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

Importance of microstructural understanding for durable and sustainable concrete

Karen L. Scrivener
Laboratory for Construction Materials, EPFL, Lausanne, Switzerland

ABSTRACT: This paper presents the importance of microstructural studies for understanding concrete durability. Three examplessulfate attack; alkali silica reaction and bacteriogenic corrosion in sewers are used to illustrate the pitfalls which can arise from conventional empirical testing, particularly when blended or nonPortland cements are used. The pressure to provide more sustainable cements with lower CO2 emissions will inevitably lead to major changes in the chemistry of concrete. Therefore it is important to properly understand durability and the microstructural mechanisms involved to design appropriate performance based criteria to using the increasing diversity of concrete which will become available. (NB a similar version of this paper will also be presented at the Conference on Microstructure Related Durability of Cementitious Composites, Nanjing, China 1315 October 2008).

INTRODUCTION

SULFATE ATTACK

Cementitious materials are the most used materials in the world, with more than one cubic metre of concrete being produced per person per year. It is a material of low environmental impact; the raw materials for fabrication are widely available; it is very flexible for fabrication on site and provides a strong durable material contributing to lower energy consumption of buildings in use. However, due to the huge volumes produced every year, sustainability is a big and growing issue. Since the turn of the century the production of cement has increased by about 50%, driven mainly by the growth in China. Forecasts indicate that the demand for cement will double or treble by 2050. It is estimated that cement production currently accounts for about 5% of man-made CO2 emissions. Therefore even to maintain current levels of GHG emissions it would be necessary to reduce the CO2 emission per tonne by half to two thirds. About half the CO2 emissions from cement production are due to the decomposition of CaCO3 to CaO as the first step in formation of the clinker phases. Therefore improving sustainability will almost certainly lead to changes in chemistry, for which the implications on durability are unknown. This challenge to provide durable sustainable concretes will require much better understanding of the mechanisms behind concrete degradation. This paper presents three examples of how microstructural studies are critical to understanding concrete durability.

The degradation of concrete due to ingress of sulfate ions from the environmentso called sulfate attack plays an important role in the durability of certain structures. Damage due to sulfate interaction can result in the cracking and softening, with loss of strength of the concrete. Eminent scientists, including Vicat, Michaelis and Le Chatelier, recognised over a century ago that adverse reactions occurred between cement paste and aqueous solutions containing sulfate. The work of Thorvaldson established the role of C3A leading to ettringite formation in degradation and this led to the development in the 1920s of sulfate resisting cements with low C3A content (ASTM type V). In general the use of low C3A cements has been successful in avoiding sulfate attacksuch that Harboe in the Verbeck symposium of 1982 wrote:
When I am asked to show someone a structure that has deteriorated due to sulfate attack, I am hard pressed to find good examples for them to see. For 40 years we have been building structure to resist sulfate attack, and the older structures that did deteriorate have now been replaced. When you add this to the fact that well over 90% of the concrete in the United States is not exposed to sulfate attack, it is not hard to understand why most people today have never seen sulfate attack [1].

However now we need to know if blended cements can be used in conditions of sulfate exposure and it becomes clear that the test methods established

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for Portland cement cannot be easily generalised to determine criteria for sulfate resistance of blended cements. Worse, when sulfate resisting cements with an excellent track record of performance in the face of exposure to sulfates are tested according to common tests, they often fail the acceptance criteria. Some other questions which arise are: High levels of slag addition are known to give good sulfate resisting blends, but what is the threshold level of slag needed, and how does this depend on the composition of the slag and cement How is the formation of ettringite related to the expansions observed and can gypsum formation also produce expansion What is the role of thaumasite formation in degradation due to sulfate ingress How do additions of limestone affect resistance to sulfate attack. A series of research programmes co-ordinated by the Nanocem network [2], based on microstructural understanding, is starting to provide answers to these questions. The essential reaction implicated in sulfate related degradation is the reaction of calcium alumina monosulfate (monosulfate) to ettringite: C3A i CS i H12 + 2Ca 2 + + 2SO2 + 20 H 4 C3A i 3CS i H 32 (1)

Figure 1. Microstructure of mortar immersed in sulfate solution in the laboratory.

