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This document is not an ASTM standard; it is under consideration within an ASTM technical committee but has not received

all approvals required to become an ASTM standard. You agree not to reproduce or circulate or quote, in whole or in part, this document outside of ASTM Committee/Society activities, or submit it to any other organization or standards bodies (whether national, international, or other) except with the approval of the Chairman of the Committee having jurisdiction and the written authorization of the President of the Society. If you do not agree with these conditions please immediately destroy all copies of the document. Copyright ASTM International, 100 Barr Harbor Drive, West Conshohocken, PA 19428. All Rights Reserved.

Item _1___
Date: To: From: Subject: 8 September 2011 ASTM Committee C01 and Subcommittee C01.10 Paul Tennis, Chairman C01.10 WK33157: Proposal to Revise ASTM C595, Provisions for Type IL Cements

Rationale
Overview This proposal defines a new type of C595 blended cement containing between 5% and 15% limestone as an ingredient. The motivation for this proposal is to provide a means of implementing proven cement technology to improve sustainability of concrete while maintaining desired performance. The proposed Type IL cements can be produced with a lower environmental footprint while permitting concrete with similar performance to existing blended cements in a wide variety of applications. Such cements have been used in Europe for decades as well as other countries around the world, and in 2008 Canada adopted provisions for portland-limestone cement containing between 5% and 15% limestone in CSA A3001. The discussion and example data below are mainly extracted from State-of-the-Art-Report on Use of Limestone in Cements at Levels of up to 15% (Tennis, Thomas and Weiss 2011) and The Durability of Concrete Produced with Portland-Limestone Cement: Canadian Studies (Thomas and Hooton 2010), both of which may be downloaded at the links provided (see References Cited) or upon request to the C01.10 chairman, Additional data and information on effects of use of limestone on fresh and hardened concrete properties, as well as several case studies on use of cements with limestone in the US and Canada are included in those reports. This change has been developed by Task Group C01.10.05 (Joint AASHTO-ASTM Harmonization Task Group, JAAHTG) and parallel changes to AASHTO M240 will be balloted to AASHTO TS3a. The approach taken by the JAAHTG in developing provisions has been to review how Canadian and European standards address issues, but to also investigate the basis for specific provisions and consider potential improvements. A similar item was balloted on Subcommittee Ballot C01.10 (2011-01). It received a persuasive negative and was withdrawn and revised to address the issue raised (regarding significance and use statements in the proposed annexes), as well as other points raised in that ballot. This item is being considered concurrently. Specific Changes under Ballot This ballot item is based on ASTM C595-11. Pages 1 through 9 of this ballot include the rationale and supporting information. Specific changes to the standard are shown beginning on page 10. Proposed additions are underlined and proposed deletions are shown in strikethrough font. Only changes so indicated are being balloted. Other text is provided for information only. Notes, footnotes, tables, and

referenced documents will be renumbered or updated editorially, if needed. Dates in Section A2.6 and A3.6 will be inserted by the ASTM Editor and will be 5 years after date of publication of the standard, per ASTMs Form and Style Manual Section A21. Primary proposed changes include: 1. Revisions to Sections 1.1 (scope), 4.1.1.3, 4.2.2, Notes 2 and 5, Sections 6.3, 6.12 and 6.13 (revised to 6.13 and 6.14), new Sections 6.19 and 6.20. These changes generally define portland-limestone blended cements as cements with more than 5.0% and up to and including 15.0% limestone content. 2. New Section 7.2 and new Table 5 with requirements for limestone to be used as an ingredient in blended cements. 3. Changes to Tables 1 and 2 to define requirements for portland-limestone blended cements. 4. New Annexes A2 on the methylene blue index test and A3 on total organic carbon content. These provide procedures for use in qualifying limestone as an ingredient. A procedure for checking conformance of a limestone with the methylene blue requirements with a single iteration is proposed as Appendix X1. These test procedures are those used in CSA A3000. Other changes (for examples, Sections 10, 14, 15, and 17) proposed throughout are for consistency and clarity. Detailed discussion Range of Limestone Content in Proposal Cements with between 5% and 15% by mass limestone are proposed as a new type of blended cement. A maximum value of 15% was chosen based in part on experience in Europe and Canada, which demonstrates that equivalent performance can be achieved with limestone contents in this range. Above this range, some loss of performance (for example strength) is commonly observed, although still useful for a wide array of applications. European cement standard EN197-1 permits limestone contents up to 35% to be used. Mechanisms affecting the performance of limestone in cement include more easily ground limestone filling in pores between larger cement grains and possibly some small amount of chemical reaction of the limestone. Relative compressive strength data for one base cement with a range of limestone content is provided in Figure 1 and shows increases in strength (relative to a control without limestone) until about 15% limestone, after which strength decreases relative to the control.

Figure 1. A correlation between estimated porosity and measured strength development with limestone for a single base cement (Matschei et al. 2007). The relative strength for this cement with limestone is higher than the control until about 15% by mass limestone.

Environmental Benefits The primary sustainability effect of using limestone as an ingredient in portland-limestone blended cements at levels of 5% to 15% by mass is that less clinker has to be produced for an equivalent amount of cement, and therefore less energy is consumed and CO2 emissions (and other greenhouse gases) are reduced. Carbon dioxide emissions for cement plants come predominantly from two sources: calcination of the limestone, a primary raw ingredient for clinker manufacture, and fossil fuel consumption to heat the raw materials to the temperature required to form clinker. Very roughly, limestone is about 50% by mass CO2 and release of this CO2 during calcination accounts for about 60% of the CO2 emissions produced at a cement plant. Both of these quantities are reduced in blended cement production as less clinker is used in the cement. These reductions are roughly proportional to the decrease in the amount of clinker in the blended cement. Figure 2 provides specific examples for CO2 emission reductions for three German cement plants (Schmidt 1992). The calculations include the total energy demand of all steps in the production process taking into account the specific demand of fuel energy. The replacement of about 15% by mass of the clinker by limestone reduces CO2 emissions on average by 12% (Schmidt et al. 2010). Similar results can be calculated for the emissions of nitrous oxides (NOx) and sulfur dioxide (SO2). An analysis of the environmental impact of up to 5% limestone in the production of portland cement is found in Nisbet (1996). Based on the approach used in that analysis, an estimate is given in Table 1 assuming 10% or 15% limestone for portland-limestone cements. These provide conservative estimates of reductions in environmental and energy impacts that can be achieved through use of limestone, as compared to a portland cement without limestone. It should be noted that portland cements in the US are permitted to contain up to 5% limestone (typical level is likely about 3% on average), which will reduce the savings noted in Table 1. Even if the maximum amount of limestone (5%) is used in portland cements, use of portland-limestone cements with a total of 10% to 15% limestone will result in significant additional reductions in energy and emissions.

Portland cement

1.0
Portland-limestone cement

0.8
kg CO2/kg cement

0.6

0.4

0.2

0.0

Plant 1

Plant 2

Plant 3

Figure 2. Specific CO2 emissions from the production of portland cement or portland-limestone cement for 3 German cement plants (adapted from Schmidt 1992).

Estimated Annual Reduction in Energy Usage and Emissions Resulting From Use of 10% or 15% Limestone in Blended Cement* 10% limestone 15% limestone (per million tons of (per million tons of cement) cement) Energy Reduction Fuel (million BTU) 443,000 664,000 Electricity (kWh) 6,970,000 10,440,000 Emissions Reduction SO2 (lbs) 581,000 870,000 NOX (lbs) 580,000 870,000 CO (lbs) 104,000 155,000 CO2 (tons) 189,000 283,000 Total Hydrocarbon, THC (lbs) 14,300 21,400 * Following the approach of Nisbet (1996). Estimates compare portland cement with 5% gypsum, no limestone, and no inorganic processing addition with blended cement containing portland cement clinker, gypsum and the amount of limestone indicated.

Table 1.

Cement Requirements The ballot proposes changes to define portland-limestone blended cements. These cements meet the same physical requirements as other C595 cement types: Identical requirements for minimum compressive strengths, autoclave expansion (soundness) testing, initial setting time, and air content would apply to portland-limestone cement Type IL and to Type IT cements containing limestone as apply to cement Types IP, IS(<70), IT(S<70). The maximum heat of hydration requirements for moderate heat cements (-MH) are also the same. This is consistent with the approach used in CSA in that portland-limestone cements in CSA A3001 must meet the same requirements as their counterparts without limestone. Chemical requirements for cements with between 5% and 15% limestone are somewhat different than for existing blended cement types. Consistent with CSA A3001, portland-limestone blended cements are proposed to have maximum loss-on-ignition (LOI) limits of 10.0% by mass (compared to 3.0% for

Type IS(<70) and 5.0% for Type IP). The higher LOI limit is specifically to accommodate the higher loss due to the presence of limestone, which loses on the order of half its mass at ignition temperatures. The proposal requires a default maximum sulfate content for Type IL blended cements of 3.0% by mass, similar to Type IS(<70). However higher sulfate contents may be used if C1038 results are below 0.020% at 14 days (as with other blended cements in C595). This is again consistent with requirements for portland-limestone cements in CSA A3001.

