ACI MATERIALS JOURNAL

Title no. 88-M9

TECHNICAL PAPER

Sulfate Attack on Concrete - Research Needs

by Menashi D. Cohen and Bryant Mather

The mechanism of sulfate attack on portland cement concrete is not well understood. This has limited the confidence that can be placed in and hence the reliability of existing standard tests and models to predict performance and service life of concrete subjected to sulfate attack. A systematic research effort on sulfate attack is necessary to establish five criteria. This would lead both to better understanding of the sulfate attack mechanism and to developing more reliable standard tests and better models to predict performance and service life. The objective of this paper is to present and discuss these five criteria. In addition, an approach for assessing the influence of pozzolans, or other cementing materials, on concrete performance and service life in sulfate environment is presented.
Keywords: accelerated tests; cement pastes; concretes; durability; ettringite; failure criteria; gypsum; magnesium sulfate; pozzolans; sodium sulfate; sulfate attack; transition zone.

Sulfate attack on concrete is a complex process. Numerous important structures have deteriorated because the concrete lacked the necessary resistance to sulfate attack. Many of these failures are attributed not to improperly selected construction practice, but to improperly selected concrete materials and mixture proportions due to a lack of complete understanding of the nature and consequences of sulfate attack and to an inability to accurately predict performance and service life of concrete. The U.S. Nuclear Regulatory Commission (NRC), in conjunction with the National Institute of Standards and Technology (NIST), has invested significant efforts to develop strategies for storing low-level radioactive waste in underground concrete vaults (Clifton and Knab 1989). These vaults are expected to have service lives of at least 500 years. Independent research is being conducted on this topic at the National Research Council of Canada, NRC (Feldman and Beaudoin 1987). Durability of concrete in a sulfate environment is one of the most important factors influencing performance and service life that is currently being studied by NIST, NRC, Purdue University, U.S. Army Corps of Engineers, and several other public agencies and research universities. More reliable standard tests and models are needed to predict performance and service life of several hun-

dred to several thousand years for concrete exposed to sulfate ions. It has been suggested (Clifton and Knab 1989) that some of the existing models, such as the one developed by the U.S. Bureau of Reclamation (Kalousek et al. 1972) which is based on expansion, are not reliable to predict long-term performance. The reliability of another method developed by the Building Research Establishment in England (Harrison and Teychenne 1981), which is based on depth of visible deterioration, has not been well-established either (Atkinson et al. 1985; Clifton and Knab 1989). There is a pressing need expressed by worldwide public concern to develop concrete containment vaults for storing radioactive and hazardous wastes that will be durable for centuries or millenia. The current need for reliably predicting long-term durability performance and service life that are based on short-term accelerated tests is more than ever justified. Many current methods are more of art than science and it is difficult to convince the public and public interest groups of the safety of concrete containment vaults designed on the basis of current state-of-the-art information on sulfate attack. In short, the current state of the art is inadequate. A systematic research effort on sulfate attack is necessary to establish five major criteria and to incorporate findings in appropriate standards and predictive models. This would lead to a better understanding of the process of sulfate attack and confidence in constructed structures. These five criteria are: 1. Establishing methods for accelerating sulfate attack. 2. Establishing appropriate measured properties or indicators. 3. Establishing failure criteria. 4. Establishing a standard methodology for systematic data analysis and development of hypotheses.
ACI Materials Journal, V. 88, No. I, January-February 1991. Received Sept. 29, 1989, and reviewed under Institute publication policies. Copyright 1991, American Concrete Institute. All rights reserved, including the making of copies unless permission is obtained from the copyright proprietors. Pertinent discussion will be published in the November-December 1991 ACI Materials Journal if received by Aug. I, 1991.

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ACI member Menashi D. Cohen is Associate Professor of Civil Engineering at Purdue University. He is Chairman of ACI Committees 231, Properties of Concrete at Early Ages, and ACI 209-1, Creep and Shrinkage; and Co-chairman of ACI Committee 125-5, Lunar Concrete. ACI Honorary Member and past president Bryant Mather is Chief, Structures Laboratory, U.S. Army Engineer Waterways Experiment Station, Vicksburg, Mississippi, and has been with that federal agency since 1941.

