Reaction Sequencing During Processing of the 123 Superconductor

Reaction sequencing studies were conducted for two precursors to the 123 superconductor in air and helium environments. In air, the reactants in both precursor systems produce an intermediate 123 phase at 1000 K without going through the BaCuO₂ and Y₂BaCuO₅ intermediate phases, observed in earlier work with mixed powder precursors. In helium, the fully developed 123 tetragonal phase is formed at temperatures as low as 880 K, but it also decomposes to Y₂BaCuO₅, BaCu₂O₂, and BaCuO₂; the extent of decomposition depends on the temperature. The 123 tetragonal phase completely decomposes by 1075 K, but it can be reformed if the atmosphere is switched back to air at a temperature above 950 K.     

High-pressure studies of dielectric relaxation in ferroelectric pyridinium tetrafluoroborate crystals

Dielectric relaxation of ferroelectric pyridinium tetrafluoroborate single crystal was measured as a function of hydrostatic pressure and temperature. High-pressure caused a shift the ferroelectric-paraelectric phase transition at T₁=238.7 K as well as the non-ferrolectric phase transition at T₂=204 K towards higher temperatures. The influence of pressure on the critical slowing down process at the ferroelectric-paraelectric phase transition was analyzed. Moreover, in the low temperature phase (below 204 K) a relaxation process, characterized by an enthalpy of 13.2 kJ/mole, was observed. The activation enthalpy of the process was found to increase linearly with pressure.     

Selective N-alkylation of aniline with methanol over a heteropolyacid on montmorillonite K10

N-methylaniline is an industrially important product in the manufacture of paper, textile dyes, drugs, perfumes and explosives. The vapour phase alkylation of aniline with methanol forming N-methylaniline is advantageous over liquid phase alkylation. In present study, vapour phase methylation of aniline over dodecatungestophosphoric acid supported on K10 montmorillonite was systematically studied and optimization of process parameters was carried out. The 20% m/m DTPA/K10 was found to be optimum with 79% aniline conversion and 99% N-methylaniline selectivity. The reaction required milder operating conditions than reported for commercial catalysts. We also studied the feasibility of 20% m/m DTPA/K10 as a catalyst for the alkylation of aniline with other alcohols like ethanol, n-propanol, iso-propanol and n-butanol. The activity of 20% m/m DTPA/K10 decreased with increasing carbon number.     

Characteristics of the High-Tc Superconducting Bi-Pb-Sr-Ca-Cu Oxides Derived from an Ethylenediaminetetraacetic Acid Precursor

The modified sol-gel method using ethylenediaminetetraacetic acid as a chelating agent to prepare high- T _c superconducting Bi-Pb-Sr-Ca-Cu oxides is reported. Results revealed that the desirable Bi-based compounds can be acquired by such a process with a high percentage of the 110 K phase and a T _c(zero) of 108 K. On the other hand, a new method is proposed to quantitatively evaluate the volume fraction of the 110 K phase in Bi-based superconducting materials, mainly composed of 85 and 110 K phases. That is a lever-rule type of relation, V = ( Y – 29.07°)/ (28.81°– 29.07°), where V is the volume fraction of the 110 K phase and Y = 2 θ for the X-ray diffraction peak emerging at about 29° with a Cu K α radiation source and 28.81° Y 29.07°. The volume fraction of the 2223 phase estimated in this way is more reliable than that estimated by measuring the area ratios of XRD peaks and it is expected to be even more reliable than those derived from conventional methods based on perfect diamagnetism.     

萃取法从盐湖卤水提取铷实验研究

研究了t-BAMBP［4-叔丁基-2-（α-甲基苄基）苯酚］/磺化煤油萃取体系,从提铯后的母液中,萃取分离钾铷的过程。考察了萃取时间、萃取剂浓度、萃取相比等萃取条件、水洗条件和反萃取条件对铷钾分离的影响。确定了适宜的工艺条件为：t-BAMBP浓度为0.7 mol/L,相比O/A=3∶1,萃取时间为5 min;以0.1 mol/L氯化钠溶液为洗涤剂,洗涤相比O/A=4∶1;以0.5 mol/L 氯化氢溶液为反萃剂,反萃相比O/A=5∶1。经过5级逆流反萃,铷的反萃率达到95.6%以上,铷钾的分离系数较高,实现了铷钾分离。     

Phase transitions and domain structures in relaxor-based ferroelectric (PbZn1/3Nb2/3O3)0.915(PbTiO3)0.085 single crystal

