Second International Conference on Microstructural-related Durability of

Cementitious Composites, 11-13 April 2012, Amsterdam, The Netherlands

TRANSPORT PROCESSES IN THE MICROSTRUCTURE OF

CONCRETE AND THEIR RELEVANCE FOR DURABILITY
Lars-Olof Nilsson

Building Materials Laboratory, University of Lund, Sweden

Abstract
The concepts of “durability” and “service-life” are extended to include the deterioration of
the protective system against various environmental actions. Examples are given on transport
processes that are decisive for a large number of deterioration mechanisms. Transport paths in
the microstructure of concrete are discussed and compared to the ones in paste. The
mechanisms of moisture and ion transport are connected to the microstructure and examples
are given where the true transport mechanisms must be better understood.

1. INTRODUCTION
The term “durability” for concrete structures usually is connected to the deterioration of
the concrete itself or the reinforcement. The concept should, however, be broadened to also
include the durability of the protective system, since deterioration of the protective system is
what is accepted during the service-life. No owner of a concrete structure will accept physical
damage to the concrete or the reinforcement; the initiation of this damage is beyond the end of
the initiation period.
A new model for durability and service-life should look like the one in figure 1, based on
the models for reinforcement corrosion by Tuutti (1982) [1] and Glass (2003) [2].
Such a model is generally applicable for most durability problems. Traditionally such a
model is used for reinforcement corrosion but it could be equally relevant for damage due to
frost, ASR, sulphates etc. Examples are given in the next section on what mechanisms are
included in the initiation and propagation periods respectively for the various durability
problems.
To quantify durability, the concept of “service-life” should be used. That means that a
required performance level is chosen and the performance is predicted by utilizing models
based on knowledge on the deterioration processes, quantification of decisive material
properties and environmental actions and relationships between degree of deterioration and
performance.
 Second International Conference on Microstructural-related Durability of
Cementitious Composites, 11-13 April 2012, Amsterdam, The Netherlands

Figure 1: A general durability/service-life model for concrete structures that includes the
deterioration of the protective system

The deterioration of the protective system in the initiation phase and the materials
themselves in the propagation phase is frequently a result of transport processes in the
microstructure. In practice, the initiation period is of most interest and the end of initiation is
more or less decided by the rate of the transport processes.

2. DURABILITY AND TRANSPORT PROCESSES

The transport processes that are relevant for various durability aspects are briefly described
here, mainly from Nilsson (2003) [3]. Transport processes and transport properties are
extremely important for ingress, internal redistribution and loss of various substances that are
damaging or preserving concrete and reinforcement. Individual transport processes or a
combination of transport processes are decisive for a large number of deterioration processes.
Important examples are i.e.
• transport of sulphates from external sources reaching and reacting with aluminates to form
ettringite,
• internal diffusion of alkalis in the pore water to reach reactive aggregate particles, to
“provide” a reactant for the alkali-aggregate reaction,
• ingress of chloride from sea water or de-icing salts and carbon dioxide from the air,
penetrating the concrete cover, destroying the passivity of reinforcing steel,
• penetration of water that saturates the capillary pores, fills the air voids and freezes to
cause frost damage,
• movement of water and moisture from external and internal sources, being absorbed by
ettringite (including delayed) or alkali silica gel causing expansion, or acting as an obstacle
to gas and vapour transport and as a pre-requisite for the movement of ions,
• diffusion of oxygen participating in the corrosion process,
• dissolution and diffusion of entrapped air in and from in the air void system that makes
further water absorption possible,
• leaching of alkalis and calcium hydroxide from the pore water to surrounding water,
• penetration of steam through a dry surface layer from an evaporation front being created at
a certain depth during a fire,
 Second International Conference on Microstructural-related Durability of
Cementitious Composites, 11-13 April 2012, Amsterdam, The Netherlands

• penetration of alkali-silica gel, more or less viscous, from an expanding reactive particle
into the pores of the surrounding cement paste,
• drying out of moisture causing shrinkage and shrinkage cracks.

These transport processes are presented in the next sections in a structured way and the
relationship between the microstructure and each type of process is discussed.

