MgAl2O4透明陶瓷粉体的研究进展

透明镁铝尖晶石陶瓷的制备,对粉体有特殊的要求.高纯、超细、分散性好、高活性的粉体是制备镁铝尖晶石透明陶瓷的首要条件.本文以制备镁铝尖晶石透明陶瓷为目标,从粉体的纯度和粉体颗粒特征两方面分析了粉体的性能对制备透明镁铝尖晶石陶瓷的影响,介绍了几种可用于制备镁铝尖晶石透明陶瓷粉体的方法,分析比较了每种方法的优缺点.     

MgAl2O4催化正丁醛羟醛缩合反应性能的稳定性研究

采用共沉淀法制备了MgAl_2O_4催化剂,分别在高压釜和固定床反应器上评价了其催化正丁醛羟醛缩合反应的性能。考察了MgAl_2O_4催化剂的稳定性,采用XRD、FT-IR、能谱仪(EDS)和电感耦合等离子体光对光谱仪(ICP-OES)对使用前后的MgAl_2O_4催化剂进行了表征。结果表明,MgAl_2O_4对正丁醛羟醛缩合反应具有较好的催化活性,并且不存在与副产物水发生水合副反应的问题,但MgAl_2O_4催化剂表面容易发生积碳而导致失活。     

添加剂对喷雾冷冻干燥MgAl2O4粉体性能的影响

以聚乙烯醇(PVA)和聚乙二醇(PEG)作为添加剂,采用喷雾冷冻干燥技术制备MgAl2O4造粒粉体.通过振实密度测量仪、扫描电镜、万能试验机等设备系统研究了不同PVA和PEG添加量下造粒粉体的流动性、颗粒形貌、粒径分布及颗粒强度等性能.通过粉体成型和烧结过程,分析了造粒粉体性能对素坯密度、微观结构和陶瓷光学质量的影响.结果 表明,添加PVA和PEG造粒粉体制备的素坯在预烧过程可以避免晶界大气孔的生成,有利于通过热等静压处理消除残余气孔.添加PEG样品的气孔尺寸较小,短波范围内的透过率提高.添加3wt％PVA和PEG造粒粉体制备的MgAl2O4透明陶瓷在400 nm波长处的透光率分别为76.3％和77.1％,明显高于无添加剂的样品.     

氮气气氛下Al对SiC-MgAl2O4复合材料物相和结构演变的影响

以SiC、MgAl₂O₄细粉为主要原料,分别添加质量分数为1%、3%、5%、7%、9%和12%的金属Al,置于流动氮气中,在1 500 ℃下保温5 h烧成得到SiC-MgAl₂O₄复合材料,对烧后试样进行XRD、SEM及EDS分析。结果表明,1 500 ℃高温烧结后,材料体系发生一系列复杂反应,试样中物相均以β-SiC、MgAl₂O₄、氮化物和sialon相为主。部分金属Al在高温下氮化形成氮化铝,并参与sialon相和MgAlON形成的反应。尖晶石则转变为富铝尖晶石和MgAlON两相共存。随着Al含量的增加,尖晶石中固溶铝含量达到极限时,析出α-Al₂O₃。Al含量的增加使得结合相Si-Al-O-N的形貌发生变化,由板带状向板柱状过渡,最终发育成形貌较为清晰的板层状。经SEM-EDS分析,sialon相中固溶一定量的Mg元素,为sialon多型体Mg-sialon相。     

SiC加入量对MgO-MgAl2O4-SiC材料性能的影响

以电熔镁砂颗粒(3~1 mm,≤1 mm)、电熔镁砂粉、镁铝尖晶石粉和SiC粉为原料,研究了SiC加入量(w)分别为5%、10%、15%、20%时对MgO-MgAl2O4材料经1 100℃和1 500℃保温3 h后的物理性能、抗氧化性能以及1 600℃保温3 h后的抗渣性能的影响。结果表明:加入SiC有利于提高材料的烧后强度。材料经1 100℃处理后,SiC几乎完全氧化;1 500℃烧后表明,当SiC加入量不超过10%时,抗氧化性能随着SiC加入量增加而增强;超过10%时,反而降低;1 600℃烧后表明,随着SiC加入量的增加,试样抗渣性能有所下降。对1 500℃烧后试样进行XRD和SEM分析发现,在试样氧化层中生成大量的镁橄榄石。     

助熔剂对固相微波法合成MgAl2O4∶Eu发光性能的影响

采用固相微波法研究了助熔剂对MgAl2O4∶ Eu3+荧光粉发光性能的影响.利用XRD和荧光光谱仪对合成产物的物相和发光光谱进行研究,分别探讨了助熔剂的类型及含量对发光性能影响.结果表明,加入NaF,CaF2,B2O3和GeO2为助熔剂时可得到红色发光材料;MgAl2O4∶Eu3+荧光粉主发射峰位于612 nm处,对应Eu3+的5D0→7 F2电偶极跃迁,次强发射峰位于589 nm处,为Eu3+的5D0→7F0的跃迁,Eu3+离子处于非对称中心格位.相对于氟化物,氧化物助熔剂有助于提高样品的发光强度,其中,以B2O3为助熔剂时荧光粉的发光强度最高,其最佳掺杂量为4.5wt％.     