a surface region (01.0 mm depth from surface) where the microstructure was characterised by crack formation between or around the aggregates (Figure 1). The cracks were either parallel or perpendicular to the sample surface and generally empty, expect in the samples exposed at the high concentration where some cracks were filled with gypsum. Figure 1 shows the microstructure of the outer zone, where the prevalence of cracks from gaps opening up around the aggregates is apparent. In this study it was observed that the rate of expansion started to increase dramatically, when the width of the outer expanded zone reached around 2030% of the specimen width (11.5 mm on each side of a 10 mm prism). A further complication in the understanding of sulfate related degradation comes when the results obtained in the laboratory are compared with samples exposed in field conditions. It seems that there may be extensive decomposition of the original cement hydrates to leave a zone of decalcified C-S-H and gypsum at the surface, without any evidence of expansion having occurred. (Figure 2) Despite the complications in relating phase changes to mechanical degradation, it is clear that aluminate containing phases play a key role in determining resistance of sulfate attack. Therefore to understand the role of supplementary materials (e.g. slag, fly ash, etc) it is important to be able to understand how these change the distribution of alumina containing hydrates. With modern analytical methodsSEM, X-ray diffraction, Thermal analysis, etc. we are now able to do this. Figure 3 shows the distribution of alumina in the microstructure of a 100% CEM 1 and the same cement blended two different slags at 40 and 70%.

When it is considered that the sulfate and water come from external sources, there is a volume increase of around 90% associated with this reaction. However, studies on temperature induced internal sulfate attack (commonly referred to as delayed ettringite formationDEF) have shown that considerable ettringite formation can occur in a system without macroscopic expansion if the ettringite forms in pre-existing pores and voids. The formation of ettringite only leads to expansion when it forms from monosulfate finely intermixed with C-S-H, where the C-S-H provides the confinement needed to generate macroscopic expansion [3]. Investigations of mortar prisms in sulfate solution [4] indicate that the same mechanism operates in samples exposed to NaSO4 solutions in the laboratory. In this study, for samples exposed at both low (4 g/l) and high (44 g/l) concentrations of sulfate, three characteristic zones developed in the microstructure: a core region characterised by a dense and compact microstructure and a good bonding between cement paste and aggregates. a transition zone (1.03.0 mm depth from surface) showed first signs of changes in the microstructure of the cement paste.

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Figure 2. Microstructure of concrete immersed in sulfate groundwater for 7 years. Despite considerable penetration of sulfate and transformation of products in outer zone to gypsum and decalcified C-S-H, there is little cracking of the sample.

reduced compared to the previous two blends. This may explain the improved performance of the material with 70% slag substitution under sulfate exposure, compared to the other 100% Portland and 60/40 blends. The ongoing studies described above indicate how degradation in the presence of sulfate is a complex phenomena, for which we should not expect to obtain all the information needed from a simple empirical test, which imposes unrealistic conditions on the samples. Nevertheless, detailed study of the microstructure gives important insights into the mechanisms taking place. This will enable us soon to identify how additions of supplementary cementitious materials affect durability and design tests which reflect field performance.

3 ALKALI SILICA REACTION

Figure 3. Distribution of alumina in Portland slag blends.

In the 100% CEM1 most of the alumina ends up in AFm phases (monosulfate and monocarbonate), where in the presence of sulfate ions it can transform to ettringite and produce expansion. However nearly 20% of the total alumina is present in the C-S-H phase where Al can substitute for Si in the structurein this phase it is unlikely to be able to react with sulfate to give ettringite. With the addition of 40% slag although the overall amount of alumina in the system increases, the amount in AFm phases stays about the same, with the extra alumina coming from the slag being combined either with magnesium in a hydrotalcite phase or in the C-S-H. The reaction of the slag lowers the calcium to silica ratio of the C-S-H and also increases the level of Al substitution in this phase. Finally in the material with 70% slag, the amount of alumina in AFm phase is drastically

The second example looks at a very different mechanism of degradationalkali silica reaction (ASR). Worldwide this is probably the second most prevalent form of concrete degradation after chloride induced corrosion of reinforcement. As time goes on more and more structures are diagnosed as suffering from ASR and it is becoming more and more difficult to find local sources of non-reactive aggregate. In the area of ASR we are currently undertaking two research projectsone to study the effect of reaction in dams and one to better identify the mechanism by which SCMs can prevent damage. 3.1 Modelling effect of ASR at a materials level

Despite the common view that alkali silicate gel forms at the edge of aggregates; in the vast majority of cases it in fact forms within the aggregates. The expansion of gel inside the aggregate causes the aggregates to crack and this leads to macroscopic expansion of the

