PCA R&D Serial No.

2182

Performance of Low C3A-Content Cements Containing Interground Limestone

by Peter C. Taylor

Portland Cement Association 1999 All rights reserved 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

 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
This work was carried out in order to provide additional data on the use of low C3A-content (Type II) cements containing limestone. Five cements with varying limestone contents were made from one clinker and performance tests on mortar and concrete samples were conducted. In terms of compressive strength of both the mortars and concretes, there was no difference between the cements; there was no measurable trend and the results were within the precision of the test methods. The results were all well above the minima required in ASTM C 150. Similarly, mortar shrinkage results were all very similar and within the precision of the test method. In sulfate expansion tests there was no significant difference between the cements at the ages referenced in ASTM C 150. All the cements were well within the requirements specified in ASTM C 150. There was no trend in sulfate resistance exhibited with the inclusion of limestone as the variable in the long-term C 1012 and C 452 tests.

KEYWORDS
Sulfate resistance, Compressive strength, Type II cement, Interground limestone

Performance of Low C3A-Content Cements Containing Interground Limestone (PCA 95-07c)

by Peter C Taylor*

INTRODUCTION
This work was carried out in order to provide additional data on the use of low C3A-content (Type II) cements containing limestone. Five cements with varying limestone contents were made from the same clinker and performance tests on mortar and concrete samples were conducted.

MATERIALS
Portland cements were ground by a commercial manufacturing plant from a single Type II clinker having C3A content of less than 8%. All the cements were ground so that at least 92% of each passed the No.-325 sieve. Two limestones, having different CaCO3 contents, were interground in the cements at three addition levels up to a nominal 5%. Table 1 describes the labeling of the five cements and their limestone contents. Two samples of each cement (labeled a and b) were provided by the manufacturer, each with different sulfate contents. The a and b samples were then blended at CTL to achieve the optimum sulfate content. Calculation of the optimum sulfate content was based on 3-day strengths and analyses provided by the manufacturer. Aggregates used in the concretes were siliceous sand and stone from Eau Claire, WI. To minimize the number of variables, no admixtures were used.

TESTS AND RESULTS

Cement Characterization The supplied cements, limestones, clinker, and gypsum were analyzed by X-ray fluorescence and the results are given in Tables 2 and 3. The compositions of the final cements with limestone were calculated according to mass, and are given in Table 4. Quantitative X-ray diffraction of the clinker showed that the C3A content was 5.4%. The amount of cement passing the No. 325 sieve and fineness of the five cements (after blending to optimum sulfate content) were determined using methods ASTM C 430 and C 204, respectively, as shown in Table 5. Mortar Tests The following tests were conducted on mortars made with the cements: ASTM C 109, Standard Test Method for Compressive Strength of Hydraulic Cement
* Engineer, Construction Technology Laboratories Inc., Skokie, Illinois, U.S.A. Tel (847) 965 7500

Mortars. The mortars were prepared at a constant water content and the flow for all mixes was within the range 105 115. The strength results are given in Table 6 and Figure 1. ASTM C 596 Drying Shrinkage of Mortar Containing Hydraulic Cement. The results are given in Table 7 and Figure 2.

ASTM C 1012 Standard Test Method for Length Change of Hydraulic Cement Mortars Exposed to a Sulfate Solution. As a point of reference, the maximum limit of expansion specified in ASTM C 1157 for type MS cements is 0.10 at 6 months when tested according to ASTM C 1012. The results are given in Table 8 and Figure 3. ASTM C 452 Standard Test Method for Potential Expansion of Portland-Cement Mortars Exposed to Sulfate. The maximum expansion limit for ASTM C 150 Type V cement is 0.04% at 14 days when tested according to ASTM C 452. The results are given in Table 9 and Figure 4

Concrete Tests Five concrete mixes were prepared as shown in Table 10. Mixes were designed to have constant materials proportions with a water-cement ratio of 0.50 and a cement content of 550 pounds per cubic yard. Samples from the mixes were used to determine slump and air content in accordance with ASTM C 143 and C 231, respectively, and compressive strength at 7 and 28 days to ASTM C 39. The properties and cylinder compressive strengths of the concrete mixes are given in Table 10.

DISCUSSION
In terms of compressive strength of both the mortars and concretes, there was no difference between the cements; there was no measurable trend and the results were within the precision of the test methods. The results were all well above the minima required in ASTM C 150. Similarly, mortar shrinkage results were all very similar and within the precision of the test method. In the sulfate expansion tests there was no significant difference between the cements at the ages referenced in ASTM C 150. All the cements were well within the requirements specified in ASTM C 150. There was no trend in sulfate resistance exhibited with the inclusion of limestone as the variable in the long-term C 1012 and C 452 tests.

CONCLUSION
Five interground cements made with low C3A-content (Type II) clinker and different amounts of high- and low-calcium limestone were subjected to several tests including their ability to resist external sulfate attack. The inclusion of limestone was shown to result in no significant difference in performance.

