eae Pulverized-fuel ash JD Matthews PhD BSc This paper summarises the effect of pulverized-fuel ash (pfa) ‘om various aspeets of concrete durability when itis used as a ‘component of the cementitious material, Comparisons with ‘conventional Portland cement concrete are made, and atten tnom is draren 1o documentation giving recommendations for the use of pia The paper is intended to provide ‘guidance for eiil and structural engineers, pariculely those omcerned with the specification of concrete, and should be ‘ead in conjunction sith Bart fof this Information Paper INTRODUCTION The long-term durability of concrete is lacgely dependent upon its permeability to liquids and gases and is resistance to penetration of ionic species such as sulphates and chlorides. Its generally recognised that the permeability of conerete is governed by its pore structure which in turn is determined by water/cement ratio and the quantity and distribution of gel produced by cement hydration. The later will be affected by temperature and moisture conditions especially during the early life of the concrete ie the curing petiod. In practice, the degree of compaction during placing will also have a major influence on the final permeability of| PERMEABILITY Ins widels accepted that pfa can reduce concrete permeability although the magnitude of ths effect will de- pend upon mis design, curing, age and temperature history fof the concrete, tis tot surprising to find thatthe influence fof pla on concrete permeability is determined by is effect fon the properties mentioned above, ie water/cement ratio and gel formation. Firstly, if the physical and chemical pro: Perties of the pfa are such that a significant edvetion in water content of concrete can be achieved without loss of workability, then a reduction in permeability, compared with an equivalent Portland cement concrete, may be ex pected 10 Follow from the corresponding reduction in the number of large pores “The sex 1 factor isthe influence of pfa on the pore seve ture of the cement/pfa paste. It has been showin that although pfa-containing pastes display a coarser pore struc ture at early ages, a modification in the pore size distribu ‘ATechnical enquiios tok Doone ee Mee gid its use in concrete Part 2 Influences on durability tion occurs at later ages resulting in a reduction in the umber of large pores and an increased number of smal pores. This effec is accompanied by a corresponding decrease in permeability. This change in pore structure has been attributed to the removal of casium) hydroxide and further al precipitation as a result of the pozzolanic reac tin? leading to pore-blocking. There i also evidence of a more discontinuous pore structure in mature pfa/Portland ent systems related to the lower calcium hydroxide con The relative in-situ behaviour of pfa and Portland cement concrete will be affected by the prevailing temperature and ‘moisture conditions. In particular, the surface layer of the ‘onerete forming the protection to ste! reinforcement isi portant in determining the overall durability of the concrete. Ie isto be expected that this surface layer will be sensitive :0 the moisture conditions, especially ducing she curing petiod to which the concrete is subjected and to temperature varia tions brought about by environmental conditions or by i teral heat generation, although tis liter factor may have s effect on the surface layer than on, for example, com crete at the heart of & large mass. Effect of curing on permeability Recent studies at BRE using the Initial Surface Absorptios Test (ISAT) have been carried out on conetetes given dit ferent curing treatments for 28 days then dried to constant weight and tested in accordance with BSIBBI: Part 5: 1979. For concretes cured in water for the whole 28 days, permeability progressively decreases as pfa content increases land the water content is correspondingly reduced. Howe ‘when only three days moist curing was applied, permeability increased at pfa levels in excess of 30% of cementitious cor: teat in comparison with a Portland cement concrete. This is illustrated in Figure 1. Although the early age of tet and the basi for comparison (at equal cementitious content) were not favourable to pfa concrete. chese results ‘demonstrate the importance of curing especially when the pfa content is high, Table 6.5 of BS8110 contains recommendations for minimum periods of curing and protection of concrete. Foral Cuig: 2 dee vere 20° core: Seman are ’ E ba a b i i Re $ [SS , em ine Figure 1 Initial surface absorption of concrete with