Thermal Behaviour of Transition Metal-Containing Zirconium Phosphate

The thermal behaviour of Co(II), Ni(II) and Zn(II)-containing zirconium phosphate of α type was investigated. XRPD analysis revealed that, for the samples containing Co(II) or Ni(II), the first reflection of the solid phase is split into a doublet. In contrast, when Zn(II) is present, a single solid phase system is formed. The thermal behaviour of the materials followed this sequence. For the samples containing Co(II) or Ni(II), phase-transition processes were found and there was also a loss of crystal water, but for the sample containing Zn(II) there was only one endothermic effect, which corresponded to the decomposition of phosphate groups. This revised version was published online in July 2006 with corrections to the Cover Date.     

氟、铈对磷酸三钙水解过程及其产物抗酸性的影响

研究了不同浓度的F- 和Ce3 +对磷酸三钙 (Ca3 (PO4) 2 ,TCP)的水解过程和水解产物的影响。XRD及IR实验结果表明 ,TCP在NaF溶液中的水解产物为羟基磷灰石 (Ca1 0 (PO4) 6(OH) 2 ,HAP)和氟基磷灰石 (Ca1 0 (PO4) 6F2 ,FAP)的混合物。氟离子浓度越高 ,FAP的含量越多。TCP水解过程的pH值变化随氟离子的起始浓度不同而不同。氟离子浓度越高 ,pH值越低。TCP在CeCl3 溶液中的水解产物为铈取代的羟基磷灰石 (CexCa1 0 -y(PO4) 6-z(OH) 2 ,Ce HAP)。溶解实验表明 ,氟处理比铈处理更有效地增强了TCP水解产物的抗酸性。当F -浓度为 0 1%或Ce3 +浓度为 5× 10 - 2 %时 ,TCP水解产物的抗酸性最强     

红外光谱法热分析液晶相变过程

液晶物质在升温过程中会发生多个相转变过程 ,DSC热分析可测量这些相转变的能量变化 ,但却不能提供变化的微观原因和细节 .而温度升高对液晶样品的红外光谱图强度、峰形和吸收频率都有显著影响 .引起这样变化的原因一是热膨胀改变了分子内部化学键的力常数和相互作用 ,从而改变了分子振动偶极矩的性质 ;二是分子中有红外吸收的基团浓度随温度升高而改变 .红外光谱可以给出样品能量变化过程中分子结构变化的细节 ,通过计算还可获得分子结构变化的表观焓变 .前人做过的探索性工作 [1～ 3]都集中在一个或几个功能团的变化上 .在能量变化上仅…     

添加磷酸氢钙对硅酸三钙骨水泥性能的影响

本文将磷酸氢钙(CaHPO₄·2H₂O,DCPD)添加到硅酸三钙(Ca₃SiO₅,C₃S)骨水泥中,采用X射线衍射(XRD),扫描电镜(SEM),万能力学测试机等手段对不同添加量的骨水泥进行表征,考察添加DCPD对硅酸三钙骨水泥性能的影响。实验表明,C₃S材料中添加10% DCPD有着优于单纯C₃S骨水泥的水化性能,骨水泥的初凝时间从92 min缩短到80 min;添加20%~30% DCPD能提高材料的短期力学强度,可以实现其短期抗压强度的优化;添加30%~40% DCPD的材料有着优良的生物活性与适中的可降解性能。结果表明,通过添加DCPD优化C₃S水泥的性能,对各种不同性能具有DCPD添加量的依赖性。通过进一步优化DCPD添加量,将可能获得优良的生物活性骨缺陷填充材料。     

Effect of Characteristics of Magnesium Oxide Powder on Composition and Strength of Magnesium Potassium Phosphate Compound for Solidifying Radioactive Waste

