PEO-LiClO4-Li1.3Al0.3Ti1.7 (PO4)3复合聚合物电解质电导率

将实验室烧制的无机快离子导体盐Li_1.3Al_0.3Ti_1.7 (PO₄)₃ 、PEO 与LiClO₄ 按照EO/ Li = 8, 两种锂盐含量为变量进行复合, 通过溶液浇注法制备得到PEO-LiClO₄-Li_1.3Al_0.3Ti_1.7 (PO₄)₃ 复合聚合物电解质膜, 以示差扫描热分析法(DSC) 与电化学阻抗( EIS) 测试其性能。DSC 测试结果表明: 按照EO/ Li = 8 将Li_1.3Al_0.3Ti_1.7 (PO₄)₃ 、LiClO₄ 与PEO 复合的聚合物电解质中PEO 的结晶度由50.34 %下降到4.36 %～28.53 %。室温下该聚合物电解质所有试样的阻抗谱图在高频区呈现为压缩的半圆, 在低频区为一条倾斜的直线, 而在较高温度时, 阻抗谱图主要为一条倾斜的直线。复合聚合物电解质PEO-LiClO₄-Li_1.3Al_0.3Ti_1.7 (PO₄)₃ 的离子电导率遵从Arrhe2nius 关系, 在Li_1.3Al_0.3Ti_1.7 (PO₄)₃ 质量分数达到15 %时, 活化能最低, 即4.494425 eV, 此时电导率值最佳, 373 K时为1.161 ×10 -3 S/ cm 和298 K时为7.985 ×10-6 S/ cm。     

Band bending at free Pb(Zr,Ti)O3 surfaces analyzed by X-ray photoelectron spectroscopy

This paper analyses in detail the core levels evolution of Pb(Zr,Ti)O₃, i.e. Pb 4f, Zr 3d, Ti 2p, O 1s in various conditions: absolutely freshly prepared sample, sample stored under air, and the effects of in vacuum annealing. The aim of the study is to quantify separately the chemical reactivity at the surface and the band bending effects due to the ferroelectric polarization. It is found that freshly prepared samples present mostly inwards (↓) polarization. This phenomenon is mostly revealed by the Ti 2p and O 1s spectra, manifested as a distinct component with 1.8 eV lower binding energy in the O 1s binding energy and by 1.1 eV in the Ti 2p binding energy. Sample aging under air suppresses the inwards polarization, and most signal comes from surfaces not presenting ferroelectric permanent polarization perpendicular to the sample surface. This process conducts also to the formation of Pb(CO₃)₂ on the surface. Annealing to temperatures up to 400 °C stabilizes a surface composed by a main part of surface without polarization perpendicular to the surface, and with some areas presenting outwards (↑) polarization. These areas have, most probably, different terminations, the polarized area being (Ti,Zr)O₂ terminated.     

Preparation and photocatalytic study of fibrous K0.3Ti4O7.3(OH)1.7–anatase TiO2 nanocomposite photocatalyst

Nanocomposite of K_0.3Ti₄O_7.3(OH)_1.7 fiber and anatase TiO₂ nanoparticle was prepared by hydrothermal treatment of the K_0.3Ti₄O_7.3(OH)_1.7 which was synthesized by calcination of K₂CO₃ and TiO₂ at 1250 °C followed by refluxing in nitric acid. Effects of hydrothermal treatment conditions such as temperature and time on morphology, phase composition and crystal structure of the nanocomposites were extensively studied. Photocatalytic activities of the catalysts prepared at various hydrothermal conditions were evaluated by means of methylene blue decomposition under blacklight irradiation.     