5. Establishing relationship between paste and concrete durability. Based on these criteria, an approach to assessing the influence of pozzolans, or other cementing materials, on concrete performance and service life in sulfate environment will also be presented.
CRITERION 1: ESTABLISHING METHODS FOR ACCELERATING SULFATE ATTACK

Most laboratory methods aimed at studying the sulfate attack mechanism are based on accelerated tests. In most practical situations, sulfate solution concentration in soil and groundwater are low ( < 1000 ppm S03). It is impractical to use such low-level concentrations in the laboratory because deterioration will not occur within a reasonable period of time. Accelerating sulfate attack is a necessity. Thus, development of models to predict long-term performance and service life must be based on short-term data obtained under accelerated testing conditions. Numerous methods have been developed to accelerate sulfate attack in concrete. ASTM E 632-82, "Standard Practice for Developing Accelerated Tests to Aid Prediction of the Service Life of Building Components," discusses the significance and importance of accelerated tests. One of the more popular methods for accelerating sulfate attack is to increase the sulfate concentration to a level much higher than that to be encountered in the field.* Although a popular way of accelerating attack, this method has been criticized. The main concern is the change in attack mechanism as a result of increased sulfate concentration. This, therefore, suggests that laboratory results obtained under accelerated tests by increasing sulfate concentration cannot be used to predict actual behavior in the field. Biczok (1967) has conducted an elaborate review of sulfate attack mechanism. He states that the intensity of sulfate attack corrosion increases with increase in sulfate concentration. At the same time, the type or mechanism of corrosion undergoes a change.
*The assumption that sulfate concentrations in the field are low may be generally correct but is by no means universally so. Much sulfate attack involves calcium sulfate of which a saturated solution only contains about 0.2 g/100 mL as compared with sodium or magnesium sulfates which may contain 10 to 70 g/100 mL. The sulfate concentration required to do harm to nonsulfate resistant concrete is 150 ppm of SO, (note: to convert SO, concentration to SO, concentration, multiply S04 by 0.833); "severe" attack only takes place when the SO, concentration exceeds 1500 ppm (ACI 201). Water with a quite low concentration of sulfate ion can produce solutions of very high concentration if it splashes on or drops on a surface, evaporates, builds up a quantity of precipitated salts that then dissolves or partially dissolves to form a saturated or nearly saturated solution. Such conditions can exist on wharves, the tops of dams where seepage from an abutment flows onto the surface, or on the exterior surface of cooling towers.

