Sintering and crystallization of off-stoichiometric SrO·Al2O3·2SiO2 glasses

Glass-ceramics with the celsian-corundum binary join composition of 88.8 wt% SrO·Al₂O₃·2SiO₂ – 11.2 wt% Al₂O₃, (SA2S-A), were fabricated by pressureless sintering and investigated for their sintering and crystallization behaviors. The (SA2S-A) glass powder showed crystallization peak and melting temperatures of 1059 and 1550 °C, respectively and high sintering ability. The (SA2S-A) glass powders containing B₂O₃, (SA2S-A)B and those containing B₂O₃ and TiO₂, (SA2S-A)BT showed lowered crystallization peak temperatures of 1033 and 997 °C, respectively. By applying Kissiger analyses to the DTA data of the (SA2S-A), (SA2S-A)B and (SA2S-A)BT glass powders, the activation energy values for crystallization were determined as 488, 370 and 333 kJ/mol, respectively. The Ozawa analyses on the DTA data gave the Avrami parameter values at 1.2, 1.1 and 1.9, respectively for the (SA2S-A), (SA2S-A)B and (SA2S-A)BT glass powders. The x-ray diffraction (XRD) patterns of the (SA2S-A) glass-ceramics, crystallized at 1100 °C for 4 h, showed formation of both the monocelsian and hexacelsian phases. The (SA2S-A)B and (SA2S-A)BT glass-ceramics crystallized at 1100 °C for 1 h, showed formation of the phase-pure monocelsian and did not show any evidence of the hexacelsian formation prior to the monocelsian formation.     

Thermal properties and devitrification behaviour of (1+x)CaO·(1−x)MgO·2SiO2 glasses

The thermal properties (glass transformation, T _g, and softening, T _s, temperatures), the crystalline phases formed during heating in a differential thermal analysis (DTA) apparatus, the kinetic parameters and the mechanism of the devitrification process, of glasses of the system diopside-wollastonite were investigated. The substitution of CaO by MgO induces an increase in T _g and the crystal growth activation energy, E _c; this is probably linked to the greater coordination number of Ca^z+ ions with respect to the Mg²⁺ ions. The substitution of CaO by MgO lowers the nucleation rates of the diopside phase; wollastonite solid solution nuclei form whose growth appears to leave a glassy matrix in which diopside formation is inhibited. Only surface nucleation was observed, but, in finely powdered samples, which soften and efficiently sinter before devitrifying, surface nuclei behave as bulk nuclei. When bulk crystallization occurs, the Avrami parameter m was found to be 2 for all glasses, except the diopside one, for which m=3.     

Mullite formation from xerogels of (0.84–2.2) Al2O3·1SiO2

Xerogels of (0.84–2.2) Al₂O₃·1SiO₂ prepared by chemical coprecipitation of Al(NO₃)₃·9H₂O and Si(OC₂H₅)₄ experience three thermal reaction paths for mullite formation. Those with pseudoboehmite are found to form mullite via the paths of either Al-Si spinel mullite transformation or -Al₂O₃ -Al₂O₃ + amorphous SiO₂ mullite, depending upon the ratios of Al₂O₃/SiO₂. Higher SiO₂ content may prefer the former reaction. Xerogels composed of bayerite form mullite via the route -Al₂O₃ -Al₂O₃ + amorphous SiO₂ mullite. Mullite thus formed exhibits a different crystal size, being 20–25 nm for that obtained from pseudoboehmite and around 37 nm for bayerite. The highest yield of mullite formation may be achieved with xerogels of pseudoboehmite with the stoichiometric mullite compositions, 3Al₂O₃·SiO₂.     

