可控膨胀Zr2P2WO12/Ni复合材料的制备及性能

采用化学共沉淀法制备陶瓷Zr2P2WO12 (ZWP)和金属Ni复合材料粉体,烧结过程中还原剂柠檬酸将金属Ni2+还原.粉体中ZWP粒径100～200 nm,金属Ni粒径50～100 nm,且混合均匀.复合材料块体的制备采用冷压和放电等离子体烧结(SPS)两种方法,结果表明SPS制备的样品具有更好的块体致密度,可达84;以上.研究表明,通过调节Ni离子的掺杂比例可制备出热膨胀系数从负值到正值的可控热膨胀系数复合材料.当Zr2P2WO12/Ni的摩尔比为5∶5时,制备出的材料为近零膨胀复合材料.     

粉体粒径及烧结工艺对ZrB2陶瓷致密化行为与晶粒长大的影响

利用热压烧结(HP)和放电等离子烧结(SPS)制备了ZrB2陶瓷,研究了粉体粒径和烧结工艺对ZrB2陶瓷致密化行为和晶粒长大的影响.结果表明,相同工艺下以平均粒径为200 nm的ZrB2粉体为原料替代平均粒径为2μm的ZrB2粉体可以明显促进粉体的致密化烧结,采用SPS替代HP工艺可以显著降低粉体的致密化温度,采用平均粒径为200 nm的ZrB2粉体在1900℃进行SPS工艺烧结即可实现ZrB2陶瓷的致密化烧结.     

La_2Zr_2O_7∶Eu发光材料的共沉淀法制备与表征

采用共沉淀法制备La2Zr2O7∶Eu纳米粉体。采用热分析和XRD研究了前驱沉淀物在不同热处理温度下的物相组成。采用SEM观察所制备纳米粉体的显微形貌。使用荧光光谱仪测试了样品的激发光谱和发射光谱。结果表明,1200℃热处理2 h制备的La2Zr2O7∶Eu纳米粉体颗粒基本上呈球状,分散性较好,粒径分布在30~50 nm。光谱分析表明,La2Zr2O7∶Eu纳米粉体的激发光谱属于Eu3+的特征谱带,其中强度最大的峰值位于285 nm的谱带,属于O2--Eu3+的电荷迁移带。样品的发射光谱分布于570~650 nm之间,主发射峰位于585 nm。Eu3+的最佳掺杂量为5 mol%。     

Y2O3添加对Yb2Si2O7无压烧结致密化的影响

以Yb2O3粉末和溶胶-凝胶法制备的活性SiO2凝胶为原料,在1550℃保温4h合成了具有单斜结构的单相Yb2Si2O7粉体.采用无压烧结方法获得了Yb2Si2O7陶瓷.通过添加Y2O3烧结助剂,获得了气孔率为3.2;的致密Yb2Si2O7陶瓷.采用XRD、SEM方法对烧结体的结构、成分和形貌进行测试与表征.结果表明:烧结体均为单相的Yb2Si2O7,不含其它杂质相.Y2O3的添加大大降低了烧结体的气孔率,促进了烧结的致密化.所得致密Yb2Si2O7陶瓷的平均晶粒尺寸为1～2 μm,大部分晶粒为颗粒状晶粒.     

La2(Zr0.7Ce0.3)2O7纳米粉体的制备与表征

采用化学沉淀法制备了高性能热障涂层用La2(Zr0.7Ce0.3)2O7陶瓷粉体.通过TG-DSC、XRD、SEM及TEM对前驱体的烧结温度、粉体物相及微观结构进行了分析.结果表明:制备的粉体为纳米级,且颗粒分布均匀,粒径大约30 ～ 50 nm;La2(Zr0.7Ce0.3)2O7是由烧绿石结构的La2Zr2O7固溶体和萤石结构的La2Ce2O7固溶体复合组成.     

红色荧光粉Bi2-xZnB2O7∶xEu3+的制备及发光特性

采用高温固相反应法合成了Bi2-xZnB2O7∶xEu3+(x=0.06,0.08,0.10,0.12,0.15)红色发光材料,并对其制备工艺及发光特性进行了研究.利用XRD和SEM等对粉体进行了结构、纯度和形貌表征,同时讨论了烧结温度对其发光性能的影响得出最佳的烧结温度为680℃.在激发波长为465 nm的条件下,材料的发射峰主要位于582nm、596 nm、617 nm、656 nm和704 nm处,分别归属于Eu3+的5D0→7FJ(J=0,1,2,3,4)电子跃迁,其中以在617nm处的Eu3+的5D0→7F2跃迁产生的电偶极跃迁发射为最强.研究了Eu3+离子掺杂浓度对Bi2ZnB2O7∶Eu3+发光性能的影响,结果随着Eu3+离子浓度的增大,样品的发光强度先增大后减小,最佳掺杂浓度为x=0.1.     