Structural properties of Pb(Zr0.53Ti0.47)O3/YBa2Cu3O7-δ heterostructures on SrTiO3 substrates

The structures of ferroelectric Pb(Zr0.53Ti0.47)O3 and high-Tc YBa2Cu3O7– superconductor integrated films on (0 0 1) SrTiO3 substrate prepared by the r.f./d.c. magnetron sputtering method have been studied by X-ray grazing incidence reflectivity, diffuse scattering and high-resolution X-ray diffraction methods combined with atomic force microscopy (AFM) and SEM techniques. The results of high-resolution X-ray diffraction show that the quality of Pb(Zr0.53Ti0.47)O3 improved as the thickness increased. On the other hand, the crystalline quality of YBa2Cu3O7– deteriorated and the superconducting transition temperature, Tc, decreased as the thickness of Pb(Zr0.53Ti0.47)O3 increased. The strain state was similar for different thickness samples and the lattice mismatch strain in the Pb(Zr0.53Ti0.47)O3 layer was almost totally relaxed. The root mean square (r.m.s.) roughness at Pb(Zr0.53Ti0.47) O3/YBa2Cu3O7– interface was determined to be about 1.7±0.3 nm by X-ray specular reflectivity. The r.m.s. roughness at the surface of Pb(Zr0.53Ti0.47)O3/YBa2Cu3O7– bilayer samples was about 1.5 to 2.0±0.3 nm which was larger than that of YBa2Cu3O7– single-layer sample measured by both X-ray specular reflectivity and AFM methods. The results from AFM and SEM show that the morphological characteristics of the Pb(Zr0.53Ti0.47)O3 layer surface were large grains covering about 10% in area distributed on a fine-grained matrix. © 1998 Chapman & Hall     

锶镁共掺对Na0.5Bi0.5TiO3氧离子导体电学性能的影响分析

通过固相反应法制备单一结构的锶镁共掺的Na0.5Bi0.48Sr0.02Ti0.98Mg0.02O2.97氧离子导体,利用交流阻抗谱和内耗温度谱分别研究锶镁共掺对Na0.5Bi0.5TiO3材料晶粒电导率及氧离子扩散的影响。在593K时,Na0.5Bi0.48Sr0.02Ti0.98Mg0.02O2.97材料的晶粒电导率可以达到5.31×10^-4S/cm,比母体Na0.5Bi0.5TiO3材料在同温度下的晶粒电导率高一个数量级,甚至超过了Na0.5Bi0.5Ti0.98Mg0.02O2.98样品在673K温度下的晶粒电导率。在锶镁共掺的Na0.5Bi0.48Sr0.02Ti0.98Mg0.02O2.97材料中观察到一个氧弛豫内耗峰,其弛豫参数为:E=0.85eV,τ0=7.4×10^-14s。结合弛豫参数和结构分析,Sr^2+的掺杂在一定程度上可以增大氧离子扩散的自由体积,较大的自由体积、较高的可动氧空位浓度和较好的氧空位可动性是NBT-SrMg2样品晶粒电导率相较于NBT-Mg2样品大幅提高的主要原因。     

Variation with added material in the effects of reactive mechanical grinding and hydriding–dehydriding cycling on the hydrogen-storage properties of Mg

Samples Mg–14Ni–6Fe₂O₃, Mg–14Ni–3Fe₂O₃–3Ti, and Mg–14Ni–2Fe₂O₃–2Ti–2Fe were prepared by reactive mechanical grinding, and their hydrogen storage properties were examined. The activated Mg–14Ni–2Fe₂O₃–2Ti–2Fe had the highest hydriding rate, absorbing 4.14 wt% H for 5 min, and 4.27 wt% H for 10 min, and 4.42 wt% H for 60 min at 573 K under 12 bar H₂. The activated Mg–14Ni–3Fe₂O₃–3Ti had the highest dehydriding rate, desorbing 3.81 wt% H for 20 min, 3.98 wt% H for 25 min, and 4.15 wt% H for 60 min. Mg–14Ni–6Fe₂O₃ dehydrided at n = 4 contained Mg, Mg₂Ni, MgO, and Mg(OH)₂. Mg(OH)₂ is considered to be formed by the reactions of MgH₂ or Mg with water vapor. The effects of reactive mechanical grinding and hydriding–dehydriding cycling are the creation of defects and cracks, and the reduction of Mg particle size. The addition of a larger amount of Ti and/or Fe has stronger effects of reactive mechanical grinding, whereas the addition of a larger amount of Fe₂O₃ has greater effects of hydriding–dehydriding cycling.     