Effects of SrO–B2O3–SiO2 glass additive on dielectric properties of Ba(Fe0.5Nb0.5)O3 ceramics

SrO–B₂O₃–SiO₂ (SBS) glass powders were prepared and employed as sintering aids to reduce the sintering temperature of Ba(Fe_0.5Nb_0.5)O₃ (BFN) ceramics. The effects of glass content on the dielectric properties and breakdown strength of BFN ceramics have been investigated. The volume density characterization results of (1 ? x) BFN ? x SBS ceramics indicate that the sintering temperature of BFN ceramics decreased by 200–350 °C with SBS glass addition (when x = 0, 0.01, 0.03 and 0.05). The XRD patterns show BFN ceramics indicate cubic crystal structure and without the formation of a secondary phase. The dielectric constant and dielectric loss decreased gradually with increasing glass content, and the dielectric loss decreased by one order of magnitude with SBS glass addition (when x = 0.05). The breakdown strength of (1 ? x) BFN ? x SBS ceramics increase with increasing glass content, in which is about 33.90 kV/cm with SBS glass addition (when x = 0.05). These improvements in the dielectric characteristics of BFN ceramics have great scientific significance for their applications.     

Fabrication of spherical CaO–SrO–ZnO–SiO2 particles by sol–gel processing

This study was concerned with the fabrication of ceramic CaO–SrO–ZnO–SiO₂ spherical particles, which are novel candidates for the glass phase in glass polyalkenoate cements (GPCs). GPCs made from these glasses have potential as bone cements because, unlike conventional GPCs, they do not contain aluminum ions, which inhibit the calcification of hydroxyapatite in the body. The glass phase of GPCs require a controllable glass morphology and particle size distribution. Sol–gel processing can potentially be used to fabricate homogenous ceramic particles with controlled morphology. However, a thorough study on preparation conditions of spherical CaO–SrO–ZnO–SiO₂ particles by sol–gel processing has, to date, not been reported. In this study, gels were prepared by hydrolysis and polycondensation of tetraethoxysilane (TEOS) in an aqueous solution containing polyethylene glycol and nitrates of calcium, strontium and zinc. It was possible to control the morphology and size of the gels by varying the H₂O/TEOS molar ratio and the metal ion content in the starting compositions. An aliquot of 3–5 μm homogenous spherical particles were obtained at a H₂O/TEOS molar ratio of 42.6 when the starting composition molar ratios were Sr(NO₃):Ca(NO₃)₂:Zn(NO₃)₂:Si(OC₂H₅)₄ = x:0.12:(0.40 − x):0.48 (0 ≤ x ≤ 0.8). Starting composition limitations are caused by the low solubility of strontium ions in the minimal amount of water used and the acceleration of hydrolysis as well as polycondensation at higher water content.     

Synthesis and Characteristics of Double Np(VI) Potassium and Pu(VI) Potassium Silicates K[(NpO2)(SiO3OH)]·H2O and K[(PuO2)(SiO3OH)]·H2O

K[(NpO₂)(SiO₃OH)]·H₂O (I) and K[(PuO₂)(SiO₃OH)]·H₂O (II) were prepared by hydrothermal synthesis at 120°C, and their IR and near-IR spectra were measured. The unit cell parameters of the compounds were determined from powder X-ray patterns [a = 7.068(1), b = 7.064(2), c = 6.640(1) Å. = 106.68(1)°, V = 317.6 ų (I); a = 7.102(1), b = 7.100(2), c = 6.637(1) Å, = 107.62(1)°, V = 318.9 ų (II)]. These compounds are isostructural with potassium boltwoodite K[(UO₂)(SiO₃OH)]·H₂O.     

Model of the (PuO2)2SiO4·2H2O Crystal Structure,Based on Powder X-ray Diffraction Data

Plutonyl orthosilicate dihydrate (PuO₂)₂SiO₄·2H₂O was prepared by a hydrothermal procedure at 180°C. Its powder diffraction pattern (Guinier camera, CuK ₁ radiation) was indexed in the tetragonal crystal system: a 6.912(3), c 18.563(3) Å, space group I4₁/amd. The structure of (PuO₂)₂SiO₄·2H₂O is similar to the known structures of (UO₂)₂SiO₄·2H₂O and (UO₂)₂GeO₄·2H₂O, but differs in the mutual orientation of the chains of coordination polyhedra of actinide atoms (pentagonal bipyramids) sharing common equatorial edges.     

