On the interfacial chemistry of aryl diazonium compounds in polymer science

This review emphasises the role of aryl diazonium compounds as a new class of coupling agents for grafting polymer thin layers onto carbon, diamond, metals, metal oxides, alloys, semi-conductors, ceramics, and polymers. Physical and chemical methods are first reported for anchoring aryl layers to the surfaces, then the review concentrates on the modification of the above substrates by thin polymer films via a range of the “grafting from” and “grafting onto” strategies. Some applications are described which highlight the important role that diazonium salts will continue to play in the near future in the polymer and surface sciences.     

钼酸盐封闭后处理的热镀锌钢板硅烷膜的耐蚀性

为进一步增强硅烷膜的耐蚀性, 将硅烷化热镀锌钢板用钼酸盐溶液进行封闭后处理, 并采用扫描电子显微镜(SEM)、中性盐雾(NSS)实验、盐水全浸实验和电化学技术研究了所得复合膜层的表面形貌和耐蚀性能. 结果表明: 经钼酸盐溶液封闭处理后, 硅烷膜的孔隙被填充, 在锌层表面形成了由硅烷膜和钼酸盐转化膜构成的连续完整致密的复合膜; 复合膜的耐蚀性能明显提高, 且与钼酸盐溶液的封闭时间有关, 封闭60 s时所形成的复合膜的耐蚀性最佳. 在5%(w, 质量分数)NaCl溶液中的电化学测量结果表明: 硅烷化热镀锌钢板经钼酸盐溶液封闭处理后, 同时抑制了腐蚀过程中的阳极和阴极反应, 但主要是抑制阴极反应, 导致腐蚀电流密度明显减小, 发挥了单一硅烷膜和单一钼酸盐转化膜腐蚀防护的协同效应, 腐蚀防护效率高达99.1%; 随浸泡时间延长, 试样低频扩散阻抗先增大后减小, 表明膜层具有一定的“自愈”能力, 其耐蚀性优于常规铬酸盐钝化膜.     

Two-dimensional Monte Carlo simulations of ionic and nonionic silane self-assembly on hydrophilic surfaces

Aqueous chemistries have recently been shown to be useful for the deposition of hydrophobic films of nonionic and cationic silanes on hydrophilic substrates for the prevention of stiction in MEMS. The Monte Carlo method is used to simulate in two dimensions the self-assembly of silane films on a hydrophilic surface. We investigate the impact of charged group in cationic silane on the overall structure of the films. We characterize the film structure with spatial pair correlations at each molecular layer of the deposited films. The simulations reveal long-range correlations for the film of cationic silanes. Based on our two-dimensional simulations, we report an average "most probable" structure for the films of nonionic and cationic silanes.     

Inorganic–organic sol gel hybrid coatings for corrosion protection of metals

Inorganic–organic hybrid coatings by sol–gel process are very suitable for fighting corrosion. Inorganic sols in hybrid coatings not only increase adhesion by forming chemical bonds between metals and hybrid coatings, but also improve comprehensive performances of polymer in the coatings. Different organic polymers or organic functionalities are introduced into gel network to achieve tailored properties, such as hydrophobic properties, increasing cross-linking density, etc. As for corrosion protection of metals organic components of hybrid coatings are selected to repel water and form dense thick films and reduce coating porosity. The factors, such as the ratio of inorganic and organic components, cure temperature, pigments in hybrid coatings, need to be optimized for attaining hybrid films with the maximum corrosion resistance. Electro-deposition technique offers relatively thick homogeneous defect-free hybrid coatings in comparison to dip or spin coating techniques. Green cerium ions and non-ionizable organic inhibitors are more developed in hybrid coatings nowadays than other corrosion inhibitors. Long-term corrosion resistance techniques of inhibitors are discussed. The inhibitors entrapped in the nanocontainers are doped in hybrid films to prolong release of the inhibitors to damaged zones, which is discussed in detail. Among all the nanocontainers of corrosion inhibitors the prospective techniques which show superior corrosion protection are cyclodextrin/organic inhibitor inclusion complexes and layer by layer assembly of organic corrosion inhibitors in nanocontainers. Super-hydrophobic property of hybrid coatings derives from low surface tension and surface roughness of hybrid coatings, which endues the films with excellent corrosion protection for metals, but the durable property of super-hydrophobic coatings needs to be improved for industrial application. An ideal multiple model of hybrid coatings for superior anti-corrosion of metals proposed is a combination of super-hydrophobic hybrid coatings and underlying hybrid coatings doped with sustained release of corrosion inhibitors on metal substrates.     

