还原气氛下SiO2在Al2O3-Al-C材料中作用机理研究

本试验借助金属过渡塑性相理论,在Al2O3-C系耐火材料中引入中金属铝粉和SiO2粉,研究空气气氛埋碳条件,不同烧成温度下Al、SiO2的高温反应行为及产物的变化.对烧成后的试样进行XRD物相检测及SEM显微结构分析,发现不添加SiO2的试样中单质Al已经不存在,在材料的气孔中生成大量A1N纤维;添加SiO2的试样中单质A1和SiO2都已经不存在,且形成了大量纤维及六方片状晶体,经XRD及EDS检测,确定该物相为SiAl5O2N5.     

镁铝尖晶石-钇铝石榴石复相材料的制备研究

以富铝尖晶石为原料,分别加入Y2O3细粉、Y2O3和α-Al2O3混合粉、钇铝石榴石前驱体,制备尖晶石-钇铝石榴石复相材料.研究了氧化钇的不同引入方式和烧结温度对尖晶石-钇铝石榴石复相材料烧结性能的影响,并通过XRD、SEM等手段对其物相组成和显微结构进行表征.结果表明:向富铝尖晶石中分别加入Y2O3细粉、Y2O3和αt-Al2O3混合粉、钇铝石榴石前驱体,均能制备出尖晶石-钇铝石榴石复相材料;当Y2O3和α-Al2O3混合粉的加入量为6;,经1750℃烧结3h后,所制备的试样的致密化程度较高,体积密度达3.34 g/cm3,显气孔率为8.0;,制备的试样中镁铝尖晶石、钇铝石榴石晶粒发育较好.     

Al2O3对氧化镁陶瓷烧结性及抗热震性的影响

本文以纳米氧化镁,硫酸铝和氨水为原料,采用共沉淀法制备表面由Al2O3前驱体包覆的MgO陶瓷.对烧后试样进行常温烧结性能和抗热震稳定性能检测.试样相组成的确定和显微结构分析是分别通过XRD和SEM手段来进行的.着重研究了由前驱体转化得到的Al2O3作为烧结助剂对氧化镁陶瓷的烧结性及抗热震性的影响.结果表明:加入Al2O3后,试样中生成了镁铝尖晶石,提高了试样的致密度,最大可达到3.48 g/cm3.在试样的显微结构中出现了大量微裂纹和粘连区域,一定程度上优化了试样的抗热震稳定性.     

稻壳灰制备Si3N4/SiC复合粉体的研究

本文主要研究不同的SiO2∶C比例对所制备Si3N4/SiC复合粉体组成的影响.采用生物质能电厂所产生的工业废弃物稻壳灰和炭黑为原料,以稻壳灰中的SiO2为标准与炭黑配成不同比例的粉料,在氮气气氛下经1550℃保温3h热处理.采用X射线衍射(XRD)和扫描电子显微镜(SEM)分析烧后试样的物相组成和显微结构.结果表明:当SiO2∶C为5∶6时得到的产物为Si3N4/SiC复合粉体;当SiO2∶C为5∶2和5∶3时,得到产物的组成为SiC、O'-Sialon和β-Si3N4.     

熔制坩埚对CaO-Al2O3-MgO-SiO2系矿渣微晶玻璃结构与性能的影响

以白云鄂博二次选后尾矿、高炉渣和粉煤灰为主要原料,采用熔融法分别在氧化铝坩埚和石墨坩埚熔制制得CaO-Al2O3-MgO-SiO2 (CAMS)系微晶玻璃,利用DSC、XRD、SEM、EDS、ICAP、XPS等测试手段,研究了不同坩埚熔制对微晶玻璃成分、显微结构及性能的影响.研究表明:高温玻璃熔液对氧化铝坩埚的侵蚀作用及石墨坩埚的还原作用,使基础玻璃中Al2O3和Fe2O3含量发生较大变化,氧化铝坩埚熔制制备的基础玻璃有一个析晶峰,温度为905 ℃,对应的微晶玻璃主晶相为含铁透辉石Ca(Mg,Al) (Si,Al)2O6,而石墨坩埚熔制制备的基础玻璃出现两个析晶峰,温度分别为866℃和805℃,对应的微晶玻璃主晶相透辉石Ca(Mg,Al) (Si,Al)2O6和次晶相柯石英SiO2,由于以上原因导致制备的微晶玻璃在显微结构及理化性能上也存在一定的差异.     