ACKNOWLEDGEMENT
The research reported in this paper (PCA R&D Serial No. 2182) 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.

TABLES
Table 1. Description and Labeling of Cements
Label 0.0% 2.5% Lo Ca 3.5% Lo Ca 3.0% Hi Ca 5.0% Hi Ca Limestone type None Low CaCO3 Low CaCO3 High CaCO3 High CaCO3 Limestone content, % by mass of cement 0.0 2.5 3.5 3.0 5.0

Table 2. Analyses of Materials as Received, % by mass

Analyte SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O TiO2 P2 O 5 Mn2O3 SrO L.O.I. Alkalis as Na2O Insoluble residue (%) C3S C2S C3A C4AF Clinker 21.31 5.23 3.50 65.46 0.96 1.07 0.28 0.70 0.19 0.19 0.16 0.19 0.19 High calcium limestone 5.29 1.17 0.62 49.10 0.36 0.10 0.06 0.22 0.03 0.09 0.12 0.09 42.29 Low calcium limestone 12.60 3.18 1.20 43.07 0.68 1.73 0.14 0.64 0.11 0.09 0.02 0.11 35.92 Gypsum 1.40 0.19 0.11 32.07 1.17 42.96 <.02 0.03 0.02 0.01 0.00 0.13 21.70 Baseline cement a 20.42 4.83 3.37 64.57 0.96 2.74 0.20 0.79 0.16 0.18 0.13 0.14 0.71 Baseline cement b 19.93 4.79 3.29 64.08 0.95 3.62 0.19 0.73 0.16 0.18 0.14 0.14 1.13

0.74 61 15 8 11

0.21 -

0.56

0.02

0.72 0.23 63 11 7 10

0.67 0.33 62 10 7 10

Calculated compounds

Table 3. Analyses of Baseline Cements with Limestone as Received, % by mass

Limestone content by weight as noted Analyte SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O TiO2 P2 O 5 Mn2O3 SrO L.O.I. Alkalis as Na2O Insoluble residue (%) 2.5% Lo Ca a 20.32 4.93 3.39 63.71 0.98 3.20 0.21 0.85 0.17 0.18 0.13 0.15 1.58 0.77 2.5% Lo Ca b 21.15 5.01 3.27 64.14 0.98 2.11 0.28 0.85 0.19 0.18 0.13 0.15 1.20 0.84 3.5% Lo Ca a 20.34 4.70 3.22 63.50 0.95 3.32 0.20 0.83 0.16 0.18 0.13 0.14 1.78 0.75 3.5% Lo Ca b 20.66 5.09 3.36 63.99 0.94 2.13 0.24 0.86 0.17 0.18 0.13 0.15 1.45 0.80 3.0% Hi Ca a 20.10 4.78 3.27 63.50 0.93 3.23 0.19 0.81 0.16 0.18 0.13 0.15 1.86 0.73 3.0% Hi Ca b 20.65 4.88 3.34 64.63 0.91 1.86 0.20 0.79 0.17 0.18 0.13 0.15 1.50 0.72 5.0% Hi Ca a 20.02 4.73 3.27 63.51 0.91 3.22 0.20 0.76 0.16 0.18 0.14 0.15 2.37 0.70 5.0% Hi Ca b 20.60 5.04 3.41 63.82 0.92 1.68 0.20 0.71 0.17 0.18 0.14 0.14 2.11 0.66

0.74

0.78

0.90

0.79

0.45

0.50

0.57

0.50

Table 4. Calculated Compositions of Cements as Used, % by mass

Analyte SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O TiO2 P2 O 5 Mn2O3 SrO L.O.I. Alkalis as Na2O 0.0% 20.25 4.82 3.34 64.40 0.96 3.04 0.20 0.77 0.16 0.18 0.13 0.14 0.85 2.5% Lo Ca 20.65 4.96 3.34 63.88 0.98 2.77 0.24 0.85 0.18 0.18 0.13 0.15 1.43 3.5% Lo Ca 20.53 4.93 3.30 63.79 0.94 2.62 0.22 0.85 0.17 0.18 0.13 0.15 1.59 3.0% Hi Ca 20.38 4.83 3.31 64.07 0.92 2.55 0.20 0.80 0.17 0.18 0.13 0.15 1.68 5.0% Hi Ca 20.23 4.84 3.32 63.62 0.91 2.65 0.20 0.74 0.16 0.18 0.14 0.15 2.27

0.70

0.80

0.78

0.73

0.69

Insoluble 0.26 0.76* 0.84* 0.48 0.54 residue (%) * Note: Exceeds allowable limit in ASTM C 150. Thus, in practice the amount of limestone would need to be reduced. For purposes of this test series, limit was intentionally exceeded.