Multivariate statistical assessment of polluted soils

This study deals with the application of several multivariate statistical methods (cluster analysis, principal components analysis, multiple regression on absolute principal components scores) for assessment of soil pollution by heavy metals. The sampling was performed in a heavily polluted region and the chemometric analysis revealed four latent factors, which describe 84.5 % of the total variance of the system, responsible for the data structure. These factors, whose identity was proved also by cluster analysis, were conditionally named “ore specific”, “metal industrial”, “cement industrial”, and “steel production” factors. Further, the contribution of each identified factor to the total pollution of the soil by each metal pollutant in consideration was determined.     

Use of diluted anion-exchange and hydrophobic properties in separating synthetic single-stranded oligodeoxyribonucleotides on mixed-ligand stationary phases

Summary Mixed-ligand or “mixed-interaction” stationary phases are composed of bonded silanes possessing both ionic and hydrophobic character. The complex retention properties exhibited by these phases have been particularly useful in separating large biomolecules, such as synthetic single-stranded oligodeoxyribonucleotides. By isolating the individual properties of separate ligands present in mixed-ligand stationary phases a better understanding of the heterogeneous surface was sought. Specifically a dilute anion-exchange mixed-ligand phase of 5% surface coverage showed dramatically different selectivity for oligomers compared to hydrophobic stationary phases. Of particular interest was the increased selectivity observed in separating oligonucleotides differing on the 3′ end over conventional reversed-phases supports.     

Features of formation of magnetite coatings on low-carbon steel in hot nitrate solutions

The process of anticorrosion magnetite coating (MC) formation on low-carbon steel is studied in alkali-free nitrate converting media at the temperatures of 70–98°C reduced as compared to those used (130–145°C) in standard technologies of steel bluing: formation of such coatings in alkaline nitrate solutions. Alongside with the conventional corrosion-electrochemical methods of analysis of the formed MCs, the regularities of the MC surface reliefs were studied using the method of atomic force microscopy combined with the technique of flicker-noise spectroscopy (FNS) for processing digitized images and obtaining the parameters of the MC surface structure in different nanometer ranges. It was shown that it is necessary to introduce additives of metal nitrates with a low cation radius into the ammonium nitrate converting solution to obtain MCs with a high corrosion stability at the first stage of MC formation and the final stage must consist in the further “passivation” of MCs: MC treatment by aqueous solutions based on nontoxic carboxylates. According to the FNS analysis of the surface structure of the formed MCs, a significant decrease of the FNS “point” factor, an indicator of MC corrosion instability, occurred during the final treatment. On this basis, one could characterize quantitatively the results of accelerated corrosion tests: no steel corrosion occurred on the thus formed coatings for 42 days under standard severe conditions: 100% relative humidity and daily “showering”. The performed study reveals fundamental possibilities for solving the problems of standardization of the anticorrosion coating surface based on the analysis of their surface profile in the nanometer range.     

Branched oligothiophene silanes with the efficient nonradiative energy transfer between the fragments

The synthesis of new dendrimers and branched oligothiophene silanes containing bithiophene groups at the periphery and quaterthiophene fragments at the center of the molecule is described. Specific features of bithiophene silane bromination were shown, and the conditions for the efficient synthesis of methyltris(5-bromo-2,2′-bithiophen-5-yl)silane have been found for the first time. The optical properties of the synthesized compounds were studied. The efficiency of the electron excitation energy transfer between the fragments of branched bi-and quaterthiophene silanes was measured.     

Formation of impurity Si<Subscript>2</Subscript>OH<Subscript>6</Subscript> in silane synthesized from silicon tetrafluoride

The possibility of the reduction of hexafluorodisiloxane by calcium hydride in the synthesis of silane from silicon tetrafluoride has been studied. This reaction is shown to be not decisive for oxygen contamination of silane. The most likely reason for the appearance of impurity Si₂OH₆ in “fluoride” silane is the Ca(OH)₂-catalyzed reaction of silane with trace water. The concentration of impurity Si₂OH₆ in silane at the stage of synthesis may be efficiently decreased by the preliminary purging of calcium hydride with a hydrogen (grade A) flow.     

Non-selective chemical sensors in analytical chemistry: from “electronic nose” to “electronic tongue”

Development, recent historical background and analytical applications of promising sensor instruments based on sensor arrays with data processing by pattern recognition methods have been described. Attention is paid to the “electronic tongue” based on an array of original non-specific (non-selective) potentiometric chemical sensors. Application results for integral qualitative analysis of beverages and for quantitative analysis of biological liquids and solutions, containing heavy metals are reported. Discriminating abilities and precision obtained allow to consider “electronic tongue” as a perspective analytical tool. Received: 17 July 1997 / Revised: 19 February 1998 / Accepted: 24 February 1998     

Ultrathin functional films of titanium(IV) oxide

Chemistry and physics of thin semiconducting layers of various types are subjects of intense research. Especially when nanotechnology methods such as self-assembly are involved, amazing structural and/or functional properties may appear. Also modern physical methods using variously organized plasma arrangements are able to produce uniform structures with distinctive functionality. In this review, based virtually on our own work, discussions on the preparation, structure, morphology, and function of titanium(IV) oxide nanoscopic thin films are presented. It was shown that structurally and functionally similar titanium(IV) oxide films can be prepared via completely different preparation techniques. Function tests were arranged as “primary”, covering the assessment of the light induced charge separation efficiency, and “secondary”, based on photocatalytic surface oxidations.     

