R_2O–RO–B_2O_3–SiO_2–Al_2O_3–P_2O_5–CaF_2系分相–析晶乳浊釉的形成机理

通过正交试验方法优化釉料组成和烧成工艺,制备了R_2O–RO–B_2O_3–SiO_2–Al_2O_3–P_2O_5–CaF_2多元系光亮无锆的分相–析晶乳浊釉。采用X射线衍射仪、透射电子显微镜/X射线能谱、场发射扫描电子显微镜等研究了釉的显微结构及分相与析晶的形成机理。结果表明析晶与分相结构并存,分相促进析晶;尺寸接近可见光波长的孤立液滴和所析出的钙钠长石晶体是釉面产生乳浊的根本原因。研究了不同烧成制度对分相–析晶乳浊釉显微结构的影响,发现缓冷釉样的分相液滴尺寸明显大于急冷釉样,急冷釉样中的第二相形貌表里存在明显差异,内部呈球形液滴状,表面则为蠕虫状。     

Hydrogen-storage properties of MgH2–10Ni–2NaAlH4–2Ti–2CNT milled in a planetary ball mill under H2

A sample with a composition of 84 wt% MgH₂–10 wt% Ni–2 wt% NaAlH₄–2 wt% Ti–2 wt% CNT (named MgH₂–10Ni–2NaAlH₄–2Ti–2CNT) was prepared by milling in a planetary ball mill under H₂. Activation of the sample was not required. At the first cycle, the sample absorbed 3.75 wt% H for 10 min, and 4.17 wt% H for 60 min at 593 K under 12 bar H₂. Reactive mechanical grinding of Mg with Ni, NaAlH₄, Ti, and CNT is thought to create defects on the surface and in the interior of Mg, as well as to reduce Mg particle size.     

电沉积α-PbO_2–TiO_2–CeO_2工艺研究

将TiO_2和CeO_2颗粒添加到由50 g/L PbO和4 mol/LNaOH组成的镀液中,通过阳极电沉积的方法在铝基体上制备了α-PbO_2-TiO_2-CeO_2复合镀层,用作铝基二氧化铅电极的中间层.通过研究镀液中固体颗粒的质量浓度和各种工艺条件对α-PbO_2-TiO_2-CeO_2复合镀层外观及结合力的影响,确定了最佳配方和操作条件为:TiO_2 15 g/L,CeO_2 10g/L,温度40℃,电流密度0.5 A/dm~2,电沉积时间3 h.在此条件下所得的复合镀层综合性能较好,其TiO_2和CeO_2含量(质量分数)分别为3.77%和2.13%.扫描电镜结果显示,固体颗粒的掺杂能抑制α-PbO_2晶胞的长大,起到细化晶粒的作用.X射线衍射分析表明,固体颗粒的加入改变了α-PbO_2镀层晶粒的择优取向,降低了其衍射峰强度.     

Antibacterial and photocatalytic active transparent TiO2 crystallized CaO–BaO–B2O3–Al2O3–TiO2–ZnO glass nanocomposites