Sintering and crystallization of off-stoichiometric BaO·Al2O3·2SiO2 glasses

Glass-ceramics with off-stoichiometric celsian composition of 50 wt% BaO·2SiO₂ – 50 wt% BaO·Al₂O₃·2SiO₂, (B2S-BA2S) were fabricated and investigated for their sintering and crystallization characteristics. (B2S-BA2S) glass powder showed a melting temperature much lowered compared to that of stoichiometric BaO·Al₂O₃·2SiO₂ (BA2S) glass powder and high sintering ability. (B2S-BA2S) glass powder containing B₂O₃, (B2S-BA2S)B and that containing B₂O₃ and TiO₂, (B2S-BA2S)BT revealed much lowered crystallization peak temperatures, but rather low sintered density. By applying Kissiger analysis to differential thermal analysis (DTA) data activation energy values for crystallization were determined as 265, 195 and 242 kJ/mol, respectively for (B2S-BA2S), (B2S-BA2S)B and (B2S-BA2S)BT glasses. X-ray diffraction (XRD) patterns from all the glass-ceramics crystallized at 1100°C for 4 h revealed formation of crystalline phases of -BaO·2SiO₂, monocelsian and hexacelsian. (B2S-BA2S) glass-ceramics crystallized at 1400°C for 4 h showed formation of -BaO·2SiO₂ and monocelsian phases with only trace of metastable hexacelsian phase.     

Properties and structure of glasses in the system 10K2O·20BaO·70(SiO2, GeO2, B2O3)

Density, refractive index, glass transiton temperature and expansion coefficient of glasses in the system 10K₂O·20BaO·(70-x-y)SiO₂·xGeO₂·yB₂O₃ (mol %) have been determined. The structure of these glasses is discussed with emphasis on the shifts occurring in the boron and germanium coordination as a function of the relative concentrations of the three network-forming oxides. In GeO₂-rich glasses part of germanium is present as GeO₆ octahedra, which, upon the introduction of B₂O₃, are completely transformed into GeO₄ tetrahedra aty>10.     

化学技术·产业经济略语(2)

CF carbon fiber碳纤维CFC chlorofluorocarbon氯氟碳(同氟利昂)CFM chlorofluoromethane氯氟甲烷(致冷剂,气溶胶喷射剂,CCl_3F,CCl_2F_2等的总称)CFR Coordinating Fuel and Equi-pment Research(美国)燃料内燃机联合研究所     

The role of fluorine in the devitrification of SiO2·Al2O3·P2O5·CaO·CaF2 glasses

A series of eight glasses based on a glass system with the generic composition 1.5(5–Z)SiO₂·(5–Z) Al₂O₃·1.5P₂O₅·(5–Z)CaO·ZCaF₂ were studied where Z = 2, 1.75, 1.5, 1.25, 1, 0.5, 0.25, 0. These glasses were characterised using differential scanning calorimetry (DSC) and x-ray powder diffraction (XRD). Glasses with high fluorine contents were found to crystallise readily to fluorapatite via a homogeneous nucleation route probably involving prior amorphous phase separation. These results are explained in terms of an approach which views glasses as being inorganic polymers where the presence of fluorine disrupts the glass network and thereby reduces the energy barrier to homogeneous nucleation and crystallisation of fluorapatite.     

