction of AFt and water with the remaining C3A between 14 and 28 days. The characteristic peaks of C3A are absent at 28d. No mineralogical changes were observed between 28d and 90d, which indicate complete reaction after 28d. The phase assemblage observed after 90d of hydration comprises mainly monosulfoaluminate, small amounts of AFt and portlandite. The peak positions of monosulfoaluminate agree well with that of the C4AsH12 reference pattern in the PDFdatabase. This indicates no extensive hydroxide substitution in the structure (see chapter 5.3.1).

The influence of limestone addition on cement hydration

122

SO4 -AFm SO4 -AFt

p ortlandite

SO4 -AFt anhydrite

p ortlandite p ortlandite
SO 4 -AFm

SO4 -AFt

SO4 -AFm

C3 A

90d 28d
SO 4 -AFt

14d 7d 48h 26h 18h 1h

Intensity 5

100counts

10

15

20

25

30

35

[2 Cuk ]
Fig. 7.1: XRD-pattern showing mineralogical changes during 90d hydration of a 1:1:2 molar mixture of C3A, CaSO4 and CaO (w/s = 5) at 25C

Fig. 7.2 demonstrates the consequences of simultaneous calcium sulfate and carbonate addition on the hydration of C3A. Similarly to the hydration of the carbonate-free sample, initially AFt and portlandite are formed. The intensities of the reflections of the main AFt peaks in the early stages of hydration up to ~26 h are slightly higher compared to the carbonate-free sample (Fig. 7.1).
calcite p ortlandite SO4 -AFt SO4 -AFt SO4 -AFt p ortlandite Hc Mc SO4 -AFt anhydrite p ortlandite C3 A Mc

90d 28d 14d


100counts

7d 48h 26h 18h 1h

Intensity 5

10

15

20 [2 Cuk ]

25

30

35

Fig. 7.2: XRD-pattern showing mineralogical changes during 90d hydration of a 1:1:1:2 molar mixture of C3A, CaSO4, CaCO3 and CaO (w/s = 5) at 25C (Hc - hemicarboaluminate, Mc - monocarboaluminate)

The influence of limestone addition on cement hydration

123

Anhydrite was fully consumed by formation of AFt after 7d of hydration. In contrast to the carbonate-free sample, the intensities of the main AFt reflections in the XRD-pattern remained unchanged between 14d and 90d of hydration, although the intensity of the main C3A reflections decreased markedly between 48h to 7d. Only weak C3A signals were detected after 14d hydration. Hemicarboaluminate and small amounts of monocarboaluminate were present after 14d which corresponds to a decrease of the intensities of the calcite reflections. However the amounts of hemicarboaluminate diminished with time while the intensities of the monocarboaluminate reflections increased significantly. Between 28d and 90d no significant changes in the mineralogy occurred; monocarboaluminate coexisted with AFt, calcite and portlandite. Fig. 7.3 shows a comparison of the kinetic mineralogical evolution arising from the C3Aexperiments in dependence of the initial carbonate content of the system. The following reaction path for C3A hydration can be derived from the experiments, which is in general agreement with the literature: Independently of the presence of carbonate, AFt is observed as only hydration product of C3A in the presence of excess calcium sulfate, due to the instability of AFm at aqueous sulfate activities generated by anhydrite and/or gypsum (see Fig. 7.4). If calcium sulfate is fully consumed, aqueous sulfate activities are buffered by ettringite and decrease significantly. Subsequently AFm precipitates and coexists with AFt. In carbonate-free systems, the initially formed SO4-AFt reacts with the remaining C3A and in dependence of the amount of reactive C3A monosulfoaluminate solid solutions and/or a mixture of monosulfoaluminate and ettringite will form. Thus, as expected, in the experiment shown in Fig. 7.3 a) (SO3/Al2O3=1) monosulfoaluminate coexisted with traces of ettringite after 90d of hydration. However if excess calcite is present, as shown in Fig. 7.3 b), carboaluminate phases form due to reaction of the remaining C3A with calcite, after calcium sulfate is fully consumed and bound in AFt. In agreement with experimental observations by Kuzel et al. [117], hemicarboaluminate was initially observed as the dominant carboaluminate phase after 14d of hydration. But hemicarboaluminate is not stable in the presence of excess calcite [49] and converts to monocarboaluminate with time. Previous results have shown that no sulfate substitution is likely in either of the carboaluminate phases. Thus the amounts of AFt are unaffected and do not depend on which carboaluminate is present.
a) carbonate-free system
presence of phase (XRD pattern) p ortlandite

b) excess calcite present


calcite p ortlandite monocarboaluminate monosulfoaluminate hemicarb. SO 4-AFt anhy drite C 3A

SO 4-AFt anhy drite C 3A

1h

18h

26h

48h

7d

14d

28d

90d 1h

18h

26h

48h

7d

14d

28d

90d

reaction time

reaction time

Fig. 7.3: Comparison of qualitative time-dependent mineralogical changes during hydration of C3A with lime and calcium sulfate (SO3/Al2O3=1) in carbonate-free systems (left) or in the presence of excess calcite (right) at 25C (dashed lines indicate the detection of only weak intensities in the XRD-pattern)

The influence of limestone addition on cement hydration

124

A comparison of Fig. 7.3 a) and b) shows that the addition of limestone slightly accelerates the reaction of C3A with calcium sulfate. Whereas in the carbonate-free sample anhydrite was consumed after ~14d of hydration, anhydrite could no longer be detected after ~7 d of hydration.

7.2.2 Phase relations between AFt-AFm phases relevant to Portland cements at 25C
The aim of this study was systematically to analyse the effects of limestone additions on the chemistry and mineralogy of hydrated Portland cement paste. It is first necessary to understand phase changes which occur as a consequence of limestone and/or carbonate addition to Portland cements. The ternary phase relations between sulfate-, carbonate- and hydroxy-AFm have been studied in chapter 5, while AFt phases were studied in chapter 6. Therefore the next logical step was to investigate the relations between AFt and AFm. Related experimental results are available in the literature [29][117] and experiments on the hydration of C3A were described in the previous chapter. Based on the thermodynamic data of the main cement hydrates and the aqueous species, listed in Table 4.1 and Table A.1, and including the derived AFt and AFm solid solution models, the stable invariant points including AFt and AFm phases in the system CaO-Al2O3-CaSO4-CaCO3-H2O were calculated. Previous works by Damidot et al. [43][46][49] dealt with this subject and are a useful basis for the following calculations. However one important outcome of the database development is the possibility that monosulfoaluminate is stable at 25C, in contrast to earlier studies. Thus it seems justified to revise previous calculations using the dataset developed in this Thesis. The phase relations between AFm, AFt, calcite and gypsum at 25C are shown as a pseudo-3D phase diagram in Fig. 7.4. As limestone blending is mainly relevant to Portland cements, calculations assume an excess of portlandite, which acts as a pH buffer (pH ~ 12.43 - 12.48). Thus calcium concentrations remain almost constant (~19.4 mmol/kg) except in phase assemblages containing gypsum where aqueous Ca ~ 30.7 mmol/kg. The aqueous phase composition at relevant invariant points is given in Table 7.1. The phase assemblages shown in Fig. 7.4 generally agree with those depicted in Fig. 5.22, except that, due to phase rule restrictions, a parallel coexistence of monocarboaluminate, monosulfoaluminate and hemicarboaluminate with portlandite and AFt is not possible. The calculations indicate that monosulfoaluminate and monocarboaluminate are incompatible in portlandite saturated conditions at 25C. However thermodynamically it is very difficult to assess this claim due to the small free energy difference of reaction between the phase assemblage monocarboaluminate and hemicarboaluminate or monocarboaluminate and monosulfoaluminate coexisting with AFt and portlandite, respectively. Experimental results by Kuzel and Pllmann [117] showed the formation of hemicarboaluminate, monosulfoaluminate and ettringite during reaction of C3A with gypsum and small amounts of calcite (initial molar composition of the mixture C3A:CaO:CaSO4:CaCO3=1:1:1/2:1/4). Later observations on hydrated Portland cements [113][115][116] blended with small amounts of calcite agreed with these findings. Experiments (shown in chapter 5.3.2, Fig. 5.19 b)) disclose the formation of increasing amounts of hemicarboaluminate due to reaction of monosulfoaluminate and monocarboaluminate in the presence of Ca(OH)2. Thus, in agreement with calculations and experiments, the stable coexistence of monocarboaluminate and monosulfoaluminate in hydrated Portland cements at ~25C is unlikely.

The influence of limestone addition on cement hydration


Excess portlandite present in all assemblages

125

Fig. 7.4: Phase relations between AFm-AFt phases as well as gypsum, hydrogarnet and calcite in the system CaO-Al2O3-CaSO4-CaCO3-H2O at 25C (Note: excess portlandite present in all assemblages, dashed lines in region K-L-M-N represent stability field of ideal monosulfoaluminate without hydroxide substitution).

Fig. 7.4 shows that all AFm phases are predicted to coexist with AFt at appropriate aqueous compositions. The calculations indicate the possibility of the coexistence of monosulfoaluminate with AFt at sulfate concentrations of ~0.01 mmol SO42-/kg. This is in contrast to calculations by Damidot et al. [46] who reported the metastability of monosulfoaluminate with respect to ettringite and C3AH6 at 25C. However their calculations used solubility data by Wells et al. [193] to derive thermodynamic data for C3AH6, which significantly differ from the dataset derived in this study (see Fig. 4.3, chapter 4). Compatibility experiments by Atkins et al. [10] did not give consistent results: on one hand formation of C3AH6 was not observed in a sample containing initially monosulfoaluminate and portlandite stored 180d at 25C but on the other hand, no formation of monosulfoaluminate was observed in a mixture of AFt and C3AH6 stored under the same conditions. As shown in chapter 5, part of the sulfate in monosulfoaluminate may be replaced by hydroxide ions. This solid solution formation has been considered during construction of Fig. 7.4. The calculations show that in the presence of portlandite and C3AH6 (points M and L, Fig. 7.4) up to ~24 mol% of the initial sulfate of monosulfoaluminate can be replaced by hydroxide. Increasing carbonate and sulfate concentrations decrease the extent of hydroxide substitution in monosulfoaluminate. However it is interesting to note that with the estimated thermodynamic data for monosulfoaluminate-hydroxy-AFm solid solutions a substitution of 11 mol% hydroxide is predicted in the presence of portlandite and AFt in the system (points N and K, Fig. 7.4), whereas as shown in chapter 5.4, Fig. 5.22, calculated for lower hydroxide activities, monosulfoaluminate approaches its ideal composition while coexisting with AFt in the absence of portlandite.

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126

Table 7.1: Composition of aqueous phase of selected stable phase assemblages and invariant points in the system CaO-Al2O3-CaSO4-CaCO3-H2O at 1bar and 25C (excess portlandite present, comparison with reported points in the literature and effect of solid solution formation)
Pt. pH CaI AlI CO3I
[mmol/kg]

SO4 I
[mmol/kg]

Solids

Reference

[mmol/kg] [mmol/kg]

12.48 12.52

19.38 21.95 19.37 21.95 19.36 21.95 19.35 21.95 19.34 21.95 30.70 33.90 30.69 33.90 19.37 19.37 21.90 19.35 21.90 19.36 19.36 21.96 19.35 19.35 19.35 19.37 19.35 19.35 30.69 31.30 31.56 30.69 33.80

0.087 0.008 0.087 0.008 0.037 0.006 0.007 0.005 0 0 0 0 5.7E-07 1.0E-07 0.007 0.007 0.005 0.037 0.006 0.038 0.044 0.018 0.087 0.087 0.087 0.087 0.038 0.044 5.7E-07 0.0003 0.06 0 0

0 0 8.3E-06 1.6E-03 0.0003 0.0050 0.0065 0.0069 0.0065 0.0069 0.0065 0.0069 0.0066 0.0069 0.0065 0.0065 0.0069 0.0003 0.0050 0.0002 0.0001 4.7E-05 8.2E-06 8.2E-06 0 0 0 0 0 0 0 0 0

0 0 0 0 0 0 0 0 0

C3AH6, CH

t.s. [49]

12.48 12.52

C3AH6, Hc, CH

t.s. [49]

12.48 12.52

Mc, Hc, CH

t.s. [49]

12.48 12.52

Mc, calcite, CH

t.s. [49]

12.48 12.52

calcite, CH

t.s. [49]

12.43 ---

12.47 12.40 12.47 12.40 0.024 0.025 0.010 0.009 0.009 0.008 0.0075 0.004 0.001 0.002 0.001 0.002 0.008 0.0075 12.47 11.40 12.33 12.47 12.40

gypsum, calcite, CH

t.s. [50]

G H H II

12.43 12.49 12.48 12.48 12.52

gypsum, AFt, calcite, CH AFt(ss, 9%CO3), Mc, calcite, CH AFt, Mc, calcite, CH

t.s. [50] t.s. t.s. [50]

12.48 12.52

AFt, Mc, Hc, CH

t.s. [50]

K K II

12.48 12.48 12.52

AFt, Hc, Ms(ss; 11%OH), CH AFt, Hc, Ms, CH

t.s. t.s. [50]

L L M M N N II O
II II

12.48 12.48 12.48 12.48 12.48 12.48 12.43 12.47 ---

C3AH6, Hc, Ms(ss, 24%OH), CH C3AH6, Hc, Ms, CH C3AH6, Ms(ss; 24%OH), CH C3AH6, Ms, CH AFt, Ms(ss; 11%OH), CH AFt, Ms, CH AFt, gypsum, CH

t.s. t.s. t.s. t.s. t.s. t.s. t.s. [46] [97]

12.43

gypsum, CH

t.s. [50]

all molalities given as total concentrations independently from the individual speciation monosulfoaluminate (Ca4Al2(SO4)(OH)126H2O) and AFt (Ca6Al2(SO4)3(OH)1226H2O)

II

calculated for ideal stoichiometry of

abbreviations:, CH - Portlandite, Mc - Monocarboaluminate, Hc - Hemicarboaluminate, Ms(ss; 11%OH) - monosulfoaluminate solid solution with a replacement of 11% SO42- by 2OH--; AFt(ss; 9%CO3) - ettringite solid solution with a calculated replacement of 9% SO42by CO32-, AFt - SO4-ettringite; t.s. - calculated in the title study

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127

The calculations shown in Fig. 7.4 are in accord with experiments by Seligmann and Greening [169]. As a result of their investigations they stated:
It is therefore proposed that another invariant point occurs that represents the liquid phase composition in equilibrium with Ca(OH)2, C3AH6 and the lowest sulfate form of calcium sulfohydroxyaluminate hydrate as the solid phases.(at 25C)

This point corresponds to the invariant M in Fig. 7.4 comprising the phase assemblage SO4-AFm (solid solution), C3AH6 and portlandite. The good agreement between both calculated and experimentally-derived results is another indication that a range of monosulfoaluminate solid solution compositions are stable at 25C. Region K-L-M-N shows the stability field of ideal monosulfoaluminate. It is apparent that due to the stabilising effect of the solid solution formation, the stability field of hydroxide substituted monosulfoaluminate is markedly increased compared to that of the ideal SO4-AFm end member. Increasing carbonate concentrations lead to the formation of carboaluminate phases in the system CaO-Al2O3-CaSO4-CaCO3-H2O at 25C. Hemicarboaluminate is stable in region B-C-I-K-L in Fig. 7.4 corresponding to a range of 8.1e-6 mmol/kg CCO32- 3e-4 mmol/kg at 25C. In agreement with calculations by Damidot et al. [49], hemicarboaluminate is not stable in the presence of calcite but does coexist with monocarboaluminate. Monocarboaluminate, in contrast to hemicarbo- and monosulfoaluminate, can coexist with calcite and is thus stable in region C-D-H-I Fig. 7.4 (3e-4 mmol/kg CCO32- ~7e-3 mmol/kg at 25C). Thus the formation of monocarboaluminate is often reported in blended cements containing >10 to 20 wt.-% calcite. As shown in point H, Fig. 7.4 , monocarboaluminate is stable up to 0.024 mmol SO42-/kg, whereas hemicarbo- and monosulfoaluminate are metastable with respect to ettringite at sulfate concentrations ~0.01 mmol/kg. The previously-developed solid solution model for carbonate- and sulfate-AFt was also considered in Fig. 7.4. AFt is stable over a wide range of sulfate and carbonate concentrations at 25C. However the resulting self-generated carbonate activities are generally too low to enable significant carbonate substitution in the AFt phase. Thus AFt is predicted to have essentially its ideal composition at invariant points I, K, N, O, G. Only at invariant point H -which is however probably of most importance to limestone blended cements- minor substitution of ~9 mol% CO32- is predicted to occur for AFt coexisting with monocarboaluminate and calcite. Previous experiments have suggested a reaction pathway of C3A hydration which is consistent with the phase diagram Fig. 7.4. Only AFt is thermodynamically stable at sulfate activities generated by excess gypsum i.e., at aqueous compositions along line O-G, Fig. 7.4. Thus independently of the addition of calcium carbonate, AFm is not predicted to form as long as a physical excess of calcium sulfate is present. The consumption of calcium sulfate leads to a decrease in sulfate activity. The precipitation of monosulfoaluminate and/or carboaluminates in presence of AFt should therefore lead to an aqueous phase composition along the line N-K-I-H. The influence of alkalis on the calculated phase assemblages is discussed in chapter 7.5.1. In experiments with excess calcite present, the intermediate formation of hemicarboaluminate was observed. One possibility to explain this behaviour is a temporary decrease of the carbonate activity to a region where hemicarboaluminate becomes stable due to the slow dissolution rate of calcite in the course of carboaluminate precipitation. With progressive hydration carbonate activities increase again, hemicarboaluminate becomes metastable, and reacts to form monocarboaluminate with time.

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128

To summarise the key findings, a close relationship exists between the composition of the aqueous phase and the nature of solid phases forming. At portlandite saturation the pH is buffered by portlandite so the construction of Fig. 7.4 is, very nearly, at constant pH. But the activities of other species, carbonate and sulfate are also buffered: sulfate by gypsum, AFt or AFm, and carbonate by calcite, mono- or hemicarboaluminate. At 25C, phases that contain sulfate do not contain carbonate, and vice versa, as a good first approximation (calculation discloses only limited substitution of carbonate for sulfate in AFt). Hence the three buffering systems, one for pH and one of several for sulfate and carbonate, act essentially independently of each other. The highest carbonate activities are obtained in the presence of calcite and the highest sulfate activity, in the presence of gypsum. However, carbonate activities are numerically low and, not surprisingly, aqueous solutions may not always achieve carbonate saturation in the presence of calcite especially during the early stages of hydration, when aluminates are react rapidly. Regarding phase compatibility, each AFm phase has a stability field where it can coexist with portlandite and other AFm and AFt phases and/or hydrogarnet at 25C. All AFm phases can coexist with AFt, whereas monocarboaluminate is the only AFm phase which is compatible with calcite. Increasing carbonate concentrations lead to the transformation of C3AH6 and/or monosulfoaluminate solid solutions to hemicarboaluminate and finally to monocarboaluminate and calcite. The composition of the AFt phase in the system CaO-Al2O3-CaSO4-CaCO3-H2O at 25C is close to ideal SO4-AFt. The selfgenerated carbonate activities are generally too low for extensive carbonate substitution in the AFt phase; maximum ~9 mol% CO32- may be substituted in the presence of monocarboaluminate and calcite in portlandite-buffered systems at 25C.

7.2.3 Reactive vs. filler calcite


The previous investigations and calculations show that, depending on the initial chemical composition of the mixture, several AFm phases might coexist: thermodynamic calculations demonstrated different possible phase assemblages among the AFm-AFt compositions included in the study. To apply these data to commercial cements it is necessary to couple the initial chemical composition of the cement to the previous thermodynamic calculations. That will (i) enable prediction of the phase assemblages expected during Portland cement hydration in the presence of calcite and (ii) to calculate amounts of phases and thereby to quantify these processes. To apply the data to commercial cements, it is argued as follows: Ca(OH)2 is of constant composition (but not necessarily in constant amount) and it is assumed for present purposes that sulfate, carbonate and aluminium included in C-S-H require a small but constant correction of the chemical totals. Quantitative studies of sulfate incorporation in C-S-H are in progress and in due course, it will be possible to correct for sulfate sorbed by C-S-H (see discussion paragraph 7.5.2). The maximum activity of carbonate is controlled by an excess of calcite, but these are too low to carbonate either Ca(OH)2 or C-S-H. In the first approach, at 25C, minor carbonate substitution in AFt is neglected, but considered in supplementary plots (see appendix B). This study concentrates on the iron-free phases. However work is also in progress to assess the stability iron substituted AFm and AFt phases [132][133]. Fig. 7.5 shows the calculated phase assemblages that will typically occur during hydration of C3A in hydrated OPC and the dependence on initial sulfate and carbonate contents, expressed as ratios of SO3/Al2O3 and CO2/Al2O3, subsequently abbreviated as sulfate and carbonate ratios respectively. This method of representation enables all the relevant chemical variables to be displayed on a twodimensional diagram without error.

The influence of limestone addition on cement hydration


excess portlandite present in all assemblages
1)

129

3.5

2)

minor hydroxide substitution possible minor carbonate substitution possible

VI

AFt +gypsum + calcite

3.0 molar bulk SO 3/Al 2O 3-ratio 2.5

2.0

AFt + monocarboaluminate + calcite

2)

1.5

I
AFt + Hc + Ms
1)

1.0

II
0.5

IV
Ms-ss + Hc AFt + hemicarboaluminate+ monocarboaluminate 0.5 0.75 1 1.25 1.5

III

0.0 0

Ms-ss+ Hc+ C3AH 6 0.25

molar bulk CO 2/Al2O 3-ratio

Fig. 7.5: Calculated phase assemblages of a hydrated mixture consisting of C3A, portlandite and varying initial sulfate (SO3/Al2O3) and carbonate contents (CO2/Al2O3) at 25C (the influence of minor carbonate substitution in AFt is not shown)

It is important to note that the calculated stability relationships were computed assuming an excess of portlandite which is typical for hydrated Portland cement paste: further reasons for this will become apparent in the subsequent exposition. Also, that the relations shown in Fig. 7.5 are unaffected by the presence of normal C-S-H; that is, C-S-H having a Ca/Si molar ratio ~ 1.6; the exact value probably lies in the range 1.6 to 1.8, such that it also coexists with portlandite, calcium hydroxide. The role of siliceous hydrogarnet formation, suppressed in the calculations, is discussed subsequently. Fig. 7.5 helps to assess the expected mineralogical constitution of hydrated limestone blended cements at 25C. Before the diagram is used for more practical applications including the estimation of the reactive calcite content, the following general conclusions arise: AFt, monocarboaluminate, calcite and portlandite (region V, Fig. 7.5) will be observed as an important stable phase assemblage in limestone blended cements with excess calcite present. However the chemistry necessary to achieve this assemblage is a function of both SO3/Al2O3 and CO2/Al2O3 ratios. The calculations indicate a possibility of minor carbonate substitution in ettringite. A maximum replacement of ~9 mol% SO42- by CO32- in the AFt structure is predicted in region V. As this is not yet experimentally proven, it is not shown in Fig. 7.5 and is not considered in the following calculation; thus the % reactive calcite is slightly underestimated. However a modified version of Fig. 7.5 is shown in appendix B, Fig. B.4. As a result of the carbonate substitution two more phase assemblages are predicted: regions IVa with monocarboaluminate, AFt solid solution and portlandite and Va with AFt-ss, calcite and portlandite (see chapter 7.4). Significant substitution of sulfate in monosulfoaluminate occurs only when the initial SO3/Al2O3 ratio is lower than 1. At SO3/Al2O3 ratio ~1 the composition of this AFm phase is close to ideal monosulfoaluminate stoichiometry (max. 11 mol% replacement of SO42- by

The influence of limestone addition on cement hydration

130

2OH-). But, with increasing carbonate contents, the stability field of monosulfoaluminate solid solution decreases markedly. Monosulfoaluminate and the monosulfoaluminate-type solid solutions are not stable in the presence of monocarboaluminate and portlandite and are unlikely to persist in cements with a carbonate ratio > 0.5. OPC with very low carbonate contents will form hemicarboaluminate as an additional AFm phase in the course of hydration. But hemicarboaluminate is not stable at 25C if excess calcite remains. Fig. 7.5 agrees well with previous experiments on the hydration of C3A in the presence of either sulfate or carbonate, or both. Depending on the availability of sulfate, alumina and carbonate, phase boundaries will be crossed during C3A hydration. At initial stages of hydration, SO3/Al2O3 is typically >3, conditioned by the presence of excess calcium sulfate and phase assemblage VI is observed. Once free calcium sulfate is depleted, the SO3/Al2O3 ratio decreases and phase assemblages containing AFm phases will be observed and, depending on the availability of carbonate, monosulfoaluminate solid solutions and/or carboaluminates will form. C3AH6 has only limited stability in the system CaO-Al2O3-CaSO4-CaCO3-H2O. It will not occur if the initial solid SO3/Al2O3 ratio is greater than 0.75 and it is not stable in the presence of monocarboaluminate. The diagram, Fig. 7.5, is constructed for ~25C. The phase relations are however sensitive to temperature and calculations for low (~5C) and elevated temperatures up to 99C reveal substantial changes of phase assemblage predictions. The effect of temperature on the AFtAFm phase assemblages is investigated in chapter 7.4.

The impact of adding calcite on the paste mineralogy can be predicted, using Fig. 7.5, as follows: select a horizontal line corresponding to the effective sulfate ratio of the cement. The intersection of this line with a vertical construction line corresponding to the appropriate carbonate ratio will enable the phase assemblage to be calculated with respect to the AFm portion and associated phases, as necessary to preserve mass balances. As can be seen from the slopes of the relevant boundaries, the appearances of hemicarboaluminate and of monocarboaluminate are functions of cement sulfate, carbonate and alumina contents. Calcite totally reacts in regions I, II, III and IV, appearing in excess only in regions V and VI, Fig. 7.5. Since the carbonate content of AFm phases is low and the total content of the phases containing alumina (AFm and AFt) is low, not much calcite is required to attain region V; this quantity will be calculated subsequently. Aged hydrated cements are normally undersaturated with respect to gypsum, so the phase assemblage corresponding to region VI is not likely to be encountered in practice (altered cements are excepted from this presentation). The boundary between regions IV and V is shown in bold to indicate its special significance as a dividing line between compositions that are either undersaturated or oversaturated with respect to calcite (see second bullet point page 124). Compositions to the left of this line are undersaturated: that is, calcite behaves as a reactive admixture and is totally consumed, while those compositions to the right of this line will contain a permanent excess of free calcite; in these regions excess calcite behaves as a filler. Of course the amount of any excess will generally be much less than the total added because some calcite will have reacted. The position of the saturation line (bold) enables the numerical saturation value to be determined in terms of sulfate and carbonate ratios for a given cement composition. The figure does not depict the composition of the pore fluid coexisting with solids, but one notes that an insignificant proportion of the total solids are dissolved in the

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aqueous phase, assuming realistic water/cement-ratios are used: but it is not recommended that the graph is applied to the very high w/s-ratios, > 10, sometimes used in laboratory simulations.

