Concrete Repair, Rehabilitation and Retrofitting II Alexander et al (eds) 2009 Taylor & Francis Group, London, ISBN 978-0-415-46850-3

Use of calcium sulfoaluminate cement to improve strength of mortars at low temperature

J. Ambroise & J. Pra
Laboratoire Gnie Civil et Ingnirie Environnementale, Institut National des Sciences Appliques de Lyon, Villeurbanne, France

ABSTRACT: One of the main properties required by mortars for concrete repair is rapid strength development regardless of the temperature. The strength development of mortars based either on Portland cement (OPC) or Calcium Aluminate Cement (CAC) is easily managed at 20C, utilizing usual accelerators. At 5C, it is more complicated. Calcium Sulfoaluminate Cement (CSA) introduced in mortars either as binder or as CAC accelerator represents a solution to solve this problem. This paper presents two examples of CSA utilization. The first example deals with the development of sealing mortar for road works using CSA as binder. Such mortar presents 2-hr strength higher than 9 MPa at 5C and time of workability higher than 20 minutes at 20C. The second utilization concerns the acceleration of self-levelling topping mortar based on CAC. When 25% CAC is replaced by CSA, the 1-day strength shifts from 1 to 8 MPa at 5C without modifying the time of workability at 20C.

INTRODUCTION

The efficient repair and replacement of concrete pavements and bridge decks often requires a rapid setting material that can be placed, cured, and opened to traffic in a relatively short period of time. Several repair materials are marketed for the repair of deteriorating concrete structures. These repair materials are classified into different types, such as cement, epoxy resins, polyester resins, polymer latex and polyvinyl acetate. Cement-based materials and polymer/epoxy resins are the most widely used among the repair materials (Shaw 1985, Allen et al. 1994, Rama 1996, Al Zahrani et al. 2003). Additives such an accelerator, a retarder, an air-entrainer, a plasticizer and a superplasticizer are used to improve setting time and workability. High early strength cement (ASTM Type III) is used when rapid strength gain is required, but it has the disadvantages of high shrinkage and slow strength in cold weather. Calcium aluminate cement (CAC) has several important characteristics including early strength gain, chemical resistance, and excellent refractory properties (French et al. 1971, El Jazieri et al. 1989, Baker et al. 1993, Scrivener et al. 1998). Accelerated OPC and CAC work very well at 20C, but their performances decrease at 5C.

According to Schwarz (1995), concrete mixes are classified as high early strength concretes if significant strength values between 612 hours at 20C, between 1224 hours at 10C and between 2448 hours at 5C develop. The requirements on the properties of the hardened concrete vary with the type of application. Early strength of 15 MPa within 56 hours have to be attained for bridge and road decks, and airfields which require works during night-shifts and ready for service runways early in the morning of the next day. In the present study, calcium sulfoaluminate cement (CSA) has been introduced in mortars either as binder or as CAC accelerator to get good performances at 5C in two cases: development of sealing mortar for road works; acceleration of self-levelling topping mortar based on CAC. Yeelimite or Kleins compound (anhydrous calcium sulfoaluminate, 4CaO . 3Al2O3 . SO3) is the key ingredient of CSA cement. Its importance derives from the fact that on hydration in the presence of lime and calcium sulphate, it rapidly hydrates to form ettringite. Advantages follow not only from the rapidity of the formation of this hydration product but also from its acicular or prismatic crystal morphology. It has been

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employed in a range of compositions under conditions taking advantage of one or more of the features of its formation: high early strength development or expansion (Su et al. 1997, Zhang et al. 1999, Odler 2000, Chatterjee 2002, Ambroise et al. 2003a, b, Pra et al. 2004).

SEALING MORTAR FOR ROAD WORKS

The following requirements had to be fulfilled: the mortar is self-compacting; the time of workability is higher than10 minutes at 30C, and 20 minutes at 5C and 20C; the 2-hr compressive strength is higher than 7.5 MPa, regardless of the temperature; the drying shrinkage is minimum. The workability was measured by means of the static spread of a truncated cone presenting the following dimensions: inf = 80 mm; sup = 70 mm; h = 40 mm. Mortar was self-consolidating when the spread was higher than 120 mm. The starting recipe of the mortar is presented in Table 3. CSA cement was composed of 75% CK and 25% RG. Borax was used as retarder and lithium carbonate (Li2CO3) was introduced as accelerator. Two points were optimized: the particle size distribution of the sand; the borax content. 3.1 Optimization of the particle size distribution of the sand