Requirements for Limestone EN 197-1 and CSA A3001 require that limestone used in portland-limestone cements have a minimum CaCO3 content of 75% by mass. ASTM C150 requires limestone used in portland cement to have a minimum CaCO3 content of 70%. These requirements are somewhat arbitrary. The JAAHTG has reviewed the provisions and recommends that C595 (and AASHTO M240) require a minimum 70% CaCO3 content for consistency with C150 (and AASHTO M85). CSA A3001 also includes methylene blue index (MBI) and total organic carbon content (TOC) limits as does EN197-1 for limestone used in portland-limestone cements. The JAAHTG recommends MBI and TOC limits consistent with CSA A3001 and has included test procedures to determine those characteristics as Annexes 2 and 3. Research from the early 1990s (Sprung and Siebel 1991) appears to justify the MBI and TOC limits on the basis of concrete freeze-thaw testing with cements made with a range of limestones. However, this research was performed on concretes that would not meet US recommendations for freezethaw durable concrete (test mixtures were not air entrained and had a high w/c), and original data indicates about 50% of the limestone that did not meet MBI or TOC limits performed well in that severe freeze-thaw testing. US cement producers have further noted that the CSA MBI or TOC requirements would preclude some limestone deposits that have been successfully used in ASTM C1157 cements and in masonry cement formulations. Given that limestone quality criteria should provide an acceptable level of confidence for producers and users that limestone does not compromise concrete durability, and should also avoid disqualifying limestones that perform well in service, consideration should be given to developing alternative criteria for acceptance of limestone used in portland-limestone cement. The JAAHTG is evaluating two possible approaches for alternate qualification criteria.

Performance: Concrete Strength In a number of full-scale plant trials in Canada, it has been demonstrated that equivalent strength can be achieved in concrete produced with PLC containing up to 15% limestone (Thomas et al. 2010a; 2010b; 2010c; 2010d). Figure 3 shows the results of compressive strength tests for ten concrete mixtures (Thomas and Hooton 2010). In all cases a higher strength is observed at early ages (1 day or 7 days) for concretes made with portland-limestone cement compared with the equivalent concrete made with portland cement. At later ages (28 days or 56 days) the differences are smaller but the strength of portland-limestone cement mixtures is generally slightly higher or similar to the equivalent portland cement mixtures.

Figure 3. Strength development of portland cement and portland-limestone cement mixtures with and without SCM at w/cm = 0.45 (Thomas and Hooton 2010).

Performance: DurabilityGeneral Results from Rapid Chloride Permeability Testing (ASTM C1202) for several concretes made with cements with and without limestone are plotted in Figure 4. It is clear from these data that w/cm, age and supplementary cementitious materials (SCM) content have a profound impact on the permeability, but that the impact of the level of limestone in the cement (4% to 12%) is not significant.

3000

Charge Passed (Coulombs)

28 days

56 days

2000
PC PLC

1000

0 No SCM No SCM W/CM = 0.40 20% Fly No SCM No SCM 35% 20% Fly Ash Slag Ash W/CM = 0.40 W/CM = 0.45 W/CM = 0.45 35% Slag

Figure 4. Rapid Chloride Permeability Test (ASTM C1202) data for PC and PLC concrete with and without SCM (Thomas et al. 2010b).

Hooton et al. (2010) performed ASTM C1556 chloride bulk diffusion tests and found that 10% to 15% interground limestone did not change diffusion coefficients appreciably, with or without 30% slag replacement, as shown in Table 3.
Table 3. Diffusion Coefficients ( 10 m /s) for Concrete after 35 days Immersion in 3% NaCl Solution (Hooton et al. 2010) GU PLC10 PLC15 GU 70% PLC10 70% PLC15 70% 100% 100% 100% SLAG 30% SLAG 30% SLAG 30% Cs (% mass) 2 -12) Da (m /s * 10 0.73 15.9 0.84 15.6 0.8 22.5 1.1 8.07 1.07 6.11 0.98 8.25
-12 2

Additional information on durability performance (carbonation, freeze-thaw, ASR, deicer scaling, shrinkage, abrasion resistance) is provided in the reviews by Thomas and Hooton (2010) and Tennis, Thomas and Weiss (2011).

Performance: DurabilitySulfate Matthews (1994) exposed 100-mm concrete cubes (w/cm = 0.62 to 0.66) to three sulfate solutions consisting of either Na2SO4 (1.5% SO3) or MgSO4 (0.35% or 1.5% SO3) for up to 5 years. Portland cement from five different sources was blended or interground (in one case) with 5% or 25% limestone. The sulfate resistance of the concrete was strongly dependent on the C3A content of the cement with no consistent difference in performance being attributed to the level of the limestone. Likewise, Irassar and coworkers (Gonzales and Irasser 1998; Irassar et al. 2000, 2005) compared the performance of three cements with varying C3A and C3S levels, and limestone contents of 0%, 10% and 20%. Generally the presence of 10% limestone had little impact on the performance of mortars compared with control mortars without limestone, but 20% limestone resulted in increased expansion.

In an extensive review of research into thaumasite, Irasser (2009) concluded that risk of thaumasite sulfate attack (TSA) is minimized with low water-to-cement ratios, sulfate resistant (low C3A content) cements, and sufficient cement contents. In other words, following established sulfate resistant concrete practice will minimize risk of TSA. Currently the evidence available would indicate that the concrete made with portland-limestone cements is potentially more vulnerable to TSA than concretes made with portland cements. However, initial research results indicate that supplementary cementitious materials (SCMs) may be able to reduce the risk of TSA when combined with portland-limestone cement. More work is needed to determine appropriate requirements for sulfate resistance of portland-limestone cement/SCM blends. For this reason, this initial proposal does not include MS or HS designations for the proposed Type IL cements or ternary cements with limestone.

References Cited
CSA A3001, Cementitious Materials for Use in Concrete EN 197-1, Cement - Part 1: Composition, Specifications and Conformity Criteria for Common Cements, European Committee for Standardization, Brussels, 2000. Gonzlez, M.A., and Irassar, E.F., Effect of Limestone Filler on the Sulfate Resistance of Low C3A Portland Cement, Cement and Concrete Research, Vol. 28, No. 11, 1998, pages 1655 to 1667. Hooton, D.; Ramezanianpour, A.; and Schutz, U., Decreasing the Clinker Component in Cementing Materials: Performance of Portland-Limestone Cements in Concrete in Combination with SCMs, 2010 Concrete Sustainability Conference, National Ready Mixed Concrete Association, April 13 to 15, 2010, Tempe, Arizona. Irasser, E. F., Sulfate Attack on Cementitious Materials Containing Limestone Filler A Review, Cement and Concrete Research, Vol. 39, No. 3, March 2009, pages 241 to 254. Irasser, E. F.; Bonavetti, V. L.; Trezza, M. A.; and Gonzlez, M. A.; Thaumasite formation in Limestone Filler Cements Exposed to Sodium Sulphate Solution at 20C, Cement and Concrete Composites, Vol. 27, 2005, pages 77 to 84. Irasser, E.F.; Gonzalez, M.; and Rahhal, V., Sulphate Resistance of Type V Cements with Limestone Filler and Natural Pozzolana, Cement and Concrete Composites, Vol. 22, 2000, pages 361 to 368. Matthews, J. D., Performance of Limestone Filler Cement Concrete, in Euro-Cements Impact of ENV 197 on Concrete Construction, (Ed. R. K. Dhir and M. R. Jones), E&FN Spon, London, 1994, pages 113 to 147. Matschei, T.; Glasser, F. P.; Herfort, D.; and Lothenbach, B., Relationships of Cement Paste Mineralogy to Porosity and Mechanical Properties, presentation at International Conference on Modelling of Heterogeneous Materials with Applications in Construction and Biomedical Engineering, Prague, Czech Republic, 25-27 June 2007. Moir, G.K., Limestone Cements: Gaining Acceptance, International Cement Review, March 2003, pages 67 to 70.Nisbet, M.A., The Reduction of Resource Input and Emissions Achieved by Addition of Limestone to Portland Cement, SN2086, Portland Cement Association, Skokie, Illinois, USA, 1996, 11 pages. Schmidt, M., "Cement with Interground Additives - Capability and Environmental Relief," Zement-Kalk-Gips, Vol. 45, No. 2, 1992 pages 64 to 69; and Vol. 45, No. 6, 1992 pages 296 to 301. Schmidt, M.; Middendorf, B.; and N. B. Singh, N.B., Blended Cements, Chapter 10 in Modern Cement Chemistry, SP409, Portland Cement Association, Skokie, Illinois, USA, in press, 2010. Sprung, V. S., and E. Siebel, E., Assessment of the Suitability of Limestone for Producing Portland Limestone Cement, ZKG International, Vol. 1, 1991, pages 1 to 11. (In German. English text in No. 3, 1991, pages 43 to 48.) Tennis, P. D.; Thomas, M.D.A.; and. Weiss, W. J., State-of-the-Art Report on Use of Limestone in Cements at Levels of up to 15%, SN3148, Portland Cement Association, Skokie, Illinois, USA, 2011, 78 pages. Available at: http://www.cement.org/bookstore/profile.asp?store=&pagenum=1&pos=0&catID=&id=17058. Thomas, M. D. A.; Hooton, R. D.; Cail, K.; Smith, B. A.; De Wal, J.; and Kazanis, K. G., Field Trials of Concretes Produced with Portland Limestone Cement, Concrete International, January 2010a, pages 35 to 41.

Thomas, M. D. A.; Cail, K.; Blair, B.; Delagrave, A.; and Barcelo, L., Equivalent Performance with Half the Clinker Content using PLC and SCM, 2010 Concrete Sustainability Conference, National Ready Mixed Concrete Association, April 13 to 15, 2010b, Tempe, Arizona. Thomas, M. D. A.; Cail, K.; Blair, B.; Delagrave, A.; Masson, P., and Kazanis, K., Use of Low-CO2 Portland Limestone Cement for Pavement Construction in Canada, International Conference on Sustainable Concrete Pavements, Sacramento, September 2010c. Thomas, M. D. A.; Kazanis, K.; Cail, K.; Delagrave, A.; and Blair, B., Lowering the Carbon Footprint of Concrete by Reducing the Clinker Content of Cement, Transportation Association of Canada Annual Conference, Halifax, September 2010d. Thomas, Michael, D. A. and Hooton, R. Doug, The Durability of Concrete Produced with Portland-Limestone Cement: Canadian Studies, SN3142, Portland Cement Association, Skokie, Illinois, USA, 2010, 28 pages. Available at: http://www.cement.org/bookstore/profile.asp?store=&pagenum=1&pos=0&catID=&id=17029.

