水泥熟料及碱盐对方镁石-镁铝尖晶石砖的侵蚀行为

对以电熔镁砂、电熔镁铝尖晶石为原料制备的方镁石-镁铝尖晶石砖进行了不同温度的抗侵蚀试验,研究了水泥熟料及碱盐(K2SO4、KCl)对方镁石-镁铝尖晶石砖的化学组成、矿物组成及显微结构的影响,从而研究其对方镁石-镁铝尖晶石砖的侵蚀行为。结果表明:1)水泥熟料对方镁石-镁铝尖晶石砖的侵蚀过程主要是向砖内渗透,侵蚀砖中方镁石及基质M2S生成低熔物CMS而使M2S、方镁石不断溶解,使砖形成致密的变质层,温度越高,渗透和侵蚀作用越剧烈。2)碱盐通过对砖的液相渗透和气相扩散,在砖中与杂质发生化学反应,生成新的气体并挥发,使砖的表层因碱盐的化学侵蚀而疏松,深层因残碱的沉积而致密。3)实际使用中,碱盐在高温层侵蚀砖中的方镁石及结合相而使高温层疏松,使水泥熟料大量渗透和侵蚀而形成致密的变质层;碱盐在低温层的析晶、沉积,使致密的变质层变厚。而致密且较厚的变质层在温度波动时将导致方镁石-镁铝尖晶石产生严重的结构剥落。     

铝镁尖晶石对镁质浇注料性能的影响

针对镁质浇注料在使用过程中抗渣渗透能力差,易剥落等问题,本实验加入铝镁尖晶石对镁质浇注料进行改性研究.实验分为两部分:先将镁砂细粉、镁质添加剂和铝镁尖晶石细粉等机压成型,进行高温热处理,研究其物相组成和显微结构;然后以电熔镁砂为骨料,电熔镁砂细粉、氧化铝微粉、铝镁尖晶石细粉和镁质添加剂为基质,按骨料:细粉=75∶25进行配制,研究铝镁尖晶石加入量对镁质浇注料性能的影响.结果表明:在镁质材料中引入尖晶石,能促进结构致密化;加入9％的铝镁尖晶石的浇注料试样显气孔率低,线变化率小,体积密度大,强度大,抗渣性能最好,由于镁铝尖晶石生成时体积膨胀,使得材料结构致密化;同时能有效吸收渣中CaO及FeOx等成分,减少渣的渗透作用,从而提高了浇注料的抗渣性能.     

钢包渣对轻质方镁石–镁铝尖晶石耐火材料的侵蚀机理

采用多孔方镁石–镁铝尖晶石陶瓷骨料、镁铝尖晶石细粉、镁砂细粉和刚玉细粉等原料制备了尖晶石细粉含量不同的轻质方镁石–尖晶石耐火材料。以钢包渣为侵蚀介质、采用静态坩埚法对材料进行了侵蚀实验,并借助扫描电子显微镜、能谱仪和Fact Sage?热化学软件研究了镁铝尖晶石细粉含量对轻质材料抗渣性能的影响。结果表明:镁铝尖晶石比方镁石具有更强的固溶Fe_2O_3和MnO的能力,能通过吸收渗透渣中Fe_2O_3和MnO增加渗透渣黏度,且当尖晶石细粉含量从0%(质量分数)逐步增大到26.5%时,材料气孔的平均孔径逐渐减小,这些有利于提高抗渣渗透性能;尽管镁铝尖晶石比方镁石更易于溶入钢包渣,但因增加尖晶石含量增强的抗渗透能力,减小了材料与渣的接触面积,减缓了尖晶石向渣中的溶解速率,进而提高了材料的抗渣侵蚀性能。随着尖晶石细粉含量从0%、8.5%、16.3%逐步增加到26.5%,轻质方镁石–尖晶石耐火材料的抗渣性能也逐步提高。     