PROPERTIES OF CSA USED IN THE STUDY

A Chinese commercially produced calcium sulfoaluminate clinker (CK) has been used in the present study and its characteristics are shown in Table 1. Its mineralogy was assessed by X-ray diffraction (Table 2). The amount of yeelimite, also called Kleins compound, was very high: 73.5%. This phase and mayenite are responsible of the development of early age strength. To prepare CSA cement, CK was mixed with re-crystallized gypsum (RG), a by-product of the manufacture of phosphoric acid by the Prayon PH2 process, with two hemihydrate stages followed by a dihydrate process producing co-crystallized gypsum with low P2O5 content. The pure gypsum content of RG determined by DTA-TGA was 89.4%. Other properties of RG are presented in Table 1.
Table 1. Properties of materials. CK Chemical analysis (%) SiO2 Al2O3 CaO TiO2 MgO P2O5 SO3 LOI Average diameter of the particle size distribution (m) BET Surface area (m2/g) Blaine specific surface area (m2/kg) Table 2. Phase Yeelimite Larnite Perovskite Mayenite Periclase Anhydrite Quartz 4.7 37.4 39.2 1.6 1.7 0.2 8.8 0.9 16 1.05 453 RG 0.3 0.3 38.5 0.01 0.8 0.03 42.6 20.3 11 1.6 425

Three particle size distributions were investigated: S1 = 50% 0/1 mm + 50% 2/5 mm; S2 = 25% 0/1 mm + 25% 1/2 mm + 50% 2/5 mm; S3 = 33% 0/1 mm + 33% 1/2 mm + 33% 2/5 mm.
Table 3. Recipe of the sealing mortar (%). Content 62.8 19.1 6.4 1.2 0.05 0.05 10.4

Components Sand CSA: CK/RG = 75/25 CK RG Color oxides Retarder: Borax Accelerator: Li2CO3 Water

Mineralogy of CK (wt %). Chemistry Ca4 Al6O12SO4 Ca2SiO4 Ca3Fe2TiO9 Ca12 Al14O33 MgO CaSO4 SiO2 % 73.5 16.1 6.9 0.6 1.7 1.0 0.2

Table 4. Influence of the sand composition on the properties of sealing mortar. Sand Properties Static spread at 20C (mm) t=0 t = 20 minutes 2-hr compressive strength at 5C (MPa) S1 165 130 7.9 S2 160 130 6.7 S3 165 145 9.2

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The performances of the different mortars are shown in Table 4. S3 led to the best performances regarding both the workability and the 2-hr compressive strength at 5C. 3.2 Optimization of the borax content

Table 7. Time 2 hrs 3 hrs 4 hrs 5 hrs 1 day 7 days 28 days

Strength of mortar stored at 30C. Compressive strength (MPa) 24.2 29.8 30.9 31.4 35 42.4 50.1

S3 was used as sand and 3 dosages of borax were investigated: 0.051, 0.056, and 0.061%. The results are presented in Table 5. The recommended borax dosage is 0.051%: the mortar presents the best workability and the higher strength between 2 and 5 hours after casting. After 5 hours, the strength at 5C is equivalent to that recorded at 20C. The difference between the strengths recorded at 20C and 5C decreases versus time and more rapidly with a dosage of 0.061% borax. The long-term strength of sealing mortars stored at 5C and 70% RH is shown in Table 6. The strength increased between 1 day and 28 days, regardless of the borax content: +30%. 3.3 Performances of mortar cast and stored at 30C and 35% RH

dropped to 10 minutes but still fulfilled the general requirements. The strengths obtained between 2 hours after casting and 28 days are presented in Table 7. They varied between 24 MPa and 50 MPa. This strength was lower than that recorded at 5C due to the storage of mortar samples at lower relative humidity: 35% instead of 70%. In these conditions the drying shrinkage was only 320 m/m at 28 days. This study shows that it is possible to develop a sealing mortar based on calcium sulfoaluminate cement presenting high strength after 2 hours at 5C. The recipe is robust and usable between 5 and 30C without major changes: only the retarder content has to be adjusted. 4 ACCELERATION OF SELF-LEVELLING TOPPING MORTAR BASED ON CAC

The recipe of the mortar was that presented in Table 3 with a borax content of 0.056%. The time of workability
Table 5. Influence of the borax content on the properties of sealing mortar. Borax dosage (%) Properties 0.051 0.056 0.061 155 145 6.4 14 20.9 25.3 21.6 25 27.3 29.7