Phase composition, particle morphology, and granulometric composition of commercial samples of MgO powders of various chemical purities (classification from technical grade to chemical grade) prepared by heat treatment at 1300°C for 3 h were studied for the subsequent synthesis of a compound based on magnesium potassium phosphate matrix MgKPO₄·6H₂O, promising for solidifying liquid radioactive waste. It has been established that to obtain a homogeneous mineral-like compound with compressive strength of about 15 MPa, which meets the regulatory requirements for solidified forms of liquid radioactive waste, it is necessary to use magnesium oxide powder with a particle size of not more than 50 μm, which have a high degree of crystallinity (the average crystallite size is not less than 40 nm). It was noted that the impurities of metal compounds, primarily silicon, calcium, and iron in the MgO powder, do not affect the synthesis conditions and the mechanical strength of the compound.

     

Thermal Property and Phase Transition of the Synthesized New Cubic Leucite-type Compounds

New cubic leucite-type compounds, CsMSi₂O₆ (M=B_0.2Al_0.8,Al_0.2Fe_0.8), Cs₂MSi₅O₁₂ (M=Cd, Mg, Ni, Zn) have been synthesized by the two-stage heat treatment of the solid-state reaction. The thermal expansion properties of the synthesized leucite-type compounds have been studied with HTXRD and LTXRD in the temperature range of 123 to 1273 K. The thermal expansion rate of CsB_0.2Al_0.8Si₂O₆ was found to be considerably smaller than that of CsAlSi₂O₆, while the thermal expansion property of Cs₂MSi₅O₁₂ (M=Mg, Zn, Cd) was found to have a linear relationship in the temperature range of 298 to 1273 K. By using Rietveld analysis it was found that the thermal expansion rate decreased with increasing the Si—O—M(Si) angle for cubic leucite-type compounds at 298 K, and that the phase transitions of CsAlSi₂O₆ and Cs_0.9Al_0.9Si_2.1O₆ were due to the relationship between the bond angle of Si—O—M(Si) of the three-dimensional framework structure and the space ratio in the unit cell at 298 K.This revised version was published online in November 2005 with corrections to the Cover Date.     

Effect of Thermal Treatment on Sorption Activity of Calcium and Magnesium Phosphates

The effect of thermal treatment in the range 20-800°C on the activity of hydrated calcium and magnesium phosphates in recovery of heavy metal ions from aqueous solutions was studied. The composition and sorption properties of materials obtained in all stages of thermal treatment of hydrophosphates and phosphates are considered. The manner in which the sorption activity of phosphates changes upon thermal treatment is interpreted.     

环糊精超分子包络物的相变行为及其热分析研究进展

本文概述了近年来国内外报道的关于环糊精(CD)超分子包络物的相变温度与热释出行为和主客体结构之间的关系.基于这些文献中热重、差示扫描量热和气相色谱耦合时间飞行质谱等方法提供的CD超分子包络物的热力学数据比较发现,在超分子包络物中CD与客体的相变温度及客体的释出形式依赖于客体被包结前的物相与主客体分子间相互作用的强度.客体的类型如:形态、结构、极性和体积等都会影响主客体之间的相互作用,进而导致包络物展现不同的相变和热释出温度.而且,主客体分子间的相互作用越强,超分子包络物的释出温度越高.     

Effect of Synthesis Method on the Phase Composition and Ion-Exchange Properties of Titanium Phosphate

Relationships between synthesis conditions, phase composition, and ion-exchange properties have been analyzed on the basis of results of physicochemical study for reaction products in the (NH₄)₂TiO(SO₄)₂–H₃PO₄–H₂O system. Mechanisms have been suggested for the formation of final titanium phosphate phase in different synthesis methods.     

Phase Transition of CuITe

The phase transition and the crystal structures of CuITe were investigated by differential thermal analysis and X-ray powder diffraction measurements in the temperature range between 300 and 683 K. The new phase transition in CuITe was observed at 592 K. The enthalpy of transition is ΔH=0.125 kJ mol^-1. The new phase above 592 K belongs to tetragonal system with the space group I4₁ /amd. This revised version was published online in August 2006 with corrections to the Cover Date.     