熔盐环境下热障涂层新材料Mg2SiO4的高温腐蚀研究

采用高温固相反应法合成了Mg2 SiO4陶瓷粉末,冷压成型后烧结成陶瓷块材.盐涂法制备V2 O5涂覆的样品,利用马弗炉在950℃空气气氛下保温不同时间.对热腐蚀后的样品进行表面形貌、截面特征的表征,并对Mg2 SiO4的高温熔盐腐蚀机制进行分析研究.结果表明:熔融的V2 O5对Mg2 SiO4陶瓷试样产生两种形式的腐蚀降解作用,即溶解-沉淀机制形成腐蚀产物Mg2 V2 O7和SiO2以及沿晶界腐蚀为主的渗透腐蚀作用.     

添加剂对超重力下燃烧合成Al_2O_3/ZrO_2(4Y)的影响

基于超重力下燃烧合成Al2O3/ZrO2(4Y),通过调整SiO2引入量,研究添加剂对材料显微结构、形态与性能的影响。结果表明:添加SiO2不改变复合陶瓷相组成,但随SiO2引入量增加,陶瓷共晶团发生胞状向棒状形态的转变,且其长径比增大、体积分数下降。陶瓷致密性随SiO2引入量增加而增大,陶瓷硬度与弯曲强度则在SiO2引入量为6%时均呈现最大值,而陶瓷断裂韧性在SiO2引入量为4%时,因裂纹偏转与桥接增韧效应显著而获得最高值。     

白光LED用铽铕共掺镓酸锌微晶玻璃的制备、结构与发光性能研究

采用溶胶-凝胶法制备了Tb3+/Eu3+共掺ZnGa2O4微晶玻璃,研究了热处理温度对材料显微结构的影响以及不同稀土离子掺杂材料的发光性能.结果表明干凝胶样品在800～900℃温度热处理后可得到透明的含尖晶石结构ZnGaO4微晶玻璃,在1000℃热处理时由于SiO2非晶基体晶化析出三方Zn2SiO4与六方SiO2晶相导致样品失透.在微晶玻璃中具有ZnGa2O4纳米晶到Tb3+与Eu3+的能量传递.在900℃热处理Tb3+/Eu3+∶ZnGa2O4微晶玻璃样品中,Tb3+与Eu3+分别发射绿光和红光,并与ZnGa2O4纳米晶发射的蓝光组合成近白光发射.     

固相反应法制备CaO-B2O3-SiO2介电陶瓷及性能研究

Ca(OH)2、H3 BO3、SiO2作为初始原料应用固相反应法在低烧结温度下制备CaO-B2 O3-SiO2(CBS)介电陶瓷材料.研究了不同烧结温度和B2 O3含量对陶瓷的致密性、介电和机械性能的影响.X射线衍射(XRD)分析表明,在875℃至975℃的温度范围内,存在主要的结晶相为β-CaSiO3和少量SiO2相.结果表明,最佳烧结温度为950℃,B2 O3含量的增加会使得烧结温度区间变窄,发生"硼反常"现象,并且致密度、介电性能和机械性能也会随之先减小后增大.并且过量的B2 O3不利于主晶相β-CaSiO3的析出.当B2 O3含量为25mol;时,在950℃烧结的试样具有最好的抗弯强度:σf=319 MPa.当B2 O3含量为5mol;时,在950℃烧结的试样具有最好的致密性和介电性能:密度为2.6869 g/cm3,εr=6.12,tanδ=7.4×10-4,ρv=6.64×10-4Ω·cm(1 MHz).     

MgO/Al2O3比率对MgO-Al2O3-4mol％SiO2复相陶瓷热震行为和微观结构的影响

本文采用MgO和Al2O3作为主要原料,SiO2为掺杂剂,MgO-Al2O3-4mol％ SiO2复相陶瓷材料通过无压烧结的方式被制备.烧后试样通过相分析和热循环次数进行表征,场发射扫描电镜也被用来观察烧后试样热震前后的微观结构.研究在掺杂4mol％ SiO2的条件下,不同MgO/Al2O3比率对复相陶瓷材料的微观结构和热震稳定性能影响.结果表明:最佳的MgO/Al2O3比率为2/1,烧后试样的相组成中除了方镁石相还包括镁铝尖晶石和镁橄榄石相,试样具有更好的热震稳定性,接近20次的热震次数才可以使试样发生断裂.观察MgO/Al2O3比率为2/1烧后试样的微观结构,其细晶化和多晶化结构明显,尖晶石以网状结构相互连接,其烧后试样经热震后,微观裂纹出现偏转和分叉的现象,主裂纹的扩展被限制并且更多的断裂能被消耗,很大程度提高了复相陶瓷的热震稳定性.     