Crystal Structure of Neptunium(V) Phthalate (NpO2)2(OOC)2C6H4·4H2O

The crystal structure of (NpO₂)₂(OOC)₂C₆H₄·4H₂O [rhombic cell: a = 15.937(3), b = 26.922(5), c = 8.020(2) Å, space group Pbcn, Z = 8, V = 3441.0(12) ų, d _calc = 2.988 g cm^{- 3}, CAD4, MoK , graphite monochromator, 2934 independent reflections; R ₁ = 0.0352, wR ₂ = 0.0951] was studied. The structure consists of NpO₂ ⁺ cations, H₄C₆(COO)₂ ^{2 -} anions, and molecules of coordinated and crystallization water. The crystal lattice involves neutral layers [(NpO₂)₂(OOC)₂C₆H₄(H₂O)₃] _n parallel to the {101} plane. The dioxocations in these layers are bonded to each other to form cationic networks [the Np···Np distance is 3.911(1)-4.202(1) Å]. The coordination polyhedra of Np(1) and Np(2) are pentagonal bipyramids (CN 7). The point group of the neptunyl(V) groups is close to D _h. These groups are bidentate ligands in the cation-cation interaction. The Np = O bond lengths are 1.852(6) [Np(1)-O(1)], 1.849(7) [Np(1)-O(2)], 1.845(7) [Np(2)-O(3)], and 1.841(7) Å [Np(2)-O(4)]; the O = Np = O bond angles are 178.6(3)° [O(2)-Np(1)-O(1)] and 177.4(3)° [O(3)-Np(2)-O(4)]. The equatorial plane of the Np(1) bipyramid consists of two oxygen atoms of adjacent Np(2)O₂ ⁺ dioxocations, two water molecules, and a single oxygen atom of the phthalate anion. The equatorial plane of the Np(2) bipyramid consists of two oxygen atoms of adjacent Np(1)O₂ ⁺ dioxocations, two oxygen atom of the phthalate anion, and a single water molecule. The bond lengths in the equatorial plane of the bipyramid lie in the following ranges: Np-Oyl 2.373(7)-2.437(7) Å (average 2.397 Å) , Np-Ophth 2.360(7)-2.474(7) Å (average 2.431 Å), and Np-Owater 2.534(8)-2.558(9) Å (average 2.544 Å). The phthalate anions are tridentate bridging ligands binding neptunium atoms only within a single cationic network.     

Phase separation of CaO·Al2O3 ·SiO2 glasses induced by electric field

By means of S-4200 SEM, phase separation of CaO-Al₂O₃-SiO₂ glasses upon application of an electric field is investigated. The experimental results show that externally applied electric field promotes the phase separation of the glass, and it leads to a different size of the droplet phase. In the vicinity of the anode of the glass, the smaller droplet phase is induced compared with the cathode of the glass. The accelerating phase separation of the glass in the presence of an electric field is due to the decrease in the free energy forming a critical nucleus size. The different size of the droplet phase of the cathode is due to the increase in the driving force of nucleation and decrease in the viscosity of the glass compared with that of the anode of the specimen.     

α-Ni(OH)2/SiO2核壳以及α-Ni(OH)2空心微球的制备及表征

采用以正硅酸乙酯(TEOS)水解为基础的硅溶胶种子生长法制备了粒径约为270nm的近单分散二氧化硅球型颗粒.采用一种新的溶液生长法,以氢氟酸作为溶液中镍离子配位剂,加入氨水调节溶液pH值的同时作为镍离子补充配位剂,60℃水浴条件下在已制得SiO2微球表面均匀包覆α-Ni(OH)₂得到Ni(OH)₂/SiO₂核壳结构,Ni(OH)₂壳层厚度约为35nm.结合多步包覆法提高Ni(OH)₂壳层厚度,三次包覆后壳层厚度达到约100nm,四次包覆后约为140nm.采用20wt％的强碱NaOH溶液对三次包覆后的Ni(OH)₂/SiO₂核壳结构进行处理,得到了壳层厚度约为95nm的α-Ni(OH)₂空心微球.空心微球具有较大的比表面积为141.06m²/g.     