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Figure 4. Microstructure of ASR reactiongel forms within aggregate.

concrete. At the low levels of expansion, which may be enough to cause structural problems in unreinforced dams, the cement paste component is virtually undamaged (Figure 4). This is important information for the correct modelling of ASR in order to calculate its consequences on the properties of concrete. In the work of BenHaha [5] in was found that there was a unique relationship between the amount of reaction in the aggregates measured by image analysis and the macroscopic expansion (Figure 5). Based on this observation a model has been developed which explicitly models the evolution of expansive zones in the aggregates (Figure 6) using XFEM [6]. This model can be used to represent a whole mortar bar with an aggregate packing fraction of close to 70% and by adjusting the mechanical properties of the ASR gel the reaction-expansion curve of BenHaha is reproduced (Figure 5). 3.2 Avoiding ASR in new structures

Figure 5. Expansion-Reaction curve from Benhaha et al [5] left and model right.

There are 3 main ways recommended to avoid deleterious AAR: 1. Avoid the use of reactive aggregate. This depends on a reliable test to diagnose reactivity, which as mentioned above can be problematic with slowly reacting aggregate. However, more important is the fact, that non-reactive aggregates are becoming rare in many localities and transporting aggregate is expensive and ecologically unsound. Furthermore for many constructions, such as tunnels and dams it is an obligation to use the aggregate available on site for environmental reasons. 2. Use low alkali cement. Laboratory experience indicates that alkali contents of concrete below 4 kg/m3 should be sufficient to avoid ASR. However, this is becoming increasingly

Figure 6. Model to study ASR reaction [6].

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discredited as a way of avoiding ASR. Indeed, if this recommendation was valid dams should never experience ASR due to their low cement content (it is conservatively estimated that around 1030% of dams worldwide suffer from ASR). Furthermore, low alkali cements are not environmentally friendly as they demand more energy and there are more waste by-products for their production. 3. Use supplementary cementitious materials (SCMs), to avoid deleterious expansion of concrete made with reactive aggregates. This is the most environmentally friendly options and if correctly done, probably the most reliable. Field experience in Canada and the UK indicates that concrete made with reactive aggregates and Portland cement blended with fly ash, performs well over more than 40 years. However there is very little knowledge available of the right type and amount of SCMs needed to control the reaction of a given aggregate and also much debate on tests which can reliable predict safe combinations of aggregate and binder. Numerous laboratory studies and decades of field experience have shown SCMs to be effective in avoiding deleterious AAR in concrete made with reactive aggregates. Nevertheless the exact mechanism by which this is brought about is unclear. Furthermore not all SCMs are equally effective and the amount of substitution needed to suppress expansion with a given aggregate is unclear. Although the contribution of silica by the SCM is usually focussed on, there is some evidence that the role of alumina is also important. For example many studies have shown silica fume to have only a temporary effect on suppressing AAR, whereas pozzolans with a higher alumina content, e.g. metakaolin seem to be very effective. Several researchers have shown that the addition of SCMs brings down the alkalinity of the pore solution [e.g. 7]. The reasons for this are not totally clear. While pozzolans reduce the amount of calcium hydroxide, there are still significant quantities of this phase present in blends which do not suffer deleterious AAR. In addition, slags, which do not significantly change the amount of calcium hydroxide, are also found to be effective in suppressing deleterious ASR. Furthermore the alkalinity of the pore solution is not determined merely by the presence of calcium hydroxide which alone only gives a pH of 12.5 (much lower than that needed to provoke degradation of most AAR susceptible aggregates), but by the potassium and sodium ions present as impurities in the cement and sometimes released by the aggregates themselves. The picture is further complicated by the observation that in trials of large concrete blocks [8] it is found that deleterious expansion can occur even when low alkali cements (Na2Oeq < 0.5) are used.

