Organosilicon compounds in supercritical carbon dioxide: Synthesis,polymerization, modification,and production of new materials

The main promising opportunities for the advantageous combination of organosilicon compounds and supercritical carbon dioxide both as a solvent and as a reagent in chemical processes are analyzed. The main processes of polymerization and modification of polymer matrices that are performed in supercritical СО₂ with the use of organosilicon materials of various types are outlined. Methods for the obtaining organosilicon polymers and polymer-inorganic composites and methods for the application of siloxane stabilizers in the dispersion polymerization of monomers in supercritical СО₂ are described. Studies of the insertion of a СО₂ molecule into Si–H, Si–N, and Si–O–Me bonds in reactions that feature exceptionally high chemical selectivity and afford a wide spectrum of products potentially useful for application in the chemistry of polymer materials are considered. It is shown that the silylation of surfaces of various types and morphologies in the medium of supercritical СО₂ is a rapidly developing green approach that makes it possible to obtain highly uniform defect-free coatings with variable desired functionality.     

New epoxy-siloxane hybrid binder for high performance coatings

The novel chemistry achieved by condensation reaction of an aliphatic epoxy with a polysiloxane results in an epoxy-siloxane hybrid binder whose unique physical characteristics allow its use as a durable binder for the protective coatings industry. The new epoxy-siloxane coating system enables the zinc primer to be protected by a single topcoat. This results in reductions in application time, less overspray and a much simplified maintenance for corrosion protection. Furthermore the reduced number of coats and overspray results in about 70% less solvent emission to the atmosphere.     

Comparative Study of the Quantity of Volatile Organic Compounds in Water-Based Paint and Solvent-Based Applied Polyurethane

Summary: The concern about the environmental impacts generated in the production of goods and services has increased last decades. The industry has used paints and varnishes in the manufacturing process have been pressed to improve air pollution prevention. Thus, the present work aims to identify the quantitative differences of VOC's and analyze the effect of VOC's in the burning rate, in a solvent and water-based paint, applied in the manufacture of automotive steering wheels. The results has showed that the solvent-based paint contains nine times more VOC's in your formulation in relation to water-based paint, when compared liquid and volatile organic compounds present in the solvent-based paint increase the speed of combustion of the polyurethanes samples. These data indicate that a discussion on the subject must be initiated in order to reduce these emissions that can harm society.     

Anthropogenic ozone,acids and mutagens: Half a century of Pandora’S Nox

It has been four decades since the phenomenon of photochemical air pollution was first characterized and, in the same year, a tragic London smog episode caused 4,000 excess deaths. Since then, there has been a substantial increase in our understanding of the chemistry involved in both types of air pollution, and a recognition that there is a very close chemical interrelationship between them. In this overview, we provide a brief historical perspective on the atmospheric chemistry of photochemical smog and illustrate how fundamental studies on the gas-phase chemistry of uv-irradiated mixtures of volatile organic compounds (VOC) and oxides of nitrogen (NO_x in polluted laboratory and ambient air masses have contributed to our understanding of three environmental problems: the atmospheric formation of ozone, nitric acid and airborne mutagens. In particular, we demonstrate the central role played by nitrogen dioxide and the hydroxyl radical in each case. We also show how certain reactive toxic and acidic species, e.g., formaldehyde and nitrous and formic acids, have been characterized in smog chambers and ambient smog by long pathlength spectroscopic techniques. It is shown that by using the same methods they now have been identified unequivocally, along with NO₂, in certain common types of polluted indoor atmospheres ... and at much higher concentrations than outdoors. This has significant health implications for indoor HCHO and quite possibly the acids. We then trace the history of the direct mutagenicity of respirable particles in polluted ambient air and show how, through use of the Ames test in biologically-directed assays of products coupled with fundamental studies of gas-phase reactions of polycyclic aromatic hydrocarbons (PAH) and NO_x in irradiated air, much of this activity can be accounted for in terms of the formation of nitro-PAH and oxygenated derivatives. Finally, we discuss the application of basic kinetic, mechanistic and analytical, experimental techniques and theoretical concepts to the development of a new set of “reactivity-based” regulatory controls on motor vehicle emissions of VOC’s. This novel regulatory approach applied by California’s Air Resources Board, which takes effect in 1994, illustrates the continuing need for fundamental research in the area of atmospheric chemistry and how it may be applied to “real world” environmental problems.     