7.2.4 Quantification of phases


A disadvantage of Fig. 7.5 is that it does not enable the amounts of phases to be calculated. Fig. 7.6 has been constructed to enable this calculation. The calculation is initially presented for one ratio, at sulfate/alumina = 1.0. A model mixture consisting of C3A, portlandite and calcium sulfate (SO3/Al2O3=1) was reacted with 500g water and blended with calcite. The total amount of solids has been kept constant to an arbitrary total of 3.25 mol. Thus, similar to blended cements, calcite addition dilutes the initial amounts of C3A, portlandite and calcium sulfate. For calculation purposes, a definite amount of portlandite has to be added although the amount in excess is not critical provided an excess is always present. Thus the amount of portlandite can be scaled up or down, as required, without affecting the relative ratios of the other phases except for dilution. It is instructive to begin the explanation of Fig. 7.6 with a calcite-free cement by projecting a vertical line at a carbonate ratio equal to zero and subsequently blending the initial mixture with carbonate, the impact of which can be visualised by moving a vertical construction line to the right in small increments, i.e., allowing the carbonate ratio to increase. It can be seen that at the outset of calcite addition, very small changes in the carbonate ratio result in the rapid consumption and decrease in amount of monosulfoaluminate, while at the same time, the amount of hemicarboaluminate increases rapidly. However sulfate released from monosulfoaluminate cannot stay in solution and, because the cement is undersaturated with respect to gypsum, sulfate thus displaced from monosulfoaluminate forms ettringite. Therefore, other factors being equal, the amount of ettringite initially increases with increasing carbonate ratio. This reaction, in turn, requires alumina and consumes portlandite with the result that portlandite contents decrease sharply from the original amount. This is why the calculation needs to be commenced with an excess of portlandite, to avoid its total depletion and thus violate a condition of the calculation.
1.5 relative amount of solids [mol] excess portlandite present; SO 3 /Al 2 O 3 =1

portlandite

1.0
monosulfoaluminate hemicarboaluminate

monocarboaluminate

calcite

0.5
AFt

0.0 0 0.25 0.5 0.75 1 1.25 1.5 1.75 2 molar bulk CO 2/Al2O 3-ratio

Fig. 7.6: Relative amount of hydrate phases of a hydrated model mixture consisting of C3A, portlandite and with fixed sulfate ratio (SO3/Al2O3=1) in dependence of changing carbonate contents (CO2/Al2O3) at 25C (constant total amount of solids, C3A+CaSO4+CH+Cc = 3.25 mol, reacted with 500 g water; data are expressed in molar units; the influence of minor carbonate substitution in AFt is not shown)

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As shown in Fig. 7.6, the amount of ettringite reaches a maximum amount when all sulfate in AFm has been replaced by carbonate, i.e., when monocarboaluminate first appears and hemicarboaluminate is maximized at a carbonate ratio equal to about 0.33. Thereafter, upon continued addition of calcite, hemicarboaluminate is progressively replaced by monocarboaluminate: the trend of portlandite consumption is reversed and it is now liberated by calcite additions at higher carbonate ratios in the range between 0.33 and 0.66, approximately. At carbonate ratios at or above 0.66, calcite saturation is achieved and increasing amounts of free calcite appear as the carbonate ratio continues to increase. This calcite effectively dilutes the other solids and their amounts gradually but slowly decrease as calcite amounts increase. However, because of the scale of the Figure, the dilution effect is only just perceptible. Because of the capacity of the system to react with calcite, carbonate reacts completely at lower CO2/Al2O3 ratios with aluminate paste components with formation of either or both hemi- and monocarboaluminate. However as the amounts of these phases change, mainly at the expense of monosulfoaluminate, mass has to be conserved and, as a result, the amount of portlandite is also affected as sulfate, progressively displaced from monosulfoaluminate, is increasingly consumed with formation of AFt. Two noteworthy results of the calculations are (i) to highlight the importance of minor components (sulfate, carbonate) in controlling mineralogical reactions in cement paste, some of which consume portlandite and others of which liberate portlandite and (ii) the role of carbonate in increasing the amount of ettringite in certain composition ranges, despite the total amount of sulfate remaining constant.
10 amount of CaCO 3,reactive [wt.-%] 9 8 7 6 5 4 3 2 1 0 0 1 2 3 4 5 6 7 8 9 10 amount of Al2 O 3 [wt.-%]
SO 3 /Al2 O3 =0.2 SO 3 /Al2 O3 =0.4 SO 3 /Al2 O3 =0.6 SO 3 /Al2 O3 =0.8 SO 3 /Al2 O3 =1.0 SO 3 /Al2 O3 =1.2 SO3 /Al2 O3 =1.4

Fig. 7.7: Calculated amount of reactive CaCO3 in dependence of the initial amount of initial solid Al2O3 content and bulk SO3/Al2O3 ratio of the paste at ~25C (data are expressed in weight units; the influence of minor carbonate substitution in AFt is not considered)

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Of course not all cements will have a sulfate/alumina ratio equal to 1.0. Therefore Fig. 7.7 and Fig. 7.8 are presented to enable the boundary between reactive and filler calcite to be determined for other ratios; that is, to make the calculation generic. Because the industry tends to work in terms of weight-%, the alumina and sulfate ratios of Fig. 7.7 and Fig. 7.8 are shown in weight units. Fig. 7.7 shows how the maximum reactive wt.-% of calcite varies with amount of alumina and with changing sulfate ratio. It can be seen that for a fixed alumina content, the amount of reactive calcite decreases with increasing amounts of sulfate present expressed as SO3/Al2O3 ratio. Fig. 7.8 shows a similar plot, of reactive calcite shown as functions of the sulfate ratio and amount of sulfate, as sulfur trioxide. This plot makes clear that if the amount of sulfate is kept constant, increasing amounts of alumina (decreasing SO3/Al2O3 ratios), will increase the amount of reacted calcite significantly.
10 9 amount of CaCO 3,reactive [wt.-%] 8 7 6 5 4 3 2 1 0 0 1 2 3 4 5 amount of SO3 [wt.-%]
SO3 /Al2 O3 =0.8 SO3 /Al2 O3 =1.0 SO 3 /Al2 O3 =1.2 SO3 /Al2 O3 =1.4 SO3 /Al2 O3 =0.6 SO 3 /Al2 O3 =0.2 SO3 /Al2 O3 =0.4

Fig. 7.8: Calculated amount of reactive CaCO3 in dependence of the initial amount of initial solid SO3 content and bulk SO3/Al2O3 ratio of the paste at ~25C (data are expressed in weight units; the influence of minor carbonate substitution in AFt is not considered)

7.2.5 Space filling by cement paste solids


It is instructive to compare the space filling ability of the solids arising in the course of hydration and the chemical bound water demand of the hydration products. As C-S-H is not directly involved in the reactions arising from calcite blending, it need not be considered in the following example calculation. Moreover, while the numbers selected for the calculations will be affected by the exact analysis of the cement as well as the water/cement-ratio, changing the water/solid-ratio affects the calculation only in the sense that the amount of free water is influenced. However the solid phase ratios remain essentially unaffected by the excess water content, up to w/s ~ 1, the calculated trends are of general applicability for all practical formulations. This additional information supplements chapter 7.3 of this Thesis. The following calculation depicts changes in mineralogical balances expressed as specific volume changes as a function of the carbonate ratio. The calculation of Fig. 7.9 has been done by applying the same conditions as were used to generate Fig. 7.6. Data for the molar volume of phases have been compiled from the literature and are integrated in the database given in Table 4.1.

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650 600 550 500 450

excess aqueous phase minimal porosity

total volume cm

400 350 300 250 200 150 100 50


hemicarboaluminate

portlandite

AFt

MS-ss

monocarboaluminate calcite

0 0.00

0.25

0.50

0.75

1.00

1.25

1.50

1.75

2.00

solid molar bulk CO2/Al2O3-ratio


Fig. 7.9: Specific volume changes of hydrate phases of a hydrated model mixture consisting of C3A, portlandite and with fixed sulfate ratio (SO3/Al2O3=1) in dependence of changing carbonate contents (CO2/Al2O3) at 25C (constant total amount of solids, C3A+CaSO4+CH+Cc = 3.25 mol, reacted with 500 g water; the influence of minor carbonate substitution in AFt is not shown).

Results of the calculation show that, commencing with a calcite-free cement (carbonate ratio = 0.0), addition of calcite and its subsequent reaction initially increases the molar volume of the solids and consumes water. Because calcite has a greater density than most cement hydrates, this trend, of increasing the volume of solids by diluting the cement by calcite, seems counterintuitive. But the initial calcite is reactive; free calcite is consumed and, as carboaluminates form, sulfate displaced from the AFm phase forms ettringite. Both AFm and ettringite have lower physical densities than calcite, although the low physical density and high water demand of the ettringite product are responsible for most of the increase in the volume of the solids. The increase in bound water is also mainly due to ettringite formation but the total amount of water in hydrates also increases because calcite, essentially anhydrous, is converted to highly hydrated phases thereby contributing to increased binding of water. In this example, the maximum solid phase volume is achieved at a carbonate ratio approximately 0.33, i.e., considerably less than the maximum amount of reactive calcite; the latter occurs at a carbonate ratio of ~0.66. Thus the point of maximum volume is sensitive to composition and does not coincide with the maximum amount of reactive calcite. It should be noted that the point of maximum volume will depend on both the carbonate and sulfate ratios but that a maximum can be expected to occur for most, if not all, commercial cement compositions. Thus the generic conclusion is that a maximum space filling will occur, but that its composition requires to be calculated for each cement; also to take into account some supplementary factors, see the discussion. However calcite additions can be controlled independently of clinker composition and can therefore be used to maximise the space filling of cement paste. Note also that the specific volume contribution of portlandite also changes because it is either consumed or produced in the course of reaction, as was explained previously.

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In commercial cements, where C-S-H develops, C-S-H will dilute the volume change effects arising from calcite reactions but its presence as a diluent does not affect the general conclusions described above. In general, these volume changes are not expected to be physically expansive because much of the reaction takes place before the cement has attained high strength.

7.2.6 Composition of the aqueous phase


With the help of thermodynamic modelling the composition of the aqueous phase of relevant AFmAFt phase assemblages (compare with Fig. 7.6 and Fig. 7.9) can also be calculated. The composition of the aqueous phase of the model system used in the previous paragraphs was calculated as functions of the sulfate and carbonate ratios. Results of a specimen calculation for a fixed sulfate ratio = 1.0 are shown in Fig. 7.10 as a function of the carbonate ratio. Calcium and hydroxide are the most abundant aqueous species and exhibit constant concentrations independent of the CO2/Al2O3 ratio. The concentrations of aluminium, carbonate and sulfate evolve along stepped profiles. The steps correspond in position to the carbonate ratios of phase boundaries shown in Fig. 7.5 and are numbered accordingly. While the change from phase assemblage I to phase assemblage IV, including the disappearance of monosulfoaluminate and the precipitation of monocarboaluminate, does not significantly change the aqueous composition except for a slight increase of carbonate concentrations, the precipitation of calcite leads to a significant increase of the carbonate and sulfate concentrations in conjunction with a decreasing aluminium concentration. Note that if the sulfate ratios were set to ~1 SO3/Al2O3 3 these sequences remain unchanged, except in position. But if the sulfate ratio would be less than ~1.0, a new step, corresponding to region II of Fig. 7.5, would be generated, while at sulfate ratios < 0.76 another additional step would emerge, corresponding to region III of Fig. 7.5. Thus each region in diagram Fig. 7.5 is related to a distinctive aqueous phase composition - which is a characteristic of a buffered system.
Hc+Ms+AFt Hc+Mc+AFt +CH +CH Mc+AFt+Cc+CH

concentration [mmol/kg]

40 30 20 10 0.1 0.01 1E-3 1E-4 0.0

IV

hydroxide calcium

aluminium

sulfate

carbonate

0.5

1.0

1.5

2.0

solid molar bulk CO2/Al2O3-ratio


Fig. 7.10: Change of composition of aqueous phases of a hydrated model mixture consisting of C3A, portlandite at a fixed sulfate ratio (SO3/Al2O3=1) in dependence of changing carbonate ratios (CO2/Al2O3) at 25C (constant total amount of solids, C3A+CaSO4+CH+Cc = 3.25 mol, reacted with 500 g water; compare with Fig. 7.5, Fig. 7.6 and Fig. 7.9 showing solid phase distributions).

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While the change in numerical values of pore fluid concentrations appears sometimes so low as to be of no practical importance, this is not so. Each aqueous phase change must be accompanied by a change in the nature of the coexisting solids. Transfer of a significant amount of chemical substance, in this instance mainly of carbonate, is required to complete the phase transformation. This requirement for mass transfer is typical of systems containing solid buffers. The amount of mass required to effect the reaction, and hence the buffering capacity, depends not only on the difference in compositions but also on mass of substance available to participate in reaction. But the principle is established that buffering reactions occur and provide a definite demonstration that cement systems have the ability to buffer aqueous concentrations of species other than hydroxide, OH. In this instance, the buffered species is carbonate but it is apparent that similar buffer systems can be defined for sulfate, e.g. as shown previously for calcium sulfate in the early stages of hydration.

7.3. Applicability to Portland cement systems 7.3.1 Experimental validation of phase changes
Seligmann and Greening [169] published one of the first evidences of the formation of mono- and hemicarboaluminate in hydrated Portland cement blended with 5 wt.-% limestone. They also showed that addition of limestone inhibits the transformation of ettringite into monosulfoaluminate for the reasons explained in chapter 7.2.4. Other researchers [37][166] came to similar conclusions which are in agreement with the calculations. Kuzel et al. [113][115][116] provide further detailed experimental validation of the calculations, as he confirmed directly the relations shown in Fig. 7.5 by systematic investigations of hydrated Portland cements containing small amounts of carbonate. Indeed Kuzel and Pllmann [117] derived similar phase relations as shown in Fig. 7.5 resulting from their interpretation of experiments.

Experimental setup
The literature review indicates that the calculations are applicable to Portland cement. Thus no extensive experimental programme deemed necessary to confirm the calculations. However two experiments were done to verify the applicability of the calculations to hydrated iron-free Portland cement paste: i) a carbonate-free cement analogue and ii) a calcite blended cement paste. To enable a direct comparison of experiments and calculations, and to ensure an initially carbonatefree system, it was decided to prepare a Portland cement analogue by mixing C3S, C3A, CaSO4 and K2SO4. The batch chemical composition is given in Table 7.2. AFm phases are often poorly crystalline and hard to detect by XRD. Therefore the aluminium content is slightly higher than in common OPC, as this study is focussed on changes with respect to alumina-containing phases, to enable a detection of possible phase changes. The sulfate content was adjusted to a molar SO3/Al2O3 ratio of ~0.8 which represents SO3/Al2O3 ratios generally encountered in modern Portland cement compositions. The total alkali content is representative for OPC. K2SO4 was used as alkali sulfate as many cements contain typically more potassium than sodium.
Table 7.2: Chemical composition of experimentally used Portland cement analogue wt.-% CaO 68.07 SiO2 19.33 Al2O3 6.93 SO3 4.55 K2O 1.12 SO3/Al2O3weight 0.66 SO3/Al2O3molar 0.84

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A batch of C3S was prepared from an aqueous slurry of calcite (analytical grade) and amorphous silica (Aerosil 300, Degussa) in a 3:1 molar ratio yielding ~30g C3S. After 15 min homogenisation using an agate mortar, excess water was evaporated by drying at 85C. The mixture was then placed in a platinum crucible and heated to 950C in a muffle furnace for decarbonation of the CaCO3. After 1 hour the temperature was increased to 1450C for a further 6 hours. The sintered material was cooled down, ground to a fineness < 75 m and reheated to 1450C for 6-10 hours. This procedure was repeated five times. Afterwards the material was checked for purity by XRD. No significant impurities, e.g. free lime, CaO, remained. A mixture of initially 12g C3S, 3g C3A, 1g CaSO4 (anhydrite) was ground in an agate mortar to 75m. 0.34g K2SO4 were dissolved in 8.2g water (w/s=0.5). Subsequently the alkali sulfate solution was added to the powder and mixed in an agate mortar for ~4 min. Afterwards the paste was divided in small parts of ~1g which were wrapped in polyethylene-film to avoid additional CO2-contamination. The samples were stored in centrifuge tubes filled with small amounts of water to ensure 100% r.h. during hydration. Subsamples were stored at 25C, 50C and 85C and the temperature-dependent reactions were described in chapter 7.4. Similarly a limestone blended mix was prepared by using the same procedure but with addition of 2g calcite to the dry mix resulting in a molar CO2/Al2O3 ratio = 1.8. The amount of water was slightly increased to 9.2g to keep the w/s-ratio constant at 0.5. The paste was prepared as described above and subsamples were stored at 25C, 50C and 85C. Hydration was stopped after 90d by grinding the sample in acetone with subsequent vacuum filtration. In a following step the mineralogy of the dried powder, ground to < 75 m, was determined by XRD using a BRUKER D8 ADVANCE powder diffractometer as described in chapter 3.2.

Results and discussion


Fig. 7.11 shows the XRD-pattern hydrated cement paste analogues in dependence of the initial calcite addition to the mixture. The observed mineralogical changes are similar to the pure C3A pastes hydrated in the presence of sulfates and carbonates (Fig. 7.1 and Fig. 7.2). Thus in the presence of excess calcite, formation of monocarboaluminate and AFt is observed, whereas monosulfoaluminate formed in the calcite-free mixture. The observed phase assemblage after 90d of hydration is in good agreement with the calculated phase assemblage using the phase relations of Fig. 7.5; for example, in the case of calcite blending at a molar CO2/Al2O3 ratio ~1.8 and a SO3/Al2O3 ratio 0.84, the phase assemblage AFt, monocarboaluminate, calcite and portlandite is predicted and was indeed observed as shown in Fig. 7.11. In contrast to the calculations shown in Fig. 7.5, silica is present in the Portland cement analogue, leading to the formation of C-S-H. C-S-H is of constant composition with respect to its Ca/Si ratio in the presence of portlandite. Divet [54] and Barbarulo [14] reported the sorption of sulfate to C-S-H, which would influence the mass balances calculations and affect the SO3/Al2O3 ratio to be applied in Fig. 7.5. However C-S-H will contain small amounts of aluminium as well as sulfate, as shown by Richardson et al.[160]. Thus the effect of sulfate sorption on the overall SO3/Al2O3 ratio will be diminished to some extent and, according to own experimental results as well as experiments on hydrated Portland cement published by Kuzel [113][115][116], diagram Fig. 7.5 is still valid to estimate the expected mineral phase assemblage of limestone blended cements although sulfate and aluminium substitution is important and will eventually have to be considered in a quantitative hydration model.

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138

portlandite

calcite blended paste 90d portlandite

SO 4-AFt CO 3-AFm SO 4-AFt

portlandite calcite SO 4-AFt CO 3-AFm

100counts

SO 4-AFm SO 4-AFm

carbonate free paste 90d SO 4-AFm

Intensity 5

10

15

20 [2 Cuk ]

25

30

35

Fig. 7.11: XRD-pattern showing the influence of calcite addition to hydrated Portland cement analogue (mixture of C3S, C3A, CaSO4 and K2SO4, SO3/Al2O3molar=0.84, w/s=0.5) at sealed conditions stored 90d at ~25C

Likewise the hydrate phase assemblage can be estimated for the calcite-free Portland cement analogue. In agreement with Fig. 7.5, the phase boundary to form ettringite was not been crossed and therefore the expected monosulfoaluminate is indeed observed as the only main aluminate phase, except for assumed minor aluminium substitution in C-S-H, at a SO3/Al2O3 ~0.84. According to the phase diagram, Fig. 7.5, small amounts of sulfate (~16%) are replaced by hydroxide in the AFm structure. However due to prevailing analytical errors in the setup of the XRDmeasurement it is impossible to obtain definite evidence for or against this small ionic substitution. Another useful tool to assess the implications of calcite blending is represented in Fig. 7.7 and Fig. 7.8. It is possible to estimate the potentially reactive calcite content of the Portland cement analogue in dependence from its chemical composition by assuming equilibrium and 100% hydration of the solids. For the composition given in Table 7.2, SO3/Al2O3=0.84, a total reactive calcite content of ~5 wt.-% is calculated, which corresponds to ~50% of the total calcite used in the cement analogue. Thus an excess of calcite should persist. Real Portland cements contain significant amounts of iron mainly present in the ferrite-phase. The formation of iron-analogues of AFt, AFm and hydrogarnet, or related solid solutions, has been reported in the literature [169][180]. Other researchers report the formation of ferric hydroxide as main hydration product of the iron in Portland cement [180]. Thus according to the literature mixtures of all these iron-containing phases may occur in hydrated cement paste. The topic is the subject of further discussion in chapter 7.5.

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139

7.3.2 Space filling vs. engineering properties


Chapter 7.2 dealt mainly with the fundamental relations arising from limestone addition. In this section an example was chosen to show the direct impact of the previous findings on the engineering properties of limestone blended cements.

Model cement calculations


Calculations are based on automated mass balance calculations using the GEMS-PSI routine and the database in Table 4.1. The formation of siliceous hydrogarnet was suppressed in the calculations (see discussion chapter 7.5). From the amount and molar volumes of the phases, the specific volume of solids and aqueous phase are calculated. The calculations use a model cement composition consisting of initially 69 wt.-% CaO, 22 wt.-% SiO2, 4.5 wt.-% Al2O3 and 4.5 wt.-% CaSO4 (~2.6 wt.-% SO3) corresponding to 83.4 wt.-% C3S, 0.2 wt.-% C2S, ~11.9 wt.-% C3A and 4.5wt.-%CaSO4. 100 g of cement are blended with increasing quantities of calcite (CaCO3) as surrogate of limestone. Thus the initial amounts of several of the cements main chemical components (SiO2, Al2O3 and CaSO4) diminish due to dilution. The water/solid-ratio was kept constant at 0.5 by mass (including CaCO3). A hydration degree of 100% and a constant temperature of 25C were assumed. Alkalis have been omitted from the scheme, as has iron oxide, to minimise the complexity of the system and due to unknowns with respect to a complete thermodynamic dataset for the iron phases. Omitting iron introduces a systematic error but does not necessarily change the principal results of the calculation, as it is believed that much of the iron in Portland cement is present after hydration as ferric oxide - an essentially inert diluent [180].

Results and discussion


The resulting molar SO3/Al2O3 ratio of the model cement is ~0.7. This ratio is broadly representative of modern cements and expresses the qualitative changes occurring upon addition of limestone. If ratios other than 0.7 are selected, the modified calculation takes only a few minutes to complete and enables mineral balances to be quantified. Fig. 7.12 shows the mineralogical evolution and the specific volume of the solids of the hydrated model cement with increasing calcite contents at 25C. A comparison with previous calculations for C3A hydration in the presence of calcite and/or sulfate gave similar results (see Fig. 7.6 and Fig. 7.9) except for the presence of C-S-H in the hydrated model cement and the estimation of a chemical shrinkage from the specific molar volumes of the constituents of the raw mix. Since C-S-H is not explicitly involved in the reactions, it behaves as an inert diluent for the other solids. Minor sulfate and aluminium substitution in C-S-H were not considered in this example. However the amount of C-S-H will diminish due to dilution by increasing the calcite content. A true mass balance calculation, as has been presented here, is required to quantify mineralogical changes associated with the reaction of calcite and the model cement. It is obvious that mineralogical changes influence the solids volume significantly. It is important to note that the changes occurring upon calcite addition to cement do not just involve carbonate-containing phases, e.g. calcite and carboaluminates, but markedly affect the amounts of other solid phases, notably ettringite and portlandite, and of liquid: sulfate, displaced from monosulfoaluminate in the course of its conversion to carboaluminates, is incorporated into ettringite (AFt), a low-density, water-rich phase with high molar volume. This conclusion, demonstrated for one composition, is nevertheless generic for all Portland clinkers containing aluminium.

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140

100

estimated chemical shrink age maximum specific volume of solids pore solution calcite
hem icarb .

total volume [Vol.-%]

75
Ms

AFt monocarboaluminate

50

portlandite

25
C-S-H (1.6CaO.SiO 2 .2H 2 O)

10

12

14

16

18

20

22

amount of added CaCO3 [wt.-%]


Fig. 7.12: Volume changes of hydrate phases and pore solution of a hydrated model cement with fixed sulfate ratio (SO3/Al2O3~0.7) in dependence of changing carbonate contents (the influence of minor carbonate substitution in AFt is not shown).

As shown in Fig. 7.12, the resulting ettringite formation increases the molar volume of the cement solids significantly and binds liquid water. As demonstrated in Fig. 7.13, the amount of chemically bonded water strongly varies with increasing amount of calcite added to the model cement. A maximum water binding capacity is calculated to occur at a calcite content of ~2 wt.-%, which represents the point where all sulfate is displaced from AFm to form ettringite and hemicarboaluminate. Due to dilution effects the amount of excess pore solution will again increase with rising carbonate contents. However, as demonstrated in Fig. 7.13, the amount of chemically bound water can be optimised with controlled additions of calcium carbonate.

excess pore solution [wt.-%]

15.0

maximum of chemically bound water

10.0

5.0 0 2 4 6 8 10 12 14 16 18 20 22 amount of added CaCO 3 [wt.-%]

Fig. 7.13: Dependence of the amount of excess pore solution from the initial CO2/Al2O3 ratio of a hydrated model cement with fixed sulfate ratio (SO3/Al2O3=0.7;w/c = 0.5) at 25C

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Much attention has been devoted in the literature to determining the porosity of cement paste. Some nanoscale porosity is an intrinsic feature of C-S-H and cannot be eliminated. But coarser porosity is related in part to the volume of the pore fluid. This porosity is undesirable: durability with respect to penetration of aggressive agents in the service environment is impaired by increasing the coarse porosity and its connectivity. Therefore it is of interest to calculate the impact of reactive limestone on the space filling properties of cement paste. Space filling is directly linked to total specific porosity i,total which is calculated according to Eq. 7.1:

Vi , hydrates i , total = 1 Vi + VH 2O , cement

100%

(7.1)

Where Vi,hydrates is the total specific volume of the hydrates [cm3] and Vi,cement the total specific volume of the model cement [cm3] at specific calcite addition i. VH2O is the amount of added water which was left constant at 50g/100g cement (~50 cm3) at 25C. Herfort [90] has demonstrated in unpublished studies the evolution of compressive strength and porosity of a cement blended with low contents of reactive limestone. As the SO3/Al2O3 ratio in his calculations equals that of the model cement used in calculation of Fig. 7.12 (SO3/Al2O3 = 0.7). It is apparent that the calculated porosity changes of the model cement correlate very well with the measured 1 year compressive strength of mortar samples made with low-limestone blended cements (Fig. 7.14). The minimum calculated porosity and maximum compressive strength occur at about 2 wt.-% calcite. Up to about 3 wt.-% calcite is calculated to react with the model cement, with any excess behaving as an inert filler. But up to ~ 9 wt.-% calcite added to the model cement will improve the space filling properties, decreasing total porosity and increasing compressive strength relative to the cement-only benchmark.

15 relative change of porosity and compressive strength [%] compressive strength 10 5 0 -5 -10 -15 0 2 4 6 8 10 12 14 16 18 20 22 amount of CaCO 3 adde d [wt.-%]
Fig. 7.14: Comparison of relative changes of calculated porosity of model cement paste (SO3/Al2O3 ~ 0.7; w/s = 0.5) and relative changes of measured 1 year compressive strength of mortars (SO3/Al2O3 ~ 0.7, w/c = 0.5); strength data were taken from Herfort [90])
measured

increase

decrease

total porosity

calculated

The influence of limestone addition on cement hydration

142

Thus controlled limestone 4 blending shows promise to improve the physical space filling of pastes, reducing free porosity, while also decreasing the clinker content. Furthermore at least one example (Fig. 7.14) has shown that engineering properties, e.g. mechanical strength, can be optimised by limestone blending. Limestone has traditionally been regarded as inert filler and the strengthenhancement effect -if any- attributed to improved packing arising from optimised granulometric properties of the mix. However this study shows that the calcite component of limestone is reactive and that mineralogical changes have a significant impact on the space filling and related physical and mechanical properties of the hydrated matrix. Furthermore, it was shown that although only a small fraction of the total limestone is reactive ( ~ 5wt.-% depending on the cement and limestone compositions) the consequences of this chemical reaction, including the displacement of sulfate from AFm and the resulting formation of AFt, affects the performance positively at much higher levels of calcite additions than the original reactive calcite fraction. Besides the mineralogical effects discussed in this work, improved granulometric properties of the paste will contribute to an enhanced performance of limestone blended cements. Thus both physical and mineralogical aspects have to be considered to achieve optimum performance of limestone blended cement.