Polarization-electric field (P-E) hysteresis loops and domain structures have been measured as a function of temperature in relaxor-based ferroelectric single crystal (PbZn_1/3Nb_2/3O₃)_0.915(PbTiO₃)_0.085 (PZN-8.5%PT). In order of increasing temperature, PZN-8.5%PT undergoes successive phase transitions: rhombohedra1 phase (below ∼375 K) → coexistence of rhombohedral and tetragonal phases (between ∼375 and ∼390 K) → tetragonal phase (between ∼390 and ∼420 K) → coexistence of tetragonal and cubic phases (between ∼420 and ∼460 K) → cubic phase (above ∼460 K). Phase coexistence suggests an inhomogeneous distribution of Ti⁴⁺ concentration in the PZN-8.5%PT crystal.     

Determination of Mechanism for Soot Oxidation with NO on Potassium Supported Mg‐Al Hydrotalcite Mixed Oxides

Soot oxidation with NO (in the absence of gas phase O₂) on potassium‐supported Mg‐Al hydrotalcite mixed oxides (K/MgAlO) was studied using a temperature‐programmed reaction and in situ FTIR techniques. Nitrite and the ketene group were identified as the reaction intermediates and thus a nitrite‐ketene mechanism was proposed in which surface active oxygen on K sites of K/MgAlO is transferred to soot by NO through nitrites. In the absence of gas phase O₂, soot oxidation with NO at lower temperatures (below 450 °C) is limited by the amount of active oxygen on the K sites. This kind of active oxygen is not reusable but can be replenished in the presence of gas phase O₂.     

Isotope effect in the phase transition of partially d euterated T1H2As 04

The complex dielectric constant of Tl(H_1-X D_X)₂AsO₄ powder pellets has been measured from 100 to 450 K. It is found that the I11 ← 11 phase transition point (T_L) shifts from 251 K(for hydrogenated crystal) to about 340 K(for partially deuterated crystal), while the I1 ← I phase transition point(T_U) goes from about 390 K to 433 K. The order of the I11 ← I1 phase transition changes from a weakly first-order to a second- order, while that of the I1 ← I phase transition from a second-order to a first-order. From the experimental results, the tentative phase diagrams of Tl(H_1-X D_X)₂AsO₄, and Tl(H_1-X D_X)₂PO₄ are proposed.     

A reorientation of the PO3-groups and radiation damage effect in ferroelectric phase transition studied by CW-EPR of PO32- radical in glycine·H3PO3 single crystal

EPR of γ-ray generated PO₃^2- radicals indicates that the four radical centers are equivalent in the paraelectric phase and become inequivalent in the ferroelectric phase due to a ±3° rotation. The phase transition temperature is shifted by irradiation from T_c = 224 K to T_c = 180 K. The molecular mechanism of the order-disorder phase transition is discussed     

癸酸-棕榈酸/SiO2复合相变材料的热性能

以SiO2为载体、癸酸-棕榈酸为相变材料,采用溶胶-凝胶法制备癸酸-棕榈酸/SiO2复合相变材料,考察了其储热性能、导热性能、微观形貌和组成结构. 结果表明,当癸酸-棕榈酸掺入量为0.08 mol时,所制材料具有最好的潜热性能,相变温度为20.02~22.08℃,相变焓为44.53~50.51 J/g,适合在建筑领域应用;当癸酸-棕榈酸掺入量为0.06 mol时,材料导热性能最好,导热系数在第一降温阶段为0.211 W/(m×K),相变平台阶段为0.017 W/(m×K),第二降温阶段为0.040 W/(m×K);材料中SiO2与癸酸-棕榈酸仅是物理嵌合,未发生明显的化学作用,癸酸-棕榈酸掺杂过量时明显包裹SiO2,导致复合相变材料潜热性能和导热性能下降.     

数字装饰瓷砖技术与设备新进展

2014年9月22日-26日,意大利博罗尼亚（Bologna）举办了一年一度的陶瓷砖CERSAIE,展示了许多用数字装饰技术与设备生产的各类瓷砖。与此同时,在意大利里米尼（Rimini）举办了两年一度的陶瓷机械设备展（Tecnargilla）,中国广东东莞琅菱企业的超细研磨设备、广东佛山康立泰（国瓷）的陶瓷墨水、广东佛山新景泰陶瓷的喷墨设备,代表中国在瓷砖数字装饰领域的一股新兴力量参加了本次展会。本文对瓷砖产品不进行讨论,对国内企业的情况也不作展开,仅从宏观角度上介绍国外一些企业在瓷砖数字装饰技术与设备领域的新进展,供国内瓷砖行业同行参考,不对之处,敬请批评指正。     

Weak ferroelectricity in monoclinic RbD2PO4 crystals

Ferroelectric phase transition was detected in monoclinic RbD₂ PO₄ at T_C3 =313K in addition to the known antiferroelectric phase transition at T_C2 =319K. The almost saturated value of the spontaneous polarisation is about P_sy = 6.10^-4 μC/cm² at 280K.     