Gd2Zr2O7/ZrO2(3Y)复相粒子原位合成的影响因素

采用原位合成法制备了Gd2Zr2O7/ZrO2(3Y)复相粒子.用XRD、SEM、TEM等测试手段分析了物相组成、产物结构和粉体形貌的影响因素.结果表明:当溶液初始浓度0.05 mol· L-1,体系温度0℃,滴定速率2 mL/min,pH=10,添加1wt;的十二烷基苯磺酸钠(SDBS)作为分散剂,经1000℃煅烧2h,获得样品的结晶度完整,颗粒较均匀,形貌近球形,粒径约50 nm,经衍射斑点分析Gd2Zr2O7为面心立方晶系,ZrO2(3Y)体心四方晶系,其中前者品格di11面的间距为0.304 nm.背散射电子像的明和暗相区分别显示出存在单相的Gd2Zr2O7和ZrO2(3Y)粒子.     

柠檬酸铵辅助溶胶-凝胶法制备Gd2Zr2O7纳米粉体及其表征

以Gd(NO3)3·6H2O、Zr(NO3)4·6H2O为原料,无水柠檬酸(C6H8O7)为螫合剂,无水乙醇做溶剂,采用柠檬酸铵(C6H17N3O7)分散剂辅助溶胶凝胶法合成分散好的Gd2Zr2O7纳米粉体.通过TG-DSC、XRD、SEM、TEM测试方法对合成的粉体进行了表征.结果表明:添加的柠檬酸铵与无水柠檬酸的摩尔量之比为1时,其溶胶的pH值为2.8左右,所制得的Gd2Zr2O7前驱体在空气中900℃煅烧4h后得到分散均匀、团聚程度轻、结晶良好的纯相Gd2Zr2O7纳米粉体,样品为缺陷型萤石结构,平均晶粒尺寸约为33 nm.     

Al2O3陶瓷非等温烧结研究

以高纯α-Al2O3粉体为原料,采用非等温烧结法制备了纯Al2O3陶瓷(AL)及掺杂MgO-Y2O3复合助剂的AJ2O3陶瓷(ALMY).研究了AL和ALMY在不同烧结温度下的相对密度、显微结构及硬度.结果表明,在非等温烧结中,纯Al2O3致密化的烧结温度范围较窄,烧结温度为1500℃时,其相对密度及硬度分别为98.1;和18.1GPa,当烧结温度为1600℃时,AL由于晶粒显著粗化,且产生了晶内气孔,相对密度及硬度分别显著下降到94.6;和12.5 GPa.MgO-Y2O3复合助剂的引入拓宽了Al2O3致密化的烧结温度范围,细化了显微结构,烧结温度在1500℃和1600℃时,ALMY的相对密度均在98;以上,硬度分别为19.2 GPa和17.6 GPa.     

水热-固相法制备Gd2Zr2O7纳米粒子

以Gd2O3和ZrOCl2.8H2O为原料,氨水为矿化剂,在200℃和12～30 h的水热条件下合成的前驱体,经固相反应获得Gd2Zr2O7纳米粒子。用X射线衍射(XRD)、热重差热(TG-DTA)、傅立叶变换红外光谱(FT-IR)、扫描电镜(SEM)等测试手段分析了样品合成过程的物相变化、产物结构及形貌特征。结果表明:在n(Gd)∶n(Zr)=1∶1,水热合成温度200℃,pH=11,保温24 h,合成的前驱体经1000℃、2 h煅烧获得分散性好、形貌近球形、粒径约23nm的Gd2Zr2O7纳米粒子。     

(C2N2H10)2Mg(HP2O7)2·2H2O synthesis and crystal structure

(C₂N₂H₁₀)₂Mg(HP₂O₇)₂·2H₂O, is a new inorganic organic hybrid structure. It has been synthetized using wet chemistry. Its crystal structure consists of cis- and trans-edge sharing [MgO₄(H₂O)₂] octahedra resulting in chains, which are linked via [HP₂O₇] units to form [Mg(HP₂O₇)₂(H₂O)₂]⁴⁻ layers. The Mg²⁺ cations and the ethylendiammonium cations are located on centers of inversion. The ethylendiammonium cations are alternately located in the interlayer space. The cohesion of the crystal is well ensured by coulombic interactions between anions and cations and by several hydrogen bonds. The diphosphate anion shows an eclipsed conformation.     

