渣向电熔尖晶石砖中的渗透

1 前言 以往作为耐火材料使用较多的铬尖晶石砖,由于环境问题在使用上受到了限制。作为替代品的高级耐火材料,铝镁系尖晶石质最近越来越受到欢迎。本次就电熔尖晶石原料,尤其是着重渣的渗透性进行了试验,结果报道如下。2 试验方法2.1 试样 试样为整个组成接近尖晶石理论组成的固溶型电熔尖晶石原料3种(以下简称S1、S2、S3),MgO     

尖晶石种类和添加量对刚玉质透气座砖性能的影响

在以板状刚玉颗粒(10~5、5~3、3~1、≤1 mm)、板状刚玉细粉(≤0.074 mm)、氧化铝微粉、铝酸钙水泥等为原料,按骨料与基质质量比为70:30制备的纯刚玉质浇注料的基础上,分别采用w(Al2O3)≈88%的电熔富铝尖晶石细粉和w(Al2O3)≈72%的常规组成尖晶石细粉分别按3%、6%、9%的质量分数替代基础配方中的板状刚玉细粉制备了刚玉-尖晶石质浇注料,经110℃24 h、1 000℃3 h和1 650℃3 h处理后,研究了两种尖晶石细粉的添加量对浇注料常温物理性能、抗热震性和抗渣性能的影响。结果表明:1)随着富铝尖晶石细粉添加量的增加,110℃24 h和1 000℃3 h处理后试样的抗折强度和耐压强度均下降;添加常规组成尖晶石细粉的试样在相同温度下处理后抗折强度变化幅度不大,而耐压强度先略微上升后降低。2)随着两种尖晶石添加量的增加,1 650℃3 h处理后试样的体积密度先降低后上升,而线变化率先上升后下降。3)当两种尖晶石添加量(w)从3%增加至6%时试样经1 100℃水冷热震3次后的强度保持率增加幅度明显增大;试样的抗渣性随两种尖晶石添加量的增加均逐步改善。4)以富铝尖晶石添加量为9%(w)的配方制备的刚玉-尖晶石质透气座砖在国内某钢厂150 t钢包中使用,寿命较纯刚玉质的提高7~8炉,较添加常规组成尖晶石的提高4~5炉。     

微孔镁尖晶石碳耐火材料的抗渣性能研究

以方镁石-尖晶石微孔陶瓷、电熔镁砂为骨料,以电熔镁砂细粉、鳞片石墨、金属铝粉为基质材料,以酚醛树脂为结合剂制备了含微孔陶瓷骨料的镁尖晶石碳试样.采用感应炉浸渍法对试样进行了抗渣试验,并对渣蚀后的试样进行了SEM和EDAX分析.结果发现:熔渣和熔钢冲刷是损毁的主要原因,熔损并不显著.显微结构分析表明,在侵蚀层和原质层之间可以发现MgO致密层的形成,MgO致密层的形成可抑制渣对试样进一步的侵蚀和渗透.渣对MSO颗粒的侵蚀主要是FeO和MnO等在方镁石中的固溶,导致MgO颗粒出现结构剥落;方镁石-尖晶石微孔陶瓷骨料的蚀损主要是尖晶石被渣中的CaO和SiO2所侵蚀,而渣对微孔骨料渗透并不严重.     

锆刚玉加入对刚玉-尖晶石浇注料性能的影响

在刚玉-尖晶石浇注料的配比组成中分别加入ZrO2质量分数为28.46%和38.47%的两种电熔锆刚玉颗粒,研究了电熔锆刚玉颗粒的粒度(5～3、3～1和1～0.5 mm)、加入量(质量分数分别为3%、5%和8%)对刚玉-尖晶石浇注料的加热永久线变化率、烧后常温抗折强度、高温抗折强度及热震后弹性模量的影响,并观察了试样的显微结构。结果表明:1)试样的加热永久线变化率随锆刚玉粒度的增大而增大,随锆刚玉加入量的增多而增大,引入锆刚玉Z40的试样的加热永久线变化率基本上比引入锆刚玉Z25的大;2)烧后试样的常温抗折强度、高温抗折强度和弹性模量均以空白试样的为最大,均随锆刚玉粒度的减小而增大,随锆刚玉加入量的增多而减小;3)在刚玉尖晶石浇注料中适当加入锆刚玉而产生微裂纹,尽管降低了材料的强度和弹性模量,但对提高抗热震性有一定的积极作用。     

