Effect of SnO2 on the photocatalytical properties of TiO2 films

TiO₂/SnO₂ thin films with different tin atomic percentages were successfully prepared on glass substrates by the spray pyrolysis method from an alcoholic solution of TiO[C₅H₇O₂]₂ with different concentrations of SnCl₄. The TiO₂/SnO₂ thin films prepared at 450 °C presented the anatase phase in polycrystalline configuration from %Sn = 0 in the starting solution up to %Sn = 20, at higher tin content the films present an amorphous configuration. The resulting thin films have a homogeneous surface structure with some porosity. The photocatalytical properties of the films were evaluated with the degradation of methylene blue. The products of the degradation reaction were identified by ¹H nuclear magnetic resonance and the film properties were studied by atomic force microscopy, scanning electron microscopy, UV–Vis spectroscopy, and X-ray diffraction.     

放电等离子烧结技术制备Fe78Si13B9块体非晶纳米晶磁性材料

通过高能球磨技术制备了Fe₇₈Si₁₃B₉磁性非晶合金粉体,采用XRD和DSC分析了Fe₇₈Si₁₃B₉非晶合金粉体的相组成、玻璃转变温度T_g、开始晶化温度 T_x 和晶化峰温度T_p;利用放电等离子烧结（SPS）技术在不同烧结温度下制备了块体磁性非晶纳米晶合金试样,利用XRD、SEM、Gleeble3500、VSM等分析了不同烧结温度下烧结块体试样的相转变特性、微观形貌、力学性能和磁学性能。结果表明,在500 MPa的烧结压力下,随着烧结温度的升高,烧结试样中的非晶相开始逐渐晶化,烧结试样的致密度、抗压强度、微观硬度、饱和磁化强度均显著提高;在500 MPa的烧结压力和823.15 K的烧结温度下,获得了密度为6.6 g/cm³,抗压强度为1500 MPa,饱和磁化强度为1.3864 T的非晶纳米晶磁性材料。     

Structural and electrochemical properties of vanadium oxide thin films grown by d.c. and r.f. reactive sputtering at room temperature

Vanadium oxide thin films were grown at room temperature by direct current and radio-frequency reactive sputtering systems to compare the structural and electrochemical properties. Rutherford backscattering spectrometry and Fourier transform infrared measurements reveal that the composition of the as-deposited films consists of the V₂O₅ phase regardless of the deposition methods. Wide-angle X-ray diffraction measurements show that the crystallinity of the as-deposited V₂O₅ films is different depending on the deposition method. Films deposited by direct current reactive sputtering were amorphous, whereas films deposited by radio-frequency reactive sputtering were crystalline. Scanning electron microscopy measurements show that the V₂O₅ films grown by radio-frequency reactive sputtering had a large grain size but the films grown by direct current reactive sputtering were amorphous. Charge–discharge measurements taken at room temperature with a constant current clearly indicate that the films grown by direct current sputtering demonstrated typical amorphous behavior, whereas the V₂O₅ films grown by radio-frequency sputtering demonstrated the discharge behavior of crystalline V₂O₅. The origin of the structural and electrochemical properties of film grown by radio-frequency reactive sputtering is a self-bias effect. The self-bias effect induces ion bombardment during the growth of vanadium oxide thin film. These results suggest that direct current reactive sputtering is more desirable for growing amorphous V₂O₅ thin film than radio-frequency reactive sputtering.     

