含镁铝尖晶石的铝酸钙水泥的合成与流变特性

doi:10.15541/jim20160582

摘要/Abstract

摘要：

在1400℃和1500℃温度下合成了不同配比的铝酸钙水泥(CMA)。检测结果显示, 当温度升高时镁铝尖晶石的粒径由5 μm生长到15 μm。合成温度达到1400℃时, 镁铝尖晶石晶粒呈团簇状并分布在铝酸钙晶粒周围; 当合成温度升高至1500℃时, 镁铝尖晶石晶粒穿插在铝酸钙晶粒中。另外, 随着水泥中镁铝尖晶石含量的增加, 水泥的凝结时间延长, 同时粘度下降。相应的, 水泥储能模量和流动点的大小分别为0.15 MPa和4.44%。提高镁铝尖晶石相的含量或增大铝酸钙晶粒尺寸会减弱水泥水化时絮凝结构的强度。

关键词: 铝酸钙水泥, 镁铝尖晶石, 合成, 流变性能

Abstract:

Calcium aluminate cements with different MgAl₂O₄ spinel (CMA) contents and particle sizes were synthesized. The results revealed that when the synthesis temperature was raised from 1400℃ to 1500℃, the particle size of MgAl₂O₄ (MA) increased from 5 μm to 15 μm. The MA particles appeared in clusters and were distributed around the CaAl₂O₄/CaAl₄O₇ (CA/CA₂) particles for CMA synthesized at 1400℃, while MA particles were inserted in the CA/CA₂ particles for CMA synthesized at 1500℃. At the same time, the setting time lengthened and the viscosity decreased with the increase in MA content and particle size for CMA. The corresponding minimum values of storage modulus and flow point were 0.15 MPa and 4.44%, respectively. It is believed that the higher content of the MA phase and the larger particle size of CA/CA₂ particles in CMA cement can result in a weak flocculation structure in hydrates.

Key words: calcium aluminate cement, MgAl₂O₄ spinel, synthesis, rheological properties

中图分类号:

TQ147

付云飞, 朱伯铨, 李享成, 陈平安. 含镁铝尖晶石的铝酸钙水泥的合成与流变特性[J]. 无机材料学报, 2017, 32(8): 884-890.

FU Yun-Fei, ZHU Bo-Quan, LI Xiang-Cheng, CHEN Ping-An. Synthesis and Rheological Property of Calcium Aluminate Cement Containing MgAl₂O₄ Spinel[J]. Journal of Inorganic Materials, 2017, 32(8): 884-890.

图/表 8

Table 1 Chemical and mineral phase compositions of CMA cements

Sample No.	Synthesis temperature	Constituent of raw materials/wt%			Designed phase composition of the cement/wt%
Sample No.	Synthesis temperature	Industrial alumina	Calcined magnesia	Calcium carbonate	MA	CA	CA₂
A	1400℃	63.1	15.9	21.0	63.3	33.8	2.9
B	1400℃	65.5	20.0	14.5	73.0	23.5	3.5
C	1500℃	63.1	15.9	21.0	63.3	33.8	2.9
D	1500℃	65.5	20.0	14.5	73.0	23.5	3.5

Fig. 1 XRD patterns of CMA cements synthesized at 1400℃ (a) (samples A and B) and 1500℃ (b) (samples C and D)

Fig. 2 XRD patterns of CMA cements containing 63wt% (a) (samples A and C) and 73wt% (b) (samples B and D)

Fig. 3 SEM micrographs of CMA cement samples A, B, C and D (a-d)

Fig. 4 Setting time of different CMA cements(a) Mortar for CMA cement A; (b) Mortar for CMA cement B; (c) Mortar for CMA cement C; (d) Mortar for CMA cement D

Fig. 5 Shear rate-shear stress curves of CMA cements

Fig. 6 Viscosity-shear rate curves of CMA cements

Fig. 7 Strain-sweep curves of different CMA cements(a) Slurry for CMA cement A; (b) Slurry for CMA cement B; (c) Slurry for CMA cement C; (d) Slurry for CMA cement D