3. TRANSPORT PROCESSES IN THE MICROSTRUCTURE OF CONCRETE

3.1 Transport paths

Transport processes generally are thought of as occurring in the pore system of cement
paste, if we neglect the macrocracks. Transport through paste compared with concrete shows,
however, a much larger flux through concrete than in pure paste. The constrictivity (transport
area/total area) is much smaller in concrete, and the tortuosity much larger, but the flux (per
unit area of concrete) of moisture is larger in spite of this [4][5]. That means that the “micro
structure” of the paste in concrete is very much different from the paste in a pure cement
paste.
The concept “microstructure” of the paste in concrete must include the air voids, the
interfacial transition zone ITZ around the aggregate grains and microcracks due to restrained
shrinkage. These are not present in pure paste but are significant in concrete paste. In
quantification of the effect of the ITZ, the air voids and the microcracks are frequently
neglected when comparing transport properties of pure paste and mortar. The role of these
“additional microstructural objects” is further pointed out in the next sections.

3.2 Non-steady state transport processes and binding capacity

Transport processes are almost always non-steady state processes, which means that
binding is important; a larger binding capacity gives a significant retardation of the ingress
process. An extreme example is carbonation where another gas than CO2 would easily
penetrate a concrete cover by diffusion but when the gas is CO2 the carbonation reaction gives
a very large “binding” of the penetrating gas. Similar binding processes occur in most other
penetration processes, though with much smaller binding capacities.
There is an obvious moisture dependency of the binding processes, different for different
processes. The carbonation reaction requires the CaO to be dissolved but is shown to be able
to occur at RH below 50 % [8]. Chloride binding increases when the moisture content drops
since the concentration increases [9].

3.3 Moisture in the microstructure

More or less all transport processes are dependent on the moisture conditions in the
microstructure. The moisture in the pores is an obstacle to gas transport and a prerequisite for
ion transport. For moisture transport the moisture conditions give a significant moisture
dependency as well.
In figure 2 a general set of desorption isotherms for Portland cement-based material is
given. The bottom curve shows what moisture content, per weight of cement, is fixed in the
gel at different relative humidity RH. The moisture content above that curve is what is fixed
in the capillary pores, depending on the w/c. For a low w/c most of the moisture is fixed in the
gel, simply because the volume of capillary pores is small. Those pores are scattered in the gel
 Second International Conference on Microstructural-related Durability of
Cementitious Composites, 11-13 April 2012, Amsterdam, The Netherlands

as “islands” that are not interconnected. The larger the w/c is, the larger the volume of the
capillary pores and capillary water is. The average distance between these larger pores, and
the water fixed in them, is smaller and smaller the larger the w/c.

Figure 2: Desorption isotherms for Portland cement-based materials with different w/c.
Based on data from Nilsson (1980) [4]

3.4 Transport of gas

Transport of gases such as air, water vapour, CO2 or O2 by diffusion or permeation is very
much a question of the available paths of connected coarse pores that are empty. Moisture in
some pores will significantly block any gas diffusion and gas permeation in those pores. The
air voids and microcracks will of course be shortcuts for the gas transport. The microstructure
and the moisture condition will create a very large moisture dependency for gas transport,
with almost negligible transport in saturated concrete. That will for instance significantly
reduce the oxygen availability at the cathode in a corrosion process. When filling the air voids
in a saturated concrete with water by first emptying those voids by air diffusion through a
saturated pore system, the transport of air by diffusion in water will give an extreme
retardation and service-lives of centuries because of this slow transport process.

3.5 Transport of moisture

Traditionally, moisture transport is described as a combination of vapour diffusion and
liquid suction. In “durable concrete” with low w/b, however, there is a very limited amount of
liquid flow and almost no actual vapour flow. The decisive part of the moisture flow should
be the transport of water adsorbed inside the reaction products. This water is here called gel
water.
 Second International Conference on Microstructural-related Durability of
Cementitious Composites, 11-13 April 2012, Amsterdam, The Netherlands

Independent of the transport mechanisms involved, isothermal moisture transport can be

quantified with any transport potential e.g. vapour content, vapour pressure, RH or pore water
pressure. Moisture transport under a temperature gradient or moisture flow carrying ions
require a more sophisticated description with at least two transport potentials [10].