Effects of Fe2O3 Nanoparticles on Water Permeability and Strength Assessments of High Strength Self-Compacting Concrete

In this work,compressive,flexural and split tensile strength together with coefficient of water absorption of high performance self-compacting concrete containing different amount of Fe2O3 nanoparticles have been investigated.The strength and the water permeability of the specimens have been improved by adding Fe2O3 nanoparticles in the cement paste up to 4.0 wt%.Fe2O3 nanoparticle as a foreign nucleation site could accelerate C-S-H gel formation as a result of increased crystalline Ca(OH)2 amount especially at the early age of hydration and hence increase the strength of the specimens.In addition,Fe2O3 nanoparticles are able to act as nanofillers and recover the pore structure of the specimens by decreasing harmful pores to improve the water permeability.Several empirical relations have been presented to predict the flexural and the split tensile strength of the specimens by means of the corresponding compressive strength at a certain age of curing.Accelerated peak appearance in conduction calorimetry tests,more weight loss in thermogravimetric analysis and more rapid appearance of peaks related to hydrated products in X-ray diffraction results indicate that Fe2O3 nanoparticles up to 4 wt% could improve the mechanical and the physical properties of the specimens.     

XRD分析TiO_2和MnO_2添加剂对固相合成NiFe_2O_4过程的影响

在1173和1273K以NiO和Fe2O3为原料,以TiO2和MnO2为添加剂,固相合成了NiFe2O4,用XRD和SEM对试样进行了表征,建立了NiFe2O4特征衍射峰强度与合成时间的关系。没有添加剂时,将温度从1173K提高到1273K时,合成NiFe2O4的反应速度并没有增加;在原料中加入0.5%(质量分数)TiO2,合成NiFe2O4的反应速率随着温度的升高而增加;用1%(质量分数)MnO2作为添加剂后,合成NiFe2O4的反应速率显著升高,扫描电镜结果证实添加TiO2和MnO2提高了试样的致密度,改善了其烧结性能。用零级反应动力学方程求得合成NiFe2O4反应的速率系数。     

A study on structural stability of bismuth titanate with lanthanum doping for improved ferroelectric properties

Bismuth titanate \((\hbox {Bi}_{4}\hbox {Ti}_{3}\hbox {O}_{12})\) with different lanthanum (La) concentrations (0.25, 0.50, 0.75 and 1.0 mol%) was successfully prepared via soft combustion route. It was found that the change of diffraction peaks shown by X-ray diffraction is attributed to the doping effect in \(\hbox {Bi}_{4}\hbox {Ti}_{3}\hbox {O}_{12}\). This was also supported by the presence of additional peak that corresponds to La in the range of 800–860 eV, proved by X-ray photoelectron spectroscopy. In addition, the enlarged region of Bi 4f, Bi 4d, Ti 2p, La 3d and O 1s of doping sample was clearly seen after deconvolution. Based on binding energy position, it can be unambiguously stated that the Ti ions in the tetravalent state are surrounded by the perovskite layer of \(\hbox {Bi}_{4}\hbox {Ti}_{3}\hbox {O}_{12}\), which may also imply the formation of oxygen vacancies in the vicinity of the \(\hbox {Bi}_{2}\hbox {O}_{2}\) layer. In comparison with \(\hbox {Bi}_{4}\hbox {Ti}_{3}\hbox {O}_{12}\), the green emission intensity was abruptly decreased with La doping. This indicates that La doping suppresses the formation of oxygen vacancies by stabilizing the adjacent oxide ions. Thus, the improved polarization shown by ferroelectric hysteresis loop is associated with the reduction in oxygen and bismuth vacancies due to La doping.     

Characteristics of BaTiO3 powders synthesized by hydrothermal process

Monodisperse BaTiO₃ powder was prepared by a hydrothermal process from a mixture of Ba(OH)₂ and Ti(OH)₄. In the process, the best synthesis conditions were a Ba(OH)₂/Ti(OH)₄ mole ratio of 1, the reaction temperature 180°C, which produced the cubic crystal structure of BaTiO₃ with 0.3 m size. The effects of synthesis conditions and the dispersion stability of powder were investigated. The reaction kinetics was also discussed from the experimental results.     