表面相变及Pt负载的BiOBr纳米片的协同光催化效应

通过热处理手段考察了BiOBr纳米片的表面相变过程。通过XRD,Raman,SEM,TEM,UV-Vis-DRS等手段对不同热处理温度下样品的结构进行表征。结果表明,高温热处理下(≥400℃),BiOBr相向Bi24O31Br10相转变,可形成BiOBr/Bi24O31Br10异质结。通过气相乙醛的降解,并与商用P25 TiO2做比较来评估催化剂的光催化性能,测得活性顺序为:P25 TiO2BiOBrBiOBr/Bi24O31Br10。能带结构分析可知BiOBr与Bi24O31Br10间形成I型异质结不利于电荷分离,因而活性降低。然而,当同样条件下于上述催化剂表面负载Pt后,测得光催化活性顺序为:(BiOBr/Bi24O31Br10)-PtBiOBr-PtP25 TiO2-Pt。(BiOBr/Bi24O31Br10)-Pt的最高活性归因于BiOBr/Bi24O31Br10异质结与Pt负载的协同分离光生载流子过程,即与BiOBr/Bi24O31Br10界面的光生空穴转移,BiOBr/Pt及Bi24O31Br10/Pt界面的光生电子转移、累积及开启双电子还原O2的一系列过程有关。     

表面相变及Pt负载的BiOBr纳米片的协同光催化效应

通过热处理手段考察了BiOBr纳米片的表面相变过程。通过XRD,Raman,SEM,TEM,UV-Vis-DRS等手段对不同热处理温度下样品的结构进行表征。结果表明,高温热处理下（≥400℃）,BiOBr相向Bi₂₄O₃₁Br₁₀相转变,可形成BiOBr/Bi₂₄O₃₁Br₁₀异质结。通过气相乙醛的降解,并与商用P₂₅TiO₂做比较来评估催化剂的光催化性能,测得活性顺序为：P₂₅TiO₂>BiOBr>BiOBr/Bi₂₄O₃₁Br₁₀。能带结构分析可知BiOBr与Bi₂₄O₃₁Br₁₀间形成I型异质结不利于电荷分离,因而活性降低。然而,当同样条件下于上述催化剂表面负载Pt后,测得光催化活性顺序为：（BiOBr/Bi₂₄O₃₁Br₁₀）-Pt> BiOBr-Pt >P25 TiO₂-Pt。（BiOBr/Bi₂₄O₃₁Br₁₀）-Pt的最高活性归因于BiOBr/Bi₂₄O₃₁Br₁₀异质结与Pt负载的协同分离光生载流子过程,即与BiOBr/Bi₂₄O₃₁Br₁₀界面的光生空穴转移,BiOBr/Pt及Bi₂₄O₃₁Br₁₀/Pt界面的光生电子转移、累积及开启双电子还原O₂的一系列过程有关。     

差热分析求可逆相变焓的模拟研究

就样品的比热在相变前后均是温度函数的一般情况 ,通过动态地模拟DTA测量样品所经历的整个相变过程 ,验证了DTA中该相变潜热公式及相应的面积方法的正确性。证明对于可逆相变 ,采用文章所建议的面积法 ,把升降温过程中测得的相变潜热取一算术平均值 ,可最大限度地减少由于样品内温度梯度及样品比热是温度函数所带来的测量误差     

Zr(OH)4的热分解及ZrO2的相变过程

利用TG-TDG-DTA热分析技术研究了由Zr（OH）4热分解制备ZrO2的脱水过程,并结合X射线粉末衍射技术研究了ZrO2的相变过程．发现在82℃的吸热峰对应Zr（OH）4的脱水,而435℃附近出现的放热峰则为四方ZrO2向单斜ZrO2的晶相转变．采用外推法确定了Zr（OH）4脱水过程遵循三维扩散机理,其函数方程为g（α）=[{1／（1-α）}^1/3-1]^2．以实验获得的动力学参数ln A和E为基础,用最小二乘法对ln A和E进行线性拟合,得到动力学补偿效应表达式为ln A=0．437E-20．69．     

ChemInform Abstract: Temperature Induced Phase Transition of CaMn0.5Zr1.5(PO4)3 Phosphate.

