纯铝酸钙水泥对刚玉-尖晶石浇注料性能的影响

以板状刚玉为骨料,电熔白刚玉、电熔尖晶石、Al2O3微粉和纯铝酸钙水泥(Secar71)为基质,研究了纯铝酸钙水泥加入量对刚玉-尖晶石浇注料常温性能、高温强度和抗热震性能的影响.用X射线衍射仪分析了材料的物相组成.结果表明: 随纯铝酸钙水泥加入的增加,烧后试样的抗折强度先增加后降低.1600 ℃烧后试样的热态强度在600～1000 ℃时变化不大,1000 ℃后快速下降.随纯铝酸钙水泥含量的增加,热震后试样的残余抗折强度和残余抗折强度保持率增加,抗热震性有所改善;纯铝酸钙水泥对浇注料的性能有显著的影响,主要与水泥中的CaO与Al2O3之间的反应产物有关.     

二铝酸钙加入量对刚玉浇注料性能的影响

为了改善刚玉浇注料的性能,以白刚玉、二铝酸钙(CA₂)、活性α-Al₂O₃微粉和纯铝酸钙水泥为主要原料,制备了刚玉浇注料,研究了CA₂加入量(加入质量分数分别为0、20%、30%、40%)对刚玉浇注料性能的影响。结果表明：1)随着CA₂的增多,刚玉浇注料的体积密度大幅减小,110℃烘干和800℃热处理后的常温耐压强度明显改善,而1 200℃热处理后的常温耐压强度变化不明显;2)随着CA₂的增多,浇注料的平均热膨胀系数逐渐降低,热导率大幅降低,试样经800℃水冷热震后的抗折强度保持率大幅提升;3)CA₂的引入大幅提升了刚玉浇注料的透气性,且不影响刚玉浇注料的抗氢气还原性能。     

SiO_2微粉对水泥结合刚玉质浇注料中低温化学键变化的影响

以电熔棕刚玉(8~5、5~3、3~1 mm)和电熔白刚玉(≤1、≤0.045 mm)为主要原料,添加α-Al2O3微粉和SiO2微粉制备铝酸钙水泥结合刚玉质浇注料,研究了经110、800和1 000℃热处理后含5%(w)Si O2微粉和不含SiO2微粉浇注料基质中化学键变化与浇注料强度的关系。采用XPS和FTIR研究Si O2微粉与水泥水化产物经110℃烘干和800℃热处理后的化学键变化。结果表明,经110和800℃热处理后,SiO2微粉和水泥水化物之间形成了Si—O—Al结合键。因此,在110~800℃,含Si O2微粉的铝酸钙水泥结合浇注料的强度较高的原因是Si O2微粉与水泥水化物之间形成了Si—O—Al化学键。     

硅溶胶对刚玉浇注料性能的影响

以5～8、3～5、1～3及≤1 mm的电熔刚玉为骨料,致密刚玉粉(≤0.074 mm)、白刚玉粉(≤0.043mm)及α-Al2O3微粉为细粉,矾土水泥和硅溶胶为结合剂,按骨料、粉料质量比为64∶36配料制成试样,自然养护后于110℃24 h烘干,然后分别于815℃3 h、1 100℃3 h和1 400℃3 h热处理。对处理后试样进行了常温抗折强度、耐压强度、体积密度、线变化率和抗热震性能的检测及显微结构分析。结果表明:硅溶胶结合浇注料于1 100℃3 h处理后的抗折强度和耐压强度分别达到27.1和178 MPa,远高于相同温度下水泥结合浇注料的;硅溶胶结合浇注料在20～1 100℃水冷热震循坏100次后基本没有出现裂纹,其耐压强度损失率仅为24.4%,而水泥结合的浇注料热震循坏49次后就完全开裂。     