Humic acid coated Fe3O4 magnetic nanoparticles as highly efficient Fenton-like catalyst for complete mineralization of sulfathiazole

Humic acid coated Fe(3)O(4) magnetic nanoparticles (Fe(3)O(4)/HA) were prepared for the removal of sulfathiazole from aqueous media. Fe(3)O(4)/HA exhibited high activity to produce hydroxyl (OH) radicals through catalytic decomposition of H(2)O(2). The degradation of sulfathiazole was strongly temperature-dependent and favored in acidic solution. The catalytic rate was increased with Fe(3)O(4)/HA dosage and H(2)O(2) concentration. When 3 g L(-1) of Fe(3)O(4)/HA and 0.39 M of H(2)O(2) were introduced to the aqueous solution, most sulfathiazole was degraded within 1h, and >90% of total organic carbon (TOC) were removed in the reaction period (6h). The major final products were identified as environmentally friendly ions or inorganic molecules (SO(4)(2-), CO(2), and N(2)). The corresponding degradation rate (k) of sulfathiazole and TOC was 0.034 and 0.0048 min(-1), respectively. However, when 3 g L(-1) of bare Fe(3)O(4) were used as catalyst, only 54% of TOC was eliminated, and SO(4)(2-) was not detected within 6h. The corresponding degradation rate for sulfathiazole and TOC was 0.01 and 0.0016 min(-1), respectively. The high catalytic ability of Fe(3)O(4)/HA may be caused by the electron transfer among the complexed Fe(II)-HA or Fe(III)-HA, leading to rapid regeneration of Fe(II) species and production of OH radicals.     

Low Temperature Synthesis of Single-crystal Alpha Alumina Platelets by Calcining Bayerite and Potassium Sulfate

Single-crystal alpha alumina (α-Al2O3) platelets were synthesized by calcining a powder mixture of bayerite (α-Al(OH)3) and potassium sulfate (K2SO4) at 900℃. The crystalline phase evolutions and morphologies of the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The synthesized samples mainly consisted of single-crystal α-Al2O3 platelets with a diameter of 0.5-1.5 μm and a thickness of 50-150 nm. Moreover, with 3, 5, and 8 wt% (referred to the obtained alumina) α-Al2O3 seeds adding into the powder mixture of bayerite and potassium sulfate, the average diameter of α-Al2O3 platelets can be reduced to 450, 240, and 220 nm, respectively. It is found that the sequence of the phase transformation is the bayerite (α-Al(OH)3) → boehmite (γ-AlOOH) →γ-Al2O3 →α-Al2O3. Further analysis indicated that K2SO4 can promote the phase transformation from γ-Al2O3 to α-Al2O3 and the formation of single-crystal α-Al2O3 platelets might be attributed to the liquid phase K3Al(SO4)3.     

Sm2O3掺杂(Ba0.7Ca0.3)TiO3-Ba(Zr0.2Ti0.8)O3无铅压电陶瓷的制备与性能

采用固相合成法制备了Sm2O3掺杂的(Ba0.7Ca0.3)TiO3-Ba(Zr0.2Ti0.8)O3(BCZT)无铅压电陶瓷.借助XRD、SEM等手段对该陶瓷的显微结构与电性能进行了研究.结果表明,Sm2O3的掺杂降低了BCZT无铅压电陶瓷的烧结温度并使居里温度点Tc从85℃提高到95℃.当Sm2O3掺杂量为0.02wt%～0.1wt%时,样品具有典型ABO3型钙钛矿结构.Sm2O3掺杂量为0.02wt%时,所得陶瓷样品具有最优综合电性能,其压电常数d33、机电耦合系数kp、机械品质因子Qm、介电损耗tanδ和介电常数εr分别为590 pC/N、0.52、43、1.3%和3372.     