HZSM-5分子筛催化合成乙酰水杨酸——推荐一个半微量有机化学实验

设计了一个以水杨酸和乙酸酐为原料,以HZSM-5分子筛为催化剂,在室温或加热条件下高效合成乙酰水杨酸的半微量有机化学实验。与经典实验方法相比,新实验具有反应易于操作、产率高、污染小等优点,更符合绿色化学教学理念。     

The challenge of achieving traditional exterior durability performance in low VOC architectural coatings

Over the years the optimization of water-borne emulsion polymers has resulted in water-borne coatings with excellent exterior durability and significantly reduced solvent emissions versus solvent-borne coatings. In recent years, pressure to further reduce emissions has necessitated the use of softer polymer compositions which can negatively impact gloss and tint retention, and dirt pick up resistance. The use of heterogeneous polymer morphologies are addressing these short comings; however care must still be taken not to affect paint durability. The development of low solvent emission thickeners and mildewcides has allowed further reduction in paint emissions.     

Measuring Sheet Resistances of Dielectrics Using Co‐Planar Hydrogel Electrochemical Cells with Practical Applications to Characterize the Protective Quality of Paints on Sculptures

Electrical properties of thin dielectric films at the solid‐liquid phase boundary are an important performance characteristic of many devices, coatings and sensors. In this paper, co‐polymeric hydrogels of polyacrylic acid co‐sulfonic acid, swollen with a salt solution to act as the solid electrolyte, were used to assess interfaces using electrochemical impedance spectroscopy (EIS) in a co‐planar geometry. Silane‐modified glasses were characterized by the co‐planar hydrogel EIS cell and found to be distinguishable based on their surface monolayer chemistry. EIS measurements were also made on primed and painted metal substrates, using both test panels and an outdoor sculpture, Tony Smith's Stinger . The panels were then exposed to accelerated and outdoor weathering and showed degradation on the surface paint layers, which was observable electrochemically using EIS and confirmed visually by SEM. Electrochemical spectral features were compared between data from a standard paint‐test cell versus this co‐planar hydrogel cell; both cell types were able to measure coating capacitance, providing useful information about the condition of the bulk coating. Yet, sheet resistance (R_s) was a spectral feature seen only by the co‐planar hydrogel cell. Thus, it can be concluded that the use of such co‐planar hydrogel cells can provide an earlier warning sign to coating degradation and such cells provide a new type of spectral information that is not assessable by the standard geometry.     

低热固相合成化学

本文介绍了固相化学反应,概述了高热、中热、低热固相反应在合成化学中的地位,重点阐述了低热固相反应的特征及其在无机、有机、材料化学中的应用,列举已在工业生产中使用的低热固相反应实例,阐明低热固相合成确实是工业生产中一条节能、高效、减污的理想通道。     

Discrimination of coatings on wooden materials using the gas sensor system

The applicability of sensor system for the discrimination of sources of indoor pollution was investigated. As examples of indoor pollution sources, paint and lacquer coatings were considered. Commercially available preparations: Akrylux, Doamlux, Bejca and White Scandinavian were selected for headspace measurements using TGS sensor array. Following issues were investigated: (1) discrimination between water- and solvent-based coatings, (2) discrimination between one component coatings, and (3) discrimination between one component and two component coatings. Following data analysis methods were used: principal component analysis (PCA), linear discriminant analysis (LDA) and probabilistic neural network (PNN). Results showed that coatings could be discriminated successfully, provided the surface covered was solid wood (0-1.8% error). The interference of fibreboard volatiles in sensor measurements of coatings was most likely encountered. It could have significantly impaired discrimination of coatings on fibreboard (2.8-5.6% error) as compared to wood. Worst results were obtained for the discrimination of coatings on unknown material(12.5-28.7% error).     

Low-temperature combustion synthesis of CuCr2O4 spinel powder for spectrally selective paints

CuCr₂O₄ spinel powder with high quality black hue, investigated as solar-absorbing pigment for spectrally selective paint, was synthesized by an environmental friendly sol–gel combustion process using citric acid as the fuel and metal nitrates as oxidizers. Single-phase CuCr₂O₄ spinel crystals were obtained after heat treatment of the as-burnt powder at a low temperature (600 °C) and the average crystallite size of the CuCr₂O₄ powders increased with the calcining temperature. Morphological analysis of powders calcined at various temperatures was done by field emission scanning electron microscopy. CuCr₂O₄ powder calcined at 700 °C was chosen as pigment to fabricate thickness sensitive spectrally selective paint coatings by simple spray-coating technique. For the sake of comparison, the as-burnt powder composed of mixed metal oxides (i.e., CuO and Cr₂O₃) was also used as pigment. The results reveal that the spinel CuCr₂O₄ based paint coatings exhibit much higher spectral selectivity (α _s = 0.88–0.91, ε ₁₀₀ = 0.27–0.35) which is depending on the coating thicknesses than that of coatings using as-burnt powder as pigment (α _s = 0.83–0.88, ε ₁₀₀ = 0.60–0.66). The CuCr₂O₄-based paint coatings showed no visible degradation after 600 h of condensation test and the performance criterion value is 0.04, indicating that the coatings have excellent long term stability.     