四种电熔镁砂颗粒对镁碳砖性能的影响

为了探究不同电熔镁砂颗粒对镁碳砖性能的影响，以粒度均为6～3、3～1、1～0.074、≤0.074 mm的97电熔镁砂、97.5电熔镁砂、97.5二钙电熔镁砂、97.5大结晶电熔镁砂4种镁砂为骨料，粒度≤0.074 mm的97.5大结晶电熔镁砂粉料为基质，酚醛树脂为结合剂，-196石墨为碳源，制备了4种镁碳砖试样。按照国标检测了4种镁碳砖试样的体积密度、显气孔率、常温耐压强度、高温抗折强度、抗渣性、抗氧化性以及试样的物相组成和显微结构。结果表明：1)方镁石晶粒大小、高温液相含量、高熔点相是影响镁碳砖试样性能的三大因素。2)方镁石晶粒越大，镁碳砖试样各种使用性能越好。3)高温液相含量是降低镁碳砖试样高温使用性能的主要因素之一。4)高熔点相会增大镁碳砖试样的显气孔率，降低其常温耐压强度和高温抗折强度，对抗氧化性和抗渣性影响明显。     

镁砂与电熔合成铁铝尖晶石-刚玉复合材料的反应

以电熔合成铁铝尖晶石-刚玉复合材料和电熔镁砂为原料制备了铁铝尖晶石-镁铝尖晶石复合材料。检测了各烧后试样的线变化率、体积密度和显气孔率,并用XRD、SEM等研究了镁砂与电熔铁铝尖晶石-刚玉复合材料之间的反应,结果未发现有单一的镁铝尖晶石相生成,在高温下,MgO与铁铝尖晶石-刚玉之间存在互扩散,形成镁铝尖晶石和铁铝尖晶石固溶体;随着镁砂细粉加入量的提高,镁铝尖晶石向铁铝尖晶石中的固溶量加大;当电熔铁铝尖晶石-刚玉复合材料以颗粒加入时,发现在某些铁铝尖晶石颗粒周围存在环形裂纹;随着镁砂加入量的提高,试样的显气孔率下降,体积密度增大。     

LF渣和ρ-Al_2O_3结合铝镁质浇注料的相互作用

以5~3 mm棕刚玉和3~1、≤1 mm板状刚玉为骨料,以0.074 mm电熔白刚玉、0.088 mm电熔镁砂和0.061 mm尖晶石为细粉,以ρ-Al2O3微粉为结合剂,研究了加入质量分数8%的90尖晶石和加入质量分数7%的97电熔镁砂细粉的铝镁质浇注料常温物理性能、抗LF渣的侵蚀和渗透性能。采用SEM对侵蚀后试样进行了显微结构分析,并利用热力学软件Factsage 6.2对侵蚀过程进行了模拟。结果表明:加入质量分数8%的90尖晶石的铝镁浇注料比加入质量分数7%的97电熔镁砂的铝镁浇注料在各温度处理后的常温强度高,显气孔率低,体积密度大,抗LF渣渗透性能优异。铝镁浇注料中引入较多MgO在高温下大量形成原位尖晶石,易造成较大的体积膨胀,对抗渣渗透性能不利,但有利于吸收渣中FeO、MnO,提高渣的黏度,对抗渣侵蚀性能有利。试验结果与热力学软件模拟结果吻合。     

电磁场作用下高铁渣对MgO-C耐火材料的侵蚀

电磁场会促使熔渣中的铁、锰离子与MgO-C耐火材料反应形成锰掺杂镁铁尖晶石相,为进一步研究锰掺杂镁铁尖晶石的生成形貌及特征,采用Fe2O3质量分数为53.62%、CaO与SiO2质量比为0.8的高铁渣,分别在有、无电磁场环境下,对碳质量分数为14%的MgO-C耐火材料进行渣蚀试验。结果表明:感应炉存在电磁场,使熔渣中部分Fe2+/Fe3+与镁砂中Mg2+发生置换形成镁铁尖晶石,其含有少量Mn2+离子;镁铁尖晶石中铁含量从渣蚀层到渗透层急剧降低,锰含量几乎维持不变;侵蚀后试样渗透层较明显。电阻炉无电磁场,则侵蚀后试样没有形成镁铁尖晶石,熔渣中Si、Ca渗透到方镁石晶格中,形成钙镁榄橄石低熔相,将镁砂溶解到熔渣中;渣蚀层有明显的MgAl2O4生成。     