7.4. The role of temperature on Portland cement hydration 7.4.1 Thermally induced mineralogy changes Phase assemblages at low temperatures ~5C
Fig. 7.15 shows the stable phase assemblages in part of the system CaO-Al2O3-CaSO4-CaCO3-H2O in dependence of the initial molar sulfate and carbonate ratios at 5C. Phase assemblages I and IV are similar to the corresponding regions in the diagram for 25C, Fig. 7.5, except that an increased substitution of SO42- by 2OH- is predicted in the monosulfoaluminate phase. Whereas at 25C, SO4AFm with ~11 mol% SO4 substitution is stable in presence of ettringite, hemicarboaluminate and portlandite (see Fig. 7.5), the maximum sulfate replacement is doubled to ~22 mol% at 5C. In region II the extent of solid solution formation between monosulfoaluminate and hydroxy-AFm increased to a maximum substitution of 50 mol% SO42- by 2OH- according to the initially fixed miscibility gap boundaries described in chapter 5.3.1. In contrast to the phase relations at 25C, no C3AH6 is predicted in region III at 5C, Fig. 7.15; hydroxy-AFm is computed to be stable, coexisting with hemicarboaluminate, the limiting SO4-OH-AFm solid solution and portlandite at 5C. A comparison of both diagrams at 25C and 5C shows considerable differences in the phase assemblages due to significant changes of the AFt composition in regions IV and V. As illustrated in Fig. B.4, only minor carbonate substitution in AFt is expected at 25C. However as shown in Fig. 7.15, this substitution increases in importance with decreasing temperature: calculations based on the thermodynamic data in Table 4.1 and the SO4-CO3-AFt solid solution model derived in this study indicate the possibility of significant carbonate substitution in the AFt phase at ~5C. In dependence of the chemical composition, up to 1/3 of the original sulfate in the AFt phase may be replaced by carbonate at low temperatures under the conditions depicted in Fig. 7.15. On the other hand essentially no carbonate substitution in AFt is predicted in regions I-IV, Fig. 7.15, due to very low carbonate activities. Once the phase boundary between region IV and IVa is crossed, hemicarboaluminate becomes unstable and carbonate substitution in AFt increases due to increasing carbonate activities resulting from increasing carbonate ratios.
4 Limestone is not necessarily 100% calcium carbonate and in assessing limestone, since the active fraction is CaCO3, a correction factor may need to be applied, which can be derived from most standard analyses reporting CO2 contents

The influence of limestone addition on cement hydration

143

excess portlandite present in all assemblages

3.5

VI

AFt +gypsum + calcite

3.0

Va
AFt-ss
(Ca6 Al2 (SO 4 ) 3x (CO 3 ) 3-3x (OH) 12 26H2 O (0.66<x<1)

molar bulk SO 3/Al 2O3-ratio

2.5

+ calcite 2.0 AFt-ss (Ca6 Al2 (SO4 ) 3x (CO3 ) 3-3x (OH) 12 26H2 O)
(0.66<x<1)

1.5

I
AFt +Hc+Ms-ss
1)

+ monocarboaluminate

V
AFt-ss
(Ca 6 Al2 (SO4 )2 (CO3 )(OH)12 .26H2 O)

1.0

IV

IVa

0.5

II

+ monocarboaluminate + calcite

Ms-ss III + Hc Ms-ss + Hc+ C4AH x 0


1) 3)

2)

AFt + hemicarboaluminate+ monocarboaluminate 0.5 0.75 1 1.25 1.5

3)

0.0

0.25

molar bulk CO 2/Al2O 3-ratio


calc. composition Ca4Al2(SO4)0.78(OH)12.446H2O 2)calc. composition Ca4Al2(SO4)x(OH)14-2x6H2O (0.5 x 0.78) calc. composition Ca4Al2(SO4)0.5(OH)136H2O at 5C

Fig. 7.15: Calculated phase assemblages of a hydrated mixture consisting of C3A, portlandite and varying initial sulfate (SO3/Al2O3) and carbonate ratios (CO2/Al2O3) at 5C

Monocarboaluminate and partially carbonate substituted SO4-CO3-AFt coexist until the phase boundary between region IVa and V (at SO3/Al2O3 ratios 2 and CO2/Al2O3=1) is crossed; calcite becomes stable and now coexists with the limiting SO4-CO3-AFt solid solution (1/3 carbonate substitution) and portlandite. Monocarboaluminate becomes unstable in region Va at SO3/Al2O3 ratios >2. Under these conditions, all alumina is bound in the AFt phase and no alumina is available to form monocarboaluminate. Thus SO4-CO3-AFt with varying carbonate contents (decreasing carbonate substitution with increasing SO3/Al2O3) coexists with calcite and portlandite in region Va. As indicated by a bold line in Fig. 7.15 the phase boundaries between regions IVa and Va and IVa and V represent the division between reactive calcite and excess (filler) calcite. In regions I-IVa, to the left of the bold line, all calcite is predicted to react to form the relevant phase assemblages shown in Fig. 7.15, whereas in regions V and Va, excess calcite is present and acts as a filler. The calculations presented in Fig. 7.15 show trends rather than absolute accuracy of the predicted results. Uncertainties in the thermodynamic data have to be considered and small changes in the data can cause significant changes of the positions of the phase boundaries in Fig. 7.15. However the calculations clearly show the amount of reactive calcite to increase with decreasing temperature. There are no experiments reported in the literature which directly deal with these

The influence of limestone addition on cement hydration

144

relationships; thus the calculations are to some extent speculative and more experimental work is needed. Of course reactions depicted here may be complicated by the appearance of thaumasite, especially at lower temperatures. Fig. 7.5 and Fig. 7.15 do not contain silica and other types of calculation are therefore required to show the relationships. Thermodynamic calculations, in the presence of additional C-S-H, have indicated that the composition of the AFt solid solution does not significantly change from that shown in Fig. 7.5 and Fig. 7.15, i.e. no significant silica substitution is expected as long as carboaluminates, portlandite and calcite are present (see composition of point I in Fig. 6.22 and Fig. 6.23 and Table 6.2). However due to a lack of thermodynamic data of silica-substituted ettringite the results are tentative and have to be subject of further investigation. In portlandite saturated systems thaumasite and ettringite-thaumasite solid solutions are calculated to be incompatible with carboaluminate phases. Thus the positions of phase assemblages I-V, in which the formation of carboaluminate phases is predicted, remain essentially unchanged in the presence of C-S-H. But, ettringite-thaumasite solid solutions would become stable in regions Va and VI at higher sulfate activities and influence the existing phase assemblages as shown in Fig. 6.22 and Fig. 6.23.

Phase assemblages at elevated temperatures


The literature review has shown that elevated temperatures significantly alter the mineralogy of hydrated Portland cements. This study concentrated on the changes in the AFm-AFt chemistry with increasing temperature and in dependence of the reactive SO3/Al2O3 and CO2/Al2O3 ratio, respectively. In the first instance mineralogical changes at slightly elevated temperatures occurring in the range up to ~50C were investigated. A mineralogical map as function of sulfate and carbonate ratios at 40C, based on thermodynamic calculations using the dataset derived in this study, is shown in Fig. 7.16. A temperature increase to about 40C decreased the stability field of hemicarboaluminate significantly. A comparison with the phase assemblages at 25C showed that the maximum amount of reactive calcite is not influenced (bold line, Fig. 7.16), except that carbonate substitution in AFt becomes negligible with increasing temperatures up to 40C and the composition of the AFt phase is always close to ideal sulfate-ettringite. But, in contrast to the diagram at 25C, regions I and IV, Fig. 7.5, disappeared and three new phase assemblages, designated as regions VII, VIII and VIIIa, develop at 40C (Fig. 7.16). Regions VIII and VIIIa contain only AFm phase assemblages and up to three AFm phases may coexist at relevant sulfate and carbonate ratios in region VIII. Note that AFt is not stable in region VIII while the stability of monosulfoaluminate increases with increasing temperature. The limits of region VIIIa are strongly temperature-dependent. In agreement with Pllmann et al. [150], the hydroxy-substituted AFm solid solutions become increasingly unstable at elevated temperatures. Thus the phase boundaries between regions III and VIIIa and VII and VIIIa will shift markedly. As a consequence, the compositional extent of region III increases at 40C relative to 25C (see Fig. 7.5 for comparison), while the released hydroxide is bound in C3AH6, which coexists with a monosulfoaluminate type solid solution with minor hydroxide-substitution and hemicarboaluminate in region III at 40C.

The influence of limestone addition on cement hydration

145

excess portlandite present in all assemblages

3.5 3.0 molar bulk SO 3/Al 2O 3-ratio 2.5 2.0

AFt +gypsum + calcite

VI

VII
1.5 1.0 0.5 0.0 0
1)

V
AFt + monocarboaluminate + calcite
1)
2)

AFt + monocarboaluminate+ monosulfoaluminate


VIIIa M c+M s-ss

III
Ms-ss + Hc+ C3AH 6 0.25
3)

VIII
Mc + Hc + Ms-ss 0.5
4)

0.75

1.25

1.5

molar bulk CO 2/Al2O 3-ratio


calc. composition Ca4Al2(SO4)0.96(OH)12.08.6H2O 2)calc. composition Ca4Al2(SO4)x(OH)14-2x.6H2O (0.86 x 0.96) 3) calc. composition Ca4Al2(SO4)0.86(OH)12.28.6H2O 4)calc. composition Ca4Al2(SO4)0.9(OH)12.2.6H2O at 40C

Fig. 7.16: Calculated phase assemblages of a hydrated mixture consisting of C3A, portlandite and varying initial sulfate (SO3/Al2O3) and carbonate contents (CO2/Al2O3) at 40C

Free energy plots help to determine the temperature range over which Fig. 7.16 can be applied. Calculations (Fig. B.5 a) appendix B) show that phase assemblage VII (at SO3/Al2O3=1 and CO2/Al2O3=0.25) is metastable with respect to a mixture of hemicarboaluminate, monosulfoaluminate and AFt, corresponding to phase assemblage I, Fig. 7.5 at temperatures <~28C. On the other hand, as illustrated in Fig. B.5 b), phase assemblages containing monocarboaluminate and AFt at SO3/Al2O3 1 become metastable with respect to monosulfoaluminate and calcite at temperatures above ~50C. The upper thermal stability limit of hemicarboaluminate was previously calculated to be ~50C (see chapter 4.4.2). Consequently Fig. 7.16 can be applied over a temperature range from ~28 to ~50C; but note that the phase boundaries separating regions III and VIII and VII and VIII will shift to slightly lower or higher SO3/Al2O3 ratios in dependence of the temperature due to the changing amount of hydroxide substitution in the AFm phase. The calculations shown above indicate that significant mineralogical changes during the hydration of the aluminate phase are expected to occur at temperatures above ~50C. Fig. 7.17 shows the phase relations relevant to C3A hydration in the presence of carbonates and sulfates at 60C. The diagram is valid over a temperature range from ~50 to ~85C, the upper thermal stability limit of monocarboaluminate. No extensive solid solution formation in either AFt or AFm are expected at temperatures >50C. Thus the phase boundaries remain fixed in the respective valid temperature range between ~50 and 85C.

The influence of limestone addition on cement hydration


excess portlandite present in all assemblages

146

3.5 3.0 molar bulk SO 3/Al 2O 3-ratio 2.5 2.0 1.5 1.0 0.5 0.0 0

VI
AFt + anhydrite (gypsum) + calcite

IX
AFt + monosulfoaluminate + calcite

X
monosulfoaluminate + monocarboaluminate + C3AH 6 0.25 0.5

XI

monosulfoaluminate + monocarboaluminate + calcite

0.75

1.25

1.5

molar bulk CO 2/Al2O 3-ratio

Fig. 7.17: Calculated phase assemblages of a hydrated mixture consisting of C3A, portlandite and varying initial sulfate (SO3/Al2O3) and carbonate contents (CO2/Al2O3) at 60C

Because of its instability at >50C, hemicarboaluminate is absent at 60C, Fig. 7.17. Furthermore anhydrite will replace gypsum as the stable calcium sulfate phase at temperatures above ~50C 55C. Due to the increasing stability of monosulfoaluminate, the regions where monocarboaluminate is predicted to occur, decrease dramatically compared to lower temperatures, <50C. An important reaction is the conversion of monocarboaluminate and AFt to monosulfoaluminate and calcite with release of water according to Eq. 7.2:
50 C 2Ca4Al2 (CO3 )(OH)12 5H2O + Ca6 Al2 (SO4 )3 (OH)12 26H2O 3Ca4Al2 (SO4 )(OH)12 6H2O + 2CaCO3 + 18H2O (7.2)

monocarboaluminate

ettringite

monosulfoaluminate

+ calcite + H2O

This reaction is predicted to occur at temperatures ~50C in the direction indicated in Eq. 7.2, but is reversed at lower temperatures. As a consequence of reaction 7.2, AFt is absent at SO3/Al2O3 ratios 1 in regions X and XI -a range which can be applied to most modern OPC- at temperatures ~50C. Thus the stabilising effect of the formation of carboaluminates on AFt formation becomes insignificant at elevated temperatures ~50C due to the preferred formation of monosulfoaluminate. Thus one essential conclusion of Fig. 7.17 is that carboaluminates become increasingly unstable at elevated temperatures and that this instability cannot be viewed in isolation as it impacts on sulfoaluminates, i.e. monosulfoaluminate and ettringite, and water balances. This leads to an important second conclusion from the calculation; that the amount of reactive limestone significantly decreases in warm curing at ~50C. The boundary of reactive calcite to filler calcite is indicated by a bold line in Fig. 7.17. Compared to phase assemblages at lower temperatures, its position changes significantly to lower SO3/Al2O3 ratios. No carboaluminate will

The influence of limestone addition on cement hydration

147

form at sulfate ratios 1; instead a mixture of monosulfoaluminate, AFt, calcite and portlandite coexists in region IX independently of the carbonate content. Calcite will be consumed due to formation of monocarboaluminate in region X; sulfate is bound to monosulfoaluminate but excess C3A will react with water to form C3AH6. A third conclusion applies to heat cured hydrated cements at temperatures >50C which will be subsequently placed in a cooler service environment. Due to the reversion of Eq. 7.2, initially formed monosulfoaluminate is predicted to react with excess calcite to form monocarboaluminate and AFt upon cooling to temperatures <<50C. Thus carbonate addition, or uptake from the service environment, or both, is another factor that needs to be considered to explain phase changes in the course of delayed ettringite formation. The experimental validation of this postulated mechanism of ettringite formation is given in chapter 7.4.2 and is confirmed in the literature. Kuzel and Strohbauch [118] showed the conversion of initially formed monosulfoaluminate to AFt and carboaluminate following exposure of initially heat cured cement at 90C to carbonate-containing water at 22C. Fig. 7.18 was developed to complete the overview of reactions occurring at 1bar total pressure up to ~99C. As shown in chapter 4.4.2, monocarboaluminate is calculated to decompose to C3AH6 and calcite at temperatures > ~85C. Thus phase assemblages X and XI, Fig. 7.17, become metastable at > 85C and will be replaced by phase assemblage XII, Fig. 7.18 a), comprising monosulfoaluminate, C3AH6, calcite and portlandite. Finally at temperatures > 92C (Fig. 7.18 b)) ettringite becomes unstable with respect to monosulfoaluminate and phase assemblage XIII (monosulfoaluminate, anhydrite, calcite) which will replace the AFt-containing phase assemblages VI and IX. This temperature is lower than the previously experimentally-derived thermal stability limits for pure ettringite given by Hall et al. [87] and Glasser et al. [195] (~1155C). However in both experiments ettringite decomposed to a mixture of monosulfoaluminate and hemihydrate instead of anhydrite. An estimation of the transition temperature using free energy plots, assuming the formation of hemihydrate and monosulfoaluminate from ettringite at 1bar total pressure, is shown in Fig. B.6 (appendix B). It gives 109C which is in good agreement with the experimental values by Hall et al. [87] and Glasser et al. [195].
a) 86C - 92C
excess portlandite present

b) >92C - 99C
excess portlandite present 3.5 molar bulk SO 3 /Al2O 3 -ratio 3.0 2.5 2.0 1.5 1.0 0.5 0.0 0 monosulfoaluminate + C3AH 6 + calcite 0.5 0.75 1 1.25 1.5 monosulfoaluminate +anhydrite + calcite

3.5
molar bulk SO 3 /Al2O 3 -ratio

VI
AFt + anhydrite + calcite

3.0 2.5 2.0 1.5 1.0 0.5 0.0 0 0.25

XIII

IX
AFt + monosulfoaluminate + calcite

XII
0.5

monosulfoaluminate + C3AH 6 + calcite 0.75 1 1.25 1.5

XII
0.25

molar bulk CO 2/Al 2O 3-ratio

molar bulk CO 2/Al 2O 3-ratio

Fig. 7.18: Calculated phase assemblages of a hydrated mixture consisting of C3A, portlandite and varying initial sulfate (SO3/Al2O3) and carbonate contents (CO2/Al2O3) at 90C(left) and 99C (right)

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148

7.4.2 Space filling vs. temperature


The previous calculations led to the development of mineralogical maps, which can be used to assess mineralogical changes in hydrated Portland cements in dependence of the temperature of the service environment and cement composition expressed as sulfate and carbonate ratios. In the course of their service life, hydrated cements might undergo temperature changes, e.g. heat curing, or temperature increases in mass concrete due to heat of hydration, which can alter the mineralogical composition. As a consequence, several phase assemblages can evolve as a function of temperature. The following calculations depict two examples of the hydration of C3A in the presence of calcite, calcium sulfate and portlandite and show the evolution of the specific solid volume changes 5 arising from the previously described mineralogical changes as functions of increasing temperatures. The first example (Fig. 7.19) shows a hydrated mixture of initially C3A, calcium sulfate (SO3/Al2O3=1), calcite (CO2/Al2O3=1.25) and portlandite, where excess calcite is present at all temperatures. To enable comparability between calculations, the same conditions were used as in the previous space filling calculations shown in Fig. 7.9. The specific volume at 25C, Fig. 7.19, corresponds to that of the phase assemblage at CO2/Al2O3=1.25 in Fig. 7.9. The total amount of solids was kept constant at 3.25 mol; 0.722mol C3A were reacted with 0.722mol CaSO4, 0.9035mol CaCO3 and 0.9025mol Ca(OH)2 and 27.75mol (500g) water. Thermodynamic data of the hydrates including the molar volumes needed for space filling calculations are given in Table 4.1. Solid solutions between sulfate- and hydroxy-AFm, as well as between sulfate- and carbonate-AFt, were considered. The calculation assumes that equilibrium is reached at each temperature but does not determine the time required for equilibration.
650 600 550 500
excess aqueous phase

total volume [cm ]

450 400 350 300 250 200 150 100 50 0 0 10 20 30 40 50 60 70 80 90 100


1)increasing

portlandite
1)

AFt-ss

CO3 substitution at low temperatures

monosulfoaluminate
calcite

monocarboaluminate

temperature [ C]
Fig. 7.19: Influence of temperature on specific volume changes of hydrate phases of a hydrated model mixture consisting of C3A, portlandite, CaSO4 and CaCO3 ; fixed sulfate ratio (SO3/Al2O3=1) and carbonate ratio (CO2/Al2O3 =1.25) (constant total amount of solids, C3A+CaSO4+CH+Cc = 3.25 mol, reacted with 500 g water).
5

No correction has been applied for the thermal dilational coefficients of the constituent phases but it is believed that the correction is negligible relative to volume changes resulting from phase transformations.

The influence of limestone addition on cement hydration

149

Fig. 7.19 shows that the total specific volume of the hydrated mixture is strongly temperaturedependent. The calculation reveals that there is a general tendency to increase the specific solid volumes with decreasing temperature. Portlandite is not directly involved in any of the reactions shown in Fig. 7.19, so its amount and specific volume remain constant. An important feature of the calculations is the phase transition: AFt + monocarboaluminate monosulfoaluminate + calcite at ~50C (Eq. 7.2). Due to this reaction the specific solid volume is significantly reduced. Assuming that the external geometry of the solid is constant, the total porosity of the hydrated mixture would be significantly increased due to the lower amount of chemically bound water and the resulting higher specific density of monosulfoaluminate and calcite compared to ettringite. On the other hand, as discussed in the previous chapter, the direction of reaction 7.2 is reversed for cements initially cured at temperatures 50C and subsequently stored at lower temperatures. Thus the transition monosulfoaluminate + calcite AFt + monocarboaluminate increases the specific solid volume significantly: consequently the presence of calcite or CO2 uptake and the resulting temperature-dependent phase transformation can be an important factor, amongst others, to explain expansive processes in the course of delayed ettringite formation. The local availability of water may be another potentially rate limiting factor. But the calculations present a new explanation of the occurrence of monosulfoaluminate at high temperatures and its transformation to ettringite at low temperatures. It should be noted that these results cannot be directly applied to predict destructive expansive processes, due to their dependence on the thermodynamics of crystal growth in porous materials [64][167], including the degree of local supersaturation, available pore space and maximum amount of ettringite formed; the V (change of volume) calculations in Fig. 7.19 are best described as a potential for expansion. Also, that in commercial cements, this potential will be diluted by the presence of C-S-H. The calculation of phase assemblages in the previous chapter has shown that there is a tendency for extensive carbonate substitution for sulfate in AFt at low temperatures. As shown in Fig. 7.19, another important conclusion from the calculations is that if carbonate substitution in AFt occurs, it will significantly increase the total specific solid volume, especially at temperatures 10C. The maximum amount of AFt will increase at the expense of monocarboaluminate and calcite, which act as additional alumina and carbonate sources (Fig. 7.19). Molar volumes are needed in order to calculate specific volume changes of the solid solutions. In the calculations the molar volume of the AFt and AFm solid solutions is estimated from the known molar volumes of the end members and their stoichiometric fractions in the solid solutions.
molar solid CO 3 /(SO 4+CO 3) in AFt 0.50 0.40 0.30 0.20 0.10 0.00 0 10 20 30 40 temperature [C] 50

Fig. 7.20: Calculated maximum amount of carbonate substitution in AFt as a function of 60 temperature; excess calcite, monocarboaluminate and portlandite present

The influence of limestone addition on cement hydration

150

Fig. 7.20 shows that the calculated maximum possible carbonate substitution in AFt increases rapidly to ~50 mol%, corresponding to a molar CO3/(SO4+CO3) ratio = 0.5 at 0C. Thus extensive carbonate substitution in AFt is most likely to occur at temperatures ~1-10C, but only if the carbonate activities are buffered by the presence of excess calcite while the pH is buffered by portlandite; monocarboaluminate acts as additional aluminate and carbonate source. The second example, Fig. 7.21, shows a hydrated mixture of C3A, calcium sulfate, calcite and portlandite with a low carbonate content (CO2/Al2O3=0.33); 0.907 mol C3A were reacted with 0.907 mol CaSO4, 0.30225 mol CaCO3 and 1.13375 mol Ca(OH)2 and 27.75 mol (500g) water. The phase assemblage at 25C corresponds to that of the calculated maximum specific solid volume shown in Fig. 7.9, and represents the point in Fig. 7.9 where all sulfate has been displaced from monosulfoaluminate, now converted to ettringite and hemicarboaluminate by calcite addition. Calcite is therefore totally consumed at 25C and only occurs at 50C. As shown in Fig. 7.21, the total specific volume decreases stepwise with rising temperatures. The first step occurs at ~28C and leads to the conversion of hemicarboaluminate and part of the ettringite to monosulfoaluminate and monocarboaluminate according to Eq. 7.3:
28 C Ca4 Al2 (CO3 )0.5 (OH)13 5.5H2O + 0.25Ca6Al2 (SO4 )3 (OH)12 26H2O 0.5Ca4Al2 (CO3 )(OH)12 5H2O +

0.75Ca4Al2 (SO4 )(OH)12 6H2O + 0.5Ca(OH)2 + 5H2O

(7.3)

hemicarboaluminate

ettringite

monocarb. + monosulf. + portlandite + H2O

Due to reaction 7.3, not only monosulfoaluminate but also the amount of portlandite increases and water is released by partial conversion of ettringite to monosulfoaluminate. As a consequence, the total specific solid volume decreases at temperatures 28C. However calcite remains reactive but is bound in monocarboaluminate instead of in hemicarboaluminate.

650 600 550 500 450 400 350 300 250 200 150 100 50 0 0 10 20 30 40 50 60 70 80 90 100
hemicarboaluminate
2) 1)

excess aqueous phase

total volume [cm ]

portlandite

AFt

1)

ideal composition as SO4 -AFt

monocarboaluminate

monosulfoaluminate

2)

minor hydroxide at <50C possible

calcite

temperature [ C]
Fig. 7.21: Influence of temperature on specific volume changes of hydrate phases of a hydrated model mixture consisting of C3A, portlandite, CaSO4 and CaCO3 ; fixed sulfate ratio (SO3/Al2O3=1) and carbonate ratio (CO2/Al2O3 =0.33) (constant total amount of solids, C3A+CaSO4+CH+Cc = 3.25 mol, reacted with 500 g water)

The influence of limestone addition on cement hydration

151

The second stepwise volume decrease is calculated to occur at 50C. At and above 50C, monocarboaluminate and AFt become unstable and react to form monosulfoaluminate and calcite according to Eq. 7.2. Due to the release of water and the formation of denser monosulfoaluminate and calcite, the specific volume of solids decreases significantly at 50C. In contrast to Fig. 7.19, the amount and specific volume of AFt remains constant at low temperatures, 28C, in Fig. 7.21. Calcite is absent under the conditions depicted to calculate Fig. 7.21. Therefore the activity of carbonate is too low to sufficiently stabilise carbonate substituted ettringite at low temperatures. Hence AFt approaches its ideal sulfate-AFt composition under the conditions applied to construct Fig. 7.21.

7.4.3 Experimental verification of thermally induced phase changes


The previous chapters have shown that temperature has a major influence on the reactions of the aluminate phase in Portland cement in the presence of carbonate and/or sulfate. Reaction 7.2 and the phase transition AFt + monocarboaluminate monosulfoaluminate + calcite are especially important to heat cured systems. Until recently, there was insufficient evidence of this reaction and its reversibility in the literature. However, Lothenbach et al. [124] investigated the hydration of calcite blended cements and showed that monosulfoaluminate appeared at the expense of monocarboaluminate and ettringite at ~50C. Later calculations based on the dataset derived in this study confirmed the experimental observations. Kuzel and Strohbauch [118] realised the influence of carbonate and its role in converting initially-formed monosulfoaluminate in heat cured cements to AFt and monocarboaluminate. However they investigated only the influence of atmospheric carbonation 6 on the phase assemblages, by storing the heat cured samples in water in contact with air. Thus leaching and carbonation occurred simultaneously, which can significantly influence the mechanism of ettringite formation. But Kuzel and Strohbauch suggested that the transition temperature between AFt monosulfoaluminate is at ~80+10C which is well above the value calculated in this study (~50C). Therefore the following experiments were set up to assess the previous calculations and to show their applicability to commercial cements.

