烧结助剂对自增韧Si3N4陶瓷显微结构和性能的影响

研究了烧结助剂质量分数及比例对热压自增韧Si3N4 陶瓷显微结构和力学性能的影响。结果表明 :材料室温抗弯强度和断裂韧性均在烧结助剂的质量分数为 15 %时达到峰值 ,其中 5 %Y2 O3 10 %La2 O3 85 %Si3N4 体系的抗弯强度达 911.3MPa,断裂韧性达10 .0 2MPa·m1 /2 。同时 ,分析了材料显微结构与力学性能的关系 ,发现自增韧Si3N4 陶瓷中 β-Si3N4 柱状晶直径的双峰分布特征对材料力学性能的提高起着很重要的作用     

氟化钙对常压烧结Si3N4/BN复相陶瓷结构与性能的影响

以微米级Si3N4和h-BN粉末为原料,CaF2–Al2O3–Y2O3为烧结助剂,采用常压烧结工艺制备了BN体积含量为25%的Si3N4/BN复相陶瓷。研究了CaF2添加量对Si3N4/BN复相陶瓷材料力学性能的影响,并通过X射线衍射和场发射扫描电镜分析了复相陶瓷的物相组成和显微组织。结果表明：随着CaF2添加量增加,制备的Si3N4/BN复相陶瓷材料气孔率逐渐增大,收缩率变小,相对密度减小。添加量为2%（质量分数）时,Si3N4/BN复相陶瓷的室温抗弯强度达145.5MPa。添加适量的CaF2可在Si3N4/BN复相陶瓷材料常压烧结过程中较大程度地破坏h-BN的卡片房式结构,将微米级的h-BN颗粒变成纳米级颗粒。     

纳米ZrO2对Al2O3陶瓷性能的影响

以纳米ZrO2,微米Al2O3为原料,采用无压烧结方式制备了ZTA复相陶瓷.结果表明:纳米ZrO2的加入有利于制备细晶ZTA复相陶瓷.此外,nano-ZrO2的加入对Al2O3陶瓷的显微结构也产生影响,ZrO2颗粒以"晶内型"和晶界型2种形式存在.合理的配方组成及制备工艺有利于ZrO2以四方亚稳相存在.ZrO2质量分数为30%时,其四方相质量分数可达69%,有利于应力诱导相变增韧,该ZTA复相陶瓷的抗弯强度、断裂韧性分别达到604MPa,6.87MPa·m1/2.     

多孔Si_3N_4/BN复相陶瓷的常压烧结制备

以微米级Si3N4和h-BN粉末为原料,Yb2O3-Al2O3-Y2O3为烧结助剂,采用常压烧结工艺制备了BN体积含量为25%的多孔Si3N4/25%h-BN复相陶瓷。研究了Yb2O3添加量对Si3N4/25%BN复相陶瓷力学性能的影响,通过X射线衍射和扫描电子显微镜分析了复相陶瓷的物相组成和显微结构。结果表明:随着Yb2O3添加量增加,制备的Si3N4/25%BN复相陶瓷的气孔率逐渐增大,收缩率变小,相对密度减小。Yb2O3添加量为2%(质量分数)时,Si3N4/25%BN复相陶瓷的气孔率为15.1%,相对密度为72.8%;当Yb2O3添加量提高至15%时复相陶瓷的气孔率增加至32.1%,相对密度则降至60.3%。同时随着Yb2O3添加量增加,复相陶瓷的室温抗弯强度先增大后减小,Yb2O3含量为4%时,室温抗弯强度呈现最大值,可达264.3MPa。     

ZrO2-Al2O3复相陶瓷的研究

以纳米ZrO 、微米Al O 为原料,采用无压烧结方式制备了ZTA 复相陶瓷。结果表明:nano-ZrO 的 2 2 3 2加入有利于制备细晶ZTA 复相陶瓷。此外,nano-ZrO 的加入对 Al O 陶瓷的显微结构也产生影响,ZrO 颗粒以 2 2 3 2“晶内型”和晶界型两种形式存在。合理的配方组成及制备工艺有利于 Z r O 以四方亚稳相存在。Z r O 含量为 2 23 0 w t % 时,其四方相含量可达 6 9 %,有利于应力诱导相变增韧,该 Z T A 复相陶瓷的抗弯强度、断裂韧性分别达到 604MPa、6.87MPa·m1/2。     