锆莫来石加入量对刚玉质耐火浇注料抗热震性的影响

以电熔刚玉、锆莫来石、α-Al2O3微粉为主要原料,以铝酸钙水泥为结合剂,制备了刚玉质耐火浇注料.研究了锆莫来石加入量(质量分数分别为0、3％、6％、9％)对刚玉质耐火浇注料物理性能、物相组成和显微结构的影响.结果表明:随着锆莫来石加入量的增加,110℃×24 h烘干后试样体积密度呈先增大后减小,显气孔率呈先减小后增大趋势,常温抗折强度变化不大;1600℃×3h处理后耐火浇注料试样体积密度和常温抗折强度呈先增大后减小的趋势,1500℃×0.5 h高温抗折强度呈明显下降趋势.锆莫来石的引入对刚玉质耐火浇注料的抗热震性有所提高.综合各项性能,认为锆莫来石的最佳加入质量分数为3％.     

锆英石加入量对刚玉质浇注料性能的影响

以电熔白刚玉(5～3、3～1、≤1 mm)、板状刚玉细粉(≤0.044 mm)、锆英石(≤0.074 mm)、α-Al2O3微粉为主要原料,以Secar 71水泥为结合剂,制备了刚玉质浇注料,经110℃24 h烘干和1 600℃3 h烧后,研究了锆英石加入量(质量分数分别为0、3%、6%、9%)对试样性能、物相组成和显微结构的影响。结果表明:随着锆英石加入量的增加,试样经110℃24 h烘干后的体积密度先增大后减小,显气孔率先减小后增大,常温抗折强度变化不大;试样经1 600℃3 h烧后的体积密度、常温抗折强度和抗热震性呈先增大后减小的趋势,高温抗折强度呈明显下降趋势。综合各项性能,认为锆英石的最佳加入质量分数为6%。     

SiO2微粉加入量对刚玉质超低水泥浇注料高温性能的影响

研究了SiO2微粉加入量为0、2%、4%、6%和8%时对刚玉质超低水泥浇注料的烧结性能、高温强度及抗热震性能的影响.结果表明随着SiO2微粉加入量的增加,试样的烧结性能和抗热震性得到明显改善,在1400℃时的高温抗折强度也显著提高.讨论认为,试样高温性能提高的主要原因是SiO2微粉与Al2O3反应生成的莫来石穿插或弥散在刚玉颗粒形成的骨架结构的孔隙中起增韧作用.     

Effects of cement content on the microstructural evolution and mechanical properties of cement-bonded corundum castables

The cement-bonded corundum castables are often subjected to great temperature gradient in the service process of purging plugs for refining ladle. The mechanical properties of such castables are of particular interest in the serviceability and the safety of purging plug, which are significantly influenced by the microstructures including the amount, size and morphology of materials. The reported cement contents in compounds of purging plugs are generally low or ultralow, which inevitably limits the adjustable range of the mechanical properties enhancement by regulating their microstructures. In the present research, a serial of comprehensive experiments have been carried out, including the high cement contents (10–15 wt%), so as to further understand the role of cement content on the microstructural evolution and mechanical properties of castables. It is found that the phase compositions and microstructure can be optimized through adjusting the cement content in corundum castables. When the cement content is below 10 wt%, the hexagonal flake CA₆ grains are platelet-shaped both in the matrix and at the border of the aggregates, their amount and size increase and distributions are more uniformly with cement content. When the cement content is above 10 wt%, small amount of granular crystals CA₂ are detected in matrix, and CA₆ crystals transform to equiaxial morphologies after cement content of 10 wt%. This research also provides quantitative relationship between the mechanical properties of the castables and the cement content. Castables with cement content of 10 wt% contain most hexagonal flake CA₆ crystals, so that they have the highest CMOR and HMOR after heating at 1600 °C. However, CMOR decreases after cement content of 10 wt% due to the porosity and volumetric expansion from the formation of in-situ CA₆ and CA₂.     

