ACI Materials Journal, V. 105, No. 6, November-December 2008. MS No. M-2007-408 received December 6, 2007, and reviewed under Institute publication policies. Copyright 2008, American Concrete Institute. All rights reserved, including the making of copies unless permission is obtained from the copyright proprietors. Pertinent discussion including authors closure, if any, will be published in the September- October 2009 ACI Materials Journal if the discussion is received by June 1, 2009. Five different supplementary cementing materials (SCM) were investigated for their resistance to sodium sulfate attack using ASTM C1012. The results showed high-calcium fly ash (HCFA) to have the lowest resistance, which was attributable to its calcium-aluminate glass. The performance of HCFA was improved when the ash was blended with an optimum amount of gypsum or 5% silica fume (SF), however, blending with SF produced better results. The X-ray diffraction patterns confirmed that blending HCFA with gypsum sustained early formation of stable ettringite rather than monosulfate. Low ion migration and reduced calcium hydroxide (CH) were behind the enhanced performance of the sample with HCFA and 5% SF. The observed differences in the sulfate resistance of the three tested fly ashes could not be attributed, even partly, to their differences in CH consumption, which were insignificant. Compared with samples with only portland cement, however, all samples with SCM showed a significant reduction in CH. Keywords: calcium content; permeability; sulfate attack; X-ray diffraction. INTRODUCTION Considerable efforts have been directed toward identifying the causes, mechanism, and prevention of sulfate attack in concrete. In general, it has been found that general-use portland cement (GUPC) is inefficient in a sulfate-bearing environment. Tricalcium aluminate (C 3 A) and calcium hydroxide (CH) are considered to be the compounds susceptible to sulfate attack. Sulfate ions present in the sulfate-bearing medium, mostly the groundwater, enter the hardened concrete and react with C 3 A or monosulfate (C 4 A H 12 ) to form ettringite (C6A 3 H 32 ). 1,2 The formed ettringite occupies 55% more solid volume within the paste, which generates internal stress leading to cracking. 2 The volume expansion may also be caused by water absorption when ettringite is in a microcrystalline form. 2 In the meantime, gypsum forms as a consequence of reaction between sulfate ions and calcium hydroxide. 2,3 Controversies exist over the effect of the formed gypsum in the hardened concrete. A school of thought believes that the formation of gypsum in the hardened paste causes expansion, 2-5 whereas another is of the opinion that gypsum does not cause expansion. 6,7 On the other hand, there is a general agreement that ettringite causes expansion and disruption in hardened concrete. 8 A structure subjected to sulfate attack is characterized by a loss of strength, expan- sion, cracking, and disintegration. 8,9 External alkali sulfate attack can be minimized by reducing the permeability of concrete through reducing the water-cementitious material ratio (w/cm) and the use of certain types of supplimentary cementing materials (SCMs). 1,10 Reduced expansion was obtained by reducing the w/cm of concrete. 11 Similar results were obtained for mortars with no SCM 12 ; however, for blended cements, the S
effect of w/cm was less significant.
12 Better sulfate resistance was obtained through reducing the permeability by using silica fume 13 and ternary blends of silica fume and fly ash. 14 The expansions in the latter study, however, were reported up to only 1 year. 14 Several studies have shown enhancement in the sulfate resistance of GUPC with the incorporation of SCMs, particularly silica fume, 15-18 low-calcium fly ash 13-15,19 and granulated blast-furnace slag 17,20,21 . However, varied results have been reported for high-calcium fly ash (HCFA). 14,22-24 The main factor behind the inconsistent and generally low sulfate resistance of high-calcium fly ash is its varied chemical and mineralogical composition. 22-25 HCFA contains reactive calcium aluminosilicate glass, 14,22,23,25 as well as cementious crystalline compounds of calcium such as C 3 A, C 4 A 3 S, CS, and CaO. 25 Such fly ashes produce more sulfate-susceptible calcium aluminate hydrate (C-A-H) during hydration. 25 In an effort to enhance the sulfate resistance of HCFA, Freeman and Carrasquillo 23 came up with a gypsum and alumina balancing approach in a fly ash/cement system. In their study, Freeman and Carrasquillo 23 succeeded in achieving sulfate-resistant blended cement using Type II portland cement (PC) interground with HCFA and gypsum. The concept was to consume the calcium aluminate by providing sufficient sulfate ion during early hydration. Another study 26 was successful in achieving sulfate resistance with incorporation of high-sulfate coal ash with HCFA. This study presents two attempts to enhance the resistance of HCFA to sodium sulfate attack when used with GUPC. These attempts are: 1) using HCFA with silica fume (SF) in ternary blends in which GUPC is the third cementing material; and 2) introducing gypsum to HCFA to optimize the ratio of the reactive aluminate phase to sulfur content. The use of gypsum to enhance the performance of HCFA has been investigated by other researchers. 