Na+, K+, Mg2+∥Cl-, SO2-4-H2O五元体系35 ℃介稳相图研究

研究得出（Na+, K+, Mg2+∥Cl-, SO2-4-H2O）五元体系35 ℃时的介稳溶解度数据,绘制了该体系35 ℃的介稳相图,共有9个为氯化钠所饱和的结晶区域：氯化钾、钾芒硝（3K2SO4*Na2SO4）、钾镁矾（K2SO4*MgSO4*4H2O）、钾盐镁矾（KCl*MgSO4*2.75H2O）、光卤石（KCl*MgCl2*6H2O）、白钠镁矾（Na2SO4*MgSO4*4H2O）、硫酸钠、六水硫酸镁（MgSO4*6H2O）和水氯镁石（MgCl2*6H2O）. 所得35 ℃介稳相图与Vant Hoff 25 ℃稳定相图比较有较大区别：软钾镁矾（K2SO4*MgSO4*6H2O）、七水硫酸镁、五水硫酸镁及四水硫酸镁结晶区域消失,钾镁矾和钾盐镁矾结晶区域显著扩大. 所得35 ℃介稳相图与25 ℃介稳相图区别很大：软钾镁矾和七水硫酸镁结晶区域消失,同时出现了钾镁矾和钾盐镁矾的结晶区域. 在该五元体系35 ℃介稳相平衡研究中发现析出的是钾盐镁矾的低水化合物（KCl*MgSO4*2.75H2O）.     

羧酸聚合物对磷酸钙的阻垢作用和机理

采用静态阻垢法评定了膦酰基羧酸聚合物(POCA)、聚丙烯酸(PAA)、丙烯酸-丙烯酸羟丙酯共聚物(T-225)、水解聚马来酸酐(HPMA)等四种羧酸类聚合物阻垢剂对磷酸钙的阻垢性能, 发现在加药量为25 mg/L时几种聚合物对磷酸钙垢的阻垢率分别为100%, 94.6%, 36.2%和30.2%. 采用分子动力学(MD)方法, 模拟计算了四种聚合物与磷酸钙晶体的(110)晶面的相互作用结合能、非键作用能等参数. 结果表明: 聚羧酸与(110)晶面结合能以及非键作用能的大小排序为POCA＞T-225＞HPMA＞PAA, 结合能以及非键作用能越大, 说明聚合物与垢晶体的结合越紧密, 抑制性能越好; 因此它们对磷酸钙阻垢能力大小排序为POCA＞T-225＞HPMA＞PAA. 该理论计算与实验室静态阻垢评定结论一致. 通过对超分子对关联函数的分析, 发现POCA和T-225聚合物中羰基O原子与晶面上Ca^2＋之间形成了较弱的离子键, 但强度远比非键作用小, 非键作用主要由库仑作用和范德华作用力提供, 且库仑作用的贡献更大. 据此合成了马来酸酐-苯乙烯磺酸钠-丙烯酸羟丙酯(MA-SS-HPA)以及苯乙烯磺酸钠-丙烯酸羟丙酯-亚磷酸(MA-SS-H₃PO₃)共聚物, 加药量为18 mg/L时对磷酸钙垢的阻垢率分别为94.2%和100%, 性能优于POCA.     

超声化学法制备不同形貌的CaF2微米晶

采用超声化学法,以CaCl2与不同氟源(NaBF4、K2SiF6)在溶液中反应,制得了不同形貌的CaF2微米晶(立方体、花状、多面体)。用XRD、SEM及TEM对产物晶相及形貌进行了表征。XRD结果显示所有产物均为结晶良好的立方相CaF2。SEM及TEM结果表明由NaBF4制得的产物形貌为均匀的立方体微米晶,而由K2SiF6制得的产物为多面体。在添加配体Na2EDTA的情况下,由NaBF4得到的产物为纳米片组成的花状结构。本文详细讨论了氟源种类、反应物比例、配体等反应参数对产物CaF2形貌的影响,并提出了可能的反应机理。     

反相气相色谱法表征聚丁二烯橡胶的表面性质

采用反相气相色谱技术测定了聚丁二烯橡胶的表面性质。以正己烷、正庚烷、正辛烷、正壬烷作为非极性探针测定其表面色散自由能,以二氯甲烷、三氯甲烷、丙酮、乙酸乙酯、乙醚和四氢呋喃作为极性探针测定其路易斯酸碱常数。经计算得出聚丁二烯橡胶在303、313、323、333和343 K的表面色散自由能分别为47.07、46.46、45.85、45.60和45.09 mJ/m2。结果表明,聚丁二烯橡胶表面色散自由能随着温度的升高呈线性降低,路易斯酸常数Ka为0.34,碱常数Kb为1.77,总酸碱作用能力2.11,该聚合物为弱碱性Lewis两性聚合物材料。此外还计算出聚丁二烯橡胶的酸碱作用吸附自由能（~ΔGsa）和吸附焓（~ΔHsa）。     