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This document is not an ASTM standard; it is under consideration within an ASTM technical committee but has not received all approvals required to become an ASTM standard. You agree not to reproduce or circulate or quote, in whole or in part, this document outside of ASTM Committee/Society activities, or submit it to any other organization or standards bodies (whether national, international, or other) except with the approval of the Chairman of the Committee having jurisdiction and the written authorization of the President of the Society. If you do not agree with these conditions please immediately destroy all copies of the document. Copyright ASTM International, 100 Barr Harbor Drive, West Conshohocken, PA 19428. All Rights Reserved.

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ASTM Designation: C 595/C 595M11


Standard Specification for

Blended Hydraulic Cements1

1. Scope 1.1 This specification pertains to blended hydraulic cements for both general and special applications, using slag or, pozzolan, or both, limestone, or some combination of these, with portland cement or portland cement clinker or slag with lime.
NOTE 1This specification prescribes ingredients and proportions, with some performance requirements whereas Performance Specification C 1157 is a hydraulic cement specification in which performance criteria alone govern the products and their acceptance.

1.2 The values stated in either SI units or inch-pound units are to be regarded separately as standard. The values stated in each system may not be exact equivalents; therefore, each system shall be used independently of the other. Combining values from the two systems may result in non-conformance with the standard. Values in SI units [or inch-pound units] shall be obtained by measurement in SI units [or inch-pound units] or by appropriate conversion, using the Rules for Conversion and Rounding given in IEEE/ASTM SI 10, of measurements made in other units [or SI units]. Values are stated in only SI units when inch-pound units are not used in practice. 1.3 The text of this standard refers to notes and footnotes which provide explanatory material. These notes and footnotes (excluding those in tables and figures) are not requirements of the standard. 2. Referenced Documents 2.1 ASTM Standards:2 C 51 Terminology Relating to Lime and Limestone (as used by the Industry) C 109/C 109M Test Method for Compressive Strength of Hydraulic Cement Mortars (Using 2-in. or [50-mm] Cube Specimens) C 114 Test Methods for Chemical Analysis of Hydraulic Cement C 150 Specification for Portland Cement C 151 Test Method for Autoclave Expansion of Hydraulic Cement C 157/C 157M Test Method for Length Change of Hardened Hydraulic-Cement Mortar and Concrete C 183 Practice for Sampling and the Amount of Testing of Hydraulic Cement C 185 Test Method for Air Content of Hydraulic Cement Mortar C 186 Test Method for Heat of Hydration of Hydraulic Cement C 187 Test Method for Normal Consistency of Hydraulic Cement C 188 Test Method for Density of Hydraulic Cement C 191 Test Methods for Time of Setting of Hydraulic Cement by Vicat Needle C 204 Test Methods for Fineness of Hydraulic Cement by Air-Permeability Apparatus C 219 Terminology Relating to Hydraulic Cement C 226 Specification for Air-Entraining Additions for Use in the Manufacture of Air-Entraining Hydraulic Cement C 227 Test Method for Potential Alkali Reactivity of Cement-Aggregate Combinations (Mortar-Bar Method) C 311 Test Methods for Sampling and Testing Fly Ash or Natural Pozzolans for Use in Portland-Cement Concrete C 430 Test Method for Fineness of Hydraulic Cement by the 45-m (No. 325) Sieve C 465 Specification for Processing Additions for Use in the Manufacture of Hydraulic Cements
1 This specification is under the jurisdiction of ASTM Committee C01 on Cement and is the direct responsibility of Subcommittee C01.10 on Hydraulic Cements for General Concrete Construction. Current edition approved XXXXXXX Published XXXXX. Originally approved in 1967. Last previous edition approved in XXXX as C 595 XX. 2 For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards volume information, refer to the standard's Document Summary page on the ASTM website.

Proposed Revision to C 595/C 595M

42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94

C 511 Specification for Mixing Rooms, Moist Cabinets, Moist Rooms, and Water Storage Tanks Used in the Testing of Hydraulic Cements and Concretes C 563 Test Method for Approximation of Optimum SO3 in Hydraulic Cement Using Compressive Strength C 688 Specification for Functional Additions for Use in Hydraulic Cements C 821 Specification for Lime for Use with Pozzolans C 1012 Test Method for Length Change of Hydraulic-Cement Mortars Exposed to a Sulfate Solution C 1038 Test Method for Expansion of Hydraulic Cement Mortar Bars Stored in Water C 1157 Performance Specification for Hydraulic Cement E 11 Specification for Wire-Cloth and Sieves for Testing Purposes E 350 Standard Test Methods for Chemical Analysis of Carbon Steel, Low-Alloy Steel, Silicon Electrical Steel, Ingot Iron, and Wrought Iron IEEE/ASTM SI 10 Standard for Use of the International System of Units (SI): the Modern Metric System 2.2 CSA Standards CSA A3004-D2 Determination of Total Organic Carbon in Limestone

3. Terminology 3.1 DefinitionsThe terms used in this specification are defined in Terminology C 219, except for the following terms: 3.1.1 binary blended cement, na blended hydraulic cement consisting of portland cement with either a slag cement, or a pozzolan, or a limestone. 3.1.2 ternary blended cement, na blended hydraulic cement consisting of portland cement with either a combination of two different pozzolans, or slag cement and a pozzolan, a pozzolan and a limestone, or a slag cement and a limestone. 4. Classification 4.1 This specification applies to the following types of blended cement that generally are intended for use as indicated. 4.1.1 Blended hydraulic cements for general concrete construction. 4.1.1.1 Type ISPortland blast-furnace slag cement. 4.1.1.2 Type IPPortland-pozzolan cement. 4.1.1.3 Type ILPortland-limestone cement. 4.1.1.3 4 Type ITTernary blended cement. 4.2 Reporting: 4.2.1 The naming practice for blended cements shall be made by adding the suffix (X) to the type designation under 4.1.1, where (X) equals the targeted percentage of slag, or pozzolan or limestone, in the product expressed as a whole number by mass of the final blended product, within the allowable variation as stated in 14.3. 4.2.2 The naming practice for ternary blended cements shall be made by adding the suffixes (AX) and (BY) to the Type IT designation under 4.1.1, where: A is either S for slag cement, or P for pozzolan, or L for limestone, whichever is present in larger amount by mass, and X is the targeted percentage by mass of constituent A, and B is either S for slag cement, or P for pozzolan, or L for limestone, and Y is the targeted percentage by mass of constituent B. Both X and Y values are expressed as a whole number by mass of the final blended product, within the allowable variation as stated in 14.3. If X and Y are the same, list the pozzolan content first two constituents in alphabetical order by constituent type (limestone, pozzolan, or slag).
NOTE 2Examples of the naming practice per 4.2.1 and 4.3 are shown below (all percentages by mass): Binary blended cement with 80 % portland cement and 20 % slag cement = Type IS(20). Binary blended cement with 85 % portland cement and 15 % pozzolan = Type IP(15). Binary blended cement with 90% portland cement and 10% limestone = Type IL(10). Ternary blended cement with 70 % portland cement, 20 % slag cement and 10 % pozzolan = Type IT(S20)(P10). Ternary blended cement with 65 % portland cement, 25 % of one pozzolan and 10 % of another pozzolan = Type IT(P25)(P10). Ternary blended cement with 60 % portland cement and 20 % of slag cement and 20 % pozzolan = Type IT(P20)(S20). Ternary blended cement with 80 % portland cement, 10 % pozzolan and 10 % limestone = Type IT(L10)(P10). Ternary blended cement with 75 % portland cement, 15 % slag cement and 10 % limestone = Type IT(S15)(L10).

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Proposed Revision to C 595/C 595M

95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142

4.2.3 A simplified naming practice is used in this standard for practicality and clarity when referring to specific requirements for binary and ternary blended cements that are applicable to a range of products or in ternary blended cements when requirements are applicable to only one constituent within a specific range (%). (See Note 3)
NOTE 3Examples of the simplified naming practices per 4.2.3 are shown below: 1) An example when requirements are applicable to a range of products can be found in Table 1, where the maximum SO 3 content of 3 % applies to: binary blended cements with slag cement contents <70 %, indicated as IS(<70); ternary blended cements with a pozzolan content less than the slag cement content and the slag cement content is less than 70 %, indicated as IT(P<S<70). 2) An example when requirements are applicable to only one constituent within a specific range (%) of that constituent can be found in 8.2, where testing is required only when the slag cement content is <25 %. Because the requirement is based on the slag cement content only with no relation to the pozzolan or limestone content, a simplified naming practice is employed and the range of ternary blended cements are indicated as Type IT(S<25).

4.3 Special Properties: 4.3.1 Air-entraining cement, when desired by the purchaser, shall be specified by adding the suffix (A) to any of the above types. The air-entraining option is specified in combination with any of the other special properties where required.
NOTE 4A given mass of blended cement has a larger absolute volume than the same mass of portland cement. This should be taken into consideration in purchasing cements and in proportioning concrete mixtures.

4.3.2 Moderate sulfate resistance or moderate heat of hydration, or both, when desired by the purchaser, shall be specified by adding the suffix (MS) or (MH), respectively, to the type designation under 4.1.1. 4.3.3 High sulfate resistance, when desired by the purchaser, shall be specified by adding the suffix (HS) to the type designation under 4.1.1. 4.3.4 Low heat of hydration, when desired by the purchaser, shall be specified by adding the suffix (LH) to the type designation under 4.1.1.
NOTE 5Special characteristics attributable to slag, pozzolan, or, limestone will vary based on quantities contained within the blended cements. Type IL and Type IT cements with limestone are not included as moderate (MS) or high (HS) sulfate resistance cements, pending results of further research.