Regarding sodium sulfate attack, the corrosive mechanism is divided into two parts, depending on sodium sulfate concentration. At low concentrations (less than 0.12 percent, i.e., S03 concentration of less than 830 mg/L - this limit changes with change in C 3 A content of portland cement) he suggests that the mechanism causing damage to concrete is by ettringite formation. When S03 concentration attains a high value, the mechanism is dominated by gypsum formation (acid attack - generally all sulfate solutions are somewhat acidic). The transition between sulfate attack and gypsum attack is not abrupt, and there is a range where the two overlap. Expansion, and subsequent microcracking, is generally attributed to ettringite formation. However, it has been suggested that not all types of ettringite are expansive (Mehta 1983), and in order for it to induce expansion, it has to have certain morphological characteristics. Unlike ettringite, the specific consequence of gypsum formation is not well established. There is no clear documentation that gypsum formation leads to expansion. Softening has also been attributed to gypsum formation. If gypsum is expansive, the source of expansion should be due to volume increase upon transformation of solid calcium hydroxide to gypsum by reaction with sulfate ions. However, this explanation is perhaps valid only when gypsum crystals form in situ or on surfaces of calcium hydroxide crystals; i.e., by topochemical reaction mechanism (Hansen 1963). This doesn't apply to concrete, since the mode of formation of gypsum is by precipitation in the solution away for calcium hydroxide particles; i.e. by through-solution mechanism. Hansen's suggestion that topochemical formation of crystals (gypsum) causes expansion by crystallization pressure was based on an almost completely impossible hypothetical mechanism, "a crystal resting on the floor of a container with another crystal resting on it under an applied load in a solution saturated with respect to the bottom crystal" (Hansen 1963, p. 934). Hansen continued this argument and concluded that, if, under this scenario a force is exerted, it isn't crystal growth, it is hydraulic pressure (Hansen 1963, p. 935). At this stage, it is suggested that precipitation and crystallization of gypsum from solution, which is what happens in concrete, is not expansive. Regarding magnesium sulfate attack, the mechanism is divided into three parts. At the lower concentration level of about 3200 mg/L S03 or less (corresponding to less than 0.48 percent magnesium sulfate), the attack is dominated by ettringite formation. The second mechanism occurs at between 0.48 and 0. 75 percent magnesium sulfate concentration, and it is controlled by a combined ettringite-gypsum formation. The third and most advanced stage is controlled by magnesium attack, and this occurs when magnesium sulfate concentration exceeds 0. 75 percent. Magnesium attack occurs when there is reaction between magnesium sulfate solution and hydrated calcium silicates to form gypsum, magnesium hydroxide

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(which is relatively insoluble as compared with calcium hydroxide), and silica gel (B. Mather 1966). Subsequently, magnesium hydroxide can react with the silica gel to form water and hydrated magnesium silicates (B. Mather 1966), which is noncementitious (Cole and Hueber 1957; B. Mather 1966; Biczok 1967; Lea 1971; Cohen and Bentur 1988). The process of decomposition of cementitious hydrated calcium silicates to a noncementitious magnesium silicate hydrate can be accomplished by magnesium sulfate and no other form of sulfate. Ettringite cannot form under high concentration of magnesium sulfate because the hydroxide-ion concentration is reduced by the resulting gelatinous magnesium hydroxide to below the value necessary for ettringite formation (Biczok 1967). Interestingly, yet surprisingly, the effects of sulfate concentration on the corrosive mechanism have not been studied much by researchers and practitioners although it is critical. Most of this work was done by V. V. Kind, and his publications were reviewed and discussed in detail by Biczok (1967). Other accelerating methods of sulfate attack have been developed. One must, however, recognize the possibility that what may lead to accelerated attack may have a profound effect on the attack mechanism itself. This may impede the practicality of correlating laboratory data to field performance. Yet one can arguethat such information is needed to better analyze and predict field performance of concrete exposed to sulfate solutions and to see where the breakoff point is: The most important rapid test methods are as follows (Biczok 1967): 1. Increasing reaction surface (i.e., small specimens/ large surface areas). 2. Increasing concentration of solution. 3. Increasing crystal pressure (i.e., continuous wetting-drying cycles). 4. Raising the temperature of solution. Items 1 and 2, increasing reactive surface and concentration, are the most practical and widely used methods. Item 2 has been used mainly for reason of accelerating attack but not so much as to study the nature and mechanism of attack as a function of sulfate solution concentration. Item 3, increasing crystal pressure, has been used but has not received wide recognition since other disruptive mechanisms may be involved that would affect interpretation of results. Item 4, raising the temperature, may have some difficulties associated with the technique. Increased temperature would have different effects depending on mixture composition and specimen size. Higher temperature could also lead to significant modifications in the chemistry and microstructure of the particular system being studied. A method of accelerated sulfate attack developed by Mehta (1975) received considerable attention. The method tests the resistance of cement paste to sodium sulfate solution held at a constant pH of 6.2 by repeatedly adding acid to the solution. Although the method