varying pfa contents concrete made with cements containing pfa, the recommend- cd times are extended by a factor ranging from 1.33 to 1.75 depending upon ambient conditions after casting. No at- tempt is made to differentiate for various pfa contents, The results of the ISA Tests carried out by BRE together with more on carbonation (see later section) and on strength development (see Part I of this Information Paper) suggest ‘that it is only at pfa proportions above about 30% that the effect of poor curing is significantly greater for pfa concrete than for comparable Portland cement concrete. However, ‘until more quantitative data emerges from the existing BRE programme it is suggested that the recommendations in BS8110 are adhered to for all pfa concrete. Effect of temperature on permeability ‘There are indications that elevated temperatures produced during cement hydration may lead to an increase in the permeability of Portland cement concrete whilst producing & reduction in the permeability of pfa concrete. It appears that permeability is determined not only by the amount of hydrated gel produced but also by where itis precipitated. ‘The higher permeability of Portland cement specimens at higher temperatures has been explained by poorer dispersion Of the precipitated hydration products#. With specimens containing pfa, the pozzolanic reaction produces a gel in the pores between cement and pfa particles, the rate of forma- tion of this gel being increased by increasing temperature. A. ‘modest temperature rise has been found to be more beneficial than a very high one. In practice, however, the effect of temperature rise in a concrete mass on the impor- tant surface layers of concrete may not be very great. published information is available on the effect of low temperature curing on the permeability of pfa concrete but it may be supposed that since the pozzolanic reaction is ‘more temperature sensitive than Portland cement hydration reactions (see Part I of this Information Paper), the coarser, pore structure attributed to pfa cements at early ages would for longer periods until the pozzolanic reaction to contribute to pore-blockin Penetration of lonie species Cement gel products formed during hydration are believed to behave as a semipermeable membrane and because of this the penetration of water and the penetration of ions in aqueous solution may be expected to take place at different rates, the penetration of ions being slowed down by the sieve effect of the gel. Penetration rates of ions such as sulphate and chloride are important when considering resistance to sulphate attack and corrosion of steel reinforce- ‘ment, Measurements of the diffusion rates of chloride ions through paste specimens have indicated® a greatly reduced rate in cements containing 30% pfa compared with Portland ‘cement species. PROTECTION OF STEEL REINFORCEMENT The protection afforded to steel reinforcement by concrete depends upon the maintenance of an alkaline environment “hich renders the steel passive, and upon the permeability of the concrete to moisture, oxygen and, if relevant,chloride ions. The effect of pfa on permeability and ionic diffusion ‘ates has already been considered but it is now necessary to consider any possible influence on the alkalinity of the con- crete. It has been suggested that the pozzolanic reaction may cause depletion of calcium hydroxide to an extent where pH is lowered beyond the level at which steel reinforcement ‘would remain in the passive state, However, studies on pore water expressed from cement pastes have shown that even, at high pfa contents the alkalinity of the pore solution is tnlikely to be reduced to levels where the passivity of steel reinforcement would be threatened. Calcium hydroxide is undoubtedly consumed to an appreciable extent by reaction with the glassy phases in pfa, but it appears that the presence of sodium and potassium hydroxides in the pore Solution supplements the residual calcium hydroxide and ‘maintains a high pH. Carbonation [Reduction in the alkalinity of concrete may also occur as @ result of carbonation. Many workers have measured and ‘compared rates of carbonation in mortars and concretes ‘with and without pfa, and absolute values may vary greatly depending upon the mix employed, the adequacy of curing and the storage or exposure conditions. A common theme to rge, however, is that carbonation rate may be conve- niently correlated with design strength, ie concretes of similar 28-day compressive strength carbonate at similar rates, irrespective of whether or not