Transparent TiO₂ crystallized 5CaO–10BaO–65B₂O₃–Al₂O₃–20TiO₂–10ZnO (CBBATZ) glass nanocomposites were fabricated using melt-quenching technique followed by specific heat treatments. As-quenched glass samples were provided three different heat treatments at 630°C for 3, 5, and 10 hours in order to obtain different amounts of TiO₂ nanocrystals in the glass. The presence of rutile phase of TiO₂ nanocrystals in glass was confirmed by X-ray diffraction. The glass nanocomposite heat treated for 10 hours showed a hydrophobic nature with contact angle of 90.90°. Contact angle decreased from 90.90 to 22.20°, when irradiated under ultraviolet (UV) radiation for 45 minutes. This photoinduced hydrophilicity showed a photocatalytic and self-cleaning properties of glass nanocomposite. During photocatalytic ink test, the maximum change in color of Resurin (Rz) ink and 60% degradation in absorbance of ink within 150 minutes under UV radiation were found for glass nanocomposite heat treated at 10 hours. Also, 78% degradation in absorbance of methylene blue dye (pollutant) within 180 minutes under UV irradiation was found for glass naocomposite heat-treated at 10 hours. Antibacterial performance of transparent glass nanocomposite against Escherichia coli was evaluated as well. More than 95% of the bacterial cells were degraded with glass nanocomposite heat-treated at 10 hours. CBBATZ glass nanocomposite found to impart the antibacterial effect through generation of reactive oxygen species (ROS) in aqueous medium. ROS species which was confirmed in the bacterial cell through intracellular ROS generation kit. During evaluation of mechanical properties using nanoindentation technique, the values of hardness and reduced modulus increased by ~26% and 10%, respectively, for glass nanocomposite heat-treated at 10 hours as compared to as-quenched glass.     

Bioactivity investigation of glass and glass ceramics in Li2O–SiO2–CaO–P2O5–CaF2 system

Abstract

Glass samples in Li₂O–SiO₂–CaO–P₂O₅–CaF₂ system with different contents of P₂O₅, CaO and CaF₂ in relative ratios responded to fluoroapatite (FA) composition (referred to P₂O₅ addition) have been prepared and heat treated at 550 and 750°C to obtain glass ceramics. Bioactivity of all samples has been proved in vitro by the presence of new layer of apatite-like phases formed after soaking in simulated body fluid (SBF). The development and the apatitic character of created layers have been demonstrated by Fourier transform infrared analysis. Scanning electron microscopy and electron probe microanalysis have demonstrated that the density and the thickness of new layer depend on P₂O₅ content, crystallisation temperature and immersion time. The bioactivity has been enhanced by P₂O₅ addition as well in the case of the base glasses as in the case of glass ceramics. The additional heat treatment appeared to inhibit the bioactive behaviour, though the longer SBF acting leads to the additional formation of apatite-like layer. The mechanical properties, expressed as Vicker hardness, have been found higher and increasing with P₂O₅ in glass ceramics treated at 750°C comparatively with base glass samples and the highest value of 7˙37 GPa has been achieved by 14 wt-%P₂O₅ addition. The same content of P₂O₅ in glass ceramics heat treated at 550°C resulted in a decrease in hardness to a minimum value from all samples. The increase and decrease in hardness responded to development and suppression of crystallisation respectively. The inhibition of crystallisation has been affected by the presence of 'amorphous' FA according to X-ray diffraction and differential thermal analysis results.     

Infrared GRIN GeS2–Sb2S3–CsCl chalcogenide glass–ceramics

Chalcogenide glasses show a unique potential for creating gradient refractive index (GRIN) lenses, which would reduce the size and weight of infrared thermal imaging system and remain/improve its performance. Here, we propose a new method that forms a GRIN chalcogenide glass–ceramics (GCs) by creating low refractive index (n) CsCl nanocrystals within a high n GeS₂–Sb₂S₃ glass matrix. After specific gradient thermal treatment, the GRIN structure of Δn ∼ 0.04 was formed through the gradient precipitation of CsCl. This work would pave a new path to design the GRIN chalcogenide GCs through a selective crystallization of halide crystals with low n.     

Surface and bulk crystallization in Nd2O3–Al2O3–SiO2–TiO2 glasses

Neodymium aluminosilicate (Nd₂O₃–Al₂O₃–SiO₂; NdAS) glasses have been investigated for the effect of concentration of TiO₂ on the crystallization mechanism and for the effect of surface condition on crystal growth. NdAS glasses with 0–10 wt.% TiO₂ were heat-treated for nucleation and crystal growth and were examined for phase separation and morphology of surface crystals as well as for crystal growth rate. All the glasses exhibit surface crystallization, however, the glass having 8 wt.% TiO₂ also exhibits internal crystallization after a two-stage heat treatment. Surface crystallization was dependent on the condition of the glass surface and the amount of TiO₂. The crystal growth on the cut surface was faster than on the fractured surface and the growth rate in surface increased with increasing TiO₂. The phase separation found in NdAS glasses containing above 8 wt.% TiO₂, was confirmed to be an important factor controlling the internal crystallization process in Nd₂O₃–Al₂O₃–SiO₂–TiO₂ glasses.     