电熔镁砂加入量对Al2O3-SiC-C浇注料性能的影响

以电熔棕刚玉颗粒(粒度为5~3 mm、3~1 mm,≤1 mm)、电熔白刚玉细粉(≤0.088 mm)、SiC颗粒(≤1 mm)和细粉(≤0.088 mm)、电熔镁砂细粉(≤0.088 mm)、活性α-Al2O3微粉、SiO2微粉、Si粉和球状沥青为主要原料,以纯铝酸钙水泥为结合剂,配制成电熔镁砂细粉加入量(质量分数)分别为0、3%、6%、9%、12%的出铁沟用Al2O3-SiC-C浇注料,经振动成型、养护、脱模、110℃24 h烘干后,分别于1 100℃3 h、1 450℃3 h热处理,测定处理后试样的体积密度、显气孔率、烧后线变化率、抗折强度、抗高炉渣侵蚀性和抗氧化性,并分析其物相组成和显微结构。结果表明:随着电熔镁砂加入量的增加,试样的显气孔率提高,体积密度、抗折强度和抗氧化性降低,抗渣性变化不大;1 450℃3 h处理后试样物相主要由3C-SiC、6H-SiC、刚玉、方镁石以及反应生成的尖晶石和莫来石组成,且随着电熔镁砂加入量的增加,尖晶石和莫来石的生成量也增加;在侵蚀面附近,刚玉颗粒边缘生成了厚度约80μm的尖晶石层。     

电熔镁砂加入量对刚玉-尖晶石轻质隔热材料性能的影响

以α-Al2O3细粉(≤74μm)、α-Al2O3微粉(d50=2μm)为主要原料,加入5%(w)的ρ-Al2O3微粉(d50=5μm)为结合剂,外加0.3%(w)的发泡剂和2%(w)的六偏磷酸钠减水剂,在1 550℃3 h煅烧后原位制备了刚玉-尖晶石轻质隔热材料,研究了电熔镁砂加入质量分数(0、5%、10%和15%)对刚玉-尖晶石轻质隔热材料物理性能、热导率及显微结构的影响。结果表明:随着电熔镁砂加入量的增加,试样的体积密度逐渐减小,强度先减小后增大,烧后线变化和重烧线变化(1 550℃3 h)由收缩逐渐表现为膨胀,试样在300～900℃下的热导率均降低;通过发泡法制得的刚玉-尖晶石轻质隔热材料气孔分布均匀,呈球形,且随着电熔镁砂加入量的增加,试样的结构疏松,微孔数量增加,但其对大孔的影响较小。综合考虑试样的各项性能,认为电熔镁砂适合的加入质量分数为15%。     

不同铁载体对镁铁铝尖晶石材料性能影响

分别以烧结铁铝尖晶石、电熔铁铝尖晶石、烧结镁铁砂及电熔镁铁砂为铁的载体,在控制试样化学组成接近前提下,按照镁铁铝尖晶石砖生产工艺制备镁铁铝尖晶石砖试样.检测试样的理化性能并采用XRD和SEM对试样的相组成和显微组织结构进行表征.结果表明:以两种镁铁砂为铁载体的试样体积密度高、显气孔率低、常温耐压强度大及热膨胀率小;以电熔铁铝尖晶石、电熔镁铁砂为铁载体的试样具有较高的荷重软化温度.以铁铝尖晶石为铁载体试样中,形成(Mg,Fe) Al2O4相,铁以Fe2+形式存在;以镁铁砂为铁载体试样中,形成Mg(Fe,Al)2O4相,铁以Fe3+形式存在;以烧结铁铝尖晶石、烧结镁铁砂为铁载体的试样显微结构中存在较多微气孔,以电熔铁铝尖晶石、电熔镁铁砂为铁载体的试样显微结构较为致密.     