they contain pfa, more especially with higher quality concretes. There is published evidence!" supported by recent work at BRE that this holds true even if the conerete is poorly cured for pfa con- tents up to about 25-30% of cementitious content. There are some indications that in lower grade concretes™ or concretes subjected to accelerated carbonation with high carbon diox- ide concentrations", pfa-containing specimens may car- bonate at an increased rate as compared with Portland ce- iment specimens of equal strength. In comparing the likely susceptibilities to corrosion of steel ‘embedded in pfa and Portland cement concretes, carbona- tion rate should not however be considered in isolation. The ‘occurrence of substantial carbonation alone does not mean that corrosion of reinforcement will be inevitable since this will also depend upon the availability of moisture, oxygen and, where appropriate, chlorides and the rate at which they can diffuse through the concrete cover to reach the stel Limited studies on concrete samples taken from existing structures have revealed no deficiencies of pfa concrete with respect to either carbonation or protection of steel againstSULPHATE ATTACK The beneficial effect of pozzolanas, including pfa, on the sulphate resistance of concrete is well established and. documented. The attack of sulphates on hardened Portland cement is generally considered to consist of two main reat tions, ie the combination of sulphate with free ealeium hhydroxide in a set cement to form gypsum, and the reaction of sulphate with hydrated calcium aluminates to form ettr ingite, Both reactions are accompanied by considerable volume increases and when occurring in hardened concrete cause cracking and disruption. ‘The various theories put forward to explain the beneficial effect of pfa include: i straightforward dilution of the CA (tri-caleium aluminate) content of the cement ii removal, by reaction with the glassy phase of pfa, of ‘uncombined calcium hydroxide which would otherwise bbe available to react with sulphates iii protection of the vulnerable aluminate compounds with coatings of ge! iv reduced permeability of the concrete preventing ingress of sulphate ions Sulphate attack on concrete is, of course, influenced by ‘many factors other than the nature of the cement, for exam- ple the quality of the concrete, the type of sulphate present, the type of suiphate-bearing soil, level of water table and groundwater flow and the geometry of the concrete member, Recommendations for minimum cement contents and max- ‘imum water/cement ratios for fully compacted coneretes ex- posed to sulphate-bearing soils and groundwaters are given in BRE Digest 250%. This Digest recognises that moderate sulphate resistance can be obtained by incorporating pfa complying with BS3892; Part 1 (ie pfa capable of producing a significant water reduction in the concrete) in the mix. Best results are obtained when the proportion of pfs in the ‘cement is in the range 25-40%. The recommendations do not, however, equate pfa/OPC combinations with SRPC which is recommended for the most severe sulphate en- vironments. The net sulphate resistance of a pfa/OPC com bination depends to some extent upon the CyA content of the OPC and although extremely good results may be ob- tained when pfa is combined with an OPC of low or ‘moderate C,A content, the Digest's recommendations make allowance for the possibility of combination with a cement Of high C,A content. BRE research on the sulphate resistance of pfa concrete is continuing with the objective of refining these recommenda tions in the future. This work also includes studies of pfa concretes exposed in a marine environment, in submerged, tidal and atmospheric conditions, at the BRE marine ex: posuce site at Shoeburyness in FROST ATTACK Literature reports of the effect of pfa on the frost resistance Of concrete are conflicting, due in part to the wide variety of test conditions which have been employed, the pre-test cur- ing conditions and the age at which the test is started. The ‘concensus view seems to be that in laboratory tess of repeated freezing and thawing cycles, pfa concrete without air entrainment deteriorates more rapidly than similar Portland cement concrete, although if airentrained and ssiven proper curing, pfa concrete exhibits satisfactory frost resistance in such tests. However, it should be noted that larger doses of air-entraining agent may be required to en- ‘rain a given volume of air in a pfa concrete than in @ similar Portland cement concrete, due to adsorption of