HAN-TEAN-H_2O 三元体系的玻璃化转变温度的依数性和微观结构的推测

用ＤＳＣ研究了九种不同ＴＥＡＮ／ＨＡＮ比率下ＨＡＮ－ＴＥＡＮ－Ｈ２Ｏ三元体系的玻璃化转变温度Ｔｇ与Ｈ２Ｏ含量的关系;根据Ｔｇ的变化规律初步推测了该三元体系的分子结构;讨论了ＴＥＡＮ的含量对玻璃化转变温度的影响,并把该三元体系与二元体系ＨＡＮ－Ｈ２Ｏ进行了对比。     

TEAN-H_2O 二元体系的 TX 和 HX 相图

用ＤＳＣ研究了ＴＥＡＮ－Ｈ２Ｏ二元体系的低温热行为，建立了该体系的液化温度与组成关系的ＴＸ－二元相图和低共熔物表观熔融焓与组成关系的ＨＸ－二元相图。发现该二元体系是一个典型的具有简单低共熔物的二元体系，其低共熔温度为－１６．２℃，低共熔物组成为ＴＥＡＮ－Ｈ２Ｏ＝１０／９０（ｍｏｌ／ｍｏｌ）。过冷体系在升温过程中有结晶现象，其结晶焓与ＴＥＡＮ浓度有线性关系。ＴＥＡＮ浓度小于２５ｍｏｌ％时，具有玻璃化转变过程，其转变温度不随试样浓度的改变而变化，平均值为－９１．２℃，而在ＴＥＡＮ浓度大于２５ｍｏｌ℃时，未发现玻璃化转变。     

HAN-H_2O 二元体系玻璃化转变温度的依数性及其突变

用ＤＳＣ研究了ＨＡＮ－Ｈ２Ｏ二元体系的玻璃化转变温度Ｔｇ与Ｈ２Ｏ含量的关系,发现在一定的Ｈ２Ｏ含量范围内,玻璃化转变温度具有依数性。根据Ｔｇ的变化规律初步推测该二元体系的分子结构,认为ＨＡＮ－Ｈ２Ｏ二元体系可随Ｈ２Ｏ含量的不同而形成ＨＡＮ／Ｈ２Ｏ摩尔比不同的分子簇,而一个ＨＡＮ分子最多能与三个Ｈ２Ｏ分子形成分子簇,当Ｈ２Ｏ含量８超过７５ｍｏｌ％（ＨＡＮ／Ｈ２Ｏ摩尔比为１／３）时,只能形成ＨＡＮ／Ｈ２Ｏ摩尔比为２／３的稳定分子簇。     

1—2折流换热器流体温度沿程变化及其LMTD的计算

１－２折流换热器流体温度沿程变化及其ＬＭＴＤ的计算梁日忠ＴＨＥＶＡＲＩＡＴＩＯＮＯＦＦＬＵＩＤＴＥＭＰＥＲＡＴＵＲＥＡＬＯＮＧＳＩＤＰＡＳＳＡＮＤＴＨＥＣＡＬＵＡＴＩＯＮＯＦＬＭＴＤＩＮ１－２ＢＡＦＦＬＥＨＥＡＴＥＸＣＨＡＮＧＥＲ１前言换热器设计中，...     

溶胶—凝胶法合成了BaAl2Si2O8超细粉末的研究

以Ｂａ（ＯＨ）２．８Ｈ２Ｏ，Ａｌ（ＮＯ３）３．９Ｈ２Ｏ，ＴＥＯＳ为原料，采用溶胶－凝胶法制备ＢａＯ－Ａｌ２Ｏ３－ＳｉＯ２三元系粉末，研究了不同因素对生成稳定溶胶和胶化时间的影响，用ＴＧ－ＤＴＡ，ＸＲＤ研究了溶胶－凝胶的热处理过程，用ＴＥＭ观察了粉体的粒径。     

CALIXE［4］ARENE AS A TEMPLATE FOR CONTROLLING REGIOCHEMISTRY OF PHOTODIMERIZATION OF 9－SUBSTITUTED AN

ＣＡＬＩＸＥ［４］ＡＲＥＮＥＡＳＡＴＥＭＰＬＡＴＥＦＯＲＣＯＮＴＲＯＬＬＩＮＧＲＥＧＩＯＣＨＥＭＩＳＴＲＹＯＦＰＨＯＴＯＤＩＭＥＲＩＺＡＴＩＯＮＯＦ９－ＳＵＢＳＴＩＴＵＴＥＤＡＮＴＨＲＡＣＥＮＥＬＩＹＩ；ＴＯＮＧＺＨＥＮ－ＨＥ（ＣＨＥＮ－ＨＯＴＵＮＧ...     