Crystal structure of Rb2[GeO2(OH)2]·2H2O

Single crystals of Rb₂[GeO₂(OH)₂] · 2H₂O are studied by X-ray diffraction. The crystals belong to the orthorhombic system, sp. gr. Pna2₁, a = 13.523(6) Å, b = 8.143(4) Å, c = 13.407(6) Å, Z = 8, R ₁ = 0.0506. In [GeO₂(OH)₂]^2? anions, the Ge-O distances (1.71–1.73(1) Å) are shorter than the Ge-OH distances (1.76–1.80(1) Å). Anions are linked to each other by pairs of hydrogen bonds to form infinite chains. The chains are linked by hydrogen bonds involving water molecules to form a 3D structure. The assignment of the bands in the IR spectrum of the compound under study is performed.     

Ultraviolet Absorption of Hg2Cl2-and Hg2Br2 Single Crystals

The optical unpolarized absorption spectra of Hg₂Cl₂ and Hg₂Br₂ single crystals were measured in the spectral range 230–400 nm. A sharp exciton peak and other absorption bands of both halides were observed near the fundamental absorption edge. The absorption peaks due to the splitting of the halogen doublet were also observed. Positions of the exciton peaks are characteristic for the Frenkel (localized) type of excitons. Possible interpretations of the other observed bands are discussed.     

Elastic properties of the dithionates Na2S2O6 · 2 H2O,K2S2O6, Rb2S2O6, CaS2O6 · 4H2O and SrS2O6 · 4 H2O

Single crystals of the title compounds having optical quality and dimensions of several cm were grown from aqueous solutions. The elastic and thermoelastic constants were determined from ultrasonic resonance frequencies of thick plates. The true point symmetry of K₂S₂O₆ and Rb₂S₂O₆, which is screened by a hexagonal hypermorphy, could be clearly revealed to be trigonal (32) by the existence of the elastic constant c₁₄. In the case of CaS₂O₆ · 4H₂O and SrS₂O₆ · 4H₂O the constant c₁₄ of the specimens appeared too small to confirm the trigonal symmetry group required from electrooptic and non-linear optic effects unambiguously. The isotypy of K₂S₂O₂ and Rb₂S₂O₆ as well as that of CaS₂O₆ · 4H₂O and SrS₂O₆ · 4H₂O is confirmed by their elastic behaviour. The mean elastic stiffness of dithionates is closely related to that of the corresponding sulphates. In the vicinity of the second-order phase transition of K₂S₂O₆ near 235 K weak anomalies of the temperature derivatives of the longitudinal elastic stiffnesses are observed.     

Optical properties of the germanate melilites Sr2MgGe2O7, Sr2ZnGe2O7 and Ba2ZnGe2O7

Refractive indices and their dispersion in the wavelength range from 365 nm to 2325 nm and transmission ranges of the tetragonal melilite‐type germanates Sr₂MgGe₂O₇, Sr₂ZnGe₂O₇ and Ba₂ZnGe₂O₇ were determined. The uniaxial positive crystals Sr₂MgGe₂O₇ and Ba₂ZnGe₂O₇ both offer the possibility for phase matched second harmonic generation, a detailed analysis of phase matching conditions is given. The refractive indices of Sr₂ZnGe₂O₇ show an isoindex (isotropic) point at 467 nm. The investigation was performed on Czochralski grown large single crystals. The crystal structure of all three germanates were determined by means of X ‐ray diffraction. The results corroborate unmodulated melilite‐type structures at room temperature. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structure of bis 4-benzyl piperidinium monohydrogenmonophosphate pentahydrate, [C6H5CH2CHCH2CH2NH2CH2CH2]2HPO4·5H2O

The salt bis 4-benzyl piperidinium monohydrogenmonophosphate pentahydrate is orthorhombic with the following unit cell dimensions: a = 11.235(2) Å, b = 27.924(6) Å, c = 9.321(4) Å space group Pca2₁ with Z = 4. The structure was solved by the Patterson method and refined to final R value of 0.049 for 1802 independent reflections. The flack parameter is 0.14 with an e.s.d. of 0.23. The structure consists of infinite parallel two-dimensional [110] planes built of mutually connected ions and water molecules by strong O—H,...,O and N—H,...,O hydrogen bonding. There are no contacts other than normal van der Waals interactions between the layers.     