Cr_2O_3对方镁石－尖晶石耐火材料抗渣性的影响

采用电熔镁砂及预合成电熔ＭＡ砂为原料，在高温下烧成方镁石－尖晶石试样，当加入少量铬矿时可提高其热震稳定性及抗渣性。用坩埚法作富ＣａＯ转炉渣对方镁石－尖晶石系耐火材料的侵蚀试验后，采用ＸＲＤ、ＳＥＭ、ＥＤＡＸ、岩相分析等方法分析Ｃｒ_２Ｏ_３对方镁石－尖晶石耐火材料抗渣性的影响。     

烧结温度对合成镁橄榄石性能的影响

以电熔镁砂、二氧化硅微粉为原料,采用固相反应法合成镁橄榄石,研究了不同烧结温度及不同配比对合成镁橄榄石材料性能的影响.研究结果表明:以镁橄榄石的理论配比配料合成镁橄榄石,在温度较低时在镁砂表面形成一层镁橄榄石,随着温度的升高,镁橄榄石层变厚,方镁石颗粒被镁橄榄石层包围;烧结温度从1350℃升到1600℃,试样的显气孔率降低,组织结构变得致密,接近镁橄榄石理论配比的试样综合性能较优.     

轻质氧化镁含量对方镁石-镁铝尖晶石砖性能的影响

以不同粒径的烧结镁砂、电熔镁铝尖晶石、镁铝尖晶石空心球为起始原料,采用固相烧结法制备了方镁石-镁铝尖晶石砖。通过X射线衍射仪(XRD)和扫描电子显微镜(SEM)表征试样的物相组成和微观结构,利用阿基米德排水法测试试样的体积密度和显气孔率,研究轻质氧化镁含量和烧结温度对方镁石-镁铝尖晶石砖性能的影响。结果表明,随轻质氧化镁含量的增加,方镁石-镁铝尖晶石砖显气孔率呈增加趋势,而体积密度变化不明显,试样表现出优异的力学性能。当轻质氧化镁含量为25%(质量分数)时,方镁石-镁铝尖晶石砖的抗折强度最大为9.56 MPa,热导率最低为1.92 W·m^-1·K^-1。显微结构表明骨料和基质结合良好,并能形成微孔状通道。利用其特殊的微孔结构,提高了试样的力学性能和耐腐蚀性,进一步保护方镁石-镁铝尖晶石砖免受碱侵蚀。     

Formation of liquid-phase isolation layer on the corroded interface of MgO/Al2O3-SiC-C refractory and molten steel: Role of SiC

Formation of a dense layer on corroded interface to suppress corrosion is always desired, but it is controlled by numerous environmental conditions. In this work, corroded microstructures of MgO/Al₂O₃-SiC-C refractories in metal bath area of ladle furnace were investigated after industrial trails. A liquid-phase isolation layer in which MgO islands and liquid phases was established on the corroded interface of refractories with 6 wt% coarse/fine SiC-additive. The formed isolation layer against steel/slag attacks led to an approximate 30% improvement in corrosion resistance than that of refractory with 3 wt% fine SiC-additive. More importantly, the liquid-phase isolation layer blocked the direct mass transfer between molten steel and refractories while it decreased exogenous pollution from refractories. SiC-additive affected the formation process of isolation layer by controlling the generation/migration of Mg(g) on refractory' surface. A further formation mechanism of liquid-phase isolation layer was discussed in detail and role of SiC was elucidated.     

