DEVELOPMENT OF COMPOSITE CEMENTS USING GRANULATED BLAST FURNACE SLAG AND FLYASH

S. Harsh, A. K. Arora, K. M. Sharma and M M Ali National Council for Cement and Building Materials, New Delhi

ABSTRACT The investigations on composite cements, prepared by intergrinding granulated blast furnace slag and flyash along with plant clinker and gypsum indicated that the physical properties of composite cement prepared using 40-60 percent clinker and 20-30 percent each of flyash and granulated blast furnace slag were in the range specified for PPC and PSC by respective Indian Standards. Further, five percent of flyash in PPC could be replaced with granulated blast furnace slag without causing any significant differences in the physical properties of the parent PPC. Similarly, ten percent of granulated blast furnace slag in PSC could be replaced with flyash without causing any significant differences in the physical properties of the parent PSC.

1.

INTRODUCTION

Hydraulic cements specified by Bureau of Indian Standards (BIS) include OPC (33, 43 & 53 Grades), PPC, PSC and various special purpose cements. Flyash conforming to IS 3812 (Part 1): 2003 and granulated blast furnace slag conforming to IS 12089: 1987 are used in the manufacture of PPC and PSC respectively. Further, addition of up to five percent of any of the following materials, viz., flyash, granulated blast furnace slag, silica fume, limestone, rice husk ash and metakaolin is permitted as performance improver in manufacture of ordinary Portland Cement. At present use of more than one mineral additive is neither permitted nor employed in the manufacture of blended cements. The blended cements, which are produced using more than one mineral addition, are generally known as composite cement. Manufacture of composite cements would be beneficial from viewpoint of resource conservation as well as enhanced waste utilization. The present study was taken up to investigate the composition and properties of composite cement prepared using granulated blast furnace slag and flyash as mineral additives so as to enable development of composite cements for Indian Market.

A perusal of the cement types as per European Standard ENV 197-1:1992 indicates that European Standards specify a number of cement types including composite cements. European Standards permit use of a variety of mineral additives and a wide range of permissible quantity of additions. The composite cement (CEM V/A), as per ENV 197-1, is permitted to have 18-30 percent each of granulated blast furnace slag and flyash/ pozzolana whereas the composite cement CEM V/B is permitted to have 31-50 percent each of granulated blast furnace slag and flyash/ pozzolana as mineral additions. Bureau of Indian Standards (BIS), presently, has no standard for composite cement. To facilitate manufacture of composite cement in India it is required to investigate the composition and properties of composite cement prior to formulation of standards.

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2.

EXPERIMENTAL

Samples of OPC clinker were obtained from three different cement plants. Three Fly ash samples, two granulated blast furnace slag samples and two gypsum samples were also obtained for preparation of composite cements. The samples of clinker, fly ash, granulated blast furnace slag and gypsum, were characterized and evaluated for their chemical and mineralogical composition. Seven sets of cement samples were prepared by intergrinding of components in a batch type laboratory ball mill. The clinker, slag and gypsum components were pre-ground to a fineness of ~200 m2/kg before feeding to ball mill for preparation of cement samples. The total SO3 content in these cement samples was controlled by taking into consideration the SO3 contributed by clinker/ flyash/ blast furnace slag and adding computed amount of gypsum to achieve the target total SO3 content in cement. The cement samples thus prepared were evaluated for their physical properties as per the test procedures specified for hydraulic cements, IS 4031-1988 (Methods of Physical Tests for Hydraulic Cement). 3. 3.1 RESULTS AND DISCUSSION Materials

The chemical analyses of clinker samples indicated normal composition (Table 1). The LSF, SM and AM of clinker samples were in the range 87.71-94.49, 2.32-2.46 and 1.09-1.66 respectively. The C3S and C3A content of clinker samples was in the range of 43.51-53.68 percent and 5.30-8.43 percent respectively. Mineralogical evaluation using x-ray diffraction analysis and optical microscopy indicated normal phase formation in all the clinker samples. The results of quantitative phase analysis by x-ray diffraction and optical microscopy are given in Table 2 and Table 3 respectively.