AlON的氧化行为及其与MgO和MgAl2O4的作用

利用TG DTA和XRD研究了氧氮化铝(AlON )在高温下的氧化行为及其与MgO和MgAl2 O4 的作用。结果表明 :AlON在 85 0℃左右开始氧化 ,1170℃左右氧化最为剧烈 ;MgO和MgAl2 O4 在 12 0 0℃都能与AlON形成固溶体 ,且后者更易形成 ;形成固溶体对AlON的氧化有一定的抑制作用。     

利用微波固态反应合成MgAl2O4尖晶石粉

通过微波固态反应，在家用微波炉(频率：2．45GHz，功率：700W)中，由氢氧化三铝和苛性MgO，在有10wt％～50wt％炭黑(以原料混合物总量为准)时，合成了化学计量MgAl2O4尖晶石粉(MWSSR粉)。业已发现，在100min内，20％的C就足以生成尖晶石含量为82％的粉末，在相同时间内，50％的C能生成尖晶石含量为93％的粉末。在常规固态反应中，为了获得相同尖晶石含量(如93％)的粉末，     

透明MgAl2O4晶须的制备与表征

本文采用MgO粉和金属Al粉为原料,在氮气气氛下制备MgAl2O4晶须,研究了TiO2、SiO2或Cr2O3等供氧添加剂和制备条件对晶须合成率的影响并分析了晶须的物相组成和结构.结果表明:最佳MgO/Al=2/3;添加SiO2或Cr2O3不利于晶须合成;添加TiO2对合成晶须有促进作用,最佳TiO2加入量为40%;采用氧化铝坩埚比采用釉面陶瓷坩埚好,最佳保温时间为6 h.合成的晶须为MgAl2O4,空间群Fd3M,晶格常数a=b=c=0.8083 nm,MgO 28.3%,Al2O3 71.7%;晶须呈透明柱状,最大长度为20～30 mm,长径比20～400.     

TiO2含量对镁铝尖晶石烧结性能的影响

以分析纯氧化镁、氧化铝、氧化钛为原料,按氧化镁与氧化铝质量比28.33∶71.67配料,在合成体系中分别引入质量分数为0、0.5％、1％、2％、4％、6％、8％和10％的氧化钛,在钼丝炉中1600℃保温2h,烧结法合成镁铝尖晶石.用X射线衍射、扫描电子显微镜和能谱对烧后试样进行分析.结果表明:引入适量的TiO2可显著提高镁铝尖晶石的烧结性能;当TiO2含量低于4％时,随着TiO2的含量增加,试样的线变化率减小,显气孔率下降,体积密度增大,常温耐压强度增大.TiO2的引入提高了镁铝尖晶石晶体空位浓度,活化了晶格,促进镁铝尖晶石的烧结.当TiO2含量高于4％时,试样的线变化率、显气孔率和体积密度没有显著变化,常温耐压强度有所下降;尖晶石晶粒尺寸没有明显变化,且生成了一定量的Mg0.6Al0.8Ti1.6O5,阻碍了镁铝尖晶石之间的接触,影响镁铝尖晶石烧结性能的提高.     

Combustion synthesis of C/MgAl2O4 composite powders using magnesium oxalate as carbon source

In order to solve the bottleneck problems including uniform distribution, and oxidation resistance of nano carbons in oxide ceramics, C/MgAl₂O₄ composite powders were prepared with MgC₂O₄·2H₂O, MgO₂, Al₂O₃, and Al as raw materials via combustion method under argon atmosphere. The maximum adding amount of MgC₂O₄·2H₂O is 34.34 wt%. The phase compositions and microstructures of combustion products were characterized through X-ray diffraction (XRD), scanning electron microscope (SEM)/EDX, and Raman spectroscopy. The results showed that the phases of products are mainly composed of MgAl₂O₄ and carbon. The prepared MgAl₂O₄ has granular and rod-like morphologies, and the free carbon (1.172 wt%) exists between particles of MgAl₂O₄. Moreover, the addition of FeC₂O₄ as catalyst in raw materials ratio would be beneficial for improving crystallization of in situ carbon generated in the products. The oxidation activation energy of the prepared C/MgAl₂O₄ composite powders was calculated as 143.01 kJ/mol which was 22.17% higher than that of carbon black/MgAl₂O₄ powders (117.06 kJ/mol), suggesting that the C/MgAl₂O₄ composite powders prepared by combustion synthesis have excellent oxidation resistance.     