Hydration of C3A
The experiment is explained in chapter 7.2.1. Two test cases were evaluated: (i) hydration of a 1:1:2 molar mixture of C3A:CaSO4:CaO and (ii) of a 1:1:1:2 molar mixture of C3A:CaSO4:CaCO3:CaO at 50C and 85C. The water/solid-ratio was kept constant at 5 in all experiments. In contrast to the experiments at 25C, PTFE bottles were used to store the samples. Freshly boiled ultra pure water previously heated to 50C and ~85C was added to the solids, which were subsequently sealed and stored at 50C and 85C. Mixing and transfer were done under N2-atmosphere to prevent CO2 contamination. To assess the kinetic pathways of hydration, mineralogical changes in the samples were monitored qualitatively by XRD at selected intervals over 90d. Sample preparation and setup for XRD measurements are described in sections 7.2.1 and 3.2, respectively.

As noted previously, adding CaCO3 contributes calcium and carbonate, while atmospheric carbonation adds CO2 but not calcium. Hence the two types of carbonation reactions differ in detail.

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SO4 -AFm SO4 -AFm


(n H2O<12)

portlandite

portlandite portlandite SO4 -AFm

SO4 -AFm

85C

100counts

50C

Intensity

SO4 -AFt

SO4 -AFt

25C
20 25 30 35

10

15

[2 Cuk ] Fig. 7.22: XRD-pattern showing the influence of temperature on phase assemblages after 90d hydration of a 1:1:2 molar mixture of C3A, CaSO4 and CaO (w/s = 5) at 25C, 50C and 85C

Fig. 7.22 shows the XRD-pattern of the hydrated carbonate-free C3A mixtures in dependence of their curing temperature after 90d. The solid phase assemblages are essentially independent of curing temperature over this range: C3A reacts fully and monosulfoaluminate coexists with portlandite, in agreement with calculations. Only at 25C does a small amount of ettringite persist. At 85C two AFm phases were detected. The origin of this second set of reflections attributed to AFm is not clear. One possibility is the formation of hemicarboaluminate as an artefact during sample preparation. If one excludes CO2-contamination during sampling it is possible that the reflections belong to SO4-AFm with a lower water content, whereas the 12H2O SO4-AFm was detected in all other measurements. A similar peak appeared in the same sample at 28d (see Fig. B.9, appendix B). Fig. 7.23 summarises the kinetics during C3A hydration in the presence of sulfate at 50C and 85C up to 90d. While a quantitative analysis was not possible, coexisting phase assemblages were determined with increasing hydration time. Fig. 7.23 was derived from the related XRD-patterns (Fig. B.8 and Fig. B.9, appendix B) of dried powder samples after hydration was stopped at several points in time. Compared to the 25C sample, Fig. 7.3 a), increasing temperatures lead to an acceleration of hydration. At 25C, C3A and anhydrite were present until 7d, whereas at 50C anhydrite was found until 26h and C3A until 48h, respectively. At 85C anhydrite and C3A were present until 26h. Ettringite was initially detected at 25C and 50C but converted to monosulfoaluminate with time. Monosulfoaluminate dominated the pattern at 85C. It could be detected after 1h of hydration at 85C, whereas it formed more slowly, and only in the absence of excess calcium sulfate, after 26h at 50C and only after 28d at 25C. Hence increasing temperatures favour the development of monosulfoaluminate.

The influence of limestone addition on cement hydration


a) 50C
presence of phase (XRD-pattern) C3AH 6 p ortlandite monosulfoaluminate SO 4-AFt anhy drite C 3A anhy drite C 3A

153

b) 85C
C3AH 6 p ortlandite monosulfoaluminate

1h

18h

26h

48h

7d

14d

28d

90d 1h

18h

26h

48h

7d

14d

28d

90d

reaction time

reaction time

Fig. 7.23: Comparison of qualitative time-dependent mineralogical changes during hydration of a 1:1:2 molar mixture of C3A, CaSO4 and CaO (w/s = 5) at 50C (left) and 85C (right) (dashed lines indicate the detection of only weak intensities in the XRD-pattern)

Small amounts of C3AH6 were present until 18h of hydration at 85C and until 28d at 50C, Fig. 7.23, whereas no C3AH6 was detected at 25C, Fig. 7.3. C3AH6 was generally absent in the aged samples at 90d independently from the curing temperature. The instability of C3AH6 under these conditions also provides confirmation of the calculations, although its appearance as a transitory phase must arise as a consequence of kinetics. In the sample at 85C, additional reflections in the XRD-pattern at 28d and 90d occurred, which apparently belonged to a second AFm phase. The reflections are believed to belong to an SO4-AFm with a lower hydration state than the usually detected 12H2O hydrate. Hydration of the samples was stopped by flushing the samples with acetone followed by subsequent XRD-analysis. Thus the relative humidity used to dry the samples was not well defined. Thus it is possible that the additional peaks are artefacts due to aggressive drying in the course of sample preparation. The hydration of C3A in the presence of sulfate (SO3/Al2O3=1) and calcite (CO2/Al2O3=1) is shown in Fig. 7.24. Whereas the patterns obtained from the samples stored at 50C and 85C are almost identical, the 25C pattern differs significantly. In agreement with previous calculations, calcite enhances AFt due to the formation of monocarboaluminate at 25C. Thus monosulfoaluminate is not present at 25C. However at 50C, both AFt and monocarboaluminate are absent while monosulfoaluminate forms and calcite is apparently not involved in the hydration reactions, as previously predicted. A temperature increase to 85C did not cause any further mineralogical changes relative to 50C. These experiments proved that increasing temperatures cause significant changes in the mineralogy of C3A hydration products in the presence of calcium sulfate and excess calcite. The experiments show that the transition temperature for formation of (AFt+monocarboaluminate) or (monosulfoaluminate+calcite) is in the range between 25C and 50C. The previous calculations in chapter 7.4.1 have shown that the conversion occurs at temperatures close to 50C (see free energy plot Fig. B.5), which is in good agreement with the experimental results, as well as with observations on Portland cement [124].

The influence of limestone addition on cement hydration

154

SO4 -AFm
p ortlandite

calcite p ortlandite p ortlandite SO4 -AFm

SO4 -AFm

85C

100counts

50C
SO4 -AFt Mc SO4 -AFt SO4 -AFt Mc SO4 -AFt

Intensity

25C
5 10 15 20 25 30 35 [2 Cuk ]

Fig. 7.24: XRD-pattern showing the influence of temperature on phase assemblages after 90d hydration of a 1:1:1:2 molar mixture of C3A, CaSO4, CaCO3 and CaO (w/s = 5) at 25C, 50C and 85C (Mc - monocarboaluminate)

A qualitative assessment of the kinetics of C3A hydration in the presence of calcium sulfate and calcite at 50C and 85C is given in Fig. 7.25. The diagrams show the phase development in the time-dependent XRD-patterns, Fig. B.10 and Fig. B.11 (appendix B). As in the carbonate-free samples, an increase of temperature accelerates the progress of hydration of C3A. At 50C and 85C both anhydrite and C3A were fully consumed after ~48h of hydration, respectively, whereas the same process took ~14d at 25C (see Fig. 7.3 b)).
a) 50C
presence of phases (XRD pattern) calcite portlandite monosulfoaluminate SO 4-AFt anhydrite C 3A
SO 4-AFt anhydrite C 3A

b) 85C
calcite portlandite monosulfoaluminate

1h

18h

26h

48h

7d

14d

28d

90d 1h

18h

26h

48h

7d

14d

28d

90d

reaction time

reaction time

Fig. 7.25: Qualitative comparison of time-dependent mineralogical changes during hydration of a 1:1:1:2 molar mixture of C3A, CaSO4, CaCO3 and CaO (w/s = 5) at 50C (left) and 85C (right) (dashed lines indicate the detection of only weak intensities in the XRD-pattern)

The influence of limestone addition on cement hydration

155

As indicated in Fig. 7.25 a), ettringite was observed at 50C due to the initial reactions of C3A with calcium sulfate. At 50C ettringite persisted until ~ 7d, although the strong decrease of the intensity of the ettringite reflections in the XRD-pattern suggested that most ettringite was being converted to monosulfoaluminate by ongoing reaction with C3A after 48h. No significant phase changes occurred after 48h, except that the remaining small amounts of ettringite were converted to monosulfoaluminate. C3AH6 was not observed at either temperature. At 85C, Fig. 7.25 b), a similar behaviour was found. Considerable amounts of ettringite formed after 18h of hydration. Due to subsequent reaction with C3A most of this ettringite was converted to monosulfoaluminate after 48h. The formation of an AFm phase, presumably monosulfoaluminate, was detected after 18h of hydration at 85C. The initial AFm XRDreflections are very diffuse, as shown in Fig. B.11, which indicates strong disorder and/or small particle size. The intensities of its reflections increased with increasing reaction time until by 48h the typical monosulfoaluminate signals appeared in the XRD-pattern of the sample stored at 85C. No significant phase changes occurred between 48h and 90d of hydration at 85C, which suggests that the main hydration reactions were finished after 48h.

Applicability to Portland cement hydration


In the next step the influence of temperature (25, 50 and 85C) and of calcite addition to Portland cement was simulated by using the same Portland cement analogue composition (w/s=0.5) as used in chapter 7.3.1, Table 7.2. Thus, compared to the previous pure C3A investigations, additional alkalis and C3S were present at the onset of hydration, to show their influence on the phase transformation. Interest was focussed on the formation of siliceous hydrogarnet and the influence of C-S-H on the solid phase assemblages, including the expected sorption of sulfate in the presence of alkalis; experimental details including sample preparation and storage conditions are given in chapter 7.3.1.
p ortlandite portlandite

SO4 -AFm

sil. HG

SO4 -AFm

p ortlandite

SO4 -AFm

85C

20counts

50C

Intensity

25C
5 10 15 20 25 30 35

[2 Cuk ] Fig. 7.26: XRD-pattern showing the influence of temperature on phase assemblages after 90d hydration of a Portland cement analogue composition (w/c = 0.5) at 25C, 50C and 85C

The influence of limestone addition on cement hydration

156

Fig. 7.26 shows the influence of temperature on the mineralogy of a hydrated Portland cement model composition (Table 7.2). As in the C3A samples, monosulfoaluminate and portlandite are the predominant crystalline phases in the XRD-pattern. No significant amounts of remaining clinker phases (C3A or C3S) could be detected which suggests that hydration is close to completion after 90d. Thus, while not detectable by XRD, considerable amounts of C-S-H are present. Siliceous hydrogarnet is absent at 25C but was observed at 50C and 85C. It is interesting to note that the reflections of AFm decreased in intensity with increasing cure temperature. If similar systematic errors apply to all samples and a similar degree of crystallinity is assumed, these observations indicate decreasing amounts of AFm with increasing temperatures, which is consistent with the observation that part of the alumina becomes bound in a hydrogarnet-type phase; it is likely that part of the sulfate is either bound in hydrogarnet as suggested by Paul and Glasser [144] or sorbed by C-S-H, or both. The number of time-dependent XRD measurements was relatively few, so it is not appropriate to give a graphical representation as was done for the C3A experiments, but the XRD-patterns, Fig. B.12 - Fig. B.14, give a qualitative view of the hydration kinetics at the relevant temperature. As expected, comparison of the XRD-patterns shows that increasing temperatures accelerate the hydration significantly. While reaction proceeds very slowly at 25C and considerable amounts of C3A and C3S were still present after 28d, at both 50C and 85C, most clinker reacted after 7d of hydration. Ettringite was present until 28d of hydration, before it was converted due to reaction with the remaining C3A to monosulfoaluminate after 90d at 25C. At 50C, ettringite was found at relatively early stages of hydration in the 1 and 2d samples but was fully converted to monosulfoaluminate after 7d of hydration. Ettringite was absent at 85C; monosulfoaluminate was detected instead after 24h of hydration. However the intensities of the monosulfoaluminate peaks in the XRD-pattern of the 85C samples were always lower compared to the 50C samples. Siliceous hydrogarnet was invariably absent in the hydrated Portland cement analogue at 25C. Traces of siliceous hydrogarnet were found in some samples at 50C but at 85C siliceous hydrogarnet forms progressively between 2d and 90d of hydration, as shown in Fig. B.14. This is again in agreement with the comparatively low intensity of the reflections of monosulfoaluminate at 85C. In a second set of experiments the influence of calcite on the hydration of Portland cement paste at 25, 50 and 85C was investigated. The CO2/Al2O3 ratio was set to 1.8. Thus, as demonstrated by previous calculations (see chapter 7.2.2 and 7.4.1) excess calcite should be present at all hydration times. The related XRD-patterns after 90d of hydration are shown in Fig. 7.27. The results are similar to the investigations of C3A in the presence of sulfate and calcite (Fig. 7.24): ettringite, monocarboaluminate and portlandite dominate the pattern at 25C, while monosulfoaluminate, portlandite and calcite are predominant at 50C and 85C. In agreement with the carbonate-free sample (Fig. 7.26), weak reflections of siliceous hydrogarnet are found at 85C, but are absent at 25C and 50C. The intensities of the reflections of monosulfoaluminate at 85C are lower than at 50C.

The influence of limestone addition on cement hydration


calcite portlandite

157

p ortlandite

SO4 -AFm

sil. HG

SO4 -AFm

p ortlandite

SO4 -AFm

85C

20counts

50C
SO4 -AFt Mc SO4 -AFt SO4 -AFt Mc SO4 -AFt

Intensity

25C
10 15 20 25 30 35 [2 Cuk ]

Fig. 7.27: XRD-pattern showing the influence of temperature on phase assemblages after 90d hydration of a Portland cement analogue blended with limestone (w/c = 0.5) at 25C, 50C and 85C (sil. HG - siliceous hydrogarnet)

The absence of the reflections of the clinker phases in all samples indicates that hydration approached completion after 90d and implies the presence of C-S-H as a result of C3S hydration. The intensities of the main calcite reflections are lower at 25C compared to 50 and 85C, which shows that significant amounts of calcite are reactive and are bound as monocarboaluminate at 25C, while calcite behaves much more as an inert filler at 50C and 85C. Additional XRDpattern obtained to assess the qualitative kinetics of hydration of the cement analogue composition are given in appendix B (Figs. B15 - B17). An AFm phase(s) with broadened reflections was observed at 50C after 24h (Fig. B.16). The composition of the AFm phase could not be derived from the pattern. It is possible that the pattern arises from a lower hydration state of monosulfoaluminate (nH2O < 12); but the diagnostic peak overlaps the hemicarboaluminate reflections (which is, however, not believed to be stable at ~50). Another possibility is, that the formation of hemicarboaluminate occurred during cooling. Likewise at 85C (Fig. B.17) a very broad diffuse pattern of a presumably sulfate-containing AFm phase was observed after 24h of hydration of the calcite blended cement analogue. After 48h of hydration this reflection becomes sharper and the typical signals of the 12 H2O SO4-AFm were observed, however with lower intensities than in the 50C sample. Similarly as in the carbonate free sample the intensities of the monosulfoaluminate reflections decreased with increasing reaction time at 85C; weak reflections of siliceous hydrogarnet were detected in the 85C samples between 2 to 90d of hydration. Thus it is possible that initially-formed monosulfoaluminate will decompose to siliceous hydrogarnet with time. The experiments have shown that the results of the previous calculations are applicable to commercial Portland cements. The presence of calcite, even in small amounts, strongly influences the sulfate distribution in Portland cements. The amount of calcite capable of reacting with cement decreases with rising temperatures in the range 25C - 85C. This has consequences for the constitution of the phase assemblages. As theoretically calculated, and as experimentally observed,

The influence of limestone addition on cement hydration

158

monocarboaluminate and AFt are the predominant aluminate phases in calcite blended cements at 25C, which is in accordance with numerous literature studies, e.g. [113]. But, in agreement with computations, monosulfoaluminate becomes predominant at curing temperatures 50C. Thus under conditions likely to occur in commercial cement pastes (SO3/Al2O3,molar 1) hydrated in warm conditions, ettringite and monocarboaluminate will be absent at temperatures 50C. On the other hand, previous calculations have shown that monosulfoaluminate and carboaluminates are metastable with respect to siliceous hydrogarnet if excess C-S-H is present. Experiments have shown that the formation of siliceous hydrogarnet must be kinetically restrained at 50C. However at 85C weak reflections of siliceous hydrogarnet were found in all samples. The experiments indicate that siliceous hydrogarnet forms slowly at the expense of monosulfoaluminate at 85C (see discussion, chapter 7.5.1).

Phase transformations upon cooling of heat cured paste


Calculation and experiments show that elevated temperatures cause significant changes to the mineralogy of calcite blended cements. Heat curing is a common technique to accelerate the hydration of precast concrete elements. However problems have been reported due to destructive delayed ettringite formation (DEF) in samples cured above ~70C. These observations have been subject of numerous investigations; e.g. Taylor et al. [182], give an excellent overview about possible reaction mechanisms causing destructive DEF. Because most of the reported experience relates to nominally carbonate-free cements, the impact of carbonate on DEF has not been assessed. But to evaluate possible changes in the paste mineralogy arising from calcite additions of initially heat cured cements subsequently placed at lower service temperatures, the following experiments were done: The same experimental protocol applies as for previous investigations using the cement analogues (see chapter 7.3.1). However in contrast to previous investigations, selected samples of the heat cured, carbonate-free and calcite-containing cement analogues were removed after 24h storage at 85C and subsequently stored at 5C. Phase changes were monitored by XRD at selected time intervals. The non-isothermal treatment implies a complex reaction mechanism could occur. To assess the experimental results one has to consider that: i) Hydration is incomplete during the brief heat treatment; anhydrous solids e.g. clinker are still present and continue to react at 5C ii) The applied temperature change can cause a reconstitution of the initial phase assemblage due to reactions amongst the initially formed phases and/or possible interactions with the unreacted anhydrous phases. Fig. 7.28 shows the XRD-pattern of the hydrated carbonate-free cement analogue composition after 24h of curing at 85C and subsequent 180d storage at 5C. Monosulfoaluminate is observed as the only sulfoaluminate phase in both patterns, beside portlandite and traces of clinker. After 24h at 85C monosulfoaluminate formed, but unreacted C3S and C3A were still present. Anhydrite was absent. No AFt formation was observed upon prolonged ageing for 180d at 5C. Indeed the intensities of the monosulfoaluminate reflections increase slightly, which is consistent with the disappearance of the C3A reflections after 180d at 5C.

The influence of limestone addition on cement hydration

159

p ortlandite p ortlandite

SO4 -AFm
SO4 -

SO4 -AFm

p ortlandite

AFm C-S-H?

20counts

180d 5C
C3 A C3 S

Intensity

24h 85C 5 10 15 20 25 30 35 [2 Cuk ]

Fig. 7.28: XRD-pattern showing the phase assemblages of carbonate-free Portland cement analogue (w/c = 0.5) after 24h heat curing at 85C and subsequent storage at 5C for 180 d. An arrow shows the sequential course of reaction

Fig. 7.29 shows the phase assemblages of hydrated calcite blended cement after 24h heat curing at 85C and subsequent 180d storage at 5C. As in the carbonate-free composition, no AFt was present after 24h heat curing at 85C; broad reflections of an AFm phase, presumably a monosulfoaluminate-type phase, occurred instead. After 60d of hydration at 5C, typical reflections of monosulfoaluminate were observed beside traces of ettringite. However, in contrast to the carbonate-free paste, and as expected from the previous calculations, monosulfoaluminate was apparently not stable in contact with calcite and fully converted to AFt and monocarboaluminate after 180d at 5C. The significant intensity decrease of the calcite reflections supports these observations.
p ortlandite Calcite p ortlandite

SO4 -AFt CO3 -AFm SO4 -AFt

SO4 -AFt CO3 -AFm p ortlandite

180d 5C
SO4 -AFm SO4 -AFt
20counts

SO4 -AFm SO4 -AFt

SO4 -

C3 S

AFm

60d 5C
(SO4 )-AFm

Intensity

(SO4 )-AFm

C3 A

48h 85C 5 10 15 20 25 30 35

[2 Cuk ] Fig. 7.29: XRD-pattern showing the phase assemblages of a calcite blended Portland cement analogue (w/c = 0.5) after 24h heat curing at 85C and subsequent storage at 5C for 180d. Arrows show the sequential course of reaction.

The influence of limestone addition on cement hydration

160

The experiments show that hydrated cements rapidly adjust their mineralogy as a function of their initial chemical composition and service temperature. Even allowing for only partial hydration in the initial 24h heat treatment at 85C, the observed mineralogical changes agree generally well with the previously predicted phase relations. The approach to 5C equilibrium demonstrates that most temperature-dependent mineralogy changes are reversible and occur within days or weeks.

7.4.4 Summary
To summarise the findings of experiments and calculations, it was shown that temperaturedependent phase transformations significantly influence the mineralogy of calcite blended cements. Focussed experiments generally agree with the calculations and experiments reported in the literature [118][124]: monosulfoaluminate becomes increasingly stable while carboaluminates become unstable at temperatures 50C. It was shown that carbonate apparently has an important influence on the conversion process of monosulfoaluminate to ettringite in initially heat cured cements, which are subsequently exposed to low temperatures <<50C. Thus warm cure results in precipitation of monosulfoaluminate and calcite at elevated temperatures 50C but with resorption of calcite and formation of carboaluminates and AFt in the course of cooling, or at some time thereafter. As very small amounts of carbonate are sufficient to trigger these reactions, it is believed that they are of importance to real cementitious systems even in nominally carbonatefree cements. While several investigations showed the importance of factors like sorption of sulfate to C-S-H in dependence of the alkali content, maximum amounts of ettringite in dependence of a pessimum SO3/Al2O3 ratio, etc. (see [182]), it is apparent that these factors may not be the only reasons which need to be considered to explain DEF. The lower temperature range is also important; predictions of the stable phases (amount, composition) differ depending on the choice of lower temperature, 5C or 25C. The influence of temperature on the related specific volume distribution of the solids was calculated. It was found that high temperatures lead generally to a decrease of the total specific volume of the calcium-aluminate phases present in calcite blended cementitious systems mainly by conversion of bound water to free water. The transition temperatures are affected by unavoidable analytical errors in the process of the database development. Therefore it is suggested that the transition temperatures given be regarded as provisional values, at which temperature the relevant reaction becomes likely, not as numerical values which are absolutely fixed. Furthermore the calculations indicate that in the presence of calcite, extensive carbonate substitution in AFt is likely at low temperatures. As a consequence the amount of AFt increases and leads to an increase of the total specific volume of the system. The calculations indicate that this process applies mainly to cements cured at or exposed to temperatures 10C. So far the calculated reactions are not supported by experiments. Thus more experimental evidence is desirable, particularly as the microstructural changes arising as a consequence of reaction cannot be predicted.

The influence of limestone addition on cement hydration

161

7.5. Discussion 7.5.1 Limitations of the methodology and of the database


The influence of carbonate, sulfate and aluminium and of the resulting sulfate and carbonate ratios on the phase assemblages of hydrated Portland cements, have been extensively investigated by calculations as well as by focussed experiments. They are realistic in terms of (i) assuming an excess of Ca(OH)2 to be present and allowing portlandite to react as required and (ii) allowing phase relations to be depicted as functions of SO3/Al2O3 and CO2/Al2O3 ratios of the reactive fractions. Note that the definition of the reactive fraction is subject to uncertainties: corrections, some of which involves the fraction of clinker minerals reacted at a given time, and hence the availability of alumina, carbonate, etc., for reaction as well, as corrections for sorbed species, such as sulfate in C-S-H (see chapter 7.5.2). The previous calculations were initially done for the system CaO-Al2O3-CaSO4-CaCO3. However in commercial cementitious systems at least three more components have to be taken into account i) silica, ii) iron oxide and iii) alkalis. Nevertheless own experiments reported here and practical experiences by Kuzel et al. [113][115][116] have shown that the results can be applied to hydrated Portland cements.

Formation of siliceous hydrogarnet


While silica is mainly bound to C-S-H, which is inert with respect to reactions with calcite, and of constant composition, except for minor sulfate and aluminium substitution, as discussed above, the possibility of siliceous hydrogarnet formation and related phase assemblages has to be considered. Fig. 7.30 shows the predicted phase assemblages as a function of sulfate and carbonate ratios, analogous to previous calculations, but the formation of siliceous hydrogarnet has not been suppressed in the presence of C-S-H and portlandite. Fig. 7.30 a) shows the phase assemblages relevant to lower temperatures ~35C, while Fig. 7.30 b) is constructed for temperatures between 35C to ~65C. As the main focus is on the formation of siliceous hydrogarnet, AFt and thaumasite were regarded as single phases in the calculations to avoid complex phase relations including solid solution formation. According to the calculations in the presence of a silica source, e.g. C-S-H, monosulfoaluminate and both carboaluminates (hemi- and mono-) are generally metastable with respect to siliceous hydrogarnet, Ca3Al2(SiO4)0.8(OH)8.8 - one member of the Ca3Al2(SiO4)3-x(OH)4x solid solution series which is currently implemented in the database. Siliceous hydrogarnet is predicted to be stable over a wide range of SO3/Al2O3 and CO2/Al2O3 ratios at various temperatures, as shown in Fig. 7.30. At low temperatures, up to 35C (Fig. 7.30 a)) siliceous hydrogarnet would be accompanied by the formation of ettringite and/or thaumasite and ettringite, or solid solutions between both, in regions 1, 2 and 3. But, thaumasite becomes increasingly unstable at temperatures > 35C (Fig. 7.30 b)). Thus phase assemblage 5 (AFt, siliceous hydrogarnet, calcite and C-S-H) dominates the cement relevant range of SO3/Al2O3 and CO2/Al2O3 ratios. At temperatures >~65C (Fig. 7.30 c)) AFt, thaumasite and gypsum are not stable and phase assemblages 1, 4 and 5 are instead replaced by assemblage 6 comprising a mixture of siliceous hydrogarnet, anhydrite, calcite, portlandite and C-S-H, as appropriate.

The influence of limestone addition on cement hydration


a) ~1-35C
excess portlandite and C-S-H (Ca/Si~1.6) present 3.5 molar bulk SO 3 /Al2O 3 -ratio 3.0 2.5 2.0 1.5 1.0 0.5 0.0 0 0.25 0.5 0.75 1 1.25 1.5 molar bulk CO 2/Al 2O 3-ratio

162

b)~35-65C
excess portlandite and C-S-H (Ca/Si~1.6) present 3.5 molar bulk SO 3 /Al2O 3 -ratio 3.0 2.5 2.0 1.5 1.0 0.5 0.0 0 0.25 0.5 0.75 1 1.25 1.5 molar bulk CO 2/Al 2O 3-ratio

AFt+Th. +gypsum

AFt+Th +gypsum

AFt+Th +calcite

2
AFt+Thaumasite + sil. hydrogarnet (C3 AS0.8 H4.4 )

5
AFt+ sil. hydrogarnet (C3 AS0.8 H4.4 ) + +calcite

3
Thaumasite +sil. hydrogarnet (C3 AS0.8 H4.4 )+ calcite

c) ~66 - 99C
excess portlandite and C-S-H (Ca/Si~1.6) present 3.5 molar bulk SO 3 /Al2O 3 -ratio 3.0 2.5 2.0 1.5 1.0 0.5 0.0 0 0.25 0.5 0.75 1 1.25 1.5 molar bulk CO 2/Al 2O 3-ratio

6
sil. hydrogarnet (C3 AS0.8 H4.4 ) + +calcite +anhydrite

Fig. 7.30: Calculated phase assemblages of a hydrated mixture consisting of C3A, C-S-H (Ca/Si~1.6), portlandite and varying initial sulfate (SO3/Al2O3) and carbonate contents (CO2/Al2O3) at different temperatures. Numbers of the assemblages are used in the text.

