Sol-gel approach to in situ creation of high pH-resistant surface-bonded organic-inorganic hybrid zirconia coating for capillary microextraction (in-tube SPME)

A novel zirconia-based hybrid organic-inorganic sol-gel coating was developed for capillary microextraction (CME) (in-tube SPME). High degree of chemical inertness inherent in zirconia makes it very difficult to covalently bind a suitable organic ligand to its surface. In the present work, this problem was addressed from a sol-gel chemistry point of view. Principles of sol-gel chemistry were employed to chemically bind a hydroxy-terminated silicone polymer (polydimethyldiphenylsiloxane, PDMDPS) to a sol-gel zirconia network in the course of its evolution from a highly reactive alkoxide precursor undergoing controlled hydrolytic polycondensation reactions. A fused silica capillary was filled with a properly designed sol solution to allow for the sol-gel reactions to take place within the capillary for a predetermined period of time (typically 15-30 min). In the course of this process, a layer of the evolving hybrid organic-inorganic sol-gel polymer got chemically anchored to the silanol groups on the capillary inner walls via condensation reaction. At the end of this in-capillary residence time, the unbonded part of the sol solution was expelled from the capillary under helium pressure, leaving behind a chemically bonded sol-gel zirconia-PDMDPS coating on the inner walls. Polycyclic aromatic hydrocarbons, ketones, and aldehydes were efficiently extracted and preconcentrated from dilute aqueous samples using sol-gel zirconia-PDMDPS coated capillaries followed by thermal desorption and GC analysis of the extracted solutes. The newly developed sol-gel hybrid zirconia coatings demonstrated excellent pH stability, and retained the extraction characteristics intact even after continuous rinsing with a 0.1 M NaOH solution for 24 h. To our knowledge, this is the first report on the use of a sol-gel zirconia-based hybrid organic-inorganic coating as an extraction medium in solid phase microextraction (SPME).     

Degree of hydration in cement paste and C<Subscript>3</Subscript>A-sodium carbonate-water systems

This research provides a fundamental understanding of the early stage hydration of Portland cement paste, tricalcium aluminate (C₃A) paste at water to cement ratio of 0.5 and C₃A suspension at water to cement ratio of 5.0 modified by 2 or 4 mass% of sodium carbonate. A high conversion of unreacted clinker minerals to gel-like hydration products in the cement-Na₂CO₃ pastes takes place rapidly between 1^st to 24^th h. Contrary the Ca(OH)₂ formation within the same time interval is retarded in the excess of CO₃²⁻ ions due to intensive rise and growth of CaCO₃ crystals in hydrated cement. Later, the conversion of clinker minerals to the hydrate phase is reduced and higher contents of calcite and vaterite relative to that of Ca(OH)₂ in comparison with those found in the Portland cement paste are observed. As a consequence a decrease in strength and an increase in porosity between hardened Portland cement paste without sodium carbonate and those modified by Na₂CO₃ are observed. C₃A hydrates very quickly with sodium carbonate between 1^st and 24^th h forming hydration products rich in bound water and characterized also by complex salts of (x)C₃A·(y)CO₂·(zH₂O type, whereas C₃A-H₂O system offers C₃AH₆ as the main hydration product. Higher content of the formed calcium aluminate hydrates in C₃A-Na₂CO₃-H₂O system also contributes to early strength increase of Portland cement paste.     

Free release static coating of glass capillary columns; Static coating at elevated pressure — Theoretical considerations and practice

Summary Static coating of glass capillary columns has hitherto solely been carried out by evaporation of the stationary phase solvents under vacuum conditions. However, since a solvent vapour pressure higher than the external pressure is the only requirement for the vapour to flow out of the column, evacuation should not be necessary. Several important factors in the static coating procedure, such as mass (solvent vapour) — and heat transfer, heat of vaporisation of the solvent and viscosity of the stationary phase solution at elevated temperature and outlet pressure are discussed, principally to rationalise an improved static coating procedure. The alternative, so-called free-release static coating procedure, was evaluated practically by coating several columns with OV-101 and SE-30. Coating speed was found to be rapid and relatively constant whereas coating efficiency was between 80 and 100%.     

Effect of solvent composition on free release static coating of capillary columns

Summary Three aspects with respect to the selection of solvents for static coating of capillary columns, i.e. coating speed, occurrence of bumping and solubility of stationary phases are discussed. Hypotheses are proposed in an attempt to explain the observed facts that mixed solvents result in much higher coating speeds than those obtained from pure solvents, that a proper choice of solvents together with a good and uniform deactivitation of the column inner wall is needed to prevent bumping. Stationary phase solubility vs. solvent composition is also briefly discussed.     