Wetting,spreading and corrosion behavior of molten slag on dense MgO and MgO-C refractory

The wetting and spreading phenomena of molten slag were observed in situ on dense MgO and MgO-C refractory substrates. Parameters associated with wetting and spreading of molten slag, such as the contact angle, droplet height, diameter, and volume, were measured and calculated. The microstructure and chemical composition of the corroded dense MgO and MgO-C refractory were studied using SEM and EDS analysis. The droplet volume of molten slag on dense MgO declined faster than that on MgO-C refractory during the first 90?s of the testing period, whereas the droplet volume exhibited little difference across the two cases after 150?s. Molten slag penetrated the dense MgO and MgO-C refractory through grain boundaries and the channels which were formed by the dissolution of MgO. Besides, the slag also penetrated into the MgO-C refractory through the pores and channels formed by the redox reaction between slag and carbon, and a reaction product (Fe) was found at the interface. The dissolution of MgO and redox reactions changed the wetting process and increased corrosion of the MgO-C refractory.     

MgO-Al2O3-C材料服役状态下MgO致密层的形成机理

一种SiC含量为6.0％的MgO-Al2O3-C(MAC)材料被用于精炼钢包包壁部位,表现出优异的抗侵蚀性能,对用后MAC材料的物相组成和显微结构进行分析.结果显示,在MAC材料侵蚀界面形成MgO致密层,提高了MAC材料的抗侵蚀性能.MAC材料内的SiC,一方面与MgO反应形成更多的Mg(g);另一方面,SiC氧化后形成的部分SiO2进入侵蚀层熔渣使熔渣碱度下降,粘度大幅上升,不但提高了MgO在熔渣中的形成速率,而且同时降低了MgO的溶解速率,促进MgO再结晶和MgO致密层的形成.     

Interaction of CaO–FeO–SiO2 Slags with Partially Stabilized Zirconia

Calcia- and magnesia-partially-stabilized zirconia samples were corroded under static and dynamic conditions in three slags from the CaO–FeO–SiO₂ system. Low–basicity and high–FeO slags corroded tht samples by leaching magnesia from the cubic phase in the specimen, causing its destabilization and ultimate dissolution. However, a higher–basicity slag which proved the most corrosive of the three promoted bulk dissolution of the cubic phase instead, the rate of which was controlled by the thickness of the adjacent slag boundary layer. The levels of sample corrosion both at and below the slag line are used to illustrate the effects of experimental variables, including slag composition, specimen density, and slag motion.     

Corrosion of MgO—MgAl2O4 Spinel Refractory Bricks by Calcium Aluminosilicate Slag

Microstructural analysis of MgO—MgAl₂O₄ refractory bricks corroded at 1400–1450°C by calcium aluminosilicate slag reveals secondary spinel, monticellite, merwinite, and MgO as microscopic corrosion products, generally forming in this sequence as the brick is penetrated. The secondary spinel forms an incomplete layer close to (but not at) the MgO grain. Thermodynamic calculations are used to support a detailed model of the corrosion mechanism.     

Electromagnetic field effects on the formation of MgO dense layer in low carbon MgOC refractories

Electromagnetic field (EMF) would speed up the corrosion of low carbon MgOC refractories. Its influence mechanism will be investigated in this paper. The slag-resistance experiments of low carbon MgOC refractories were carried out under the condition of an induction furnace and a resistance furnace, respectively. Low carbon MgOC refractories with carbon of 6% (in mass) and a slag with the basicity (CaO/SiO₂) of around 0.87 were used in the experiments. The slag line of MgOC refractories corroded by the slag under the different conditions were analyzed by X-ray diffractometer (XRD), scanning electron microscope (SEM) and energy dispersive spectrometer (EDS). The results show that in the induction furnace with an electromagnetic field (EMF), no MgO dense layer exists in the interface. However, MgO dense layer could be formed in the interface without any EMF. The formation mechanism of MgO dense layer indicates that the EMF could enhance the solution of MgO and power of Mg (g) discharge. As a result, EMF restrains the formation of MgO dense layer.     