反相气相色谱法研究1,3,5-三氨基-2,4,6-三硝基苯的表面特性

采用反相气相色谱技术(IGC)研究了4种不同粒度的1,3,5-三氨基-2,4,6-三硝基苯(TATB)的表面性质。4种不同粒度的TATB表面自由能的色散分量（γds）随着温度的升高而增加;粒度越大的粒子,其色散自由能上升越快;在较高温度下,粗颗粒TATB显示了更强的色散作用(γds=193.2 mJ/m2,353 K),粒度最小的亚微米TATB显示了最弱的色散作用(γds=64.0 mJ/m2,353 K)。由于制备方法不同和粒子大小的差异,4种TATB的表面酸碱性质显示了明显的差别,细颗粒TATB表面有较强的亲电子特性;而其他3种TATB在极性探针分子的作用下的吸附均表现为吸热吸附,表现出在分子内和分子间具有强烈的相互作用,其Ka和Kb值均为负。     

Tumor targeting of HPMA copolymer conjugates containing sulfadiazine groups

To develop new tumor targeting macromolecular conjugates,poly（HPMA）-SD-APMA-DTPA（HPMA:N-（2-hydroxypropyl）- methacrylamide;APMA:N-（3-ammopropyl）methacrylamide;DTPA:diethylenetriaminepentaacetic acid;SD:sulfadiazine） was synthesized and characterized.The poly（HPMA）-SD-DTPA conjugates were radiolabeled with the radionuclide ^99mTc and tested for uptake by cultured H22 cells in vitro.DTPA-^99mTc（radiotracer 1） and poly（HPMA）-DTPA-^99mTc（radiotracer 2） were also synthesized and characterized for comparison.The uptake of poly（HPMA）-SD-DTPA-^99mTc（radiotracer 3,34.76%） was significantly higher than that of poly（HPMA）-DTPA-^99mTc（16.40%）,indicating that uptake of the poly（HPMA）-SD-DTPA-^99mT was active binding.The uptake of poly（HPMA）-DTPA-^99mTc was significantly higher than that of DTPA-^99mTc（2.98%）, suggesting that uptake of the poly（HPMA）-DTPA-^99mT was passive binding.The data suggest that the poly（HPMA）-SDAPMA -DTPA conjugates might be useful as tumor targeting macromolecular conjugates.     

碱金属助剂类型及前驱物对改性NiAl复合氧化物催化分解N2O活性的影响

制备了不同Ni/Al原子比的NiAl类水滑石样品,焙烧获得NiAl复合氧化物,用于N₂O分解反应,研究了NiAl复合氧化物组成对催化活性的影响。在活性较高的NiAl复合氧化物表面浸渍碱金属碳酸盐溶液,制备改性NiAl复合氧化物,考察了碱金属类型（Na、K、Cs）和钾前驱物（K₂CO₃、K₂C₂O₄、CH₃COOK、KNO₃）对改性催化剂活性的影响。用XRD、ICP-AES、FT-IR、BET、H₂-TPR、XPS技术表征了催化剂的组成结构。结果表明,Ni/Al原子比为2.7的NiAl复合氧化物催化活性较高;Na、K、Cs碳酸盐改性NiAl复合氧化物均提高了催化剂活性,其中K的助剂效应最强。钾前驱物对K改性NiAl复合氧化物的催化活性有显著影响,其中碳酸钾、醋酸钾、草酸钾的加入明显提高了改性催化剂的催化活性,而加入硝酸钾反而降低了催化剂活性。     

苯封端还原态苯胺四聚体结晶形态的研究

研究了用溶液滴膜、甘油表面成膜以及溶液旋涂成膜等方法制备的苯封端还原态苯胺四聚体的结晶形态.晶体的晶片厚度、晶体尺寸及结晶完善性均随溶液等温结晶温度的升高而增大.齐聚物在较低过冷度下易于形成尺寸较大的晶体.详细讨论了溶剂及基底与结晶形态的关系.     