accelerates attack, it is possible that sulfate attack mechanism becomes limited to gypsum action. However, it is believed that this test can provide valuable information in that one can analyze effects of gypsum formation and distinguish it from ettringite formation. Other methods used to accelerate sulfate attack include using high w/c mortar and addition of stet gypsum to the mixture. The first method, high w/c, makes the mortar more permeable and thus more prone to sulfate attack at an earlier age. However, it generally fails to provide reproducible results (Wolochow 1952; K. Mather 1978). On this basis, K. Mather used a lower level w/c (by mass: 0.485 for non-air-entraining portland cement, and 0.460 for air-entraining portland cement). This makes concrete less permeable and the attack less rapid, but the results are more reproducible. Expansion measurement is conducted for one year to allow for adequate penetration of sulfate ions to the interior of concrete. This recommendation now forms the basis of ASTM C 1012-89, which is the standard test method for determining length change of hydraulic-cement mortars exposed to a sulfate solution. The test is suitable for evaluating sulfate resistance of blended cements as well as portland cements. The latter, addition of stet gypsum, appears to be an effective way for accelerating sulfate attack. This method requires adding gypsum to the mixture in an amount sufficient to provide a total of 7 percent S03 by mass of portland cement when the so3 already present in the cement is also considered. This method forms the basis of ASTM C 452-89, which is the standard test method for determining the potential expansion of portland cement mortars exposed to sulfate. Although results are reproducible and can be obtained within 14 days, this test is not suitable for blended cements or blends of portland cement with slag or pozzolan. ASTM C 1012 is suitable for blends because it provides for substantial hydration.
CRITERION 2: ESTABLISHING APPROPRIATE MEASURED PROPERTIES OR "INDICATORS"

What property, or "indicator," best represents the nature and mechanism of sulfate attack? What are the failure criteria for sulfate resistance? These are important questions raised repeatedly in the literature (Thorvaldsen et al. 1932; Hansen 1966; Cement Research Institute of India 1981; Bentur et al., 1987; Cohen and Bentur 1988). According to reports published by the Cement Research Institute of India (1981) and Wong and Poole (1988), different parameters or indicators give different information. The indicator may be a decrease in a measured engineering property of concrete (e.g., a change in length, mass, compressive strength, flexural strength, or modulus of elasticity) which relate to the functional behavior of structures. Measurements of compressive and flexural strengths are adequate in this case, but these measurements may not reflect the early stages of the softening-spalling type of sulfate attack. Also, under some conditions, sulfate attack may produce hydration products that would fill the pores in
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concrete and actually lead to an increase in strength (Kalousek and Benton 1970). Under this condition, change in strength and the actual destructive nature of sulfate attack may not be correlated. Although each indicator may have some advantages, none is ideal for all considerations. Hansen (1966), in reviewing the sulfate durability data of Polivka and Brown (1959) for concrete, indicated that loss in mass appears to be the best indicator of the degree of deterioration - as opposed to changes in length and compressive strength, visual observations, and photographic records. Data in the literature, in general, point to the fact that cement paste (and concrete) respond differently to the different nature of sulfate attack. For example, they respond to ettringite formation by expanding. A drop in strength, however, does not always correspond to ettringite formation because the paste can often withstand relatively large local tensile strains (approximately 150 microstrains) before cracking. Thus, the paste may well be at the advanced stage of sulfate attack without showing any sign of strength drop. Another example is gypsum formation. This action leads to softening and mushiness of concrete. When the concrete is wet, the gypsum can be removed easily. Thus, loss of mass can be a measure of sulfate attack due to gypsum formation. Expansion is not expected to accompany gypsum formation, but Mehta's work (1983) suggests otherwise. The matter is therefore complicated due to the fact that it is not certain whether strength drop, if it accompanies expansion, signifies gypsum or ettringite formation. Mehta's method (1975) of accelerating sulfate attack which limits attack to gypsum formation, may shed some light to this question. As discussed earlier, it is yet not clear whether gypsum causes expansion, and this uncertainty needs to be investigated.

