PCA R&D Serial No.

2182b

Sulfate Resistance Tests on Type V Cements Containing Limestone

by Peter C. Taylor

Portland Cement Association 2001 This information is copyright protected. PCA grants permission to electronically share this document with other professionals on the condition that no part of the file or document is changed

ABSTRACT
The purpose of the work described in this report was to compare the sulfate resistance of two Type V cements with that of two additional cements made from the same clinkers and containing a nominal 3% interground limestone. This report summarizes the results from two laboratories and compares them with other available data. The cements with added limestone had, on average, lower measured ASTM C 109 compressive strengths than those without. This may be attributed to differences in the clinker fineness and to the fact that the cements had not been optimized for sulfate content. The long-term data from the sulfate resistance tests indicate that there was either no difference, or improved sulfate resistance, with the addition of limestone. Related data available from other studies also indicate, that there is no difference in sulfate resistance when up to 5% limestone is added to low-C3A cements.

KEYWORDS
sulfate resistance, Type V cement, interground limestone

REFERENCE
Taylor, Peter C. Sulfate Resistance Tests on Type V Cements Containing Limestone, PCA R&D Serial No. 2182b, Portland Cement Association, 2001, 10 pages.

Sulfate Resistance Tests on Type V Cements Containing Limestone

By Peter C. Taylor* INTRODUCTION

The purpose of the work described in this report was to compare the performance of Type V cements made with and without interground limestonein particular, the effect of limestone on sulfate resistance. Four cements were produced by a commercial manufacturer from two clinkers. One cement from each clinker contained no added limestone and the other contained a nominal 3% limestone. Tests were performed by CTL and by the manufacturer on cement and mortar samples. This report summarizes the results from both laboratories and compares them with other available data.

MATERIALS
Two Type V portland cement clinkers, each having a C3A content of less than 5%, were provided by a cement manufacturer. A pair of cements was prepared from each clinker. For each pair, one cement was made without added limestone (control) and the other contained nominally 3% limestone by mass (see Table 1). All cements were ground so that at least 92% passed the No. 325 sieve. Gypsum was incorporated in the final grinding of each cement, but because of time constraints in this program, the sulfate contents in the cements were not optimized.
Table 1. Sample Designations Label A0 A3 B0 B3 Clinker source A A B B Nominal limestone addition, % by mass 0.0 3.0 0.0 3.0

TESTS
The following tests were performed on all four cements by both laboratories: Analysis of cements by X-ray fluorescence (XRF) ASTM C 430, Fineness of Hydraulic Cement by the 45-m (No. 325) Sieve ASTM C 204, Fineness of Hydraulic Cement by Air Permeability Apparatus ASTM C 109, Compressive Strength of Hydraulic Cement Mortars ASTM C 452, Potential Expansion of Portland Cement Mortars Exposed to Sulfate ASTM C 1012, Length Change of Hydraulic Cement Mortars Exposed to a Sulfate Solution The following tests were performed by the manufacturer only:

ASTM C 191, Time of Setting of Hydraulic Cement by Vicat Needle ASTM C 151, Autoclave Expansion of Portland Cement ASTM C 185, Air Content of Hydraulic Cement Mortar Carbon dioxide content of cements and limestone by thermogravimetric analysis

RESULTS
The cement compositions as determined by each laboratory using XRF and the calculated Bogue compounds are provided in the following tables. The reduction in CaO content of the cements with addition of the limestone is due to dilution by the limestone.
Table 2. Compositions of Cements Made from Clinker A and Limestone, % Analyte CTL A0 SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O TiO2 P2O5 Mn2O3 SrO L.O.I. Alkalis as Na2O Insoluble residue C3S C2S C3A C4AF 22.01 3.54 3.65 64.16 2.12 2.05 0.26 0.57 0.20 0.24 0.05 0.13 0.77 0.63 0.20 59 19 3 11 A3 21.40 3.48 3.53 63.64 2.04 1.99 0.23 0.53 0.19 0.30 0.06 0.15 2.08 0.58 0.35 N.D. N.D. N.D. N.D. Manufacturer A0 21.78 3.46 3.83 64.41 2.11 2.08 0.25 0.54 0.25 0.27 N.D. N.D. 1.02 0.60 0.10 62 16 3 12 A3 21.14 3.12 3.67 63.98 2.21 2.01 0.22 0.47 0.19 0.35 N.D. N.D. 2.24 0.53 0.29 59 16 2 11

Limestone 2.64 0.52 0.40 51.22 2.90 0.04 0.05 0.10 N.D. N.D. N.D. N.D. 41.67 N.A.* N.A. N.A. N.A. N.A. N.A.