Table 5. Particle Size Data for Cements as Used

Residue on No. 325 Sieve (ASTM C 430) (%) 0.0% 415 3.5 2.5% Lo Ca 406 4.6 3.5% Lo Ca 414 4.6 3.0% Hi Ca 410 4.4 5.0% Hi Ca 442 3.9 * - The specific gravity of the cements was assumed to be 3.15 Label Specific surface (ASTM C 204)* (m2/kg)

Table 6. Cube Compressive Strengths (ASTM C 109)

Label 0.0% 2.5% Lo Ca 3.5% Lo Ca 3.0% Hi Ca 5.0% Hi Ca 1 day 20.2 19.4 19.4 20.1 18.8 Compressive strength, MPa 3 days 7 days 28 days 32.5 38.8 45.2 31.4 36.1 42.8 29.1 34.6 42.6 30.0 35.6 44.1 30.3 36.7 43.1 56 days 46.3 44.6 41.3 46.3 43.0

Table 7. Drying Shrinkage Results (ASTM C 596)

Label 0.0% 2.5% Lo Ca 3.5% Lo Ca 3.0% Hi Ca 5.0% Hi Ca 1 week 0.064 0.064 0.062 0.064 0.072 2 week s 0.079 0.082 0.081 0.081 0.090 3 week s 0.092 0.097 0.096 0.095 0.101 % length change 8 4 week week s s 0.098 0.107 0.103 0.112 0.103 0.113 0.102 0.112 0.108 0.114 16 week s 0.121 0.126 0.127 0.125 0.127 32 week s 0.126 0.131 0.132 0.129 0.132 64 weeks 0.130 0.136 0.137 0.135 0.137

Table 8. Expansion in Sulfate Solution (ASTM C 1012)

Label 0.0% 2.5% Lo Ca 3.5% Lo Ca 3.0% Hi Ca 5.0% Hi Ca 1 week 0.004 0.005 0.004 0.005 0.005 2 week 0.006 0.007 0.007 0.006 0.007 3 week 0.007 0.008 0.008 0.006 0.007 4 week 0.010 0.011 0.010 0.004 0.003 Expansion, % 8 4 week month 0.010 0.016 0.009 0.021 0.010 0.017 0.010 0.014 0.011 0.016 6 month 0.021 0.025 0.020 0.020 0.022 9 month 0.025 0.030 0.018 0.016 0.021 12 month 0.023 0.031 0.023 0.019 0.021

Table 9. Expansion in Sulfate Solution (ASTM C 452)

Label 14 days 28 days 0.0% 0.025 0.034 2.5% Lo Ca 0.026 0.034 3.5% Lo Ca 0.026 0.033 3.0% Hi Ca 0.022 0.031 5.0% Hi Ca 0.027 0.034 * - Samples inadvertantly dried between 180 and 365 days. Expansion, % 56 days 90 days 0.050 0.049 0.049 0.046 0.047 0.061 0.054 0.055 0.053 0.054 180 days 0.080 0.065 0.073 0.065 0.063 367 days * 0.077 0.093 0.079 0.073

Table 10. Properties of Concrete Mixes

Label Cemen t kg/m3 Fine Agg. kg/m3 807 806 807 811 808 Coarse Agg. kg/m3 1117 1115 1117 1123 1118 Water kg/m3 Slump mm Unit weight kg/m3 2422 2419 2422 2435 2425 Air content % 1.6 1.3 1.5 1.1 1.5 Strength, MPa 7 days 32.3 35.0 34.3 33.9 35.9 28 days 43.8 43.4 41.9 42.3 46.1

0.0% 2.5% Lo Ca 3.5% Lo Ca 3.0% Hi Ca 5.0% Hi Ca

333 333 333 336 334

165 165 165 166 165

165 160 195 190 150

FIGURES
50 40 Strength, Mpa 30 20 10 0 0 10 20 30 Age (days) 40 50 60 0.0% 2.5% Lo Ca 3.5% Lo Ca 3.0% Hi Ca 5.0% Hi Ca

Figure 1. Cube Compressive Strengths (ASTM C 109)

0.150

Shrinkage, %

0.100 0.0% 2.5% Lo Ca 3.5% Lo Ca 3.0% Hi Ca 5.0% Hi Ca

0.050

0.000 0 20 40 60 Age, days 80 100 120

Figure 2. Drying Shrinkage Results (ASTM C 596)

0.100 0.0% 2.5% Lo Ca 3.5% Lo Ca 3.0% Hi Ca 5.0% Hi Ca 6 month limit specified in ASTM C 1157

0.080 Expansion (%)

0.060

0.040

0.020

0.000 0 100 200 Age (days) 300 400

Figure 3. Expansion in Sulfate Solution (ASTM C 1012)

0.10 0.08 Expansion (%) 0.06 0.04 0.02 0.00 0 100 200 Age (days) 300 400 0.0% 2.5% Lo Ca 3.5% Lo Ca 3.0% Hi Ca 5.0% Hi Ca 14 day limit specified in ASTM C 150

Figure 4. Expansion in Sulfate Solution (ASTM C 452)