纳米TiN-Al_2O_3基复相陶瓷的电学及力学性能

以纳米Al2O3和TiN为原料,以SiO2为助烧剂,热压烧结后获得TiN-Al2O3复相陶瓷。TiN-Al2O3复相陶瓷具有较优异的力学性能:三点弯曲强度最高达到565.8MPa,断裂韧性在4～6MPa·m1/2之间。复相陶瓷中立方TiN均匀地分布在Al2O3基体中,TiN颗粒主要分布在Al2O3晶界处。当TiN颗粒的体积含量为5%时,TiN-Al2O3复相陶瓷的电阻率在1012～104Ω·cm范围内,其加载电压可达0.75kV/mm。     

以柠檬酸铵为TiO2分散剂控制Si3N4-TiN复相陶瓷的显微结构

以Si3N4,AlN和TiO2为原料,Y2O3和Al2O3为烧结助剂,通过添加柠檬酸铵作为TiO2的分散剂,采用原位反应合成法制备TiN体积分数为5%的Si3N4-TiN复相陶瓷,在高温烧结过程中原料中的TiO2和AlN反应生成TiN.通过扫描电子显微镜观察了柠檬酸铵分散剂用量对Si3N4-TiN复相陶瓷显微结构的影响.结果表明:添加柠檬酸铵分散剂降低原料混合粉体中TiO2的团聚,获得组分均匀的Si3N4-TiO2-AlN复合粉体,从而提高Si3N4-TiN复相陶瓷中TiN相在Si3N4基体中的分散性,烧结后获得显微结构均匀的Si3N4-TiN复相陶瓷.当在体系中添加0.20g柠檬酸铵分散剂可以显著改善Si3N4-TiN复相陶瓷的显微结构,TiN晶粒被控制在0.2～0.3μm.     

Y-TZP/A12O3/Mo纳米复合材料的制备及其力学性能

纳米复相陶瓷材料是目前最接近于产业化的纳米陶瓷材料,已成为国际研究热点.添加金属第二相有可能同时提高纳米复相陶瓷材料的力学和摩擦学性能.为此,在钇稳定多晶氧化锆(yttria-stabilized teWagonal zirconia polycrystais,Y-TZP)/Ai2O3纳米陶瓷的基础上,用ZrO2-Y2O3-A12O3纳米复合粉体和金属Mo粉采用热压烧结的方法成功制备了Y-TZP/A12O3/Mo纳米陶瓷-金属复合材料.研究了Mo含量对材料显微结构和力学性能的影响.结果表明:复合材料结构主要由晶界型、晶内型和纳米-纳米型3种类型的混合型组成,这种结构使材料具有非常高的断裂韧性,在Mo的质量分数为60%时,断裂韧性可达20.8 MPa·m1/2.     

稀土氧化物对Si3N4陶瓷力学性能和显微组织的影响

采用常压烧结工艺制备了Si3N4-Y2O3-La2O3陶瓷,并对Si3N4陶瓷的力学性能、相组成和显微组织进行了分析和讨论。结果表明:添加4%Y2O3～4%La2O3的复合稀土氧化物后,Si3N4陶瓷呈长柱状的β-Si3N4晶粒,抗弯强度为960MPa,断裂韧性为7.5MPa.m1/2,具有较好的力学性能。     

ZrN+AlN+Y2O3复合助烧结剂对Si3 N4陶瓷烧结性能的影响

对比了ZrN+AlN助烧结剂与ZrN+AlN+Y2O3助烧结剂对1800℃、25 MPa下热压烧成Si3N4陶瓷显微结构和力学性能的影响,并着重对ZrN+AlN+Y2O3复合助烧结剂促进Si3N4陶瓷烧结的机理进行了探讨.结果表明加ZrN+AlN+Y2O3助烧结剂能明显促进Si3N4陶瓷的烧结,提高陶瓷强度,其相对密度可达97.84%,常温弯曲强度为601.21 MPa,断裂韧性达8.9 MPa·m1/2;而加ZrN+AlN助烧结剂的Si3N4陶瓷未致密化.     

