钛铁矿原位合成金属陶瓷复合材料的研究

钛铁矿资源储量丰富,充分利用钛铁矿中的钛和铁来制备金属陶瓷复合材料是天然钛铁矿综合开发利用中的一个重要方面.通过原位铝热、碳热还原法,以天然钛铁矿为主要原料,合成制备出了TiC-Al2O3/Fe陶瓷复合材料.研究了产物的物相、结构和性能,分析了铝热、碳热的反应过程.实验表明:反应产物主要为TiC相、Al2O3相和Fe相,还有少量Fe-Al相.大部分晶体颗粒尺寸约为3～5μm,分布较为均匀.金属添加剂改善了Fe对陶瓷相的润湿性,同时抑制了Al2O3和TiC间的高温化学反应,减少了气体的放出,界面结合得到了改善,促进了陶瓷材料的烧结致密.     

钛铁矿原位碳热还原合成TiC/Fe复合材料的研究

以天然矿物钛铁矿（FeTiO3)、C（石墨）为原料,采用原位碳热还原法,实现合成与烧结一体化,真空烧结制备TiC/Fe复合材料,探索了一条低成本合成高性能TiC/Fe复合材料的新途径,对反应的热力学过程进行理论分析和实验研究,分析了产物的结构、组织和性能。研究表明：反应产物主要存在两组,即TiC相和Fe的固溶相,球形的TiC颗粒相被包围在网状结构的Fe及Fe合金粘结相中,TiC颗粒尺寸均匀,大小约2－5μm。Mo的加入可以改善金属相对TiC的润湿性。产物中有少量游离碳存在。     

热压烧结工艺制备Fe3Al/Al2O3复合材料的物相组成和显微结构研究

本实验采用机械合金化工艺结合热处理工艺制备Fe3Al金属间化合物粉末,并将Fe3Al粉末与Al2O3粉末相混合制备Fe3Al/Al2O3复合粉末,并通过热压烧结工艺制备Fe3Al/Al2O3复合材料块材试样,对Fe3Al/Al2O3复合材料的物相组成,显微结构和力学性能进行研究.结果表明采用机械合金化工艺球磨60h后得到Fe-Al金属间化合物粉末.并经过800℃和1000℃热处理后得到Fe3Al金属间化合物粉末.经过热压烧结后得到的Fe3Al/Al2O3复合材料块材主要有Fe3Al相和Al2O3相.Fe3Al/Al2O3复合材料的显微结构均匀致密.Fe3Al晶粒均匀分布在Al2O3基体中,Fe3Al晶粒的平均颗粒尺寸为3～4μm,而Al2O3基体颗粒尺寸为4～5 μm.随着基体中Fe3Al合金含量的增加,Fe3Al/Al2O3复合材料的密度和相对密度逐渐增加;Fe3 Al/Al2O3复合材料的抗弯强度和断裂韧性逐渐增加;Fe3Al/Al2O3复合材料的洛氏硬度和弹性模量逐渐降低.Fe3Al/Al2O3复合材料具有较高的力学性能是由于复合材料具有均匀致密的显微结构.     

等轴晶ZrO2(Al2O3, Fe2O3)复相陶瓷的制备

讨论了以硝酸盐溶液为原料，经喷雾干燥、热解、成型、烧结或直接烧结制备等轴晶ZrO2(Al2O3, Fe2O3)复相陶瓷的过程. 研究了成型压力、烧结温度、恒温时间及Al3+, Fe3+的加入对ZrO2陶瓷的相组成、晶粒大小和形貌的影响. 结果表明：成型压力对相组成及晶粒尺寸无明显影响；无论是直接采用硝酸盐复合粉末还是采用氧化物粉末压坯作为前驱物，烧结产物的形貌、相组成不变；加入Fe2O3可克服微观结构层状堆垛，获得相对细小均匀的等轴晶粒，且随Fe2O3含量的增加，单位体积中a-(Al, Fe)2O3核心的数量增加，晶粒尺寸更加细小、均匀，Fe2O3含量相对于Al2O3在20%左右时效果最佳；各相晶粒在长时间高温烧结时生长速度较为缓慢，0.5 h为0.5 mm左右，烧结12 h才到2.0 mm左右.     