the agent on to the high-surface area residual carbon in the pfa. ‘A major problem with freeze-thaw tests is the difficulty in ‘obtaining correlations between the results of laboratory tests, many of which are very severe, and performance in the field. There are, however, no reports of frost damage ccccurring in actual structures containing pfa that are directly attributable to the presence of pfa, possibly because any reduced capacity to accommodate ice formation due to the ‘modified pore structure is offset by the lower permeability which reduces the likelihood of the critical degree of satura- tion being exceeded. It appears that as long as pfa concrete is given adequate curing, and sufficient strength develop- ‘ment is ensured before removal of shuttering, it will perform satisfactorily in practice in relation to frost attack. This assumes, of course, that the recommendations of BS8110 for producing durable concrete in conditions of exposure of varying severity are adhered to. ACID ATTACK ‘All calcarous cements are susceptible to attack by acids, and in highly acid solutions (eg pH less than 3.5) dissolution of the cement matrix and subsequent loss of integrity of con- crete will occur. However, pH is not the sole criterion of the potential aggressiveness of acidic conditions, and some moorland waters with low hardness and containing dissolved ‘carbon dioxide and with pH values in the range 4-7 may be very aggressive to conerete, Such conditions, however, lead to leaching of the cement matrix from the concrete and do not generally threaten the integrity of the concrete except where thin sections, eg pipes or culverts, are exposed to flowing water or one-sided hydrostatic pressure. In general, the quality of the conerete has been considered to be of areater importance than the type of cement used in such ag- gressive conditions. Although pozzolanic cements are recom- ‘mended for use in acid conditions in the standards of a number of European countries” it seems likely that the beneficial effect of such cements will be, at best, marginal ‘The performance of pfa concrete in moorland waters of pH around 4.0, but with little dissolved CO,, is being studied by BRE at an exposure site in South Yorkshire. Durability of concrete in acidic soils and ground waters has recently been discussed by W H Harrison. ALKALI-SILICA REACTION Recommendations for minimising the risk of alkalisilica reaction in concrete have been given in BRE Digest 258” and also in the Report of a Working Party chaired by Hawkins# subsequently revised and issued as a Concrete Society Draft for Comment”. Among the recommendations given in all of these documents is the use of pfa. The Con- ete Society Draft Report recommends the use of a blend of ordinary Portland cement to BS12 with a minimum of 30% ppfa to BS3892: Part I, or the use of a Portland pfa cement to BS6588 containing @ minimum of 30% pfa so long as the alkali content of the concrete provided by the Portland ce ‘ment component is less than 3.0 kg/m?. It is recognised that, although pfa may have significant total alkali levels, ‘most of the alkali is combined in the glassy phase and is released only slowly as the ash particles react in the con- crete. The effect of this on the alkalinity of the pore solu- tion is not fully understood. A small proportion of the alkalies are, however, water soluble and contribute to the alkalinity of the pore solution in the early stages and should bbe included in any calculation relating to the reactive alkali content of the concrete.CONCLUSIONS AND RECOMMENDATIONS 1 PFA can lower the permeability of concrete by virtue of reduced water contents and the removal of calcium hhydronide and further gel precipitation due to the poz zolanic reaction, leading to a finer, more discontinuous pore structure. This can have a beneficial effect in preventing or reducing the rate of flow or diffusion through concrete of gases, liquids or ionic species which may otherwise be deleterious to concrete durability in- cluding protection of steel reinforcement. 2 The extent to which pfa affects permeability will depend ‘upon concrete mix design, temperature, curing and age of the conerece 3. Moderate temperature rises will accelerate the pozzolanic reaction resulting in earlier reduction of permeability in ppfa conerete, Low temperatures may be expected to result in delayed reduction of permeability but this has not yet been demonstrated. 