Ferroelectric Ceramics in the PbMg1/3Nb2/3O3-PbCd1/3Nb2/3O3 System

Solid solutions (1-x)PbMg_1/3Nb_2/3O₃ + xPbCd_1/3Nb_2/3O₃ with x = 0-0.30 are investigated with purpose to work out a capacitor ceramics with good dielectric properties and low sintering temperature. It is found that the perovskite phase forms at sintering near to 980°C and begins to decompose at higher temperatures. When x grows from 0 to 0.30, the Curie temperature linearly grows from -10°C to +25°C, the dielectric permittivity ε_m in the Curie point T_C decreases from 18000 to 6800 and the phase transition becomes more diffused. The dielectric permittivity at room temperature is rather high and the temperature stability is improved. The system is of interest, because it can serve as a base for working out some ceramic materials for capacitors with low sintering temperature, which needs of no special atmosphere at burning.     

3-叠氮甲基-3-甲基氧丁环的合成

以三羟甲基乙烷与碳酸二乙酯为原料,经环化反应合成了3-羟甲基-3-甲基氧丁环(HMM O)。在低温下,HMM O与对甲苯磺酰氯反应生成3-磺酸酯甲基-3-甲基氧丁环(M TM O)。M TM O和叠氮化钠发生叠氮化反应形成叠氮单体3-叠氮甲基-3-甲基氧丁环(AMM O)。三步反应收率分别为76%,96%,85%。用核磁、红外、元素分析和DSC表征了化合物的结构与性能。结构鉴定表明为目标化合物AMM O。     

3-溴甲基-3-甲基氧杂环丁烷的合成

以2,2-二溴甲基丙醇（BBMP）为初始原料,通过与碱发生关环反应生成3-溴甲基-3-甲基氧杂环丁烷（BrMMO）。讨论了碱的种类和用量对BBMP关环产率的影响以及反应体系中碱的浓度、反应温度和反应时间对合成BrMMO产率的影响。通过实验确定的最佳工艺条件为：BBMP与NaOH摩尔比为1.0∶1.1,NaOH醇溶液的质量分数为12%,反应温度为78℃,反应时间为4h时,BrMMO产率为65%。最终产品经元素分析、IR和1HNMR检测确定为BrMMO。该试验工艺简单,原料易得,且溶剂便于回收、污染小。     

Tunable color emission in LaScO3:Bi3+,Tb3+,Eu3+ phosphor

LaScO₃:xBi³⁺,yTb³⁺,zEu³⁺ (x = 0 − 0.04, y = 0 − 0.05, z = 0 − 0.05) phosphors were prepared via high-temperature solid-state reaction. Phase identification and crystal structures of the LaScO₃:xBi³⁺,yTb³⁺,zEu³⁺ phosphors were investigated by X-ray diffraction (XRD). Crystal structure of phosphors was analyzed by Rietveld refinement and transmission electron microscopy (TEM). The luminescent performance of these trichromatic phosphors is investigated by diffuse reflection spectra and photoluminescence. The phenomenon of energy transfer from Bi³⁺ and Tb³⁺ to Eu³⁺ in LaScO₃:xBi³⁺,yTb³⁺,zEu³⁺ phosphors was investigated. By changing the ratio of x, y, and z, trichromatic can be obtained in the LaScO₃ host, including red, green, and blue emission with peak centered at 613, 544, and 428 nm, respectively. Therefore, two kinds of white light-emitting phosphors were obtained, LaScO₃:0.02Bi³⁺,0.05Tb³⁺,zEu³⁺ and LaScO₃:0.02Bi³⁺,0.03Eu³⁺,yTb³⁺. The energy transfer was characterized by decay times of the LaScO₃:xBi³⁺, yTb³⁺, zEu³⁺ phosphors. Moreover absolute internal QY and CIE chromatic coordinates are shown. The potential optical thermometry application of LaScO₃:Bi³⁺,Eu³⁺ was based on the temperature sensitivity of the fluorescence intensity ratio (FIR). The maximum S_a and S_r are 0.118 K⁻¹ (at 473.15 K) and 0.795% K⁻¹ (at 448.15 K), respectively. Hence, the LaScO₃:Bi³⁺,Eu³⁺ phosphor is a good material for optical temperature sensing.     