Separation of oligonucleotides and DNA fragments by capillary electrophoresis in dynamically and permanently coated capillaries,using a copolymer of acrylamide and β-D-glucopyranoside as a new low viscosity matrix with high sieving capacity

New copolymers of acrylamide and β-D -glucopyranoside were synthesized and characterized. The different reactivity of the two monomers towards radical polymerization meant we could control the growth of the polymer chains whose length was inversely related to the number of glucose residues incorporated in the copolymers. The properties of these polymers were investigated in the separation of oligonucleotides and double-stranded DNA by capillary electrophoresis (CE) in coated and uncoated capillaries. The new copolymers were a suitable matrix for CE due to their high-resolving capacity and low viscosity. We also looked into the advantages of a new method of dynamic suppression of electroosmotic flow based on the addition of small amounts (0.03–0.05%) of dimethylacrylamide to the sieving and to the running buffer. A complete test was run on the reproducibility and efficiency of separations carried out in a permanently and dynamically coated capillary, and the advantages and disadvantages of the two methods were compared.     

一种高分子电阻型湿度传感器的制备及研究

以苯乙烯-马来酸酐共聚物钠盐(Na-SMA)为湿敏材料,采用浸涂的方法,在小型叉指金电极上成膜,制备了高分子电阻型湿度传感器.研究了浸涂液组成对传感器响应特性的影响.研究表明,随着浸涂液中Na-SMA浓度的提高,元件的电阻、湿滞降低;而随着浸涂液中聚乙烯醇(PVA)浓度的提高,元件的电阻降低,湿滞增加.     

基体的梯度结构对涂层硬质合金性能的影响

通过控制烧结气氛制备了均质和梯度结构的硬质合金基体，并用化学气相沉积制成涂层硬质合金及切削刀片。采用光学显微镜和扫描电镜观察，通过显微硬度抗弯测试和切削试验对均质基体和梯度基体的涂层硬质合金的组织特征与性能进行对比研究。研究结果表明，梯度结构的硬质合金基体可以提高涂层硬质合金的抗弯强度；相对于均质基体的涂层硬质合金刀片，梯度基体的涂层硬质合金刀片在保持耐磨性能的同时能显著提高抗冲击性能。基体涂层合金的组织结构及断口特征显示，梯度基体表层韧性区可阻碍裂纹的扩展。     

电弧喷涂铝涂层的抗高温空气氧化性能

采用电弧喷涂技术在Q235钢基体上制备铝涂层。用Q235钢、铝涂层和封孔铝涂层3种试样进行400℃和500℃涂层氧化和失效试验，并绘制了氧化动力学曲线。结果表明，在500℃以下，在Q235钢基体上电弧喷涂铝涂层和封孔铝涂层可以提高试样的抗氧化能力，但只是在短期内有效。在相同的温度下，封孔铝涂层试样氧化速度最低，铝涂层试样和Q235钢试样的氧化速度大约分别是它的2倍和3倍。氧化过程中，氧化气体渗透到涂层内部，Al2O3膜不断生成、破碎和剥落，并在涂层颗粒机械结合部位堆积，产生的张应力造成涂层的内聚强度降低，塑性和密封性能变差，防腐作用减弱，这是涂层氧化和失效的主要原因。     

渤海连续冰层关键力学参数预报模式

为反映海冰的物理和力学特性，利用实验室获取水平方向加载冰样的单轴压缩强度、三点弯曲强度和侧限剪切强度与孔隙率间的统计关系，把海冰温度、盐度和密度对强度的效应统一起来，建立了预报模式。之后，依据渤海海冰多年调查资料和近期研究成果，将冰层内的温度、盐度和密度表示成气温、水温和冰厚的函数，获得冰层的孔隙率剖面，进而得到冰层力学参数剖面。在选取冰层平均强度时还考虑了渤海冰层底部骨架部分有厚度无强度的特点，实现了利用已知冰厚、气温和水温预报冰层水平方向强度分布的目标。     

电弧喷涂铝及铝-锌涂层在动态腐蚀介质中的耐蚀性研究

对钢铁基体表面电弧喷涂铝及铝锌涂层进行了动态腐蚀实验 ,以失质量法计算了腐蚀速度 ,并探讨了腐蚀机理。采用SEM对铝及铝锌涂层腐蚀前后的外表形貌进行了观察 ,并对铝及铝锌涂层表面进行了能谱分析 ,采用电化学系统测试了涂层的自腐蚀电位。实验结果表明 ,在 3 %NaCl水溶液中铝涂层的耐蚀性优于铝锌涂层 ;其原因是铝涂层表面上氧化膜的自愈能力及自腐蚀电位高于铝锌涂层。研究还表明 ,铝及铝锌这些阳极涂层不仅能有效地保护它所覆盖的钢铁表面 ,还能保护暴露于腐蚀介质中的钢铁基体表面。在铝、铝锌涂层上刷涂有机涂料 ,有机涂料能渗透到金属涂层的孔隙中 ,将孔隙封闭。同时 ,有机涂层和金属涂层能构成复合涂层 ,其防腐效果更佳