Application of BaO–CaO–Al2O3–B2O3–SiO2 glass–ceramic seals in large size planar IT-SOFC

BaO–CaO–Al₂O₃–B₂O₃–SiO₂ (BCAS) glass–ceramics can be used as sealant for large size planar anode-supported solid oxide fuel cells (SOFCs). BCAS glass–ceramics after heat treatment for different times were characterized by means of thermal dilatometer, X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that the coefficients of thermal expansion (CTE) of BCAS glass–ceramics are 11.4×10⁻⁶ K⁻¹, 11.3×10⁻⁶ K⁻¹ and 11.2×10⁻⁶ K⁻¹ after heated at 750 °C for 0 h, 50 h, and 100 h, respectively. The CTE of BCAS matches that of YSZ, Ni–YSZ and the interconnection of SOFC. Needle-like barium silicate, barium calcium silicate and hexacelsian are crystallized in the BCAS glass after heat-treatment for above 50 h at 750 °C. The glass–ceramics green tape prepared by aqueous tape casting can be directly applied in sealing the cell of SOFCs with 10 cm×10 cm. The open circuit voltage (OCV) of the cell keeps 1.19 V after running for 280 h at 750 °C and thermal cycling 10 times from 750 °C to room temperature. The maximum power density is 0.42 W/cm² using pure H₂ as fuel and air as oxidation gas. SEM images show no cracks or pores exist in the interface of BCAS glass–ceramics and the cell.     

电积锌用铝基β-PbO_2–WC–TiO_2–ZrO_2–SnO_2复合阳极的电沉积制备

在铝上电沉积制备了新型[β-PbO2-WC-ZrO2-SnO2-TiO2复合电极材料.通过正交试验,研究了固体微粒质量浓度及工艺条件对镀层的外观及其作为电积锌阳极使用时槽电压的影响,得到最佳工艺条件为:Pb(NO3)2 250 g/L,HNO3 10 g/L,NaF 1～2 g/L,SnO24g/L,WC4g/L,ZrO2 2g/L,TiO2 2g/L,温度50 ℃,pH 1.5,电流密度3A/dm2,时间4h.     

Dielectric Characteristics of Ceramics in BaO–Nd2O3–TiO2–Ta2O5 System

Dielectric ceramics in the BaO–Nd₂O₃–TiO₂–Ta₂O₅ system were prepared and characterized. The ceramics with tungsten–bronze structure based on the compositions Ba₂NdTi₂Ta₃O₁₅ and Ba₅NdTi₃Ta₇O₃₀ had a high dielectric constant (>100) with a lower frequency-dependency when complete densification was achieved; a low dielectric loss was obtained in the former.     

Thermodynamic prediction of the nonstoichiometric phase Zr1–zCezO2–x in the ZrO2–CeO1.5–CeO2 system

A thermodynamic estimation of the ZrO₂–CeO₂ and ZrO₂–CeO_1.5 systems, as well as the cubic phase in the CeO_1.5–CeO₂ system has been developed and the complex relation between the nonstoichiometry, y, in Ce_zO_2–y and the oxygen partial pressure at different temperatures is evaluated. The behavior of the nonstoichiometry phase Zr_1–zCe_zO_2–x is described based on the thermodynamic estimation in the ZrO₂–CeO₂, CeO_1.5–CeO₂ and ZrO₂–CeO_1.5 systems. Additionally, the interdependence among miscellaneous factors, which can be used to describe the change in oxidation states of cerium such as the oxygen partial pressure, the CeO_1.5 fraction in CeO_1.5–CeO₂ in the quasi-ternary system, the nonstoichiometry y and the difference between the activity of CeO₂ and CeO_1.5 are predicted. The calculated results are found to be very useful to explain the influence of pressureless sintering at different O₂ partial pressures on the mechanical properties of CeO₂-stabilised ZrO₂ ceramics     