Sol-gel synthesis and characterization of adsorbent and photoluminescent nanocomposites of starch and silica

Using sol-gel method, mesoporous and photoluminescent silica nanocomposites of soluble starch have been synthesized and characterized. Different ratios of H₂O, TEOS and EtOH were used at fixed template (soluble starch) and catalyst (NH₄OH) concentrations to obtain materials of different performances in terms of heavy metal binding from a solution which has been monitored using Cd(II) as representative divalent heavy metal ion. Optimum material was obtained when H₂O, TEOS and EtOH were used in 14:1:2 ratio. This sample was not only an efficient metal ion adsorbent but also had an intense luminescence in ultra-violet region and potentially may be used in silicon-based UV-emitting devices. Metal binding by the material was further enhanced after calcination (at 800 °C in air) while its luminescence had a multipeak profile in UV-visible region. In a batch adsorption study, calcined hybrid composite (0.25 g/L) could remove 98.5% Cd(II) from 100 mg/L Cd(II) solution in 2 h. The chemical, structural and textural characteristics of the synthesized materials have been investigated using Fourier Transform Infrared Spectroscopy (FTIR), X-rays Diffraction (XRD), Thermal Analysis (TGA/DTA), Photoluminescence (PL), Brunauer-Emmett-Teller Analysis (BET) and Scanning Electron Microscopy (SEM).     

Syntheses and structures of N-phenylmaleimidetriazoles and by-products

The syntheses, properties, and structures of N-phenylmaleimidetriazole derivatives are described. Intermediates and by-products are also discussed. 1b. a = 43.997(7) Å, 5.7610(9) Å, 8.245(1) Å, = 99.339(4), C₂/c; 2a. a = 13.646(4) Å, b = 7.744(2) Å, c = 10.612(3) Å, = 91.979(6), P2₁/c. 3a. a = 22.245(1) Å, b = 22.245(1) Å, 10.010(1) Å, P42/n. 3a. a = 11.727(2) Å, b = 14.075(3) Å, c = 16.080(3) Å, = 105.859(3), = 105.331(3), = 98.187(3), P-1. 3b. a = 8.561(3) Å, b = 14.755(5) Å, c = 22.771(7) Å, = 97.006(5), P2₁/c. 3c. a = 10.500(2) Å, b = 12.189(2) Å, c = 13.040(2) Å, = 109.091(3), = 106.089(3), = 101.022(3), P-1. 8a. a = 16.389(8) Å, b = 5.749(3) Å, c = 19.316(3) Å, = 97.467(9), P2₁/n. 8b. a = 5.822(2) Å, b = 10.114(3) Å, c = 16.705(4) Å, = 84.681(5), = 82.840(5), = 75.769(4), P-1. 9b. a = 11.251(1) Å, 13.335(3) Å, 13.376(3) Å, = 102.456(4), P2₁/n. 9c. a = 15.836(3) Å, b = 8.236(2) Å, c = 5.447(3) Å, = 92.551(3), P2₁/c. 10a. a = 13.177(2) Å, b = 14.597(2) Å, c = 5.5505(8) Å, = 110.979(2), Cc. 11a. a = 14.720(2) Å, b = 13.995(2) Å, c = 38.245(6) Å, = 94.430(3), P2₁/n. 12b. a = 15.067(5) Å, b = 20.378(6) Å, c = 8.669(5) Å, = 99.16(4), = 99.32(3), = 105.23(3), P-1. 13b. a = 8.2824(6) Å, b = 10.5245(7) Å, c = 15.518(1) Å, = 92.305(1), = 100.473(1), = 100.124(1), P-1. 15a. a = 15.357(3) Å, b = 7.778(2) Å, c = 22.957(2) Å, Pbca. 16b. a = 18.0384(4) Å, b = 12.474(3) Å, c = 20.078(5) Å, Pbca.     

Surface topography and crystal and domain structures of films of ferroelectric copolymer of vinylidene difluoride and trifluoroethylene

The crystallization of a copolymer from a solution at room temperature is found to lead to the formation of a metastable structure, characterized by the coexistence of ferroelectric and paraelectric phases. The fraction of the latter decreases after annealing above the Curie point. Atomic force microscopy (AFM) has revealed a difference in the surface topographies between the films contacting with air and the films contacting with a glass substrate. The microstructure of copolymer chains has been investigated by ¹⁹F NMR spectroscopy. The chain fragments with “defect” attached monomeric units are ejected to the surface. The character of the ferroelectric domains formed during crystallization and their size distribution are analyzed.

     

Preparation and characterization of PbSe nanopowder and quasi-ceramics

By means of the reduction of Pb(II) and Se(IV) with hydrazine, oval monodispersed PbSe nanoparticles characterized by sizes ～100 nm and the cubic symmetry were obtained. Their compaction and sintering into quasi-ceramic state were performed. The samples were investigated by means of scanning electron microscopy, X-ray diffraction and FTIR spectroscopy. The results obtained are discussed.     