23 These researchers interground the clinker of moderate sulfate resistance (Type II) cement with gypsum and fly ash, however, and evaluated the performance of the blended cement using the United States Bureau of Reclamation Procedure 4908. In this study, GUPC is used and the blended materials were evaluated using ASTM C1012. Moreover, in this study, gypsum is added to the ingredients in two different ways: 1) during mixing (as an additive); or 2) premixed with the fly ash (without PC). In addition to attempts to enhance the sulfate resistance of HCFA, this paper investigated the effects of Title no. 105-M67 Long-Term Durability of Blended Cement Against Sulfate Attack by Medhat H. Shehata, Giri Adhikari, and Shaun Radomski 595 ACI Materials Journal/November-December 2008 other types of SCMs, namely, SF, slag, and low-calcium fly ash on sodium sulfate attack. RESEARCH SIGNIFICANCE It is well documented that the use of SCM enhances concrete resistance to sodium sulfate attack. HCFA has been found less effective than other SCM in this regard, however. This research focuses on enhancing the sulfate resistance of mortar containing HCFA through two approaches: 1) blending the fly ash with gypsum, and 2) using SF in the mixture. The research aims at developing the required levels of gypsum and SF, comparing the effectiveness of the two approaches and providing insights into the mechanisms by which each approach enhances the performance of HCFA. EXPERIMENTAL PROCEDURES Materials The materials used in this study are GUPC with C 3 A = 10.3%, reagent grade gypsum, three fly ashes, one slag cement, and one SF. One fly ash was classified as Class F or Type F and the other two as Class C, as per ASTM C618, or Type CH (HCFA with CaO > 20%) according to Canadian Standard Association CSA A3001. The chemical analyses of the materials used in the study are listed in Table 1. Specimens and items of investigation Mortar barsMortar bars containing GUPC and different levels and types of SCM were prepared and tested in accordance with ASTM C1012. All supplementary cementing materials were added to the PC during mixing. Table 2 lists the samples tested in this program. Gypsum was added to the mixture in two different ways: 1) added to the ingredients at the time of mixing; or 2) premixed with the HCFA for 1 hour in a Micro-Deval apparatus used to test the resistance of fine aggregates to degradation by abrasion as per Canadian standards CSA A23.2-23A. The apparatus is basically a jar rolling mill with stainless steel balls of 9.5 mm (0.374 in.) diameter. The main purpose of premixing the ash and gypsum in a Micro-Deval apparatus is to provide intimate contacts or better mixing of fly ash and gypsum. Different levels of gypsum were used to obtain the optimum level(s) for each HCFA. For all the tested blends, parallel sets of mortar bars were tested in lime solution at 73.4 F (23 C). X-ray diffractionTo study the different hydration products in samples containing HCFA with SF or gypsum, three different paste samples were prepared and tested using qualitative X-ray diffraction (XRD). The three samples tested were: 1) 80% GUPC with 20% CH1 fly ash; 2) 80% GUPC with 20% CH1 premixed with optimum gypsum (4.92% SO 3 per mass of PC + FA + gypsum); and 3) 75% GUPC, 20% CH1 and 5% SF. Paste samples were prepared using a high-speed, high-shear food blender. The w/cm was maintained at 0.50. Each paste sample was then poured into a polyethylene cylinder 50 mm (2 in.) in diameter and 100 mm (4 in.) in height that was capped from the top and placed in the warm water at 95 F (35 C) for 24 hours. The samples were cured further for 27 days in saturated lime solution at 73.4 F (23 C), constituting a total curing period of 28 days. After 28 days, each cylinder was taken out of the lime solution and broken into small pieces. The broken samples were dried using the solvent replacement method by soaking in reagent grade alcohol for 7 days. After they were removed from the alcohol solution, the samples were stored under vacuum in a desiccator with silica gel and soda lime (to reduce humidity and prevent carbonation) at 30 C (86 F). After 2 weeks, each sample was removed from the desiccator, ground into fine powder passing a No. 200 sieve (75 m), and tested for XRD. Raw samples from the three fly ashes and slag were also examined using XRD to identify the different phases in each SCM. The diffraction patterns were collected using an X-ray diffractometer with Cu K radiation ( = 