Growth-microstructure relationship in MgO-MgAl2O4 eutectic fabricated by micro-pulling down method with MgAl2O4 seed crystals

The MgO-MgAl₂O₄ eutectic was directionally solidified via micro-pulling down method in the form of rods with 2–3 mm diameter. MgAl₂O₄ single crystals (with <111> orientation) were used as crystallization seeds. At low pulling rates, especially 0.15 mm/min triangle-like cross-section was observed, which was linked to the eutectic MgAl₂O₄ following the crystallographic direction of the seed. MgO precipitates in the form of lamellae and rods with median equivalent diameter ranging from 0.19 to 0.85 μm, depending on the pulling rate. The preferred crystallization direction was <111> for both phases, however notable traces of other directions, e.g. <100>, <110> and <331> were found as well.     

铝镁双醇盐制备MgAl2O4尖晶石陶瓷超滤膜

Spinel (MgAl2O4) ultrafiltration membranes were prepared on porous α-Al2O3 plates via the sol-gel route. Mg-Al double alkoxide [MgAl2(iprO)s] was first synthesized as the precursor, then hydrolyzed and peptized in aqueous solution. The gel layer was coated from the colloidal sol on the intermediate layer (α-Al2O3), which was formerly prepared to modify the porous substrate, and then thermally treated at 900℃. The processing parameters such as pH, temperature and sol composition during the sol preparation were optimized for controlling particle size. The pore size of the 2μm thick top layer is about 13 nm as estimated by both the BSA (Bovine Serum Albumin)retention test and an empirical equation.The water permeability of the obtained spinel membrane is 55～143 kg/(min.cm2.Pa).     

Self-segregation and solubility in nonstoichiometric MgAl2O4 nanoparticles

Magnesium aluminate spinel (MAS) has a wide range of technological applications owing to its exceptional mechanical properties and good chemical stability. MAS phase diagrams indicate that only stoichiometric MgAl₂O₄ is stable at ∼25°C and Mg²⁺ and Al³⁺ exhibit solubility in nonstoichiometric MAS only at temperatures higher than ∼1200°C. In this study, the synthesis of nonstoichiometric single-phase spinel nanopowders at low temperatures is reported, and the role of the chemical distribution of Al³⁺ and Mg²⁺ excess on the stability of these nanopowders is examined. We performed selective lixiviation to examine the surface segregation of Mg²⁺ and Al³⁺ in nonstoichiometric MAS to investigate its effect on interfacial solubility and consequently the stability of nonstoichiometric MAS. Furthermore, we plotted an experimental phase diagram of nano MAS that predicts the crystallite size limits for the nonstoichiometric single-phase MAS.     

化学共沉淀法制备镁铝尖晶石粉末的研究

以ＭｇＣｌ２·６Ｈ２Ｏ和ＡｌＣｌ３·６Ｈ２Ｏ为主要原料,利用化学共沉淀法制备ＭｇＯ－Ａｌ２Ｏ３系中唯一稳定的二元化合物ＭｇＡｌ２Ｏ４粉末。与机械球磨混合法相比,湿化学法制备的均匀超细ＭｇＡｌ２Ｏ４粉末,具有纯度高、比表面积大、且活性高、易于较低温度（９００℃）下煅烧获得等特点。     

Improved properties of low-carbon MgO-C refractories with the addition of multilayer graphene/MgAl2O4 composite powders

The paper investigated the effects of different amounts (0%, 3%, 6%, 9%) of in situ multilayer graphene/MgAl₂O₄ composite powders on the slag resistance, thermal shock resistance, and oxidation resistance of low-carbon MgO-C refractories. Comparing with commercial MgAl₂O₄, the MgAl₂O₄ in in situ multilayer graphene/MgAl₂O₄ composite powders has higher lattice strain of crystal, which can trap more Mn and Fe ions, resulting in the better slag resistance. The oxidation decarbonation layer of MgO-C specimen with 3% composite powders is 9.71 mm, which is lower than not only the specimen with other contents but also specimen containing carbon black/MgAl₂O₄ powders. Moreover, the residual strength ratio of the specimen C/MA-3 was 47.47%, which is 28.5% and 8.08% higher than specimens with no additive and with carbon black/MgAl₂O₄ powders, respectively. Both improving thermal shock and oxidation resistance properties are related with the unique nano structure, multilayer graphene in situ formed between MgAl₂O₄ grains, of added composite powders. The former is due to higher strain energy consumed by multi-deflection of cracks inside the multilayer graphene/MgAl₂O₄ composite powders. And the latter is due to the higher energy of oxidation activation of multilayer graphene/MgAl₂O₄ composite powders due to effective protection of multilayer graphene by MgAl₂O₄.