In figure 3 measured moisture transport coefficients for a number of concretes are shown
[11]. The moisture transport coefficient δ(RH) has the water vapour content as transport
potential and δ(65,100) is the average value in the RH-interval between 65 and 100 % RH.
This moisture transport property is significantly influenced by the coarse porosity of the
concrete, including the air voids; some of the concretes have up to 6 % entrained air. The
porosity p(>75%RH) in the figure is the porosity corresponding to the pores that are empty
when concrete is dried to 75 % RH. The pore volume, however, says little about the
connectivity between the pores. The coarse pores, including the air voids, dominate the
transport paths for moisture. Moisture transport through the microstructure obviously has
some shortcuts through air voids [4][7].

Figure 3: Average moisture diffusion coefficients δ(65,100) for well cured concrete with
different binders, w/B and air content, as a function of the part of
the porosity that is empty at 75 % RH, including the air voids.
Data from Nilsson (2002) [11], curves from Nilsson (2006) [10]

From the curves in figure 3 [11] there is an indication that the moisture transport properties
of the unreacted binder and the reaction products between these coarse pores and voids are
very different between Portland cement concretes and concretes based on binders with small
additions of fly ash and silica fume. A composite model that includes only these two
components could very well be enough to describe the relationship in figure 3.
Moisture transport properties have a strong moisture dependency; stronger with higher w/c,
cf. figure 4. The higher the RH, and the moisture content, the larger is the moisture flow at the
same gradient.
A simple composite model as sketched above cannot easily explain the very different
moisture dependency in a concrete with w/c=0.40 with almost no moisture dependency and
concretes with w/c > 0.5 with stronger and stronger moisture dependency. Filling more and
 Second International Conference on Microstructural-related Durability of
Cementitious Composites, 11-13 April 2012, Amsterdam, The Netherlands

more of the capillary pores in the high w/c concretes should not be able to explain why the
total flux is much larger since the main obstacle to moisture flow is the reaction products.
Here, the transport properties must be different in the different parts of the reaction products
and some of those parts should have a moisture dependent moisture transport property.

Figure 4: An example of significant moisture dependency of the moisture transport

coefficient δ(RH) for a series of Portland cement concretes. Data from Hedenblad (1983) [5]

Moisture transport under a temperature gradient is important in some cases, for instance to
fill the air voids in a concrete where the capillary pores are saturated. Temporary or long-term
temperature gradients will cause water vapour transport and condensation in the air voids.
That transport process could very well fill part of the air void system during a winter season
in a concrete that is open to moisture flow.
Moisture transport carrying ions is dealt with in the next section.
Transport of seawater into submerged concrete seems to be very much retarded by
densification of the concrete surface [10]. Submerged concrete may very well be fairly dry for
years, due to self-desiccation, and is saturated first after long-term exposure to seawater,
depending on the type of binder and w/B.

3.6 Transport of ions

Ions are transported in concrete by diffusion due to concentration differences, electrical
migration due to the potential field created by the movement of the different ions and
convection when carried by water movement. Air voids are obstacles for ion transport,
contrary to moisture transport, except when laboratory specimens are vacuum saturated.
Large capillary pores are short cuts; the reaction products are the actual resistances to ion
transport. Obviously, ions can move through the reaction products with its content of gel
water.
The possibility of ion transport under difficult conditions is shown in figure 5. The
moisture and chloride profiles show simultaneous ingress of ions and water if w/c < 0.40 for a
concrete with 5 % silica fume replacement. Obviously, ion can penetrate the reaction products
even though there is little water in the capillary pores in advance.
 Second International Conference on Microstructural-related Durability of
Cementitious Composites, 11-13 April 2012, Amsterdam, The Netherlands

0.9
Scap

0.8

0.7

0.6
0 10 20 30 40 50
Depth [mm]

Figure 5: Simultaneous ingress of chloride and water after two years submersion in seawater,
initially self-desiccated SRPC-concrete with w/B=0.40 and 5 % silica fume; data from Tang
(2003) [12]. Scap=degree of capillary saturation

For unsaturated ion transport we have a similar question on what water can be a solvent for
the ions during the ion movement. A few studies have indicated that significant unsaturated
chloride transport may occur below 75 % RH [13]. This transport must be through the
reaction products even though the gel pores are empty to some extent.