5. Ordering Information 5.1 Orders for material under this specification shall include the following: 5.1.1 Specification number, 5.1.2 Type or types required, 5.1.2.1 Indicate allowable slag, or pozzolan, or limestone % maximum or minimum percentage by mass, or both, if required. 5.1.3 Optional special properties required (see 4.3): 5.1.3.1 MS if moderate sulfate resistance is required; 5.1.3.2 HS if high sulfate resistance is required; 5.1.3.3 MH if moderate heat of hydration is required; 5.1.3.4 LH if low heat of hydration is required; 5.1.3.5 A if air entraining is required; 5.1.3.6 Accelerating addition, if required; 5.1.3.7 Retarding addition, if required; 5.1.3.8 Water reducing addition, if required; 5.1.3.9 Water reducing and accelerating addition, if required; and 5.1.3.10 Water reducing and retarding addition, if required. 5.1.4 Certification, if desired (see Section 14).
NOTE 6It is important to check for availability of various options. Some multiple options are mutually incompatible or unattainable.

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Proposed Revision to C 595/C 595M

143 144 145 146 147 148 149 150 151 152 153 154 155 156 157 158 159 160 161 162 163 164 165 166 167 168 169 170 171 172 173 174 175 176 177 178 179 180 181 182 183 184 185 186 187 188 189 190 191 192 193 194

6. Materials and Manufacture 6.1 Blast-Furnace SlagBlast-furnace slag shall be the nonmetallic product, consisting essentially of silicates and aluminosilicates of calcium and other bases, that is developed in a molten condition simultaneously with iron in a blast furnace. 6.2 Granulated Blast-Furnace Slag Granulated blast-furnace slag shall be the glassy granular material formed when molten blast-furnace slag is rapidly chilled, as by immersion in water. 6.3 LimestoneLimestone, as defined in ASTM C 51, shall be naturally occurring and comply with the requirements indicated in 7.2. 6.3 4 Slag CementSee Terminology C 219. 6.4 5 Portland CementSee Terminology C 219. For purposes of this specification, portland cement meeting the requirements of Specification C 1157 or Specification C 150 are suitable. Portland cement or other hydraulic materials, or both, containing high free lime are not prohibited from use as long as the autoclave test limits for the blended cement are met. 6.5 6 Portland Cement ClinkerPortland cement clinker shall be partially fused clinker consisting primarily of hydraulic calcium silicates. 6.6 7 PozzolanPozzolan shall be a siliceous or siliceous and aluminous material, which in itself possesses little or no cementitious value but which will, in finely divided form and in the presence of moisture, chemically react with calcium hydroxide at ordinary temperatures to form compounds possessing cementitious properties. 6.7 8 Hydrated LimeHydrated lime used as part of a blended cement shall meet the requirements of Specification C 821, except that when interground in the production process there shall be no minimum fineness requirement. 6.8 9 Air-Entraining AdditionWhen air-entraining cement is specified, an addition meeting the requirements of Specification C 226 shall be used. 6.910 Processing AdditionsWhen processing additions are used in the manufacture of cement, they shall have been shown to meet the requirements of Specification C 465 in the amounts used or greater, (see Section 14.2). 6.1011 Functional AdditionsWhen functional additions (used at the sole option of the purchaser) are used they shall have been shown to meet the requirements of Specification C 688 when tested with the cement to be used, in the amount used or greater, (see Section 14.2). 6.11 12 Other AdditionsThe cement covered by this specification shall contain no additions except as provided for above except that water or calcium sulfate (see Terminology C 219), or both, if added, shall be in amounts so that the limits shown in Table 1 for sulfate reported as SO3 and loss on ignition are not exceeded. 6.12 13 Binary Blended CementBinary blended cement shall be a hydraulic cement consisting of an intimate and uniform blend (see Note 7) produced either by intergrinding portland cement clinker with a pozzolan or a granulated blast-furnace slag, or a slag cement, or a limestone, or by blending portland cement with a pozzolan or a slag cement, or limestone, or a combination of intergrinding and blending. Any granulated blast-furnace slag, slag cement, or pozzolan, or limestone used as an ingredient or addition in portland cement used to manufacture a binary blended cement shall be included in the total amount of those materials reported in 4.2 or 14.1. The maximum constituent requirements of 6.1415, and 6.1617, and 6.19 shall apply. 6.13 14 Ternary Blended CementTernary blended cement shall be a hydraulic cement consisting of an intimate and uniform blend (see Note 7) produced either by intergrinding portland cement clinker with 1) two different pozzolans, 2) granulated blast-furnace slag or slag cement and a pozzolan, 3) a pozzolan and a limestone, or 4) a granulated blast-furnace slag or slag cement and a limestone; or by blending portland cement with 1) two different pozzolans, or 2) slag cement and a pozzolan, 3) a pozzolan and a limestone, or 4) a slag cement and a limestone; or 3) by a combination of intergrinding and blending these materials. Ternary blended cement Type IT(S70) shall have a maximum limestone content of 15% by mass. All other tTernary blended cements Type IT(PS) and Type IT(P<S<70) shall have a maximum pozzolan content of 40% by mass of the blended cement, a maximum limestone content of 15% by mass of the blended cement, and the total content of pozzolan, limestone, and granulated blast-furnace slag or slag cement shall be less than 70% by mass of the blended cement. Any granulated blast-furnace slag, slag cement, or pozzolan, or limestone used as ingredient in portland cement used to manufacture a blended cement shall be included in the total amount of those materials reported in 4.2 or 14.1.
NOTE 7The attainment of an intimate and uniform blend of two or more types of fine materials is difficult. Consequently, adequate equipment and controls must be provided by the manufacturer. The purchasers should assure themselves of the adequacy of the blending operation.

6.14 15 Portland Blast-Furnace Slag Cement Portland blast-furnace slag cement shall be a hydraulic cement in which the slag cement constituent is up to 95 % by mass of the blended cement. Binary or ternary blended cement with a slag cement content equal to or exceeding 70 % by mass, is permitted to contain hydrated lime.

14

Proposed Revision to C 595/C 595M 6.15 16 Air-Entraining Portland Blast-Furnace Slag Cement Air-entraining portland blast-furnace slag cement shall be portland blast-furnace slag cement to which sufficient air-entraining addition has been added so that the resulting product complies with the air content of mortar requirements. 6.16 17 Portland-Pozzolan CementPortland-pozzolan cement shall be a hydraulic cement in which the pozzolan constituent is up to 40 % by mass of the blended cement. 6.17 18 Air-Entraining Portland-Pozzolan CementAir-entraining portland-pozzolan cement shall be portland-pozzolan cement to which sufficient air-entraining addition has been added so that the resulting product complies with the air content of mortar requirements. 6.19 Portland-Limestone CementPortland-limestone cement shall be a hydraulic cement in which the limestone content is more than 5% but less than or equal to 15% by mass of the blended cement. 6.20 Air-Entraining Portland-Limestone CementAir-entraining portland-limestone cement shall be portland-limestone cement to which sufficient air-entraining addition has been added so that the resulting product complies with the air content of mortar requirements.

195 196 197 198 199 200 201 202 203 204 205 206 207 208 209 210 211 212 213 214 215 216 217 218 219 220 221

7. Chemical Composition 7.1 Blended CementCement of the type specified shall conform to the applicable chemical requirements prescribed in Table 1.
NOTE 8There are cases where performance of a cement is improved with SO 3 in excess of the Table 1 limits in this specification. Test Method C 563 is one of several methods a manufacturer can use to evaluate the effect of sulfate content on cement characteristics. Whenever SO3 content of a cement exceeds Table 1 limits, Test Method C 1038 results provide evidence that excessive expansion does not occur at this higher sulfate content.

7.2 1.1 If the purchaser has requested the manufacturer to state in writing the composition of the blended cement purchased, the composition of the cement furnished shall conform to that shown in the statement within the following tolerances (see Note 9).
Tolerance, % Silicon dioxide (SiO2 ) Aluminum oxide (Al2O 3) Calcium oxide (CaO) 3 2 3

222 223 224 225 226 227 228 229 230 231 232 233 234 235 236 237 238 239 240 NOTE 9This means that if the manufacturer's statement of the composition says SiO 2: 32 %, the cement when analyzed, shall be found to contain between 29 and 35 % SiO2.

7.2 LimestoneLimestone for use in the manufacture of portland-limestone cement, or a ternary blended cement in which limestone is an ingredient, shall have a calcium carbonate content of at least 70 % by mass. Such limestone shall meet the requirements of Table 5 for methylene blue index and total organic carbon content.

8. Physical Properties 8.1 Blended CementBlended cement of the type specified shall conform to the applicable physical requirements prescribed in Table 2. 8.2 Pozzolan or SlagPozzolan or granulated blast-furnace slag or slag cement that is to be blended with cement shall be tested in the same state of subdivision as that in which it is to be blended. Pozzolan shall conform to the fineness requirement and the activity index requirement of Table 3. Slag cement that is to be used for portland blast-furnace slag cements Type IS(< 25) or ternary blended cements Type IT(S<25) shall conform to the activity index requirement of Table 3. Such pozzolan, or granulated blast-furnace slag, or slag cement that is to be interground with portland cement clinker shall, before testing for conformance with requirements of Table 3, be ground in the laboratory to a fineness at which it is believed to be present in the finished cement. It is the manufacturer's responsibility to decide on the fineness at which the testing is to be carried out, and when requested to do so by a purchaser, to report the information upon which the decision was based.

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Proposed Revision to C 595/C 595M

241 242 243 244 245 246 247 248 249 250 251 252 253 254 255 256 257 258 259 260 261 262 263 264 265 266 267 268 269 270 271 272 273 274 275 276 277 278 279 280 281 282 283 284 285 286 287 288 289

8.3 Pozzolan for use in the manufacture of portland-pozzolan cement, Type IP(< 15) and IP(< 15)-A or ternary blended cements Type IT(P<15) and Type IT(P<15)-A, shall meet the requirements of Table 3 when tested for mortar expansion of pozzolan as described in 10.1.13. If the alkali content of the clinker to be used for the production lots changes by more than 0.2 % total as equivalent Na2O, calculated as Na2O + 0.658 K 2O, from that of the clinker with which the acceptance tests were carried out, the pozzolan shall be retested to show compliance with the requirements of Table 3.