2,2,3-三氯-3-苯基-3-(3-甲基苯甲酰基)丙腈的合成研究

以苯甲酰氯、四氯化碳、间甲基苯甲酰氰为原料,合成了标题化合物。重点考察了氰化过程中不同原料配比、反应温度、时间、溶剂和催化剂用量对收率的影响。实验结果表明,其最佳反应条件为:n(1,1,2-三氯-2-苯基乙烯)∶n(3-甲基苯甲酰氰)=1∶1.2,二氯甲烷为反应溶剂,3 mmol催化剂三乙胺,室温反应5 h,总收率达80.6%。     

3-溴甲基-3-甲基氧杂环丁烷的合成

以2,2-二溴甲基丙醇(BBMP)为初始原料,通过与碱发生关环反应生成3-溴甲基-3-甲基氧杂环丁烷(BrMMO).讨论了碱的种类和用量对BBMP关环产率的影响以及反应体系中碱的浓度、反应温度和反应时间对合成BrMMO产率的影响.通过实验确定的最佳工艺条件为:BBMP与NaOH摩尔比为1.0∶1.1,NaOH醇溶液的质量分数为12%,反应温度为78℃,反应时间为4 h时,BrMMO产率为65%.最终产品经元素分析、IR和1HNMR检测确定为BrMMO.该试验工艺简单,原料易得,且溶剂便于回收、污染小.     

Ba3Tb(BO3)3:Eu3+的制备与发光性质

采用高温固相法合成了Ba3Tb(BO3)3:Eu3+红色荧光粉,并研究了Ba3Tb(BO3)3:Eu3+的发光特性。Ba3Tb(BO3)3:Eu3+的激发光谱包含250nm～330nm和350nm～400nm的2个宽带,最大峰值位于383nm,可以被紫外-近紫外发光二极管(light-emitting diodes,LED)有效激发。Ba3Tb(BO3)3:Eu3+的发射谱显示出4组发射峰,其主发射峰位于620nm,对应Eu3+的5D0→7F2跃迁;Eu3+掺杂摩尔分数为2%时,Ba3Tb(BO3)3:Eu3+发光亮度最高。经分析发现Ba3Tb(BO3)3:Eu3+存在Tb3+→Eu3+的能量传递。     

The Preparation and Crystal Structure of TlMnCl3, TlFeCl3, TlCoCl3 and TlNiCl3

The compounds TlMnCl₃, TlFeCl₃, TlCoCl₃ and TlNiCl₃ were prepared by heating T1C1 with the corresponding transition metal dichloride in an evacuated ampoule. Atomic positions were determined from powder photographs. All four compounds were found to be related to the perovskite type structure. TlMnCl₃ has a cubic structure, space group Pm3m, with a_o = 5.025 Å. The other three compounds are hexagonal, probable space group P6₃mc, with cell dimensions (in Å) a₀ = 6.976 and c₀ = 6.008 for the Fe compound, a₀ = 6.907 and c₀ = 5.981 for the Co compound and a₀ = 6.863 and c₀ = 5.881 for the Ni compound. The three hexagonal compounds are isomorphous. A measureable concentration of basal plane stacking faults was found to occur in TlFeCl₃ and also, to a lesser degree, in TlCoCl_3.     

Thermal analyses of poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate), and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)

Thermal analyses of poly(3-hydroxybutyrate) (PHB), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(HB–HV)], and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [P(HB–HHx)] were made with thermogravimetry and differential scanning calorimetry (DSC). In the thermal degradation of PHB, the onset of weight loss occurred at the temperature (°C) given by T_o = 0.75B + 311, where B represents the heating rate (°C/min). The temperature at which the weight-loss rate was at a maximum was T_p = 0.91B + 320, and the temperature at which degradation was completed was T_f = 1.00B + 325. In the thermal degradation of P(HB–HV) (70:30), T_o = 0.96B + 308, T_p = 0.99B + 320, and T_f = 1.09B + 325. In the thermal degradation of P(HB–HHx) (85:15), T_o = 1.11B + 305, T_p = 1.10B + 319, and T_f = 1.16B + 325. The derivative thermogravimetry curves of PHB, P(HB–HV), and P(HB–HHx) confirmed only one weight-loss step change. The incorporation of 30 mol % 3-hydroxyvalerate (HV) and 15 mol % 3-hydroxyhexanoate (HHx) components into the polyester increased the various thermal temperatures T_o, T_p, and T_f relative to those of PHB by 3–12°C (measured at B = 40°C/min). DSC measurements showed that the incorporation of HV and HHx decreased the melting temperature relative to that of PHB by 70°C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 90–98, 2001