β-Si3N4晶种的制备、性能与机理研究

本论文通过对β-Si3N4粉末的加入量、烧结助剂的种类及煅烧温度等参数的合理选择及优化,达到对β-Si3N4晶粒尺寸和形貌的有效控制,并探讨分析β -Si3N4晶种的反应机理.以MgO、Y2O3及SiO2为助烧剂,加入一定量的β-Si3N4粉末,通过对原始α-Si3N4粉末进行热处理,经去除掉玻璃相等漂洗工艺后,制备出相变充分、具有柱状形貌β-Si3N4晶种.重点研究了β-Si3N4粉末加入量及助烧剂种类对Si3N4相变、晶体形貌及晶粒尺寸分布的影响.研究结果表明:β-Si3N4粉末添加量10 wt;、MgO添加量5wt;时,在1750℃下热处理1.5h能得到具有比较理想长径比、缺陷少且晶粒尺寸与长径比分布较均匀β-Si3N4品种,平均长径比接近于7.0.     

Y2O3-Al2O3含量对Si3N4陶瓷相组成、致密化、显微结构和力学性能的影响

以α-Si3N4粉为原料,通过添加不同含量的Y2O3-Al2O3烧结助剂(6wt;、8wt;和10wt;),在1800℃下采用热压烧结制备了Si3 N4陶瓷,研究了Y2 O3-Al2 O3含量对Si3 N4陶瓷的物相、致密度、显微结构与力学性能的影响,结果表明:添加6wt;的Y2 O3-Al2 O3助剂即可获得高致密的Si3 N4陶瓷,继续增加助剂含量对Si3 N4陶瓷的致密度影响不大,但是显著影响 α-Si3 N4相和β-Si3 N4相的含量,较高的Y2 O3-Al2 O3助剂含量有利于α-Si3 N4转化为β-Si3 N4.不依赖于Y2 O3-Al2 O3助剂含量,Si3 N4陶瓷均包含细小的等轴晶粒和大尺寸的棒状晶粒,呈现双峰结构,但是Y2 O3-Al2 O3助剂含量增加到10wt;时,可以显著增加棒状晶粒的数量,形成更显著的双峰结构.基于当前研究,发现加入低含量的Y2O3-Al2O3助剂(6wt;),可以获得高硬度高强度的Si3N4陶瓷,而引入高含量的Y2O3-Al2O3助剂(10wt;),则可以获得高韧性高强度的Si3N4陶瓷.     

立方氮化硼(cBN)对Si3N4/cBN复合材料力学性能及Si3N4相变的影响

以不同粒径和含量的cBN在六面顶压机中高温高压制备了Si3N4/cBN复合材料.观察了样品的微观形貌、β-Si3N4含量,测试了抗弯强度和密度.结果发现,cBN颗粒形貌和分布状态对β-Si3N4颗粒生长有很大影响,cBN含量在一定范围内,随着cBN粒径的减小,试样的密度和抗弯强度增大.cBN含量达到70;时,由于出现大量“搭桥”结构,影响断面上的正应力和剪力,结果使材料抗弯强度减小.同时“搭桥”结构不利于试样的致密.实验结果对新型刀具材料Si3N4/cBN有指导意义.     

烧结助剂及β-Si3N4添加量对多孔氮化硅陶瓷性能的影响

通过添加不同烧结助剂(Lu2O3、Y2O3和Al2O3)及β-Si3N4粉末含量,采用常压烧结工艺制备出性能优异的多孔氮化硅陶瓷.研究了烧结助剂种类及β-Si3N4添加量对多孔氮化硅陶瓷物相、微观组织和力学性能的影响.结果表明:当Lu2O3添加量为5 wt;、β-Si3N4为3 wt;时,制备了由长柱状β-Si3N4晶粒组成、平均长径比为6.87、直径为0.6μm长度为4.4～10.4 μm的多孔氮化硅陶瓷,其抗弯强度可达330.7 MPa.β-Si3N4添加量至5 wt;时,柱状晶粒发育良好,长径比增加至7以上,气孔率高达48;,但抗弯强度下降.     

Yb2O3-Al2O3烧结助剂对气压烧结氮化硅陶瓷性能的影响

以Yb2O3-Al2O3体系为烧结助剂,采用气压烧结法制备了氮化硅陶瓷.研究了烧结温度对气压烧结氮化硅陶瓷的致密度、失重率、物相、力学性能与显微结构的影响及材料的烧结机理.结果表明:随着烧结温度的升高,氮化硅的致密度、抗弯强度、断裂韧性和硬度均呈现先增加后降低的趋势,而失重率呈现一直升高的趋势;当烧结温度为1780℃、烧结气压为6 MPa时,所得氮化硅烧结体的体积密度(3.31 g·cm-3)、抗弯强度(967.2)、断裂韧性(8.9 MPa·m1/2)和硬度(17.1 GPa)达最大值,晶粒以长柱状的β相为主;烧结温度高于或等于1700℃时,材料中的α相可完全转化为β相,β-Si3 N4晶粒的平均长径比达12.31.     