Na^+, K^+//Cl^-, SO4^2^-, CO3^2^——H2O五元体系25℃介稳相图的研究

用等温蒸发方法研究了NaCl饱和下的Na^+, K^+//Cl^-, SO4^2^-, CO3^2^--H2O五元体系25℃介稳相图, 测定了溶液的密度、粘度、折光率、电导率、PH和蒸汽压, 并由蒸汽压数据求得了水活度和渗透系数。在Janecke相图上有五个结晶区, 即Na2SO4,Na2CO3·2Na2SO3, Na2SO4·3K2SO4, Na2CO3·7H2O和KCl相区, 与Harvie和Weare计算相图比较, 无水芒硝和七水碳酸钠结晶区明显扩大, 碳钠矾相区明显缩小, 钾石盐和钾芒硝相区基本相近。用经验或半经验公式描述了溶液的密度、折光率和粘度随浓度的变化规律。用Pitzer电解质溶液模型计算了水活度和析出盐的溶度积。结果是令人满意的。     

Na^+, K^+//Cl^-, SO4^2^-, CO3^2^——H2O五元体系25℃介稳相图的研究

用等温蒸发方法研究了NaCl饱和下的Na^+, K^+//Cl^-, SO4^2^-, CO3^2^--H2O五元体系25℃介稳相图, 测定了溶液的密度、粘度、折光率、电导率、PH和蒸汽压, 并由蒸汽压数据求得了水活度和渗透系数。在Janecke相图上有五个结晶区, 即Na2SO4,Na2CO3·2Na2SO3, Na2SO4·3K2SO4, Na2CO3·7H2O和KCl相区, 与Harvie和Weare计算相图比较, 无水芒硝和七水碳酸钠结晶区明显扩大, 碳钠矾相区明显缩小, 钾石盐和钾芒硝相区基本相近。用经验或半经验公式描述了溶液的密度、折光率和粘度随浓度的变化规律。用Pitzer电解质溶液模型计算了水活度和析出盐的溶度积。结果是令人满意的。     

聚天冬氨酸的合成

缓蚀阻垢;热稳定性;水解稳定性;生物降解性;聚天冬氨酸的合成     

The Influence of Alkali Metal Ions on Homogeneous Nucleation of Al(OH)(3) Crystals from Supersaturated Caustic Aluminate Solutions

Homogeneous nucleation of Al(OH)(3) crystals from synthetic, optically clear, caustic aluminate solutions and the influence of alkali metal ion (Na(+) versus K(+)) have been investigated under isothermal, batch crystallization conditions. The nucleation kinetics showed a seventh-order dependence upon Al(III) relative supersaturation and a strong temperature effect. Activation energy of 160 kJ mol(-1) and interfacial energy of 33 mJ m(-2) were estimated and found to be independent of alkali ion, as was the Al(OH)(3) equilibrium solubility. The nucleation rate, however, was faster in aging sodium than in potassium aluminate solutions. It appears that Na(+) ions provide greater stability for the formation and densification of Al(III)-containing, supramolecular clusters which grow more rapidly into Al(OH)(3) crystallites than do K(+) ions. The development of the Al-OH octahedral structure of Al(OH)(3) nuclei is an alkali metal ion-mediated, chemical reaction-controlled condensation process, displaying specific gibbsite (gamma-Al(OH)(3))-bayerite (alpha-Al(OH)(3)) dimorphism. Furthermore, significant differences in the level of alkali ion incorporation, reflecting in the purity and morphology of the crystalline product, were observed. Copyright 2000 Academic Press.     

How charging corannulene with one and two electrons affects its geometry and aggregation with sodium and potassium cations

Bowl-shaped mono- and dianions are prepared by reduction of corannulene (C(20)H(10), 1) with sodium and potassium metals in the presence of [18]crown-6 ether. Single-crystal X-ray diffraction studies of two sodium salts, [Na(THF)(2)([18]crown-6)](+)[1(-)] (2a) and [Na([18]crown-6)](+)[1(-)] (2b), reveal the presence of naked corannulene monoanions 1(-) in both cases. In contrast, the potassium adduct, [K([18]crown-6)](+)[1(-)] (3), shows an η(2)-binding of the K(+) ion to the convex face of 1(-). For the first time, corannulene dianions have been isolated as salts with sodium, [Na(2)([18]crown-6)](2+)[1(2-)] (4a) and [Na(THF)(2)([18]crown-6)](+)[Na([18]crown-6)](+)[1(2-)] (4b), and potassium counterions, [K([18]crown-6)](2)(+)[1(2-)] (5). Their structural characterization reveals geometry perturbations upon addition of two electrons to a bowl-shaped polyarene. It also demonstrates η(5)- or η(6)-binding of metals to the curved carbon surface of 1(2-), depending on the crystallization conditions. Both mono- and doubly-charged corannulene bowls show the preferential exo binding of Na(+) and K(+) ions in all investigated compounds. Various types of C-H···π interactions are found in the crystals of 2-5. The UV/Vis, ESR, and (1)H NMR spectroscopic studies of 2-5 indicate different coordination environment of corannulene anions in solution, depending on the metal ion.     