The most abundant hydrate phase is calcium silicate hydrate this has been shown to reversibly absorb alkalis [9]. Furthermore the amount of alkalis absorbed increases as the calcium to silica ratio of the C/S decreases. This would then appear to be a reasonable explanation for the action of pozzolans which both decrease the C/S ratio of the C-S-H and increase the amount of C-S-H, thereby increasing the capacity for absorption of alkalis. It is well known that aluminium can substitute for silicon in the structure of C-S-H in so called bridging sites, and it is known that this substitution of can further increase the adsorption of alkalis [10]. This would appear to explain the relative effects of silica fume and metakaolin mentioned above. Based on the above discussion, it is suggested that the suppression of deleterious AAR requires the formation of a sufficient amount of C-S-H of a composition which can absorb the alkalis ions in the pore solution so as to keep the pH below the level at which deleterious AAR occurs. This hypothesis offers a new approach to establishing the combination of SCMs needed in a blended cement to suppress AARmeasure the amount and composition of the C-S-H formed. At first sight this may seem much more complicated and difficult to do, but in fact the C-S-H composition can be reliably measured in concretes (even with SCMs) form around 28 daysmuch sooner than 1 year. More importantly, generic behaviours can be established for given chemical combinations of cement and pozzolans in advance and then an appropriate blend chosen to give the combination producing an innocuous pore solution for a given aggregate. We are currently investigating the above hypotheses with the aim of providing better ways of formulating non reactive concretes.

BACTERIOGENIC CORROSION IN SEWERS

Well functioning sewage network are critical to public health. Increasing urbanisation puts rising demands on existing networks and creates a need for new networks, especially in developing countries. Sewage networks provide a very aggressive environment for cementitious materials. At the same time their relative inaccessibility poses challenges for maintenance and repair. The main cause of degradation is the corrosion of concrete due to the in-situ production of sulphuric acid by bacteria. The production of sulphuric acid is the final step in a complex chain of processes which comprise bacteriogenic corrosion, illustrated in Figure 7. Sewage contains organic matter. When the flow of sewage is sluggish, and availability of oxygen limited; anaerobic bacteria breakdown this organic matter and in so

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5 H2S 1
Figure 8. State of concrete pipe section in test sewer after 12 years. Portland/siliceous section (left) is heavily corroded, in parts the earth behind the pipe is visible. CAC/ siliceous section (right) is relatively unaffected; only black part around the water line shows up to 10 mm of erosion.

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Figure 7. H2S Bacterial corrosion. 1 Sulphates produced by bacteria; 2 Reduction of sulphates to sulphide by anaerobic bacteria living in the slime layer; 3 Turbulence ejects H2S dissolved in the effluent into the pipe atmosphere where it is carried by convection to the pipe crown; 4 Oxidation of H2S to sulphur; 5 Transformation of sulphur to sulphuric acid by aerobic bacteria; 6 Destruction of the concrete.

doing produce H2S gas. This gas in turn serves as a food source for another group of aerobic bacteria, which colonise the walls and roof of the sewer above the water line. These bacteria breakdown the H2S to produce sulphuric acid, which dissolves the concrete. Damage is usually concentrated at the crown and water line of the sewer, Figure 7. The nature of the process means that the amount of acid produced is limited by the extent of activity of the bacteria so the phenomenon is very poorly modelled by tests in which mineral acid is used, especially where the quantity of acid is large in comparison the amount of cementitious materials. In fact the colonisation of the concrete surfaces is progressive. The bacteria responsibleThiobacilli is a whole family of bacteria, the various strains of which thrive at different pH levels. Initially the surface of the concrete is highly alkaline, due to the nature of the hydrates, particularly, Portlandite, Ca(OH)2. The first colonisation is by the strains of bacteria capable of flourishing at the highest pH. Through the production of sulphuric acid they lower the pH level of the concrete surface and facilitate colonisation by new strains, adapted for lower pH conditions. The final stage of the process is colonisation by thiobacilli thioxidans, the most aggressive, these bacteria thrives best at a pH of 2 or less and is capable of generating enough sulphuric acid to bring the surface pH down to 1, which is highly aggressive to all cementitious materials. Even when colonies of thiobacilli thioxidans are well established the process of dissolution of the

Figure 9. Test results from Chamber to study bacteriogenic corrosion[13]. Mass loss left and surface pH right. SC and CC, dotted lines are calcium aluminate cement mortars. The samples with solid lines are all Portland based systems, OPC = plain Psortland; srPC = sulfate resisting Portland cement and BFC = Portland/Blast Furnace slag blend.

concrete tends to neutralise the acid created. Of the major oxides present in cementitious materials, CaO; SiO2; Al2O3 and Fe2O3 (C, S, A, F for short); S and F are virtually insoluble even at very low pH. Lime (C) is readily soluble at all acid pH and each mole

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crete. Furthermore the pressure to provide concrete with lower associated CO2 emissions means that concrete will be much more diverse in the future. The changes in microstructure brought about by mineral additions (or supplementary cementitious Materials, SCMs) or nonPortland cements mean that conventional empirical tests are unreliable or outright misleading to determine the performance of concrete in the field.