* N.A. = Not applicable N.D. = Not determined C3S and C2S values corrected for CaO content of the added limestone

Table 3. Compositions of Cements Made from Clinker B, % Analyte CTL Manufacturer SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O TiO2 P2O5 Mn2O3 SrO L.O.I. Alkalis as Na2O Insoluble residue C3S C2S C3A C4AF B0 21.24 3.96 4.20 62.43 3.24 2.45 0.30 0.30 0.19 0.06 0.05 0.07 1.01 0.49 0.23 53 21 3 13 B3 21.04 3.86 4.00 61.55 3.55 2.27 0.32 0.32 0.19 0.07 0.05 0.07 2.51 0.53 0.53 N.D. N.D. N.D. N.D. B0 21.20 4.48 4.11 63.02 3.21 2.57 0.28 0.28 0.19 0.07 N.D. N.D. 1.00 0.46 0.12 52 21 5 13

B3 20.74 3.64 4.23 61.75 3.65 2.43 0.28 0.28 0.19 0.07 N.D. N.D. 2.42 0.46 0.42 49 23 2 13

N.D. = Not determined C3S and C2S values corrected for CaO content of the added limestone

The amount of added limestone in each cement was determined by the manufacturer and is listed in Table 4.
Table 4. Calculated Amount of Added Limestone in Cements, % by Mass Cement CO2 in cement CO2 in limestone Limestone in cement A3 1.64 41.06 3.99 B3 1.47 41.06 3.58

The calcium carbonate content of the limestone was determined by the manufacturer as 93.3%. Results of the Blaine specific surface tests (ASTM C 204) and No. 325 sieve residue tests can be found in Table 5. ASTM C 109 test results can be found in Tables 6 and 7. Results of expansion due to sulfate exposure tests (ASTM C 452 and C 1012) can be found in Table 8 and Figures 1 and 2, respectively.

Table 5. Blaine Specific Surface (ASTM C 204) and No. 325 Sieve Residue (ASTM C 430) CTL Manufacturer Label Residue on Specific surface*, Residue on Specific surface*, No. 325 Sieve, % m2/kg No. 325 Sieve, % m2/kg A0 351 2.1 339 2.9 A3 357 2.5 353 2.8 B0 404 3.4 399 4.9 B3 437 4.0 433 4.7 *The density of all the cements was assumed to be 3150 kg/m3. Table 6. Water Content and Flow Data for ASTM C 109 Mixes (9 Specimen Mixes) Label A0 A3 B0 B3 Water, ml 359 359 359 359 Flow, % 121 132 111 122

Table 7. Compressive Strength (ASTM C 109), MPa Label A0 A3 B0 B3 CTL 3 days 22.6 21.7 21.6 21.1 7 days 29.4 29.4 29.2 28.3 Manufacturer 3 days 23.0 22.9 22.7 22.4 7 days 31.8 30.9 32.0 30.2 28 days 42.6 43.4 43.1 41.4

Table 8. Expansion Due to Sulfate Exposure (ASTM C 452) Length change at 14 days, % (ASTM C 1157 allows a maximum of 0.04%) Label CTL Manufacturer A0 A3 B0 B3 0.038 0.025 0.038 0.041 0.027 0.024 0.038 0.037

0.16 A0 A3 B0 B3

0.12 Expansion, %

0.08

0.04

0.00 0 100 200 Age, days 300 400

Figure 1. Expansion due to sulfate exposure (ASTM C 452).

0.100 0.080 0.060 0.040 0.020 0.000 -0.020 0 50 100 150 Age (days) 200 250 300 A0 A3 B0 B3

Figure 2. Expansion due to sulfate exposure (ASTM C 1012).