In view of a known structural phase transition at 800—875 °C and the by 10 times increased luminescence of Mn²⁺ in the high‐temperature phase, low‐ (LT) and high‐temperature (HT) polymorphs of CaMn_0.5Zr_1.5(PO₄)₃ are prepared by sol—gel reaction of Mn(O‐Ac)₂, Ca(NO₃)₂, ZrOCl₂, and NH₄H₂PO₄ in ethylene glycol followed by a final annealing (700 or 900 °C, 20 h, resp.).     

Synthesis of Porous Magnesium Oxide by Thermal Decomposition of Basic Magnesium Carbonate

On calcination of basic magnesium carbonate at 20-800°C, an induction period was observed in the initial stage of thermal decomposition. At the decomposition degree higher than 20% of the weight loss, the specific surface area varied in proportion with the decomposition degree, which points to equal rates of gas liberation and recrystallization of intermediate products into an active oxide. The individual phase of magnesium oxide alone is identified at the minimal temperature of 500°C. As the calcination temperature and time increase, the MgO phase is structured further, which decreases in its specific surface area and basicity.     

Thermochemical Properties and Decomposition Kinetics of Ammonium Magnesium Phosphate Monohydrate

Ammonium magnesium phosphate monohydrate NH4MgPO4·H2O was prepared via solid state reaction at room temperature and characterized by XRD, FT-IR and SEM. Thermochemical study was performed by an isoperibol solution calorimeter, non-isothermal measurement was used in a multivariate non-linear regression analysis to determine the kinetic reaction parameters. The results show that the molar enthalpy of reaction above is （28.795 ± 0.182） kJ/mol （298.15 K）, and the standard molar enthalpy of formation of the title complex is （-2185.43 ± 13.80） kJ/mol （298.15 K）. Kinetics analysis shows that the second decomposition of NH4MgPO4·H2O acts as a double-step reaction： an nth-order reaction （Fn） with n=4.28, E1=147.35 kJ/mol, A1=3.63×10^13 s^-1 is followed by a second-order reaction （F2） with E2=212.71 kJ/mol, A2= 1.82 × 10^18 s^-1.     

Confined‐Volume Effect on the Thermal Properties of Encapsulated Phase Change Materials for Thermal Energy Storage

We have encapsulated the heat exchange material, n‐docosane, into polyurethane capsules of different sizes. Decreasing the size of the capsules leads to changes of the crystallinity of phase‐change material as well as melting/crystallization temperature. The novelty of the paper includes 1) protection of the nanostructured energy‐enriched materials against environment during storage and controlled release of the encapsulated energy on demand and 2) study of the structure and surface‐to‐volume properties of the energy‐enriched materials dispersed in capsules of different sizes. The stability of energy nanomaterials, influence of capsule diameter on their energy capacity, homogeneity and operation lifetime are investigated.     

团簇动态相变催化

正识别和表征催化活性位点对于理解活性的起源至关重要。随着原位光谱,显微成像技术以及理论计算的发展使我们可以得到几个原子特殊排列组成的活性位的构效关系。然而,在探索更具挑战性的催化剂的活性位点方面研究进展甚微,对于这些催化剂来说,催化剂结构对环境极度敏感,在     

高分子凝胶的体积相变

本文概要地介绍了高分子凝胶体积相变的基础理论,较系统地综述了近10年来利用温度、pH值、光、电、生化反应等控制体积相变研究的进展,对有关的应用也作了简单的介绍.