9. Sampling 9.1 Sample the materials in accordance with the following methods: 9.1.1 Sampling Blended CementsPractice C 183. 9.1.1.1 When the purchaser desires that the cement be sampled and tested to verify compliance with this specification, perform sampling and testing in accordance with Practice C 183. 9.1.1.2 Practice C 183 is not designed for manufacturing quality control and is not required for manufacturer's certification. 9.1.2 Sampling PozzolanTest Methods C 311. One 2 kg [4 lb] sample shall be taken from approximately each 360 Mg [400 tons] of pozzolan. 10. Test Methods 10.1 Determine the applicable properties enumerated in this specification in accordance with the following test methods: 10.1.1 Chemical AnalysisTest Methods C 114, with the special provisions noted therein applicable to blended cement analyses. 10.1.2 Fineness by SievingTest Method C 430. 10.1.3 Fineness by Air-Permeability ApparatusTest Method C 204. 10.1.4 Autoclave ExpansionTest Method C 151, except that, in the case of portland blast-furnace slag cement IS(70) or ternary blended cement IT(S70), the test specimens shall remain in the moist cabinet for a period of 48 h before being measured for length, and the neat cement shall be mixed for not less than 3 min nor more than 3 min. 10.1.5 Time of SettingTest Method C 191. 10.1.6 Air Content of MortarTest Method C 185, using the actual specific gravity of the cement, if it differs from 3.15 by more than 0.05, in calculating the air content. 10.1.7 Compressive StrengthTest Method C 109/C 109M. 10.1.8 Heat of HydrationTest Method C 186. 10.1.9 Normal ConsistencyTest Method C 187, except that in the case of portland blast-furnace slag cement IS(70) or ternary blended cement IT(S70), the paste shall be mixed for not less than 3 min nor more than 3 min. 10.1.10 Specific GravityTest Method C 188. 10.1.11 Water RequirementThe mass of mixing water added to the six-cube batch in accordance with Test Method C 109/C 109M, as a percentage of the total cementing ingredients. 10.1.12 Mortar Expansion of Blended Cement Test Method C 227, using crushed Pyrex glass No. 77403 as aggregate and the grading prescribed in Table 4. 10.1.13 Mortar Expansion of Pozzolan for Use in Portland-Pozzolan Cement Types IP(< 15) and IP(< 15)-A or Ternary Blended Cement Types IT(P<15) and IT(P<15)-AUsing the pozzolan and the clinker or cement that are to be used together in the production of the blended cement, prepare portland-pozzolan cements Types IP(< 15) and IP(< 15)-A or Ternary Blended Cement Types IT(P<15) and IT(P<15)-A containing 2.5, 5, 7.5, 10, 12.5, and 15 mass % of the pozzolan. These blends shall be tested in accordance with Test Method C 227 using a sand judged to be a nonreactive by the mortar bar test in Test Method C 227. The expansion of the mortar bars shall be measured at 91 days, and all the six blends shall meet the expansion requirement in Table 3. 10.1.14 Drying ShrinkageTest Method C 157/C 157M. Make three specimens using the proportion of dry materials of 1 part of cement to 2.75 parts of Test Method C 109/C 109M graded Ottawa sand. Use a curing period of 6 days and an air storage period of 28 days. Report the linear contraction during air storage based on an initial measurement after the 6-day water-curing period. 10.1.15 Activity Index with Portland CementTest in accordance with Annex A1. 10.1.16 Sulfate Resistancesee Test Method C 1012. 10.1.17 Methylene Blue Index of LimestoneAnnex A2.
Pyrex Glass No. 7740 is available as lump cullet from the Corning Glass Works, Corning, NY; this is the sole source of supply of the apparatus known to the committee at this time. If you are aware of alternative suppliers, please provide this information to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the responsible technical committee, 1 which you may attend.
3

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Proposed Revision to C 595/C 595M

290 291 292 293 294

10.1.18 Total Organic Carbon Content of LimestoneAnnex A3.

11. Testing Time Requirements 11.1 The following periods from time of sampling shall be allowed for the completion of testing:
3-day test 7-day test 14-day test 28-day test 8-week test 8 days 12 days 19 days 33 days 61 days

295 296 297 298 299 300 301 302 303 304 305 306 307 308 309 310 311 312 313 314 315 316 317 318 319 320 321 322 323 324 325 326 327 328 329 330 331 332

12. Inspection 12.1 Facilities shall be provided to the purchaser for careful inspection and sampling of the finished cement. Inspection and sampling of finished cement shall be at the mill or distribution site controlled by the manufacturer, or at any other location as agreed by the purchaser and seller. 12.2 The manufacturer shall provide suitable facilities to enable the inspector to check the relative masses of the constituents used, and the intergrinding or blending operation used to produce the cement. The plant facilities for intergrinding or blending and inspection shall be adequate to ensure compliance with the provisions of this specification. 13. Rejection 13.1 At the option of the purchaser, cement shall be rejected if it fails to meet any of the requirements of this specification applicable to the cement. Such rejection shall apply to an optional requirement only if that option has been invoked for the cement. 13.2 When the purchaser requires, cement in bulk storage for a period greater than six months shall be resampled and retested and, at the option of the purchaser, shall be rejected if it fails to meet any of the applicable requirements of this specification. Cement so rejected shall be the responsibility of the owner of record at the time of sampling for retest. 13.3 When the purchaser requires, packages more than 2 % below the mass marked thereon shall be rejected; or if the average mass of packages in any shipment, as shown by determining the mass of 50 packages taken at random, is less than that marked on the packages, the entire shipment, at the option of the purchaser, shall be rejected. 14. Certification 14.1 At the request of the purchaser, the manufacturer shall state in writing the source, amount, and composition of the essential constituents used in manufacture of the finished cement and the composition of the blended cement purchased. 14.2 At the request of the purchaser, the manufacturer shall state in writing the nature, amount, and identity of any processing, functional, or air-entraining addition used; and also, if requested, shall supply test data showing compliance of any such processing addition with the provisions of Specification C 465, and of any such functional addition with the provisions of Specification C 688, and of any such air-entraining addition with the provisions of Specification C 226. 14.3 At the request of the purchaser, the manufacturer shall also state in writing that the amounts of pozzolan, or slag, or limestone in the finished cement will not vary more than 5.0 mass % of the finished cement from lot to lot or within a lot. 14.4 Upon request of the purchaser in the contract or order, a manufacturer's certification shall be furnished indicating that the material was tested during production or transfer in accordance with this specification, that it complies with this specification, and a report of the test results shall be furnished at the time of shipment (to include both amount retained on the 45-m (No. 325) sieve and specific surface by the air permeability method). 15. Packaging and Package Marking 15.1 When the cement is delivered in packages, the words, portland blast-furnace slag cement, portland-pozzolan cement, portland-limestone cement, or ternary blended cement as appropriate; the type of cement, name and brand of the manufacturer, and the mass of the cement contained therein, shall be plainly marked on each package. When the cement contains a functional addition listed in 5.1.3.55.1.3.10, the type of functional addition shall be plainly marked on each package. Similar information shall be provided in the shipping documents accompanying the shipment of packaged or bulk cement. All packages shall be in good condition at the time of inspection.

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333 334 335 336 337 338 339 340 341

16. Storage 16.1 The cement shall be stored in such a manner as to permit easy access for proper inspection and identification of each shipment, and in a suitable weathertight building that will protect the cement from dampness and minimize warehouse set. 17. Keywords 17.1 blended hydraulic cement; fly ash cement; hydraulic cement; portland blast-furnace slag cement; portland-limestone cement, portland pozzolan cement; pozzolanic cement; slag; granulated blast-furnace slag

Cement Type

Magnesium oxide (MgO), max, % B Sulfate reported as SO3, max, % 2Sulfide reported as S , max, % C Insoluble residue, max, % Loss on ignition, max, % 342 343 344 345 346 347 348 349 350
A B

TABLE 1 Chemical Requirements Applicable IS(< 70), IS(70), Test IT(P<S<70), IT(S70) Method IT(L<S<70) C 114 ... ... C 114 3.0 4.0 C 114 2.0 2.0 C 114 1.0 1.0 D D 3.0 4.0 C 114

IP, IT(PS), IT(P>L) 6.0 4.0 ... ... D 5.0

IL IT(LS), IT(LP) ... 3.0 ... ... 10.0

The chemical requirements in this table are applicable to all air-entrained cement equivalents. It is permissible to exceed the values in the table for SO3 content, provided it has been demonstrated by Test Method C 1038 that the cement with the increased SO3 will not develop expansion exceeding 0.020 % at 14 days. When the manufacturer supplies cement under this provision, supporting data shall be supplied to the purchaser. See Note 8. C Insoluble residue maximum limit does not apply to ternary blended cements. D For ternary blended cements with limestone loss on ignition is a maximum of 10.0% by mass.

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Proposed Revision to C 595/C 595M


351 352 TABLE 2 Physical Requirements IS(< 70), IT(P<S<70), IP, IS(< 70)(MS), IT(PS), IT(P<S<70) (MS), IL IP(MS), IT(L<S<70), IT(PS)(MS) IT(P>L), IT(LS), IT(LP)
C C

Cement Type

Applicable Test Method

IS(< 70)(HS), IT(P<S<70)(HS), IP(HS), IT(PS)(HS)

IS( 70), IT(S70)

IP(LH), B IL(LH), B IT(PS)(LH), B IT(L<S<70)(LH), B IT(P>L)(LH), B IT(LS)(LH), B IT(LP)(LH)


C

Fineness Autoclave expansion, max, % Autoclave contraction, max, % D Time of setting, Vicat test: E Set, minutes, not less than Set, hours, not more than A Air content of mortar, volume %, max Compressive strength, min A, MPa [psi]: 3 days 7 days 28 days Heat of hydration, max, kJ/kg [cal/g]: 7 days 28 days Water requirement, max weight % of cement Drying shrinkage, max, % Mortar expansion, max, %: G 14 days, 8 weeks, Sulfate resistance, max, %: H Expansion at 180 days Expansion at 1 year

C 204, C 430 C 151 C 151 C 191

0.80 0.20 45 7 12 13.0 [1890] 20.0 [2900] 25.0 [3620]

0.80 0.20 45 7 12 11.0 [1600] 18.0 [2610] 25.0 [3620] 290 [70] F 330 [80] F ... ... 0.020 0.060 0.10 ...

