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Vol. 18 No.

Journal of Wuhan University of Technology- Mater. Sci. FA.

Dec. 2003

Microstructure and Composition of Hydration Products of Ordinary Portland Cement with Ground Steel-making Slag
LI Yong-xin CHEN Yi-min ZHANG Hong-tao HE Xing-yang WEI Jiang-xiong ZHANG Wen-sheng China Building Materials Academy ( Received: March 1,2003; Accopted:Oct. 18,2003)
Abstract: The effect of ground steel-making slag on microstructure and composition of hydration products of ordinary Portland cement (OPC) was investigated by mercury intrusion porosimetry (MIP), X- ray di~ac~ion (XRD) and differential thermal analysis ( DTA ). Results show that ground steel-making slag is a kind of high activity mineral additives and it can rai.~ethe longer-age strength of OPC mortar. The total porosity and average pore diameter of OPC paste with ground steel-making slag increase with the increase of the amount of ground steelmaking slag replacing OPC at vario~ ages, while after 28 days most pores in OPC paste with ground steel-making slog do not influence the strength becatLsethe diameter of those pores is in the rang of 20 to 50ran. The hydration mechanism of ground steel-making slag is similar to that of OPC but differentfrom that of fly ash and blast furnace slag. The hydration products of ground steel-maJdng slag contain quite a lot of Ca( 0H )2 in long age.

Key words: groundsted-ma~ slog; m/o'osmanure; ~ / t i o n ;

hydrationproducts

1 Introduction
Steel-making slag is the waste of steel-making industry and nearly sixteen million tons steel-making slag is produced in China per year[~1 . Just as fly ash and blast furnace slag, it is one of three kinds of dominant industry wastes in our country. Even though steel-making slag cement has developed for more than twenty years in China [2'31 , compared with other two wastes, the study and application on steel-making slag in cement and concrete axe insufficient yet. Most steel-making slag cements are prepared by inter-grinding process, so the particle si~ of steel-making slag is quite large and its activity is quite low. Now the total production of steel-making slag cement is less than one million tons E41. Study on ground steelmaking slag used as cement and concrete mineral additive has just begun in recent years :5 sl and most studies focus on grinding process and mechanic properties. The microstructure and composition of hydration products of ordinary Portland cement (OPC) with ground steel-making slag are still seldom reported. Therefore, MIP, XRD and DTA-TG measurement were carried out on the microstructure and composition hydration products of paste with 10% to 40% ground steel-making slag.

2 Experimental
2.1 Materials Ground steel-making slag was provided by Wuhan Steel Ltd (Wuhan, P. R. China). The chemical composition and physical properties of ground steel-making slag and OPC are listed in Table 1. The basic parameter of ground steel-making slag, CaO/(SiO2 + P2 05 ), is 3.18, which means it belongs to C3S type steel-making slag on the view of Mason. B [9i . The mineral composition of gromM steel-making slag and OPC is listed in Table. 1. XRD pattems show that ground steel-making slag contains alite, bellite, Ca( OH)=, CaCO3, and RO phase based on FeO. Moreover, alite and belite in ground steel-making slag arc less than those in OPC. Samples of blend cement were obtained by using 10% to 40 % ground steel-making slag replacing OPC on weight basis. Control cement without ground steel-making slag is named as OPC; OPC containing 10% ,20% ,30% and 40% ground steel-making slag is named as ST1, ST2, ST3 and ST4, respectively. 2.2 Methods The Strength measurement was conducted according to Chinese National Standant GB177-96. The ratio of binder : sand : water was 1 : 3 : 0 . 4 4 in all samples. All samples (4 x 4 x 16cm3 ) were cured in water at 20 + 2~ and strength tests were carried out after 3 , 7 , 2 8 , 9 0 and 180 days.

LI Yong-xin(~:~K~): Born in 1975;Postgraduate for doctor; Cement Institute, China Building Material Academy, Beijing 100024. Email: liyongxin-c @ sina. corn Supported by National Key Basic Research Development Project (973 High-tech plan) (No. 2001CB610703)

Vol. 18 No.4

LI Yong-xin et d: Microstructure and Compositionof Hydration Products of...