Growth mechanism of titanium dioxide nanowires for dye-sensitized solar cells

Mesoporous films made of titanium dioxide nanowires are desirable for dye-sensitized solar cells because nanowires provide direct conduction pathways for photogenerated electrons. Anatase titanium dioxide nanowires with polycrystalline microstructure were synthesized on titanium foil using a three-step process. First, the top surface of the titanium foil was transformed to Na(2)Ti(2)O(4)(OH)(2) nanotubes through hydrothermal oxidation in NaOH. Next, the Na(2)Ti(2)O(4)(OH)(2) nanotubes were converted to H(2)Ti(2)O(4)(OH)(2) nanotubes by ion exchange. Finally, the H(2)Ti(2)O(4)(OH)(2) nanotubes were converted to polycrystalline anatase nanowires through a topotactic transformation. The film morphology evolution, crystal structure transformations and growth mechanism are described in detail. Titanium foil reacts with NaOH to form Na(2)Ti(2)O(4)(OH)(2) sheets, which exfoliate and spiral into nanotubes. The Na(2)Ti(2)O(4)(OH)(2) nanotubes are immersed in HCl solution to replace the Na(+) ions with H(+) ions. During the topotactic transformation of H(2)Ti(2)O(4)(OH)(2) nanotubes to anatase TiO(2) nanowires, the sheets made of edge bonded TiO(6) octahedra in the H(2)Ti(2)O(4)(OH)(2) nanotubes dehydrate and move towards each other to form anatase crystals oriented along the nanotube axis which creates a polycrystalline nanowire. These mesoporous TiO(2) nanowire films were suitable for use as dye-sensitized solar cell photoanodes.     

Bi4Ti3O12光催化粉体的制备及性能研究

采用溶胶-凝胶法制备Bi4Ti3O12粉体,通过DSC-TGA、XRD以及光催化降解甲基橙的分析,研究了热处理温度、蒸馏水加入量及溶胶陈化时间等制备条件对光催化活性的影响.结果表明,通过优化制备条件后,所制备样品的带隙能约为2.89eV,在普通日光灯下对甲基橙的降解率普遍大于相同条件下P25的降解率.     

Preparation of vermiculite nanoparticles using thermal hydrogen peroxide treatment

Powdered natural Mg-vermiculite (Letovice, Czech Republic), with the formula (Mg0.35K0.02Ca0.01) (Mg2.39Fe0.51(3+)Fe0.02(2+)Al0.08) (Si2.64Al1.33Ti0.03) O10(OH)2 x 4.97H2O and particle size < 5 microm, was used for the investigation of exfoliation after hydrogen peroxide and/or microwave treatment (600 W). A sample heated in the microwave oven for 40 min exhibits a 11% mass loss and reduction of the 001 peak intensity in the X-ray diffraction pattern. The basal 001 peak intensity of untreated Mg-vermiculite sample (/001 = 100%) drops to 35% in the microwave treated sample. Only the sample treated for 5 h at 80 degrees C fully rehydrated after 120 min at room temperature. A more pronounced reduction of the 001 peak intensity (to 8%) was observed after hydrogen peroxide treatment of the sample at 25 degrees C. The combination of a five-hour hydrogen peroxide treatment at 80 degrees C and subsequent microwave heating leads to an effective extinction of the 001 diffraction in the XRD pattern. The 001 diffraction profile becomes very diffuse with peak intensity less than 1%. The degree of reduction of the 001 diffraction intensity also depends on the time and temperature of hydrogen peroxide treatment and on the peroxide concentration. An even more pronounced reduction of the peak intensity is caused by exfoliation of particles to nano-domains coupled with a randomization of the c-axes.     

Preparation of iron oxide nanoparticles by microwave synthesis and their characterization

In this study production of fine particle Fe2O3 via microwave processing of Fe(NO3)3.nH2O followed by low temperature annealing was reported. XRD was used to characterize the structural properties of nanoparticles. Approximate particle sizes were between 3-13 nm according to Scherrer's equation. Single point BET measurement results also show that samples have large surface area and they are nanometer sized particles. TEM study was conducted to examine the structure of the nanoparticles. TEM figure is in good agreement with the results obtained from Scherrer's equation using XRD spectra. In order to characterize the magnetic properties of the nanoparticles VSM (Vibrating Sample Magnetometer) was used. From these results it can be concluded that the sample containing only maghemite phase exhibits superparamagnetic behaviour, on the other hand sample containing both hematite and maghemite phases shows paramagnetic behaviour above 300 K, superparamagnetic behavior at lower temperatures.     