0.80 0.20 45 7 12 11.0 [1600] 18.0 [2610] 25.0 [3620] 290 [70] F 330 [80] F ... ... 0.020 0.060 0.05 0.10

0.80 0.20 45 7 12 ... ... 5.0 [720] 11.0 [1600] ... ... ... ... 0.020 0.060 ... ...

0.80 0.20 45 7 12 ... ... 11.0 [1600] 21.0 [3050] 250 [60] 290 [70] 64 0.15 0.020 0.060 ...I ...I

C 185 C 109/C 109M

C 186

C 109/C 109M C 157/C 157M C 227

290 [70] F 330 [80] F ... ... 0.020 0.060

C 1012 ... ...

353 354 355 356 357 358 359 360 361 362 363 364 365

A B

Air-entrained cements shall have a mortar air content of 19 3 % by volume and the minimum compressive strength shall be no less than 80 % of the comparable non-air-entrained cement type. Applicable only when higher strengths at early ages are not required or when low heat is required. C Both amount retained when wet sieved on 45-m (No. 325) sieve and specific surface by air permeability apparatus, m 2/kg, shall be reported on all mill test reports requested under 14.4. D The specimens shall remain firm and hard and show no signs of distortion, cracking, checking, pitting, or disintegration when subjected to the autoclave expansion test. E Time of setting refers to initial setting time in Test Method C 191. The time of setting of cements containing a user-requested accelerating or retarding functional addition need not meet the limits of this table, but shall be stated by the manufacturer. F Applicable only when moderate heat of hydration (MH) is specified, in which case the strength requirements shall be 80 % of the values shown in the table. G The test for mortar expansion is an optional requirement to be applied only at the purchaser's request and is not required unless the cement will be used with alkali-reactive aggregate. H In the testing of HS cement, testing at one year shall not be required when the cement meets the 180-day limit. An HS cement failing the 180-day limit shall not be rejected unless it also fails the one-year limit.
I

If specifically invoked for Type IP(LH) and Type IT(PS)(LH), the optional sulfate resistance criterion that applies for MS is a maximum of 0.10% expansion at 180 days and for HS is a maximum of 0.05% expansion at 180 days or a maximum of 0.10% expansion at one year (see Footnote H). Type IL and Type IT cements with limestone are not included as moderate (MS) or high (HS) sulfate resistance cements.

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366 367 368 369 370 371 TABLE 3 Requirements for Pozzolan for Use in Blended Cements and for Slag for Use in Portland Blast-Furnace Slag Cement Type IS(< 25) and Ternary Blended Cement Type IT(S<25)
Pozzolan and Slag, as applicable Fineness: Amount retained when wet-sieved on 45-m (No. 325) sieve, max, % Alkali reactivity of pozzolan for use in Types IP(< 15); IT(P<15) and IP(< 15)-A; IT(P<15)-A cements, six tests, mortar bar expansion at 91 days, max, % Activity index with portland cement, at 28 days, min, % Applicable Test Method C 430 20.0 C 227 0.05 75

(see Annex A1)

372 373 374 TABLE 4 Aggregate Grading Requirements for Mortar Expansion Test
Sieve Size Passing 4.75-mm (No. 4) 2.36-mm (No. 8) 1.18-mm (No. 16) 600-m (No. 30) 300-m (No. 50) Retained on 2.36-mm (No. 8) 1.18-mm (No 16) 600-m (No. 30) 300-m (No. 50) 150-m (No. 100) Weight % 10 25 25 25 15

375 376 377 378

TABLE 5 Requirements for Limestone for Use in Blended Cements Applicable Test Method 70 CaCO3 content, min. % by mass C114 Methylene blue index, max, g/100 g See Annex A2 1.2 Total organic carbon, max, % by mass See Annex A3 0.5 A The calcium carbonate content of limestone shall be determined by multiplying the CaO content of the limestone determined by Test Methods C114 by a factor of 1.785.
A

379 380 381 382

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383 384 385 386 387 388 389 390 391 392 393 394 395 396 397 398 399 400 401 402 403 404 405 406 407 408 409 410 411 412 413 414 415 416 417 418 419 420 421 422 423 424 425 426 427

ANNEXES (Mandatory Information) A1. ACTIVITY INDEX WITH PORTLAND CEMENT

A1.1 Specimen Preparation A1.1.1 Mold, cure, and test the specimens from a control mix and from a test mix in accordance with Test Method C 109/C 109M. The portland cement used in the control mix shall meet the requirements of Specification C 150, and shall be the type, and if available, the brand of cement to be used in the work. Make three-cube batches as follows: (For 6- or 9-cube batches, double or triple, respectively, the amounts of dry ingredients.) A1.1.1.1 Control Mix: 250 g of portland cement 687.5 g of graded Ottawa sand X mL of water required for flow of 100 to 115 A1.1.1.2 Pozzolan Test Mix: 162.5 g of portland cement g of pozzolan: 87.5 sp gr of the sample/sp gr of the portland cement 687.5 g of graded Ottawa sand Y mL of water required for flow of 100 to 115 A1.1.1.3 Slag Test Mix: 75 g of portland cement g of slag: 175 sp gr of the slag/sp gr of the portland cement 687.5 g of graded Ottawa sand Z mL of water required for flow of 100 to 115 A1.2 Storage of Specimens A1.2.1 After molding, place the specimens and molds (on the base plates) in the moist room or closet at 23.0 2.0 C [73.5 3.5 F] for 20 to 24 h. While in the moist room or closet, protect the surface from dripping water. Remove the molds from the moist room or closet and remove the cubes from the molds. Place the cubes in close-fitting metal or glass containers (Note A1.1), seal the containers airtight, and store at 38.0 2.0 C [100.0 3.5 F] for 27 days. Allow the specimens to cool to 23.0 2.0 C [73.5 3.5 F] before testing.
NOTE A1.1Use any metal container having a capacity of three cubes if it can be sealed airtight by soldering. Containers of light-tinned sheet metal with inside dimensions of 52 by 52 by 160 mm [2 by 2 by 6.25 in.] have been found to be satisfactory. Wide-mouth Mason jars of 1-L capacity have been found to be satisfactory, provided care is taken to prevent breakage. (WarningFresh hydraulic cementitious mixtures are caustic and may cause chemical burns to skin and tissue upon prolonged exposure.)4

A1.3 Compressive Strength Test A1.3.1 Determine the compressive strength of the three specimens of the control mix and of the test mix at an age of 28 days in accordance with Test Method C 109/C 109M.

Section on Safety, Manual of Cement Testing, Annual Book of ASTM Standards, Vol. 04.01.

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428 429 430 431 432 433 434 435

A1.4 Calculation A1.4.1 Calculate the activity index with portland cement as follows:

where: A B

= =

average compressive strength of test mix cubes, MPa, and average compressive strength of control mix cubes, MPa.

436 437 438 439 440 441 442 443 444 445 446 447

A1.5 Precision and Bias A1.5.1 PrecisionSingle operator precision, on blended cements using fly ash is essentially the same as on fly ash/cement blends in Research Report C09-10015 and it was found to have 3.8 % coefficient of variation (1s %). This indicates that results of two properly conducted tests by the same operator are not expected to differ by more than 10.7 % (d2s) of the average of two results. Since the test is performed solely for the purpose of manufacturer certification of raw material quality, no multilaboratory precision is applicable. A1.5.2 BiasSince there are no standard reference materials, bias cannot be determined.

Supporting data have been filed at ASTM International Headquarters and may be obtained by requesting Research Report RR: C09-1001.

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448 449 450 451 452 453 454 455 456 457 458 459 460 461 462 463 464 465 466 467 468 469 470 471 472 473 474 475 476 477 478 479 480 481 482 483 484 485 486 487 488 489 490 491 492 493 494 495 496

A2. METHYLENE BLUE INDEX TEST FOR LIMESTONE

A2.1 Scope A2.1.1 This annex describes the laboratory procedures for the quantitative determination of methylene blue dye adsorption index of limestone for use as an ingredient in blended cement. A2.1.2 The text of this annex references notes and footnotes which provide explanatory material. These notes and footnotes (excluding those in tables and figures) shall not be considered as requirements of the annex. A2.1.3 UnitsThe values stated in SI units are to be regarded as standard. No other units of measurement are included in this annex. A2.1.4 This annex does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. A2.2 Summary of test A2.2.1 The sample is reduced to a fine powder prior to testing. Increments of methylene blue dye solution are added successively to a suspension of the prepared test portion in water. The adsorption of dye solution by the suspension is checked after each addition of solution by carrying out a stain test on filter paper to detect the presence of free dye. When the presence of free dye is confirmed, the methylene blue index value (MBI) is calculated and expressed as grams of dye adsorbed per 100 g of the sample tested.

A2.3 Significance and Use A2.3.1 This annex provides a means to determine the amount of methylene blue dye adsorbed by a sample of finely ground limestone. Methylene blue dye is preferentially adsorbed by clay minerals that may be present in limestone. The amount of dye adsorbed is related to the clay type and content. Certain clays may increase the water demand or affect other properties of cements if present in sufficient quantity in the limestone when used an ingredient in cement. The specification places a limit on the methylene blue index of limestone permitted as an ingredient in blended cement.