尖晶石组成和含量对RH浸渍管用方镁石-尖晶石质耐火材料性能的影响

为了研究不同尖晶石组成和含量对RH浸渍管用方镁石-尖晶石质耐火材料性能的影响,以高纯烧结镁砂、电熔镁砂、三种预合成烧结镁铝尖晶石(Al2O3的质量分数分别为50%、66%和78%)为原料制备了方镁石-尖晶石耐火材料试样。研究表明:1)加入尖晶石会降低试样的力学性能和热膨胀系数,但可显著提高试样的抗热震性;2)由于原位生成尖晶石的影响,当加入富铝尖晶石时试样的力学性能和热膨胀系数下降,抗热震性提高;3)加入的尖晶石种类和含量不同,试样的断裂机制有所不同,随着尖晶石加入量的增加以及由富镁尖晶石转变为富铝尖晶石,试样由穿晶断裂转变为沿晶断裂。综合考虑,选择富镁尖晶石且尖晶石加入量(w)为16%~18%时,试样的综合性能较优。     

化学组成对轻烧镁铝尖晶石结构与性能的影响

相比传统电熔镁铝尖晶石和烧结镁铝尖晶石,轻烧镁铝尖晶石晶格畸变大,反应活性高,所制备的铝镁浇注料抗渣渗透性更好。本文以工业氧化铝和轻烧镁砂细粉为原料,在1 600 ℃下烧结合成Al₂O₃质量分数在68%~76%的富镁尖晶石(68%和70%)、正尖晶石(72%)和富铝尖晶石(76%)试样,研究Al₂O₃含量对尖晶石试样常温物理性能、物相组成、晶体结构参数和显微结构的影响。结果表明:Al₂O₃含量的增加提高了试样的显气孔率;富镁尖晶石试样的物相为尖晶石和少量方镁石,其余试样只有尖晶石相;富铝尖晶石的晶格畸变大于富镁尖晶石和正尖晶石,晶粒尺寸和平均孔径小于富镁尖晶石和正尖晶石。     

微孔富镁尖晶石对低碳MgO-C材料性能的影响

分别以微孔富镁尖晶石(5~3和3~1 mm)和电熔镁砂(5~3和3~1 mm)为粗骨料,以<1 mm的电熔镁砂为细骨料,以镁砂粉(≤0.088 mm)、鳞片石墨粉(≤0.088 mm)、金属铝粉(≤0.074 mm)为细粉,以酚醛树脂为结合剂,制备了w(C)=6%的两种低碳MgO-C材料,经220和1 500℃(埋焦炭)热处理后,测定其显气孔率、常温耐压强度、常温抗折强度、加热永久线变化率、抗热震性和抗渣性。结果表明:1)用微孔富镁尖晶石骨料取代普通低碳MgO-C材料中的部分镁砂骨料后,经220和1 500℃热处理后试样的显气孔率均比普通低碳MgO-C试样的大,体积密度均比普通低碳MgO-C试样的小;220℃固化后试样的强度比普通低碳MgO-C试样的小,但1 500℃热处理后试样的强度比普通低碳MgO-C试样的大;1 500℃热处理后试样的加热永久线变化率比普通低碳MgO-C试样的小。2)使用微孔富镁尖晶石骨料代替电熔镁砂骨料能有效提高低碳MgO-C材料的抗热震性,但对低碳MgO-C材料的抗侵蚀性不利。     

Effect of Rapid Solidification on Microstructural Evolution in MgO–MgAl2O4

The response of the MgO–20 and 30 mol% Al₂O₃ compositions to rapid solidification has been studied. The oxides were twin-roller quenched and the resulting flakes were characterized by X-ray diffraction and transmission electron microscopy. The results indicate that metastable extensions of spinel and periclase occurred and the microstructural pathway was determined from the final microstructure. The flakes having MgO–20 mol% Al₂O₃ show a dendritic structure consisting of periclase and spinel. In the MgO–30 mol% Al₂O₃ composition, the liquid transforms to spinel partitionlessly. The spinel is believed to undergo decomposition by a modulation in composition, and the resulting microstructure consists of spinel and periclase. Kinetic and thermodynamic aspects of phase selection have been rationalized based on the metastable extensions of the different phase fields in the phase diagram. It has been proposed that composition fluctuations in spinel are stabilized because of the formation of disordered phases with a continuous range of order parameter on the tetrahedral sublattice.     

