稀土氧化物对反应烧结合成镁铝尖晶石的影响

以分析纯MgO(粒度<5 um)和活性仅α-Al2O3微粉(粒度<5 um)为主要原料,分别添加不同量的4种稀土氧化物粉末(Y,,2O3、La2O、Nd2O3和CeO2),共混4 h后,在100 MPa下压制成φ30 mm×20 mm的试样,经110℃干燥6 h后,分别于1 100、1 200、1 300、1 400、1 500和1 650 ℃保温3 h烧成.借助DSC、XRD、SEM和能谱分析研究稀土氧化物对反应烧结合成镁铝尖晶石的影响.结果表明:(1)添加稀土氧化物降低了镁铝尖晶石'的结晶温度,促进了尖晶石的晶粒发育;(2)添加3%Nd2O3的试样经1 650℃保温3 h制备出相对密度为92%的镁铝尖晶石;(3)稀土氧化物促进镁铝尖晶石致密化的机理不同:Y2O3和Nd2O3在试样中形成复杂氧化物活化了晶格,而La2O3和CeO2在试样中主要是形成液相,从而促进了镁铝尖晶石的烧结致密化.     

烧结气氛对合成镁铁铝系复合尖晶石的影响

以电熔镁砂、活性氧化铝、氧化铁和石墨作为原料,按质量比24:61:10:5进行配料,制得φ20 mm×10 mm的试样,在空气气氛、还原气氛(埋碳)、氮气气氛三种不同烧结气氛条件下,1550℃ ×3 h高温处理.采用XRD、SEM、EDS等手段对烧后试样进行了表征.分析结果表明:在三种不同烧结条件下,都合成了铁含量不同的镁铁铝复合尖晶石;在还原气氛烧结条件下,试样中镁铁铝复合尖晶石相中铁是+2价的,在空气气氛和N2气氛烧结条件下,试样中镁铁铝复合尖晶石相中铁是+3价的;试样的晶面间距随铁固溶量的增加而增大;还原气氛烧结条件相比其他两种烧结气氛,晶粒尺寸大且合成率高.     

烧结法合成镁铁铝复合尖晶石

以氢氧化铁、活性氧化铝和轻烧镁粉为原料,外加3％石墨,按质量比37:36:27进行配料,制得φ20 mm×10 mm的试样,经1550℃保温3 h和6 h高温烧成.采用XRD、SEM和EDS等手段对烧后试样的物相组成和显微结构进行表征.结果表明:经过XRD物相分析,保温3 h的试样中物相组成为镁铁铝复合尖晶石相、刚玉相和铁铝尖晶石相三相;保温6 h的试样中存在两种矿物相Mg8.13 Al14.75 Fe1.13O32和Al15.44 Fe6.16 Mg2.32O32;XRD精修处理后,保温6 h的试样中两种镁铁铝复合尖晶石的结构分别为(Mg0.23 Fe2+0.54 Fe3+0.06 Al0.17)Ⅳ(Mg0.03 Fe2+0.065 Fe3+0.02 Al0.88)ⅥO4.000和(Mg0.708Fe0.056Al0.237)Ⅳ(Mg0.154Fe0.0425Al0.8035)ⅥO4.000;通过SEM和EDS微观结构分析,保温3 h的试样由深灰色的FeO·Al2O3和浅灰色的镁铁铝复合尖晶石两种物质组成;保温6 h的试样中FeO·Al2O3和MgO·Al2O3互相扩散,生成两种镁铁铝复合尖晶石,一种呈灰色Mg含量低、Fe含量高,另一种呈亮白色Mg含量高、Fe含量低.     