Structural and optical properties of (100 − x)(Li2B4O7) − x(SrO–Bi2O3–0.7Nb2O5–0.3V2O5) glasses and glass nanocrystal composites

Glasses of various compositions in the system (100 − x)(Li₂B₄O₇) − x(SrO–Bi₂O₃–0.7Nb₂O₅–0.3V₂O₅) (10  x  60, in molar ratio) were prepared by splat quenching technique. The glassy nature of the as-quenched samples was established by differential thermal analyses (DTA). The amorphous nature of the as-quenched glasses and crystallinity of glass nanocrystal composites were confirmed by X-ray powder diffraction studies. Glass composites comprising strontium bismuth niobate doped with vanadium (SrBi₂(Nb_0.7V_0.3)₂O_9−δ (SBVN)) nanocrystallites were obtained by controlled heat-treatment of the as-quenched glasses at 783 K for 6 h. High resolution transmission electron microscopy (HRTEM) of the glass nanocrystal composites (heat-treated at 783 K/6 h) confirm the presence of rod shaped crystallites of SBVN embedded in Li₂B₄O₇ glass matrix. The optical transmission spectra of these glasses and glass nanocrystal composites of various compositions were recorded in the wavelength range 190–900 nm. Various optical parameters such as optical band gap (E_opt), Urbach energy (ΔE), refractive index (n), optical dielectric constant and ratio of carrier concentration to the effective mass (N/m^*) were determined. The effects of composition of the glasses and glass nanocrystal composites on these parameters were studied.     

Effect of heat treatment on photoluminescence behavior of BaMgAl10O17:Eu phosphors

The blue phosphor of BaMgAl₁₀O₁₇:Eu²⁺ (BAM) powders were prepared by solid-state reaction. The thermal degradation of BAM phosphor significantly reduces the intensity of the blue emission. BAM is reduced by an amount of 50% after heating at around 800 °C for 1 h. Photoluminescence (PL) excitation and emission spectra showed that the blue emission of 450 nm peak decreased with increasing annealing temperature. The ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ transition of Eu³⁺ were observed at 590 and 615 nm emission lines over 1100 °C. Electron paramagnetic resonance (EPR) spectrum also detected two signals of Eu²⁺, corresponding to g=3.7156(9) for 88 mT, and g=2.9507(9) for 133 mT. X-ray absorption near edge structure (XANES) spectrum decreased the intensity of Eu²⁺ for 6977 eV with increasing annealing temperature, while high-energy peak of Eu³⁺ for 6984 eV was increased. The combined use of X-ray and neutron data by the Rietveld refinement appears to support that the secondary phase of EuMgAl₁₁O₁₉ magnetoplumbite structure in BAM may be formed by heat treatment.     

Pyroelectric properties of BST/PLT composite thick films with addition of xPbO–(1 − x)B2O3 glass

The Ba_xSr_1−xTiO₃ (BST)/Pb_1−xLa_xTiO₃ (PLT) composite thick films (20 μm) with 12 mol% amount of xPbO–(1 − x)B₂O₃ glass additives (x = 0.2, 0.35, 0.5, 0.65 and 0.8) have been prepared by screen-printing the paste onto the alumina substrates with silver bottom electrode. X-ray diffraction (XRD), scanning electron microscope (SEM) and an impedance analyzer and an electrometer were used to analyze the phase structures, morphologies and dielectric and pyroelectric properties of the composite thick films, respectively. The wetting and infiltration of the liquid phase on the particles results in the densification of the composite thick films sintered at 750 °C. Nice porous structure formed in the composite thick films with xPbO–(1 − x)B₂O₃ glass as the PbO content (x) is 0.5 ≥ x ≥ 0.35, while dense structure formed in these thick films as the PbO content (x) is 0.8 ≥ x ≥ 0.65. The volatilization of the PbO in PLT and the interdiffusion between the PLT and the glass lead to the reduction of the c-axis of the PLT phase. The operating temperature range of our composite thick films is 0–200 °C. At room temperature (20 °C), the BST/PLT composite thick films with 0.35PbO–0.65B₂O₃ glass additives provided low heat capacity and good pyroelectric figure-of-merit because of their porous structure. The pyroelectric coefficient and figure-of-merit F_D are 364 μC/(m² K) and 14.3 μPa^−1/2, respectively. These good pyroelectric properties as well as being able to produce low-cost devices make this kind of thick films a promising candidate for high-performance pyroelectric applications.     