Visible rays cutoff and infrared transmission properties of TeO2–GeO2–V2O5–PbF2 glass systems

Visible rays cutoff infrared transmitting glasses in TeO₂–GeO₂–V₂O₅–PbF₂ glass systems were investigated. Glasses without OH⁻ absorption band transmitting wavelength regions from 2·0 to 5·0 nm were obtained. The addition of fluoride to these glasses and the treatment of dry-air-bubbling during melting decreased markedly absorption coefficient and reflectivity of OH⁻ bands. Reflectivity of OH⁻ bands increased with increasing absorption coefficient. Values of glass transition points from 520 to 540 °C and flow points from 560 to 580 °C were obtained.     

Microstructure and properties of CaO–ZrO2–SiO2 glass–ceramics prepared by sintering

For the development of a new wear resistant and chemically stable glass-ceramic glaze, the CaO–ZrO₂–SiO₂ system was studied. Compositions consisting of CaO, ZrO₂, and SiO₂ were used for frit, which formed a glass-ceramic under a single stage heat treatment in electric furnace. In the sintered glass-ceramic, wollastonite (CaSiO₃) and calcium zirconium silicate (Ca₂ZrSi₄O₁₂) were crystalline phases composed of surface and internal crystals in the microstructure. The internal crystal formed with nuclei having a composition of Ca_1.2Si_4.3Zr_0.2O₈. The CaO–ZrO₂–SiO₂ system showed good properties in wear and chemical resistance because the Ca₂ZrSi₄O₁₂ crystals positively affected physical and mechanical properties.     

CaO–Al–Al_2O_3–CaCO_3–O_2体系燃烧合成铝酸钙热力学研究

计算了CaO–Al–Al_2O_3–CaCO_3–O_2体系燃烧合成铝酸钙的绝热温度,运用物质自由能函数理论,对主要反应进行了热力学计算,分析了燃烧合成铝酸钙的物相生成过程。结果表明:体系绝热温度随产物中CA_2含量的增加而降低,但均大于1800K,说明反应可自持;在反应初期,C_(12)A7的生成驱动力最大,其次是CA、CA_2的生成驱动力,C_(12)A_7为主要生成物相;随着反应的进行,铝酸钙不同物相间会发生转化,C_(12)A_7转化CA_2的驱动力最大,其次是C_(12)A_7转化为CA;C_(12)A_7和CA2共同转化成CA的驱动力最小,因此形成以CA、CA_2为主要物相的产物,且CA的含量大于CA_2的含量。燃波前端C_(12)A_7特征峰强度最大;反应区C_(12)A_7的特征峰强度减小,而CA、CA_2的特征峰强度增加;产物区C_(12)A_7特征峰强度消失,且CA的特征峰强度大于CA2的特征峰强度,表明产物中CA的含量大于CA2的,与热力学分析结果一致。在反应区有片状CA和颗粒状CA_2生成;在产物区CA_2弥散在CA中。     

正向脉冲占空比对Ni–W–P–CeO_2–SiO_2纳米复合镀层性能的影响

通过Ni、W、P与CeO2、SiO2纳米颗粒的脉冲共沉积,在普通碳钢表面制备了Ni–W–P–CeO2–SiO2纳米复合镀层。在一定的脉冲频率和平均电流密度下,研究了正向脉冲占空比对纳米复合镀层的化学组成、沉积速率、显微硬度和显微组织的影响。结果表明:增大正向脉冲占空比时,纳米复合镀层的晶粒尺寸增大,沉积速率和显微硬度降低。当正向脉冲占空比控制在10%时,沉积速率最快(为48.6μm/h),显微硬度最高(为696HV)。纳米复合镀层中的P含量随着正向脉冲占空比的增大而增加,但CeO2、SiO2纳米颗粒及W的含量不断降低,正向脉冲占空比对W的沉积量影响最明显。     