Table 1 Chemical composition of clinker samples Sl. No. 1 2 3 Sample LOI Code CL-1 CL-2 CL-3 2.04 1.99 1.45 CaO 61.93 60.97 62.50 SiO2 21.52 19.91 21.18 Al2O3 4.83 5.16 5.25 Fe2O3 4.43 3.10 3.37 MgO 1.52 6.12 2.39 SO3 2.10 0.77 2.00 LSF 87.71 94.49 90.13 SM 2.32 2.41 2.46 C3S 43.51 53.68 51.30 C3A 5.30 8.43 8.21

Table 2 mineralogical compositions of clinker samples as determined by X-ray diffraction

Sl. No. 1 2 3 Clinker No. Alite CL-1 CL-2 CL-3 56 61 57 Phase Composition, Percent Belite C3A C4AF 25 20 24 2 5 4 12 9 10

Minor Phases 5 5 5

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Table 3 Mineralogy and granulometry of clinker samples as determined by optical microscopy Sl. No. Clinker Mineral Phase Alite Belite Interstitial matter Alite Belite Interstitial matter Alite Belite Interstitial matter Quantity (%) 44 37 19 45 38 17 54 39 7 1 1 1 1 1 1 Granulometry () Min CL-1 Max 39 36 36 30 24 22 Avg. 29 25 24 21 18 15 -

CL-2

CL-3

Table 4 Chemical composition of flyash, granulated blast furnace slag, limestone and gypsum samples Sl. No. 1 2 3 4 5 6 7 ## Material Fly ash Fly ash Fly ash GBFS GBFS Gypsum Gypsum Sample Code FA-1 FA-2 FA-3 SL-1 SL-2 GYP-1 GYP-2 LOI 3.24 0.89 0.63 1.38 (Gain) 0.58 (Gain) 14.07## 5.80## CaO 4.98 5.21 1.03 39.76 29.53 24.59 28.27 SiO2 58.37 61.64 65.00 35.24 31.30 24.40 20.06 Al2O3 Fe2O3 21.83 23.39 25.71 14.11 23.27 0.88 0.71 5.43 4.48 3.24 0.61 1.83 1.53 0.65 MgO 1.95 0.43 0.59 8.70 10.59 0.80 2.44 SO3 1.32 0.32 0.40 0.24 0.12 32.75 34.95 Na2O 0.27 0.14 0.11 0.32 0.21 0.07 K 2O 0.72 1.02 0.40 0.35 0.82 0.02

Combined water

The chemical analyses of flyash, granulated blast furnace slag and gypsum samples are given in Table 4. The results indicated normal composition for the materials used. The SiO2 content of flyash samples was in the range of 58.37-65.00 percent. The CaO content of slag samples was in the range of 29.53-39.76 percent. The purity of gypsum samples was in the range of 70-75 percent. 3.2 Evaluation of Cement Samples

The cement samples were evaluated for Blaine's fineness, setting time, compressive strength and soundness as per relevant Indian Standards. The results obtained are given in Tables 5-9. The composition of cement samples, that is the proportion of clinker and blending components is also included in these Tables. The results obtained with various sets of cement samples are discussed below.

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Table-5 Composition and Physical Properties of Composite Cement (SET I) Sl. No. Property Composition CL-3 FA-3 SL-2 Physical Properties Surface Area (m2/kg) Setting Time (Mts.) Initial Final Compressive Strength (MPa) 3d 7d 28d Soundness Autoclave (%) Le-Chatelier (mm) COM- I/1 COM- I/2 COM- I/3 COM- I/4 COM- I/5

60 20 20 291.0

50 25 25 297.0

40 30 30 318.0

35 45 20 334.0

35 32 33 333.0

1. 2.

110 204

80 180

107 185

235 295

203 353

3.

24.0 29.6 43.0 0.04 1.0

21.6 28.4 43.7 0.034 1.5

18.8 27.8 40.7 0.036 1.0

15.3 19.3 27.9 0.058 1.0

13.7 27.3 36.1 0.047 1.5

4.