Anomalies and error limits in electrical-conductivity measurements in plasticized transparent poly(vinyl chloride) films

The anomalous behavior of the electrical conductivity of transparent poly(vinyl chloride) films is experimentally studied at field voltages approaching the breakdown threshold, above the threshold, and far below the threshold. The effects of strong nonlinearity, relaxation drifts, and spontaneous reversible transitions between states with high and low electrical conductivities are revealed for the first time in “thick” (20–100 μm) plasticized transparent poly(vinyl chloride) films. When a certain threshold is exceeded, relaxation oscillations in the test sample are generated and their frequency is proportional to the applied voltage. During a “mild” breakdown, the polymer film passes into the high-conductivity state (the current increases by four or more orders of magnitude), which is identical to the states observed during low-voltage transitions. A simple qualitative model explaining the anomalous character of the electrical conductivity of plasticized poly(vinyl chloride) films is advanced.     

Normalized Lempel-Ziv complexity and its application in bio-sequence analysis

In this article, we propose a new method to measure DNA similarity based on a normalized Lempel-Ziv complexity scheme. The new method can weaken the effect of sequence length on complexity measurement and save computation time. Firstly, a DNA sequence is transformed into three (0,1)-sequences based on a scheme, which considers “A” and “non-A” , “G” and “non-G”, “C” and “non-C” bases respectively. Then, the normalized Lempel-Ziv complexity of the three (0,1)-sequences constitute a 3D vector. Finally, by the 3D vector, one may characterize DNA sequences and compute similarity matrix for them. The examination of similarities of two sets of DNA sequences illustrates the utility of the method in local and global similarity analysis.     

Multivariate analysis of HT/GC-(IT)MS chromatographic profiles of triacylglycerol for classification of olive oil varieties

The ability of multivariate analysis methods such as hierarchical cluster analysis, principal component analysis and partial least squares-discriminant analysis (PLS-DA) to achieve olive oil classification based on the olive fruit varieties from their triacylglycerols profile, have been investigated. The variations in the raw chromatographic data sets of 56 olive oil samples were studied by high-temperature gas chromatography with (ion trap) mass spectrometry detection. The olive oil samples were of four different categories (“extra-virgin olive oil”, “virgin olive oil”, “olive oil” and “olive-pomace” oil), and for the “extra-virgin” category, six different well-identified olive oil varieties (“hojiblanca”, “manzanilla”, “picual”, “cornicabra”, “arbequina” and “frantoio”) and some blends of unidentified varieties. Moreover, by pre-processing methods of chemometric (to linearise the response of the variables) such as peak-shifting, baseline (weighted least squares) and mean centering, it was possible to improve the model and grouping between different varieties of olive oils. By using the first three principal components, it was possible to account for 79.50% of the information on the original data. The fitted PLS-DA model succeeded in classifying the samples. Correct classification rates were assessed by cross-validation.     

Probing the dependence of the properties of cellulose acetates and their films on the degree of biopolymer substitution: use of solvatochromic indicators and thermal analysis

Although cellulose acetates, CAs, are extensively employed there is scant information about the systematic dependence of their properties on their degree of substitution, DS; this is the subject of the present work. Nine CAs samples, DS from 0.83 to 3.0 were synthesized; their films were prepared. The following solvatochromic probes have been employed in order to determine the empirical polarity, E _T(33); “acidity, α”; “basicity, β”, and “dipolarity/polarizability, π*” of the casted films: 2,6-dichloro-4-(2,4,6-triphenyl-pyridinium-1-yl) phenolate, WB; 4-nitroaniline; 4-nitroanisole; 4-nitro-N,N-dimethylaniline; 2,6-diphenyl-4-(2,4,6-triphenyl-pyridinium-1-yl)phenolate, RB. Additionally, two systems, ethanol plus ethyl acetate (EtOH–EtAc), and cellulose plus cellulose triacetate, CTA, were employed as models for CAs of different DS. Regarding the model systems, the following was observed: (i) For EtOH–EtAc, the dependence of all solvatochromic parameters on the “equivalent-DS” of the binary mixture was non-linear because of preferential solvation; (ii) The dependence of E _T(33) on equivalent DS of the cellulose–CTA films is linear, but the slope is smaller than that of the corresponding plot for CAs. This is attributed to the more efficient hydrogen bonding in the model system, a conclusion corroborated by IR measurements. The dependence of solvatochromic parameters of CAs on their DS is described by the simple equations; a consequence of the substitution of the OH by the ester group. The thermal properties of bulk CAs samples were investigated by DSC and TGA; their dependence on DS is described by simple equations. The relevance of these data to the processing and applications of CAs is briefly discussed.     