以β-Si3N4为晶种多孔氮化硅陶瓷的制备

以β-Si3N4为晶种、α-Si3N4为原料、Mgo-Al2O3-SiO2体系为烧结助剂,制备了气孔率约为30;的多孔氮化硅陶瓷,研究了β-Si3N4晶种添加量对其物相、微观形貌和弯曲强度的影响.结果表明,加入β-Si3N4晶种能有效地促进α-Si3N4转化为β-Si3N4,经1580℃烧结的氮化硅陶瓷中出现了明显的长柱状晶粒,随着晶种添加量的增加,柱状晶的长径比逐渐增大,且柱状晶的产生可提高材料的强度.     

ZrB2粒径对Si3N4-ZrB2陶瓷相组成、显微结构及电阻率的影响

以20vol; ZrB2粗粉和细粉为导电相,以3vol; MgO-2vol; YB2O3烧结助剂,通过热压烧结在1500℃制备了Si13N4-ZrB2复相陶瓷,研究了ZrB2粒径对致密度、相组成、显微结构以及电阻率的影响.结果表明,不依赖于Zrl2粒径,通过引入MgO-YB2O3烧结助剂,均可以获得高致密Si3N4-ZrB2陶瓷.以Zrl2粗粉为原料时,Si3N4-ZrB2陶瓷包含主要的αt-Si3N4 、β-Si3N4和ZrB2相以及微弱的Yb4 Si2N2O7相,由于ZrB2晶粒保持孤立状态,样品电阻率较高,为9.5×103 Ω·m;而以ZrB2细粉为原料时,其与Si3N4发生轻微的高温反应,除了包含主要的d-Si3N4、β-Si3N4和ZrB2相及微弱的Yb4Si2N2O7相之外,Si3 N4-ZrB2陶瓷还含有新生成的微弱ZrSi2和ZrN导电相,由于ZrB2晶粒保持连通状态,样品电阻率显著降低,仅有6.8 Ω·m.     

以β-Sialon为过渡层的Si3N4-Al2O3梯度材料的微波烧结行为及性能

在粉末叠层基础上于1550℃,保温30 min的微波烧结条件下,合成了以β-Sialon为过渡层,Si3N4和Al2O3为端元组分的梯度材料.SEM分析显示烧结试样表面气孔少,晶粒之间排列紧密,结构均匀;XRD分析表明由于组分之间的固溶反应,梯度材料中β-Sialon相的z值在1～3范围内呈现规律性变化.各烧结试样的体积密度在2.9～3.5 g/cm3之间,相对密度在90; ～ 96;之间,热膨胀系数随着成份的变化而呈现出从Al2O3端到Si3N4端呈逐渐下降的趋势.     

高热导率Si3N4陶瓷的高压合成及性能研究

在高温高压条件下(HPHT,4 ～5 GPa,1430 ～1530℃),采用高压烧结技术,利用Y2O3、MgO作为烧结助剂,通过和不同质量配比的氮化硅(a-Si3N4,β-Si3N4)粉体复合,制备了具有高热导率和高致密性的Si3N4陶瓷.本实验采用X射线衍射(XRD)、扫描电子显微镜(SEM)、能谱EDS、热导率测定仪、维氏硬度计对样品进行了分析和表征,研究了压强、烧结温度、保温时间对热导率和致密性的影响.结果 表明:超高压条件有效降低了烧结温度,缩短了烧结时间.当烧结条件在5 GPa,1490℃,1h时,其硬度为16.5 GPa,此时β-Si3N4复合陶瓷的致密化最优,气孔率(0.26;)和晶格缺陷显著改善.研究发现适当的延长烧结时间可以促进晶粒正常长大,同时产生较高的热导率,最高可达到64.6W/(m· K).     

MgO-Al2O3-Re2O3(Re=Lu,Y)对无压烧结Si3N4陶瓷显微结构和性能的影响

研究了MgO-Al2O3-Re2O3(Re=Lu,Y)三元烧结助剂体系对无压烧结Si3N4陶瓷显微结构和力学性能的影响.研究结果表明,添加MgO-Al2O3-Lu2O3三元助剂制备的Si3N4陶瓷显微结构具有明显的双峰分布,晶粒较粗化,致密度、硬度、弯曲强度、断裂韧性分别为96.4;、14.59 GPa、964 MPa、7.64 MPa·m1/2;而添加MgO-Al2O3-Y2O3三元助剂制备的Si3N4陶瓷具有细化的显微结构,致密度、硬度、弯曲强度、断裂韧性分别为99.9;、15.29 GPa、758 MPa、6.60 MPa·m1/2.     