1.540562 ). Ion migration testingTo investigate the role of ion migration on sulfate resistance of the mortar samples, the rapid chloride permeability test (RCPT) as per ASTM C1202 was conducted on mortar samples. The test is intended for concrete but was used in this research as a quick method to obtain a rough comparison of the permeability of the different samples. Cylinders (100 mm [4 in.] in diameter and 200 mm [8 in.] in height) were cast with mortars like those used in the mortar bar testing. Sand, w/cm, mixing procedure, and curing method were kept identical to the method used in preparing mortar bars. The test was conducted on samples at the ages at which they were immersed in sulfate solution, which corresponded to a cube strength of 3000 150 psi (20 1 MPa) as per ASTM C1012. In addition, samples were also tested at 28 and 56 days. The total charge passed after 6 hours was measured and recorded as the chloride ion permeability value. The coulomb values at 56 days are reported in Table 2. Thermal gravimetric analysisTo investigate the role of Ca(OH) 2 content of different samples on their sulfate resistance, selected paste samples prepared in a manner similar to that ACI member Medhat H. Shehata is an Associate Professor in the Department of Civil Engineering at Ryerson University, Toronto, ON, Canada, and a Professional Engineer in the Province of Ontario. He received his PhD from the University of Toronto, Toronto, in 2001. His research intersests include concrete durability, sulfate attack, alkali-aggregate reaction, recycled concrete aggregate, and the use of supplementary cementing materials in concrete. Giri Adhikari is working for the Ministry of Transportation of Ontario and is a Professional Engineer in the Province of Ontario. He received his MASc from Ryerson University in 2007. Shaun Radomski works for AMEC Earth & Environmental, Calgary, AB, Canada. He received his MASc from Ryerson University in 2005. Table 1Chemical composition of portland cement and SCM Sample SiO 2 Al 2 O 3 Fe 2 O 3 CaO MgO SO 3 K 2 O Na 2 O TiO 2 P 2 O 5 GUPC * 19.58 5.35 2.29 62.84 2.43 4.10 1.13 0.21 0.31 0.11 Fly ash (CH1) 33.72 18.47 7.04 27.16 5.08 2.84 0.33 1.72 1.41 0.91 Fly ash (CH2) 40.49 18.50 6.13 22.97 5.00 1.62 0.62 1.36 1.45 1.00 Fly ash (F) 61.29 16.81 4.62 6.42 2.15 1.12 0.98 3.68 0.95 0.54 Slag 34.40 7.40 0.94 43.20 9.30 0.83 0.58 0.57 0.44 175 ppm Silica fume 96.19 0.35 0.10 0.27 0.91 0.23 0.51 0.11 0.13 0.13 *General-use portland cement. 596 ACI Materials Journal/November-December 2008 of XRD samples were tested using thermal gravimetric anal- ysis at the age of 28 days. The analysis was conducted using a thermal gravimetric analyzer apparatus with nitrogen as an inert gas and a heating rate of 10 K per minute. The selected samples and their Ca(OH) 2 contents are listed in Table 2. Scanning electron microscopyAt the age of 2.5 years, the fractured surface of the ternary blend samples with SF and CH1 were examined using a scanning electron micro- scope equipped with an energy dispersive X-ray analysis (EDS) system. The secondary electron images (SEI) were taken at an accelerated voltage of 20 Kv. RESULTS AND DISCUSSION Expansion of mortar bars containing different SCM The effects of different blends of SCM and replacement levels on the expansion of mortar bars at the ages of 6 months, 1 year, 1.5 years, 2 years, 2.5 years, and 3 years are listed in Table 2. The table also includes the expansion results of HCFAs CH1 and CH2 when premixed with the corresponding optimum amounts of gypsum. Using the ASTM C595 expansion limit of 0.05% at 6 months and 0.10% at 1 year for high-sulfate-resistance blended cement, it is clear that appropriate levels of SF, slag, and low-calcium fly ash were effective in meeting the expansion limits at 6 months and 1 year. On the other hand, the HCFAs CH1 and CH2 were not effective in meeting any of the expansion limits. In fact, the samples containing 20% and 40% fly ash CH1 broke before the age of 6 months. The samples containing HCFA CH2, however, showed lower expansion than the control (GUPC) sample or the samples with CH1 at ages up to 1 year. Beyond that age, the samples with 20% and 40% CH2 broke before reaching 1.5 years and 2 years, respectively. It is also interesting to see the effects of SCM replacement levels on sulfate resistance. As listed in Table 2, increasing the replacement level for the fly ash F, SF, or slag enhances the mortar resistance to sulfate attack, but this was not the case for the HCFA CH1. Increasing the replacement level for fly ash CH2 enhances the resistance; however, the improvement was not significant. Figures 1 and 2 show the expansion versus time for samples containing binary blends of GUPC and silica fume, low-calcium fly ash, or slag. The graphs also include, for comparison, the expansion of mortar bar sample containing sulfate-resisting cement (SRC) from a paper by Khatri et al. 11 