CsCl-PEG8000-H2O三元体系288.2、298.2、308.2K相平衡测定

采用等温溶解法和浊点法研究了288.2、298.2、308.2 K下三元体系CsCl-PEG8000-H₂O的相平衡关系,采用经验方程分别对双液线和结线数据进行了拟合,绘制了完整相图。研究发现CsCl-PEG8000-H₂O体系在288.2、298.2、308.2 K下同时存在固液平衡与液液平衡关系,其完整相图均由不饱和液相区（L）、两个一液一固区（L+S）、双液相区（2L）、两液一固区（2L+S）和两固一液区（2S+L）构成;随着温度升高,不饱和液相区（L）、双液相区（2L）、一液一固区（L+S）、两液一固区（2L+S）均增大,两固一液区（2S+L）减小。对比288.2、298.2、308.2 K下三元体系CsCl-PEG1000/4000/6000/8000-H₂O完整相图,结果表明：288.2、298.2 K时,仅CsCl-PEG1000-H₂O体系存在固液平衡关系,CsCl-PEG4000/6000/8000-H₂O体系同时存在固液和液液平衡关系;308.2 K时,CsCl-PEG1000/4000/6000/8000-H₂O体系同时存在固液和液液平衡关系;双液相区（2L）随聚乙二醇分子量增大而增大。     

Fiber Debonding in Residually Stressed Brittle Matrix Composites

The competition between initial fiber debonding versus fiber failure marks a crucial event of the microstructural failure process in fiber-reinforced brittle matrix composites. In this study, the role of a thermal residual stress field on the debonding conditions is examined theoretically and analytically. The analysis is based on two critical observations, the first being that the mechanics at the tip of a kink crack are driven only by the singularity at the main crack tip. Following from the first is the second observation that any thermal stress effects on the debonding criteria should enter only through the phase angle ψ ^T of the total stress intensity factor at the main crack tip. In general, this stress intensity factor has a thermal as well as a mechanical load contribution. It is shown that when the thermal and mechanical stress intensities, K ^R and K ^t , respectively, are in phase , i.e., ψ ^R =ψ ^t , the existing debonding conditions are universal and can be used even in the presence of thermal loads. On the contrary, when K ^R and K ^t are out of phase , i.e., ψ ^R ≠ψ ^t , events such as the delamination of thick films or debonding of inclined aligned fibers in brittle matrix composites become sensitive to the presence of the thermal stresses.     

铁精粉还原炉用Si3N4（Sialon）/SiC材料在H2O—H2—N2气氛中热力学计算分析

根据热力学原理对Si—C—N—H—O五元系统进行了平衡状态下的相稳定性计算,绘制了在1 073 K和1 223 K下的SiC、Si₃N₄、Si₂N₂O和SiO₂4个稳定相的稳定性与N₂分压和H₂O分压的关系图,即优势区域图,分析了其凝聚相的稳定区域。同时结合SEM显微结构分析氢气还原炉中Si₃N₄/SiC和Sialon/SiC制品抗H₂O—H₂—N₂气氛的侵蚀性能。     

K+/Cl-,Br- -H2O三元体系298 K,313 K,333 K时的相平衡

用等温溶解平衡法测定了三元体系 K /Cl-,Br--H2O 298 K、313 K、333 K时的相平衡数据,同时还测定了饱和溶液的密度、折光率等物化性质,依据湿渣法与X射线衍射相结合的方法对平衡固相组成进行了鉴定.该三元体系 298 K、313 K、333 K的溶解度等温图有 1 个固相区:K(Cl,Br),有 1 条单变量曲线,该体系属于固体溶液型.用Pitzer模型计算测得的三元体系 298 K、313 K、333 K溶解度,并用经验公式对平衡液相的密度、折光率进行了计算,计算值与实验值基本吻合.     