Nanocrystallization of SrBi2Nb2O9 from glasses in the system Li2B4O7---SrO---Bi2O3---Nb2O5

Transparent glasses in the system (100−x)Li₂B₄O₇–x(SrO---Bi₂O₃---Nb₂O₅) (10≤x≤60) (in molar ratio) were fabricated by a conventional melt-quenching technique. Amorphous and glassy characteristics of the as-quenched samples were established via X-ray powder diffraction (XRD) and differential thermal analyses (DTA) respectively. Glass–ceramics embedded with strontium bismuth niobate, SrBi₂Nb₂O₉ (SBN) nanocrystals were produced by heat-treating the as-quenched glasses at temperatures higher than 500 °C. Perovskite SBN phase formation through an intermediate fluorite phase in the glass matrix was confirmed by XRD and transmission electron microscopy (TEM). Infrared and Raman spectroscopic studies corroborate the observation of fluorite phase formation. The dielectric constant (_r) and the loss factor (D) for the lithium borate, Li₂B₄O₇ (LBO) glass comprising randomly oriented SBN nanocrystals were determined and compared with those predicted based on the various dielectric mixture rule formalism. The dielectric constant was found to increase with increasing SBN content in LBO glass matrix.     

碳钢坩埚表面渗铝复合涂层

以碳钢板为基板材料, 通过表面渗铝和高温化学反应在其表面形成复合保护涂层。研究了反应层厚度与反应温度、时间之间的关系, 并用光学显微镜、XRD对涂层形貌、相组成进行了表征。实验结果表明: 反应产物层厚度随反应温度、时间的增加而增加; 复合涂层由过渡层和反应产物层组成, 过渡层组成为Fe₃Al及少量Fe₂Al₅、Fe₁₄Al₈₆、Al₂O₃, 反应产物层组成为TiB₂、MgO和少量的Mg₂TiO₄、Mg₂B₂O₅、Fe₃Al、FeAl、Ti₂B₅。      

大尺寸La2O3-TiO2-ZrO2非晶塑性烧结行为

La₂O₃-TiO₂-ZrO₂玻璃具有很高的折射率, 在镜头材料和上转换发光基质材料等领域表现出良好的应用前景, 但其玻璃形成能力低, 通常只能采用快速冷却的方法制备, 因此难以获得大尺寸材料。为了获得大尺寸La₂O₃-TiO₂-ZrO₂玻璃, 本研究采用La₂O₃-TiO₂-ZrO₂非晶粉末为原料, 利用非晶在玻璃转变温度以上的塑性行为, 在温度动力学窗口ΔT内进行热压烧结制备了大尺寸La₂O₃-TiO₂-ZrO₂玻璃, 在保持非晶的前提下实现了La₂O₃-TiO₂-ZrO₂粉末的完全致密化。采用SEM、XRD等方法研究了样品的显微结构和相组成。研究发现, 当烧结温度高于910 ℃时, 烧结过程中会析出La₄Ti₉O₂₄晶相; 当烧结温度低于900 ℃时, 样品保持良好的非晶性, 并随着烧结温度的增加, 样品的致密度有所升高。烧结压力也会影响烧结过程, 样品的致密度随着烧结压力升高而增加。大尺寸La₂O₃-TiO₂-ZrO₂非晶材料具有很高的折射率, 在587.6 nm处折射率可达到2.33。在La₂O₃-TiO₂-ZrO₂非晶粉末烧结过程中, 塑性流动是其主要的传质机理。     

Preparation of Pt-PtOx thin films as electrode for memory capacitors

Pt-PtO_x thin films were prepared on Si(100) substrates at temperatures from 30 to 700°C by reactive r.f. magnetron sputtering with platinum target. Deposition atmosphere was varied with O₂/Ar flow ratio. The deposited films were characterized by X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. Resistively of the deposited films was measured by d.c. four probe method. The films mainly consisted of amorphous PtO and Pt₃O₄ (or Pt₂O₃) below 400°C, and amorphous Pt was increased in the film as a deposition temperature increased to 600°C. When deposition temperature was thoroughly increased, (111) oriented pure Pt films were formed at 700°C. Compounds included in the films strongly depended on substrate temperature rather than O₂/Ar flow ratio. Electrical resistivity of Pt-PtO_x films was measured to be from the order of 10⁻¹ Ω cm to 10⁻⁵ Ω cm, which was related to the amount of Pt phase included in the deposited films.     