Expansion data from this reference were used because the experimental program presented in this paper did not include samples with SRC. The sample containing 20% slag did not meet any of the high-sulfate-resistance expansion limits at 6 months or 1 year. The two samples with 3% SF and 20% low-calcium fly ash, however, met the 1-year limit but marginally failed the 6-month limit. An interesting observation, though, is the rate of expansion of these samples after the age of 78 weeks. For the 3% SF sample, the rate increased significantly, exceeding that of the SRC cement and reaching an expansion value above 2.0% at the age of 2.5 years Table 2Expansion, permeability, and calcium hydroxide contents of cementing blends Sample Expansion, % RCPT, coulombs at 56 days Ca(OH) 2 of paste samples at 28 days, % 6 months 1 year 1.5 years 2 years 2.5 years 3 years Control GU 0.306 1.568 Broke 6627 19.2 3% SF 0.053 0.086 0.217 0.604 2.216 * Broke 4641 11.50 5% SF 0.036 0.048 0.074 0.147 0.492 0.833 1376 20% F 0.056 0.094 0.134 0.218 0.337 0.351 2635 11.25 40% F 0.042 0.057 0.061 0.070 0.072 0.076 1744 20% CH1 Broke 6988 11.29 40% CH1 Broke 20% CH2 0.222 0.365 Broke 4714 10.90 40% CH2 0.119 0.329 0.711 Broke 20% slag 0.069 0.209 0.367 0.883 1.840 2.774 5209 11.50 30% slag 0.043 0.079 0.216 3874 40% slag 0.037 0.045 0.072 0.140 0.284 0.351 2689 9.43 3/20 SF/CH1 0.044 0.113 0.241 0.443 0.718 1.278 2172 5/20 SF/CH1 0.027 0.040 0.048 0.058 0.063 0.072 1291 8.89 20% CH1 + optimum SO 3 0.106 0.349 Broke 7557 20% CH2 + optimum SO 3 0.067 0.152 0.335 5773 * Sample showed cracking and warping, but did not break.
Measurements are not yet due.
Fig. 1Expansion of mortar bar samples with 20% low- calcium fly ash, slag, and 3% silica fume. ACI Materials Journal/November-December 2008 597 prior to the sample breakage before 3 years. The expansion rate for 20% slag also increased after 78 weeks. A similar two-stage expansion behavior has also been reported by other researchers. 27 On the other hand, the 20% F sample continue to expand at a very low rate even beyond 2 years. A similar trend, but with lower expansion values, was found for higher replacement levels of the same SCM (Fig. 2). The rate of expansion of both 5% SF and 40% slag samples increased after 78 weeks; however, the expansion beyond 2 years for the sample with 40% slag was much lower than that of the sample with 5% SF. The sample with 40% low-calcium fly ash F performed exceptionally well even beyond 2 years, with very low rate of expansion. It is believed that the rate of expansion increased when a considerable amount of sulfate penetrates the samples either through the pore structure or through microcracks that result from sulfate attack over the first 78 weeks of sulfate exposure. The sample with 5% SF has much lower ion migration than that of the sample with 40% slag. This low ion migration kept the expansion low until the age of 2 years. Beyond that age, and when considerable sulfate penetrated the sample, the expansion was governed mainly by the phases vulnerable to sulfate attack in the samples. Having 95% GUPC, the sample with 5% SF was more susceptible to sulfate attack than that of the sample with 40% slag, which had only 60% GUPC. It should be noted that the conditions of the ASTM C1012 do not reflect actual field conditions and, hence, the results are used mainly to compare the relative performances or perhaps relative service life of different blends. Performance of SF/HCFA blends Fly ash CH1 was chosen to be tested with silica fume, as this ash showed the least resistance to sulfate attack. As shown in Fig. 3, the ternary blend sample containing 3% SF and 20% CH1 met the expansion criterion for high sulfate resistance at 6 months (0.044%) but exceeded the 0.10% expansion limit at 1 year (0.113%). In addition, the expansion of this sample exceeded that of the SRC at ages beyond 78 weeks and continued to expand at a high rate. On the other hand, adding 5% SF to CH1 fly ash significantly enhances the resistance to sulfate. The expansion of the 5/20 SF/CH1 sample was 0.072% at 3 years. The expansion rate of this sample was much lower than that of the SRC, and the rate continued to be low even beyond 2 years. The enhanced performance of the 5/20 SF/CH1 sample compared with 3/20 SF/CH1 could be attributable, at least partly, to the lower ion migration of the former sample (Table 2) as will be discussed in the following. It is also interesting to compare the expansions of the two samples 5% SF and 5/20 SF/CH1. Both samples have the same ion migration at 56 days; however, the 5/20 SF/CH1 had a much lower late expansion. The exact reason for this observation is not known; however, there is a possibility that more hydration products were formed at later ages in the sample with 5/20 SF/CH1 resulting in more enhancement in the pore structure. It is known that fly ash continues to hydrate at later ages while SF hydrates at early