参考文献 28

[1]	ABO-EL-ENEIN SALAH A, ABOU-SEKKINA MORSY M, KHALIL NAGY M, et al. Microstructure and refractory properties of spinel containing castables.Ceram. Int., 2010, 36(5): 1711-1717.
[2]	BRAULIO M A L, RIGAUD M, BUHR A, et al. Spinel-containing alumina-based refractory castables.Ceram. Int., 2011, 37(6): 1705-1724.
[3]	SAKO E Y, BRAULIO M A L, BRANT P O, et al. The impact of pre-formed and in situ spinel formation on the physical properties of cement-bonded high alumina refractory castables.Ceram. Int., 2010, 36(7): 2079-2085.
[4]	MUKHOPADHYAY S, DAS PODDAR P K. Effect of preformed and in situ spinels on microstructure and properties of a low cement refractory castable.Ceram. Int., 2004, 30(3): 369-380.
[5]	ARACELI ELISABET LAVAT, MARIA CRISTINA GRASSELLI, EUGENIA GIULIODORI LOVECCHIO.Effect of α andγ polymorphs of alumina on the preparation of MgAl2O4-spinel- containing refractory cements.Ceram. Int., 2010, 36(1): 15-21.
[6]	BRAULIO M A L, MORBIOLI G G, MILANEZ D H, et al. Calcium aluminate cement source evaluation for Al2O3-MgO refractory castables.Ceram. Int., 2011, 37(1): 215-221.
[7]	ZHANG ZHI-HUI, LI NAN.Effect of polymorphism of Al2O3 on the synthesis of magnesium aluminate spinel.Ceram. Int., 2005, 31(4): 583-589.
[8]	HAN BING-QIANG, WANG PENG, KE CHANG-MING, et al.Hydration behavior of spinel containing high alumina cement from high titania blast furnace slag.Cem. Concr. Res., 2016, 79: 257-264.
[9]	SOUZA T M, LUZ A P, PAGLIOSA CARLOS, et al.Mineralizing alumina-magnesia cement-bonded castables containing magnesium borates.Ceram. Int., 2015, 41(9): 11143-11152.
[10]	XIAO GUO-QING, GAO YUN-QIN, DUAN FENG.Preparation and corrosion resistance of aluminous cement containing magnesium aluminate spinel.J. Chin. Ceram. Soc., 2008, 36(8): 1172-1177.
[11]	GEHRE P, ANEZIRIS C G, VERES D, et al.Improved spinel-containing refractory castables for slagging gasifiers.J. Eur. Ceram. Soc., 2013, 33(6): 1077-1086.
[12]	BRAULIO M A L, BITTENCOURT L R M, PANDOLFELLI V C. Selection of binders for in situ spinel refractory castables.J. Eur. Ceram. Soc., 2009, 29(13): 2727-2735.
[13]	NANDI P, GARG A, SINGH R K, et al.Effects of cement and magnesia fines on in situ spinel formation in alumina-magnesia castable.Adv. Appl. Ceram., 2005, 104(2): 83-88.
[14]	LUZ A P, BRAULIO M A L, TOMBA MARTINEZ A G, et al. Slag attack evaluation of in situ spinel-containing refractory castables via experimental tests and thermodynamic simulations.Ceram. Int., 2012, 38(2): 1497-1505.
[15]	TOMBA MARTINEZ A G, LUZ A P, BRAULIO M A L, et al. CA6 impact on the corrosion behavior of cement-bonded spinel- containing refractory castables: an analysis based on thermodynamic simulations.Ceram. Int., 2015, 41(3): 4714-4725.
[16]	LI JIN-HONG, CAI BI-YA, FENG WU-WEI, et al.Investigations on phase constitution, mechanical properties and hydration kinetics of aluminous cements containing magnesium aluminate spinel.Ceram. Int., 2013, 39(7): 8393-8400.
[17]	AUVRAY JEAN-MICHEL, GAULT CHRISTIAN, HUGER MARC.Microstructural changes and evolutions of elastic properties versus temperature of alumina and alumina-magnesia refractory castables.J. Eur. Ceram. Soc., 2008, 28(10): 1953-1960.
[18]	ZHU BO-QUAN, WANG YU-LONG, LI XIANG-CHENG.Effect of phase distribution on rheological behavior of calcium aluminate cement with built-in alumina-magnesia spinel.J. Chin. Ceram. Soc., 2014, 42: 1383-1388.
[19]	STARK JOCHEN.Recent advances in the field of cement hydration and microstructure analysis.Cem. Concr. Res., 2011, 41(7): 666-678.
[20]	SILVA ABILIO P, SEGADÃES ANA M, PINTO DEESY G, et al. Effect of particle size distribution and calcium aluminate cement on the rheological behaviour of all-alumina refractory castables.Powder Technol., 2016, 226: 107-113.
[21]	OLIVEIRA I R, ORTEGA F S, PANDOLFELLI V C.Hydration of CAC cement in a castable refractory matrix containing processing additives.Ceram. Int., 2009, 35: 1545-1552.
[22]	WANG YU-LONG, ZHU BO-QUAN, LI XIANG-CHENG, et al.Effect of dispersants on the hydrate morphologies of spinel- containing calcium aluminate cement and on the properties of refractory castables. Ceram. Int., 2016, 42: 711-720.
[23]	LONG BIN, BUHR ANDREAS, XU GUI-YING.Thermodynamic evaluation and properties of refractory materials for steel ladle purging plugs in the system Al2O3-MgO-CaO.Ceram. Int., 2016, 42: 11930-11940.
[24]	DIAZ L A, Torrecillas R.Hot bending strength and creep behaviour at 1000-1400℃ of high alumina refractory castables with spinel, periclase and dolomite additions.J. Eur. Ceram. Soc., 2009, 29: 53-58.
[25]	ZHU BO-QUAN, SONG YA-NAN, LI XIANG-CHENG, et al.Synthesis and hydration kinetics of calcium aluminate cement with micro MgAl2O4 spinels.Mater. Chem. Phys., 2015, 154: 158-163.
[26]	PENG JIAN-WEI, DENG DE-HUA, LIU ZAN-QUN, et al.Rheological models for fresh cement asphalt paste.Constr. Build. Mater., 2014, 71: 254-262.
[27]	MEZGER THOMAS G. The Rheology Handbook, 3rd, Vincentz Network: Hannover Press, 2011, 3: 38-51.
[28]	HAFIANE Y EL, SMITH A, BONNET J P, et al.Effect of a carboxylic acid on the rheological behavior of an aluminous cement paste and consequences on the properties of the hardened material.J. Eur. Ceram. Soc., 2005, 25(7): 1143-1147.