-Fe2O3 thin films prepared by metalorganic deposition (MOD) from Fe(III) 2-ethylhexanoate

-Fe₂O₃ thin films were prepared by metalorganic deposition (MOD) using Fe(III) 2-ethylhexanoate as the metalorganic precursor. A series of experiments were conducted on the metalorganic spin-coated films and their correspondingly annealed samples by employing experimental techniques ranging from thermal gravimetric analysis, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and scanning electron microscopy (SEM) to optical property characterization. In this way a better understanding has been achieved regarding the decomposition process of the metalorganic precursor, the solid state -Fe₂O₃ film formation and crystallization process, and the relationship between the structure and the optical properties of the prepared films. The conclusions of our experiments are the following. The decomposition of Fe(III) 2-ethylhexanoate is a multistep process that is characterized by distinct transition temperatures and thermogravimetric loss rates. Amorphous -Fe₂O₃ film is formed at an annealing temperature of around 460°C, further annealing at higher temperatures induces the amorphous-to-crystalline phase transition and grain growth. FTIR, XRD and SEM data for structural characterization are correlated and in good agreement. A new FTIR absorption band, peaking at 1085 cm^-1, is assigned to the vibration of crystalline Fe-O mode, therefore this peak is useful in monitoring the amorphous-to-crystalline phase transition of -Fe₂O₃ material. Instead of columnar structure in physical vapour deposition-prepared films a granular structure is typical of MOD prepared films, the grain size is much larger near the surface of the film than near the substrate. Optical characterization shows that the refractive index and extinction coefficient of the -Fe₂O₃ thin films increase with the increase of annealing temperatures. The potential interesting applications of the MOD-prepared -Fe₂O₃ thin films include gas sensor materials, photoelectrodes and storage media.     

微晶玻璃焊料在连接过程中的晶化行为研究

采用一种添加Li₂O和Fe₂O₃的CaO-Al₂O₃-SiO₂基微晶玻璃连接氧化铝陶瓷。通过采用热分析(DTA)、扫描电镜(SEM)和X射线衍射分析(XRD)等方法, 研究了微晶玻璃焊料在连接过程中的晶化行为及其对接头力学性能的影响。结果表明, 在传统的晶化处理过程中, 此玻璃中能够析出锂辉石(LiAlSi₂O₆)、硅灰石(CaSiO₃)、钙铁镏石(Ca₃Fe₂Si₃O₁₂)和钙长石(CaAl₂Si₂O₈)四种晶体。然而, 当采用此玻璃连接氧化铝陶瓷时, 微晶玻璃的晶化过程与连接工艺密切相关。由于缺少足够的形核驱动力, 采用焊后直接冷却的连接工艺只能获得完全玻璃态的接头中间层。通过在降温过程中引入形核-晶化的热处理工艺, 促进了玻璃中间层的晶化, 并且能够通过改变晶化温度来调整中间层的相组成。另外, 晶化相的种类对接头力学性能有重要影响。当中间层中只形成钙长石时, 接头强度达到247.5 MPa; 而当中间层中有锂辉石或钙铁镏石析出时, 接头强度仅为10~135 MPa。     

Characterization and microstructural evolution of SiC(OAl) fibers to SiC(Al) fibers derived from aluminum-containing polycarbosilane