3.2.1

Physical Testing Results of SET I of Cement Samples

Set I comprised of five cement samples prepared using clinker CL-3. Clinker content in these samples was varied from 60 percent to 35 percent. The balance was made up with flyash FA-3 and slag, SL-2 (Table-5). Gypsum (GYP-2) was added to achieve total SO3 content of 2.7 percent. The specific surface area of cement samples was in the range of 291.0-334.0 m2/kg. The initial setting time of the cement samples was in the range of 80-235 minutes. The three-day strength of composite cement samples was in the range of 13.7-24.0 MPa. The 7-day and 28-day strengths were in the range of 19.3-29.6 MPa and 27.9- 43.7 MPa respectively. The composite cement samples COM- I/1, COM- I/2 and COM- I/3 had compressive strength meeting the requirement of IS 455-1989(Indian Standard- Specifications for PSC). The autoclave and Le-chatelier expansions for all the samples were in the range of 0.034-0.058 percent and 1.0-1.5 mm respectively and met the requirement of IS 455-1989. 3.2.2 Physical Testing Results of SET II of Cement Samples

Set II comprised of seven cement samples prepared using clinker CL-3. Clinker content in these samples was varied from 30 percent to 25 percent. The balance was made up with flyash FA-3 and slag, SL-2 (Table-6). Gypsum (GYP-2) was added to achieve total SO3 content of 2.7 percent. The specific surface area of cement samples was in the range of 321.0-368.0 m2/kg. The initial setting time of the cement samples was in the range of 90-210 minutes. The three-day strength of composite cement samples was in the range of 11.5-16.1 MPa. The 7-day and 28-day strengths were in the range of 15.5-22.6 MPa and 24.7-28.7 MPa respectively. Two of the composite cement samples COM- II/2 and COM- II/4 had compressive strength meeting the requirement of IS 455-1989(Indian Standard- Specifications for PSC). The autoclave and Le-chatelier expansions for all the samples were in the range of 0.006- 0.035 percent and 0.5-2.0 mm respectively and met the requirement of IS 455-1989.

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Table-6 Composition and Physical Properties of Composite Cement (SET II) Sl. No. Property Composition CL-3 FA-3 SL-2 Physical Properties Surface Area (m2/kg) Setting Time (Mts.) Initial Final Compressive Strength (MPa) 3d 7d 28d Soundness Autoclave (%) Le-Chatelier (mm) COMII/1 30 45 25 340.0 COMII/2 30 35 35 337.0 COMVI/3 30 30 40 368.0 COMII/4 30 25 45 354.0 COMII/5 30 20 50 357.0 COMII/6 25 45 30 339.3 COMII/7 25 35 40 321.0

1. 2.

180 295

90 205

132 372

110 385

90 215

180 298

210 345

3.

13.6 16.8 26.3 0.006 1.0

16.1 22.6 28.7 0.025 0.5

11.5 21.4 26.8 0.02 1.0

16.1 22.0 28.0 0.016 1.0

15.0 21.0 26.8 0.014 1.0

11.6 17.4 24.7 0.009 2.0

12.2 15.5 26.1 0.035 1.0

4.

Table-7 Composition and Physical Properties of Composite Cement (SET III) Sl. No. Property Composition CL-2 FA-3 SL-2 Physical Properties Surface Area (m2/kg) Setting Time (Mts.) Initial Final Compressive Strength (MPa) 3d 7d 28d Soundness Autoclave (%) Le-Chatelier (mm) COMIII/1 60 20 20 346.0 COMIII/2 50 25 25 364.0 COMIII/3 40 30 30 326.0 COMIII/4 35 32 33 334.0 COMIII/5 30 35 35 337.0 COMIII/6 25 35 40 326.0

1. 2.

240 345

270 405

285 305

219 332

320 -

205 325

3.

26.20 32.60 51.66 0.12 2.0

17.32 26.80 46.13 0.01 1.0

16.00 22.88 35.00 0.004 2.0

12.7 24.7 35.8 0.006 1.0

12.44 22.48 27.06 0.014 1.0

10.1 19.7 28.6 -

4.