低品位菱镁矿与工业铝灰制备镁铝尖晶石

以低品位菱镁矿与工业铝灰为原料制备镁铝尖晶石材料。分析讨论了不同煅烧温度对工业铝灰材料组成与微观结构的影响,并进一步研究了煅烧温度对制备镁铝尖晶石材料的组成、镁铝尖晶石相晶胞常数及材料微观结构的影响。用X射线衍射（XRD）和扫描电镜（SEM）对煅烧后试样的物相和显微结构进行研究。利用X′ pert plus软件对试样中主晶相的晶格常数进行计算,比较不同温度煅烧试样的相对结晶度。结果表明：随着工业铝灰煅烧温度的升高,材料中主晶相六方晶型的刚玉相晶胞常数呈现各向异性的变化趋势。低品位菱镁矿与工业铝灰经1 400 ℃高温煅烧可以制备出以镁铝尖晶石为主晶相的镁铝尖晶石材料,该温度煅烧的镁铝尖晶石材料晶粒相对均匀、结构相对致密,主晶相镁铝尖晶石相晶格常数最大。     

反应烧结法合成镁铝尖晶石耐火材料

以合成镁铝尖晶石(分为<350μm、<177μm和<74μm三种粒级)、镁砂(粒度<88μm)和刚玉粉(粒度<44μm)为原料,配制成尖晶石粒度不同,n尖晶石:n镁砂:n刚玉粉分别为80:10:10、60:20:20、40:30:30、30:35:35、20:40:40和10:45:45的试料,分别以100MPa、150MPa和200MPa的压力压制成50mm×20mm的柱状试样,在120℃干燥24h后于1600℃2h烧成,通过反应烧结法合成镁铝尖晶石耐火材料。测量烧后试样的线变化率、显气孔率和体积密度,并利用XRD和SEM分析烧后试样的相组成和显微结构。试验结果表明:随着镁砂和刚玉粉含量的增加以及尖晶石原料粒度的增大,烧后试样的线收缩率和体积密度减小,显气孔率增大;随着成型压力的增大,试样的线收缩率和显气孔率减小,体积密度增大;采用粒度<177μm的尖晶石原料,按n尖晶石:n镁砂:n刚玉粉=20:40:40的比例配料,在200MPa压力下成型,经1600℃2h烧成,可获得显气孔率为16.3%,烧成线收缩率为0.42%的镁铝尖晶石耐火材料。     

利用铝铬渣与废弃镁碳砖合成镁铝尖晶石材料

以铁合金厂铝铬渣和钢厂废弃镁碳砖为主要原料,通过固相烧结反应合成MgAl2O4材料,研究分析铝铬渣与废弃镁碳砖细粉比例关系对合成MgAl2O4材料组成和结构的影响.用XRD、SEM及Rietveld quantification软件对材料中结晶相组成和结构进行表征.结果表明:铝铬渣和废弃镁碳砖细粉经1500℃保温2h煅烧,可以合成出镁铝尖晶石材料.当镁碳砖含量为40％,铝铬渣为60％时,合成材料微观结构中出现典型的镁铝尖晶石八面体形貌特征,结晶相发育完整,结构致密,镁铝尖晶石含量达到94％.     

反应烧结铁铝尖晶石添加量对镁铁铝尖晶石耐火材料性能影响

以反应烧结铁铝尖晶石和镁砂为原料,研究了添加1％、3％、5％、7％、9％和11％反应烧结铁铝尖晶石对制备镁铁铝尖晶石耐火材料的性能影响。利用XRD分析试样的物相组成,SEM观察试样的微观结构。结果表明：在1％～11％范围内,随着铁铝尖晶石添加量的增加,镁铁铝尖晶石耐火材料的热震稳定性和挂窑皮性能提高,但荷重软化温度降低;铁铝尖晶石加入量为5％时,镁铁铝尖晶石耐火材料有较大的体积密度、较高的常温耐压强度和较小的显气孔率。     

铝源种类对熔盐法合成镁铝尖晶石的影响

分别以分析纯Al2 O3和AlCl3为铝源,以分析纯MgO为镁源,在NaCl和KCl混合熔盐介质中,分别在1000、1100、1200和1250℃保温3 h合成了镁铝尖晶石粉体,研究了试样的物相组成、微观形貌和化学组成.结果表明:1)温度的升高有利于MgAl2 O4的形成和结晶.2)以Al2 O3为铝源合成的镁铝尖晶石在Al2 O3原料表面成核生长,晶体结构随着温度的升高趋于完善;以AlCl3为铝源合成的镁铝尖晶石颗粒粒径约为3μm且呈正八面体结构.     