CRITERION 3: ESTABLISHING FAILURE CRITERIA

There also is no consensus as to what values of loss of mass, expansion, and strength drop best represent failure. To complicate things, the values are different for pastes, mortars, and concretes. Based on previous research (Cohen and Bentur 1988) the following dividing lines were suggested for pastes. The values were selected on the basis of experience, visual observation, and literature data: Loss of mass: 5 percent (beam), 2.5 percent (cube) Expansion: 0.4 percent Strength drop: 25 percent Values greater than these indicated failure and those less than these indicated satisfactory performances. The value of loss in mass for a beam (5 percent) was twice that for a cube (2.5 percent), simply because of the higher surface-to-volume ratio (approximately 2: 1).
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These values correlated well with the appearance and integrity of the specimens. The classification or failure criterion value used for expansion was based on works of McMillnn et al. (1949) on mortars as quoted by Neville (1973), K. Mather's on mortar (1980), and the U.S. Bureau of Reclamation's on concrete. McMillan used a failure criterion value of 0.1 percent for expansion at 28 days after exposure for mortars, a similar value to K. Mather's. The U.S. Bureau of Reclamation used a value of 0.2 percent at 28 days for concrete. A value of 0.4 percent was used in the recent work (Cohen and Bentur 1988) taking into account that expansion i.n paste is considerably greater than in mortars and concretes. K. Mather (1982) and Patzias (1987) have suggested limits based on length increase of mortar bars using ASTM C 1012. Ouyang (1989) has established, using a "' damage model, that the values suggested agree well with those obtained using his model. The strength classification was after Mehta (1986). Reduction in strength for pastes of less than 25 percent indicated satisfactory performances, and those above, failure (i.e., poor or very poor performance according to Mehta). Perhaps it is necessary not only to look at changes in strength, expansion, and mass but also at other properties. Recent unpublished experimental works on expansive cements by one of the authors (M. D. Cohen), suggest that changes in bulk density and total porosity can indicate the extent of damage due to ettringite formation and expansion. The development of expansion due to the use of expansive cement is a form of controlled sulfate attack. Changes in bulk density and total porosity also correlate well with changes in strength and dynamic modulus values measured during expansion. Measurements of changes in porosity, as determined by the amount of evaporable water at 105 C of saturated-surface-dry specimens, can also reveal the extent of damage. To establish failure criteria for sulfate resistance one must therefore measure a wide spectrum of properties. These must be monitored periodically to examine and assess durability. The properties include: 1. Visual appearance of test specimens. 2. Change in mass, length, and volume, bulk density, total porosity. 3. Change in compressive strength, flexural strength, and elastic modulus. A special visual rating system (Item 1) should be developed to identify progress, type, and magnitude of sulfate deterioration. Although such a method is subjective, the mean value of ratings obtained by different observers for a certain experiment can give results in agreement with strength and modulus of elasticity values (Biczok 1967). The physical and mechanical properties, Items 2 and 3, respectively, are the most important factors that should be investigated. These include compressive and flexural strength, length change, and static and dynamic Young's modulus of elasticity.

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delayed expansion

+
%A!,_
Lo

+
normal
expansion/swelling

normal flexural strength increase

%M._
fro

lexp

delayed flexural strength drop

Fig. 1 - Percentage of change in length (% ..1LIL versus duration of exposure (tex.J

+
%~
mo
normal mass gain

0 )

Fig. 6 - Percentage of change in flexural strength (% ..1.f/fr) versus duration of exposure (texp)
+
%~
Eo

normal increase in modulus

lexp

delayed mass loss

delayed drop in modulus

Fig. 2 - Percentage of change in mass (% ..1mlmj versus duration of exposure (texp)

+
%_M_
Po

Fig. 7 - Percentage of change in elastic modulus (% ..1BIBo) versus duration of exposure (texp)
CRITERION 4: ESTABLISHING A STANDARD METHODOLOGY FOR SYSTEMATIC DATA ANALYSIS AND DEVELOPMENT OF HYPOTHESIS

normal density increase

texp

delayed density drop

Fig. 3 - Percentage of change in bulk density (% llp/pJ versus duration of exposure (texp)
+
normal densification

%..M...