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3.2.3

Physical Testing Results of SET III of Cement Samples

Set III comprised of six cement samples prepared using clinker CL-2. Clinker content in these samples was varied from 60 percent to 25 percent. The balance was made up with flyash FA-3 and slag, SL-2 (Table-7). Gypsum (GYP-2) was added to achieve total SO3 content of 2.7 percent. The specific surface area of cement samples was in the range of 326.0-364.0 m2/kg. The initial setting time of the cement samples was in the range of 205-320 minutes. The three-day strength of composite cement samples was in the range of 10.1-26.2 MPa. The 7-day and 28-day strengths were in the range of 19.732.6 MPa and 27.06- 51.66 MPa respectively. The composite cement samples COM- III/1, COM- III/2 and COM- III/3 had compressive strength meeting the requirement of IS 455-1989 (Indian StandardSpecifications for PSC). The autoclave and Le-chatelier expansions for all the samples were in the range of 0.004-0.12 percent and 1.0-2.0 mm respectively and met the requirement of IS 455-1989. 3.2.4 Physical Testing Results of SET IV and SET V of Cement Samples

Set IV comprised of two cement samples prepared using CL-1 (Table 8). One of these was a PPC sample (PPC-IV/1) prepared using 30 % flyash (FA-1). The other cement sample (COM-IV/2) was prepared by replacing 5 % flyash with equal amount of granulated blast furnace slag (SL-1). The specific surface area of samples was 358.0 and 360.0 m2/kg, respectively. The initial setting time of both the cement samples was 30 minutes. The three day strength of the samples was 16.7 and 16.1 MPa, respectively. The 7-day and 28-day strengths were 25.1 & 23.0 MPa and 42.1 & 43.0 MPa respectively. Both the cement samples had compressive strength meeting the requirement of IS 1489-1991 ( Indian Standard- Specifications for PPC). The autoclave and Le-chatelier expansions for both the samples were in the range of 0.03-0.04 percent and 1.0 mm respectively and met the requirement of IS 269/ IS 1489.

Table-8 Composition and Physical Properties of Composite Cement (Set IV and Set V) Set IV Sl. No. Property Composition CL-1 + GYP-1 FA-1##/ FA2** SL-1##/ SL-2** Physical Properties Surface Area (m2/kg) Setting Time (Mts.) Initial Final Compressive Strength (MPa) 3d 7d 28d Soundness Autoclave (%) Le-Chatelier (mm) PPC-IV/1 COMIV/2 70 25## 5## 360.0 30.0 45.0 16.1 23.0 43.0 0.04 1.0 PSC-V/1 Set V COMV/2 50 10** 40** 338.0 160 358 26.7 34.0 49.9 0.004 1.0 COMV/3 50 10## 40** 361.0 50 70 22.0 27.8 42.3 0.01 1.5

70 30## 358.0 30.0 43.0 16.7 25.1 42.1 0.03 1.0

50 50** 345.0 160 350 26.9 36.8 46.3 0.014 1.5

1. 2.

3.

4.

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Set V comprised of three cement samples (Table 8). One of these was PSC sample (PSC-V/1) containing 50 percent granulated blast furnace slag (SL-2). The other two cement samples, COM V/2 and COM V/3 were prepared by replacing 10 percent slag by 10 percent flyash FA2 and by 10 percent flyash FA1 respectively (Table 8). The specific surface area of the samples was in the range of 338.0-361.0 m2/kg. The initial setting time of both the PSC and composite cement sample COM V/2 was 160 minutes. The sample COM-V/3 showed a relatively shorter setting time of 50 minutes. The three-day strength of PSC and composite cement samples was in the range of 22.0- 26.9MPa. The 7-day and 28-day strengths were in the range of 27.8-36.8 MPa and 42.3-49.9 MPa respectively. All the cement samples had compressive strength meeting the requirement of IS 455-1989(Indian Standard- Specifications for PSC). The autoclave and Le-chatelier expansions for all the samples were in the range of 0.004-0.014 percent and 1.0-1.5 mm respectively and met the requirement of IS 269/ IS 455.

3.2.5

Physical Testing Results of SET VI and SET VII of Cement Samples

Set VI comprised of two cement samples prepared using clinker CL-2 (Table 9). One of these was PSC sample (PSC-VI/1) containing 50 % granulated blast furnace slag, SL-2. The other cement sample (COM-VI/2) was prepared by replacing 10 percent granulated blast furnace slag by 10 % flyash (FA-2). The specific surface area of PSC-VI/1 and COM-VI/2 was 361.0 and 359.0 m2/kg, respectively. The initial setting time of the samples was 60 and 80 minutes, respectively. The three-day strength of PSC and composite cement samples was 37.0 and 37.2 MPa, respectively. The 7-day and 28-day strengths were 44.5 & 39.7 MPa and 49.1 and 43.4 MPa respectively. Both the cement samples had compressive strength meeting the requirement of IS 455-1989 (Indian Standard- Specifications for PSC). The autoclave and Le-chatelier expansions for both the samples met the requirement of IS 455-1989.