Surface properties and structures of diblock copolymer and homopolymer with perfluoroalkyl side chains

The surface free energy of diblock copolymer, composed of methyl methacrylate and 2-perfluorooctylethyl methacrylate (PMMA-b-PFEMA), was compared with that of PFEMA homopolymer (P-PFEMA) in correlation with their structures in the solid state and in the solution using dynamic contact angle, X-ray photoelectron spectroscopy, X-ray diffraction, and dynamic light scattering. The PMMA-b-PFEMA film cast from chloroform solution was found to possess very low surface free energy (7.8 mJ/m(2)) compared with the surface free energies of the P-PFEMA (8.5 mJ/m(2)) and the PMMA-b-PFEMA (9.8 mJ/m(2)) films cast from CF(3)CF(2)CHCl(2) solutions. These differences in the surface free energy were brought about by the variations in their surface structures. The very low surface free energy was considered to have originated from the surface segregation of the PFEMA segments highly self-assembled by the presence of chloroform.     

Effects of Na2SiF6 on Preparing Mullite Material with Sludge from the Aluminum Profile Factory and Pyrophyllite

In this research,the mullite material with sludge from aluminum profile factory and pyrophyllite as primary raw materials was prepared. Based on the optimal formula,optimal calcining temperature and holding time determined in the research,effects of Na2SiF6 mineralizer on crystal structure,microstructure and properties of mullite were discussed to determine the optimal addition of Na2SiF6 mineralizer. With XRD and SEM methods,crystal structure and microstructure of the test samples were characterized; with Rietveld Quantification method,contents of various crystal phases in the test samples were determined; properties of the test samples were tested. In combination with the structural and property analysis results,the optimal Na2SiF6 addition was determined to be 2%. Correspondingly,the content of solid solution of mullite-Al4.59Si1.41O9.7 was 96.9wt%,the bulk density was 2.10 g/cm3,the degree of porosity was 27.0%,the water absorption rate was 12.8%,the rupture strength was 24.30 MPa and primary thermal-shock rupture strength retention rate was 87.4%.     

Modulation of Tartrates with Various Counterions on the Phases of Calcium Oxalate in Gelatinous Systems

Effect of various counterions of tartrate on the crystallization of calcium oxalate in gel system was investigated using scanning electron microscopy and X-ray diffraction. Various tartrates with hydrogen (H2tart), sodium (Na2tart), potassium (K2tart), ammonium ((NH4)2tart), and a mixture of sodium and potassium cations (NaKtart) were considered. For H2tart, Na2tart, and (NH4)2tart, calcium oxalate dihydrate (COD) was induced. However, for K2tart and NaKtart,calcium oxalate trihydrate (COT) was obtained.     

五元交互体系Li+,Na+,K+//CO32-,Cl--H2O在298.15K的相平衡研究

针对西藏扎布耶盐湖卤水组成,采用等温溶解平衡法研究了五元交互体系Li+,Na+,K+//CO32-,Cl--H2O于298.15K时的相平衡,并绘制了相图(空间立体图和Li2CO3饱和的投影图).结果表明,该五元体系相图含有7个结晶区、13条单变量线和4个无变量点.7个结晶区由6个单盐结晶区和1个复盐结晶区组成,分别为LiCl·H2O,NaCl,KCl,Li2CO3,K2CO3·3/2H2O,Na2CO3·10H2O和NaKCO3·6H2O,没有形成固溶体和天然碱(Na2CO3·NaHCO3·2H2O).4个无变量点标记成K1,K2,K3和K4,所对应的平衡固相盐分别是:Li2CO3+NaKCO3·6H2O+Na2CO3·10H2O+KCl,Li2CO3+NaKCO3·6H2O+K2CO3·3/2H2O+KCl,Li2CO3+NaCl+KCl+LiCl·H2O和Li2CO3+NaCl+Na2CO3·10H2O+KCl.     

超细NaY分子筛的深度脱铝

通过优化和组合不同脱铝补硅方法,依次经氟硅酸铵处理、600oC水热处理、硅溶胶+草酸处理和800oC水热处理过程,成功实现了200nm超细NaY分子筛的深度脱铝,最终产品骨架硅铝比高达27.3,比表面积为581.9m2/g,分子筛结晶度保持在65%以上.结果表明,对于超细NaY分子筛脱铝,第一步采用氟硅酸铵进行部分缺陷修补尤为重要.根据分子筛晶粒尺寸不同,需严格控制氟硅酸铵用量和处理次数.当晶粒为200nm时,氟硅酸铵与分子筛骨架铝的摩尔比为0.16,处理一次较为适宜.在连续脱铝过程中及时补修脱铝产生的缺陷是保障超细NaY分子筛成功脱铝的关键,而采用氟硅酸铵、硅溶胶、800oC高温水热处理,可有效实施这种骨架修正作用.