The SiC(OAl) fibers and the SiC(Al) fibers were fabricated by the use of aluminum-containing polycarbosilane (Al–PCS) precursor. The two types of fibers have been characterized. Chemical element analysis, AES, SEM, XRD, RMS and NMR have been employed. The chemical formula of SiC(OAl) fibers is SiC_1.31O_0.25Al_0.018 with C and O rich on the surface. The microstructure of SiC(OAl) fibers is a mixture of β-SiC nanocrystals, free carbon, and an amorphous silicon oxycarbide (Si–C–O phase), which have been confirmed by an amount of SiC₂O₂, SiCO₃, SiO₄ and SiC₃O units in the ²⁹Si MAS NMR spectrum. A small quantity of aluminum is embedded uniformly in the Si–C–O amorphous continuous phase. For SiC(Al) fibers, nearly stoichiometric composition was confirmed as chemical composition of SiC_1.03O_0.013Al_0.024. The fiber is composed of a large number of β-SiC crystallites, a small amount of -SiC crystalline and SiC amorphous phase. The aluminum in the SiC(Al) fibers mainly exists in two manners: Al–C bonds connected with the surfaces of the β-SiC grains and Al–O bonds, or Al₂O₃, to the amorphous phase.     

A simple and an effective method for the fabrication of densified glass-ceramics of low temperature co-fired ceramics

This study reports a new, simple and effective pre-calcined method for fabrication BaO–TiO₂–B₂O₃–SiO₂ low temperature co-fired ceramics (LTCC) at a sintering temperature below 900 °C, and with dielectric losses (tan δ) lower than 2 × 10⁻³. The research results have shown that the addition of 2–5 wt% Al₂O₃ could easily eliminate the porosity of the glass-ceramics because of the excellent wetting behavior between alumina and the BaO–B₂O₃–SiO₂ glass liquid phase in the low temperature co-fired ceramic system.     

Semiconducting barium titanate ceramics prepared by using yttrium hexaboride as sintering aid

Nb-doped BaTiO₃ semiconducting ceramics have been prepared at 1150 °C by employing YB₆ as the sintering aid. The low-temperature sintered samples exhibit a positive temperature coefficient of resistivity (PTCR) effect. The room-temperature resistivity and the magnitude of PTCR effect depend on the amount of YB₆ added, the Nb₂O₅ content and the sintering conditions. At 1 mol% of YB₆, the sample has a low room-temperature resistivity and a resistivity jump of about 10⁴. Transmission electron microscope studies revealed that the intergranular region between the crystalline BaTiO₃ grains has an amorphous structure. Y, Ba and Ti are present in the intergranular region but no Y is detectable in the crystalline grains. A liquid phase is believed to be present during sintering and it helps to facilitate the densification process and to enhance the PTCR effect.     

Raman scattering study on ferroelectric (Ba0.32Sr0.68)2Nb2O7 ceramics

Raman scattering technique was applied to examine the Ba-doping effect to the two low temperature phase transitions of Sr₂Nb₂O₇ (SN) in the temperature range from −190 to 600 °C. The line shape of Raman spectra can be well fitted by multidamped harmonic oscillator model. We did not observe any soft mode related to the two low temperature phase transitions corresponding to those of the pure SN. It is correlated to the disappearance of the incommensurate phase in (Ba_0.32Sr_0.68)₂Nb₂O₇ ceramics. However, the temperature dependence behavior of the three low frequency modes indicates another new structural phase transition around 270 °C. It is considered that the reduction of the interlayer interaction caused by partial replacement of Sr-site by Ba-site, whose ionic radius is larger than that of Sr, may be the reason for the disappearance of the incommensurate phase transition in (Ba_0.32Sr_0.68)₂Nb₂O₇ ceramics.     

Preparation of ZnO varistors by solution nano-coating technique

This paper introduces a new method to produce nano-composite powder for the preparation of high performance ZnO varistors. ZnO particles were coated with Bi₂O₃, Sb₂O₃, Co₂O₃, Cr₂O₃ and other additives via liquid nano-coating technique. Then the prepared powder was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermal gravity and differential scanning calorimetry (TG-DSC) and particle size distribution. The results showed that the ZnO composite powder is homogeneously coated and ultrafine. The densification, phase composition and microstructure of ZnO varistors was studied by linear shrinkage, X-ray diffraction (XRD) and SEM, respectively. The preliminary electrical parameters of ZnO varistors showed that the breakdown voltage V_b (1 mA/cm²) and nonlinear coefficient is 5400 V/cm and 50, respectively, much higher than that of conventional ball milling method. This result shows that nano-coating is a promising route to prepare ZnO varistors.     

