柠檬酸-凝胶燃烧法制备钇铝石榴石(Y_3Al_5O_(12))纳米粉体的研究

透明YAG多晶陶瓷具有优良的光学、力学与化学性能,逐渐成为新一代固体激光基质材料。分散均匀、团聚轻的纳米粉体有利于制备出高度透明的激光陶瓷。以Y2O3、Al(NO3)3·9H2O和柠檬酸为原料,采用柠檬酸凝胶燃烧法制备出黑色粉体,经1100℃烧结出尺寸小于50nm的YAG粉体。采用TG-DTA、XRD、FT-IR和TEM测试手段对YAG纳米粉体进行表征,采用谢莱公式计算出不同烧结温度下的晶粒尺寸。研究结果表明:YAG的析晶温度范围为850～900℃,烧结过程中出现赝YAG相物质,1050℃转变成纯YAG相,随着热处理温度的升高,晶粒呈线性增长,纳米粉体的TEM尺寸和采用谢莱公式计算的结果相一致。     

Effect of content of Mg(NO3)2 x 6H2O on fabrication of alpha-alumina nanopowders by thermal decomposition of ammonium aluminum carbonate (AACH)

An alpha-Al2O3 and MgAl2O3 spinel phase doped alpha-Al2O3 nanopowders were fabricated by the thermal decomposition and synthetic of ammonium aluminum carbonate hydroxide (AACH). Crystallite size of 5 to 8 nm were fabricated when reaction temperature of AACH was low, 8 degrees C, and the highest [NH4+][AlO(OH)2-][HCO3] ionic concentration of pH 10 from the ammonium hydrogen carbonate (AHC) aqueous solution. The phase transformation of amorphous-s, theta-, alpha-Al2O3, MgAl2O3 spinel phases was examined at each temperature according to the amount of Mg(NO3)2 x 6H2O and AACH. A time-temperature-transformation (TTT) diagram for thermal decomposition in air was determined. Homogeneous, spherical alpha-Al2O3 nanopowders with a particle size of 60 nm were obtained by firing the crystallites, which had been synthesized from AACH at pH 10 and 8 degrees C, at 1050 degrees C for 6 h in air.     

粒径与掺杂对ZrO2纳米粉相结构的影响

用Ｘ射线衍射仪和透射电镜研究了粒径和Ｙ，Ｃｅ掺杂元素对ＺｒＯｗ纳米粉相结构的影响。结果表明，在室温下平均粒径为￣１０ｎｍ的ＺｒＯ２粉单斜相不足２０ｖ．％，而加入２ｍｏｌ％Ｙ２Ｏ３或２ｍｏｌ％ＣｅＯ２可使单斜相更少，试验测得纯ＺｒＯ２，ＺｒＯ２－２ｍｏｌ％ＣｅＯ２，ＺｒＯ２－２ｍｏｌ％Ｙ２Ｏ３纳米粉在室温下单斜相和四方相保持平衡共存的临界粒径分别为１７．５，２１．０和３２．５ｎｍ。     

Preparation of nanocrystalline alpha-Al2O3 using plant fiber

Nanocrystalline alpha-Al2O3 ceramic powders have been prepared from aqueous poly vinyl alcohol (PVA)-aluminum nitrate solution and jute (plant fiber). Soluble Al-ion-PVA solution formed a uniform coating on the surface of jute once it dried completely. Slow hydrolysis of aluminum ion with ammonium hydroxide deposited aluminum hydroxide on the jute surface. Decomposition of the dried aluminum hydroxide-coated jute at high temperature (1150 degrees C/2 hrs) resulted in the formation of single-phase, nanocrystalline alpha-Al2O3 with the corresponding average X-ray and TEM particle size approximately 50 nm. Precursor and heat-treated powders have been characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) analysis. This method can be used to produce high-temperature as well as low-temperature nanocrystalline oxides.     

Synthesis and Enhanced Superplasticity of the Zirconia-dispersed Alumina Nanocomposite

A series of alumina-zirconia composites with various grain sizes were prepared from the nano-sized powders with different agglomerations. Microstructural analysis of the sintered compacts indicates that the as-sintered material is a typical intra/inter granular nanocomposite with uniform distribution of the zirconia grains in the alumina matrix. Superplastic deep drawing test under different conditions demonstrates that dense Al2O3/ZrO2 samples with average grain size of 230 nm can be elongated to a dome height of at least 12 mm at the punch rate of 0.6 mm·min-1 at 1400℃. Further drawing tests show that for the composites with larger grain size, such elongation cannot be achieved at such a strain rate.     