"

lexp

delayed pore

fonnation

Fig. 4 - Percentage of change in total porosity (% ..17J/7JJ versus duration of exposure (texp)
+
% M'c nonnal compressive strength increase

a. Obtain quantified relationships Basically, the following quantified relationships should be obtained easily for concrete specimen after exposure to the sulfate solutions: 1. Percentage of change in length (OJo ALlL 0) versus duration of exposure (texp). 2. Percentage of change in mass (OJo fl.mlm 0) versus duration of exposure (texp). 3. Percentage of change in bulk density (OJo fl.plp 0 ) versus duration of exposure (texp). 4. Percentage of change in total porosity (OJo fl11l11o) versus duration of exposure (texp). . 5. Percentage of change in compressive strength. (OJo llf:lf' co) versus duration of exposure (texp). 6. Percentage of change in flexural strength (OJo ll.frlfr0) versus duration of exposure (texp). 7. Percentage of change in elastic modulus (OJo /lEI E 0) versus duration of exposure (texp). All changes are with respect to original values as indicated in the denominators. b. Expected relationships For each of the relationships just listed, the expected behavioral patterns are as follows in Fig. 1 through 7.

r'c.
0

delayed compressive
strength drop

Fig. 5 - Percentage bf change in compressive strength (% ..1f; !f;J versus duration of exposure (texp)

c. Identification of mechanism of sulfate attack and development of hypothesis While physical and mechanical studies will reveal only behavioral patterns, such as normal and delayed
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behaviors, the chemical and microstructural studies will assist in identifying the mechanisms of sulfate attack and specifically the events that trigger the delayed activities (for example delayed expansion, strength drop, etc.) that are common in sulfate attack. These studies will also help develop new hypotheses or confirm earlier ones. The different types of relationships obtained in the laboratory and in the field are described in the preceding figures in part (b) which are based on physical and mechanical tests. Based on data obtained one must select appropriate specimens for further testing. Identical specimens must be prepared and tested in-depth for their chemical and microstructural features. The chemical study should involve the use of XRD and EDXA for phase and elemental analyses, TGA/DTA for calcium hydroxide and other hydrates. Microstructural studies will involve the uses of SEM, MIP, image analysis, and backscatter electron analysis methods. Delayed expansion and delayed strength and modulus decreases have been subjects of interest and controversy among scientists and practitioners (Kerdegari 1978; Cohen 1981; Cohen and Richards 1982; Mehta 1983), and it is not clear which action causes the triggering of delayed expansion, which almost always occurs simultaneously with delayed strength and modulus drops. It is also uncertain which of these (delayed expansion or delayed strength and modulus drops) is the cause or the result. With the data obtained, one could attempt to find out the sequence and consequences of events, such as the timing of ettringite formation, gypsum formation, and consequently their effects on length, mass, density, porosity, compressive and flexural strengths, and modulus. The effects of a pozzolan on these events can be clarified. Researchers have yet to address these issues in such a comprehensive and systematic research program as described previously. Chemical and microstructural analyses must also be conducted periodically on various layers of the specimens, starting at the exposed surface. These would give the rate, intensity, and depth of penetration of sulfate attack. The morphologies and quantities of gypsum and ettringite developed at each level should be determined. Different methods have been developed and used to determine the quantities of gypsum (Cohen and Bentur 1988) and ettringite (Uchikawa and Uchida 1974; Cohen 1981; Cohen and Richards 1982; Odler and AbdulMaula 1984) formed during sulfate attack. For the determination of quantity of ettringite the methods of Uchikawa and Uchida (1974), Odler and Abdul-Maula (1984), and recently by Lobo and Cohen* can be conducted and compared with standards to determine which of the three methods is more appropriate. These quantitative results can be tied in with SEM observations to assess the relationship between ettringite morphology and expansion, which has long been a controversial issue (Mehta 1973, 1983; Cohen, 1983,
*Lobo, C. and Cohen, M. D., unpublished work on sulfate attack and expansive cements.