Role of different rare earth oxides on the reaction sintering of magnesium aluminate spinel

Role of three rare earth oxides, viz., La₂O₃, CeO₂ and Yb₂O₃ on reaction sintering of magnesium aluminate spinel having molar ratio of MgO:Al₂O₃?=?1:2 from its solid oxide precursors was investigated in static and dynamic heating conditions. Effect of these additives (3?wt%) on densification behavior, phase assemblage and microstructure development were studied in the temperatures of 1500–1700?°C. Yb₂O₃ enhanced the sintering of spinel, while La₂O₃ and CeO₂ negatively impacted the sintering of magnesium aluminate spinel which can be discerned from the shrinkage curve of TMA as well as from static firing regime. This is ascribed to the formation of secondary phases in La₂O₃ and CeO₂ containing samples which have different crystalline structures to that of spinel. This anisotropy due to different crystallinity hindered the pore shrinkage and pore removal and thereby retarded the densification. Whereas, the cubic structure of the secondary phase formed in Yb₂O₃ containing sample which is isotropic with the crystalline orientation of the parental spinel phase assisted the densification.     

Low-temperature sintering of magnesium aluminate spinel doped with manganese: Thermodynamic and kinetic aspects

This work describes the role of manganese (Mn) as a sintering aid for magnesium aluminate (MgAl₂O₄) nanoparticles. Mn-doped MgAl₂O₄ nanoparticles, synthesized by coprecipitation method, showed increased surface area when contrasted to undoped MgAl₂O₄. Fast firing of compacted-doped nanoparticles achieved high degree of densification at temperatures as low as 1100°C with very moderate grain growth, resulting in average sizes at the nanoscale (~60 nm). Differential scanning calorimetry was used to quantify the exothermic heat effects of sintering, which combined with quantitative microstructural evolution analysis enabled calculation of both surface and grain boundary energies. The results revealed that Mn effectively reduces the surface and grain boundary energies which led to dihedral angle broadening and consequently increased sintering stress. Experimental data also revealed a concomitant decrease in the activation energy of sintering with Mn doping which dropped from 644 kJ/mol for undoped MgAl₂O₄ to 285 kJ/mol, informing Mn acts as a sintering aid in a thermokinetic manner.     

Effect of Yb2O3 and TiO2 on reaction sintering and properties of magnesium aluminate spinel

Magnesium aluminate spinel with an initial MgO: Al₂O₃ molar ratio of 2:1 was prepared from its constituent oxides through a solid-state sintering process at temperatures ranging from 1550 to 1700 °C in a normal air atmosphere. The effect of varying amount (0.25–1.0 wt%) of TiO₂ and Yb₂O₃ on densification, phase assemblage, mechanical, thermo-mechanical properties and microstructure of magnesia-rich spinel were investigated under static heating condition. The addition of TiO₂ and Yb₂O₃ favours the densification of magnesia-rich spinel, which is discernible up to 1650 °C. This beneficial effect may be attributed to the development of the secondary phase and formation of solid solution due to the dissolution of the additive ions in the spinel structure. A marginal increase in the average grain size of the samples along with a narrower grain size distribution occurred with the incorporation of both the additives. Both the additives improved the mechanical properties of the magnesia-rich spinel; however, better room temperature flexural strength was achieved with Yb₂O₃ as compared to TiO₂ addition. For the samples sintered at 1550 °C, 1.0 wt% Yb₂O₃ addition resulted in 30% increase in flexural strength; however, same amount of TiO₂ addition increased the strength by 20%. In case of thermal shock resistance, 1.0 wt% TiO₂ and 0.25 wt% Yb₂O₃ addition demonstrated promising result among all the samples.     