水热介质pH值对纳米(Ce)ZrO_2晶粒制备的影响

用水热法制得纳米 (Ce)ZrO2 粉体 ,其晶粒粒度为 3～ 7nm ,而且为单一分散。用XRD、TEM分析了水热媒介pH值对粒度、m相含量、晶粒形貌的影响关系。结果表明 :水热煤介 pH值增大 ,ZrO2 晶粒也增大 ;pH值减小至酸性时 ,ZrO2 晶粒中出现部分m相 ,且晶粒易团聚     

水热介质pH值对纳米(Ce)ZrO2晶粒制备的影响

用水热法制得纳米 (Ce)ZrO2 粉体 ,其晶粒粒度为 3～ 7nm ,而且为单一分散。用XRD、TEM分析了水热媒介pH值对粒度、m相含量、晶粒形貌的影响关系。结果表明 :水热煤介 pH值增大 ,ZrO2 晶粒也增大 ;pH值减小至酸性时 ,ZrO2 晶粒中出现部分m相 ,且晶粒易团聚     

粉末粒度对等离子喷涂Al2O3-13%TiO2陶瓷涂层组织结构及性能的影响

等离子喷涂粉末的粒度影响涂层组织结构与性能。选用4种不同粒度的Al2O3-13%TiO2(AT13)粉末等离子喷涂陶瓷涂层,研究了喷涂粉末粒度对涂层组织结构、孔隙率、显微硬度和沉积效率的影响。结果表明:采用较细的喷涂粉末制备的AT13涂层致密、均匀,孔隙率低;随着喷涂粉末粒度增大,涂层的孔隙率增加,显微硬度降低,沉积效率先增后减;采用粒度为38～44μm的粉末喷涂涂层时沉积效率最高,达到51%,涂层组织也较致密,这是等离子喷涂AT13陶瓷层较理想的粒度。     

固相法合成La2Ni0.5M0.5O4+δ(M=Co,Cu)材料及电性能

使用金属氧化物La2O3,NiO,CuO和Co2O3作为原料,固相反应法能够合成出具有K2NiF4型结构单一相的、且晶粒尺寸在35～50nm范围的La2Ni0.5M0.5O4 δ(M=Co,Cu)粉料,用XRD、SEM和直流四极探针电导测试法研究了合成La2Ni0.5M0.5O4 δ(M=Co,Cu)粉料的煅烧工艺条件和掺杂元素对电性能的影响以及粉料的颗粒形貌.随着煅烧温度的升高和保温时间的延长,晶粒尺寸在不断长大;合成的粉料在1300℃烧结5h后所有样品的电导率在空气条件下于100～800℃范围内都在增加.掺杂C0或Cu后的材料La2NiO4 δ的电导率均有增加,但掺杂Co后材料电导率要大于掺杂Cu的电导率.为此确定La2Ni0.5M0.5O4 δ(M=Co,Cu)类粉料固相法合成的适宜煅烧条件为1400℃下保温时间14h.     

CaCu3Ti4O12 nanoparticles using polyvinyl pyrrolidone: synthesis and dielectric properties

Nanocrystalline CaCu3Ti4O12 powders with particle sizes of 39.28 8.12 nm were synthesized by a simple modify sol-gel using PVP (Poly-vinyl-pyrrolidone). The synthesized precursor was characterized by TG-DTA to determine the thermal decomposition and crystallization temperature which was found to be at above 500 degrees C. The precursor was calcined at 800 degrees C in air for 8 h to obtain nanocrystalline powders of CaCu3Ti4O12. The calcined CaCu3Ti4O12 powders were characterized by XRD, FTIR, SEM and TEM. Sintering of the powders was conducted in air at 1100 degrees C for 16 h. The XRD results indicated that all sintered samples have a typical perovskite CaCu3Ti4O12 structure and a small amount of CaTiO3. SEM micrographs showed the average grain sizes of 1.86 +/- 0.69 /m for the sintered CaCu3Ti4O12 ceramic prepared using the CaCu3Ti4O12 powders calcined at 800 degrees C. The sintered samples exhibit a giant dielectric constant, epsilon' of approximately 10(3)-10(4). The large low-frequency dielectric permittivity at low temperature is closely related to sub-grain boundary distribution, including conductivity effect. Furthermore, the ceramic shows three semicircles in the complex impedance plane. However, at low frequency, semicircles of sub-grain boundary and grain boundary are considered to represent collapse different electrical mechanisms. The another is ascribed to the contribution of grain. The dielectric behavior at several frequencies and temperatures of these samples can be attributed to electronic inhomogeneities present in material and can be explained based on a microstructural model.     