Low degree of substitution cellulosic textile coatings with improved physiological parameters

To further improve the physiological properties of textiles, solutions of low degree of substitution cellulose derivatives, i.e. carbamates and acetates, containing finely dispersed sub-micron scaled NaCl particles (d₁₆ = 269 nm, d₅₀ = 275 nm, d₈₄ = 283 nm) serving as templates were coated on textiles. By wet milling of NaCl particles in a 12.5 wt% solution of polyvinylpyrrolidone in dimethylacetamide (DMAc) as dispersing agent, a stable, processable dispersion was obtained, which could be diluted with LiCl/DMAc without any flocculation. For the preparation of the coating solution, the NaCl/DMAc dispersions were diluted with LiCl/DMAc and added to the DMAc-swollen cellulose derivatives. After application onto the textiles, the NaCl particle-containing coating had to be coagulated directly after application in a solvent bath, otherwise slow replacement of hygroscopic DMAc by water lead to the dissolution and recrystallisation of NaCl on the surface of the coating, thereby changing particle distribution and diameter. The solvent for the coagulation bath was chosen in a way that it allows for a high coagulation speed for the cellulose derivative matrix while possessing a low solubility product for NaCl (e.g., 2-propanol) in order to prevent any loss of the NaCl particles. Due to the highly porous structure created, increased water retention values and increased water vapour permeabilities were observed under preservation of the number of accessible hydroxyl groups of the cellulose derivatives. Both the templated and non-templated coatings could be processed on various textile substrates (e.g., on PET and PP). An important feature of these new materials, i.e. the possibility to apply an antibacterial finish, is discussed within the context of a potential use in the medical sector.     

Fourier transform infrared analysis of paint solvents

The composition of solvent mixtures employed in the paint industry was determined by Fourier transform infrared spectrometry. A procedure based on the use of the ratio between the absorbance of characteristic bands of each component permits the ratio between two solvents in a binary mixture to be determined, independently of the thickness of the sample film. Typical mixtures of xylol with butan-1-ol and with butyl acetate (xylol=mixture of o-, m- and p-xylenes) were used as model systems to develop the proposed procedure and the accuracy was determined using synthetic formulations. Another possible application of the procedure is the characterization of azeotropic mixtures.     

我国胶体与界面化学的发展

胶体与界面化学在能源、材料、生物、化学制造和环境科学等领域具有广泛的应用,并渗透到国民经济的各个主要领域中。所涉及到其中的一些重大科学问题,如土壤改良、功能与复合材料、三次采油、人造血浆、药物缓释与定向、润滑和油漆涂料等,与国家安全、能源开发、环境保护和人民生活等方面密切相关,发展胶体与界面化学学科对社会与经济的可持续发展具有重要的意义。本文综述了我国胶体与界面化学学科30年来的研究进展,尤其是近10年所取得的成就,主要包括新型两亲分子有序组合体的设计与构建、界面化学与有序分子膜、胶体与界面化学在微纳米功能材料合成中的应用新进展、胶体与界面化学在生物医药中的研究新进展,以及胶体与界面化学的研究新方法,并对该学科的发展前景与趋势进行了分析。     

Anticorrosive self-stratified PDMS-epoxy coating for marine structures

Four self-stratified coatings were prepared by dispersion of titanium dioxide (TiO₂) and hydrophobic fumed silica (SiO₂) nanoparticles in polydimethylsiloxane (PDMS)-Epoxy mix separately and in combination. Incorporating a definite ratio of nanofillers in PDMS-Epoxy incompa ible polymer blend to form a single coat paint system with anticorrosive and improved hydrophobic properties by the self-stratifying process is the chief highlight of this research work. The appropriate characterization techniques like Fourier Transform Infrared (FTIR) spectroscopy in Attenuated Total Reflection (ATR) mode of the coatings top and bottom layers emphasized the intended stratification. The Field Emission Scanning Electron Microscopy (FESEM) displayed the morphology of the coated samples top and bottom layers and the existence of the intended stratification in the coatings cross-section. The PDMS-Epoxy coating inclusive of both the nanofillers exhibited improved hydrophobic nature, appreciable surface free energy, augmented adherence to the substrate and lesser shear force in pseudo barnacle strength test in terms of shear. This innovative formulation pertains to the application on underwater substrates with improved anti-biofouling properties.     