Gel-casting of transparent magnesium aluminate spinel ceramics fabricated by spark plasma sintering (SPS)

In this paper, a transparent magnesium aluminate spinel ceramic was fabricated through the newest colloidal gel casting method, using a synthetic powder with the average particle size of 90 nm and Isobutylene-Maleic Anhydride (ISOBAM) additive. ISOBAM served as both a dispersant and a gelation agent to achieve a dense body. Also, the suspension rheological behavior was optimized by the solid loading of 85 wt%, the additive content of 0.7 wt%, and the gelation time of 350 s. This led to a green body with a density equal to 65% of theoretical density and the green strength of 14.48 MPa. The results revealed that the reduction of porosity and the uniform distribution of pores in the green body (smaller than half of the initial powder particle size, 35 nm), as accompanied by spark plasma sintering (SPS), resulted in the final body density of 99.97%, as well as the high in-line transmittance of 86.7% at the wavelength of 1100 nm.     

烧结合成致密尖晶石的试验研究

采用粒度≤0.058mm、MgO质量分数为96.28%的轻烧镁砂和粒度≤0.043mm的αAl2O3为原料,分别在50MPa、100MPa、150MPa和200MPa的成型压力以及1600℃、1650℃、1700℃、1750℃和1800℃的烧成温度下进行合成尖晶石的试验研究。结果表明:通过控制合理的工艺参数,特别是m(MgO):m(Al2O3)的比约为1:1,成型压力约100MPa,烧成温度>1700℃时,可一步煅烧制得体积密度>3.30g·cm-3、尖晶石含量较高的致密镁铝尖晶石。     

Direct measurement of interface energies of magnesium aluminate spinel and a brief sintering analysis

Surface and grain boundary energies are key parameters for understanding and controlling microstructural evolution. However, reliable thermodynamic data on interfaces of ceramics are relatively scarce, limiting the realization of their relevance in processes such as sintering and grain growth. In this work, the heat of sintering itself was used to quantify both surface and grain boundary energies in MgAl₂O₄ spinel. Nanoparticles were compacted and heated inside a Differential Scanning Calorimeter (DSC) when densification and grain growth were observed. The evolved heat signal was quantitatively attributed to the respective microstructural evolution in terms of interfacial area change, allowing determination of average surface and grain boundary energies for MgAl₂O₄ as 1.49 J m⁻² and 0.57 J m⁻², respectively. The data was then used to interpret the thermodynamics involved in density and grain growth during isothermal sintering of MgAl₂O₄.     

Transparent magnesium aluminate spinel: Effect of critical temperature in two-stage spark plasma sintering

The discolouration of magnesium aluminate spinel caused by carbon contamination is a main drawback of fabricating transparent bodies by spark plasma sintering (SPS). In this study, a two-stage heating rate profile was used to produce transparent MgAl₂O₄ without using sintering aids by SPS at 1250°C. The effect of critical temperature (Tc), at which the heating rate is decreased, on transparency and carbon contamination was investigated: higher critical temperature resulted in higher contamination. Non-uniform densification indicated that fast heating results in a hot-zone formation in the centre of sintered pellets; the higher temperature of centre favoured reaction of graphite die with spinel and formation of disordered carbon structures in residual pores.     

含镁铝尖晶石的铝酸盐水泥的制备与应用

按天然白云石(≤0.1mm)与工业氧化铝粉(≤0.088mm)的质量比为45∶55配料,经混合、成型和烘干后,于1600℃3h煅烧,细磨烧结体得到含镁铝尖晶石的新型铝酸盐水泥。测量了新型铝酸盐水泥的凝结时间、耐火度以及用其所结合高铝矾土制成的耐火浇注料的早期强度;利用XRD、SEM和EDS分析了新型铝酸盐水泥的物相组成及其形貌和分布,同时采用静态坩埚法对比了新型铝酸盐水泥和纯铝酸钙水泥结合刚玉浇注料的抗渣性差异。结果表明:新型水泥的物相组成为镁铝尖晶石(MA)、一铝酸钙(CA)和二铝酸钙(CA2),且这3个物相的分布较为均匀;新型水泥的凝结时间正常,耐火度高于纯铝酸钙水泥;用新型水泥制得的刚玉浇注料抗渣性好;其原因是新型水泥组成中引入了镁铝尖晶石相,而镁铝尖晶石具有较高的熔点和抗熔渣侵蚀能力。