ages. Other contributing mechanisms could be the lower amount of GUPC in the 5/20 SF/CH1 sample and the possibility of the reactive alumina being tied in the secondary CSH resulting from the hydration SF and CH1, as will be discussed in the following. Performance of gypsum/HCFA blends Figure 4 shows the 6-month expansion of CH2 and CH1 mixed with different levels of gypsum expressed as total SO 3 from (PC + gypsum + FA) per total mass of the three ingre- dients. The graph shows that premixing or preblending gypsum with HCFA resulted in lower optimum SO 3 and lower expansion than that obtained when gypsum was added as an admixture. In other words, premixing the gypsum with fly ash is more effective in enhancing sulfate resistance than adding gypsum during mixing. It should be noted that premixing the fly ash with gypsum in the Micro-Deval apparatus could have increased the fineness of the fly ash- gypsum mixtures. This in turn could have enhanced the performance of the mixture by increasing the reactivity or the rate at which reactive alumina is released from the ash to form ettringite while the mortar is still plastic. Adding 4.92% SO 3 per total mass of cementing materials to fly ash CH1 lowered the 6-month expansion to 0.106%, which is almost at the limit of moderate sulfate resistance (0.10%) of blended cement as specified by ASTM C595. This is a significant improvement in the performance of this fly ash. Similarly, at the optimum SO 3 (4.84%) for the second high-calcium fly ash CH2, the expansion at 6 months was 0.067%, which is less than the 0.10% expansion limit for moderate sulfate resistance. This expansion value corresponds to 70% reduction in the expansion of the sample containing the same fly ash but without gypsum. The increase in expansion Fig. 3Expansion of mortar bars with silica fume, high- calcium fly ash, and ternary blends thereof. Fig. 2Expansion of mortar bar samples with 40% low- calcium fly ash, slag, and 5% silica fume. 598 ACI Materials Journal/November-December 2008 beyond the optimum SO 3 content could be attributable to combined internal and external sulfate attack due to excess SO 3 in the mixture. For all tested SO 3 , however, there was an improvement over the performance of the ash when used without gypsum. It should be noted that with the development of a more effective intergrinding or blending technique for fly ash and gypsum, lower expansion, and lower optimum content of gypsum may be obtained. In addition, blending the cement, fly ash, and gypsum may also produce better results. However, this study focused on using gypsum as a fly ash beneficiation method that can be performed in fly ash processing facilities. It should also be noted that the optimum gypsum contents need to be established for each particular fly ash/portland cement combination as a variation in their reactive alumina contents would require adjustment in the optimum SO 3 . This is of special importance for some fly ashes like CH1 where the enhancement in the performance took place over a relatively narrow range of SO 3 . Expressing the optimum SO 3 as percentage of reactive alumina is a viable option as suggested in other research 23 ; however, accurate determination or estimation of the reactive alumina content may be a concern. Figure 5 compares the expansion of samples containing CH2 and CH1 with the optimum SO 3 contents to the expansion of Type II portland cement (moderate sulfate resistance) from reference. 28 The expansion rate of CH1 with optimum SO 3 was identical to that of the moderate sulfate resistance cement (Type II). However, the CH1-SO 3 sample broke after 1 year. No record of expansion beyond 1 year for the sample with Type II cement was provided in Reference 28. The expansion rate and values of the CH2-SO 3 was better than that of Type II cement. The graph also includes the expansion of the two ashes without gypsum to illustrate the enhancement in sulfate resistance when gypsum was used. The expansion of gypsum/fly ash samples stored in lime solution was very small, suggesting that the SO 3 levels investigated in this study are not likely to cause internal sulfate attack at normal temperature (73.4 F [23 C]), especially when gypsum is premixed with the fly ash. Indeed up to an SO 3 content of 5.05%, the 2-year expansions of fly ash-premixed gypsum were less than 0.035%, as shown in Fig. 6. The expansion of the sample with SO 3 content of 6.34% at 1.5% was also in the same range. A high expansion (0.128% at 1.5 years) is recorded, however, when the sulfate content was raised to 7.9%, which is beyond the optimum levels developed in this research. The data in Fig. 6 also show that premixing or preblending the gypsum with fly ash produces less expansion than samples in which the gypsum was added as an admixture. This is due to the fact the premixing produces a homogenous blend in which the sulfate and aluminate phases are intimately close. This