Hydrothermal synthesis of Ca2(SiO3)(OH)2 microbelts and their transformation to β-Ca2SiO4 microbelts by microwave heating

Calcium silicates possess potential applications in biomedical fields such as drug delivery and bone tissue regeneration owing to their comparatively good bioactivity, biocompatibility and biodegradability. In this paper, we report the preparation of monoclinic β-Ca₂SiO₄ microbelts by microwave thermal transformation of Ca₂(SiO₃)(OH)₂ microbelts at 670 °C for 2 h. Ca₂(SiO₃)(OH)₂ microbelts are successfully used as both the precursor source material and the template for the preparation of β-Ca₂SiO₄ microbelts. The morphology and size of Ca₂(SiO₃)(OH)₂ microbelts can be well preserved during the microwave thermal transformation process. Ca₂(SiO₃)(OH)₂ microbelts are synthesized using Na₂SiO₃?9H₂O, NaOH and Ca(NO₃)₂?4H₂O in the solvent of water by a hydrothermal method at 200 °C for 24 h. The products are characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM).     

P(St-co-AA)聚合物模板法制备中空SiO2微球研究

以无皂乳液聚合法制备的苯乙烯(St)和丙烯酸(AA)阴离子型无规共聚物[P(St-co-AA)]微球为模板,不经过分离和离心、表面改性等任何后处理过程,采用溶胶-凝胶方法直接进行二氧化硅(SiO_2)包覆,成功制得中空SiO_2微球。探究了氨水用量、正硅酸乙酯(TEOS)用量以及不同AA用量对中空SiO_2微球的影响,并对制得的SiO_2微球进行了表征。研究结果表明,制得的中空SiO_2微球分散性优异,体系中无SiO_2实心小粒子,粒径均一,表面形貌呈树莓状,微球壁厚可控制在5～30nm范围内。     

SiO2/Si(111)表面Ge量子点的生长研究

Si衬底用化学方法清洗后,表面大约残余1.0 nm厚SiO2薄膜.利用原子力显微镜(AFM)和反射高能电子衍射(RHEED)来研究温度和Ge蒸发厚度对在SiO2薄膜表面生长的Ge量子点的影响.实验结果表明,当衬底温度超过500 ℃时,SiO2开始与Ge原子发生化学反应,并形成与Si(111)表面直接外延的Ge量子点.在650 ℃时,只有Ge的厚度达到0.5nm时,Ge量子点才开始形成.     

SrO分子在GaN(0001)表面吸附的密度泛函理论研究

建立了SrO/GaN(0001)2×2表面吸附模型,采用基于第一性原理的密度泛函理论平面波超软赝势方法对SrO分子的吸附生长进行了计算,详细研究了SrO分子在表面的吸附位置、吸附能及表面化学键特性。计算发现,SrO分子在GaN(0001)表面吸附不会发生分解,最稳定吸附位为Ga桥位,吸附能达到7.257~7.264 eV。通过电荷布居数和态密度分析,SrO分子吸附后O与表面的一个Ga原子形成的化学键表现出共价键特征,电子由SrO转移给表面部分Ga原子,GaN(0001)仍存在表面态。     

SiO2–TiO2 porous materials prepared using (2-hydroxyethyl)trimethylammonium silicate as a silica source

SiO₂–TiO₂ porous materials containing anatase as the crystalline TiO₂ phase have been synthesized by heat-treatment at 650°C of gels formed from methanolic solutions of (2-hydroxyethyl)trimethylammonium silicate, which had the cubeoctameric silicate structure in its backbone, and titanium bis(triethanolaminate). Gelation time of the solutions ranged from 12 to 250 h, which depended on the Ti-to-Si atomic ratio within the limits of 0.1 and 2.0. However, addition of a small amount of H₂O drastically reduced the gelation time. Hydrolysis of the titanium compound seemed to promote the sol–gel reaction. A gel prepared from the methanolic solution with a Ti-to-Si ratio of 1.0 gave the porous substance with the highest BET surface area (496 m² g⁻¹) by the heat-treatment, and the average pore diameter of the substances increased with increasing Ti-to-Si ratio. The product prepared from a solution with an extra amount of H₂O revealed similar porous properties to that prepared without the addition of H₂O, indicating that the addition of H₂O to the starting solution is effective for producing the porous materials in a shorter reaction time.