Chemistry and Electrocrystallization of Organic Metals and Superconductors

Abstract

Considerable variation in the conditions of electrochemical crystal growth of TMTSF₂X (i.e., constant current versus constant potential, ambient versus inert atmosphere, etc.) and in the purity of the constituents (donor, electrolyte, solvent) does not significantly affect the unusual low-temperature properties of this class of materials. Our results suggest that the electrocrystallization procedure may be self-purifying by selecting for conducting crystal phases with constituents having specific oxidation potentials and solubility properties. However, doping solutions with structurally and chemically similar constituents (i.e., TMTTF, and IO^? ₄ in CIO^? ₄) leads to their incorporation in the crystal structure where they have a profound effect. Several mole percent of these dopants suppress superconductivity in the PF^? ₆ and CIO^? ₄ salts, and increase and broaden the metal-insulator phase transition.     

Hydrothermal Synthesis and Morphology of Thomsonite and Edingtonite

The hydrothermal treatment of different glasses of the composition 2 Na₂O–8 CaO–10 Al₂O₃– 20 SiO₂ and 2 BaO–2 Al₂O₃–6 SiO₂ at one kilobar pressure in a temperature-range between 80 °C and 230 °C lead to the formation of the zeolite-minerals thomsonite (orthorhombic symmetry space-group Pbmn, a = 13.05 Å, b = 13.09 Å and c = 13.22 Å), and edingtonite (orthorhombic symmetry, space-group: P2,2,2, a = 9.55 Å, b = 9.67 Å and c = 6.52 Å). Under the chosen hydrothermal conditions both mineral phases are formed in the whole temperature interval.     

Structural and spectral studies of N-trans-cinnamylidene-m-toluidine and N-trans-cinnamylidene-m-chloroaniline

N-trans-cinnamylidene-m-toluidine (1) C₁₆H₁₅N, and N-trans-cinnamylidene-m-chloroaniline (2) C₁₅H₁₂NCl form isomorphous crystals which are monoclinic, space group P2_l/c, with unit cell dimensionsa=5.967(2),b=13.793(3),c=15.048(5) Å, =91.97(3)° anda=5.868(2),b=13.788(4),c=15.191(4) Å, =91.87(3)°, respectively. The single-crystal X-ray structure determinations of the title compounds revealtrans structures. Ring (A) C_10–15 and ring (B) C_1–6, are practically planar in both structures with dihedral angels of 61.3(3) and 63.6(2)°, respectively.¹H nmr, u.v. and i.r. spectra are also reported.     

Numerical and experimental analysis of periodic patterns and sedimentation of lysozyme

This paper deals with experimental investigation, mathematical modelling and numerical simulation of the crystallization processes induced by counter diffusion method of a precipitant agent in a lysozyme protein solution. Novel mathematical strategies are introduced to simulate the experiments and in particular to take into account the kinetics of the growth process and the motion of the crystals due to the combined effect of gravitational force and viscous drag if the sedimenting process is allowed (protein chamber free of gel). Comparison between experimental observations and numerical simulations in the presence of convection and sedimentation and without them provides a validation of the model. The crystal formation in gel results modulated in space. If the gel matrix is not present, convective cells arise in the protein chamber due to local inversions in the density distribution associated to nucleation phenomena. As time passes, these vortex cells migrate towards the top of the protein chamber exhibiting a different wave number according to the distance from the gel interface. The sedimentating particles produce a wake due to depletion of protein from the surrounding liquid. The models and the experiments may represent a useful methodology for the determination of the parameters and conditions that may lead to protein crystallization.     

Crystal and molecular structures of benz-p-nitroanilide and benz-p-methoxyanilide

The crystal structures of the two carboxylic amides C₁₃H₁₀N₂O₃ (I) and C₁₄H₁₃NO₂ (II) have been determined by direct methods and refined by full-matrix least squares. The predominant structural feature is the hydrogen bonding (N-H?O=C) which influences the conformations of both structures.     

Crystal structure and conformational analysis of N-formyl and N-nitroso derivatives of piperidinone

Single crystal X-ray studies for N-formyl-2,6-diortho chlorophenyl-3,5-dimethyl piperidin-4-one (FOCDMPO) and N-nitroso-2,6-di(3,4,5-trimethoxyphenyl)-3,5-dimethyl piperidin-4-one (NTMPO) are reported. Crystals of FOCDMPO and NTMPO belong to the monoclinic space groups P2₁/n and C2/c, respectively. FOCDMPO: a = 9.147(2), b = 14.586(3), c = 13.665(5) Å and = 101.68(2)° NTMPO: a = 38.52(2), b = 13.727(5), c = 9.564(3) Å and = 98.60(1)°. In both the structures, the piperidine ring adopts a boat conformation with slight distortion. In FOCDMPO, one of the phenyl and methyl groups are in axial positions while the other phenyl and methyl groups are in equatorial orientations. In NTMPO, the situation is reversed. The molecules are stabilized by weak intermolecular C—H ··· O interactions in addition to van der Waals forces.