Preparation of novel calcia-stabilized TZP ceramics

The preparation of tetragonal zirconia polycrystal (TZP) ceramics stabilized by the addition of calcia is presented. These novel ceramics were obtained by means of a fast-firing treatment applied to compacts of nanocrystalline powders with a composition of ZrO₂ — 4 mol% CaO. Powders were synthesized by a nitrate-citrate gel-combustion process and they exhibited the tetragonal phase at room temperature due to their small crystallite size (12–13 nm). These powders were compacted by uniaxial pressing and fired at 1400–1500 °C for 3–5 min, obtaining fine-grained, dense ceramics, which also retained the metastable tetragonal phase. Longer heat treatments increased the average grain size leading to large amounts of the monoclinic phase. It was also found that the critical grain size for the tetragonal-to-monoclinic transformation is about 150 nm for this composition. This small value explains the necessity of a fast-firing treatment of the samples, allowing densification but avoiding a significant grain growth.     

纳米氧化铝粉体的绿色合成及其物相转变控制研究

以氯化铝、碳酸钠为原料,采用直接沉淀法,并于500～1,200℃煅烧,制备纳米Al2O3粉体。然后用TiO2、BaO对纳米Al2O3粉体掺杂,控制其物相转变过程。通过X射线衍射仪、差式扫描量热仪和透射电子显微镜分析纯净和掺杂后的纳米Al2O3的物相转变过程。结果表明,直接沉淀法所得水合Al2O3,经500℃煅烧后可转变为纳米活性Al2O3,粒径约为10 nm;纯净和掺杂Al2O3样品经1,200℃煅烧2 h后均为纳米粉体,其粒径为40～50 nm;在较高温度下,掺杂氧化钡对Al2O3的物相转变具有强烈抑制作用,粉体直至1,200℃仍未转变为结晶良好的α-Al2O3物相;而氧化钛则对其物相转变有显著促进作用,在1,000℃时粉体的主要物相即为α-Al2O3,1,100℃之后粉体已完全转变为α-Al2O3。     

Preparation of nano-grained zirconia ceramics by low-temperature, low-pressure spark plasma sintering

Ce- and/or Y-doped zirconia nanopowders having average particle sizes ranging 12–18 nm have been synthesized by a technique based on mechanochemical processing (MCP). Despite their small particle size, the powders had excellent compactibility with green densities exceeding 50% achieved under a moderate uniaxial pressure of 150 MPa. Nearly fully dense ceramics having grain sizes of around 100 nm were successfully produced from these powders by spark plasma sintering (SPS) at temperatures of 1,050–1,150 °C for 5 min under pressures of 50–80 MPa; these temperatures and pressures are considerably lower than those required for achieving near full density with conventional nanopowders. Hardness and fracture-toughness measurements showed that the ceramics prepared by SPS had superior mechanical properties to those prepared by conventional pressureless sintering. It is argued that the high sinterability of the MCP nanopowders is ascribed to their ability to form uniform powder compacts under relatively low pressure, and that that ability in turn originates in two features of the MCP powders: absence of hard agglomeration and pseudo-spherical particle morphology.     

Sintering Behavior and Microwave Dielectric Properties of MgTiO3 Ceramics Doped with B2O3 by Sol-Gel Method

The B2O3-doped MgTiO3 powders and ceramics have been prepared by sol-gel method using Mg(NO3)2·6H2O, Ti(C4H9O)4 and H3BO3 as the starting materials. The sintering behavior and microwave dielectric properties of ceramics prepared from powders with different particle sizes were investigated. The gels were calcined at 650, 700, 750, 800, 850 and 900 C and the derived particle sizes of powders were 20-30 nm, 30-40 nm, 40-60 nm, 60-90 nm, 90-120 nm and 120-150 nm, respectively. The nanoparticles with the size of 30-60 nm benefited the sintering process with high surface energy whereas nanoparticles with the size of 20-30 nm damaged the microwave dielectric properties due to the pores in the ceramics. The addition of B2O3 used as a liquid sintering aid reduced the sintering temperature of MgTiO3 ceramic, which was supposed to enter the MgTiO3 lattice and resulted in the formation of (MgTi)2(BO3)O phase. The B2O3-doped MgTiO3 ceramic sintered at 1100 C and prepared from the nanoparticles of 40-60 nm had compact structure and exhibited good microwave dielectric properties: εr=17.63, Q × f=33,768 GHz and τ f= 48×10 6 C 1.     