Expansion (%)

Table 9 lists other results provided by the manufacturer.

Table 9. Additional Test Results Test Time of setting, Vicat (ASTM C 191), min Autoclave expansion, (ASTM C 151), % Air content, (ASTM C 185), % A0 130 0.02 8.5 A3 145 0.00 8.3 B0 170 0.07 6.5 B3 160 0.09 6.5

OTHER REPORTED DATA

Table 10 summarizes data for ASTM C 452 tests carried out by CTL (Taylor, 1999) on Type II cements made with two different limestones, one with a high calcium content and one with a low calcium content. The C3A contents of these cements were 8% or less and the cements had been optimized for sulfate content.
Table 10. Sulfate Resistance (ASTM C 452) of Type II Cements (Taylor, 1998) Label Expansion, % (ASTM C 452) 14 days 28 days 56 days 0.0% Limestone 0.025 0.034 0.050 2.5% Low calcium limestone 0.026 0.034 0.049 3.5% Low calcium limestone 0.026 0.033 0.049 3.0% High calcium limestone 0.022 0.031 0.046 5.0% High calcium limestone 0.027 0.034 0.047

Matthews (1994) has reported sulfate resistance data for concretes made with low C3A cements containing 5% added limestone. 100-mm cubes were stored in water or solutions of sodium or magnesium sulfate and compressive strengths were measured at 1, 2, and 5 years. As shown in Table 11, there was essentially no difference in resistance to sulfate attack for a 5.3%-C3A cement with or without limestone. In fact, the percentage of strength retained by concretes made with cements containing limestone was, on average, higher. Matthews concluded that the C3A content of the parent clinkers appeared to influence the sulfate resistance of the cements more than the presence of limestone.
Table 11. Ratio of Compressive Strength of Samples Stored in Various Sulfate Solutions to Samples Stored in Water (Matthews, 1994) Time, Na2SO4 (1.5%) MgSO4 (0.35%) MgSO4 (1.5%) 0% 5% 0% 5% 0% 5% Years Limestone Limestone Limestone Limestone Limestone Limestone 1 1.01 1.01 1.00 1.00 0.96 0.96 2 1.03 1.02 1.02 1.04 0.94 1.00 5 0.85 0.91 0.91 0.94 0.57 0.68

DISCUSSION
Comparison of the experimental data from CTL and the manufacturers laboratories provides an indication of the amount of variability inherent in the sampling and test procedures. The difference between the data sets was within the precision indicated for each method. The cements with added limestone had compressive strengths similar to those without. Minor differences may be attributed to differences in the test procedures, differences in the clinker fineness, and to the fact that the cements had not been optimized for sulfate content. The ASTM C 452, Standard Test Method for Potential Expansion of Portland Cement Mortars Exposed to Sulfate, test results (Table 8) of Cements A and B indicate essentially the same performance with or without added limestone at 14 days. The long-term data (Figures 1 and 2) from the ASTM C 452 and C 1012 tests also indicate that there was either no difference, or improved sulfate resistance, with the addition of limestone. Related data available from other studies (Tables 10 and 11) also indicate that there is no difference in sulfate resistance when up to 5% limestone is added to low-C3A cements.

CONCLUSION
From the tests performed as part of this study and as reported elsewhere, low-C3A cements containing up to 5% added limestone show equivalent or improved sulfate resistance to those containing no added limestone.

ACKNOWLEDGEMENT
The research reported in this paper (PCA R&D Serial No. 2182b) was conducted by Construction Technology Laboratories, Inc., with the sponsorship of the Portland Cement Association (PCA Project Index No. 95-07c). The contents of this paper reflect the views of the author, who is responsible for the facts and accuracy of the data presented. The contents do not necessarily reflect the views of the Portland Cement Association.

REFERENCES
Matthews, J. D., Performance of Limestone Filler Cement Concrete, Euro-Cements: Impact of ENV 197 on Concrete Construction, R. K. Dhir and M. R. Jones, Eds., E&FN Spon, London, 1994. Taylor, P. C., Performance of Low C3A-Content Cements Containing Interground Limestone, PCA R&D Serial No. 2228, In preparation, 1999.