铝酸钙水泥对刚玉基浇注料性能的影响

以电熔白刚玉颗粒及细粉为主要原料,α-Al2O3微粉、铝酸钙水泥以及Alphabond300为结合系统,研究了铝酸钙水泥加入量(质量分数分别为0、0.75%、2.25%和3.75%)对刚玉基浇注料性能的影响。结果表明:1)水泥的加入使浇注料基质的粘度增大,浇注料的流动性降低。2)随着水泥加入量的增加,110℃以及800℃处理后的冷、热态抗折强度均逐渐提高;1 100℃、1 400℃和1 600℃烧后的冷、热态强度均先降低后升高,其中水泥加入量(质量分数,下同)为0.75%时值最小。3)随着水泥含量的增加,浇注料抗热震性提高。4)少量水泥的加入使浇注料的抗渣性能降低,进一步增加水泥加入量,浇注料的抗渣性能逐步改善;在本试验范围内,水泥加入量为3.75%的浇注料和不含水泥的浇注料抗渣性能基本相当。     

水泥加入量对刚玉浇注料性能的影响

讨论了使用电熔白刚玉做骨、粉料,纯铝酸钙水泥作结合剂时,纯铝酸钙水泥加入量对制品性能的影响。结果表明,刚玉浇注料的重烧膨胀是由于刚玉与水泥发生反应生成了密度较低的CA6。     

添加剂对MgO-CaO浇注料性能的影响

以36%(质量分数,下同)的镁钙砂(5~3 mm)、16%的镁钙砂(3~1 mm)和20%中档镁砂(≤1 mm)为骨料,21%~28%的高纯镁砂粉(≤0.088 mm)为细粉,外加3%的硅灰为结合剂,分别比较了不同量的3种添加剂ZrO2(分别为2%、4%、6%)、Al2O3(分别为3%、5%、7%)、TiO2(分别为2%、4%、6%)对MgO-CaO浇注料性能的影响。结果表明:加入ZrO2可提高MgO-CaO浇注料的体积密度和常温抗折强度,ZrO2含量为4%的效果最好;加入Al2O3时,随Al2O3量的增加,MgO-CaO浇注料的体积密度和常温抗折强度增大,但高温下形成的低熔点铝酸盐相也较多,可能导致材料的高温性能下降,综合考虑认为,Al2O3以添加3%较好;加入TiO2可显著促进材料的烧结,使其结构致密,体积密度提高,常温抗折强度提高,TiO2含量为2%~4%时,对改善材料性能的作用较理想,但超过4%时,材料的性能开始变差;添加剂ZrO2、Al2O3、TiO2均能改善MgO-CaO浇注料的抗热震性,其中,添加ZrO2的试样抗热震性最好,其次为加Al2O3的,加TiO2的稍差。     

Effect of particle size of hydromagnesite on properties of calcium aluminate cement bonded corundum based castables

Calcium aluminate cement was premixed with hydromagnesite having different particle sizes, as a calcium magnesium aluminate cement precursor, to investigate the influence of particle size of hydromagnesite on the volume stability and thermo-mechanical properties of corundum based castables after firing at 1550 °C. The impact of particle size of hydromagnesite on the phase composition and microstructure evolution of fired castables matrix were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The results demonstrate that hydromagnesite with smaller particle size has a better volumetric stability and thermo-mechanical properties of castables, because of the more homogeneously distributed micro-pores, and smaller size MA and CA₆ resulted from the more uniformly distributed hydromagnesite in castables.     