丙烯酸-丙烯酸酯共聚物对钛酸铋水悬浮液性质的影响

研究了丙烯酸－丙烯酸酯共聚物对钛酸铋（Bi4Ti3O12)悬浮液表面化学性质及流变性的影响。结果表明，共聚物的加入使Bi4Ti3O12的等电点向低pH值方向偏移。共聚物在粉体表面的吸附属于物理吸附，其含量的变化可以引起共聚物在粉体表面吸附构型的变化，当共聚物含量＞1．5wt%时，部分高分子脱附。共聚物的加入可以显著改善悬浮液的稳定性，在低共聚物含量和高共聚物含量均可制备稳定的悬浮液，共聚物含量≤1．5wt%时，浆料的稳定通过静电位阻稳定机理来实现，共聚物含量≥2.0wt%时，可能通过空位稳定机理来实现。     

Kinetics and phase evolution during carbothermal synthesis of titanium carbide from ultrafine titania/carbon mixture

The kinetics and phase evolution of the TiC formation process by carbothermal reduction of ultrafine titania/carbon mixture were investigated using thermogravimetric analysis (TGA), X-ray diffraction (XRD) and oxygen analysis. Titania (TiO2) first lowered its oxidation state to Ti3O5 via an unidentified phase (possibly one of the Magneli phases). Then Ti3O5 was further reduced to Ti2O3, followed by the formation of titanium oxycarbide (TiCxOy) phase and its purification toward high purity TiC thereafter. Ti2O3 was the oxide phase with the lowest oxidation state before forming TiCxOy phase. In the isothermal TGA trace, the formation of Ti3O5 showed a diffusion-controlled process; possibly carbon diffusion limited the solid state reaction. The formation of Ti2O3 and TiCxOy was interpreted to be associated with CO gas-assisted reduction reaction, based on constant reaction rate for each process. The activation energy for the formation of Ti2O3 (from Ti3O5) and TiCxOy (from Ti2O3) phase were calculated to be 415.6 and 264.3 kJ mol-1, respectively. The TiC powder synthesized at 1550 °C for 4 h in flowing argon atmosphere showed fine particle size (0.3–0.6 m) with oxygen content of 0.7 wt % and lattice parameter of 0.4328 nm while interparticle agglomeration was moderate. © 1998 Chapman & Hall.     

钴掺杂Sr_4Fe_6O_(13)混合导体氧化物结构及透氧测定

用湿化学法合成了Ｓｒ４ＣｏｘＦｅ６－ｘＯ１３±δ系列混合导体氧化物,对其相结构与透氧性能进行了研究．钴离子的引入导致材料中钙钛矿型杂相的出现,Ｘ＝２．０时材料中还产生了ＣｏＯ杂相,ｘ＝２．６时材料呈现钙钛矿型结构．Ｓｒ４Ｆｅ４Ｃｏ２Ｏ１３±δ的相结构还与焙烧温度及环境气氛中的氧浓度密切相关．随着氧浓度的降低,材料从纯相Ｓｒ４Ｆｅ６Ｏ１３结构（纯氧气气氛下）转变为Ｓｒ４Ｆｅ６Ｏ１３结构、钙钛矿型结构和ＣｏＯ共存（空气气氛下）,直至转变为针镍矿结构、 Ｓｒ４Ｆｅ６Ｏ１３结构和 ＣｏＯ共存． Ｓｒ４Ｆｅ６Ｃｏ１３±δ导体膜在ａｉｒ／Ｈｅ氧浓差梯度下的透氧量为 １．５×１０８ｍｏｌ／ｃｍ２·ｓ（８５０℃）,在６５０～８５０℃范围内透氧活化能为７０ｋＪ／ｍｏｌ．