promotes early reaction of the two phases to form ettringite. On the contrary, adding the gypsum as an admixture did not produce as homogenous of a mixture, which results in more free sulfur and unstable aluminate phases (monosulfate or calcium-aluminate hydrates) to react at a later age, forming ettringite and causing expansion. This is also believed to be the reason for the recorded higher expansion of samples with added gypsum compared with those with premixed gypsum when immersed in sulfate solution. In such a case, however, the reaction of the unstable aluminate phases was aggravated by the abundant supply of sulfate from the external solution. Role of ion migration and Ca(OH) 2 content The RCPT results showed that at the age of immersing the bars into the sulfate solution, all the samples had very high coulombs within the first hour of RCPT testing with estimated Fig. 5Expansion rates of mortar bars containing high- calcium fly ashes CH1 and CH2 with optimum SO 3 levels. Fig. 4Six months of expansion of mortar bars containing high-calcium fly ashes CH1 and CH2 and different levels of SO 3 . Fig. 6Two-year expansions of mortar bars samples containing CH1 and gypsum stored in limewater. (Note: The expansions at SO 3 = 6.34% and 7.94% are reported at 1.5 years.) ACI Materials Journal/November-December 2008 599 6-hour values exceeding 8000 coulombs. The only exception was the 5% SF sample that had a 6-hour estimated value of 7200 coulombs. At later ages, however, the permeability of the samples changed and results were different for each sample, as listed in Table 2. The role of ion migration, as determined by RCPT, on sulfate resistance is illustrated in Fig. 7 in which the 56-day RCPT value was taken as a measure of the sample permeability within the first 6 months. It is clear from the data that the sulfate resistance of the tested samples cannot be explained based only on their resistance to ion migration. If the GUPC and the samples with HCFA were to be excluded from the graph, however, a good correlation would exist between the ion migration and the 6-month expansion for samples containing different blends of SCM including ternary blends of SF/HCFA. In addition, when optimum SO 3 was used with the two HCFAs, their 6-month expansion followed the same trend as that of the other samples with SCM. This suggests that the main reason behind the low performance of binary blends containing HCFA is the presence of reactive alumina. When the reactive alumina was balanced by an adequate amount of sulfur, the samples with HCFA followed the same expansion- permeability trend as the rest of the samples containing SCM. The enhanced resistance of the HCFA CH1 when blended with SF, despite the presence of high amount of reactive alumina from the ash, could be attributable to the very low ion migration of these samples. This had likely delayed the migration of sulfate to the samples, resulting in low 6-month expansion. The mechanism by which SF/HCFA blends resist sulfate attack is discussed later in this paper. It should be noted that ion migration can help explain the durability of samples prior to cracking or at relatively early ages. After cracking, sulfate penetrates the samples mainly through the cracks rather than the sample pores. At that time, the deterioration is governed mainly by the amount if sulfate-susceptible phases in the samples. The determined RCPT values at 56 days are also a measure of the amount of hydration products formed in each sample: the lower the permeability the larger the amount of hydrates. There is a possibility that the trend found in Fig. 7 is due to combined effects of permeability and amount of hydration products. Increased hydration products can have a positive role in resisting sulfate by incorporating the reactive alumina within calcium silicate hydrates (CSH) as will be discussed later in this paper. The portlandite or Ca(OH) 2 contents of selected paste samples are listed in Table 2. The Ca(OH) 2 contents of the tested samples containing SCM are significantly lower than that of the sample with only GUPC. This shows that calcium consumption is a contributing factor that enhances the sulfate resistance of concrete or mortar with SCM, as it is well documented. The difference in calcium contents between samples with different SCM is not that significant, however, except for the ternary blend sample with 5% SF and 20% CH1, which showed the lowest Ca(OH) 2 content (8.89% compared with approximately 11% for samples with 20% low- or high-calcium fly ashes). This shows that for the three fly ashes tested in this program, calcium consumption has practically no role in affecting the resistance of the ash to sulfate attack. For the 5% SF-20% CH1 sample, the calcium consumption is noticeably higher than the samples with other SCM, suggesting that the low calcium hydroxide content is a contributing factor behind the high sulfate resistance of this sample. Role of mineralogical composition of SCM The XRD patterns of the raw fly ashes and slag are shown in Fig. 8. The glass phase in CH1 and CH2 represented by the diffraction hump with a maximum at 2 32 degrees is mainly calcium aluminate glass. 