Ge-added TiO2–Ta2O5–CaCO3 varistor ceramics

The influence of doping with Ge on the nonlinear coefficient α and the breakdown electric field E_B of TiO₂–Ta₂O₅–CaCO₃ varistor ceramics was investigated. In this study, TiO₂–Ta₂O₅–CaCO₃ varistor ceramics added with Ge was successfully prepared using the traditional method of ball milling–molding–sintering. The electrical performance, including the nonlinear coefficient α, the breakdown electric field E_B, and the leakage current J_L, are tested using a varistor direct current parameter instrument. The average barrier height Φ_B of each sample is calculated using the relevant formula. X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and scanning transmission electronic microscopy analyses demonstrated that Ge doping notably changed the microstructure of TiO₂–Ta₂O₅–CaCO₃ ceramics, thereby increasing α and decreasing E_B. When the doping contents of Ta₂O₅ and CaCO₃ were 0.2 and 0.4 mol%, respectively, the optimum doping content of 0.9 mol% Ge exhibited high α (10.2), low E_B (14.1 V mm⁻¹), and high Φ_B (0.95 eV). These results are superior to previous findings. In addition, Ge as sintering aid reduced the sintering temperature caused by the low melting point. The optimal sintering temperature was 1300 °C for the TiO₂–Ta₂O₅–CaCO₃ ceramics doped with Ge.     

Chemical Stability of ZnO–Na2O–SO3–P2O5 Glasses

We report on chemical stability and corrosion behavior of highly depolymerized sulfophosphate glasses from the system ZnO–Na₂O–SO₃–P₂O₅ in aqueous solution, providing data on weight loss, ion release rates, and modifications of surface topology as a function of time, temperature and pH value. Observations seem consistent with the previously developed structural model of chemical heterogeneity, where cations Na⁺ and Zn²⁺ cluster selectively in the vicinity of sulfate and phosphate anions, respectively.     

Processing–microstructure–properties relationships of MoSi2–SiC composites

Silicon carbide green bodies with and without carbon-fibre reinforcement have been infiltrated with MoSi₂–Si–X in order to produce high-temperature resistant materials. X is Cr, Ti, Al or B respectively. By adding silicon and one of these components to MoSi₂ the melting point is lowered dramatically. The composites therefore could be gained by melt infiltration at max. 1600 °C. During infiltration the additives react within the infiltrated body with carbon or silicon to form high-temperature resistant carbides or silicides. Thermodynamic calculations have been performed to analyse the reactions during infiltration. The infiltration parameters have been studied with respect to the resulting microstructure and properties. By fitting the amount of additives to the quantity of carbon in the SiC-body (or vice versa) no decrease in strength could be observed up to 1500 °C. The fracture toughness can be increased by the use of high-modulus carbon fibres. The most promising X-element for a high-temperature resistant material is titanium.     

1,1–二甲基–1–烷基胺–2–辛酰亚胺的合成与表征

以偏二甲肼、溴代(十二、十四、十八)烷和辛酰氯为原料,合成了3种脂肪族胺基酰亚胺。分别采用FT–IR和1H–NMR表征了产物的结构,以DSC法分别测试了各产物的熔点和热分解温度,最后探讨了各步反应的最佳条件。结果表明:烷基化最佳反应温度为35~40℃,反应时间为120 min;酰基化最佳反应温度为80~85℃,反应时间为120 min;脱氢反应最佳温度为10~30℃,反应时间为180 min。3种胺基酰亚胺的熔点和热分解温度随胺基碳链的增长而升高。