HBA／PET／HQ—TPA液晶共聚芳酯的合成与表征

采用熔融缩聚方法合成了ＨＢＡ／ＰＥＴ及ＨＢＡ／ＰＥＴ／Ｈ１－ＴＰＡ液晶共聚酯。应用ＤＳＣ，偏光显微镜等对共聚酯性能进行了表征。结果表明：加入第三单体后，可以改善二元聚酯ＨＢＡ／ＰＥＴ的共聚反应条件，并且所有样品匀具有较大的特性粘度，较小的熔融热焓，二元体系的玻璃化转变较明显，加入第三单体后的三元共聚体系玻璃化转变消失，并且随着第三单体含量的增加，共聚酯熔点上升。     

液体发射药的玻璃化转变温度及其体积弛豫活化焓

用ＤＳＣ测定了三种硝酸羟胺－三乙醇胺硝酸盐－水（ＨＡＮ－ＴＥＡＮ－Ｈ２Ｏ）为主成分的液体发射药的玻璃化转变温度，研究了玻璃化转变温度与升温速率的关系，导出了玻璃化转变时体积弛豫的活化焓的表达式，并计算得到了这种活化焓，为改进预测液体发射药低温粘度的方法打下了基础。     

UNIFAC法预测甲苯,苯甲醛,苯甲酸体系汽液平衡关系

本文增补和修订了适用于芳烃的ＵＮＩＦＡＣ基因相互作用参数（ａＣＨＯ，ＣＯＯＨ，ａＣＯＯＨ，ＣＨＯ）；（ａＡｃＣＨ２，ＣＨＯ、ａＣＨＣ，ＡｃＣＨ２）；（ａＡｃＣＨ２，ＣＯＯＨ、ａＣＯＯＨ，ＡｃＣＨ２）。将其用于计算甲苯、苯甲醛、苯甲酸体系三对二元ＶＬＥ和预测三元ＶＬＥ数据，均获得令人满意的拟合结果。     

胺对镍系催化了二烯聚合规律的影响

以二乙胺为例研究了胺对Ｎｉ（ｎａｐｈ）２－Ａｌ（－Ｂｕ）３－ＢＦ３·ＯＥｔ２＋ｎ—Ｃ８Ｈ１７ＯＨ（简称Ｎｉ－Ａｌ－Ｂ＋ＲＯＨ）和Ｎｉ（ｎａｐｈ）２－Ａｌ（ｉ－Ｂｕ）３－ＢＦ３·ＯＥｔ２＋ＣＨ３ＣＯＯＣ４Ｈ９（简称Ｎｉ—Ａｌ—Ｂ＋ＢＡ）两体系聚合活性和聚合物分子量的影响，并与Ｎｉ—Ａｌ—Ｂ体系进行了对比．考察了通常条件下肢的允许含量，讨论了有胺存在时Ｎｉ／Ｂｄ、Ａｌ／Ｎｉ、Ａｌ／Ｂ摩尔比的变化对聚合规律的影响。结果表明：胺的含量高于２０ｐｐｍ时将使聚合活性和分子量降低，提高催化剂用量可以抑制胺的不利影响。     

Thermodynamic modeling and phase diagram prediction of salt lake brine systems. I. Aqueous Mg2+–Ca2+–Cl− binary and ternary systems