A voltammetric sensor on the basis of bismuth nanoparticles prepared by the method of gas condensation

A procedure is developed for the immobilization of bismuth nanoparticles prepared by the method of gas condensation on inert supports manufactured by the screen printing method using carbon-containing inks. The electrochemical behavior of the immobilized bismuth nanoparticles is investigated, and the conditions of their electrochemical activation are found. The composition of the modifying suspension “bismuth nanoparticles-liquid” is optimized. The elaborated thick-film carbon-containing electrode modified by bismuth nanoparticles is shown to be similar in its analytical parameters to the commercially available thick-film carbon-containing electrode premodified by calomel, and substantially exceeds carbon-containing electrodes with electrolytically deposited bismuth films in its properties. The limits of detection for heavy metals by stripping voltammetry are as follows (μg/L): 0.38 for Zn(II), 0.40 for Cd(II), and 0.55 for Pb(II) at the preconcentration time 180 s.     

新型十二烷基三甲氧基硅烷/氧化石墨烯复合膜对430不锈钢耐蚀性能的影响

使用一步电沉积法在430不锈钢上制备出十二烷基三甲氧基硅烷(DTES)/氧化石墨烯(GO)复合膜。 拉曼光谱(Raman)与扫描电子显微镜(SEM)测试表明,氧化石墨烯均匀地混合在硅烷膜中,并用电化学交流阻抗与极化曲线方法对这种复合膜所保护的430不锈钢进行耐蚀性能测试。 结果显示,在3.5%NaCl溶液中,430不锈钢会发生腐蚀反应,而存在硅烷复合膜的430不锈钢的耐蚀性能显著地提高。 研究表明,由于氧化石墨烯出色的阻隔性能一定程度上弥补了硅烷膜的缺陷,而且延长了腐蚀介质通过硅烷基质的路径,因此复合膜有着对基底物质更强的保护性能。     

Linearly polarized white fluorescence from shish-kebab type liquid crystalline poly(P-phenylenevinvlene)s with (P-phenylene)s as kebab

Liquid crystalline(LC) polymers with a shish-kebab-type moiety on their cross-conjugated(p-phenylene)s-poly(p-phenylenevinylene) s main chains were synthesized through Gilch polymerization in order to develop a kind of polymers available for linearly polarized white-light-emitting from single chain.In this system,the 2,5-bis(4’-alkoxyphenyl)benzene as the "kebabs" connects with poly(p-phenylenevinylene)(PPV) main chain backbone using its molecular gravity center and the PPV as the "shish" or "skewer"(the "shish-kebab").The polymers possess desirable properties such as excellent solubility and liquid crystalline properties.To drop the "kebabs" of the 2,5-bis(4’-alkoxyphenyl)benzene into the orientation microgroove of aligned polyimide film,not only the "shish" of polymer main chain can be aligned by the virtue of orientation of "kebabs" but also the uniform cross-conjugated structure between the "kebabs" and "shish" can be broken. Then,the alignment of the polymer main chain showed yellow light emission and was also accompanied by orientation of the LC side chains showing blue light emission,this gave rise to a notable linearly polarized white fluorescence.     

AFM,ellipsometry, XPS and TEM on ultra-thin oxide/polymer nanocomposite layers in organic thin film transistors

Here we report on the fabrication and characterization of ultra-thin nanocomposite layers used as gate dielectric in low-voltage and high-performance flexible organic thin film transistors (oTFTs). Reactive sputtered zirconia layers were deposited with low thermal exposure of the substrate and the resulting porous oxide films with high leakage currents were spin-coated with an additional layer of poly-α-methylstyrene (PαMS). After this treatment a strong improvement of the oTFT performance could be observed; leakage currents could be eliminated almost completely. In ellipsometric studies a higher refractive index of the ZrO₂/PαMS layers compared to the “as sputtered” zirconia films could be detected without a significant enhancement of the film thickness. Atomic force microscopy (AFM) measurements of the surface topography clearly showed a surface smoothing after the PαMS coating. Further studies with X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) also indicated that the polymer definitely did not form an extra layer. The polymer chains rather (self-)assemble in the nano-scaled interspaces of the porous oxide film giving an oxide–polymer “nanocomposite” with a high oxide filling grade resulting in high dielectric constants larger than 15. The dielectric strength of more than 1 MV cm⁻¹ is in good accordance with the polymer-filled interspaces.