First Intemational Conference on Advances in Chemically-activated Materials (CAM"2010-China), May 9-12, 2010, Jinan, Shandong, China THE STUDY OF ALKALINE-ACTIVATED MAGNESIUM SLAG CEMENTITIOUS MATERIAL. School of material Science & Engineering, Jilin Institute of Architecture and Engineering, ‘Changchun, 130021, China ABSTRACT: Magnesium slag cementitious material was prepared suecessfully using the magnesium slag-furnace slag-clinker system and different activators in this paper. The effect of activator on the mechanical property of the material was studied. The hydration and microstructure of this composite cement were analyzed by X-ray diffraction and scanning electron microscopy and the interaction mechanism was researched. The results showed that the activity of magnesium slag was enhanced significantly for the best effect by adding a small amount of activator. The activators have no effect on the species of hydration products of magnesium slag cementitious materials mortar which are composed of anorthite, gismondine, paragonite, margarite and so on Keywords: Magnesium slag, activators, interaetion mechanism, cementitious materials 1, INTRODUCTION Magnesium slag is the sub-product generated in the production of metalic magnesium. The magnesium slag was obtained by the reduction of dolomite by Fe- (Si), resulting in several loxides, being constituted of dicalciumsilicate (2CaO-Si0;), which was also present in cements and slags [I]. It was nothing more than a latent hydraulic binder and must be activated in practice to react and provide strength. It was recognized that alkali additions ean activate pozzolanic materials to set and harden in their own right [2], The result showed that cementitious materials composed of magnesium slag and little clinker did not meet the engineering demand in the previous study. By learning from the use of other slags, furnace slag was added to the magnesium slag cementitious materials. Magnesium slag cementitious materials consisted of clinker, magnesium slag, furnace slag and activators, consisting of sodium silicate, gypsum and sodium silicate. 2. EXPERIMENTS 2.1 Materials Magnesium slag was supplied by Dong Feng colored metal industry of Jilin, Furnace slag and clinker were supplied by YaTai cement industry. Details of the chemical composition of the materials used are given in Table 1. Activators were liquid Sodium silicate, Sodium sulfate and gypsum. Liquid Sodium silicate was bought in the market and the modulus of 66First Intemational Conference on Advances in Chemically-activated Materials (CAM"2010-China), May 9-12, 2010, Jinan, Shandong, China sodium silicate was 1.5, with a consistency of 49%. Sodium sulfate was an industrial grade chemical reagent, Gypsum was supplied by YATAI cement industry of Jilin, and the content of SO, was 40%. Table | Chemical composition (by mass) of raw materials (%) Materials SiO» ALO; | FeO; a0 Mgo Others Clinker 22 5 6 64 15 13 MS. 31.78 2.61 173 48.53 8.42 1.65 FS 30.67 i798 0.73 40.03 8.50 2.09 * MS was magnesium slag, FS was furnace slag 2.2 Specimens and Test Methods The original materials were ground in the ball grinding mill according to proportion fixed in the previous study until the final fineness was 3.6%. The liquid Sodium silicate was added by dissolving in water while gypsum and Sodium silicate were added by mixing with the other dry materials. Determination of strength was tested according to GB/T 17671-1999; water requirement of normal consistency, setting time and soundness of the material were tested according to GBT 1346-2001; fineness of material was tested according to GBT 1345- 2005. A water-to-binder ratio of 0,5 was used. The type of X-tay machine used was Ultimaly with the following conditions: 40 KV, 20 mA. The type of SEM machine used was KYKY2800_ 3, RESULTS AND DISCUSSION: 3.1 The Determination of Minerals of Magnesium Slag The minerals phases of magnesium slag were determined by XRD. The results are shown in Figure 1. It can be seen from the figure above that the mineral phases of magnesium slag were C:8, MgO, CF and so on. Magnesium slag could harden because there was plenty of CS, which was also used primarily in Portland cement 4000 900 2000 1000 . «0 oo 99 «0 90 eo 70 60 oD angie Figure .1 Curves of XRD-ray analysis, 67First Intemational Conference on Advances in Chemically-activated Materials (CAM"2010-China), May 9-12, 2010, Jinan, Shandong, China 3.2 Effect of Activators on the Magnesium Slag Cementitious Material The experiment was conducted according to the proportion fixed in the previous study (clinker: magnesium slag: furnace slag were 35%!32.5%:32.5% by mass). The effects of single activator and composite activators were studied. Table 2 Effect of activators on the mechanical property of magnesium slag cementitious material weurvaiar Compressive Flexural NO strength/MPa strength/Mpa Kind Dosage! 3d, 28d 3d 28d 1 0 106 258 2.45 3.90 2 a 1s 109 28.3 2.60 470 3 b 2 154 303 32 4 c 3 129 305 2.92. 