热处理制度对LZAS系微晶玻璃析晶行为的影响

采用烧结法制备了Li2O-ZnO-Al2O3-SiO2 (LZAS)系微晶玻璃.采用DTA曲线初步确定了LZAS系微晶玻璃的成核和晶化温度范围,再用传统方法确定其最佳热处理制度.分别研究了核化温度、核化时间和晶化温度对LZAS系微晶玻璃析晶行为的影响.此外,还对比分析了两步和一步热处理制度对此玻璃析晶行为的影响.研究结果表明:核化温度和核化时间严重影响LZAS微晶玻璃的结晶度,对析出物相种类影响较小;晶化温度对LZAS微晶玻璃析出晶体的种类、晶粒的大小和晶体尺寸的均匀性有重要影响;两步法和一步法热处理对析出晶相的种类和材料的微观结构影响不大,但经历两步法热处理析出晶体的数量更多;LZAS系微晶玻璃在热处理过程中产生了2种相变:方石英转化为β-石英固溶体,γⅡ-LZS转化为γ0-LZS.     

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.     

P2O5对CaO-MgO-Al2O3-SiO2系微晶玻璃析晶的影响

采用熔融法制备了不同P2O5含量的CaO-MgO-Al2O3-SiO2玻璃样品,研究了P2O5对该系微晶玻璃析晶的影响规律.结果表明:在所研究的CaO-MgO-Al2O3-SiO2玻璃中,P2O5的最大溶解量在10.0;质量分数左右,超过其饱和溶解度后将析出α-磷酸钙相.玻璃中添加4.0;质量分数P2O5时以表面析晶为主,析出晶体为钙长石和少量硅灰石.随着P2O5含量的提高, α-磷酸钙逐渐析出,同时钙长石和硅灰石的析出逐渐降低.进一步提高P2O5含量抑制了玻璃的表面析晶,促进了玻璃的分相和整体析晶.当P2O5的含量达到10;时,玻璃以整体析晶为主,在分相区内外区域析出晶体的形态非常相似,均呈现为细小粒状.     

Fe2O3含量对SiO2-Al2O3-MgO-F系微晶玻璃析晶特征的影响

为研究Fe2O3含量对SiO2-Al2O3-MgO-F系微晶玻璃析晶特征的影响,采用高温熔融法制备不同Fe2O3含量的基础玻璃,利用差示扫描量热仪(DSC)、x射线衍射(XRD)及扫描电子显微镜(SEM)分别研究此基础玻璃的热效应、相组成及组织形貌.结果表明:在不同Fe2O3含量的样品中析出的晶相主要有云母、ZrO2莫来石及柱晶石,Fe2O3含量超过0.5;时莫来石相消失.随着Fe2O3含量的增加,云母的析出量逐渐提高,且晶体尺寸逐渐变大.但是当样品中Fe2O3含量超过0.8;时,云母晶体析出量反而减少且晶体尺寸变小.     

高热膨胀Na2O-MgO-Al2O3-SiO2微晶玻璃的制备及性能研究

采用传统熔体冷却法制备了Na2O-MgO-Al2 O3-SiO2玻璃并采用整体析晶工艺制备了微晶玻璃.利用DSC、XRD、SEM等测试手段研究了微晶玻璃的析晶行为和显微结构,探讨了热处理制度对该体系微晶玻璃热膨胀系数、密度、抗弯强度、显微硬度等性能的影响.研究结果表明,当晶化温度为800℃时该体系微晶玻璃主晶相为颗粒状霞石晶体(NaAlSiO4);当晶化温度达到900℃时玻璃中开始析出镁橄榄石(Mg2SiO4)晶体;延长保温时间可显著促进析晶但对晶体种类没有影响.析晶后微晶玻璃的密度、热膨胀系数、抗弯强度和显微硬度值显著增加,其最高热膨胀系数可达14.1×10-6℃-1.所制备的微晶玻璃具有很好的机械性能,当热处理温度为1000℃时,其抗弯强度和显微硬度分别达160 MPa和7.8 GPa.     

