低温耦合固相氮化反应合成β-Sialon

本研究拟在氮化气氛下,以金属Al粉、Si粉、α-Al2O3为原料,添加Y2O3,耦合氮化反应制备β-Sialon.通过在不同温度下的氮化反应烧结试验,研究了Y3+对β-Sialon晶相组成、晶粒大小、晶格常数及显微结构的影响.采用XRD和SEM表征试样中的晶相和显微结构,利用X'Pert Plus软件对试样进行晶胞参数分析,通过Semi-quantification法对试样各晶相组成进行计算.结果表明:随着温度的升高,合成β-Sialon相的含量不断提高,在1550℃时达到最高;添加Y2O3可以在相对较低温度条件下合成β-Sialon相,y3+对Al3+的置换作用导致β-Sialon相结构畸变,且随耦合氮化反应烧成温度的升高,晶胞体积可由1350℃时的0.208448 nm3增大到1550℃时的0.236776 nm3,合成β-Sialon相呈现增加的趋势.同时在合成β-Sialon结构中,由于过量助烧结剂Y2O3易与原料中Al2O3形成针状YAG.     

Co2+,Er3+:Y3Al5O12晶体的生长及其吸收特性

应用中频感应提拉法成功生长出新型的Co2+,Er3+:Y3Al5O12晶体.研究了室温下晶体的吸收光谱性能.结合Er3+:Y3Al5O12晶体的光谱,并利用调Q判据对Co2+,Er3+:Y3Al5O12晶体调Q特性进行了简单的分析.结果表明Co2+,Er3+:YAG晶体是一种很有潜力的自调Q激光晶体.     

TiO2和Cr2O3作晶核剂对金矿尾砂微晶玻璃结晶性能的影响

以金矿尾砂为主要原料,方解石、硼砂等为添加原料,采用熔融法制备CaO-Al2O3-SiO2系微晶玻璃.采用X射线衍射分析(XRD)、差热分析(DSC)、扫描电镜(SEM)等分析手段对所制备样品进行性能测试与结构表征,研究了TiO2和Cr2O3对金矿尾砂微晶玻璃结晶性能的影响.结果表明,以2; TiO2为晶核剂,金矿尾砂微晶玻璃只有表面析晶,晶相从表面向内部生长;以4; TiO2为晶核剂,样品内部析出少量团聚晶体;以2; Cr2O3为晶核剂,样品内部析出少量团聚粒状晶体;以2; TiO2和2; Cr2O3为复合晶核剂,样品内部析出大量均匀分布的颗粒状晶体,极大地提高了金矿尾砂微晶玻璃的整体析晶能力,主晶相为透辉石(CaMgSi2O6),次晶相为钙长石(CaAl2Si2O8).     

Al2O3-ZrO2-YAG复相粉末的低温合成研究

用低温原位合成技术制备了Al2O3-ZrO2-YAG复相粉末,在1100℃,5h热处理后,Al-Zr-Y-O体系中的主相为ZrO2四方相,其余为无定形相,表明ZrO2抑制了Al2O3和YAG晶粒的生长,同时Al2O3和YAG抑制了ZrO2从四方相向单斜相的转变.在1580℃,1h热处理后,Al-Zr-Y-O体系中的复相组成为(115+90x)Al2O3+54(Y2O3)x·ZrO2+(32-36x)YAG,其中0 ≤x＜0.88(mol).     

Cr2O3对白云鄂博西尾矿微晶玻璃显微结构及性能的影响

以白云鄂博西尾矿和粉煤灰为主要原料,采用熔融法制备了添加0～2.0wt; Cr2O3的CaO-MgO-SiO2-Al2O3系微晶玻璃,利用DTA、XRD、FESEM、EDS和综合力学性能仪等测试手段,研究了Cr2O3含量对该体系微晶玻璃显微结构及性能的影响.实验结果表明:少量Cr2O3 (0.5wt;)可有效降低样品的晶化温度,促进主晶相辉石相(Ca(Mg,Fe,Al) (Si,Al)2O6)的形成,同时细化其显微组织,从而提高样品的密度、抗折强度和耐酸碱性;当Cr2O3含量大于等于1.5wt;时,析晶峰温度由804℃提高到816℃,同时微晶玻璃中形成不规则块状结构的镁铁铬尖晶石(MgFeo.9 Cr1.1O4)第二相,并进而引起周围辉石相晶粒异常长大,降低其抗折强度.     