Siliceous hydrogarnet is apparently very stable over a wide range of sulfate and carbonate activities. However siliceous hydrogarnet is only rarely reported to occur in commercial cements, whereas carbo- and monosulfoaluminate are often described as hydration product of Portland cement at ambient temperatures, in agreement with own investigations. For example Gebauer and Harnik [74] observed the formation of monocarboaluminate in 84 year old hydrated concrete, showing it to be persistent, although no information was available to determine when it was initially formed. But the introduced metastability constraint with respect to siliceous hydrogarnet in the calculations presented in chapter 7 seems to be justified as it reproduces the actual hydration behaviour of Portland cements, as recorded from field observations. The reason why siliceous hydrogarnet does not form is not yet clear. One possibility is that the thermodynamic data are not correct and overestimate the stability of siliceous hydrogarnet. Until recently there has not been a consistent dataset available which describes the solid solution properties of Ca3Al2(SiO4)3-x(OH)4x. Miscibility gaps in the solid solution series between C3AH6 and C3ASH4 siliceous hydrogarnet, as observed by Jappy et al. [95], could indicate non-ideal mixing behaviour. The limits of the miscibility gap could not be fixed exactly and related solubility data necessary to estimate the thermodynamic properties of this apparently non-ideal solid solution

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are incomplete. More work is needed to confirm the existence and extent of miscibility gaps and to derive missing data; at the moment it is only possible to speculate about the inhibition of siliceous hydrogarnet formation at ambient temperatures. Damidot et al. [43] used solubility data, obtained from Jappys hydrogarnet syntheses, and published by Atkins et al. [9], to estimate the thermodynamic stability of two hydrogarnet compositions with different silica contents (Ca3Al2(SiO4)0.3(OH)10.8, and Ca3Al2(SiO4)0.8(OH)8.8). Their compatibility study concluded, that similarly to results in this Thesis, the high silica phase Ca3Al2(SiO4)0.8(OH)8.8 is not compatible with the carboaluminate phases, whereas the low silica phase, Ca3Al2(SiO4)0.3(OH)10.8, can coexist with both carboaluminates. This is in agreement with experiments by Kuzel and Baier [114], who have shown that Ca3Al2(OH)12 reacts rapidly with calcite to form monocarboaluminate. After 3h traces of monocarboaluminate were observed and reaction was almost completed after 12d at 25C at w/s=1. In contrast, a siliceous hydrogarnet with a composition Ca3Al2(SiO4)0.4(OH)10.4 showed no signs of reaction with calcite. After 21d, Ca3Al2(SiO4)0.4(OH)10.4 coexisted with calcite at 25C at w/s=1. Furthermore zur Strassen [198] has shown that increasing silica substitution in hydrogarnet with x 2.65 in Ca3Al2(SiO4)3-x(OH)4x enhances resistance against conversion into ettringite, if exposed to saturated gypsum solution. These observations suggest that even minor silica substitution leads to a significant stabilisation of siliceous hydrogarnet. The experiments agree very well with calculations by Damidot [43], who has shown that siliceous hydrogarnet is more stable to higher sulfate and carbonate concentrations than C3AH6, before undergoing conversion to ettringite, monocarboaluminate or calcite, respectively. There are reports in the literature about the formation of siliceous hydrogarnet in heat cured cements [69][144], which agree with observations in chapter 7.4 of this Thesis. Whereas experiments indicate that the formation of siliceous hydrogarnet is kinetically restrained at 50C, weak reflections of siliceous hydrogarnet were found in the samples at 85C independently of the presence of calcite. Hence temperature seems to be an activator of hydrogarnet formation. As a result of investigations in this Thesis, and in agreement with the literature, Fig. 7.31 was constructed showing schematically the kinetics of hydrogarnet formation as a function of temperature. Thus significant hydrogarnet formation is most likely in aged warm cured samples preferably at 85C and above, whereas its formation at ambient temperatures is apparently kinetically restrained.
100
-f HG t io ma r o n

Temperature [C]

75
Pr o

it y bil ba

of

significant hydrogarnet

50

traces of hydrogarnet

25

no hydrogarnet formation

Time

Fig. 7.31: Schematic showing the probability of hydrogarnet formation as function of time and temperature (solid lines indicate that formation is likely, dashed lines indicate formation is uncertain). The time axis still requires to be calibrated,

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The experiments suggest that siliceous hydrogarnet does form at the expense of monosulfoaluminate. However this process of conversion of monosulfoaluminate to hydrogarnet is relatively slow, as observed in experimental studies. If one assumes a partly decomposition of initially formed monosulfoaluminate to siliceous hydrogarnet two possible scenarios arise: i) Siliceous hydrogarnet is the thermodynamically favoured phase, as indicated by calculations, but its formation is kinetically restrained at low temperatures 50C; monosulfoaluminate will decompose to hydrogarnet at elevated temperatures and the released sulfate is either bound in the hydrogarnet phase, as suggested by Paul and Glasser [144] or sorbed on C-S-H, or both. ii) The amount of monosulfoaluminate is affected by a strong increase of the sulfate sorption to C-S-H at high temperatures. Thus sulfate is increasingly removed from the pore solution and monosulfoaluminate has to dissolve to maintain saturation. Due to the sorption of sulfate on C-S-H an excess of calcium and aluminate arises and the resulting supersaturation with respect to siliceous hydrogarnet reaches a critical point which, once exceeded, nucleates and crystallises hydrogarnet from the pore solution. The presence of alkalis promotes this process as increasing amounts of alkalis lead to a strong increase of the sulfate solubility in the presence of ettringite and monosulfoaluminate as shown in Fig. B.7. Therefore the sorption of sulfate on C-S-H increases strongly with increasing temperature and alkali content.

Role of iron and alkalis


Ferrite (Ca2AlxFe1-xO5) is one of the four main components of Portland cement clinker. However compared to aluminate, C3A, the number of literature studies on the hydration of the ferrite solid solution type phase is limited. Although the kinetics of ferrite hydration are generally considered to be slow compared to aluminate, experiments by Seligmann and Greening [169] suggests that iron can be treated analogous to aluminium. As a consequence, solid solutions between aluminium and iron bearing AFt and AFm may form as ferrite hydrates. From a literature review, including an assessment of Mssbauer spectra, Seligmann and Greening [169] suggested that most of the iron becomes bound into a SO4-AFm type phase. On the other hand a review by Taylor [180] led to the conclusion that the formation of iron hydroxides, amongst other phases, is likely. In addition to the database derived in this Thesis, the derivation of thermodynamic data on ironcontaining AFt and AFm phases is in progress. Preliminary calculations, based on solubility experiments by Mschner et al. [132][133], in agreement with the conclusions by Seligmann and Greening [169], indicate that iron stabilises the AFm phase whereas significant iron substitution in the AFt phase does not occur. This would imply a possible increase of the amounts of carboaluminate in connection with an increase of the reactive calcite content. However, although a complete dataset for Fe-ettringite and provisional values for monocarboferrite and monosulfoferrite hydrate were derived by Mschner et al. [132][133], a complete dataset for iron AFm and hydrogarnet phases including solid solutions with the Al-analogues was not available and experimental validation for Portland cement systems containing both iron and aluminium has not yet been undertaken. Due to these uncertainties an exact assessment of the state of iron in hydrated Portland cement paste is not possible at the moment.

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Table 7.3: Influence of alkalis on the composition of aqueous and solid phases at selected invariant points at 25C (see Fig. 7.4 for original phase diagram)
Pt.
[Fig. 7.4]

pH

Na
[mmol/kg]

Ca

Al

CO3
[mmol/kg]

SO4
[mmol/kg]

Solids

[mmol/kg] [mmol/kg]

12.48 13.58

0 500 0 500

19.35 0.58 19.37 0.61

0.086 1.3 0.007 0.11

0 0 0.0065 0.86

0.001 0.350 0.024 6.98

C3AH6, Ms(ss, 24%OH), CH C3AH6, Ms(ss, 22%OH), CH AFt(ss, 9%CO3), Mc, calcite, CH AFt(ss, 8%CO3), Mc, calcite, CH

12.48 13.58

Alkalis in Portland cement, potassium and sodium, are partly present as alkali sulfates and partly substituted in the clinker phases, mainly in the C3A-type phase of Portland cement. Alkali sulfates are readily soluble and influence the composition of the pore solution of hydrated cements significantly. As part of the sulfate is removed in the course of hydration, due to formation of ettringite and SO4-AFm, the pH of the pore solution rises quickly to values higher than 13 as OH- is released to charge balance the positive alkali cations. Thus the hydroxide activity increases markedly. A recalculation of the aqueous and solid phase composition of the invariant points M and H (Fig. 7.4) in the presence of 500 mmol Na+/kg (Table 7.3) shows that sulfate, carbonate and aluminium concentrations and related corrected activities (not shown here) increase significantly while calcium concentrations decrease. However, despite these complex changes in the aqueous phase, the solid composition is not significantly affected. Hence the effects of increasing aqueous hydroxide or carbonate activities are balanced to some extent by the increasing sulfate activities. In hydrated cements made to low w/c-ratios the mass of excess pore solution is small compared to the mass of solids. Thus despite changes in the solubility of the solid phases only minor changes of the total solid mass balance result from the presence of alkalis: hence the phase relations shown in diagrams Fig. 7.5 and Figs. 7.15-7.18 are not significantly affected. As shown in Table 7.3, the presence of high amounts of alkalis is accompanied by a significant increase in the aqueous sulfate, aluminium and carbonate concentrations. However, C-S-H is known to bind significant amounts of alkalis, sulfate and aluminium, dependent on the aqueous concentration of the related species. Thus increasing alkali contents can lead to an increased incorporation of these elements in C-S-H, either by surface processes e.g. adsorption or by substitution of ions in the bulk. Thus the amounts of sulfate and alumina, available to form AFm and AFt decrease and can result in significant mass balance changes (see chapter 7.5.2).

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7.5.2 Kinetic factors: availability of sulfate, carbonate and alumina in the course of hydration
The foregoing calculations are based on the simplistic assumption that all chemical components of the cement, as revealed by a bulk chemical analysis, are available for reaction. This is probably not true for real cements. Clinker grains have a range of sizes and complex internal microstructures, with the result that different clinker phases hydrate at different rates and may be partly protected from hydration, perhaps by occlusion in hydrate envelopes with low permeability. Thus, for example, alumina in tricalcium aluminate may become available at an earlier stage of hydration than alumina in ferrite. Kuzel [115] suggested using only the C3A-content to estimate the available alumina content during hydration. Seligmann and Greening [169] showed a case where ferrite remained unreactive in hydrated cement paste (20% C3S, 51% C2S, 3.4% C3A , 15.2% C4AF and 1.98% SO3, at w/c = 0.5) for more than 14 years, which impacted on the effective SO3/Al2O3 ratio and the related hydration products of the cement. However, it is likely that the reactivity of ferrite is strongly influenced by minor element concentration e.g. Mg, Ti, as well as by its A/F ratio. The role of iron in the distribution of hydrate phase assemblages is discussed further in chapter 7.5.1, but at present, it is not possible to estimate ferrite reactivity, or to assume that it will remain constant from one clinker to another. Sulfate, nominally in the form of added calcium sulfate and alkali sulfates, is typically available for reaction at an early stage of hydration, although it is not unknown for sulfates to be physically occluded within clinker grains only becoming available for hydration at longer ages [110]. Cements contain carbonate from many sources some of which are not obvious. For example, during clinker cooling in contact with kiln gases, sulfates may condense onto the clinker. Sulfur oxide is swept through the kiln together with alkalis, water, carbon dioxide, etc. As the hot gas stream cools, it may reach the dew point of alkali sulfates. Calculations on vapor - melt equilibria by Barry and Glasser [18], assuming a realistic partial CO2 pressure in the kiln, disclose that these alkali-sulfates are actually alkali sulfate-alkali carbonate solid solutions. Thus vapour condenses onto cooling clinker, introducing significant carbonate as well as sulfate. Carbonate contributions may also arise in the same manner if clinker kiln dust is recovered and added to clinker. Moreover gypsum interground with cement often contains significant calcite. These several sources of carbonate are often sufficient to stabilise hemicarboaluminate in the course of hydration, even of fresh and nominally uncarbonated limestone free Portland cement. Thus key components, including alumina, sulfate and carbonate are present in clinker in a range of forms and, while these range in dissolution rates, with few exceptions all sulfate becomes available early within the hydration process. Typically most of the gypsum interground with clinker is consumed within the first few days of hydration whereas some of the alumina, mainly in ferrite, becomes available only over much longer time scales. Therefore detailed and realistic calculations would have to make use of the reactive fraction of these phases: the composition that determines the hydrate mineralogy is not necessarily the bulk composition as determined from a total chemical analysis but is instead the sum of the reactive fractions of each component liberated from the clinker solid phases. To quantify these amounts requires a series of snapshots on the state or condition of the system with changing time. While the relevant hydration kinetics are not sufficiently well known- and indeed almost certainly vary with non-chemical factors such as clinker granulometry and microstructure of the individual grains- it is known in general that sulfate ratios tend to be 3 at the outset of hydration owing to readily soluble alkali sulfates and calcium

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sulfates, i.e. gypsum and/or anhydrite. Thus, in agreement with previous calculations supported by focussed experiments it was shown that ettringite is the initially formed hydrate phase in cement systems at early ages while still saturated with respect to calcium sulfates at 25C. AFm phases including (monosulfoaluminate type solid solutions and carboaluminates) are not stable under these conditions (SO3/Al2O3 3) and are not observed if the system is saturated with respect to gypsum. However due to the consumption of calcium sulfate, the sulfate ratio decreases to 3 as hydration progresses. As a consequence monosulfoaluminate and/or carboaluminate tend to become stable as a function of changing carbonate and sulfate ratios; the influence of temperatures other than 25C is discussed in chapter 7.5.4. Fig. 7.5 shows the phase relations between AFt-AFm phase assemblages in dependence of the sulfate and the carbonate ratio of the system. Thus as hydration approaches completion, ettringite and calcite will partly or fully react with the remaining alumina to form monosulfoaluminate and hemicarboaluminate in regions I-III (Fig. 7.5). However owing to the comparatively higher thermodynamic stability of the carboaluminates, the remaining aluminate tends to react preferably with calcite rather than ettringite. Thus at sulfate and carbonate ratios relevant to regions IV and V (Fig. 7.5), the conversion of ettringite to monosulfoaluminate is suppressed by the formation of carboaluminates in the progress of hydration. As the clinker silicates react, large amounts of C-S-H dominate the mineralogy of hydrated cements. Owing to the high specific surface of C-S-H, significant amounts of sulfate can be taken up by C-S-H; the sorption depends on the Ca/Si and Al/Si ratio of the C-S-H, the sulfate content in the pore solution and the reaction temperature [14][54]. As shown by Richardson et al. [160], significant amounts of aluminium can be substituted in C-S-H. Thus, while the phase boundaries shown in Fig. 7.5 are broadly unaffected by sulfate and aluminium uptake of C-S-H, the amount of available sulfate and aluminium may be significantly lower than are disclosed by the total chemical analysis, which will affect subsequent mass balance calculations. A correction for sulfate and aluminium uptake by C-S-H will be useful to improve the accuracy of the mass balance computations. It is not known how carbonate ratios are affected by the kinetics of hydration and an important task for those who determine reaction kinetics is to quantify how reactive calcite fractions change as a function of time, as well as with changing bulk composition and formulation. The intermediate formation of hemicarboaluminate in systems with excess calcite present has been shown in own experiments as well as by Kuzel and Pllmann [117], while calculations in this Thesis, in agreement with calculations by Damidot et al. [49], have shown that hemicarboaluminate is not stable in the presence of excess calcite. The precipitation of carboaluminates from a supersaturated solution involves the removal of carbonate ions from the solution. Apparently due to a disequilibrium between the kinetics of carboaluminate precipitation and a slower dissolution of calcite, the resulting carbonate activities in the pore solutions decrease to levels such that monocarboaluminate may become unstable and hemicarboaluminate is formed in the presence of portlandite as shown in Fig. 7.4. Data obtained in the course of this study also apply in principle to the reactivity of coarse limestone aggregate. In theory, limestone aggregate is predicted to be reactive with cement in the same way as is limestone with high specific surface. The same conditions apply to aggregate except that for coarse aggregate, the kinetics of reaction with cement are likely to be appreciably slower: not only is the surface area available for reaction much reduced but diffusion paths for other species, e.g., aluminium, tend to lengthen. When clinker is interground with limestone, the many observations in the literature show rapid formation of monocarboaluminate in hydrating pastes within the first days

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or weeks of hydration. It is likely that the potential of coarse limestone aggregate to react with cement can be reduced or even eliminated by saturating the cement matrix in carbonate, as occurs when sufficient fine-grained reactive calcite is included in the formulation. Thus if the matrix is calcite saturated, the potential for subsequent reaction of cement with limestone aggregate can be reduced to zero, with consequences for the development of bond between aggregate and paste and spacefilling in the interstitial transition zone, i.e., at the interface between paste and aggregate. Carbonation from external sources is not included in this study and will always follow a slightly different reaction path, because a mass unit of CO2 in the form of CaCO3 also adds a unit of CaO; this equivalence does not however apply to atmospheric CO2. But the differences at low carbonate contents are minor and cements undergoing atmospheric carbonation develop carbonate gradients and may also experience the sequence of mineralogical changes described here. Spatially these zones are most likely to develop ahead of the main carbonation front. It is also noteworthy that adding carbonate in the form of calcium carbonate to cement slightly reduces its buffering capacity towards subsequent carbonation, for example in atmospheric carbonation. If protection of embedded steel is important, it is desirable that improvements in cement performance, for example reduced permeability arising from calcite addition, should outweigh loss of buffering capacity. In summary, the foregoing calculations assume that the bulk chemistry is relevant but, almost certainly, kinetic controls operate somewhat to modify the picture presented here. Typically the effective sulfate ratio will be somewhat higher during early hydration than is assumed in the calculations. Reference to the figures shows that, other factors remaining unchanged, increasing the sulfate ratio decreases the potential for consuming calcite. Thus calcite will initially react in response to the effective sulfate ratio, leaving potential for slower secondary reactions to occur. These slow reactions will result in continuing calcite consumption with time as clinker hydration approaches completion.

7.5.3 Volume changes


Volume changes were calculated by attending calcite additions in the expectation that these calculations, or very similar calculations, will eventually be used to develop property-composition correlations for hardened cement pastes. The calculations implicitly assume that the volume changes attending reaction of calcite with cement components occur after paste has hardened but do not lead to changes in external dimensions of a paste monolith, i.e., they are not expansive. If this supposition is correct, calcite addition can be used creatively, to improve space filling by solid hydration products and thereby lower product porosity. Because the relationships between porosity and permeability are complex, lowering porosity will not necessarily reduce permeability and indeed, no consistent pattern emerges from a study of the literature. Nevertheless the space filling property-composition correlations developed here, as confirmed by at least one experimental example [90], should give fresh direction and focus to these studies leading, for example to concentration on the impact of additions in critical concentration ranges. The critical concentration may be low, a few wt.-% in the case of calcite. But each case depends on the cement composition and requires separate calculation.

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7.5.4 Thermally induced phase changes


Hydrated cements experience a wide range of service temperatures and may encounter strong selfheating early in their life cycle, as heat of hydration is not always readily dissipated. This study has shown that the temperature dependence of the thermodynamic properties of AFm-AFt phases impact significantly on phase development. It was shown that carboaluminates become increasingly unstable at elevated temperatures, whereas monosulfoaluminate, although stable at 25C, is stabilised by increasing temperatures up to at least 99C. Calcite is shown to be a reactive component and forms carboaluminates at temperatures 50C, but increasingly behaves as inert filler at higher temperatures. At sulfate ratios 1 AFt is stabilised due to the formation of carboaluminates at temperatures 50C. However, prolonged curing at elevated temperatures, 50C, leads to the formation of monosulfoaluminate at SO3/Al2O3 ratios typical of Portland cements, ~ 1 or less, independently from the calcite content. Thus a subsequent lowering of the service temperature induces an extra potential for ettringite formation in calcite or carbonate-containing cements. Ettringite will form in increased amount due to partial displacement of sulfate by carbonate in the AFm structure at ambient temperatures ~20C - 25C. This process will increase the specific solid volume significantly. It should be noted that the approach used in this work is only able to predict phase changes and associated mass balance and specific volume changes, but not necessarily actual expansion. While phase changes are often a precondition of destructive processes, e.g. DEF, the resulting volume changes cannot be used directly to calculate %expansivity. To assess the implications of phase changes on the development of mechanical stress the thermodynamics of crystal growth, including the evolution of crystal pressures in dependence of the temperature changes, has to be taken into account as described by Scherer [167] and Flatt and Scherer [64]. Much interest centres on the role of heat curing in concrete. With the discovery that excessive heat cure results in subsequent re-formation of ettringite (DEF), the relations between upper cure temperature and duration of the warm cure period and of the thermal cycle to factors like cement composition and fineness have created a web of complexity, which has proven almost impossible to resolve into an action plan. The present calculations enable a method to elaborate a phase development model, independently from long-term experiments. Of course some relevant factors, e.g. cement fineness and the degree of hydration of the cement in the elevated temperature curve are either not included or have to be estimated in order to apply the method. But even so, there are a range of other inputs still needed. For example, in studies of DEF described in the literature, it is often not stated whether limestone (calcite) has been added to the cement. However the present study discloses that the calcite content has an important bearing on the phase development in the course of thermal cycling. Moreover, while many literature studies of DEF test different maximum temperatures it is usually assumed that the expansive potential can be measured at 25C. The present study shows that this assumption is untentable: in a thermal cycle with an arbitrarily set maximum temperature, e.g. 60C, the amount of mineralogical reconstitution needed to reequilibrate a cement paste at 10C differs significantly from that at 25C, e.g. due to the possible formation of SO4-CO3-AFt solid solutions. It is therefore concluded that the potential for DEF depends on both maximum cure temperature and on the service temperature.

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The divergence in literature studies on the causes and avoidance of DEF is perhaps not surprising and quantitative modelling of DEF is as yet not possible. It is not claimed that this study solves the problems, but it provides an analytical tool to anticipate changes, to harmonise experimental observations and to design simplified experiments, which, although simplified, will unambiguously illustrate selected aspects. Some examples are given in the subsequent paragraph. The reaction of monosulfoaluminate, calcite and water to form AFt and carboaluminates at temperatures <50C can be an important factor, amongst others, to explain expansive processes in the course of DEF. For example, Kuzel and Strohbauch [118] have shown that initially formed monosulfoaluminate in heat cured samples subsequently converts to AFt and monocarboaluminate upon subsequent water storage in contact with atmospheric CO2 at 22C. Furthermore self heating might occur in mass concretes. If the heat of hydration is not released quickly, prolonged cure at 50C can result in a formation of monosulfoaluminate, which will be converted to carboaluminate and AFt, if the service temperature is << 50C and if sufficient carbonate and water are available. The local availability of water can be another potentially rate limiting factor. Depending on conditions in warm cure, water liberated by phase transformations may be lost, i.e. the system is not isochemical. So the reverse reactions encountered in the post-warm cure phase may also be kinetically controlled by need to uptake water and its availability. Nevertheless, the calculations present another explanation of the occurrence of monosulfoaluminate at high temperatures and its transformation to ettringite at low temperatures. The previous calculations have shown that phase changes are not limited to elevated temperatures, e.g. hydroxide substituted AFm phases, e.g. C4AHx, or SO4-OH-AFm solid solutions and hemicarboaluminate, are stabilised at lower temperatures. Furthermore AFt solid solutions, including SO4-CO3-AFt and ettringite-thaumasite solid solutions, are preferably formed at low temperatures. Service temperatures in the northern hemisphere are often less than 10C. Although direct experimental evidence is absent, calculations indicate that a substitution of carbonate in AFt is favoured at low temperatures. Thus the maximum amount of AFt is not restricted by the cement sulfate content alone. The amounts of ettringite and its specific solid volume increase with decreasing temperature in the presence of calcite, which would significantly influence the space filling properties of the hydrated cement paste. As long as experimental evidence of this reaction is absent, the results should be regarded as tentative, but indicate that more research is needed to explore the influence of low temperatures on cement hydration. The previous experimental and theoretical studies have shown that they have obvious implications for the dimensional stability, porosity and permeability of concretes in service and reflect on the binder design, formulation and thermal cure regime. Future studies need to link these factors. But it is possible to envisage tailoring cement compositions to optimise performance in specific service environments without dependence on purely empirical results.

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171

8. Summary and conclusions


8.1. Thermodynamic quantification of cement hydration
In the past decades applications of thermodynamic methods to cement hydration have long been considered as too theoretical and without any practical use for the cement industry and mineralogical evolution in the course of cement hydration was often regarded as too complex to model. However the development of advanced geochemical codes, e.g. GEMS-PSI, enabled the treatment of complex systems. Although these codes were originally developed to solve geochemical problems, they can readily be applied to other chemical systems, e.g. hydrated cements. But to attain meaningful results it is necessary to couple these geochemical codes with a comprehensive thermodynamic database including all main cement hydrates expected to form in cementitious systems. Available databases for cement hydrates are often incomplete and with few exceptions are limited to isothermal systems at 25C. Therefore the main goal of this work was to develop a database, capable of dealing with the complexity of modern cement compositions, including reactions occurring over a broad range of temperatures to quantify the mineralogical evolution during cement hydration. A database was developed for commonly-encountered cement substances including C-S-H, AFm phases -namely monosulfoaluminate, monocarboaluminate, hemicarboaluminate and hydroxyAFm, AFt -including SO4-AFt, CO3-AFt and thaumasite- and hydrogarnet compositions, C3AH6 and C3As0.8H4.4. The formation of solid solutions, if observed experimentally, was taken into account by appropriate models. The database is valid in a temperature range of ~1-99C at 1 bar total pressure. Available literature data were critically assessed and completed with experimental determinations. The final thermodynamic properties were derived by a harmonisation of the available data. The overall conclusion of this Thesis is that thermodynamics is a useful method to quantify cement hydration, provided an accurate database is available. A big advantage of thermodynamic calculations is its generic character. Thus once the model is setup correctly it can be applied to a wide range of cement compositions and temperatures. Another advantage of thermodynamic methods is that mass is conserved in all calculations and allows a quantification of cement hydration independently from existing detection limits often encountered in experimental methods. Of course as with every other method there are still limitations of the thermodynamic approach used in this study e.g.: i) database development: there are still missing gaps in the database, e.g. the extent of alkali, sulfate and aluminium substitution and/or adsorption in C-S-H. However work is in progress to account for these processes. ii) the lack of a kinetic model describing hydration as a function of time. However successful attempts are reported in the literature using a fractional reactivity approach to overcome this problem [123][125]. It is argued that the user of this method has to appreciate the significance of the calculated results. In this respect, the computer is still servant, not master and the need for a thorough understanding of cement science is strengthened, not reduced, by the advent of thermodynamic computations.