A2.4 Apparatus A2.4.1 The equipment and materials, including the temperature and humidity of the testing room, dry materials, and mixing water, shall meet the requirements of C511, unless otherwise specified. A2.4.2 The following equipment shall be included to perform this test: (a) burette, with capacity of either 100 mL or 50 mL and graduation of either 1/10 mL or 1/5 mL, or one 5 mL and one 2 mL micro-pipette; (b) filter paper, quantitative and ash-free (< 0.010%); 95 g/m2; thickness 0.20 mm; filtration speed 75 s; pore size 20 m; (c) glass rod, 300 mm in length and 8 mm in diameter; (d) impeller agitator, capable of controlled variable rotation rates up to 600 r/min 60 r/min with either three or four impeller blades of 75 mm 10 mm diameter.
NOTE A2.1: Alternative types of mixers can be used if it can be shown that results obtained agree with results produced using an impeller agitator as specified above.

(e) balance, readable to 0.1% of the mass to be weighed; (f) stopwatch or stopclock, readable to 1s; (g) test sieve, 2 mm aperture, with guard sieve, if applicable; (h) beaker, glass or plastic, capacity about 1 L or about 2 L. (i) volumetric flask, capacity 1 L; (j) ventilated oven, thermostatically controlled to maintain a temperature of 105 C 5 C (see Note A2.2); (k) thermometer, readable to 1C; (l) spatula; (m) desiccator;

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497 498 499 500 501 502 503 504 505 506 507 508 509 510 511 512 513 514 515 516 517 518 519

(n) tinted-glass storage bottle; and (o) a 63-m (No. 230) sieve conforming to the requirements of ASTM Specification E11.

A2.5 Reagents and Materials A2.5.1 The following materials shall be included to perform this test: (a) methylene blue (C16H18CIN3S, nH2O (n = 2 to 3) purity 98.5%; (b) kaolinite; and (c) water. A2.6 Procedure A2.6.1 Preparation of methylene blue solution (10 g/L) A2.6.1.1 Determination of moisture content of methylene blue powder The determination of the moisture content of methylene blue powder shall be as follows: (a) weigh 5 g 0.01 g of methylene blue powder and record the mass; (b) dry the powder at 100 C 5 C to constant mass;
NOTE A2.2: Above 105 C, methylene blue powder can be altered.

(c) cool the powder in the desiccator and weigh immediately after taking out of the desiccator, and record the mass to the nearest 0.01 g; (d) calculate and record the water content of the methylene blue, to the nearest 0.01% by mass, using the following equation:

W =((Mh Mg)/ Mh) 100


where W Mh Mg = = = moisture content, % by mass mass of methylene blue powder, g mass of dried methylene blue powder, g

Eq. A2.1

520 521 522 523 524 525 526 527 528 529 530

The moisture content shall be determined for the preparation of every new batch of methylene blue dye solution. A2.6.1.2 Preparation of methylene blue dye solution The preparation of methylene blue dye solution shall be as follows: (a) calculate the mass of methylene blue powder required to provide 10 g 0.01 g of dry powder according to the equation:

M = (100 + W)/10
where M W = = mass of undried (as received) methylene blue powder, g moisture content of powder as determined in Section A2.6.1.1, % by mass

531 532 533 534 535 536 537 538 539 540 541

(b) warm between 500 and 700 mL of distilled or demineralized water in a beaker not exceeding 40 C; (c) agitate the contents of the beaker while slowly pouring the methylene blue powder as calculated in Section A2.6.1.2(a) into warm water; (d) continue to agitate for 45 min to achieve complete dissolution of the powder, and then allow to cool to 20 C; (e) pour the solution quantitatively into a 1 L volumetric flask, ensuring the flask and water are at a temperature of 20 C 1 C, and dilute to volume; (f) shake the flask to ensure complete mixing and transfer the contents into a tinted-glass storage bottle; (g) Mark the storage bottle with the preparation name, preparation date, expiration date and the solution strength "10 g/L methylene blue." Methylene blue solution older than 28 days shall not be used.

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542 543 544 545 546 547 548 549 550 551 552 553 554 555 556 557 558 559 560 561 562 563 564 565 566 567 568 569 570 571 572 573 574 575 576 577 578 579 580 581 582 583 584 585 586 587 588 589 590 591 592 593 594 595

A2.6.2 Description of the stain test After each injection of dye, the stain test shall be conducted by taking a drop of suspension by means of a glass rod and depositing it on the filter paper. The stain which is formed is composed of a central deposit of material, of a generally solid blue color, surrounded by a colorless wet zone. The amount of drop taken shall be such that the diameter of the deposit is between 8 mm and 12 mm. The test shall be deemed positive if, in the wet zone, a halo consisting of a persistent light blue ring of about 1 mm is formed around the central deposit.
NOTE A2.3: As the end-point is approached, the halo will appear, but can then disappear again because the clay minerals can take some time to complete their adsorption of the dye. For this reason the end-point is confirmed by repeating the stain test at 1 min intervals for 5 min without adding more dye solution. NOTE A2.4: A test on kaolinite of known MBK value should be carried out at regular intervals to check the constancy of results. This procedure should also be used to check a new dye solution.

A2.6.3 Sample preparation A2.6.3.1 Kaolinite. Dry the kaolinite to constant mass at 110 C 5 C in a quantity sufficient to obtain at least 30 g of dry material. Allow the sample to cool in a desiccator to constant mass. A2.6.3.2 Limestone. A sample of at least 100 g shall be dried at 110 C 5 C to constant mass and allowed to cool in a desiccator. Reduce the dried sample to pass through a 63-m (No. 230) sieve.
NOTE A2.5: Samples ground to completely pass through 212-m and 75-m (ASTM E 11 No. 70 and No. 200) sieves have been found to yield similar and consistent results on a limestone with a known/previously determined methylene blue value. The approximate Blaine fineness results on these sieves were found to be 250 m2/kg and 630 m2/kg, respectively. Experience in Europe suggests passing through a 63-m sieve (ASTM E 11 No. 230) is adequate in approximating similar Blaine fineness.

A2.6.4 Suspension Preparation: Prepare the sample suspension as follows: (a) If an impellor agitator is used, ensure the impellor of the mixer is approximately 10 mm above the base of the mixing container. (b) Stir the dye solution or, alternatively, mix it thoroughly, fill the burette with dye solution, and return the stock of dye solution to a dark place. (c) Weigh 30.0 g 0.1 g of dry sample (kaolinite or limestone) and record the mass of kaolinite as MKl, limestone mass as MLl . (d) Pour the sample into a beaker containing 500 mL of distilled or demineralized water, stirring at sufficient speed to disperse the sample as added. (e) Increase the speed of agitation to ensure the contents are completely in suspension, and agitate the contents of the beaker for 5 minutes.
Note A2.6: For an impellor agitator a speed of agitator to 600 r/min 60 r/min is required.

(f) Inject 5 mL of the methylene blue dye solution into the suspension and reduce the agitation speed to 400 r/min 40 r/min for the remainder of the test. (g) Carry out the stain test in accordance with A2.6.5. (h) If insufficient fines are present in the limestone test portion to obtain a halo, 30.0 g 0.1 g of kaolinite (dried at 110 C) should be added together with Vk mL of dye solution, where Vk = the volume of dye solution adsorbed by 30 g of kaolinite. A2.6.5 Determination of the quantity of dye adsorbed. Determine the quantity of dye adsorbed as follows: (a) Place the filter paper on top of an empty beaker, or some other suitable support, so that most of its surface is not in contact with any solid or liquid. (b) After at least 1 min of agitating at the slower speed of 400 r/min 40 r/min following the injection of the dye, carry out a stain test on the filter paper. (c) Ensure that the amount of the drop taken is such that the deposit has a diameter of between 8 mm and 12 mm. (d) If after the addition of the initial 5 mL of dye solution the halo does not appear, add a further 5 mL of dye solution, continue agitating for 1 min, and carry out another stain test. (e) If a halo still does not appear, continue agitating, making additions of dye and doing stain tests in this manner until a halo is observed. When this stage is reached, continue agitating and without further additions of dye solution, perform stain tests at 1 min intervals.

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596 597 598 599 600 601 602 603 604 605 606 607 608 609 610 611 612 613

(f) If the halo disappears during the first 4 min, add a further 5 mL of dye solution. If the halo disappears during the fifth minute, add only 2 mL of dye solution. In either case, continue agitating and doing stain tests until a halo persists for 5 min. (g) Record the total volume of dye solution (for kaolinite as Vk, for limestone as Vt) added to produce a halo that persists for 5 min, to the nearest 1 mL. (h) If for the limestone test portion a halo does not appear, repeat the test with the addition of materials as described in Section A2.6.4 (h). (i) If the sample under test was kaolinite, calculate and record the MBK value in accordance with Equation A2.3. For limestone, calculate and record the MB value in accordance with Equation A2.4.
NOTE A2.7: Containers should be cleansed thoroughly with water as soon as the tests are completed. Traces of any detergents used should be removed by thorough rinsing. It is recommended that containers used in methylene blue tests are reserved specifically for that test.

A2.7 Calculation and reporting A2.7.1 The methylene blue value of kaolinite, MBK, expressed in g of dye per 100 g of the processed sample shall be given by the following equation:

MBK = VK/ MK1


where MK1 VK = = the mass of the kaolinite sample, g the total volume of dye solution injected, mL

Eq. A2.3

614 615 616 617 618 619 620 621 622

The MBK value shall be recorded to the nearest 0.01 g of dye per 100 g of the processed sample. A2.7.2 The methylene blue value of limestone, MB, expressed in g of dye per 100 g of the processed sample shall be given by the following equation:

MB = (Vt VK)/ ML1


where VK MLl Vt = = =

Eq. A2.4

volume of dye solution adsorbed by 30 g kaolinite, if kaolinite and additional dye added, mL the mass of the test portion, g the total volume of dye solution injected, mL

623 624 625 626 627 628 629 630 631 632 633 634

The MB value shall be reported to the nearest 0.01 g of dye per 100 g of the processed sample.