MgAl2O4:Cr3+单晶光纤生长与荧光温度特性研究

采用激光加热基座法制备了0.5at;Cr3+掺杂镁铝尖晶石单晶光纤.通过XRD、荧光光谱、荧光寿命测试对所制备的单晶光纤的晶相、荧光温度特性进行了实验研究,结果表明所制备的MgAl2O4:Cr3+单晶光纤的主晶相为MgAl2O4晶相,镁铝尖晶石晶相结构并没有因Cr3+掺入而发生改变,在405nmLED激发下,随着温度升高MgAl2O4:Cr3+单晶光纤荧光强度下降,尤其是2E→4A2能级跃迁产生的荧光强度下降明显,同时随着温度的升高,MgAl2O4:Cr3+单晶光纤的荧光寿命随温度单调下降,系统荧光寿命从室温293K的7.74ms下降到723K的0.5ms左右.由于其相对较长的荧光寿命,MgAl2O4:Cr3+单晶光纤非常适合作为荧光温度敏感材料应用于荧光寿命型光纤温度传感器.     

ZrO2 (Y2O3) 增韧SiC中介结合的金刚石聚晶烧结体的相结构与性能

本文采用恒沸腾水解法制备了颗粒度均一的亚微米晶ZrO2 (Y2O3)粉体,并以其为增韧相,在高温(1350℃)超高压(5GPa)条件下制备ZrO2 (Y2O3)+SiC+金刚石的聚晶烧结体(PCD).用XRD、SEM背散射分析、冲击韧性测定和磨耗比测定研究了不同含量Y2O3稳定的ZrO2粉体对SiC-金刚石聚晶烧结体结构及机械性能的影响,结果表明:ZrO2 (Y2O3)粉体中Y2O3含量＜2.2mol;时,ZrO2以四方t相+单斜m相的混合相形式存在于烧结体的结合剂基体上,t相量随Y2O3含量增加而增加,对SiC-金刚石聚晶烧结体的增韧来源于相变增韧和微裂纹增韧的叠加,当Y2O3含量＞2.2mol;时,ZrO2以100;t相存在,增韧机制为相变增韧.在2.0mol;～2.2mol;Y2O3含量范围内,PCD可获得较高的磨耗比和冲击韧性.     

Mg^2＋取代Ca^2＋对Ca1-xMgxYAl0．92Cr0．08O4晶体结构稳定性及其呈色的影响

本文以CaYAl0.92Cr0.08O4组成为基础,采用Mg2 逐步取代Ca2 ,探讨晶体的组成变化对其结构的稳定性与呈色的影响.研究表明,当Mg2 的取代量增加时,样品的晶体结构由CaYAlO4型逐步过渡到Y3AlY5OY12型,随着Mg2 的量增加,Y3Al5O12型晶体的晶胞参数c值逐渐增大,样品的红度亦随之增加.该晶体可作为陶瓷着色剂使用.     

基于多元晶粒生长抑制效应的Al2O3-TiC复相陶瓷的制备与性能研究

基于多元晶粒生长抑制效应,利用热压烧结方法制备了细晶高致密的Al2O3-TiC复相陶瓷.研究发现,仅利用第二相TiC的晶界钉扎效应,即使其含量高达30wt;,也不能有效地抑制Al2O3基体的晶粒生长.在TiC作为第二相的基础上,引入微量MgO和Y2O3,通过TiC晶界钉扎、MgO溶质滞阻和Y2O3晶界偏析等多元晶粒生长抑制作用,Al2O3基体晶粒尺寸从5.12 μm显著减小到1.82 μm,Al2O3-TiC复相陶瓷的断裂韧性从3.99±0.18 MPa·m1/2提高到5.24±0.22 MPa·m1/2.研究结果表明:利用多元晶粒生长抑制效应的协同作用,可显著细化Al2O3基复相陶瓷的显微结构,改善其力学性能.     