4 Good curing is important for all concrete but may be particularly so for pfa coneretes when the proportion of pfa is in excess of about 30% of the cementitious ‘material. Iti recommended that the extended periods of curing advocated for pia concrete in Table 6.5 of BSS110 are adhered to REFEREN 1 Manmohan D and Mehta P K. ‘Influence of pozzolanic, slag, and chemical admixtures on pore size distribution and permeability of hardened cement pastes’, Cement, Concrete and Aggregates, 1981, 3(1), 63-67. 2. Bakker RF M, “Permeability of blended cement con- cretes' Proceedings of the First International Conference (on the Use of Fly Ash, Silica Fume, Slag and Other Mineral By-Products in Concrete, 1983, American Concrete Institute SP-79, Vol I, $89-605. 3 Feldman R F, ‘Significance of porosity measurements on blended cement performance’, Proceedings of the First International Conference on the Use of Fly Ash, Silica Fume, Slag and Other Mineral By-Products in Concrete, 1983, American Concrete Institute SP-79, Vol, 415-433, 4 Owens P L, “Effect of temperature rise and fall on the strength and permeability of concrete made with and without fly ash’, Temperature Effects on Concrete, ASTM STP 858, TR Naik, Ed, American Society for Testing and Materials, Philadelphia, 1985, 134-149. 5 Page CL, Short N R and El Tarras A, ‘Diffusion of chloride ions in hardened cement pastes’, Cement and Concrete Research, 1981, 11, 395-406, 6 Diamond §, “Effects of two Danish fly ashes on alkali contents of pore solutions of cement-fly ash pastes', Ce- ‘ment and Concrete Research, 1981, 1, 383-394, lasser F P and Mare J, “The effect of mineral additives fn the composition of cement pore fluids’, Proceedings of the Chemistry and Chemically Related Properties of Cement, London, 1984, F P Glasser Ed, Brit Ceram Proc, 1984, (35), 419, Price group 2 For curren areas please const Publeatons Sale, Building Reeareh Inormetan Papers ee so ovataie by ssbsargton, Sng ry wbsetton ae: Bee Aton Sheets - commer Full dota of al recent isues of BRE leatiats ana other pubtestons are avon im BRE News set 8 Nixon P J, Page CL, Bollinghaus, Rand Canham 1, “The effect of a pfa with a high total alkali content on pore solution composition and alkali silica reaction’, Mag Coner Res, 1986, 38 (134), 30-35. 9 Nixon P J and Page CL, ‘Pore solution chemistry and alkali aggregate reaction’, Proc Mather International Conference on Concrete Durability, Atlanta, 1987, ‘American Conerete Institute SP-100 Vol 2 1833-1862, 10 Matthews J, “Carbonation of ten-year old concretes with and without pfa’, Proc 2nd International Con- erence on Ash Technology and Marketing, London, 1984, 398A and Late Paper folder. See also references therein, 1 Weshche K, Schubert P and Weber JW, ‘Strength and durability of concrete with coal fly-ash as an additive’, Betonwerk and Fertigteil Technik, 1984 (6), 367-374. 12 Gebauer J, ‘Some observations on the carbonation of fly ash concrete’, Silicates Industriels, 1982, (6), 155-159. 13 Ho D W S and Lewis RK, ‘Carbonation of concrete in- corporating fly ash or a chemical admixture’, Proc First International Conference on the Use of Fly Ash, Silica Fume Slag and Other Mineral By-Products in Concrete, 1983, American Concrete Institute SP-79, Vol I, 333-346, 14 Newman JB, Sullivan P J E and Bell A M, “In-service performance of reinforced conerete structures containing pulverized-tuel ash’, Concrete, 1983, (12), 912, 15 Cabrera J G and Woolley G R, *A study of twenty-five year old pulverized-fuel ash conerete used in foundation structures’, Proc Inst Civ Engrs, Part 2, 1985, 79, Mar, 149-165. 16 Building Research Establishment, ‘Concrete in sulphate- bearing soils and groundwaters', Digest 250, Reprinted with minor revisions 1984, HMSO. 17 Eglinton M S, ‘Review of concrete behaviour in acidic soils and ground waters’, CIRIA Technical Note 69, 1975. 18 Fattuhi N Land Hughes B P, ‘Effect of acid attack on conerete with different admixtures or protective coatings’, Cement and Concrete Research, 1983, 13, 655-665. 19 Harrison W H, ‘Durability of conerete in acidic soils and eroundwaters', Concrete 1987, 21 (2) 18-24, 20 Building Research Establishment, ‘Alkali aggregate reac- tions in conerete’, BRE Digest 258, 1982, HMSO. 21 Cement and Conerete Association, ‘Minimising the risk of alkali-silica reaction — guidance notes", Report of a Working Party chaired by M R Hawkins, 1983. 22 Concrete Society Draft Technical Report, ‘Minimising the risk of alkal-slica reaction, Guidance notes and model specification clauses’, Report of a Working Party, Oc- tober 1985. pets Mrat.oa29 674080) SRE ows nt fee Yo eubscribrs, © Crown copyright 1987. 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