Ti(C,N)对刚玉质浇注料性能的影响

骨料采用电熔白刚玉,基质采用白刚玉细粉、活性α-Al2O3微粉、SiO2微粉及Ti(C,N)微粉,按骨料与基质质量比为70:30,α-Al2O3微粉和Ti(C,N)微粉总质量分数固定为10%,制备了Ti(C,N)含量(质量分数)分别为0、5%和10%的三种刚玉质浇注料,对比了三种材料的常温物理性能、抗碱(K2O)性能及抗渣性能,并借助XRD和光学显微镜研究了材料的物相组成和显微结构。结果表明:加入Ti(C,N)后,刚玉质浇注料经1500℃3h热处理后强度显著增大,抗碱(K2O)性能及抗渣性能随Ti(C,N)加入量的增加而逐渐提高。其主要机理为:Ti(C,N)促进了材料的高温烧结,改善了材料的显微结构;同时Ti(C,N)化学稳定性优良,难于被熔渣润湿,材料基质中均匀分散的Ti(C,N)减弱了碱(K2O)及熔渣对刚玉质浇注料的渗透和侵蚀。     

Effect of Zn(OH)2 on properties of corundum based castables bonded with calcium aluminate cement

In this work, the effect of Zn(OH)₂ on properties of corundum based castables bonded with calcium aluminate cement (CAC) was investigated. The phase composition and microstructure of castable matrixes containing Zn(OH)₂ after firing 800 °C, 1100 °C and 1550 °C were characterized by X-ray diffraction, scanning electron microscopy and energy dispersive spectra, respectively. The results indicate that a small amount of Zn(OH)₂ can dramatically improve the medium temperature strength of castables because the generation of zinc aluminate spinel increases the ceramic bonding of castables. In addition, the addition of Zn(OH)₂ also improves the volume stability of CAC-bonded castables due to the enhanced formation of pores from Zn(OH)₂ decomposition in castables.     

负压浇注对刚玉浇注料性能的影响

按板状刚玉颗粒70%(w)、板状刚玉细粉和氧化铝微粉26%(w)、纯铝酸钙水泥3%(w)和减水剂1%(w),加适量水配制成刚玉浇注料,搅拌均匀后倒入真空浇注设备的模具中,分别于真空度为0、-0.03、-0.06和-0.09 MPa的时刻开始振动浇注成型,振动时继续抽真空2 min,试样经养护、烘干和1 500℃3 h热处理后,研究负压浇注对刚玉浇注料物理性能、抗热震性和抗渣性的影响,并借助压汞仪测定试样孔径分布,采用SEM观察试样断口形貌.结果表明:与常压浇注的试样相比,负压浇注可使试样中的气孔直径从10～20μm降到0.5～2μm,使试样结构更加致密,从而提高其机械强度和抗渣侵蚀性;负压浇注对试样的抗热震性略有负面影响,但负压浇注的试样热震后强度仍高于常压浇注的;在真空度为-0.03～-0.06 MPa之间开始振动浇注时,得到的浇注料试样综合性能最好.     

Optimized microstructure with nano-alumina and its effects on properties of corundum spinel castables

The mechanical properties, thermal shock resistance, and microstructure evolution of corundum spinel castables with different nano-alumina contents were investigated. The results show that the addition of nano-alumina has advantages on the microstructure evolution and properties of castables. An optimum nano-alumina amount is 2 wt%. When nano-alumina addition changes from 0 to 2 wt%, the cold modulus of rupture (CMOR) and cold compressive strength (CCS) improved by 69.7% and 78.1% after firing at 1100°C, respectively. The CMOR and CCS increased by 42.5% and 35.2% after firing at 1500°C, respectively. Meanwhile, the hot modulus of rupture (HMOR) was enhanced by 21.5% to 13.4 MPa. The retained Young's modulus values of castables were improved from 49.6% to 59.6% after eight thermal shock cycles. Furthermore, the HMOR and the retained Young's modulus values of castables slightly reduced when nano-alumina content up to 3 wt%. XRD, DSC, SEM, and EDS analyses revealed that the addition of nano-alumina leads to the formation of calcium dialuminate (CaO·2Al₂O₃) at 1100°C and it is beneficial to the formation of more platelet hibonite (CaO·6Al₂O₃) at 1500°C. As a result of using nano-alumina with large surface area, the solid phase sintering of the nanoscale particles can occur at lower temperatures. Moreover, the mechanical properties and thermal shock resistance of the castables were improved remarkably.