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172

8.2. Implications for cement hydration


This section summarises the main conclusions arising from thermodynamic calculations and experiments of this work. The main focus was to investigate hydrate phase assemblages, including the distribution of sulfate and carbonate between AFm and AFt phases, and to derive generic conclusions to assess the chemistry and mineralogy of commercially available hydrated Portland cement paste. To highlight the practical importance of this problem the impact of limestone addition, mainly as calcite, on cement hydration was systematically investigated. The constitution of the AFm phase was assessed by thermodynamic calculations and focussed experiments at 25C. Experiments and calculations reveal that AFm phases, containing as principal anions OH-, SO42- and CO32-, are incompletely miscible with each other, except for limited replacement of sulfate by hydroxide in monosulfoaluminate. Carbonate and sulfate provide thermodynamic stabilisation for the AFm phase. Thus monocarboaluminate, hemicarboaluminate and part of the monosulfoaluminate-hydroxy-AFm solid solution series (up to 24 mol% sulfate substitution) series are stable at 25C. Therefore it is likely that many hydrated cements will contain mixtures of AFm phases in dependence of their initial chemical composition. Although the existence of solid solutions based on ettringite has long been known, and syntheses of these solid solutions are reported in the literature, no assessment of the thermodynamic stability of these solid solutions was possible, due to lack of data and of appropriate models. Thus, to assess the formation of AFt solid solutions in cementitious systems, it was necessary to derive their thermodynamic properties. Based on a binary solid solution model and available experimental data, the non-ideal mixing behaviour of SO4-AFt and CO3-AFt, as well as of SO4-AFt and thaumasite were investigated. Subsequent calculations indicate that carbonate substitution in AFt is strongly dependent on temperature. Whereas at 25C only minor carbonate substitution is likely in ettringite, low temperatures, 10C, promote the incorporation of carbonate in the AFt structure. Pathways of thaumasite formation have been discussed. According to the calculations there is no single route of thaumasite formation as often suggested in the literature. The simultaneous occurrence of several pathways to form thaumasite is likely. The initial formation of AFt-thaumasite solid solutions is an essential precursor to form thaumasite in calcium-rich zones. In agreement with field observations the amount of AFt is likely to increase significantly before thaumasite first appears. The extent of this increase will be more important at low temperatures. On the other hand, in decalcified regions, e.g. zones undergoing extensive leaching, thaumasite may form directly without preliminary AFt formation. Hence the distinction between conventional sulfate attack and thaumasite form of sulfate attack seems not to be appropriate as carbonate is widely abundant in most service conditions and the conventional sulfate attack including the conversion of AFm to AFt is likely to be a precursor of thaumasite formation. EN 197 specifications permit addition of up to 5% limestone, mainly calcite, in Portland cement, while much higher additions are often used in special cements. However concerns exist about the performance of limestone-rich cements. Thus another main part of this work was to systematically investigate the mineralogical consequences of carbonate addition on cement hydration. Thermodynamic calculations enable a qualitative and quantitative prediction of phase assemblages including AFm and AFt relations as a function of SO3/Al2O3 and CO2/Al2O3 ratios of the cement.

Summary and conclusions

173

At ambient temperatures, ~25C, and in the presence of portlandite, carbonate stabilises carboaluminate phases while the sulfate thus displaced from AFm forms additional AFt. Specific volume calculations have shown that the space filling of hydrated cement paste can be optimised by adjusting the calcite content such that the AFt content is maximised. Experiments indicate that engineering properties respond to changes of the space filling properties. Controlled calcite addition can therefore be used to improve physical and mechanical properties of hydrated cement paste. Temperature has an important influence of the expected hydrate phase assemblages. While at temperatures 50C, and in dependence of the chemical composition of the cement, considerable amounts of calcite react to form carbonate substituted AFm and/or AFt phases, calcite behaves increasingly inert, as a consequence of the instability of carboaluminates, at elevated temperatures; monosulfoaluminate is the preferred AFm phase at high temperatures. On the other hand, carbonate substituted AFt phases, which usually coexist with monocarboaluminate and calcite, are stabilised at low temperatures, preferably <10C. In dependence of the service temperature up to ~50 mol% of the initial sulfate in AFt can be theoretically replaced by carbonate, which suggests that the maximum AFt content in hydrated cement is no longer restricted by the cement sulfate content. Hence temperature has important influence on the space filling properties of hydrated cement and a general conclusion arose from this work: the higher the temperature the lower the total specific volume of hydrated calcite blended cement paste; other factors being equal, e.g. the specific volume of C-S-H remaining approximately constant. On the contrary, if cements are initially cured at high temperatures 50C, e.g. by heat curing or self-heating due to heat of hydration, solids with low specific volume tend to form, e.g. monosulfoaluminate, and calcite behaves inert. If these hydrated cements are subsequently exposed to low service temperatures << 50C, carboaluminates and AFt will form as a consequence of this mineralogical reconstitution. The amounts of ettringite are predicted to increase with decreasing temperatures due to the possible substitution of carbonate in the AFt structure. Experiments have shown that these mineralogical changes occur relatively rapid, within weeks or months in laboratory simulations. Thus carbonate is another factor which has to be considered by assessing temperature-related phenomenoms, e.g. the occurrence of DEF in heat cured cement systems. This work has shown that carbonate, mainly present in cements as blended calcite, is an important variable, which has to be considered for a correct assessment of cement hydration. Most literature studies tend to neglect the influence of minor limestone addition on cement hydration, the outstanding experimental contributions by Kuzel and co workers or Seligmann and Greening being an exception. Calcite has two functions in hydrated cement, one as an active participant in the hydration process, the other as an inert filler. The mineralogical changes arising from calcite addition are significant and are likely to influence the performance of hydrated cement paste and therefore cannot be neglected. However first results indicate that controlled limestone or calcite addition can be used to optimise engineering properties, e.g. porosity or permeability, of hydrated cements.

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Related publications by the author of this Thesis

Material of this Thesis has already been accepted for publication as follows:

Journals
Matschei, T.; Lothenbach, B.; Glasser, F.P.: Thermodynamic properties of Portland cement hydrates in the system CaO-Al2O3-SiO2-CaSO4-CaCO3-H2O. Cement and Concrete Research, 37, (see chapter 4) 2007, 1379-1410 Matschei, T.; Lothenbach, B.; Glasser, F.P.: The AFm phase in Portland cement. Cement and (see chapter 5) Concrete Research, 37, 2007, 118-130 Matschei, T.; Lothenbach, B.; Glasser, F.P: The role of calcium carbonate in cement hydration. Cement and Concrete Research, 37, 2007, 551-558 (see chapter 7) Matschei, T.; Glasser, F.P.: Zum Einfluss von Kalkstein auf die Zementhydratation. Zement Kalk (see chapter 7) Gips, 59, 12/2006, 78-86

Conference Proceedings
Matschei, T., Glasser, F.P.: Interactions between Portland cement and carbon dioxide. Proceedings of the 12th ICCC, Montreal, 2007 Matschei, T., Skapa, R.; Lothenbach, B.; Glasser, F.P.: The distribution of sulfate in hydrated Portland cement paste. Proceedings of the 12th Intern. Congress on the Chemistry of Cements, Montreal, 2007 Matschei, T.; Herfort, D.; Lothenbach, B.; Glasser, F.P.: Relationships of Cement Paste Mineralogy to Porosity and Mechanical Properties. Modelling of Heterogenous Materials with Applications in Construction and Biomedical Engineering, Prague, 2007, extended abstract Matschei, T.; Glasser, F.P.: New Approaches to Quantification of Cement Hydration. Proceedings of the 16th Ibausil, Weimar, 2006, Vol. I, 1-0389 - 1-0400 Matschei, T.; Glasser, F.P.: Carbonation - The early stages. International Conference on Accelerated Carbonation for Environmental and Materials Engineering, London, 2006, extended abstract Matschei, T.; Lothenbach, B.; Glasser, F.P.: The AFm phase in Portland cement. IoMMM 25th Cement and Concrete Science, London, 2005, extended abstract

Abbreviations

187

Abbreviations
Nomenclature in cement chemistry
C c CaO CO2 A H Al2O3 H2O S SiO2 s SO3

AFm

Al2O3-Fe2O3-mono phase

AFt C3A

Al2O3-Fe2O3-tri phase Tricalcium aluminate

C-S-H Calcium silicate hydrate C3S Tricalcium silicate

Abbreviations used in calculations


A i B bi Cp0 Debye-Hckel solvent parameters dependent on the dielectric constant of water and temperature (A = 0.5114 at 25C) parameter dependent on the size of species, i, taken from Kielland`s table (cited in [143]) Debye-Hckel solvent parameters dependent on the dielectric constant of water and temperature (B = 0.3288 at 25C) common extended Debye-Hckel parameter (bi ~ 0.064 at 25C) standard molar heat capacity of species at T, P (J K-1 mol-1)

rCp0T standard molar heat capacity change of reaction at T (J K-1 mol-1) rCp0T0 standard molar heat capacity change of reaction at T0 =298 K (25C) (J K-1 mol-1) fG0T0 standard molar Gibbs energy (of formation from elements) at T0 = 298 K (25C) (kJ mol-1) rG0T Gex fG0i Gid GM Gss i rH
0 T

standard Gibbs energy change in a reaction (kJ mol-1) excess molar Gibbs energy of mixing for the solid solution series (kJ mol-1) standard molar Gibbs energy of formation of end member i of a solid solution series (kJ mol-1) molar Gibbs energy of mixing of an ideal solid solution (kJ mol-1) molar Gibbs energy of mixing for end members i of the solid solution series (kJ mol-1) molar Gibbs energy of a solution between different end members i (kJ mol-1) Activity coefficient of species i standard change of enthalpy of reaction at T (kJ K-1 mol-1)

rH0T0 standard change of enthalpy of reaction at T0 = 298 K (25C) (kJ K-1 mol-1) fH0T0 standard molar enthalpy at T0 = 298 K (25C) (kJ K-1 mol-1) I KT R rS0T effective molal ionic strength of aqueous solution thermodynamic equilibrium constant of reaction at T total solubility product in Lippmann phase diagrams universal gas constant (8.31451 J K-1mol-1) standard entropy change in reaction at T (J K-1 mol-1)

Abbreviations rS0T0 standard entropy change in reaction at T0= 298 K (25C) (J K-1 mol-1) S0 T0 T T0 V0 Xaq,i Xi standard molar absolute entropy at T0 = 298 K (25C) (J K-1 mol-1) Temperature of interest (K) Reference temperature (298 K) standard molar volume (cm3 mol-1) aqueous activity fractions of the substitutable species i mole fraction of end member i in solid solution

188

Other abbreviations
BSE DEF DTA DTG EN ESEM GEMS GSE HDPE MBSSAS OPC PP PDF PE PSI PTFE SSAS TG TSA w/c w/s XRD XRPD Backscattered electron Delayed ettringite formation Differential thermal analysis Derivative thermogravimetry European standard Environmental scanning electron microscope Gibbs energy minimisation selector Gaseous secondary electron High-density polyethylene Margules binary solid solution aqueous solution (computer code by Glynn et al. [81]) Ordinary Portland cement Polypropylene Powder diffraction file Polyethylene Paul Scherre Institute Polytetrafluoroethylene (Teflon) Solid solution aqueous solution Thermogravimetry Thaumasite form of sulfate attack water/cement weight-ratio water/solid weight-ratio X-ray diffraction X-ray powder diffraction

Figures and Tables

189

Figures and Tables


Figures
Fig. 4.1: Estimation of the silicon-content of siliceous hydrogarnet .............................................. 16 Fig. 4.2: Comparison of XRD-patterns of C3AH6 following annealing at 5C, 25C and 105C . 27 Fig. 4.3: Calculated solubility products of C3AH6 from solubility experiment^ .......................... . 28 Fig. 4.4: Recalculated solubility data for hydrogarnet, C3AH6, based on fitted thermodynamic data from Fig. 4.3 .................................................................................................................. . 28 Fig. 4.5: Comparison of XRD-patterns of siliceous hydrogarnet following ageing at temperatures in the range 5C - 85C.................................................................................................. . 29 Fig. 4.6: Calculated solubility products of siliceous hydrogarnet, C3AS0.8H4.4, from solubility experiments .................................................................................................................... . 30 Fig. 4.7: Recalculated solubility data for hydrogarnet, C3AS0.8H4.4, based on fitted thermodynamic data from Fig. 4.6........................................................................................................... . 30 Fig. 4.8: ESEM micrographs of synthetic monosulfoaluminate a) after synthesis at 90C and b) after 4 weeks redispersion in deionised water at 25C .................................................. . 30 Fig. 4.9: Comparison of XRD-patterns of monosulfoaluminate after ageing at temperatures in the range 5C - 90C............................................................................................................ . 31 Fig. 4.10: Calculated solubility products of monosulfoaluminate from solubility experiments .... . 32 Fig. 4.11: Recalculated solubility data for nominally monosulfoaluminate based on fitted thermodynamic data from Fig. 4.10............................................................................... . 32 Fig. 4.12: Comparison of XRD-patterns of monocarboaluminate after annealing at temperatures in the range 5C - 110C .................................................................................................... . 33 Fig. 4.13: Calculated solubility products of monocarboaluminate from solubility experiments ... . 34 Fig. 4.14: Recalculated solubility data for nominally monocarboaluminate based on fitted thermodynamic data from Fig. 4.13............................................................................... . 34 Fig. 4.15: Comparison of XRD-patterns of nominally hemicarboaluminate after ageing at temperatures in the range 5C - 85C ............................................................................ . 34 Fig. 4.16: Calculated solubility products of hemicarboaluminate from solubility experiments .... . 35 Fig. 4.17: Recalculated solubility data for nominally hemicarboaluminate based on fitted thermodynamic data from Fig. 4.16............................................................................... . 35 Fig. 4.18: Calculated mass balance of initially hemicarboaluminate (2g hemicarb. reacted in 60 g water at selected temperatures between 1C - 99C).. ................................................... . 36 Fig. 4.19: Calculated solubility products of C4AH13 (left) and C2AH8 (right) from literature solubility data................................................................................................................. . 36 Fig. 4.20: Calculated solubility products of CAH10 from literature solubility data........................ . 37 Fig. 4.21: Solubility relations between C2AH8, C4AH13 and CAH10 in the system CaO-Al2O3-H2O at 5C (left) and 25C (right). ............................................................................................ . 38 Fig. 4.22: Comparison of XRD-patterns of nominally strtlingite after ageing at temperatures in the range 5C - 85C............................................................................................................ . 39 Fig. 4.23: ESEM image of strtlingite (left) and corresponding TG-and DTG curves (right)....... . 40 Fig. 4.24: Calculated solubility products of strtlingite from solubility experiments.................... . 40

Figures and Tables

190

Fig. 4.25: Recalculated solubility data for strtlingite based on fitted thermodynamic data from Fig. 4.24 ................................................................................................................................ . 40 Fig. 4.26: Calculated solubility product of ettringite according to solubility experiments by Perkins &Palmer and other literature sources............................................................................. . 41 Fig. 4.27:XRD-pattern (left) and scanning electron micrograph (right) of CO3-AFt used for solubility determinations................................................................................................ . 42 Fig. 4.28: Calculated solubility product of CO3-AFt from solubility experiments. ....................... . 43 Fig. 4.29: Free energy plot of CO3-AFt and monocarboaluminate ................................................ . 43 Fig. 4.30: Comparison of recalculated solubility of C-S-H at 25C (solid line) with experimental values from literature (markers) at temperatures between 20C -30C ......................... . 44 Fig. 4.31: Comparison of solubility products calculated from the three-term temperature extrapolation (solid black line) and integrated Vant Hoff extrapolation (dashed black line) with values calculated from the HKF equation of state (grey line) and experimentally-derived solubility products of siliceous hydrogarnet (markers)............ . 47 Fig. 4.32: Influence of sulfate and carbonate on the relative stabilities of aluminate hydrates...... . 50 Fig. 4.33: Influence of silicon on the relative stabilities of aluminate hydrates............................. . 51
Fig. 5.1: Brucite-like [Ca2Al(OH)6]+ main layer projected onto the c-axis according to Allmann [5] . 53

Fig. 5.2: Structure of monosulfoaluminate according to Allmann [5] ......................................... . 53 Fig. 5.3: XRD-pattern of selected solid solutions between monosulfoaluminate and hydroxy- AFm aged 28d ......................................................................................................................... . 62 Fig. 5.4: Observed interplanar distances d0001 of monosulfoaluminate type solid solution (top) and hydroxy-AFm type solid solution (bottom) ................................................................... . 63 Fig. 5.5: Refined lattice parameter for the monosulfo-aluminate type phase with changing sulfate ratio ................................................................................................................................ . 64 Fig. 5.6: Calculated volume change for the monosulfoaluminate type phase with changing sulfate ratio ................................................................................................................................ . 64 Fig. 5.7: ESEM micrographs of the monosulfoaluminate end member and ettringite (a) and the monosulfoaluminate type solid solution (~10 mol% of sulfate substituted by hydroxide) (b)................................................................................................................................... . 64 Fig. 5.8: ESEM micrograph of cubic C3AH6 crystals on the surface of a crystal of the hydroxyAFm end member .......................................................................................................... . 65 Fig. 5.9: Lippmann diagram for the monosulfoaluminate-hydroxy-AFm system at 25C with a0=0.188 and a1=2.49 for miscibility gap fractions 0.03 x 0.5 (equation 5.1) ......... 66 Fig. 5.10: Gibbs free energy of ideal mixing, Gid, excess Gibbs free energy of mixing, Gex, and resulting Gibbs free energy of mixing, GM, calculated from Eq.4.14 for the monosulfoaluminate-hydroxy-AFm solid solution series.............................................. . 68 Fig. 5.11: Comparison of calculated (lines) and mean experimental (markers) solubility data for the SO4-AFm and OH-AFm solid solution series at 25C................................................... . 69 Fig. 5.12: XRD-pattern of solid solutions between monosulfoaluminate and hydroxy-AFm aged 2 years ............................................................................................................................... . 70 Fig. 5.13: Formation of C3AH6 in dependence of the initial molar bulk SO4/(SO4+2OH)-ratio of the solid solution preparations at 25C ................................................................................ . 70 Fig. 5.14: calculated thermodynamic metastable solid mass balance changes of the monosulfoaluminate-hydroxy-AFm solid solution series at 25C................................. . 71

Figures and Tables

191

Fig. 5.15: Calculated thermodynamic stable solid mass balance changes of the monosulfoaluminate-hydroxy-AFm solid solution series at 25C................................. . 71 Fig. 5.16: Changes of interplanar distances d0001 of monosulfoaluminate type solid solution with prolonged ageing up to 2 years at 25C ......................................................................... . 71 Fig. 5.17: Comparison of calculated (solid lines = stable phase assemblage including C3AH6; dashed lines metastable phase assemblage, formation of C3AH6 suppressed) and mean experimental (markers) solubility data for the SO4-AFm and OH-AFm solid solution series in dependence of the sample age at 25C ............................................................ . 72 Fig. 5.18: Change of pH due to prolonged ageing of the solid solution preparations at 25C (markers = experimentally measured; solid lines = calculated stable phase assemblage including C3AH6; dashed lines calculated metastable phase assemblage, formation of C3AH6 suppressed)......................................................................................................... . 73 Fig. 5.19: Comparison of XRD-pattern of 1:1 molar mixtures of synthesised sulfate- and carbonateAFm end members ......................................................................................................... . 73 Fig. 5.20: Comparison of d0001 spaces for C4AHx-C4AcH11 mixed solids at25C.......................... . 74 Fig. 5.21: Calculated metastable phase assemblages between different AFm phases at 25C. A possible range of stoichiometry of hemicarboaluminate and C4AHx is not shown........ . 75 Fig. 5.22: Calculated stable phase assemblages between different AFm phases at 25C. A possible range of stoichiometry of hemicarboaluminate and C4AHx is not shown...................... . 77 Fig. 6.1: Crystal structure of ettringite ......................................................................................... . 82 Fig. 6.2: XRD-patterns of selected SO4-CO3-AFt phase solid solutions...................................... . 87 Fig. 6.3: Lippmann diagram for the SO4-CO3-AFt solid solution series at 25C with a0=-0.823 and a1=2.82 for miscibility gap fractions 0.12 x 1.25 (Eq. 6.1) ..................................... . 89 Fig. 6.4: Comparison between calculated and theoretical changes of the relative energy of mixing of the SO4-CO3-solid solution series.............................................................................. . 90 Fig. 6.5: Comparison of calculated (lines) and mean experimental (markers) solubilities for the SO4-AFt and CO3-AFt solid solution series at 25C...................................................... . 91 Fig. 6.6: Comparison of the XRD-pattern of synthetic thaumasite with SO4-AFt and CO3-AFt . . 93 Fig. 6.7: ESEM micrograph of synthetic thaumasite at 5C ........................................................ . 93 Fig. 6.8: Thermal analysis (TG and DTG data) of synthetic thaumasite...................................... . 93 Fig. 6.9: XRD-pattern of synthetic thaumasite and related and related decomposition products upon redispersion at temperatures from 1C to 70C .................................................... . 95 Fig. 6.10: ESEM micrograph of partly decomposed synthetic thaumasite embedded in a matrix of C-S-H and calcite at 55C.............................................................................................. . 95 Fig. 6.11: ESEM micrograph of C-S-H and calcite resulting from thaumasite decomposition at 70C ............................................................................................................................... . 95 Fig. 6.12: Thermal analysis (TG data left; DTG data right; heating rate 10K/min; N2-atmosphere) of synthetic thaumasite and related decomposition products following redispersions at temperatures from 1C to 70C...................................................................................... . 96 Fig. 6.13: Calculated solubility products of synthetic and natural thaumasite samples from solubility experiments .................................................................................................... . 97 Fig. 6.14: Recalculated solubility data for thaumasite based on fitted thermodynamic data (Table 6.1) and for other relevant cement hydrates (Table 4.1). ............................................... . 98 Fig. 6.15: Calculated mass balance changes due to the decomposition of thaumasite with increasing temperatures (water/solid-ratio = 120)........................................................................... . 99

Figures and Tables

192

Fig. 6.16: Free energy-plot of the relative thermodynamic stability of thaumasite in the system CaO-SiO2-CaCO3-H2O .................................................................................................. 100 Fig. 6.17: Temperature dependence of the phase relations between thaumasite and ettringite, SO4AFt (according to Macphee and Barnett [99]) ............................................................... 101 Fig. 6.18: Comparison of theoretically calculated (solid lines denote single solid phase regions) and dashed lines two solid phase regions), using the Guggenheim parameters a0 = -0.05 and a1 = 2.74) and experimentally-derived solubility products. ........................................... 102 Fig. 6.19: Comparison of calculated (lines) and experimental (single markers, taken from Macphee and Barnett [99]) solubility data for the ettringite-thaumasite solid solution series at 15C ....................................................................................................................................... 103 Fig. 6.20: XRD-pattern of a mixture of initially C3A, CaSO4, Na2CO3 (molar ratio 1 : 1.8 : 1.2) and excess Ca(OH)2 reacted 4 weeks in deionised water (w/s~30) at 25C......................... 105 Fig. 6.21: Calculated stable assemblages in the SO4-CO3-AFt system buffered by excess portlandite at 25C ........................................................................................................................... 105 Fig. 6.22: 3D-representation of part of the system CaO-Al2O3-SiO2-CaCO3-CaSO4-H2O at 25C, 1bar total pressure (excess calcite present) .................................................................... 107 Fig. 6.23: 3D-representation of part of the system CaO-Al2O3-SiO2-CaCO3-CaSO4-H2O at 5C 1bar total pressure (excess calcite present) ............................................................................ 110 Fig. 7.1: XRD-pattern showing mineralogical changes during 90d hydration of a 1:1:2 molar mixture of C3A, CaSO4 and CaO (w/s = 5) at 25C....................................................... 122 Fig. 7.2: XRD-pattern showing mineralogical changes during 90d hydration of a 1:1:1:2 molar mixture of C3A, CaSO4, CaCO3 and CaO (w/s = 5) at 25C ......................................... 122 Fig. 7.3: Comparison of qualitative time-dependent mineralogical changes during hydration of C3A with lime and calcium sulfate (SO3/Al2O3=1) in carbonate-free systems (left) or in the presence of excess calcite (right) at 25C ................................................................ 123 Fig. 7.4: Phase relations between AFm-AFt phases as well as gypsum, hydrogarnet and calcite in the system CaO-Al2O3-CaSO4-CaCO3-H2O at 25C (excess portlandite present in all assemblages) .................................................................................................................. 125 Fig. 7.5: Calculated phase assemblages of a hydrated mixture consisting of C3A, portlandite and varying initial sulfate (SO3/Al2O3) and carbonate contents (CO2/Al2O3) at 25C (the influence of minor carbonate substitution in AFt is not shown) ........................... 129 Fig. 7.6: Relative amount of hydrate phases of a hydrated model mixture consisting of C3A, portlandite and with fixed sulfate ratio (SO3/Al2O3=1) in dependence of changing carbonate contents (CO2/Al2O3) at 25C (the influence of minor carbonate substitution in AFt is not shown) .............................................................................. 131 Fig. 7.7: Calculated amount of reactive CaCO3 in dependence of the initial amount of initial solid Al2O3 content and bulk SO3/Al2O3 ratio of the paste at 25C (data are expressed in weight units; the influence of minor carbonate substitution in AFt is not considered) ... 132 Fig. 7.8: Calculated amount of reactive CaCO3 in dependence of the initial amount of initial solid SO3 content and bulk SO3/Al2O3 ratio of the paste at 25C (data are expressed in weight units; the influence of minor carbonate substitution in AFt is not considered) ............. 133 Fig. 7.9: Specific volume changes of hydrate phases of a hydrated model mixture consisting of C3A, portlandite and with fixed sulfate ratio (SO3/Al2O3=1) in dependence of changing carbonate contents (CO2/Al2O3) at 25C (the influence of minor carbonate substitution in AFt is not considered). ................................................................................................... 134

Figures and Tables

193

Fig. 7.10: Change of composition of aqueous phases of a hydrated model mixture consisting of C3A, portlandite at a fixed sulfate ratio (SO3/Al2O3=1) in dependence of changing carbonate ratios (CO2/Al2O3) at 25C. ........................................................................... 135 Fig. 7.11: XRD-pattern showing the influence of calcite addition to hydrated Portland cement analogue (mixture of C3S, C3A, CaSO4 and K2SO4, SO3/Al2O3molar=0.84, w/s=0.5) at sealed conditions stored 90d at ~25C........................................................................... 138 Fig. 7.12: Volume changes of hydrate phases and pore solution of a hydrated model cement with fixed sulfate ratio (SO3/Al2O3~0.7) in dependence of changing carbonate contents. .... 140 Fig. 7.13: Dependence of the amount of excess pore solution from the initial CO2/Al2O3 ratio of a hydrated model cement with fixed sulfate ratio (SO3/Al2O3=0.7;w/c = 0.5) at 25C .... 140 Fig. 7.14: Comparison of relative changes of calculated porosity of model cement paste (SO3/Al2O3 ~ 0.7, w/s=0.5) and relative changes of measured 1 year compressive strength of mortars (SO3/Al2O3 ~ 0.7, w/c=0.5)............................................................................................ 141 Fig. 7.15: Calculated phase assemblages of a hydrated mixture consisting of C3A, portlandite and varying initial sulfate (SO3/Al2O3) and carbonate ratios (CO2/Al2O3) at 5C................ 143 Fig. 7.16: Calculated phase assemblages of a hydrated mixture consisting of C3A, portlandite and varying initial sulfate (SO3/Al2O3) and carbonate contents (CO2/Al2O3) at 40C ......... 145 Fig. 7.17: Calculated phase assemblages of a hydrated mixture consisting of C3A, portlandite and varying initial sulfate (SO3/Al2O3) and carbonate contents (CO2/Al2O3) at 60C ......... 146 Fig. 7.18: Calculated phase assemblages of a hydrated mixture consisting of C3A, portlandite and varying initial sulfate (SO3/Al2O3) and carbonate contents (CO2/Al2O3) at 90C(left) and 99C (right) .................................................................................................................... 147 Fig. 7.19: Influence of temperature on specific volume changes of hydrate phases of a hydrated model mixture consisting of C3A, portlandite, CaSO4 and CaCO3 ; fixed sulfate ratio (SO3/Al2O3=1) and carbonate ratio (CO2/Al2O3 =1.25) ................................................. 148 Fig. 7.20: Calculated maximum amount of carbonate substitution in AFt as a function of temperature; excess calcite, monocarboaluminate and portlandite present ................... 149 Fig. 7.21: Influence of temperature on specific volume changes of hydrate phases of a hydrated model mixture consisting of C3A, portlandite, CaSO4 and CaCO3 ; fixed sulfate ratio (SO3/Al2O3=1) and carbonate ratio (CO2/Al2O3 =0.33) ................................................. 150 Fig. 7.22: XRD-pattern showing the influence of temperature on phase assemblages after 90d hydration of a 1:1:2 molar mixture of C3A, CaSO4 and CaO (w/s = 5) at 25C, 50C and 85C ............................................................................................................................... 152 Fig. 7.23: Qualititative comparison of time-dependent mineralogical changes during hydration of a 1:1:2 molar mixture of C3A, CaSO4 and CaO (w/s = 5) at 50C (left) and 85C (right)153 Fig. 7.24: XRD-pattern showing the influence of temperature on phase assemblages after 90d hydration of a 1:1:1:2 molar mixture of C3A, CaSO4, CaCO3 and CaO (w/s = 5) at 25C, 50C and 85C ............................................................................................................... 154 Fig. 7.25: Qualitative comparison of time-dependent mineralogical changes during hydration of a 1:1:1:2 molar mixture of C3A, CaSO4, CaCO3 and CaO (w/s = 5) at 50C (left) and 85C (right) ............................................................................................................................. 154 Fig. 7.26: XRD-pattern showing the influence of temperature on phase assemblages after 90d hydration of a Portland cement analogue composition (w/c = 0.5) at 25C, 50C and 85C ............................................................................................................................... 155 Fig. 7.27: XRD-pattern showing the influence of temperature on phase assemblages after 90d hydration of a Portland cement analogue composition blended with limestone (w/c = 0.5) at 25C, 50C and 85C ................................................................................................. 157