Table 1 Chemical Composition and Physical Properties of Groand Steel-making Slag and OPC
Chemical comt~sition/% SiO2 A1203 Fe203 0.94 5.11 22.45 3.34 MnO 0.73 CaO 43.13 63.33 MgO 6.63 2.06 S03 0.19 2.33 P20s 2.33 Special gravity 3.33 3.14 Blain special sufface/(m2/kg) 373 328

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Steel-making slag OPC

11.22 23.03

Table 2
No. OPC ST1 ST2 ST3 ST4 2000 1800 1600 1400 1200 1000 800 600 Ground s t e e l making slag c. 40O 200 0 3d 35.8 33.3 29.6 23.5 18.1 7d 45.4 43.2 42.7 38.1 32.1

Compressive Strength of OPC with and Without Ground Steel-malting Slag at Different Ages
Relative compressive strength/% 180d 57.6 63.6 60.1 58.8 57.9 3d 100.0 93.2 82.7 65.6 50.6 7d 100.0 95.1 94.1 83.9 70.8 28d 100.0 100.0 92.0 86.7 81.1 90d 100.0 108.5 108.7 104.2 98.1 180d 100.0 110.6 104.3 102.2 100.7 28d 54.4 54.4 50.0 47.l 44.1 90d 55.2 60.0 60.0 57.6 54.2

Compressive strength/MPa

^
B L A |t~tt ^-Mite B-Belite RO-RO phase Ctt- Ca(0H)2

ii
^B
AB

cac0s-CaC0~
BA A

CaC03

B tt~w

BA

Ro
.~,,~~

: . " " f " ~ . %.-,,~.,.,~. '~. ~ t ~ "

8 12 16 20 24 28 32 36 40 44 48 52 56 60

Fig. 1 XRD patterns of ground steel-making slag and OPC Paste specimens (2 x 2 x 2 cm3 ) for MIP, XRD and DTA-TG test were prepared. The ratio of water to binder was 0.44 in all samples. All samples were cured in water at 20 _+2~ and the hydration was stopped by using alcohol at the given age. Samples for MIP were pre-dried at 105~ for 4 - 5h. Samples for DTA-TG and XRD were pre-ground with enough alcohol and pre-dried in a vacuum desiccator to avoid the carbonation. MIP test was carried out in the mercury porosimeter (Micrometrics AutoPore III 9420). XRD patterns were recorded with a X-ray diffractmeter (Rigaku D/max-3a). DTA-TG test was carried out in a thermal analysis apparatus (NETZSCH STA499).

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3. 1

Results and Discussion

Strength development of OPC mortar with ground steel-making slag The strength of OPC mortar with and without ground steel-making slag at different ages is listed in Table 2. Before 28 days, compressive strength of samples decreases with the increase of the amount of ground steelmaking slag replacing OPC. At 28 days, the compressive strength of sample ST1 has approached to that of OPC and the relative compressive strength of sample ST2, ST3 and ST4 is 9 2 . 0 % , 8 6 . 7 % , and 8 1 . 1 % , respectively. Mter

90 days, the compressive strength of all samples with ground steel-making slag exceeds that of OPC sample. These results show that ground steel-making slag is a kind of high activity mineral additives and can raise the strength of OPC mortar. The compressive strength of all samples increases with the hydration process, while the extent of the strength increase of OPC with ground steel-making slag is more than that of OPC, which means ground steel-making slag can accelerate the strength development of OPC. Other mineral additives, such as fly ash and blast furnace slag, have same results according to S P Pandey's study~1~ . 3.2 Pore structure of OPC paste with ground steelmaking slag The total porosity and average pore diameter of OPC pastes with and without ground steel-making slag are listed in Table 3. The porosity and average pore diameter of OPC paste with ground steel-making slag increase with the increase of the amount of ground steel-making slag replacing OPC. The porosity of all samples decreases with the hydration process due to the gradual filling of large pores by hydration products of cementitous materials I"'123 . The porosity and pore diameter of OPC paste have a little change after 28 days , while those with ground steelmaking slag decrease obviously during 28-day to 180-day ages. That means the microstructure of OPC paste with ground steel-making slag forms and develops more slowly than that of OPC paste. Fig. 2 gives the pore size distribution of OPC paste. Fig. 3 gives the pore size distribution of sample with 30 % ground steel-making slag and those of others with ground steel-making slag are similar to it. At the age of 3 days, there are many big pores larger than 100nm in both OPC and ST3 samples. At the age of 7 days, the diameter of most pores is in the range of 20 to 50nm in the OPC paste, while the diameter of most pores is still larger than 100nm in the sample ST3.

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Journal of Wuhan University of Technology- Mater. Sci. Ed.