Crystal and molecular structures of three trimethylamine-boron halide adducts: (CH3)3NBCl3, (CH3)3NBBr3, and (CH3)3NBI3

X-ray diffraction data from single crystals of the trimethylamine complexes of the three boron halides, BCl₃, BBr₃, and BI₃, lead to aP2₁/m monoclinic cell containing two molecules for each complex. The unit cell dimensions area = 6·68(1),b = 10·247(3),c = 6·502(6) Å, =116·2(1)° (chloro);a = 6·86(1),b = 10·612(4),c = 6·737(6) Å, = 115·8(1)° (bromo);a = 6·92(2),b = 10·86(1),c = 7·147(6) Å, = 93·9(1)° (iodo). The structures were solved by three-dimensional sharpened Patterson functions and show only the chloro and bromo compounds to be isomorphous. Refinement of 662,718 and 954 observed reflexions for the chloro, bromo and iodo complexes, respectively, using anisotropic thermal parameters yielded conventionalR factors of 0·045, 0·087 and 0·054.The molecules are shown to possess a B—N dative bond, a staggered conformation, and effective 3m (C _3v) symmetry. Average C—N bond lengths are 1·52(1) Å for all three complexes. Boronhalogen bond lengths average 1·864(4), 2·04(2) and 2·28(2) Å, while B—N bond distances are 1·609(6), 1·60(2) and 1·58(3) Å, respectively, for the chloro through iodo compounds. Bond angles are approximately tetrahedral with the C—N—C angle decreasing by several degrees in the Cl Br I series.Based in part on a dissertation submitted by Patty H. Clippard to the Rackham School of Graduate Studies of the University of Michigan, January 1969 in partial fulfillment of the requirements of the Ph.D. Degree.     

The structures of three trimethylarsine-boron trihalide adducts: (CH3)3AsBCl3, (CH3)3AsBBr3, and (CH3)3AsBI3

An X-ray structure analysis of three trimethylarsine-boron trihalide adducts has been undertaken. Crystals of (CH₃)₃AsBCl₃ and (CH₃)₃AsBBr₃ are monoclinic with space groupP2₁/m (No. 11) withZ=2 while those of (CH₃)₃AsBI₃ are orthorhombic with space groupPnma (No. 62) withZ=4. For (CH₃)₃AsBCl₃,a=6.497(3) Å,b=10.735(3) Å,c=7.070(2) Å,=111.8(3)°,V=458.4(3) ų,R=0.0343. For (CH₃)₃AsBBr₃,a=6.672(4) Å,b=11.135(7) Å,c=7.199(4) Å,=111.5(1)°,V=497.7(5) ų,R=0.0434. For (CH₃)₃ÅsBI₃,a=13.113(7) Å,b=11.733(5) Å,c=7.387(3) Å,V=1136.5(5) ų,R=0.0329. The As-B bond lengths are 2.065(6), 2.04(1), and 2.03(1) Å, respectively, for the chloride, bromide, and iodide. These and other structural parameters are discussed with reference to previous predictions based on vibrational spectra and previous structural studies on the trimethyl-phosphine and trimethylamine adducts.     

Growth and characteristic of Sr3Tb(BO3)3 crystal

A new borate single crystal of Sr₃Tb(BO₃)₃ with dimension Ф20×25 mm² has been grown by the Czochralski method. The grown crystal was characterized by DTA–TGA, FTIR and X-ray powder diffraction analysis. The results showed the crystal with [BO₃]^3? is congruently melting at 1351.35 °C which belongs to hexagonal structure. The hardness of Sr₃Tb(BO₃)₃ crystal is 422.5 VDH, and is equal to 5.0 moh. The thermal expansion coefficients were determined to be 2.08×10^?5/°C along (1 0 0) direction and 7.43×10^?6/°C along (0 0 1) direction and the transmission spectrum was measured in 320–1800 nm at room temperature. The magnetic properties of the single crystal were studied which showed its paramagnetism and magnetic anisotropy. The specific Faraday rotation of single crystal was measured at room temperature in 532, 633, and 1064 nm wavelength. The Verdet constants and magneto-optical figures of merit were investigated. The primary emphasis is laid to explore a new magneto-optical material, all the magneto-optical properties of Sr₃Tb(BO₃)₃ are comparing to the ones of TGG.     