Figures and Tables

194

Fig. 7.28: XRD-pattern showing the phase assemblages of carbonate-free Portland cement analogue (w/c = 0.5) after 24h heat curing at 85C and subsequent storage at 5C for 180 d. . ....................................................................................................................................... 159 Fig. 7.29: XRD-pattern showing the phase assemblages of a calcite blended Portland cement analogue (w/c = 0.5) after 24h heat curing at 85C and subsequent storage at 5C for 180d.. . ....................................................................................................................................... 159 Fig. 7.30: Calculated phase assemblages of a hydrated mixture consisting of C3A, C-S-H (Ca/Si~1.6), portlandite and varying initial sulfate (SO3/Al2O3) and carbonate contents (CO2/Al2O3) at different temperatures. .......................................................................... 162 Fig. 7.31: Schematic showing the probability of hydrogarnet formation as function of time and temperature (solid lines indicate that formation is likely, dashed lines indicate formation is uncertain).................................................................................................................... 163

Tables
Table 4.1: Standard molar thermodynamic properties of cement hydrates at 25C, 1 bar .............. 20 Table 4.2: Reference reactions used to estimate unknown heat capacities of cement minerals ...... 21 Table 4.3: Dissolution reactions used to calculate solubility products ............................................ 22 Table 4.4: Metastable and stable invariant points in the system CaO-Al2O3-H2O at 5 and 25C ... 38 Table 5.1: Thermodynamic stabilities of selected AFm phases at 25C ......................................... 55 Table 5.2: Sulfate- and carbonate-contents of minerals relevant to Portland cement..................... 55 Table 5.3: Observed phase assemblages and their dependence of the initial solid carbonate ratio at 25C ................................................................................................................................ 74 Table 6.1: Standard molar thermodynamic properties of thaumasite at 25C ................................. 97 Table 6.2: Composition of aqueous phase of selected stable phase assemblages and invariant points in the system CaO-Al2O3-SiO2-CaSO4-CaCO3-H2O at 1bar and 5 and 25C............... 108 Table 6.3: Comparison of calculated activities for selected aqueous species relevant to .point I, Fig. 6.22, in dependence of the alkali content of the aqueous phase at 25C ...................... 113 Table 7.1: Composition of aqueous phase of selected stable phase assemblages and invariant points in the system CaO-Al2O3-CaSO4-CaCO3-H2O at 1bar and 25C ................................ 126 Table 7.2: Chemical composition of experimentally used Portland cement analogue .................. 136 Table 7.3: Influence of alkalis on the composition of aqueous and solid phases at selected invariant points at 25C ............................................................................................................... 165

Appendix

195

Appendix

A B
B.1 B.2 B.3 B.4 B.5 B.6

Thermodynamic data of the aqueous species and solubility data of cement hydrates ......................................................................................................................II Additional figures ................................................................................................ XVII
AFm solid solutions ........................................................................................................... XVII Thermodynamic calculations and free energy plots .........................................................XVIII Additional XRD-patterns C3A hydration - carbonate-free system...................................... XXI Additional XRD-patterns C3A hydration - excess calcite present ..................................... XXII XRD-patterns Portland cement analogue - carbonate-free system ...................................XXIII XRD-patterns Portland cement analogue - excess calcite present .....................................XXV

Additional details - AFm experiments ............................................................ XXVII

Appendix

II

A Thermodynamic data of the aqueous species and solubility data of cement hydrates

Appendix
Table A.1: Standard (partial molal) thermodynamic properties of aqueous species used in GEM Calculations at 25C, 1 bar G0 I) H0 S0 Cp0 V0 a1IV) a2 IV) a3 IV) species
[kJ/mol] Al AlO+ ( + H2O = Al(OH)2+ ) AlO2- ( + 2H2O = Al(OH)4- ) AlO2H ( aq) ( +2H2O = Al(OH)3 (aq ) AlOH2+ AlSO4+ Al(SO4)2Ca2+ CaOH+ CaCO3 (aq) CaHCO3+ CaSO4 (aq) CaHSiO3+ ( +H2O = CaSiO(OH)3+ ) Na+ NaOH (aq) NaCO3NaHCO3 (aq) NaSO4CO2 (aq) CO32HCO3SO42HSO4OHHSiO3- ( + H2O = H3SiO4-)
3+

III

a4 IV)
[calK/mol] -20758 -26763 -29441 -28140 -26639 -25974 -31466 -24792 -27322 -24179 -28310 -27004 -25649 -27260 -26826 -26982 -30805 -29414 -30879 -26143 -28266 -26970 -31618 -27821 -27575

c1 IV)
[cal/Kmol] 10.7 -2.5983 15.2391 -23.4129 29.7923 -11.6742 -12.022 9 11.1286 -11.5309 41.722 -8.4942 30.8048 18.18 4.0146 15.3395 33.879 13.4899 40.0325 -3.3206 12.9395 1.64 20.0961 4.15 8.1489

c2 IV)
[calK/mol] -80600 -91455 -54585 -132195 -3457 -129914 -161447 -25220 -27493 -90641 83360 -81271 36619 -29810 -36863 -55686 67193 -45256 88004 -171917 -47579 -179980 -19550 -103460 -73123

w IV)
[cal/mol] 275300 95700 174180 -3000 172470 117290 211990 123660 44960 -3800 30800 -100 58310 33060 -3000 178700 -3800 126060 -2000 339140 127330 314630 117480 172460 155110

RefV)
[172] [172] [172] [172] [172] [179] [179] [172] [172] [179] [96] [179] [179] [172] [172] [184]VII) [184]VII) [184]VII) [172] [172] [172] [172] [172] [172] [179]

[kJ/mol] -530.63 -713.64 -925.57 -947.13 -767.27 -1422.67 -2338.40 -543.07 -751.65 -1201.92 -1231.94 -1448.43 -1686.48 -240.28 -470.14 -938.56 -929.50 -1146.66 -413.84 -675.31 -690.01 -909.70 -889.23 -230.01 -1144.68

[J/(Kmol)] -325.10 -112.97 -30.21 20.92 -184.93 -172.38 -135.50 -56.48 28.03 10.46 66.94 20.92 -8.33 58.41 44.77 -44.31 154.72 101.76 117.57 -50.00 98.45 18.83 125.52 -10.71 20.92

[J/(Kmol)] -128.70 -125.11 -49.04 -209.21 55.97 -204.01 -268.37 -30.92 6.05 -123.86 233.70 -104.60 137.80 38.12 -13.40 -51.28 200.33 -30.09 243.08 -289.33 -34.85 -266.09 22.68 -136.34 -87.20

[cm /mol] -45.24 0.31 9.47 13.01 -2.73 -6.02 31.11 -18.44 5.76 -15.65 13.33 4.70 -6.74 -1.21 3.51 -0.42 32.32 18.64 32.81 -6.06 24.21 12.92 34.84 -4.71 4.53

[cal/(barmol)] -0.33802 0.21705 0.37221 0.35338 0.20469 0.13869 0.68275 -0.01947 0.27243 -0.03907 0.3706 0.24079 0.10647 0.1839 0.22338 0.23862 0.6173 0.47945 0.62466 0.28524 0.75621 0.83014 0.69788 0.12527 0.29735

[cal/mol] -1700.71 -248.11 399.54 84.85 -278.13 -439.2 889.25 -725.2 -113.03 -873.25 126.7 -189.92 -517.87 -228.5 -232.87 -195.21 729.43 392.84 747.11 -398.44 115.05 -198.46 925.9 7.38 -51.81

[calK/(barmol)] 14.5185 6.7241 -1.5879 5.4132 6.8376 7.4693 2.2479 5.2966 6.1958 9.1753 5.252 6.4895 7.7785 3.256 6.6683 6.5103 2.876 4.199 2.8136 6.4142 1.2346 -6.2122 2.1108 1.8423 5.9467

-483.71 -660.42 -827.48 -864.28 -692.60 -1250.43 -2006.30

II)

-552.79 II) -717.02 -1099.18 -1146.04 -1310.38 -1574.24 -261.88 II) -418.12 -797.11 -847.39 -1010.34 -386.02 -527.98 -586.94 II) -744.46 II) -755.81 -157.27 -1014.60

silica species (temperature correction using Cp(T) integration)


SiO2 (aq) ( + 2H2O = H4SiO4 (aq)) AlSiO4- ( + 3H2O = Al(OH)6SiO-)IX) AlHSiO32+ (+ H2O = AlSiO(OH)32+) CaSiO3 (aq) ( + H2O = CaSiO2(OH)2 (aq)) SiO32- ( + H2O = H2SiO42-)
I)

a0
41.34
III)

a1
[J/(molK2)] 0.034 III) A1[-] 0 0 0 0

a2
[J/(molK0.5)] -1.13E+06 III) A2[-] 1073.34 2206.31 1371.49 -3917.5

(Cp0=a0+a1T+a2T-2)

-833.41

VIII

-887.86 -1833.98 -1717.55 -1668.06 -1098.74

44.47

III)

16.06 25.53 -40.72 15.69 34.13

[J/(molK)] 46.94 III) A0 [-] 0 0 0 -10.0006

silica species (estimated temperature correction by one and two term temperature extrapolation) IX)
-1681.44 -1540.55 -1517.56 -938.51 11.13 -304.18 -136.68 -80.20 -4.58 -215.90 88.90 119.83

(LogK=A0+A1T+A2T-1)

recalculated by Thnen et al. [184] based on log_k values given in Hummel et al. [93] if not stated otherwise II) taken from Shock et al. [172] III)Cp parameters calculated using reference reaction SiO2 (aq) = SiO2(amorph) see Table 2 IV)parameters to solve the HKF-equation of state; given in original calorimetric units (see [96][172][179] as used in GEMS V) references for HKF parameters and S0 (see [184] for additional information) VII) HKF parameters predicted using program PRONSPREP [179] VIII) taken from slop98.dat (see [96]) IX)AlO2- + SiO2(aq) AlSiO4- (rS0=rCp0=0); Al3+ + HSiO3- AlHSiO32+ (rS0=rCp0=0); SiO2(aq) + H2O SiO32- + 2H+ (rCp0=0; rH0 taken from [93]); SiO32- + Ca2+ CaSiO3 (aq) (rS0=rCp0=0)

Appendix
Table A.2: Solubility data for C3AH6 at different temperatures 5C - 105C and ages
C3AH6 (samples cooled down from initially ~105C)
Age [d] 28 56 Temp. [C] 5 5 Ca [mmol/l] 6.57 7.20 Al [mmol/l] 4.17 4.10 pH Log_Ksp Phases
n.d.

IV

12.63 12.68 12.65 11.91 (11.98 ) 11.92 (11.902)) 11.81 (11.793)) 11.01 11.01 11.01 10.60 10.62 10.27 10.27 10.26 9.89 9.88 9.85
1)

-20.59 -20.29 -20.31 -20.52 -20.34 -20.84 -20.91 -20.80 -20.73 -21.25 -21.22 -21.80 -21.55 -21.55 -22.22 -22.17 -22.11

84 28 56 84 28 56 84 56 84 28 56 84 28 56 84

5 25 25 25 55 55 55 70 70 85 85 85 105 105 105

7.11 6.91 7.29 6.31 6.66 6.87 7.01 6.34 6.39 5.73 6.18 6.19 5.64 5.70 5.81

4.77 4.24 4.80 5.07 4.20 4.59 4.90 4.44 4.24 3.64 4.39 4.60 3.44 3.76 4.44

n.d. C3AH6, C2AH8, C4AcH11 n.d. n.d.

C3AH6
n.d. n.d.

C3AH6
n.d.

C3AH6
n.d. n.d.

C3AH6
n.d. n.d.

C3AH6

C3AH6 (from undersaturation)


n.d. 28 5 6.79 4.63 12.62 -20.47 n.d. 56 5 7.03 5.07 12.64 -20.36 C3AH6, C2AH8 84 5 7.01 4.40 12.65 -20.37 n.d. 28 25 7.20 4.73 11.91 (11.961)) -20.38 n.d. 56 25 7.34 4.55 11.93 (11.902)) -20.32 84 25 7.31 3.94 11.95 (11.913)) -20.36 C3AH6 n.d. 28 55 6.93 4.33 11.03 -20.78 n.d. 56 55 6.84 4.04 11.03 -20.83 84 55 7.16 4.44 11.04 -20.68 C3AH6 n.d. 56 70 6.39 3.97 10.63 -21.23 84 70 6.31 4.37 10.61 -21.26 C3AH6 n.d. 28 85 6.15 4.14 10.28 -21.57 n.d. 56 85 6.13 3.88 10.29 -21.59 84 85 6.11 4.27 10.27 -21.59 C3AH6 n.d. 28 105 5.57 3.67 9.87 -22.24 n.d. 56 105 5.63 4.46 9.83 -22.21 84 105 5.66 4.07 9.86 -22.19 C3AH6 1) temperature of solution 24C at time of measurement 2) temperature of solution 26C at time of measurement 3) temperature of solution 25C at time of measurement

Appendix

Table A.3: Solubility data of siliceous hydrogarnet (C3AS0.8H4.4) at different temperatures 5C - 85C
C3AS0.8H4.4 (from undersaturation1))
Temp. [C] Ca [mmol/l] Al [mmol/l] Si [mmol/l] Na [mmol/l] pH Log_Ksp Phases

5 5 5 25 25 25 55 55 55 70 70 70 85 85 85
1)

0.46 0.52 0.48 0.56 0.55 0.57 0.72 0.72 0.70 0.70 0.67 0.65 0.67 0.62 0.60

0.29 0.23 0.22 0.26 0.24 0.26 0.28 0.29 0.30 0.33 0.30 0.34 0.30 0.30 0.31

0.10 0.08 0.06 0.11 0.10 0.08 0.15 0.16 0.17 0.18 0.18 0.17 0.18 0.19 0.22

0.83 0.35 0.20 0.87 0.30 0.17 0.96 0.26 0.13 0.87 0.26 0.10 0.87 0.30 0.16

11.84 11.75 11.65 11.19 (11.13 ) 11.00 (10.94 ) 10.97 (10.902)) 10.41 10.23 10.16 10.02 9.84 9.74 9.72 9.52 9.43
2) 2)

-30.05 -30.42 -30.90 -29.58 -30.22 -30.29 -28.94 -29.43 -29.64 -28.97 -29.64 -29.90 -29.22 -29.87 -30.14

n.d. n.d. C3AS0.8H4.43), C-S-H n.d. n.d. C3AS0.8H4.43), C-S-H n.d. n.d. C3AS0.8H4.43), C-S-H n.d. n.d. C3AS0.8H4.43), C-S-H. n.d. n.d. C3AS0.8H4.43), C-S-H

all samples analysed after 4 week stored at the given temperature. After each analysis the removed solution (~20 ml) was replaced with ultra pure degassed water. 2) temperature of solution 26C at time of measurement 3) estimated composition

Appendix

VI

Table A.4: Solubility data of nominally monosulfoaluminate (C4AsH12) at temperatures 5C - 100C


C4AsH12
Ag e [d] Temp. [C] Ca [mmol/l] Al [mmol/l] SO42[mmol/l] pH Log_Ksp Phases

42 42 28 56 84 373 750 28 56 56 42 42 56 42 42 56 42 42 56
1)

5 5 25 25 25 25 25 25 25 40 50 50 65 70 70 85 90 90 100

us ss ss ss ss ss ss us us us us ss us ss us us ss us us

4.70 14.6 5.51 5.06 5.14 5.01 4.47 4.87 4.95 3.95 4.40 4.49 4.09 4.88 4.37 4.62 5.19 5.19 4.45

2.92 <0.02 2.91 3.13 3.29 3.71 3.26 3.93 3.42 3.31 2.84 2.64 3.13 2.57 2.18 2.63 2.57 1.87 2.67
3)

0.005 9.300 0.009 0.009 0.010 0.012 0.012 0.014 0.011 0.240 0.398 0.253 0.520 1.264 1.053 1.310 1.788 2.333 1.510

12.49 12.63 11.84 (11.90 ) 11.79 (11.83 ) 11.77 (11.82 ) 11.73 (11.771)) 11.69 (11.80 ) 11.71 (11.703)) 11.75 (11.801)) 11.10 10.91 10.97 10.44 10.37 10.36 9.99 9.91 9.87 9.62
2) 1) 1) 1)

-29.92 n.d. -29.24 -29.48 -29.43 -29.43 -29.66 -29.44 -29.45 -29.26 -28.84 -28.86 -29.29 -28.79 -29.17 -29.33 -29.12 -29.47 -29.86

C4AsH12, AFt,
C4Ac0.5H11.5

C4AsH12, AFt, C4Ac0.5H11.5, C3AH6 C4AsH12, AFt C4AsH12, AFt C4AsH12, AFt C4AsH12, AFt C4AsH12, AFt C4AsH12, AFt C4AsH12, AFt,
C4Ac0.5H11.5

C4AsH12, AFt C4AsH12, AFt4) C4AsH12, AFt n.d. C4AsH12, AFt3) C4AsH12 n.d. C4AsH12 C4AsH12 n.d.

measured at 24C, 2)measured at 23C

measured at 24C 4)very weak signal

Appendix

VII

Table A.5: Solubility data of monocarboaluminate(C4AcH11) at temperatures 5C - 110C


C4AcH11
Age [d] Temp. [C] Ca [mmol/l] Al [mmol/l] CO321)

pH

Log_Ksp

Phases

[mmol/l]

42 42 42 56 84 42 42 42 42 42 42 42 42

5 5 5 25 25 50 50 50 70 70 70 90 110

us us us
2)

2.58 2.52 2.35 3.19 3.73 4.42 4.46 4.30 5.24 5.35 5.11 6.54 6.05

1.60 1.56 1.63 2.32 2.16 2.34 2.51 2.40 3.30 3.42 2.94 5.02 4.56

0.008 0.008 0.008 0.008 0.008 0.007 0.007 0.007 0.007 0.007 0.007 0.006 0.005

12.24 12.24 12.18 11.56 (11.593)) 11.67 (11.62 ) 11.01 11.00 10.99 10.56 10.56 10.56 10.17 9.78
3)

-32.28 -32.36 -32.60 -31.66 -31.12 -30.94 -30.89 -31.02 -30.78 -30.71 -30.88 n. d. n. d.

C4AcH11, Calcite n. d. C4AcH11, Calcite C4AcH11, Calcite C4AcH11, Calcite C4AcH11, Calcite n. d. C4AcH11, Calcite C4AcH11, Calcite n. d. C4AcH11, Calcite C4AcH114), Calcite, C3AH6. C4AcH114), Calcite, C3AH6.

us ss us us us2) us us us
2)

us us

1) calculated values assuming equilibrium with calcite 2)prepared from a stoichiometric mixture of Al(OH)3, CaCO3 and CaO in 0.1 mol KOH-solution at 50C 3)measured at 25C 4) weak signals

Appendix

VIII

Table A.6: Solubility data of nominally hemicarboaluminate(C4Ac0.5H12) at temperatures 5C - 85C


C4Ac0.5H12
Age [d] Temp. [C] Ca [mmol/l] Al [mmol/l] CO321)

pH

Log_Ksp

Phases
C4Ac0.5H11.5, C4AcH11, C3AH6 C4Ac0.5H11.5, C4AcH11, C3AH6. C4Ac0.5H11.5, C4AcH11, C3AH6 C4Ac0.5H11.5, C4AcH11, C3AH6 C4Ac0.5H11.5, C4AcH11, C3AH6

[mmol/l]

28 56 28 56 28 28 365 28 56 28 56 28 56 28 56 84
1)

5 5 25 25 25 25 25 40 40 50 50 70 70 85 85 85

ss us ss us ss us us ss us ss us ss us ss us us

8.01 7.21 13.08 11.43 11.32 10.48 9.55 15.02 12.81 16.03 17.02 10.31 12.39 12.02 10.53 10.80

1.19 0.81 0.12 0.40 0.48 0.49 0.80 0.20 0.41 0.31 0.30 0.62 0.45 0.53 0.62 0.53

2.1E-06 8.2E-06 1.5E-04 3.3E-05 2.1E-05 3.4E-05 2.3E-05 1.4E-04 8.4E-05 1.2E-04 9.2E-05 1.3E-03 1.6E-03 3.1E-03 1.1E-03 5.1E-03

12.84 12.80 12.32 (12.312)) 12.26 (12.242)) 12.25 (12.272)) 12.22 (12.222)) 12.18 (12.303)) 11.90 11.83 11.64 11.67 10.97 10.97 10.71 11.04 10.67
2)

-29.67 -30.01 -29.35 -29.08 -29.00 -29.14 -29.12 -28.82 -28.79 n.d. n.d. n. d. n. d. n. d. n. d. n. d.
3)

n.d.
C4Ac0.5H11.5, C3AH6

n.d.
C4Ac0.5H11.5, C4AcH11, C3AH6 C4AcH11, C3AH6, Ca(OH)2 C4AcH11, C3AH6

n.d.
C4AcH11, C3AH6 C4AcH11, C3AH6, Ca(OH)2

n.d.
C4AcH11, C3AH6

calculated values assuming equilibrium with monocarboaluminate measured at 25C measured at 23C

Appendix

IX

Table A.7: Solubility data of nominally hydroxy-AFm (C4AH13) at 25C


C4AH13 (from supersaturation)
Age [d] Temp. [C] Ca [mmol/l] Al [mmol/l] pH Log_Ksp Phases
C4AH13, C3AH6 C4AH13, C3AH6 C3AH6, Ca(OH)2, C4AH13 )trces C3AH6, Ca(OH)2, C4AH13 )trces

28 56 373 750

25 25 25 25

17.64 20.11 19.91 19.96

0.21 0.20 0.17 0.09

12.44(12.40) 12.49(12.46) 12.48(12.43) 12.49(12.49)

-25.60 -25.21 (-25.38) (-25.93)

Appendix
Table A.8: Solubility data of strtlingite (C2ASH8) at temperatures 5C - 85C
C2ASH8 (samples from undersaturation1))
Age Temp. [C] Ca [mmol/l] Al [mmol/l] Si [mmol/l] Na [mmol/l] pH Log_Ksp Phases

28 561) 841) 28 56 84 28 28 28 561) 56 56 28 56 84 28 56 84 28 561) 28 56 841) 28 56 84 28 56 28 56


1) 1) 1) 1) 1) 1) 1) 1)

5 5 5 5 5 5 25 25 25 25 25 25 25 25 25 40 40 40 50 50 50 50 50 70 70 70 85 85 85 85

1.78 1.38 1.44 1.68 1.95 1.32 1.75 1.75 1.21 1.55 1.58 1.75 1.66 1.94 1.23 2.04 2.03 1.42 1.93 2.14 1.95 1.90 1.49 1.98 2.03 1.77 1.95 1.80 2.09 2.07

0.47 0.28 0.17 0.40 0.44 0.31 0.32 0.33 0.35 0.24 0.24 0.23 0.50 0.45 0.33 1.00 1.00 0.53 0.50 0.43 0.79 0.76 0.49 1.56 1.60 1.22 1.01 0.71 1.50 1.55

0.05 0.06 0.05 0.05 0.04 0.06 0.07 0.07 0.09 0.09 0.09 0.10 0.05 0.05 0.07 0.05 0.04 0.08 0.09 0.11 0.05 0.05 0.08 0.04 0.04 0.06 0.07 0.11 0.04 0.03

<0.2 <0.2 <0.2 2.35 2.80 0.91 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 2.17 2.60 0.90 2.17 2.60 1.05 <0.2 <0.2 2.26 2.40 1.14 2.28 2.20 1.50 <0.2 <0.2 2.30 2.30

12.18 12.08 12.12 12.41 12.49 12.20 11.45(11.58) 2) 11.45(11.54) 2) 11.26(11.35) 11.41(11.37) 11.46(11.42) 11.73(11.75) 11.41(11.48) 11.21 11.24 11.02 10.74 10.79 10.95 10.95 10.78 10.13 10.14 10.12 9.89 9.89 10.13 10.12
2)

-19.89 -20.46 -20.92 -20.08 -20.03 -20.35 -19.82 -19.82 -20.00 -20.05 -20.06 -19.95 -19.64 -19.61 -20.14 -18.91 -18.99 -19.57 -19.23 -19.14 -19.13 -19.13 -19.53 -18.76 -18.74 -18.87 -18.89 -19.06 -18.79 -18.87

n.d. n.d. C2ASH8, C-S-H n.d. n.d. C2ASH8, C-S-H, Calcite n.d. n.d. C2ASH8, C-S-H n.d. n.d. C2ASH8, C-S-H n.d. n.d. C2ASH8, C-S-H, Calcite n.d. n.d. C2ASH8, C-S-H, Calcite n.d. C2ASH8, C-S-H n.d. n.d. C2ASH8, C-S-H, Calcite n.d. n.d. C2ASH8, C-S-H, Calcite n.d. n.d. n.d.

11.40(11.40) 2)
2) 2)

11.65(11.70) 3)
3) 2)

n.d. C2ASH8, C-S-H, 84 85 1.75 1.08 0.07 1.50 10.03 -19.02 Calcite 1) solids filtered and redissolved after previous extraction 2)measured values at 23C 3) measured values at 24C

Appendix
Table A.9: Solubility data of CO3-AFt at 25C
C6Ac3H32
Age [d] Temp. [C] Ca [mmol/l] Al [mmol/l] CO321)

XI

pH2)

Log_Ksp

Phases

[mmol/l]

35 70 70 70 70 70 70 270 270

25 25 25 25 25 25 25 25 25

us us us us us us us us us

6.04 6.65 6.16 5.59 5.69 5.81 5.96 5.74 5.49

3.59 3.94 3.49 3.23 3.21 3.15 3.51 3.82 3.59

0.007 0.007 0.007 0.007 0.007 0.007 0.007 0.007 0.007

11.86(11.93) 11.90(11.83) 11.88(11.83) 11.83(11.81) 11.84(11.78) 11.86(11.83) 11.86(11.80) 11.82(11.96) 11.80(11.90)

-46.43 -46.10 -46.37 -46.70 -46.64 -46.58 -46.47 -46.59 -46.74


3)

CO3-AFt, Calcite CO3-AFt, Calcite. CO3-AFt, Calcite

n.d. n.d. n.d. n.d.