62 = atbte O.5+2+2 14.7 ALT 3.52 73 * where a was Sodium silicate, b was Sodium sulfate, ¢ was gypsum. ‘As was shown im the table, the mechanical properties of magnesium slag cementitious material were enhanced by adding activator, and the combined activators have the best effect ‘on the material, The hydration process and mechanism were explained as follows, The hydration of clinker and hydrolyzation of sodium silicate resulted in high concentration of OH. The structure of magnesium slag and furnace slag is destroyed under high concentration of OH It can be described as the breaking of Me-O(Me = Ca, Mg), Si -Q-Si, Al-O-Al and Al- 0-Si bonds in the slag grains resulting in high concentrations of ions such as HySiOyand HAI,” in the solution. These ions react with Na’, which result in some hydration products of natrolite, The reactions proceed according to the following equations [3]: HAO +H,S10+Ca* +kCaOALOmSiOynH,0 i) HyA1O¢+H;SiOy+ Ca? +Na’— pNazO-kCa0-1A1,0smSiOy nH,0 @ The reaction above absorbed lots of Ca® and other ions, which accelerated the rate of destruction of magnesium slag and fumace slag gradually. At the same time, the gypsum and sodium sulfate provided the SO,” ions which reacted with C,AHro.Thus the Aft was produced when the gypsum and sodium sulfate were added. The products formed at later times fill in the porous area; furthermore these products formed a compacted net structure through superposition, The result was that the strength of material was enhanced finally, The cementitious material had good mechanical properties the compressive strength was 42.7MPa and the flexural strength was 7.3MPa Properties of the material were also tested ‘The water requirement of normal consistency was 34.4%, the initial time was 116min, the final time was 175 min, soundness of the material corresponded with the standard of cement. 3.3. SEM Observations The microstructure of this composite cement was analyzed by scanning electron microscopy, and as a comparison, two SEM images were obtained, Figure 2. shows micrographs of this material. 6kFirst Intemational Conference on Advances in Chemically-activated Materials (CAM"2010-China), May 9-12, 2010, Jinan, Shandong, China (a) material without activators (b) materials mortar with activators * where the pattern of a was NOI,b was NOS mentioned above: Fig 2 SEM images of Magnesium slag cementitious material mortar (28d) It can be obviously noticed that there exists quite a large difference in the microstructure of the magnesium slag cementitious materials whether the activator was added, The latter generally exhibits compacted and continued integrated morphological characteristics, while the former exhibits some incompact area, ie,, some remaining porous area, We can see this result from the former picture where lots of needle core produet exists in the material, and little product linked to each other. It was proved that both magnesium slag and furnace slag hydrated incompletely, with the microstructure of the products showing compacted structure correspondingly. It proved that the activators accelerate the rate of hydration, and more hydration products were formed. 3.4 X-ray Microanalysis (XRD) The hydration products have much effect on the properties of cement, such as durability and other mechanical properties. So the kinds of hydration produets were analyzed by XRD and the result was showed in the following picture From the Figure 3, the result can be observed that the activators have no effect on the kinds of products, which contain the zeolite group and mica group and so on. This results were in accordance with those of other papers on the alkali-slag cements [4, S]. It can be see n from the figure above that anorthite, gismondine, parngonite and margarite existed in the hardened cement. 4. CONCLUSION Magnesium slag cementitious material was prepared successfully using the magnesium slag-furnace slag-clinker system and several activators, and whose performance was in accordance with the standards of composite cement of 32.SMPa, The activity of magnesium slag was enhanced significantly by adding small a amount of activator. The cementitious material performed well mechanically when activators were combined. The species of hydration products of this material were anorthite, gismondine, paragonite, margarite and so on. ooFirst Intemational Conference on Advances in Chemically-activated Materials (CAM"2010-China), May 9-12, 2010, Jinan, Shandong, China 200 18102 2.CaAlz, Si2Alz) O10( OH) 2 ‘-Caanzsizos aHz0 a-canizsizo3 S.Naalz{ AIS) 01 CH) 2 500 00 z 2 00 2 = 200 +00 0 0 2-Thota( degree) (a) material without activators 4 1000 +-Ceausi08 +20 20d SZAz2) O10 OM) 2 ia 3-canzsi208 45:02 5-MgSi0a 2 sa 00 2001 cr a ee ne nn 2-Thetal degree) (b) material with activators * where the pattem of a was NOI,b was NOS mentioned above Fig.3 XRD pattems of magnesium slag cementitious materials mortar 70First Intemational Conference on Advances in Chemically-activated Materials (CAM"2010-China), May 9-12, 2010, Jinan, Shandong, China REFERENCES [1] Carlos A, S. Oliveira, Adriana G. Guinieti, Abdias M. Gomes, Wander L, Vasconcelos. (Characterization of Magnesium Slag Aiming the Utilization as Mineral Admixtuer in Mortar[A]. Intemational RILE Conference on the Use of Recycled Materials in Buildings and Structures{C] Barcelona: [Spain].2004, [2] Darko Krizan, Branislav Zivanovic. Effects of dasage and modulus of waterglass on early hydration of alkali- slag cements [J], Cement and Concrete Research 32 (2002) 1181-1188 [3] XU yuan hui, LU wen xiong, WANG xiu juan,SHAO xia, Research and Develapment in Activation of Stee! Slag Activity[,J] Journal of shanghai university(natural sci« ‘ence},2004, 10(1);91-95, [4] Shao-Dong Wang and Karen L. Scrivener, Hydration Products of Alkali Activated Slag cement, Cement end Concrete Research, Vol. 25, No. 3, pp. $61-571.1995 [5] VD. Glukhovsky, G.S, Rostovskaja and G.V, Rumyna, 7th ICCC, Paris, 111, V164-V168(1980). 1