3.7 Time-dependency of chloride transport processes

Today it is well known that the “apparent chloride diffusivity” Da is not a constant but
decreases with exposure time. Not so well known, however, is that also the achieved surface
chloride content Csa in submerged concrete increases with time [12].
These time-dependencies are still not very well understood. Recently, it was shown [14],
however, that both time-effects could be explained by time-dependent chloride binding.
Obviously, the time-dependent Csa follows from a time-dependent binding. The time-
dependency of Da can also be explained [14] by time-dependent binding when assuming a
constant chloride diffusion coefficient. The time-dependency of binding remains, however, to
be explained and understood.
 Second International Conference on Microstructural-related Durability of
Cementitious Composites, 11-13 April 2012, Amsterdam, The Netherlands

4. CONCLUSIONS
• The concept of “durability” should mainly refer to controlled deterioration of the
“protection system” that retards the physical damage of concrete and reinforcement. The
length of this initiation period depends mainly on one or more decisive transport processes.
• The role of different parts of the microstructure is different for different transport
mechanisms.
• The microstructure in paste in concrete is very different from pure cement paste when it
comes to transport processes, due to the ITZ, air voids and microcracks.
• Most transport processes are well understood today but some phenomena remains to be
explained. Especially the transport properties of the different parts of the reaction products
should be addresses in the future.

REFERENCES
[1] Tuutti, K. (1982) Corrosion of steel in concrete. Research report No.4.82. Swedish Cement and
Concrete Research Institute (CBI), Stockholm 1982
[2] G. Glass (2003) Reinforcement corrosion, Chapter 9 in Advanced Concrete Technology. Concrete
Properties. Butterworth-Heinemann, Elsevier Ltd, London 2003.
[3] Nilsson, L.-O. (2003) Durability concept - Pore structure and transport processes. Chapter in
Advanced Concrete Technology Book, Vol. 2 – Durability, Butterworth Heinemann, London
2003.
[4] Nilsson, L.-O. (1980) Hygroscopic moisture in concrete - drying, measurements & related
material properties. Report TVBM-1003. Lund Institute of Technology. Lund 1980
[5] Hedenblad, G. (1993) Water vapour permeability of cement based materials. Report TVBM-1014,
Building Materials. Lund Institute of Technology, Lund
[6] van Breugel, K. & Koenders, E.A.D (2000) Numerical simulation of hydration-driven moisture
transport in bulk and interface paste in hardening concrete. Cement & Concrete Research 30 (12),
December 2000, Pages 1911–1914
[7] Wong, H.S., Pappas, A.M., Zimmerman, R.W. & Buenfeld, N.R. (2011) Effect of entrained air
voids on the microstructure and mass transport properties of concrete. Cement and Concrete
Research, 41 (10), October 2011, Pages 1067–1077
[8] Goodbrake, C.J., Young, J.F. & Berger, R.L. (1979) Reaction of hydraulic calcium silicates with
carbon dioxide and water. Journal of American Ceramic Society, 62, No 9-10, pp.488-.
[9] Larsen, C.K. (1998) Chloride binding in concrete. Effect of surrounding environment and
concrete composition. PhD-thesis. Dept. of Structural Technology, NTNU, Trondheim 1998.
[10] Nilsson, L.-O. (2006) Modelling moisture conditions in cementitious materials – some present
challenges. 2nd International Symposium on Advances in Concrete through Science and
Engineering, September 11-13, 2006, Quebec City, Canada.
[11] Nilsson, L.-O. (2002) Long-term moisture transport in high performance concrete. Matériaux et
Constructions, 35, December 2002, pp. 641-649
[12] Tang, L. (2003) A collection of chloride and moisture profiles from the Träslövsläge field site –
from 0.5 up to 10 years investigations. Publication P-03:3, Building Materials dept., Chalmers
university of technology, Göteborg
[13] Francy, O (1998) Modélisation de la pénétration des ions chlorures dans les mortier partiellement
saturés en eau. These du doctorat, LMDC, Université Paul Sabatier, Toulouse 1998
[14] Nilsson, L.-O. (2011) Modelling of Chloride Ingress. Chapter 4 in Resistance of Concrete to
Chloride Ingress – Testing and Modelling. (Tang Luping, L-O Nilsson, Muhammed Basheer)
Taylor & Francis Group Ltd, Oxford 2011.