CO3-AFt, Calcite CO3-AFt, Calcite

Recalculated values for the metastable dissolution of CO3-AFt 1)

25

Calc.

5.90

3.93
2)

0.007

11.82

-46.50
3)

CO3-AFt, Calcite

calculated values assuming equilibrium with calcite measured values at 25C in parethesis metastability with respect to carboaluminates suppressed

Appendix

XII

Table A.10: Solubility data of monosulfoaluminate-hydroxy-AFm solid solutions at 25C (early age values)

C4AsxH14-2x
values from supersaturation Age [d] x [C] Ca [mmol/l] Al [mmol/l] SO42[mmol/l] pH1) Phases

28 28 28 56 28 28 28 56 28 28 56 28 28 56 28 28 56 28 28 56 28 28 56 28 28 28 28 28 28 28 28 28 28 28 28 28

0.98 0.95 0.90 0.90 0.90 0.85 0.80 0.80 0.80 0.70 0.70 0.70 0.60 0.60 0.60 0.50 0.50 0.50 0.40 0.40 0.40 0.20 0.20 0.20 0.05 0.98 0.95 0.90 0.85 0.80 0.70 0.60 0.50 0.40 0.20 0.05

5.15 6.69 8.28 7.58 7.36 7.72 8.36 8.56 8.31 9.73 9.68 9.47 10.73 10.70 10.56 10.85 10.95 11.01 11.03 11.18 10.92 11.00 11.08 11.18 11.15 4.78 4.71 6.61 7.15 7.82 8.86 9.63 10.19 10.43 10.53 15.12

2.40 2.30 1.01 1.51 3.30 3.50 2.51 2.73 2.22 1.60 2.04 2.86 1.56 2.10 1.99 1.84 1.77 1.82 1.84 1.89 1.83 1.53 1.75 1.74 1.84 3.48 2.99 3.54 3.90 4.05 3.34 2.57 2.04 1.80 1.78 0.39

1.0E-02 3.0E-03 3.6E-03 2.8E-03 1.6E-03 1.0E-03 1.7E-042) 1.7E-042) 1.7E-042) 9.3E-05 9.3E-05
2)

11.83 11.97 12.11 12.06 11.98 12.00 12.07 12.08 12.08 12.17 12.15 12.12 12.21 12.20 12.19 12.21 12.22 12.22 12.22 12.22 12.21 12.22 12.22 12.23 12.22

(n.d.) (n.d.) (12.12) (12.05) (12.05) (n.d.) (12.04) (12.03) (12.14) (12.16) (12.14) (12.16) (12.18) (12.18) (12.25) (12.18) (12.23) (12.25) (12.19) (12.21) (12.26) (12.22) (12.25) (12.26) (12.24)

ms-type (ss), AFt ms-type (ss) ms-type (ss) ms-type (ss) n.d ms-type (ss) ms-type (ss) ms-type (ss) n.d ms-type (ss), C2AH8 ms-type (ss), C2AH8 n.d. ms-type (ss), C2AH8) ms-type (ss), C2AH8 n.d. ms-type (ss), C2AH8 ms-type (ss), C2AH8 n.d. ms-type (ss), hydroxyAFm-type(ss), C2AH8 ms-type (ss), hydroxyAFm-type(ss), C2AH8 n.d. ms-type (ss), hydroxyAFm-type(ss), C2AH8 ms-type (ss), hydroxyAFm-type(ss), C2AH8 n.d. hydroxy-AFm-type(ss) ms-type (ss), AFt ms-type (ss), AFt ms-type (ss) ms-type (ss) ms-type (ss) ms-type (ss) ms-type (ss), hemicarb. ms-type (ss), hemicarb. ms-type (ss), hemicarb. ms-type (ss), hemicarb. hemicarb., C3AH6

9.3E-052)
2) 2)

5.7E-05

5.7E-052) 5.7E-052) 4.0E-05 4.0E-05


2)

4.0E-052)
2)

3.7E-052) 3.7E-052) 3.7E-05


2)

3.7E-052) 3.7E-052) 3.7E-052) 3.7E-052) 1.4E-02 1.3E-02 1.4E-02 2.6E-03 1.7E-042) 9.3E-05
2)

values from mixed end members

11.70 11.72 11.75 11.91 11.94 11.99 12.08 12.14 12.18 12.19 12.20

(11.68) (11.71) (11.75) (11.85) (11.87) n.d. n.d. n.d. n.d n.d. n.d

5.7E-052) 4.0E-052) 3.7E-052) 3.7E-052) 3.7E-052)

Appendix
(Table A.10 continued)
values from undersaturation Age [d]
3)

XIII

x [C]

Ca [mmol/l]

Al [mmol/l]

SO42[mmol/l]

pH

Phases

28 28 28 28 28 28 28 28 28
1)

0.98 0.95 0.80 0.70 0.60 0.50 0.40 0.20 0.05

4.97 5.09 7.49 8.28 9.04 9.96 11.00 11.30 12.29

3.43 3.17 3.78 4.04 3.32 2.68 2.19 1.83 1.35

1.2E-02 1.2E-02 1.7E-04 9.3E-05


2) 2)

11.75 11.78 11.97 12.02 12.09 12.15 12.21 12.23

(11.75) (11.76) (11.98) (12.01) (12.08) (12.15) (12.20) (12.22)

ms-type (ss), AFt ms-type (ss), AFt ms-type (ss) ms-type (ss) ms-type (ss), hemicarb. ms-type (ss), hemicarb. ms-type (ss), hemicarb. ms-type (ss), hemicarb.

5.7E-052) 4.0E-052) 3.7E-052) 3.7E-052) 3.7E-052)


2)

hemicarb., C3AH6 12.27 (12.30) calculated values, measured values given in parenthesis calculated values; experimental values below limit of detection <~2.0E-3 mmol SO4/l 3)time of experiment; original samples from supersaturation experiments aged 56 d

Appendix

XIV

Table A.11: Solubility data of monosulfoaluminate-hydroxy-AFm solid solutions at 25C (aged samples)

C4AsxH14-2x
values from supersaturation Age [d] x [C] Ca [mmol/l] Al [mmol/l] SO42[mmol/l] pH1) Phases

373 373 373r 373 373 373 373 373 373 373 750 750 750 750 750 750 750 750 750

0.98 0.95 0.90 0.80 0.70 0.60 0.50 0.40 0.20 0.05 0.95 0.90 0.80 0.70 0.60 0.50 0.40 0.20 0.05

4.62 4.97 6.44 8.16 9.93 12.72 15.89 16.07 16.22 16.29 4.67 5.86 7.36 10.33 13.47 17.34 19.24 19.09

2.87 2.15 3.13 4.05 1.51 0.74 0.31 0.30 0.25 0.36 1.85 3.19 4.08 1.18 0.42 0.13 0.06 0.07

1.2E-02 1.2E-02 2.1E-03 2.1E-03 <2.0E-3 <2.0E-3 <2.0E-3 <2.0E-3 <2.0E-3 <2.0E-3) 2.1E-02 8.5E-03 4.2E-03 <2.0E-3 <2.0E-3 <2.0E-3 <2.0E-3 <2.0E-3

11.74 11.83 11.92 12.01 12.18 12.30 12.40 12.40 12.40 12.41 11.81 11.86 11.95 12.20 12.33 12.43 12.47 12.47 12.47

(11.82.) (11.87.) (11.93) (12.02) (12.12) (12.23) (12.38) (12.40) (12.40) (12.39) (11.84) (11.95) (12.01) (12.15) (12.26) (12.36) (12.43) (12.43) (12.41)

n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. ms-type (ss) ms-type (ss) ms-type (ss) ms-type (ss), C3AH6 ms-type (ss), C3AH6 ms-type (ss), C3AH6 ms-type (ss), hemicarb, C3AH6 ms-type (ss), hydroxyAFm-type(ss), C3AH6 hydroxy-AFm-type(ss), C3AH6

<2.0E-3 19.19 0.15 1) calculated values, measured values given in parenthesis

Appendix
Table A.12: Solubility data of SO4-CO3-AFt solid solutions at 25C

XV

C6As3xc3-3xH32
Age [d] x Ca [mmol/l] Al [mmol/l] SO42[mmol/l] CO322)

pH1)

Phases
n.d. n.d. SO4-AFt n.d. SO4-AFt-type, calcitetraces n.d.s SO4-AFt-type, calcitetraces n.d. n.d. SO4-AFt-type, calcite SO4-AFt-type, calcite n.d.s n.d. n.d. SO4-AFt-type, calcite SO4-AFt-type, calcite n.d. n.d. SO4-AFt-type, CO3-AFt-typetraces, calcite SO4-AFt-type, CO3-AFt-typetraces, calcite n.d n.d. SO4-AFt-type, CO3-AFt-typetraces, calcite SO4-AFt-type, CO3-AFt-typetraces, calcite n.d. SO4-AFt-type, CO3-AFt-typetraces, calcite n.d. SO4-AFt-type, CO3-AFt-typetraces, calcite n.d. n.d. CO3-AFt-typetraces, calcite

[mmol/l]

28 35 84 35 84 28 35 28 35 84 84 35 28 35 84 84 28 35 84 84 28 35 84 84 28 84 35 84 28 35 84
1)

1 1 1 0.95 0.95 0.9 0.9 0.8 0.8 0.8 0.8 0.7 0.6 0.6 0.6 0.6 0.5 0.5 0.5 0.5 0.4 0.4 0.4 0.4 0.3 0.3 0.2 0.2 0.05 0.05 0.05

2.00 2.20 1.93 2.96 1.95 3.00 3.04 5.20 4.59 2.80 2.72 4.99 6.00 5.09 5.14 5.03 6.15 5.24 5.59 5.61 6.10 5.09 5.69 5.72 6.30 5.81 5.31 6.18 6.50 5.31 5.96

0.60 0.64 0.58 1.12 0.65 2.10 2.33 3.46 3.72 1.88 1.70 3.75 3.20 3.83 3.39 3.21 3.50 3.83 3.23 3.44 3.40 3.83 3.21 3.51 3.20 3.15 3.33 3.43 3.20 3.50 3.51

1.460 1.500 1.174 0.360 0.974 0.030 0.043 0.004 0.006 0.070 0.070 0.005 0.003 0.006 0.005 0.009 0.003 0.005 0.003 0.004 0.002 0.006 0.004 0.003 0.002 0.003 0.004 0.002 0.002 0.004 0.002

------0.008 0.010 0.008 0.008 0.007 0.007 0.008 0.008 0.007 0.007 0.007 0.007 0.007 0.007 0.007 0.007 0.007 0.007 0.007 0.007 0.007 0.007 0.007 0.007 0.007 0.007 0.007 0.007
2)

10.90(11.01) 10.85(10.90) 10.93 11.56(11.26) 11.07 11.53(11.66) 11.51(11.54) 11.78(11.87) 11.68(11.75) 11.51 11.51 11.73(11.77) 11.88(11.90) 11.74(11.83) 11.77 11.77 11.87(11.92) 11.76(11.83) 11.83 11.82 11.88(11.93) 11.74(11.83) 11.84 11.83 11.90(11.93) 11.86 11.80(11.87) 11.88 11.92(11.96) 11.79(11.88) 11.86

calculated values, measured values given in parenthesis calculated values assuming equilibrium with calcite

Appendix
Table A.13: Solubility data of thaumasite from undersaturation at different temperatures 1C - 70C
Synthetic thaumasite (C3SscH15) Age1) [d] Temp. [C] Ca [mmol/l] Si [mmol/l] SO42[mmol/l] CO322)

XVI

Na [mmol/l]

pH

Log_Ksp

Phases
C3SscH15, Calcite traces n.d. C3SscH15, Calcite traces C3SscH15, Calcite traces n.d. C3SscH15, Calcite traces C3SscH15, Calcite traces n.d. n.d. n.d. C3SscH15, Calcite traces C3SscH15, Calcite traces C3SscH15, Calcite traces n.d. C3SscH15, Calcite traces C3SscH15, Calcite, C-S-H n.d. C3SscH15, Calcite, C-S-H Calcite, C-S-H n.d. Calcite, C-S-H

[mmol/l]

28 56 84 28 56 84 28 28 56 56 84 84 28 56 84 28 56 84 28 56 84

1 1 1 5 5 5 25 25 25 25 25 25 40 40 40 55 55 55 70 70 70

0.62 0.65 0.70 0.80 0.67 0.70 1.07 1.12 1.07 1.12 1.02 1.07 1.87 1.90 1.97 8.93 6.54 6.49 13.75 5.54 5.29

0.69 0.52 0.54 0.74 0.50 0.53 0.65 0.66 0.62 0.64 0.64 0.66 0.91 0.91 0.95 0.10 0.11 0.11 0.07 0.12 0.13

0.52 0.40 0.45 0.62 0.38 0.39 0.54 0.54 0.50 0.48 0.51 0.49 0.85 0.76 0.80 7.40 5.47 5.56 11.04 4.57 4.21

0.056 0.020 0.019 0.029 0.018 0.017 0.013 0.013 0.013 0.013 0.014 0.013 0.010 0.010 0.010 0.007 0.008 0.008 0.007 0.008 0.008

0.10 0.02 0.03 0.10 0.02 0.03 0.07 0.07 0.02 0.02 0.03 0.03 0.07 0.03 0.03 0.08 0.03 0.03 0.07 0.04 0.04

9.94 10.76 10.76 10.20 10.90 10.91 10.67(10.50)3) 10.73(10.57)3) 10.71(10.61)3) 10.78(10.61)3) 10.62(10.79)3) 10.70(10.88)3) 10.57 10.62 10.64 10.52 10.36 10.31 10.38 9.97 10.02

-27.09 -26.10 -26.00 -26.19 -25.79 -25.70 -24.78 -24.69 -24.79 -24.69 -24.89 -24.78 -23.90 -23.88 -23.80 -23.14 -23.47 -23.52 n.d. n.d. n.d.

natural thaumasite (C3SscH15)

180 180
1) 3)

5 25

0.92 1.32

0.71 1.00

0.61 0.96

0.018 0.020

~0.01 ~0.01

10.57 9.94(9.68)3)

-25.61 -25.10

C3SscH15, Calcite traces C3SscH15, Calcite traces

solids filtered and redissolved after previous extraction 2) calculated values assuming equilibrium with calcite calculated values, measured values at 25C given in parenthesis

Appendix

XVII

B B.1

Additional figures AFm solid solutions


H - hy droxy -AFm ty p e ss M - monosulfoaluminate ty p e ss P - p ortlandite C3AH 6 C3AH 6 M, H M H P

0
HC ? - hemicarboaluminate

hydroxy-AFm

0.05 0.20 0.40

0.50 0.60 0.80 0.90


AFt

Intensity

10

15 [2 Cuk ]

20

25

1.00 monosulfoaluminate

Fig. B.1: XRD-pattern of synthesised solid solutions between hydroxy-AFm and monosulfoaluminate by mixed end members.

H - hy droxy -AFm M c - monocarboaluminate H Hc - hemicarboaluminate

H
C3AH 6 C3AH 6

Hc

Hc

500 cps

0.50
Mc Mc

Intensity

0.80

1.00 monocarbo5 10 15 [2 CuK ] 20 25


aluminate

Fig. B.2: XRD-pattern of solids obtained from various initial CO3/(CO3+2OH) (C3A+xCaO+1-xCaCO3) ratios by supersaturation

CO 3/(CO 3+2OH)-ratio [-]

Hc

0 0.20

SO 4/(SO 4+2OH)-ratio [-]


hydroxy-AFm

500 cps

Appendix

XVIII

B.2 Thermodynamic calculations and free energy plots


280 270 - G0 r [kJ/mol] 260 250 240 230 220 0 10 20 30 Temperature [C] 40 50 (2) 0.666C3 A + CaO + SiO2 (am) + 0.333CaCO3 + CaSO4 + 15.8188H2 O
--> 0.333C6 As 3 H32 + CaO.SiO2 .1.486H2 O + 0.333C4 AcH11

(1) 0.666C3 A + CaO + SiO2 (am) + 1.666CaCO3 + CaSO4 + 22.333H2 O


--> C3 SscH15 + 0.666C4 AcH11

Fig. B.3: Free energy plot of the formation of the phase assemblage thaumasite+CO3-AFm vs. ettringite+C-S-H+CO3-AFm
excess portlandite present in all assemblages
1)minor

3.5

2)

hydroxide substitution possible AFt -composit ion see region Va

VI
AFt-ss

AFt +gypsum + calcite

3.0

Va
IVa
AFt-ss + MC
2)

(Ca 6 Al2 (SO 4 ) 3x (CO 3 ) 3-3x (OH) 12 26H 2 O (0.91<x<1)

+ calcite

molar bulk SO 3/Al 2O3-ratio

2.5

2.0 1.5

V
AFt-ss
(Ca6 Al2 (SO4 )2.73 (CO3 )0.27 (OH)12 .26H2 O)

I
AFt + Hc + Ms
1)

+ monocarboaluminate + calcite

1.0

II
0.5

IV
Ms-ss + Hc AFt + hemicarboaluminate+ monocarboaluminate 0.5 0.75 1 1.25 1.5

III

0.0 0

Ms-ss+ Hc+ C3AH 6 0.25

molar bulk CO 2/Al2O 3-ratio

Fig. B.4: Calculated phase assemblages of a hydrated mixture consisting of C3A, portlandite and varying initial sulfate (SO3/Al2O3) and carbonate contents (CO2/Al2O3) at 25C (including SO4-CO3-AFt solid solutions)

Appendix

XIX

a)

240

C 3A + 0.25C a C O 3 + C a S O 4.2H 2O +14.75H 2O +0.25C a (OH)2 --> 0.25C 6As 3H 32 + 0.25C 4As H 12 + 0.5C 4Ac 0.5H 12

250 240 [kJ/mol] 230 220 210 200 190


C3 A + CaSO 4 .2H2 O +10H 2 O --> C4 AsH12 C3 A + CaCO3 + CaSO4 .2H2 O +16H2 O -->~0.33 C6 As3 H32 +~0.67C4 AcH11 +~0.33CaCO3

b)

[kJ/mol]

230

28C

50C
X

- G

C3 A + 0.25CaCO3 + CaSO4 .2H2 O +12.25H2 O --> 0.125C6 As3 H32 + 0.625C4 AsH12 + 0.25C4 AcH11

210 0 10 20 30 Temperature [C] 40 50

- G

220

10

20

30

40 50 60 70 Temperature [C]

80

90 100

Fig. B.5 : Free energy plots showing the influence of temperature on the stability of the phase assemblage a) hemicarboaluminate., monosulfoaluminate and AFt vs. monocarboaluminate, monosulfoaluminate and AFt and b) monocarboaluminate and AFt vs. monosulfoaluminate and calcite

300 280 260 240 220 200 180 0


C3 A + 3CaSO4 .2H2 O +6H2 O --> C4 AsH12 + 2CaSO4

C3A + 3CaSO 4.2H 2O +26H 2O --> C6As 3H 32

- G r [kJ/mol]

92C

109C

C3 A + 3CaSO4 .2H2 O +7H2 O --> C4 AsH12 + 2CaSO4 .0.5H2 O

10

20

30

40

50 60 70 80 Temperature [C]

90 100 110 120

Fig. B.6: Free energy plots showing the formation of ettringite and monosulfoaluminate and anhydrite or hemihydrate

Appendix

XX

160 140 SO 42- [mmol/kg] 120 100 80 60 40 20 0 0 10 20 30 40 50 60 70 80 90 100 mM NaOH 50 mM NaOH alkali free 200 mM NaOH

te mpe rature [C]


Fig. B.7: Influence of temperature and aqueous sodium hydroxide concentration on the equilibrium sulfate concentration of a mixture of ettringite-monosulfoaluminate-aqueous phase

Appendix

XXI

B.3

Additional XRD-patterns C3A hydration - carbonate-free system


SO4 -AFm SO4 -AFt
SO4 -AFt

p ortlandite

SO4 -AFt anhydrite

p ortlandite p ortlandite
SO 4 -AFm

SO4 -AFm
C3 AH 6

C3 A

90d 28d 7d
100counts

48h 26h 18h 1h

Intensity 5

10

15

20

25

30

35

[2 Cuk ]
Fig. B.8: XRD-pattern showing mineralogical changes during 90d hydration of a 1:1:2 molar mixture of C3A, CaSO4 and CaO (w/s = 5) at 50C

portlandite

portlandite portlandite

SO4 -AFm
SO 4-AFm
(n H2O <12) ??

SO4 -AFm

C3 A

anhydrite

SO 4 -AFm

90d 28d 7d

100counts

48h 26h 18h 1h

Intensity 5

10

15

20

25

30

35

[2 Cuk ]
Fig. B.9: XRD-pattern showing mineralogical changes during 90d hydration of a 1:1:2 molar mixture of C3A, CaSO4 and CaO (w/s = 5) at 85C

Appendix

XXII

B.4

Additional XRD-patterns C3A hydration - excess calcite present

SO 4-AFm SO4 -AFt

p ortlandite SO4 -AFm


SO 4 -AFt SO4 -AFt
S O 4-AF t

calcite p ortlandite

anhydrite p ortl.

C3 A

S O 4-AF m

90d 28d 7d
100counts

48h 26h 18h 1h

Intensity 5

10

15

20 [2 Cuk ]

25

30

35

Fig. B.10: XRD-pattern showing mineralogical changes during 90d hydration of a 1:1:1:2 molar mixture of C3A, CaSO4, CaCO3 and CaO (w/s = 5) at 50C

SO 4-AFm SO4 -AFt

p ortlandite SO4 -AFm


SO 4 -AFt SO 4 -AFt
S O 4-AF t

calcite p ortlandite

anhydrite p ortl.

C3 A

S O 4-AF m

SO4-AFm ?? (nH2O < 12) ??

90d 28d 7d

100counts

48h 26h 18h 1h 10 15 20 [2 Cuk ] 25 30 35

Fig. B.11: XRD-pattern showing mineralogical changes during 90d hydration of a 1:1:1:2 molar mixture of C3A, CaSO4, CaCO3 and CaO (w/s = 5) at 85C

Intensity 5

Appendix

XXIII

B.5 XRD-patterns Portland cement analogue - carbonate-free system


p ortlandite

SO4 -AFm

p ortlandite p ortlandite SO -AFm 4

SO4 -AFm

90d
SO4 -AFt SO4 -AFt
C3 S C3 A

28d
20counts

7d
anhydrite

Intensity

48h 24h 10 15 20 25 30 35 [2 Cuk ]

Fig. B.12: XRD-pattern showing mineralogical changes during 90d hydration of a Portland cement analogue (w/c = 0.5) at 25C

portlandite

SO4 -AFm sil. HG

portlandite portlandite SO -AFm 4

SO4 -AFm

90d

28d
C3 S 20 coun ts

7d
SO4 -AFt SO4 -AFt
C3 A

Intensity

48h 24h 10 15 20 25 30 35 [2 Cuk ]

Fig. B.13: XRD-pattern showing mineralogical changes during 90d hydration of a Portland cement analogue (w/c = 0.5) at 50C (sil. HG - siliceous hydrogarnet)

Appendix

XXIV

portlandite

SO4 -AFm sil. HG

portlandite portlandite SO -AFm 4

SO4 -AFm

90d

28d
C3 S 20counts

7d
C3 A

Intensity

48h 24h 10 15 20 25 30 35 [2 Cuk ]

Fig. B.14: XRD-pattern showing mineralogical changes during 90d hydration of a Portland cement analogue (w/c = 0.5) at 85C (sil. HG - siliceous hydrogarnet)

Appendix

XXV

B.6

XRD-patterns Portland cement analogue - excess calcite present

p ortlandite

SO4 -AFt

Mc

SO4 -AFt

calcite p ortlandite

SO4 -AFt Mc p ortlandite

90d
C3 S C3 A

anhydrite
20counts

28d 7d 48h 24h

Intensity 5

10

15

20

25

30

35

[2 Cuk ]
Fig. B.15: XRD-pattern showing mineralogical changes during 90d hydration of a Portland cement analogue (w/c = 0.5) in the presence of excess calcite at 25C (Mc - monocarboaluminate)

SO4 -AFm

p ortlandite

calcite p ortlandite

p ortlandite

sil. HG

SO4 -AFm

SO 4 -AFm

90d

28d
C3 S 50counts

7d
C3 A

Intensity

48h
??-AFm ??-AFm

24h 25 30 35

10

15

20

[2 Cuk ]
Fig. B.16: XRD-pattern showing mineralogical changes during 90d hydration of a Portland cement analogue (w/c = 0.5) in the presence of excess calcite at 50C (sil. HG - siliceous hydrogarnet)

Appendix

XXVI

portlandite

calcite portlandite

portlandite

SO4 -AFm

sil. HG

SO4 -AFm

SO4 -AFm

90d

28d
C3 S 50counts

7d
C3 A

Intensity

48h
??-AFm ??-AFm

24h 25 30 35

10

15

20

[2 Cuk ]
Fig. B.17: XRD-pattern showing mineralogical changes during 90d hydration of a Portland cement analogue (w/c = 0.5) in the presence of excess calcite at 85C (sil. HG - siliceous hydrogarnet)

Appendix

XXVII

Additional details AFm experiments

Table C.1: composition of mixtures between monosulfoaluminate and hydroxy-AFm (supersaturation) OH-SO4-AFm SO4/(SO4+2OH) 1 0.98 0.95 0.9 0.85 0.8 0.7 0.6 0.5 0.4 0.2 0.05 0 C3A 2 2 2 2 2 2 2 2 2 2 2 2 2 CaSO4 1.0077 0.9876 0.9573 0.8566 0.9069 0.8062 0.7054 0.6046 0.5039 0.4031 0.2015 0.0504 0.0000 CaO [g] 0.0000 0.0083 0.0208 0.0623 0.0415 0.0830 0.1245 0.1660 0.2075 0.2491 0.3321 0.3943 0.4151 H2O 125 125 125 125 125 125 125 125 125 125 125 125 125

Table C.2: composition of mixtures between monosulfoaluminate and hydroxy-AFm (mixed end members) OH-SO4-AFm SO4/(SO4+2OH) 1 0.98 0.95 0.9 0.85 0.8 0.7 0.6 0.5 0.4 0.2 0.05 0 monosulfoaluminate 2 1.4 2 1.8 1.8 1.6 1.4 1.2 1 0.8 0.4 0.1 0 hydroxy-AFm [g] 0 0.0257 0.0948 0.1801 0.2860 0.3601 0.5402 0.7203 0.9003 1.0804 1.4405 1.7106 2.0000 H2O 60 60 60 60 60 60 60 60 60 60 60 60 60

Appendix

XXVIII

Table C.3: composition of mixtures between monocarboaluminate and hydroxy-AFm (supersaturation) OH-CO3-AFm CO3/(CO3+2OH) 1 0.8 0.5 0.2 0 C3A 2 2 2 2 2 CaCO3 [g] 0.7409 0.5927 0.3704 0.1482 0.0000 0.0000 0.0830 0.2075 0.3321 0.4151 CaO

Table C.4: composition of mixtures between monocarboaluminate and hydroxy-AFm (mixed end members) OH-CO3-AFm CO3/(CO3+2OH) 1 0.8 0.5 0.2 0 monocarboaluminate [g] 2.0 1.6 1.0 0.4 0.0 0.0000 0.3944 0.9860 1.5775 2.0000 hydroxy-AFm

Table C.5: composition of mixtures between monocarboaluminate and monosulfoaluminate (mixed end members) SO4-CO3-AFm CO3/(CO3+SO4) 1 0.5 0 monocarboaluminate [g] 2.0 1.0 0.0 0.0000 1.0951 2.0000 monosulfoaluminate

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