Table-9 Composition and Physical Properties of Composite Cement (SET VI and SET VII) SET VI Sl. No. Property PSCVI/1 COMVI/2 50 10** 40 359.0 80 230 37.2 39.7 43.4 0.036 1.5 PSCVII/1 50 50 360.0 130 215 34.8 42.2 51.9 0.045 0.5 SET VII COMVII/2 50 10** 40 341.0 131 255 29.1 35.0 46.1 0.067 0.5 COMVII/3 50 10## 40 359.0 46 76 33.1 44.5 50.0 0.042 1.0

1. 2.

3.

4.

Composition CL-2 + GYP-1 50 CL-3 + GYP-1 FA-1##/ FA2** SL-2 50 Physical Properties Surface Area (m2/kg) 361.0 Setting Time (Mts.) Initial 60 Final 215 Compressive Strength (MPa) 3d 37.0 7d 44.5 28d 49.1 Soundness Autoclave (%) 0.078 Le-Chatelier (mm) 1.0 *Bars bent during test, expansion not measurable

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Set VII comprised of three cement samples prepared using CL-3 (Table 9). One of these was PSC sample (PSC- VII/1) containing 50 % granulated blast furnace slag, SL-2. The other two cement samples, COM VII/2 and COM VII/3 were prepared by replacing 10 percent slag by 10 percent flyash FA-2 and by 10 percent flyash FA-1, respectively (Table 9). The specific surface area of the samples was in the range of 341.0-360.0 m2/kg. The initial setting time of the PSC-VII/1 and composite cement sample COM VII/2 was in the range of 130-131 minutes. The sample COM-VII/3 showed a relatively shorter setting time of 46 minutes. The 3-day strength of PSC and composite cement samples was in the range of 29.134.8MPa. The 7-day and 28-day strengths were in the range of 35.0-44.5 MPa and 46.1-51.9 MPa respectively. All the cement samples had compressive strength meeting the requirement of IS 455-1989 (Indian Standard- Specifications for PSC). The autoclave and Le-chatelier expansions for all the samples were in the range of 0.042-0.067 percent and 0.5-1.0 mm respectively and met the requirement of IS 4551989. 3.3 Discussion

The evaluation of data indicated that the physical properties of cement samples depended on the proportion and quality of constituent materials. Results of SET-I and SET III indicated that the physical properties of composite cement prepared using 40-60 percent clinker and 20-30 percent each of flyash and granulated blast furnace slag were in the range specified for PPC and PSC by respective Indian Standards. Results of SET-I, SET II and SET III indicated that the composite cements prepared using 25-35 percent clinker may not be able to meet the compressive strength requirement specified for PPC and PSC by respective Indian Standards. Results of SET IV indicated that PPC prepared using 30 percent flyash and composite cement prepared using 25 percent flyash and 5 percent granulated blast furnace slag had comparable compressive strengths. Results of SET V, VI and VII indicated that PSC prepared using 50 percent granulated blast furnace slag and composite cement prepared using 40 percent granulated blast furnace slag and 10 percent flash could have comparable compressive strengths. 4.0 i. CONCLUSION The investigations on composite cement, carried out at NCB, have indicated that cements prepared using granulated blast furnace slag and flyash along with clinker and gypsum, depending on the proportion of constituents used, can have physical properties in the same range as specified for PPC and PSC by IS 1489:1991 and IS 455:1989 respectively. The results indicated that the physical properties of composite cement prepared using 40-60 percent clinker and 20-30 percent each of flyash and granulated blast furnace slag were in the range specified for PPC and PSC by respective Indian Standards. 5 percent of flyash in PPC could be replaced with granulated blast furnace slag without any significant differences in the physical properties. 10 percent of granulated blast furnace slag in PSC could be replaced with flyash without any significant differences in the physical properties.

ii.

iii. iv.

ACKNOWLEDGEMENT This paper is based on R & D studies carried out at National Council for Cement and Building Materials, New Delhi, India. The authors have freely drawn upon from the completed R & D project reports of NCB. This paper is published with the permission of the Director General of the Council.

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