Salt lake brine is a complex salt-water system under natural environment. Although many models can express the thermodynamic properties and phase equilibrium of electrolyte aqueous solution, the multi-temperature characteristics and predictability are still the goals of model development. In this study, a comprehensive thermodynamic model system is re-established based on the eNRTL model and some improvements: (1) new expression of long-range electrostatic term with symmetrical reference state is proposed to handle the electrolyte solution covering entire concentration range; (2) the temperature dependence of the binary interaction parameters is formulated with a Gibbs Helmholtz expression containing three temperature coefficients, the liquid parameters, which associated with Gibbs energy, enthalpy, and heat capacity contribution; and (3) liquid parameters and solid species data are regressed from properties and solubility data at full temperature range. Together the activity coefficient model, property models and parameters of liquid and solid offer a comprehensive thermodynamic model system for the typical bittern of MgCl₂–CaCl₂–H₂O binary and ternary systems, and it shows excellent agreement with the literature data for the ternary and binary systems. The successful prediction of complete phase diagram of ternary system shows that the model has the ability to deal with high concentration and high non-ideality system, and the ability to extrapolate the temperature.     

Thermodynamic modeling and phase diagram prediction of salt lake brine systems Ⅱ.Aqueous Li+-Na+-K+-SO4-and its subsystems

It is still a challenging task to accurately and temperature-continuously express the thermodynamic properties and phase equilibrium behaviors of the salt-lake brine with multi-component,multi-temperature and high concentration.The essential subsystem of sulfate type brine,aqueous Li+-Na+-K+-SO42-and its subsystems across a temperature range from 250 K to 643 K are investigated with the improved comprehensive thermodynamic model.Liquid parameters(ΔgIJ,ΔhIJ,and ΔCp,IJ)associated with the contributions of Gibbs energy,enthalpy,and heat capacity to the binary interaction parameters,i.e.the temperature coefficients of eNRTL parameters formulated with a Gibbs Helmholtz expression,are determined via multi-objective optimization method.The solid constants ΔfGk°(298.15)and ΔfHk°(298.15)of 11 solid species occurred in the quaternary system are rebuilt from multi-temperature solubilities.The modeling results show the accurate representation of(1)solution properties and binary phase diagram at temperature ranges from eutectic points to 643 K;(2)isothermal phase diagrams for Li2SO4-Na2SO4-H2O,Li2SO4-K2SO4-H2O and Na2SO4-K2SO4-H2O ternary systems.The predicted results of com-plete structure and polythermal phase diagram of ternary systems and the isothermal phase diagrams of quaternary system excellently match with the experimental data.     

超临二氧化碳萃取分离异丙醇-水的相平衡研究

用静态法测定了高压下CO_2-i-C_3H_7OH二元系和CO_2-i-C_3H_7OH-H_2O三元系的相平衡数据.实验证明超临CO_2能从水溶液中萃取分离异丙醇,并打破了常压下异丙醇-水的恒沸组成.用SRK方程和Huran-Vidal混合规则,建立了CO_2-i-C_3H_7OH-H_2O三元系的热力学模型.此模型只用二元作用系数,能成功地预测三元气液平衡和平衡系线随温度压力剧烈变化的行为.最后,通过实验数据分析和模型预测,探讨了影响超临CO_2从水溶液中萃取分离异丙醇的各种条件.     

MgSO_4和Li_2SO_4对乙醇-水体系互溶性的影响

测定了 Mg SO4- C2 H5 OH- H2 O三元系在 - 5℃ ,0℃ ,30℃ ,35℃及 5 0℃和 L i2 SO4- Mg SO4- C2 H5 OH- H2 O四元系在 2 5℃的互溶度和相关系。结果表明 :Mg SO4可使完全互溶的乙醇 -水体系分层 ,且 Mg SO4在两层液相中的含量明显不同。L i2 SO4和 Mg SO4作为混合盐在乙醇 -水体系中的行为表现出加和性。L i2 SO4本身在室温范围下不会使乙醇 -水体系分层 ,但适量的 L i2 SO4与 Mg SO4混合可使乙醇 -水体系的分层温度从33℃下降至 15℃以下。另一方面 ,乙醇的存在不仅可以降低 Mg SO4和 L i2 SO4的溶解度 ,而且可促成 Mg SO4· 7H2 O的脱水。该三元系中 Mg SO4的溶解度随温度升高而增大 ,在乙醇中几乎不能溶解。在 30℃ ,35℃和 5 0℃下体系的平衡固相为 Mg SO4· 6 H2 O,其他温度下是 Mg SO4· 7H2 O。提出一个经验公式对互溶性进行了关联 ,效果很好     