中间包镁质干式工作衬残衬分析

为了探讨中间包熔渣对中间包镁质干式振动料的侵蚀机理,采用化学分析、SEM、EDS、XRD等手段对现场使用40h后的中间包镁质干式工作衬残衬各层的化学组成、显微结构和相组成进行了分析。结果表明在中间包使用过程中,熔渣对中间包工作衬进行渗透;在渗透的同时,熔渣对干式料产生化学侵蚀,干式料对熔渣产生化学过滤作用,方镁石溶于熔渣,都提高了熔渣的熔点和粘度,在干式振动料-熔渣界面形成致密的结构,阻碍熔渣的进一步渗透;此后,熔渣对干式料侵蚀的主要途径是对界面致密层的溶蚀。     

Enhanced performance of low-carbon MgO–C refractories with nano-sized ZrO2–Al2O3 composite powder

Low-carbon MgO–C refractories are facing great challenges with severe thermal shock and slag corrosion in service. Here, a new approach, based on the incorporation of nano-sized ZrO₂–Al₂O₃ composite powder, is proposed to enhance the thermal shock resistance and slag resistance of such refractories in this work. The results showed that addition of ZrO₂–Al₂O₃ composite powder was helpful for improving their comprehensive performances. Particularly, the thermal shock resistance of the specimen containing 0.5 wt% composite powder was enhanced significantly which was related to the transformation toughening of zirconia and in-situ formation of more spinel phases in the matrix; also, the slag resistance of the corresponding specimen was significantly improved, which was attributed to the optimization of pore structure and formation of much thicker MgO dense layer.     

镁锆砖和镁铬砖的抗RH炉渣侵蚀性对比

为取代RH炉用镁铬材料,以电熔镁砂为主原料,分别加入单斜锆、脱硅锆、单斜锆与脱硅锆的混合粉、锆英石制备了ZrO2质量分数分别为15%和20%的镁锆砖,并利用静态坩埚法对比研究了镁锆砖和镁铬砖的抗RH炉渣侵蚀性。结果表明:对于Al2O3含量高且碱度(CaO/SiO2比)大的RH炉渣,镁锆砖抗侵蚀性能优于镁铬砖的;镁锆砖的侵蚀机理是砖中的ZrO2与渣中的CaO迅速反应,形成高熔点物相CaZrO3,能堵塞砖中的孔隙而形成致密保护层,从而阻止钢渣对镁锆砖的进一步侵蚀;而镁铬砖的侵蚀机理是渣中的Al2O3、Fe2O3等R3 和镁铬尖晶石中Cr3 交换,渣与砖反应生成的镁铝尖晶石和镁铁尖晶石使得材料变性,同时由于体积效应使镁铬材料鼓胀开裂,从而导致镁铬砖的严重侵蚀。     

烧结MgO在SiO2—FeO—CaO与FeS—Cu2S熔体界面区的局部侵蚀

采用坩埚法，借助自行设计的高温Ｘ射线透射影视设备，通过Ｘ射线照像主电视观察，研究了烧结ＭｇＯ材料在炉渣（ＳｉＯ２－ＦｅＯ－ＣａＯ）与冰铜（ＦｅＳ－Ｃｕ２Ｓ）界面区局部优先侵蚀过程。发现：ＭｇＯ材料在渣中ＦｅＯ形成致密的（Ｆｅ，Ｍｇ）Ｏ层，紧邻（Ｆｅ，Ｍｇ）Ｏ层形成渣膜，而界面张力流的存在使渣膜产生运动，促进渣膜层中ＭｇＯ的传质过程，加速ＭｇＯ材料的侵蚀，从而引起ＭｇＯ材料在渣－冰铜界面区局部优先侵