The aim of this study was to investigate the accelerating effect of CSA on a topping mortar based on CAC. The initial composition of the dry matter contained in the mortar was as follows: sand + filler + admixtures: 71.7%; CAC + anhydrite: 26.8%; OPC: 1.5%. The water/solids ratio was maintained at 0.24. The following requirements had to be fulfilled: sufficient fluidity, assessed by the measurement of the time taken by 80 mL of mortar to flow through an aperture of 8 mm (9 sec. t 15 sec.); self-levelness, measured by means of the static spread (SS) of a truncated cone presenting the following dimensions: inf = 80 mm; sup = 70 mm; h = 40 mm. The following values had to be reached: 145 mm SS 165 mm after 5 minutes, 135 mm SS 160 mm after 20 minutes; 1-day compressive strength at 5C 5 MPa. In a first step, CSA cement was composed of 75% CK and 25% RG (CSA25). CSA25 replaced the initial binder (CAC + anhydrite + OPC) at different contents varying from 5 to 25%. In a second step, the influence of CSA composition was investigated.

Static spread at 20C (mm) t=0 165 155 t = 20 minutes 145 140 Compressive strength at 5C (MPa) 2 hrs 9.2 8.2 3 hrs 19.5 14 4 hrs 25.1 20.4 5 hrs 29 24 Compressive strength at 20C (MPa) 2 hrs 22.7 22.7 3 hrs 26 25.4 4 hrs 28.7 27.4 5 hrs 30 28.7 Table 6.

Long-term strength of mortar stored at 5C. Borax dosage (%)

Compressive strength (MPa) 1 day 7 days 28 days

0.051 46 56.1 59.7

0.056 46.5 54.5 59.1

0.061 46 54.2 58.9

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4.1

Performances of CSA25

The results are presented in Table 8. They can be summarized as follows: the flowing time and the static spread are not influenced by the percentage of CSA25 introduced in the mortar; a strength of 5 MPa is reached when the amount of CSA25 is higher than 15%; the performances at 7 and 28 days do not depend on the quantity of CSA25 present in the mixture; the best accelerating effect is obtained with 25% of CSA25. 4.2 Influence of the composition of CSA

Their behavior was compared to that of control mortar (0% CSA) and CSA25. The results are presented in Table 9. The results seem independent of the CSA composition.

CONCLUSIONS

Two other CSAs were investigated: CSA 15: 85% CK + 15% RG; CSA 30: 70% CK + 30% RG;
Table 8. mortar. Influence of CSA 25 on the properties of topping CSA25 (%) Properties Static spread at 20C (mm) t = 5 minutes t = 20 minutes Flowing time (seconds) 1-d compressive strength at 5C (MPa) Compressive strength at 20C (MPa) 7-d 28-d 0 5 10 15 20 25

156 154 18

165 158 160 158 18 18

155 158 19

160 159 159 155 19.5 16.6

The use of calcium sulfoaluminate cement is interesting to solve the problem of strength development at low temperature (<5C). When mixed with re-crystallized gypsum in the following proportions (75% clinker + 25% gypsum), it can be used as either a binder in the design of sealing mortar or an accelerator in topping mortar based on calcium aluminate cement. In sealing mortar, the strength reaches 9 MPa, 2 hours after casting at 5C. The workability at 20C is not modified. The recipe is robust and usable between 5 and 30C without major changes: only the retarder content has to be adjusted. In topping mortar, it is possible to replace 25% of the initial binder without affecting the workability. The 1-day strength is 8 times higher at 5C. The composition of CSA has not any influence on the properties of the mortar. In the present study, the performance of such mortars in environmental exposure conditions as defined in European Standard EN 206-1 has not been assessed. This will be done for the sealing mortar usable in road works. The topping mortar will be used inside buildings and therefore, will be only prone to carbonation.

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21. 23 25.2 23.7 23.7 23.7 32.6 31.1 33 34.1 32.6 33.3

Table 9. Influence of CSA composition on the properties of topping mortar. Type of CSA Properties Control CSA15 CSA25 CSA30

Static spread at 20C (mm) t = 5 minutes 156 t = 20 minutes 154 Flowing time 18 (seconds) 1-d compressive strength at 5C 1.0 (MPa)

158 153 16.8 8.1

159 155 16.6 8.6

159 155 18.2 8.4

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