Dec. 2003

No. OPC ST1 ST2 ST3 ST4

Table 3 TotalPorosity and AveragePore Size of OPC Paste with and WithoutGroundSteel-MakingSlag at VariousAges Total porosity/% Averagepore diameter/nm 3d 7d 28d 90d 180d 3d 7d 28d 90d 38.11 31.85 21.76 20.64 20.81 50.48 31.36 11.63 11.54 37.07 32.57 23.54 20.51 20.37 70.83 33.67 15.63 14.49 40.53 35.89 26.38 24.22 22.86 90.38 41.94 17.55 16.19 41.77 37.03 29.67 26.36 25.82 104.28 51.98 21.73 20.46 44.95 40.16 32.82 29.55 29.63 137.27 68.60 26.48 21.25
tar.

180d 11.20 13.63 13.89 19.56 20.00

After 28-day age, there is a few of big pores larger than 50nm in samples of OPC and ST3. Moreover, the diameter of most pores in OPC paste is in the range of 5 to 10nm,while the diameter of most pores in ST3 paste is in the range of 20 to 50nm. In fact, the pores whose diameter is in the range of 20 to 50 nm do not affect the strength and permeability according to Mehta' s view I"l . So, although ground steel-making slag increases the porosity of 180 [] 3d [] 7d 9 28d 150 l--190d 9 180d 120
90

paste, it still can improve the longer-age strength of mor-

3.3

XRD analysis of hydrated samples with ground steel-making slag


Fig.4 shows XRD patterns of hydration products of

paste with and without ground steel-making slag at 28 days and 90 days. 180[ [] 3d 150 1 I-]90d [] 7d 9 28d [] 180d

30 <5 5-10 10-20 20-50 50-100 Porediameter/nm > 100 <5 5-10 10-20 20-50 50-100 Porediameter/nm > 100

Fig. 2 pore size distribution of OPC paste A-Alite B-Belite CH-Ca(OH)2 CH A-Alite B-Belite CH-Ca(OH)2

Fig. 3 Pore size distribution of ST3 paste

28 days CH

90 days

ST3

gT3 ~2

ST2

t
ST,

oPc
5 8

i)

opc
12 16 20 24 28 32 36 40 44 48

12 16 20 24 28 32 36 40 44 48 5 8 Fig.4

XRD patterns of OPC hydration in the presence of 10% to 40% ground steel-making slag The amount of Ca(OH)2 and total bond water were determined by DTA-TG. For the purpose of calculation, the curve of TG is divided into three parts (Fig. 5 ), namely,TG, (50 - 420~ TG2 (440 - 520~ and TG3 ( 5 2 0 - 800~ ),which are the temperature ranges of CSH gel dehydration, Ca(OH)2 dehydration and CaCO3 decomposition, respectively9 CaCO3 is the product of carbonated Ca(OH)2, so the total amount of Ca(OH)2 should include this part of ear-.

From Fig. 4 it can be seen that hydration products of OPC with some ground steel-making slag is similar to that of OPC at 28-day and 90-day age. XRD patterns show that 28-day hydrated samples still remain some alite and belite, but 90-day hydrated samples hardly contain any alite and belite, which means that most alite and belite in OPC and ground steel-making slag have hydrated after 90 days.

3.4

DTA-TG analysis of hydrated samples with ground steel-making slag

Vol. 18

No. 4

LI Yong-xin et a/: Microstmcture and Composition of Hydration Products o f . . . TG~ l CSH gel dehydration 50-420~
........

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bonated Ca(OH)2. The total bond water mainly includes water of CSH and bond water of Ca(OH)2. The amount of Ca(OH) and total bond water are determined according to Equation (1) and Equation (2). IgcH = 74 x ( G2[18+ G3[44 ) (1)
I

t I*~"

W = Gj + G2 + 18

G3]44

(2)

CHdehydration 52O%

CaC0~d~0mp~si~0~ 620-800~

Where, WcH is the amount of total Ca(OH)2; W is the amount of total bond water; Gj, G2 and G3 are weigh loss of TG1, TG2 and TG3,respectively. The amount of Ca( OH)2 and total bond water are
I CIO 2CIO 300 400