29 On the other hand, the maximum of the diffraction hump of the glass in F fly ash was at 2 22 degrees, indicating that the glass in F ash is of siliceous type. 29 As for the slag, the maximum of the diffrac- tion hump is at 29 or 30 degrees, suggesting that the silica glass is modified by calcium and probably aluminum but less than those in CH1 and CH2. It is believed that the aluminate glass in the HCFAs served as a source of reactive alumina that lowered the sulfate resistance of mortars containing these fly ashes. The XRD patterns did not show crystalline C 3 A in any of the two HCFAs, which implies that the content of C 3 A in these ashes is either nil or below the detection limit of qualitative XRD analysis. The noticeable difference in composition between CH1 and CH2 is the stronger peaks of free CaO in CH1. However, this did not result in much higher Ca(OH) 2 content in the sample containing CH1 compared with that in the sample with CH2, as listed in Table 2. Moreover, the stronger peak of CaO or free lime in CH1 did not result in major soundness problem in mortar with CH1 compared with CH2, as mortar bars of both samples stored in lime solution showed close values of expansions at 2 years (0.030 and 0.034% for CH2 and CH1, respectively). Fig. 7Six-month expansion or mortar bars versus 56-day RCPT value. Fig. 8XRD of raw supplementary cementing materials (Q: quartz; M: mullite). 600 ACI Materials Journal/November-December 2008 An earlier research work 30 suggested that the higher the ratio of free CaO/Fe 2 O 3 in fly ash, the higher the expansion. However, the mechanism by which this ratio affects the expansion was not provided. In addition, the researchers used ASTM C452 where sulfate was added to the mixture. The permeability of samples containing CH1 and CH2 could help explain the difference in expansion between the two samples. The coulombs values of CH1 and CH2 at the age of 56 days were 6988 and 4714, respectively. The lower permeability of CH2 delayed the expansion but did not prevent it, as the reactive ingredients are available in the two samples and the permeability of both samples was relatively high. Indeed, the sample with 20% CH2 broke after 1 year. The low permeability of CH2 sample may be attributable to the formation of larger amount of CSH, which could be due to higher amount of reactive silica in CH2. This was not quantitatively investigated in this research; however, the total SiO 2 content in CH2 was higher than that in CH1. Mechanism of sulfate resistance of SF/HCFA and gypsum/HCFA blends The diffraction patterns of the hydration products of CH1, SF/CH1, and gypsum/CH1 are shown in Fig. 9. The main objective of running this test was to qualitatively investigate the changes in the hydration products that result from the addition of SF or gypsum to CH1. The most obvious feature of the diffraction patterns is the strong ettringite peaks obtained for the sample containing CH1/gypsum. It is clear that much of the aluminate phases were consumed during hydration to form ettringitte. This was not the case for the other two samples (CH1 and SF/CH1) where the ettringite peaks were not as strong. In addition, monosulfate was detected in the three samples; however, the monosulpahte peak for the sample with gypsum was not as strong as that in the other two samples. It should be noted that while the diffraction patterns do not show other differences in the hydration products, the samples may have contained some other products that were not detected by the XRD, either due to being in amounts smaller than the detection limit or in a form that is not well crystallized. However, it is evident from the XRD that the addition of gypsum sustained the formation of more ettringite rather than monosulfate. The high-sulfate resistance of the 5/20 SF/HCFA blend could not be explained on the basis of the qualitative XRD. The Ca(OH) 2 content of this sample was the lowest, as listed in Table 2; however, this low level of Ca(OH) 2 alone may not be enough to justify the superior improvement achieved when 5% SF was added to mortar with 20% CH1. The permeability of this sample was also the lowest among the other samples. It is possible that the permeability was low enough to the extent that it prevents the migration of considerable sulfate ions to the sample. The low permeability may have also prevented the formation of surface cracking, which helped keep the sulfate out of the sample. Examining the two samples containing SF/CH1 (3/20 and 5/20 SF/CH1) under scanning electron microscope supported this mechanism. The sample with 5/20 SF/CH1 had some ettringite but only within 4 mm (0.16 in.) from the