1984; B. Mather, 1984.

CRITERION 5: ESTABLISHING RELATIONSHIP BET\YEEN PASTE AND CONCRETE DURABILITY It has been shown (Bentur et al. 1987; Bentur and

Cohen 1987) that neat cement paste and concrete are two different things that can't be compared due to the transition zone effect which is present in concrete but absent in paste. Researchers have been arguing that it is not appropriate to use paste as a representative model to explain concrete behavior. Earlier Winslow and Liu (1990) and more recently Winslow and Cohen* at Purdue University have shown that the microstructures of pure paste and paste within the concrete are two different things because the effects of transition zones extend far beyond the aggregate surface and individual effects of surfaces in concrete overlap, and there is little or no paste in concrete that isn't affected. This is further confirmed in the earlier experimental investigation of Diamond et al. (1982). Bentur and Cohen (1987), however, have shown that paste located 50 #Lm or more away from the aggregate surface are not affected by the aggregate. The transition zone appears to be limited to 50 #Lm from the aggregate surface. Thus, with calculated modifications, it is possible to use paste as a model to explain concrete behavior. This is a crucial degree, of freedom since it will allow one to tie in results with the earlier literature. Use of paste as a concrete model was taken for granted in the earlier literature dealing with modeling of creep, shrinkage, strength, and modulus behaviors of cement pastes and concretes. It should be added that in mortars and concretes containing silica fume, SEM study indicated absence of a transition zone (Bentur and Cohen 1987) and that there appeared no microstructural difference between the transition zone and bulk pastes. This leads one to suggest that pure paste and pastes in mortars and concretes become more identical in their microstructural and engineering properties in the presence of silica fume. The influence of the transition zone in concrete on sulfate durability and performance can be studied by comparing paste and concrete data. A recent report (Bentur and Cohen 1987) revealed filling of the transition zone due to silica fume addition. This filling process was attributed to the small sizes of silica fume particles and their ability to pack the interface and reduce bleeding. The consequence of packing is the minimizing or elimination of water-filled cavities at the interface. Interfacial filling and packing and consequently improved impermeability are expected to improve durability. But recent work (Bentur and Cohen 1987; Cohen and Bentur 1988) indicate that this expectation is not necessarily valid when magnesium sulfate attacks
*Winslow, D. N., and Cohen, M. D., unpublished work on pore structure of silica fume concrete.

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portland cement-silica fume concrete. This unexpected performance must be clarified.

ASSESSING THE ROLE OF POZZOLANS

The great public awareness in the early 1980s of the deteriorated infrastructure in the United States has created an expectation that any new civil engineering material ought to be extremely durable and free from requirements for major maintenance and rehabilitation costs. Unfortunately, our understanding of fundamental mechanism of physico-chemical actions of pozzolan, specifically silica fume, in portland-cement concrete is inadequate. Research and field data on the effects of pozzolan on durability and service life are incomplete, or at best inconclusive. The five research criteria described in this paper would enable one to characterize influence of pozzolan, or other cementing materials, on sulfate-attack durability. In so far as pozzolans are concerned, one can compare the durability in sulfate solution of CSH produced by pozzolanic reaction and the CSH produced by portland-cement hydration. Pozzolanic CSH gel is suspected to behave differently due to its differences in atomic structure and arrangement (Buck and Burkes 1981; Regourd et al. 1983; Cheng-yi and Feldman 1985; Cohen and Bentur 1988). Basically, three steps are necessary to obtain information on sulfate attack mechanism in portland-pozzolan cement concrete. These are: 1. Identify the accelerated test with cement pastes and concrete without pozzolan. Subsequently, define failure criteria and threshold concentration of sulfate for different w/c. 2. Examine effect of gypsum and ettingite according to the chosen failure criteria. This step would shed light on the mechanism of sulfate attack. 3. Examine effects with pozzolan and compare with reference paste and concrete according to the failure criteria and the sulfate attack mechanism. Monitor changes in microstructure of cement with pozzolan in the presence of the sulfate solution. Clearly, the interpretation of data depends on definition of "reference" paste and concrete. The methodology of data interpretation, as indicated previously, is based on the reference being paste and concrete without pozzolan. One must also interpret the data on the basis that the reference is paste and concrete with pozzolan. The conclusions that are based on these two interpretations must be compared so that the significance of reference can be examined and established.
SUMMARY AND CONCLUSIONS