CaO和ZrO2对Ba2TiSi2O8极性玻璃陶瓷晶化和压电特性的影响

本文采用恒温场晶粒定向晶化工艺制备了Ba2TiSi2O8(BTS)极性玻璃陶瓷.以1.2BaO-1.0TiO2-2.6SiO2为基础玻璃,分别加入20;摩尔CaO和10;摩尔ZrO2,研究添加氧化物对Ba2TiSi2O8极性玻璃陶瓷的晶化和压电性能的影响.实验表明,加入CaO和ZrO2都影响主晶相的析出过程,特别是,加入ZrO2使玻璃陶瓷中产生BaZrSi3O9第二相.同时,测试结果显示,加入20;摩尔CaO有利于BTS晶体的定向析晶;而加入ZrO2不利于BTS晶体的定向析晶.     

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).     

云母/莫来石可加工微晶玻璃的制备与析晶

通过调整SiO2-MgO-Al2O3-K2O-F基础玻璃的组成和热处理条件,制备了云母/莫来石复合可加工微晶玻璃.应用扫描电子显微镜和X射线衍射技术研究了可加工微晶玻璃的析晶特征.结果表明:添加3.0;ZnO(质量分数)的基础玻璃析出了锌尖晶石相,而锌尖晶石的析出抑制莫来石相的形成,没有得到云母/莫来石复合材料.当玻璃中添加3.0;的V2O5后,在试样中同时析出莫来石和云母晶体,但没有形成莫来石/云母复合的组织.含V2O5 8.0;的玻璃在等温析晶中,从表面析出莫来石和粗大枝状的云母晶体,云母间相互交错程度较低,只有在随炉升温的情况下,云母晶体以莫来石相为核心异质生长,形成均匀分布的云母/莫来石复合微晶玻璃材料.     

铁含量及价态对白云鄂博尾矿微晶玻璃析晶特性及性能的影响

以白云鄂博尾矿及粉煤灰等固体废弃物为主要原料,采用熔融法、经退火、核化及晶化热处理制备得到了以辉石为主晶相的CaO-MgO-Al2O3-SiO2 (CMAS)系尾矿微晶玻璃.利用化学分析方法测定了不同氧化铁及碳含量对微晶玻璃中Fe3+/Fe2+的影响;利用XRD、DTA、SEM等研究了不同氧化铁及碳含量对微晶玻璃结构及析晶特性的影响.结果表明,不同氧化铁添加量对微晶玻璃中Fe3+/Fe2影响很小,因此对微晶玻璃的析晶特性无本质影响.而随着还原碳粉的加入,Fe3+/Fe2与未加碳粉相比减小明显,微晶玻璃中FeO质量分数的增加极大地提高了微晶玻璃的析晶特性.但过量的碳粉加入导致单质铁的析出,反而降低了微晶玻璃的析晶能力.上述析晶特性的变化直接影响到微晶玻璃的耐酸度及抗折强度.     

Nd3+∶ZnO-B2O3-Al2O3-SiO2系透明玻璃陶瓷的制备及表征

制备了Nd3+∶ZnO-B2O3-Al2O3-SiO2系透明玻璃陶瓷.运用差热分析(DTA)、X射线衍射(XRD)、扫描电镜(SEM)、NV-Vis-Nir(紫外可见近红外分光光度计)、傅里叶变换荧光光谱等测试方法,研究了晶核剂的含量对Nd3∶ZnO-B2O3-Al2O3-SiO2系透明玻璃陶瓷的核化和晶化性能的影响.利用修正的Kissinger方程研究了晶核剂对玻璃析晶动力学参数,析晶活化能E和析晶动力学判据k(Tp),利用Augis-Bennett方程计算出Avrami参数n.并分析其显微形貌同光透过率的关系,对光学性能进行了研究.     

(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.