纯LaAlO3和Ce3+:LaAlO3单晶的吸收谱和透过谱研究

本文采用中频感应提拉法成功生长了LaAlO3和Ce3+:LaAlO3晶体.沿生长方向即α轴方向切割、抛光后得到实验样品.测试了氢气退火前后纯LaAlO3和Ce3+:LaAlO3从190nm到2500nm的吸收谱和透过谱.测试结果表明:纯LaAlO3晶体在196～220nm处出现宽带吸收,氢气退火后此一波段的吸收系数明显降低;未退火的Ce:LaAlO3晶体在196～209nm,246nm,314nm出现明显的吸收波段,氢气退火后其吸收谱发生显著变化,在198,206,214,246和314nm处出现对应于Ce3+的4f-5d的跃迁吸收;Ce:LaAlO3晶体较之纯LaAlO3晶体在红外区的透过率要高;氢气退火后,Ce:LaAlO3晶体和纯LaAlO3晶体在红外区的透过率下降.     

Infrared vibrational Modes in Tl3SbS3, Tl3AsS3, and Tl3AsSe3 crystals

Reflectivity spectra of Tl₃SbS₃, Tl₃AsS₃, and Tl₃AsSe₃ crystals have been investigated in the wave number range 50–600 cm⁻¹ for the polarizations E∥c and E⟂c. The fundamental phonon parameters, the limiting dielectric constants ϵ_∞ and ϵ_S and the reflectivity spectra contours have been calculated by using classical dispersion relations for both E∥c and E⟂c configurations. The Szigeti effective charges and the relative ion charges of As, Tl, Sb, Se, S anions and cations have been calculated in dependence on the incident light polarization.     

Crystal Growth and Spectroscopic Characterisation of BiB3O6:RE3+ (RE3+ = Pr3+, Nd3+, Gd3+, Er3+, Tm3+)

Large single crystals of optical quality of BiB₃O₆:RE³⁺ (RE³⁺ = Pr³⁺, Nd³⁺, Gd³⁺, Er³⁺, Tm³⁺) were grown from nearly stoichiometric melts using the top‐seeding growth technique to dimensions up to 12 x 12 x 18 mm³. Absorption spectra were measured in the wavelength range from 10000 cm^‐1 to 30000 cm^‐1 with an absorption spectrometer to estimate the doping concentration of RE³⁺. For the determination of the phonon energies and the quenching behaviour of the host lattice IR and Raman spectra were recorded.     

Growth and magnetic‐optical properties of Sr3Gd(BO3)3 and Sr3TbxGd1‐x(BO3)3 single crystals

Single crystals of Sr₃Gd(BO₃)₃ (SGB) and Sr₃Tb_xGd_1‐x(BO₃)₃ (TSGB) with dimension Ø 20 mm×20 mm have been grown by Czochralski method. The grown crystals were characterized by X‐ray powder diffraction analysis which showed the crystals belong to hexagonal structure with lattice parameters of a=b=1.254 nm, c=0.926 nm (SGB) and a=b=1.253 nm, c=0.925 nm (TSGB). In TSGB, x=17.7% was obtained by X‐ray fluorometry which showed the segregation coefficient of Tb is closed to 1. The transmission spectrum was measured, which indicated the crystals have high transmittance in 400‐1100 nm region. The Faraday rotation of single crystals at 532 nm wavelength was measured at room temperature. Finally, the Verdet constants were investigated, (SGB) V=17.9 degcm^‐1T^‐1 and (TSGB) V=21.3 degcm^‐1T^‐1. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

不同热处理氛围改善CH3NH3PbI3钙钛矿薄膜形貌和结晶

有机-无机金属卤素钙钛矿太阳能电池作为新一代光伏技术已经吸引到众多关注.近期研究表明,不管是在介空结构还是平面异质结结构的钙钛矿电池中,每次钙钛矿效率的重大突破都归因于钙钛矿薄膜质量的提高.钙钛矿太阳能电池与其他多晶薄膜太阳能电池相似,增加晶粒尺寸和减少晶界可以极大的增加器件效率.在本文中,钙钛矿薄膜形貌和结晶度在最优化的热处理过程可以得到极大的改善和提高.我们制备的高性能平面异质结钙结构钙钛矿太阳能电池,获得了17.81;的最高效率和17.44; ±0.5;的平均效率.     

Na3La2(BO3)3晶体生长及光谱特性

本文以起始摩尔比为1:1的Na2CO3:H3BO3,并添加5;质量分数的NaF为助熔剂,用顶部籽晶法生长出φ35mm×5mm的透明Na3La2(BO3)3单晶.该晶体属正交晶系,空间群:Amm2,晶胞参数为a=0.51580(10)nm,b=1.1350(2)nm,c=0.73230(15)nm,α=β=γ=90°.测量了Na3La2(BO3)3晶体在室温下的透过光谱,紫外截止波长约为200nm.该晶体常温下稳定,不吸潮,但却易溶于稀酸.