CaO-MgO-Al2O3-SiO2-P2O5-(F)微晶玻璃的析晶及特征

采用熔融法制备了不同P2O5及F含量的CaO-MgO-Al2O3-SiO2-P2O5-(F)基础玻璃试样,研究了CaO-MgO- Al2O3-SiO2-P2O5-(F)系微晶玻璃的析晶及特征.结果表明:在CaO-MgO-Al2O3-SiO2-8.0wt;P2O5玻璃中,表面析晶和内部析晶同时存在,析出晶体主要为钙长石(CaAl2Si2O8)相、硅灰石(CaSiO3)和α-磷酸钙(Ca3(PO4)2).玻璃中P2O5含量的提高抑制玻璃的表面析晶,同时促进了玻璃的整体析晶和α-磷酸钙晶体析出.同时添加P2O5和F的玻璃试样以整体析晶为主,析出晶体为块状氟磷灰石和粒状钙长石相.     

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.     

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.     

Second harmonic generation properties of Ca3(O3C3N3)2 ‐Sr3(O3C3N3)2 solid solutions

Solid solutions of the second harmonic generation (SHG) materials Ca₃(O₃C₃N₃)₂ (CCY) and Sr₃(O₃C₃N₃)₂ (SCY) were prepared via exothermic solid state metathesis reactions from appropriate amounts of the corresponding metal chlorides and potassium cyanate at 525 °C. The change in SHG intensity caused by the successive cation substitution is reported. Differential thermal analyses are used to explore the SCY–K(OCN) phase diagram as a medium for the growth of SCY crystals.     

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.     

Tb3+,Yb3+共掺杂LuBO3荧光粉的下转换发光

利用水热法成功合成了近红外量子剪裁荧光粉LuBO3∶15;Tb3+,x; Yb3+(x=0,1,2,4,8,12).通过X射线衍射(XRD)、光致发光谱(PL)、激发谱(PLE)和荧光寿命测试了合成物质的物相结构与发光性质.在286 nm(Tb3+∶7 F6→5D)紫外光激发下,观察到了Tb3∶5D4→7Fj(J=6,5,4,3)可见波段特征发射光和Yb3+:2F5/2→2F7/2的近红外光.研究了Yb3+浓度与激发发射光谱和荧光寿命之间的关系,表明Tb3+和Yb3+之间存在能量传递.当Tb3和Yb3+掺杂摩尔浓度分别为15;和2;时,近红外发射最强.计算得知,其最大下转换量子效率为160.74;.     

铒镱双掺的钒酸钇和铌酸锂晶体中的铒离子的上转换发光

利用J-O理论,计算了在铒、镱双掺的钒酸钇和铌酸锂晶体中的铒离子在室温下的晶场唯象参数Ωλ(λ=2,4,6)及辐射跃迁几率、无辐射跃迁几率和共振跃迁几率.考虑到铒、镱间的能量转移,写出了在这些晶体中的铒离子的速率方程.速率方程的解表明,在铒、镱双掺的钒酸钇晶体中的铒离子的550 nm的上转换发光,比它在铒、镱双掺的铌酸锂晶体中更为有效.这一理论结果与我们的实验观察结果一致.     

Na3La2(BO3)3的晶体结构

以Na2CO3-H3BO3-NaF为助熔剂,使用顶部籽晶法生长出Na3La2(BO3)3透明单晶.测定了Na3La2(BO3)3的晶体结构,该晶体属正交晶系,空间群:mm2(No.38),晶胞参数为a＝0.51580(10)nm,b=1.1350(2)nm,c=0.73230(15)nm,α＝β＝γ＝90°,V＝0.42871(15)nm3,密度:.053g/cm3.晶体结构中的硼氧基团是平面的BO3基团,BO3基团相互独立,且与Na(1)O6、Na(2)O8、Na(3)O6和La(1)O9配位多面体连结形成三维网络骨架结构.讨论了Na3La2(BO3)3的晶体结构与倍频效应的关系.     

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)