surface. Beyond that, there was no evidence of the presence of ettringite (Fig. 10). On the contrary, a considerable amount of ettringite was found throughout the 3/20 SF/CH1 sample, even in its core (Fig. 11). Compared with the 5/20 SF/CH1, this sample had higher ion migration value (almost double that of the 5/20 SF/CH1) and much higher expansion. This higher ion migration facilitated the penetration of sulfate ions to the sample at relatively early ages, causing some cracking and expansion. At late ages, however, sulfates continued to penetrate the samples at a much higher rate through the already formed cracks in the samples. In addition to reducing the permeability, the use of adequate level of silica fume with HCFA could have improved sulfate resistance by incorporating the reactive alumina into the secondary CSH formed by the reaction of silica fume. The low Ca/Si ratio of the secondary CSH can promote the inclusion of aluminum and alkalis into the hydrates. 31 Research by Rodger and Groves 32 has shown the formation hydrogarnet (C 12 A 3 FS 3 H 16 ) in the vicinity of a siliceous particle of fly ash. The authors explained that the Fig. 9XRD patterns comparing the composition of paste samples containing: (top) 5/20 SF/CH1; (middle) PC + 20% CH1 + gypsum; and (bottom) PC + 20% CH1. 601 ACI Materials Journal/November-December 2008 alumina reach the reaction site through the pore solution of the sample. The incorporation of reactive alumina in the CSH or silica fume was not investigated in this study. Never- theless, it is evident from the results that the addition of 5% silica fume to HCFA significantly enhances the performance of the latter in terms of sulfate attack. The improvement in the performance was much more noticeable than that produced when gypsum was premixed with HCFA. In addition, the use of ternary blends of SF and fly ash has been found to have many positive effects on concrete properties, especially durability. 14,33 FURTHER RESEARCH The study of the hydration products of SF/HCFA blends requires further investigation. Using techniques such as quantitative XRD, nuclear magnetic resonance (NMR) spectroscopy and transmission electron microscopy (TEM) will assist in determining the types and perhaps the amount of different hydration products. This will confirm if there are mechanisms, in addition to low permeability and high calcium consumption, by which SF/HCFA blends resist sulfate attack. CONCLUSIONS Based on the results obtained from this study, the following conclusions are drawn: 1. The partial substitution of general-use portland cement (GUPC) with low-calcium fly ash, SF, or slag cement enhances the sulfate resistance of the blend. The efficacy of these SCMs increases with the increase in their replacement levels; 2. The low sulfate resistance of high-calcium fly ashes investigated in this study was attributable to their reactive aluminate glass. By blending an optimum amount of gypsum with the fly ash, a more balanced sulfur-to-reactive alumina ratio was achieved. When these blends were used with GUPC, the expansion trends up to 1 year were similar to or better than that of moderate sulfate-resistant cement; 3. The addition of 5% SF to HCFA significantly enhances the ashs resistance to sulfate attack. The expansion was very low even after 3 years of immersion in sulfate solution. Ion migration test results and examination by scanning electron microscopy and energy dispersive X-ray analysis showed that the reduced permeability plays the major role to achieve the high sulfate resistance of this blend. The reduction in calcium hydroxide was also a contributing factor; 4. The expansion of mortar bars suggested that adding 5% SF to HCFA produces better sulfate resistance than premixing the ash with gypsum; 5. Paste samples containing SCM showed considerable reduction in calcium hydroxide compared to that of the sample without SCM. This confirmed that calcium consumption is one of the mechanisms by which some supplementary cementing materials enhance sulfate resistance compared to mortar or concrete with no SCM. However, differences in calcium hydroxide contents in samples with the low- or high-calcium fly ashes investigated Fig. 11Example of ettringite found in core of 3/20 SF/ CH1 sample after 2.5 years of exposure to sulfate solution. Fig. 10Example of ettringite found in a void at depth of 3.67 mm (0.14 in.) from surface of 5/20 SF/CH1 after 2.5 years of exposure to Na 2 SO 4 solution. 602 ACI Materials Journal/November-December 2008 in this study were very small and could not justify the differences in the performance of these ashes. ACKNOWLEDGMENTS Funding of this research work was provided by a grant from the Natural Science and Engineering Research Council (NSERC) of Canada. The authors acknowledge the financial support of this organization. The authors also appreciate the help of G. 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