制备方法对FeC2O4制备的费托合成铁催化剂的影响

引入一种新的铁前体草酸亚铁,并考察4种制备方法（并流共沉淀,正加共沉淀,沉淀-浸渍K,沉淀-浸渍K、SiO₂）对费托合成铁基催化剂晶体结构、物化性质以及催化性能的影响。研究发现,制备方法显著影响催化剂的晶体结构和织构性质,由并流共沉淀制备的催化剂由于具有较好的结晶度和还原性,并且助剂与活性相结合程度更为均匀,使得催化剂展现出最佳的活性和稳定性,CO转化率可达96.2%。还发现并流共沉淀制备的催化剂表现出较高的烃类产物收率和C₂～C₄烯烃选择性,对液相产物和固相产物进行碳数分析发现,并流共沉淀所得的液相产物中汽油组分的含量高达85.8%,且C₄₊重质烃产物中,C₄～C₁₈含量高达91.0%;正加共沉淀的液相产物中煤油组分的选择性较高;沉淀-浸渍K的液相产物中柴油组分含量较高。     

Orthorhombic to monoclinic phase transition in high-Ti-loaded TS-1: an attempt to locate Ti in the MFI framework by low temperature XRD

The orthorhombic to monoclinic phase transition in an high-titanium-loaded Ti-silicalite sample (2.6 wt.% in TiO₂) has been studied by means of temperature-dependent high resolution powder X-ray diffraction data collected at the ESRF BM16 beam line. We observed that the transition temperature between the orthorhombic phase (Pnma space group), and the monoclinic phase (P2₁/n space group) is at 160 K, as monitored by the splitting of the 1 3 3 peak into  1 3 and 3 1 3 reflections. The structural data obtained after Rietveld refinement in both the orthorhombic (170 K) and monoclinic (80 K) phases are also reported. Refinement of the former data gives weak evidence that about half of the total Ti content is located in T(10) and T(11), that Ti does not show any tendency to be hosted in T(4) and T(12) and that the remaining Ti atoms seem to be spread among the remaining eight T sites.     

Si－C－O－N系统相稳定性和相稳定性图

对Ｓｉ－Ｃ－Ｏ－Ｎ系统进行了平衡状态下的相稳定性计算，绘制了在１４７３Ｋ和１５７３Ｋ下的Ｓｉ３Ｎ４、ＳｉＣ、Ｓｉ２Ｎ２Ｏ和ＳｉＯ２相稳定性与Ｎ２分压和Ｏ２分压的关系图以及Ｎ２分压和ＳｉＯ分区的关系图，Ｓｉ３Ｎ４／Ｓｉ２Ｎ２Ｏ／ＳｉＣ、ＳｉＯ２／Ｓｉ２Ｎ２Ｏ／ＳｉＣ两个三固相平衡点与Ｎ２分压、Ｏ２分压和ＳｉＯ分压以及温度的函数关系日。并以此确定Ｃ纤维－ＳｉＣ纤维转变和Ｃ纤维上涂层ＳｉＣ过程中，为获得稳定ＳｉＣ相的气体分压。     

Transient shrinkage behavior of wustite-centered binary/ternary/quaternary/quinary-component oxide packed beds in a reducing atmosphere up to 1773 K

Wustite (FeO)-centered multicomponent oxides play an important role in the ironmaking process, and a complete understanding of their high temperature behaviors is of great importance for process optimization to achieve high efficiency and low emissions during industrial production. In this work, the transient shrinkages of FeO-centered multicomponent oxide packed beds are quantitatively determined in a reducing atmosphere up to 1773 K, and the effects of the interactions between the oxides on the shrinkage rate (SR) are qualitatively evaluated. The results show that although mixing CaO with FeO increases the SR to 0.42%/K below 1173 K, further mixing with SiO₂ or Al₂O₃ significantly limits this enhancement effect due to the formation of an olivine or spinel phase. However, in the subsequent stage, the SR increases to as high as 0.44%/K after CO is injected. The interaction between FeO and MgO leads to an SR of greater than 0.20%/K at lower temperatures, but it causes a decrease in the SR from 0.33%/K to 0.16%/K between 1173 K and 1273 K. Meanwhile, adding SiO₂ slows the reduction reaction, and the SR correspondingly decreases further to 0.04%/K. On the other hand, the interaction between CaO and Al₂O₃ takes precedence over the interaction between SiO₂ and MgO and dominates the shrinkage process in the quinary-component case, and the preferentially formed CaAl₂O₄ spinel phase hinders the formation of the Mg₂SiO₄ olivine phase.