Effect of composition,quantity, and synthesis temperature of spinels,and some properties of periclase — Spinel compositions

Conclusions The incorporation of spinel (5–10%) into the composition of the solid solution leads to periclase grain growth and to its sintering. Excess spinel in combinations with periclase over this quantity prevents recrystallization sintering of the specimens.A reduction in the synthesis temperature of most the spinels from 1750 to 1450°C contributes the sintering of the compositions under investigation, and improves their technical properties.In the periclase—spinel compositions the maximum influence on the grain growth and the properties of the specimens is exerted by the temperature conditions used for synthesizing the high-alumina spinels, while the conditions used to obtain the highly chromic spinels, and especially the magnesiochromite, have little or no effect on the technical properties of the fired product.With an increase in the spinel phase concentration from 5 to 30%, and also when there is a change in its composition in the direction from magnesia-alumina spinel to magnesiochromite, such factors as strength, porosity, and spalling are impaired.In the MgO-Mg(Al_1–X, Cr_X)₂O₄ system it is possible to obtain strong, dense, and simultaneously spalling-resistant refractories by using small additions of alumina spinel, synthesized at low temperatures ensuring the completion of the spinel-forming reaction.Translated from Ogneupory, No. 3, pp. 53–57, March, 1971.     

Structure and Microwave Dielectric Properties of (Zn1−xCox)TiO3 Ceramics

Dielectric ceramics in the system (Zn_{1− x} Co _x )TiO₃ ( x = 0–1) were synthesized by the solid-state reaction route. The phase distribution, microstructure, and dielectric properties were characterized by using powder X-ray diffraction analysis, electron microscopy, and microwave measurement techniques. Three phase composition regions were identified in the specimens sintered at 1150°C; [spinel + rutile] at 0 ≤ x ≤ 0.5, [spinel + ilmenite + rutile] at 0.5 < x ≤ 0.7, and [ilmenite] phase at 0.7 < x ≤ 1. For the 0 ≤ x ≤ 0.5 region, the amount of Ti-rich precipitates incorporated into the spinel phase decreased with the Co content at 0 ≤ x ≤ 0.5, with a concomitant increase of the rutile phase. The ilmenite phase appeared for high Co content. The microwave dielectric properties depended on the phase composition and volume according to the three phase regions, where the relative amount of rutile to the spinel or ilmenite determined the dielectric properties. The dielectric constant as a function of Co addition was modeled with a Maxwell mixing rule. An optimum phase distribution was determined in this system with dielectric constant of 25, a Q * f 70 000 GHz, and a low temperature coefficient of the resonant frequency.     

TiO2加入量对固相烧结合成镁铝尖晶石致密化行为的影响

以低品位菱镁矿和工业α氧化铝微粉为主要原料固相烧结合成镁铝尖晶石,探讨TiO2添加剂对合成镁铝尖晶石致密化行为的影响.用X射线衍射(XRD),扫描电镜(SEM)及相关分析软件对烧后试样的相组成和显微结构进行研究,以揭示镁铝尖晶石烧结致密化的过程机理.研究结果表明:添加剂TiO2与形成镁铝尖晶石的置换固溶作用是促进固相合成镁铝尖晶石烧结致密化的重要机理,阳离子空位的产生以及镁铝尖晶石的晶格缺陷,高温下有利于镁铝尖晶石的晶体发育和长大,在空间位阻效应的作用下,达到排除气孔使试样致密化的目的;随着TiO2加入量的增多,镁铝尖晶石的致密化程度也逐渐升高,能够有效的改善制品的烧结性能和显微结构.     

氧化镁-尖晶石浇注料的组成与性能的关系

以中档烧结镁砂、矾土基尖晶石和电熔白刚玉为主要原料,制备了不同基质组成的试样,并研究了浇注料的流动性、强度、永久线变化率、抗渣性和抗热震性。结果表明：基质的组成（特别是Ａｌ２Ｏ３／ＭｇＯ比）对浇注料的抗渣性、线变化率、抗剥落性和热震稳定性有显著影响,通过调整Ａｌ２Ｏ３／ＭｇＯ比可制得综合性能优良的氧化镁－尖晶石浇注料     

Effect of compositional variation and fineness on the densification of MgO–Al2O3 compacts