优势区相图在A l-T i O2-C-ZrO2燃烧合成体系热力学分析中的应用

以TiO2, Al, C和ZrO2为原料, 燃烧合成制备Al2O3-TiC-ZrO2纳米复相陶瓷是一种方法简单、节时省能的新工艺. 对Al-TiO2-C-ZrO2体系进行了热力学分析,计算出该体系的绝热燃烧温度, 并利用Al-O-N,Ti-O-N,Zr-O-N,C-O-N四个体系的叠加优势区相图, 分析了各相间反应进行的趋势和最终稳定存在的平衡相. 热力学分析表明:绝热燃烧温度为2327 K, 燃烧合成产物包括Al2O3,TiC,ZrO2三相. XRD检测未发现其它杂相, 证实热力学分析结果可信.     

优势区相图在Al-TiO2-C-ZrO2燃烧合成体系热力学分析中的应用

以TiO2, Al, C和ZrO2为原料, 燃烧合成制备Al2O3-TiC-ZrO2纳米复相陶瓷是一种方法简单、节时省能的新工艺. 对Al-TiO2-C-ZrO2体系进行了热力学分析,计算出该体系的绝热燃烧温度, 并利用Al-O-N,Ti-O-N,Zr-O-N,C-O-N四个体系的叠加优势区相图, 分析了各相间反应进行的趋势和最终稳定存在的平衡相. 热力学分析表明：绝热燃烧温度为2327 K, 燃烧合成产物包括Al2O3,TiC,ZrO2三相. XRD检测未发现其它杂相, 证实热力学分析结果可信.     

添加Fe2O3对碳热还原含钛高炉渣的影响

以攀枝花含钛高炉渣为原料,针对碳热还原含钛高炉渣的还原产物TiC晶粒粒径较小而难以分离的问题,在原料中添加不同比例的Fe2O3促进TiC与渣相分离. 结果表明,原料中加入Fe2O3后,还原产物中Fe在渣中呈弥散分布,渣中TiC晶粒依附Fe相生长. Fe2O3添加量为5wt%时,依附于Fe相形核长大的TiC明显沉降,富集于还原产物底部,含钛高炉渣还原产物中TiC初步富集.     

Al2O3/Fe纳米复合粉体的制备及其陶瓷的性能研究

以纳米α-Al2O3和Fe(NO3)3·9H2O为原料,采用非均相沉淀法制备了Fe包裹Al2O3的纳米复合粉体.经XRD、SEM分析发现:复合粉体前驱体经500 ℃焙烧,在H2中700 ℃还原可以得到纳米Fe包裹Al2O3的纳米复合粉体.粉体分散良好,Al2O3表面的纳米Fe粒子呈非连续状态,颗粒为球形,尺寸为30 nm左右,分布均匀.将复合粉体在热压下(30 MPa)烧结获得Al2O3/Fe复合陶瓷,当加入5mol%Fe时,陶瓷的热压烧结温度比单相Al2O3陶瓷降低将近100 ℃.含量为10mol%Fe的陶瓷样品在1500 ℃热压烧结后,断裂韧性可达到5.62 MPa,与相同条件下烧结的单相Al2O3陶瓷(KIc=3.57 MPa)相比提高了近57%.     

Al-TiO2-C体系热力学分析及Al2O3-TiC复相陶瓷的燃烧合成

对Al-TiO2-C燃烧合成体系进行了热力学计算,并利用Al-O-N、Ti-O-N、C-O-N三个体系的叠加优势区相图分析了该燃烧合成体系的平衡产物相.结果表明,Al-TiO2-C燃烧合成体系的绝热燃烧温度为2398 K,燃烧合成平衡相为Al2O3和TiC.XRD检测结果与热力学分析结果相吻合,说明该燃烧合成反应进行得较为彻底,证实热力学分析结果可信.原位生成的Al2O3和TiC两相分布较均匀,燃烧合成产物疏松多孔,易于通过球磨方式达到破碎、磨细的目的.     

Al2O3/LiTaO3陶瓷复合材料的制备与力学性能

采用氮气保护热压烧结工艺制备Al2O3/LiTaO3(简称ALT)陶瓷复合材料，系统研究了其微观组织和力学性能。ALT陶瓷复合材料的相对密度比烧结纯LiTaO3陶瓷的高得多，表明Al2O3起到烧结助剂的作用。TEM观察表明，Al2O3p分布均匀，两者结合紧密，界面上有非常微量的分解物。ALT陶瓷复合材料的力学性能均随Al2O3p含量的增加而提高，Al2O3p的体积分数为40％时，其各项力学性能都是最高。     

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-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。     

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。     

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