Effect of Grain Size on Phase Transformation and Photoluminescence Property of the Nanocrystalline ZrO_2 Powders Prepared by Sol-Gel Method

Nanocrystalline zirconia （ZrO2） powders were prepared by a sol-gel process followed by annealing treatments from 500 to 1200 ℃. Phase transformation, microstructural features and photoluminescence properties were characterized by X-ray diffraction, transmission election microscopy and photoluminescence spectra, respectively. The results show that both monoclinic phase and tetragonal phase exist in the nanocrystalline ZrO2 powders at annealing temperature in the range of 500-900 ℃, and the concentration of monoclinic phase increases with increasing the annealing temperature. Tetragonal phase is totally transformed to monoclinic phase when annealing temperature is up to 900 ℃. The average grain size of the powders also increases when annealing temperature increases. Two emission peaks centered at 390 nm （named as /390） and 470 nm （named as /470） exist in the photoluminescence spectra, and the intensity ratio of /390 to /470 decreases with increasing annealing temperature. The grain size is proposed to be responsible for the phase transformation in the nanocrystalline ZrO2 powders.     

Consolidation behavior of L12 phase (Al + 12.5 at.% Cu)3Zr powder with nanocrystalline structure during CIP and subsequent sintering

The mechanically alloyed (Al + 12.5 at.% Cu)₃Zr powders were consolidated by cold isostatic pressing (CIP) and subsequent sintering. Effects of CIP pressure and sintering temperature on the stability of metastable L1₂ phase and nanocrystalline structure were investigated. Before sintering, the powders were CIPed at 138, 207, 276, and 414 MPa. The relative densities of the CIP compacts were not greatly affected by the CIP pressure. However, the L1₂ phase of the specimen CIPed at pressures greater than 276 MPa was partially transformed into D0₂₃. The optimum consolidation conditions for maintaining L1₂ phase and nanocrystalline microstructure were determined to be CIP at 207 MPa and sintering at 800 °C for 1 h for which the grain size was 34.2 nm and the relative density was 93.8%. Full density specimens could be prepared by sintering above 900 °C, however, these specimens consisted of L1₂ and D0₂₃ phases. The grain sizes of all the specimens were confirmed by TEM and XRD, and were found to be less than 40 nm. This is one of the smallest grain sizes ever reported in trialuminide intermetallic compounds.     

非均相沉淀法制备纳米α-Al2O3/金属复合粉体

利用非均相沉淀法制备了平均粒径小于50 nm的α-Al₂O₃/W(Ni)复合粉体,并研究对比了纳米钨和镍对α-Al₂O₃相转变温度的影响。结果表明:纳米钨和镍的存在均可降低过渡型氧化铝向α型氧化铝转变的相变温度,但降低程度有所不同,含钨氧化铝于1000℃完成相变,而含镍氧化铝于1150℃完成相变;并且纳米第二相体积比越大,对相变温度的影响也越大。     

共沸蒸馏法制备超细氧化铝粉体及其表征

用改进的溶胶－凝胶法（ｓｏｌ－ｇｅｌ）制备了单分散纳米级Ａｌ_２Ｏ_３粉体,研究了不同干燥方法对产品粒子性能的影响．结果表明,共沸蒸馏法能够有效地对氢氧化铝凝胶脱水,防止了硬团聚体的形成．在１１５０℃的温度下煅烧,可制得尺寸分布均匀、呈球形的α－Ａｌ_２Ｏ_３超细粉体,其平均粒径为６８ｎｍ．以透射电镜（ＴＥＭ）、Ｘ射线衍射（ＸＲＤ）、热重（ＴＧ）、差热（ＤＴＡ）、比表面测定（ＢＥＴ）等手段对所得的超细Ａｌ_２Ｏ_３粉体进行了表征．     

纳米Y2O3:Eu3+的荧光特性

本文采用均相沉淀法制备纳米Ｙ２Ｏ３：Ｅｕ＾３＋，并控制反应条件，得到不同粒径的生粉，与非纳米粉体相比。纳米Ｙ２Ｏ３：Ｅｕ＾３＋的Ｘ－ｒａｙ衍射粉变宽，２θ角增大，同时发射光谱存在蓝移现现象，谱峰波长及强度与粒径有密切联系。     

Structure of polycrystals produced by sintering nanocrystalline powders of cubic and wurtzitic boron nitrides

The structure and some properties of polycrystals produced by sintering nanocrystalline powders of the dense modifications of shock—wave-synthesized BN have been studied. The sintering was conducted at a static pressure of 7.7 GPa and temperatures from 1100 to 1800° C. The highest density (3 g/cm³) and microhardness (up to 20 GPa) have been exhibited by polycrystals produced by sintering the powder containing wurtzitic and cubic modifications in amounts that are approximately equal. In the temperature range from 1100 to 1300° C the wurtzitic phase transformed into the cubic one. In this temperature range the average size of cBN grains changed from 20 to 50 nm. The structure of compacts is characterized by the presence of grain (grain-boundary) interlayers 2–5 nm in thickness.