High-pressure phase equilibria of Polystyrene dissolutions in Limonene in presence of CO2

Dissolution with terpenic solvents is presented as an alternative and original route to recycle Polystyrene wastes at room temperature. Limonene was the chosen solvent to carry out the dissolution process because it presents high compatibility with Polystyrene besides being natural, non toxic and relatively low cost. The solvent removal is possible thanks to supercritical CO₂ since it provides high solubility of Limonene and complete PS insolubility at moderated pressures and temperature. In order to determine the proper working conditions to conduct the precipitation of the polymer, accurate knowledge of the phase equilibrium for mixtures of carbon dioxide, Limonene and Polystyrene should be known.In this work, the solubility of Limonene in the ternary system CO₂/Limonene/Polystyrene was determined. The phase equilibrium experiments were conducted in a variable-volume view cell employing the static method. These experiments were carried out in the temperature range of 298.15–313.15 K, at pressures up to 15 MPa and in the concentration range of 0.05–0.80 g PS/ml Limonene. Initially the binary systems were studied by means of equations of state: Peng–Robinson in the case of CO₂/Limonene and Sanchez–Lacombe in the case of Limonene/PS and CO₂/PS. Predicted data were collected together with the experimental to check the agreement and to determine the limits of the ternary system formed by CO₂–Limonene–PS. It is indispensable to determine the behaviour of the ternary system to know completely the fluid phase equilibrium. The results indicate that the solubility of Limonene in the vapour phase is favoured by high pressure and temperature as well as low concentration.     

Thermodynamic modeling and phase diagram prediction of salt lake brine systems. I. Aqueous Mg2+-Ca2+-Cl- binary and ternary systems

Salt lake brine is a complex salt-water system under natural environment. Although many models can express the thermodynamic properties and phase equilibrium of electrolyte aqueous solution, the multi-temperature characteristics and predictability are still the goals of model development. In this study, a comprehensive thermodynamic model system is re-established based on the eNRTL model and some improvements: (1) new expression of long-range electrostatic term with symmetrical reference state is proposed to handle the electrolyte solution covering entire concentration range; (2) the temperature dependence of the binary interaction parameters is formulated with a Gibbs Helmholtz expression containing three temperature coefficients, the liquid parameters, which associated with Gibbs energy, enthalpy, and heat capacity contribution; and (3) liquid parameters and solid species data are regressed from properties and solubility data at full temperature range. Together the activity coefficient model, property models and parameters of liquid and solid offer a comprehensive thermodynamic model system for the typical bittern of MgCl₂-CaCl₂-H₂O binary and ternary systems, and it shows excellent agreement with the literature data for the ternary and binary systems. The successful prediction of complete phase diagram of ternary system shows that the model has the ability to deal with high concentration and high non-ideality system, and the ability to extrapolate the temperature.     

Measurement and prediction of phase diagrams of the enantiomeric 3-chloromandelic acid system

The identification of racemic species of enantiomeric 3-chloromandelic acid (3-ClMA) as well as ternary solubility measurement in a mixture of water and isopropanol (IPA) was studied in this paper. Thermal analyses were carried out for mixtures of the two enantiomers with different compositions. The binary fusion diagram suggested the presence of a racemic compound for racemate 3-ClMA. It was verified with the ternary solubility phase diagram by dissolving various mixtures into the H₂O/IPA solution. Ternary phase diagram revealed a strong temperature dependency of solubility for the 3-ClMA system. In order to shorten the experimental time in the solubility measurement, a semi-empirical thermodynamic model (UNIQUAC) was used to predict the solubility of various compositions of enantiomers at different temperatures. Results indicate that UNIQUAC model can provide good predictions in the solubility of racemate, eutectic and (R)-3-ClMA in both pure water and H₂O/IPA (9/1 weight ratio) system. In addition, structures of racemate and pure (R)-3-ClMA were also studied using a powder X-ray diffractometer. Thermodynamic prediction, thermal analysis, and structural study are in excellent agreement for identifying the enantiomeric 3-ClMA system as a racemic compound forming system.