Lu2.94Al5O12:0.06Ce3+绿色荧光粉的制备及光致发光

采用高温固相法制备了Lu_2.94Al₅O₁₂:0.06Ce³⁺绿色荧光粉。通过X射线粉末衍射(XRD)、扫描电子显微镜(SEM)和光致发光光谱(PL)对样品的物相、形貌及发光性能进行了表征。结果表明,所合成的Lu_2.94Al₅O₁₂:0.06Ce³⁺绿色荧光粉为立方晶系,表面为类球形。激发光谱中,位于340和450 nm的激发峰分别归属于4f的两个能级到5d能级的跃迁而产生的吸收,340 nm处的激发峰是由于发光是由于²F_5/2到5d的跃迁,而450nm处的激发峰是由于²F_7/2到5d的跃迁。发射光谱中,位于525 nm的发射峰对应Ce³⁺的4f-5d电子跃迁。当Ce₃₊掺杂量为6%,1500℃煅烧5 h时,Lu_2.94Al₅O₁₂:0.06Ce³⁺绿色荧光粉CIE色坐标为(0.3683,0.5959),是一种可以用作白光LED的绿色荧光粉。     

Ferroelectric, dielectric and piezoelectric properties of potassium lanthanum bismuth titanate K0.5La0.5Bi4Ti4O15 ceramics

The Aurivillius type bismuth layer-structured compound potassium lanthanum bismuth titanate (K_0.5La_0.5Bi₄Ti₄O₁₅) is synthesized using conventional solid-state processing. The phase analysis is performed by X-ray diffraction (XRD) and the microstructural morphology is conducted by scanning electron microscopy (SEM). The ferroelectric, dielectric and piezoelectric properties of K_0.5La_0.5Bi₄Ti₄O₁₅ (KLBT) ceramics are investigated in detail. The remnant polarization (P_r) and coercive field (E_c) are found to be 8.6 μC cm⁻² and 60 kV cm⁻¹, respectively. The Curie temperature T_c and piezoelectric coefficient d₃₃ are 413 °C and 18 pC N⁻¹, respectively.     

特高压气体绝缘金属封闭开关设备用Al2O3/环氧树脂复合材料的非等温固化动力学及蠕变性能

针对特高压气体绝缘金属封闭开关设备（GIS）用Al₂O₃/环氧树脂（EP）复合材料,采用非等温差示扫描量热（DSC）法研究了Al₂O₃/EP复合材料的固化行为,对其DSC曲线进行分峰处理,利用等转化率方法求得不同反应阶段的表观活化能。根据Málek判据得到Al₂O₃/EP复合材料的固化行为符合的模型类型,并求得不同反应阶段的各个动力学参数及固化动力学方程。利用SEM观察Al₂O₃/EP复合材料的微观形貌,通过动态热力学分析仪（DMA）分析其动态热力学性能和高温蠕变性能,利用时温等效预测了Al₂O₃/EP复合材料的长时蠕变行为。结果表明,DSC热流曲线表现为双峰分布;Al₂O₃/EP复合材料的两个反应阶段的表观活化能分别为35.3 kJ/mol及48.1 kJ/mol,Sestak-Berggren自催化模型能够很好地描述Al₂O₃/EP复合材料体系在不同固化阶段的固化行为。Al₂O₃颗粒均匀分散于树脂基体中,填料的加入使裂纹发生偏转。Al₂O₃/EP复合材料的储能模量（E'）随温度的升高而降低,损耗因子（tanδ）峰值对应的玻璃化转变温度（T_g）为120.03℃。Al₂O₃/EP复合材料的抗蠕变性能随着拉伸应力和温度的增加而减弱,随着时间的延长,其蠕变速率减小。