ACKNOWLEDGEMENTS I am very grateful to the students and associates who provided some of the figures for this paper from their on-going work and to the sponsors who have financed much of this research (names in brackets)Thomas Schmidt (Cemsuisse), Aude Chaberlie (EU/Nanocem), Emmanuel Gallucci, Gwenn le Saout, Victor Fernandez (EU/Nanocem), Cyrille Dunant (Swiss Federal Office of Energy).

Figure 10. Microstructure of Concrete from 30 year old sewer lining made of calcium aluminate cement (CAC).

of calcium which dissolves will neutralise 2 moles of acid: Ca(OH)2 + 2H Ca + 2H2O

+ 2+

REFERENCES
[1] Harboe, E.M., Long-Time Studies and Field Experiences with Sulfate Attack, In P. Klieger (ed) George Verbeck Symposium on Sulfate Resistance of Concrete, SP-77, American Concrete Institute, Farmington Hills, MI, 1982, 120. http://www.nanocem.org Taylor, H.F.W., Famy, C., Scrivener, K.L., Delayed Ettringite Formation, Cem. Concr. Res, 31 (2001), 683693. Schmidt, T., Lothenbach, B., Romer, M., Neuenschwander, J., Scrivener, K.L., Physical and microstructural aspects of sulfate attack on ordinary and limestone blended Portland cements, submitted to Cem. Concr. Res. Benhaha, M., Gallucci, E., Guidoum, A. Scrivener, K.L., Relation of expansion due to alkali silica reaction to the degree of reaction measured by SEM image analysis Cem. Concr. Res. 37 (8): 12061214. Dunant, C., Scrivener, K.L., Modelling ASR reaction, submitted to Cem. Concr. Res. Shehata, M.H., Thomas, M.D.A., Bleszynski, R.F. The effects of fly ash composition on the chemistry of pore solution in hydrated cement pastes, Cem. Conc. Res. 29 (1999) 19151920. Private communciation, K. Folliard and J. Ideker, U. Texas, for blocks exposed in field site. Hong, S.-Y., Glasser, F.P., Alkali binding in cement pastes: Part I. The C-S-H phases. Cem. Concr. Res. 29 (1999), pp. 18931903. Hong, S.-Y, Glasser, F.P., Alkali sorption by C-S-H and C-A-S-H gels Part II. Role of alumina, Cem. Conc. Res. 32 (2002) 11011111. Goyns, A.M., Calcium aluminate cement linings for cost-effective sewers : In Calcium Aluminate Cements 2001, 2001, 617631.

(2)
[2] [3] [4]

(equivalent equations can be written for C-S-H which will also decalcify) Alumina is virtually insoluble above pH4, but below this pH dissolves to neutralise 3 moles of acid. Field experience shows outstanding performance of concretes made with calcium aluminate cements subject to bacteriogenic corrosion (Figure 8) [11]. However laboratory tests, using strong acids fail to show this improved performance due to the fact that they do not include the colonisation process of the bacteria. There is now overwhelming evidence, both from the field [12] and in laboratory studies [13], that the pH on the surface of CAC subject to bacteriogenic corrosion only drop to just below 4 (as opposed to around 1 for Portland concrete) due to suppression the growth of bacteria (Figure 9). In such condition hydrous alumina has very low solubility and blocks the pore structure (Figure 10) [14].

[5]

[6] [7]

[8] [9]

CONCLUSIONS

[10] [11]

The examples presented here illustrate the importance of microstructural studies to understand the mechanisms leading to degradation of cementitious materials. Such studies are essential to be able to produce durable con-

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[12]

[13]

Lamberet, S., Guinot, D., Lempereur, E., Talley, J., Alt, C. Field Investigations Of High Performance Calcium Aluminate Mortar For Wastewater Applications In Calcium Aluminate Cements. Proceeding of the Centenary Conference, Avignon, France, 30 June2 July 2008, IHS BRE Press, 2008, 269277. Ehrich, S., Helard, L., Letourneux, R., Willocq, J., Bock, E., Biogenic and chemical sulfuric acid cor-

[14]

rosion of mortars, Journal of Materials in Civil Engineering/November 1999, 340344. Scrivener, K.L., Cabiron, J.L., Letourneux, R. High Performance concretes from calcium aluminate cements, Cem. Concr. Res. 29 (1999) 12151223.

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