damental questions that have remained unanswered even after decades of research. Some of these questions that need to be specifically investigated relate to the following list: 1. Consequences of gypsum and ettringite formation. 2. Correlation between morphology and amount of ettringite formed and expansion. 3. Causes, effects, and mechanics of delayed expansion, mass loss, density drop, pore formation, compressive strength drop, flexural strength drop, and modulus drop. 4. Failure criteria. 5. Performance classification. 6. Effect of sulfate solution concentration on the sulfate attack mechanism. 7. Role of concrete impermeability in durability. 8. Importance of the "transition zone" on strength and durability. 9. Validity of using paste as a representative model for concrete. 10. Identification of an accelerated test that would not alter the mechanism of sulfate attack. 11. Identification of the threshold concentration of sulfates above which concrete deterioration is inevitable and below which there would be no deterioration.
REFERENCES
Atkinson, A.; Goult, D. J.; and Hearne, J. A., 1985, "An Assessment of the Long-Term Durability of Concrete in Radioactive Waste Repositories," Proceedings, Materials Research Society Symposium Basis for Nuclear Waste Management IX, V. 50, Stockholm, pp. 239246. Bentur, A., and Cohen, M.D., 1987, "Effect of Condensed Silica Fume on the Microstructure of the Interfacial Zone in Portland Cement Mortars," Journal of the American Ceramic Society, V. 70, No. 10, pp. 738-743. Bentur, A.; Goldman, A.; and Cohen, M.D., 1987, "Contribution of the Transition Zone to the Strength of High Quality Silica Fume Concretes," Proceedings, Materials Research Society Symposium on Bonding in Cementitious Composites, V. 114, Boston, pp. 97-103. Biczok, Imre, 1967, Concrete Corrosion Concrete Protection, Chemical Publishing Company, Inc., N.Y., 543 pp. Buck, A. D., and Burkes, J.P., 1981, Characterization and Reactivity of Silica Fume, Final Report, Misc. paper MP SL-81-13, U.S. Army Engineer Waterways Experiment Station, Vicksburg, 10 pp. Cement Research Institute of India, 1981, Evaluation of Sulphate Resistance of Concrete, Report No. RB-20-1981, New Delhi, 28 pp. Clifton, James R., and Knab, Lawrence I., 1989, Service Life_ of Concrete, Report from U.S. Department of Commerce, National Institute of Standards and Technology, NISTIR 89-4086, p. 119. Cohen, M.D., 1981, Micromechanics of Expansive Mechanism in Expansive Cement Concretes, Ph.D. dissertation, Department of Civil Engineering, Stanford University, Stanford. Cohen, M. D., 1983, "Theories of Expansion in Sulfoaluminatetype Expansive Cements: Schools of Thought," Cement and Concrete Research, V. 13, No.6, pp. 809-818. Cohen, M. D., 1984, A reply to a discussion by B. Mather of the paper, "Theories of expansion in sulfoaluminate-type expansive cements: Schools of thought," Cement and Concrete Research, V. 14, No. 4, pp. 610-612. Cohen, M.D., and Bentur, A., 1988, "Durability of Portland Cement-Silica Fume Pastes in Magnesium Sulfate and Sodium Sulfate Solutions," ACI Materials Journal, V. 85, No. 3, May-June 1988 pp. 148-157.

Research is necessary to establish five criteria as discussed in this paper. This would lead both to better understanding of sulfate attack mechanism and to developing more reliable standard tests and models in order to predict better the performance and service life of concrete. Furthermore, the findings would help lay the groundstones for obtaining answers to numerous fun-

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