Single stage densification of magnesia—alumina compacts were studied with MgO to Al₂O₃ molar ratios 1:1 (stoichiometric spinel), 2:1 (magnesia rich spinel) and 1:2 (alumina rich spinel). Attritor milling has been adopted to produce variation in fineness. Milling greatly improved the densification. Densification was found to be easier for the magnesia rich composition and difficult for the alumina rich one. X-ray diffraction patterns showed the expected phases in stoichiometric and magnesia rich spinel. Alumina rich composition showed no free corundum phase on sintering at 1650°C and only spinel phase marks the complete solid solution of excess alumina in spinel at this composition. EDAX analysis also supports the event and also reflects that the impurities are mainly present at the grain boundaries.     

Thermal hydrolysis as a new method of synthesis of the CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> spinel ferrite

A new method has been proposed for synthesizing spinel ferrites, i.e., thermal hydrolysis, which makes it possible to obtain a single-phase product of high purity for a short time. A polycrystalline sample of the CoFe₂O₄ composition has been prepared. The phase composition and morphology of the sample have been investigated and its crystal structure has been refined. The static magnetic characteristics have been measured.     

Range of solid solutions of silica in spinel type phase

Abstract

Al₂O₃–SiO₂ mixed gel of varying compositions has been synthesised by using aluminium nitrate nonahydrate (AR) and tetraethyl orthosilicate (BDH) by coprecipitation technique. Phase evolution studies of these gels have been made by X-ray diffraction technique and ²⁹Si MAS NMR analysis. The lattice parameter of intermediate Al–Si spinel phase has been measured. The calculated data indicate that the composition of spinel phase does not alter irrespective of the composition of mixed gels chosen. Results demonstrate that slightly <28 wt-%SiO₂ is likely to be present as solid solution with γ-Al₂O₃ in Al–Si spinel structure. Mullitisation reactions of mixed gels of compositions on two sides of mullite stoichiometry are described.     

二氧化锆对低品位菱镁矿制备镁铝尖晶石材料组成结构的影响

以低品位菱镁矿与工业氧化铝为原料制备镁铝尖晶石材料,分析研究二氧化锆对以低品位菱镁矿为原料制备的镁铝尖晶石的组成、结晶度、晶胞参数和微观结构的影响,用XRD和SEM对烧后试样的相组成和显微结构进行研究。利用X’pert plus软件对试样中结晶相的相对结晶度进行计算,并对镁铝尖晶石相的晶胞参数进行分析。结果表明:适量引入二氧化锆有利于以低品位菱镁矿与工业氧化铝为原料制备镁铝尖晶石材料;材料中结晶相的结晶度随二氧化锆加入量的增加呈现出先增加后降低的现象;镁铝尖晶石材料中主晶相镁铝尖晶石的晶胞参数及晶胞体积受到锆离子的置换固溶作用的影响;当二氧化锆加入量为1.2%时,镁铝尖晶石的晶胞参数和晶胞体积最大,结构中镁铝尖晶石形成量最大,而玻璃相形成量最小。因此对于以低品位菱镁矿与工业氧化铝为原料制备的镁铝尖晶石材料,二氧化锆的最佳引入量为1.2%。     

Features of the phase transformations in titanium-containing zinc aluminosilicate glasses doped with cobalt oxide

We demonstrated the efficiency of the Raman spectroscopy method in the study of the process of the formation of the amorphous zinc aluminotitanate (ZAT) phase during the phase decomposition of the titanium-containing zinc aluminosilicate glasses doped with cobalt oxide. The quantitative dependences of the variation of the intensity of the Raman bands characteristic for amorphous and crystalline phases on the temperature of the thermal treatment and the cobalt oxide concentration have been obtained. The speed of phase decomposition with the separation of the nanosize crystals of zinc aluminate spinel (gahnite) and ZAT phase increases at low-temperature thermal treatments with increasing cobalt oxide concentration. The addition of cobalt oxide increases the amount of the amorphous ZAT phase separated during phase decomposition and increases its thermal stability during high-temperature treatments. It has been shown that the Co²⁺ ions enter the zinc aluminate spinel (gahnite) crystals precipitated during phase decomposition. It has been supposed that the composition of the residual glass is close to that of the quartz glass and it contains a very small amount of titanium-oxygen tetrahedra.