A2.8 Precision and Bias A2.8.1 PrecisionA complete interlaboratory study has not been completed for this test method. Therefore the precision of the method has not been determined. The precision of this test method is being determined and will be available on or before (date). A2.8.2 Bias No information can be presented on the bias of the procedure in this annex for determining the methylene blue dye adsorption index of limestone because no material having an accepted reference value is available. .

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635 636 637 638 639 640 641 642 643 644 645 646 647 648 649 650 651 652 653 654 655 656 657 658 659 660 661 662 663 664 665 666 667 668 669 670 671 672 673 674 675 676 677 678 679 680

A3. TOTAL ORGANIC CARBON CONTENT OF LIMESTONE

A3.1 Scope A3.1.1This annex specifies the laboratory procedures for the quantitative determination of the total organic carbon content of limestone for use as an ingredient in blended cement. A3.1.2 The text of this annex references notes and footnotes which provide explanatory material. These notes and footnotes (excluding those in tables and figures) shall not be considered as requirements of the annex. A3.1.3 UnitsThe values stated in SI units are to be regarded as standard. No other units of measurement are included in this annex. A3.1.4 This annex does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

A3.2 Summary of test A3.2.1 Total organic carbon is determined either on a sample from which the inorganic carbon has been removed through hydrochloric acid extraction or by difference of inorganic carbon from total carbon. A3.3 Significance and Use A3.3.1 This annex provides a means to determine the total organic carbon content of a sample of finely ground limestone. The organic carbon content of a limestone used as an ingredient in cement may increase the air-entraining agent dosage required to achieve a specific air content in concrete. The specification places a limit on the total organic carbon content of limestone permitted as an ingredient in blended cement. A3.4 Apparatus A3.3.1 The equipment shall meet the requirements of Specification C 511, unless otherwise specified. A3.3.2 The following equipment shall be included to perform this test: (a) analytical balance, precision = 0.1 mg; (b) beaker, 800 mL; (c) vacuum flask, 1000 mL; (d) glass frit, 40 mm diameter, and porosity = G4; (e) magnetic stirrer; (f) magnetic stir bar; (g) oven, able to maintain a temperature of 45C 5 C; (h) mortar and pestle made of agate (i) induction furnace equipped with carbon detection; and (j) thermogravimetric analyzer.

A3.5 Reagents and Materials A3.5.1 The following materials shall be included to perform this test: (a) hydrochloric acid, analytical grade, w(HCl) = 32%; (b) nitric acid, analytical grade, w(HNO3) = 65%; (c) silver nitrate solution, C(AgNO3) = 2 mol/L; (d) gas sources as required for the analyzers, (i.e., oxygen, air, or nitrogen); and (e) demineralized water. A3.6 Sample preparation A3.6.1 The sample shall be dried at 45 C 5 C and prepared to a pass through a 150-m (No. 100) sieve conforming to the requirements of ASTM Specification E 11.

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681 682 683 684 685 686 687 688 689 690 691 692 693 694 695 696 697 698 699 700 701 702 703 704 705 706 707 708 709 710 711 712 713 714 715 716 717 718 719 720 721 722 723 724 725 726 727 728 729 730 731 732

A3.7 Methods to determine carbon A3.7.1 Methods to determine organic carbon Determination of organic carbon shall be conducted in accordance with one of the following options: (a) remove the inorganic carbon in accordance with Section A3.7.3, followed by determining the remaining organic carbon directly in accordance with Section A3.8; or (b) determine the inorganic carbon in accordance with Section A3.7.2 and, on a separate sub-sample, determine the total carbon in accordance with Section A3.8. The organic carbon will be calculated by the difference between the total carbon and the inorganic carbon. A3.7.2 Determination of inorganic carbon by thermogravimetric analysis. This method involves the determination of sample mass loss at various temperatures. The heating of a sample through a temperature range allows for mass loss differentiation based on mineral form (for example, CaCO3, MgCO3, Ca(OH)2, etc.). Specific operational information is provided by the equipment manufacturers. If free carbon is present, an inert atmosphere (for example, nitrogen) shall be used for sample analysis. The inorganic carbon shall be calculated from the total carbon dioxide released during .the analysis. The inorganic carbon as determined shall be recorded as Ti. The total inorganic carbon shall be calculated in accordance with Equation A3.1. A3.7.3 Removal of inorganic carbon by hydrochloric acid extraction. Inorganic carbon shall be removed from the sample by hydrochloric acid extraction as follows: (a) Pour 100 mL of demineralized water and 80 mL of hydrochloric acid, at 10 mL intervals, into a beaker. Add a magnetic stir bar and stir. (b) Add 2 g of the sample, weighed to the nearest 0.1 mg, to the diluted hydrochloric acid. (c) After the carbon dioxide evolution has stopped, add 100 mL of demineralized water and stir the solution for 2 hours. (d) Filter the solution through a tared glass frit, which was previously dried at 105 C 5 C. The filtrate must be clear. Filter the filtrate again if it is still cloudy. (e) Wash the residue with demineralized water till a negative chloride reaction occurs. Control with nitric acid and silver nitrate. (f) Dry the glass frit with the residue in the oven at a temperature of 45 C 5 C to its constant mass. (g) Pulverize the residue in the mortar and use for further analysis. (h) Analyze for carbon in the residue in accordance with one of the options detailed in Section A3.8. (i) Calculate the total inorganic carbon in accordance with Equations A3.2 and A3.3.
NOTE A3.1: The residue must be free of residual hydrochloric acid. Hydrochloric acid fumes can damage the inner parts of the induction furnace.

A3.8 Determination of carbon by instrumental methods A3.8.1 General. These instrumental methods will report the carbon directly. If the sample being tested has previously had the inorganic carbon removed through acidification, the resulting value will correspond to the result C1 as listed in Equation A3.3. If the sample being analyzed has not previously had the inorganic carbon removed, the resulting value will correspond to Tc as listed in Equation A3.1. A3.8.2 Induction furnace and infrared absorption. This method shall use volatilization of the sample by induction furnace and detection of carbon by infrared absorption. Suitable calibration standards (for example, calcium carbonate and synthetic carbon) are available from some instrument manufacturers. NIST cement SRMs with known additions of NIST argillaceous limestone (or other suitable standards) should also be considered to check instrument calibration.
NOTE A3.2: See ASTM E1019 for more information on the determination of carbon by the combustion instrumental measurement method.

A3.8.3 Combustion gravimetric method The combustion gravimetric method, performed in accordance with ASTM E350, is suitable for the determination of carbon in concentrations from 0.05 % to 1.80 % by mass (as carbon dioxide in concentrations from 0.18 % to 6.60 % by mass). In this Test Method, the sample shall be burned in a stream of oxygen. The carbon dioxide in the evolved gases shall then be collected in a suitable absorbent and its mass determined. Time of analysis shall be less than 10 min.
NOTE A3.3: See ASTM E 350 for more information on the determination of carbon by the combustion gravimetric method.

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733 734 735 736 737 738 739 740 741

A3.9 Calculation and reporting A3.9.1 The total organic carbon shall be reported to the nearest 0.1 % by mass. A3.9.2 Total organic carbon calculation by difference. The total organic carbon shall be calculated by subtracting the inorganic carbon determined in accordance with Section A3.7.2 from the total carbon as determined by one of the options detailed in Section A3.8 as follows:

TOC = Tc Ti
where TOC Tc Ti = = =

Eq. A3.1
total organic carbon, % by mass total carbon determined on the sample (Section 3.8), % by mass total inorganic carbon determined on the sample (Section 3.7.2), % by mass

742 743 744 745 746 747

A3.9.3 Total organic carbon calculation by decarbonation method. The insoluble residue shall be calculated as follows:

R = ((m3 - m2) 100)/ m1


where R m1 m2 m3 = = = = insoluble residue, % by mass sample weight, g glass frit empty, g glass frit with insoluble residue, g

Eq. A3.2

748 749 750 751 752 753 754

The total organic carbon shall be calculated as follows:

TOC = (C1 R)/100


where TOC R C1 = = = total organic carbon, % by mass insoluble residue, % by mass content of the hydrochloric acid treated sample, g

Eq. A3.3

755 756 757 758 759 760 761 762 763 764 765 766 767 768

A3.10 Precision and Bias A3.10.1 PrecisionA complete interlaboratory study has not been completed for this test method. Therefore the precision of the method has not been determined (Note A3.4). The reproducibility of this test method is being determined and will be available on or before (date).
NOTE A3.4: CSA A3004-D2, upon which this procedure is based, states that for a properly conducted decarbonation test: (a) The detection limit has been found to be 0.02 % by mass carbon. (b) The limit of quantitation has been found to be 0.05 % by mass carbon.

A3.10.2 BiasNo information can be presented on the bias of the procedure in this annex for determining the total organic carbon content of limestone because no material having an accepted reference value is available. .

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769 770 771 772 773 774 775 776 777 778 779 780 781

APPENDIX (Non-Mandatory Information) X1. TEST OF CONFORMITY IN RELATION TO A SPECIFIED MB VALUE X1.1 A check on conformity with a specified methylene blue value can be carried out by making a single addition of dye solution. The volume of dye solution to be injected at one time is given in the following equation:

V2 = (MB1 M1 + V1)
where V2 M1 MB1 V1 = = = = volume of dye solution to be injected, in mL the mass of the test portion, in g the specified MB value, in g of dye per 100 g of the processed sample the volume of dye solution in mL adsorbed by any added kaolinite

782 783 784 785 786 787 788 789

X1.2 After preparation of a test portion, the suspension should be prepared using the test portion, the water and, if necessary, the kaolinite, but including the volume of dye solution. The stain test should be carried out after stirring the suspension for 8 min at 400 r/min 40 r/min. If the stain test is positive, the limestone can be assumed to conform to the specification. If this stain test is negative however, the complete determination described in Annex A2 should be carried out.

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