5;o 6;o 7;o 8oo 9;o


Temperature/~

calculated according to Equation ( 1 ) , (2) and their reFig.5 Analysis of DTA-TG-DTG curve suits are listed in Table 4. Table 4 Results of Ca(OH)2 and Total Bond Water of All Samples
No. OPC ST1 ST2 ST3 ST4 3d 15.43 14.94 14.10 13.67 13.12 7d 18.03 17.13 15.52 15.50 15.48 Ca(0H)2/% 28d 21.65 20.76 20.21 20.18 19.84 90d 20.62 19.69 20.28 19.64 18.47 180d 21.21 23.06 23.05 22.01 21.60 3d 13.68 13.79 11.41 12.04 11.05 7d 16.55 15.39 12.89 14.31 13.34 Total bond water/% 28d 20.52 19.71 18.92 18.30 17.26 90d 20.08 19.68 20.19 18.94 17.64 180d 22.75 20.98 20.54 19.04 17.91

As a whole, C a ( O H ) 2 and total bond water increase with the hydration process and decrease with the amount of ground steel-making slag replacing OPC before 90-day age. It is obvious that the amount Ca(OH)2 in hydrated samples with ground steel-making slag is greater than that in OPC hydrated sample at 180-day age, which indicates that the hydration products of ground steel-making slag contain quite a lot of Ca(OH)2 in long age. Results of XRD and DTA-TG show that the hydration mechanism of ground steel-making slag is similar to that of OPC but different from that of fly ash and blast furnace slag. Fly ash and blast furnace slag reduce Ca(OH)2 in long-age hydration products of OPC as a result of pozzolanic reactionI131, but ground steel-making slag liberates quite a lot of Ca(OH)2 in long age.

References
1 Wu Qibing, Yang Jiakuan, et al. A New Technique for Recycling Molten Steel Slag. Industrial Safety and Enviromnental Protection, 2001,27(9) : 11 - 12( Chinese) Li DongXue, Fuxinhua, et ol. Durability Study of Steel Slag Cement. Cement and Concrete Research, 1997,27 (7) : 983 - 987 Hu shu-guang,Jiang Cong-sheng, et d . Rescarch on Hydration of Steel Slag Cement Activated with Waterglass. Journal of Wuhan University of Techno/ogy - Mater. Sci. Ed. ,2001,16(1) :37-47 Hou Xinkai, Li Hushen. How to Produce Steel Slag Cement in a Better Way. Cement Engineering ,997,1:43 - 45 (Chinese) Chen Yimin,Zhang Hongtao et al .Research on a New Kind of Mineral Additives of Cement:Fine Powder of Steel-making Slag. 11'h Intemat/ona/Congress of Cement Chem/stry,2003,South Africa. Chen Yimin, Zhang Hongtao et al. Study on Pulverized Steel Slag Used as High Reactivity Blending Materials of Cement. Cement, 2001,5 : 1 - 4(Chinese) M Tufekci, A Demirbas, H Genc. Evaluation of Steel Slags as Cement Additives. Cement and Concrete Research, 1997, 27 (11):1713- 1717 I Akm Alttm, I sroail Yilmaz. Study on Steel Furnace Slag with High MgO as Additive in Portland Cement. Cement and Concrete Research, 2002,32(11) : 1713 - 1717 Wu Xuequan, Zhu Hong, Hou Xinkai, Li Husen. Study on Steel Slag and Fly Ash Composite Portland Cement. Cement and Concrete Research ,1999 , 29 : l103 - 1106 P Pandey, R L Sharma. The Influence of Mineral Additive on Strength and Porosity of OPC Mortar. Cement and Concrete Research,2000,30( 1) : 19 - 23 Odler, M Robler. Investigation on the Relationship between Porosity, Structure and Strength of Hydrated Portland Cement Paste. (II) Effect of Pore Structure and Degree of Hydration. Cement and Concrete Research, 1985,15(4) :401 - 410 Anmohan D, Mehata P K. Study on Blended Portland Cements Containing Santirin Earth. Cement and Concrete Research, 1981,11(4) :575 - 579 L Sharma, S P Pandey. Influence of Mineral Additives on the Hydration Characteristics of Ordinary Portland Cement. Cement and Concrete Research,1999,29:1525- 1529

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Conclusions

a)Ground steel-making slag is a kind of high activity mineral additives. It can accelerate the strength development of OPC mortar and raise the longer-age strength of OPC mortar. b) The total porosity and average pore diameter of OPC paste with the ground steel-making slag are increased with the increase of the amount of ground steel-making slag replacing OPC at the respective age. While after 28 days most pores in paste with ground steel-making stag do not influence the strength because the diameter of those pores is in the range of 20 to 50nm. c) The hydration mechanism of ground steel-making slag is similar to that of OPC but different from that of fly ash and blast furnace slag. Hydration products of ground steel-making slag contain quite a lot of Ca(OH)2 in long
age.

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