Identification of a new family of diphosphate compounds, AI2BII3(P2O7)2: Structures of Ag2Co3(P2O7)2, Ag2Mn3(P2O7)2, and Na2Cd3(P2O7)2

Syntheses and single-crystal X-ray structural results are reported for three new mixed diphosphates of the family A^I ₂B^II ₃(P₂O₇)₂; Ag₂Co₃(P₂O₇)₂ (I), Ag₂Mn₃(P₂O₇)₂ (II), and Na₂Cd₃(P₂O₇)₂ (III). All crystallize in the triclinic system, space group P1 bar: (I) a = 5.351(4), b = 6.375(4), c = 16.532(4) Å, = 80.83(6) = 81.45(4), = 72.87(5)°, V = 528.9(6) ų, Z = 2, D _calc = 4.649 mg/m³, R/Rw = 0.0428/0.0548 for 3949 obs. reflns; (II) a = 5.432(7), b = 6.619(6), c = 16.51(3) Å, = 80.78(8) = 82.43(9), = 72.82(7)°, V = 557.7(13) ų, Z = 2, D _calc = 4.338 mg/m³, R/Rw = 0.0679/0.1303 for 2100 obs. reflns and (III) a = 5.67(3), b = 7.08(4), c = 7.90(4) Å, = 77.0(2), = 82.5(2), = 67.8(2)°, V = 286(3) ų, Z = 2, D _calc = 4.249 mg/m³, R/Rw = 0.0307/0.0342 for 1945 obs. reflns. (I) and (II) are isostructural but (III) is of a different type. All three structures are characterized by layers of P₂O₇ groups alternating with layers of mixed metal atoms. Differences are seen in the conglomerate bonding patterns of B atoms and in the irregular geometry of Ag in (I) and (II) compared to the octahedral bonding seen for Na in (III). The differences in structure may be understood in terms of the ratios of the ionic radii of A and B atoms.     

Synthesis and characterization of (NH4)2CuBr2Cl2·2H2O crystals

Single crystals of a new compound, (NH₄)₂CuBr₂Cl₂.2H₂O, were grown from saturated aqueous solution at room temperature by slow evaporation method. The grown crystals were characterized through elemental, powder XRD, thermal and DSC analyses and FTIR and far IR spectra. The elemental analysis and the decomposition pattern formulated using the TG‐DTG studies confirm the stoichiometry of the compound. The crystallinity of the compound is confirmed from the powder XRD pattern. A preliminary single crystal X‐ray diffraction structural analysis reveals that the title compound belongs to the orthorhombic system with a = 7.7466 Å, b = 7.783 Å and c = 8.1211 Å. The low temperature DSC shows thermal anomalies at –161.1, –156.5, –152.4, –145.2, –134, –18.5, and 1.4°C during the heating run and at –4.3, –54.8, –66.1, –90.6, –109.7 and –147.2 °C during the cooling run. The thermal hysterses indicate first order phase transitions in the title compound at these temperatures. The FTIR spectra were used to assign the characteristic vibrational frequencies due to NH₄⁺, CuX₄^2– ions and other chemical bonds. The effect of substitution of two bromine atoms on the phase transitions of a closely related crystal, diammonium tetrachloro cuprate dihydrate is also discussed. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optical Properties of MnIn2S2Se2 Single Crystals

Optical transmittance and reflectance spectra of MnIn₂S₂Se₂ single crystals are measured in the wavelength range from 0.5 to 30 μm. The interference method is used to determine the refractive index of the compound for wavelengths between 0.8 and 12 μm. From an analysis of the absorption spectrum it follows that the fundamental edge is due to forbidden indirect transitions between parabolic bands for the polarization E ⊥ c with a gap energy of 1.50 eV at room temperature.     

Oxygen-conducting compounds with La2Mo2O9 structure in the ternary system La2Mo2O9-Sm2W2O9-Sm2Mo2O 9 + : Synthesis and properties

Polycrystalline samples in the ternary system La₂Mo₂O₉-Sm₂W₂O₉-Sm₂Mo₂O ₉ ⁺ were synthesized in air. The region of the existence of compounds with the lanthanum molybdate (La₂Mo₂O₉) structure in this system was determined. The polymorphism of the synthesized compounds was studied. Doping with samarium or with samarium and tungsten was shown to lead to the suppression of the transition between the monoclinic and cubic phases α → β and the appearance of the transition β _ms → β between two cubic phases. In samples with a high samarium content, the phase transition β _ms → β manifests itself as significant anomalies in the temperature dependences of the dielectric permeability and electric conductivity. An increase in the concentration of samarium in the samples leads to a substantial decrease in the conductivity compared with the nondoped compound La₂Mo₂O₉.