New generation decorative paint technology

The growth of waterborne paints in the higher performance decorative paint segments (like in high gloss paints, trim paints and also in stains and varnishes) has been slowed down due to a lack of open time, rheology, film build and scratch resistance. Over the years the improvement of the open time has been an intense area of research, but to date the typical paint rheology and brushing performance of a solvent based paint could not be achieved in a waterborne system. In this paper very low viscosity oligomers are presented as a solution for the open time problem. These oligomers remain liquid even after the evaporation of water and are self-crosslinking to achieve good final properties. The oligomers are combined with a dispersed polymer to reduce tack free times of the resulting coatings and to increase the rate of development of the properties. A model system is described where this effect is demonstrated.     

Radiation Curing of Coatings

Abstract

Printing inks, paints, and other coatings are applied as a liquid or paste but must change to a solid and nontacky state before the painted or coated article can be used. The change is known as curing or drying. Sometimes it occurs by physical means, the evaporation of a solvent or dispersion medium for example, and sometimes by chemical changes such as polymerization and cross-linking. These chemical processes connect the many relatively small molecules of the original liquid or paste into a large molecular network or insoluble solid, which may be either rigid or rubbery in consistency depending upon the requirements of a particular application. Among traditional materials, gravure inks and many lacquers dry by solvent evaporation while paints and inks based upon linseed oil “dry” by chemical cross-linking promoted by oxygen in the air. Considerable time is usually required for curing in both methods, and the evaporation of solvents can result in air pollution and potential fire hazards. There is also a tendency of the media to dry upon presses, brushes, sprayers, and other application equipment. The long cure time requirement raises difficulties in modern production lines; the other factors have become more acute since the rapid rise of petroleum prices and the advent of air pollution legislation.     

Hydrated alumina surface treatment on a titanium dioxide pigment: changes at acidic and basic pH

Amphoteric, inorganic particles used as pigments and extenders in dried coatings are not completely inert, particularly when exposed to acidity similar to atmospheric pollution, or when in a water-borne paint suspension at alkaline pH. Changes to these materials may harm the integrity of the dried coating and thus its performance during weathering or affect the colloidal stability during storage within liquid paint. The effect on aqueous titanium dioxide pigment suspensions was examined under various pH conditions. A substantial amount of aluminum was dissolved, but little silicon or titanium. Dissolution occurred at both acid and alkali pH leaving a different balance of hydrated alumina phases and overall surface composition. Changes in particle surface were apparent in topography, colloidal properties and by thermogravimetry. Such changes show that other, more complicated, changes may be possible, particularly in an aqueous paint medium where there are many other ingredients in solution or suspension.     

Rapid isoelectric focusing of proteins in hydrolytically stable capillaries.

Three new types of capillary coatings for capillary isoelectric focusing that avoid siloxane chemistry, resulting in hydrolytically stable coatings, are described and tested: phenyl-silica, acrylamide-reacted vinyl-silica, and pure PTFE. Capillaries of these three types were compared using standard proteins and a biological mixture of proteins similar to what might be encountered in actual use. Of these, the acrylamide-coated capillary produced the highest-quality results. In contrast to capillaries prepared using siloxane reactions, the capillaries described herein exhibited greatly enhanced stability at high pH.     

Tribo charging powder coatings

At present tribo-guns have captured a fairly large market share of the electrostatic spraying equipment used in the powder coating industry for powder paint applications. However, powder paint system based on carboxyl functional polyesters and some special powder paint formulations cannot be sufficiently charged with tribo guns to obtain a good deposition efficiency of the powder on the object. Attempts have been made to solve this problem through addition of special additives to the powder coatings premix or to the ready-to-use powder. Additives of this type have been proven not to be ideal because they can have a catalytic activity and thus effect the powder coatings properties. We developed oligomeric additives that enhance the tribo charging of carboxylic polyester resins based powder coatings, without influencing to the kinetics of the curing process and other properties of the coating.     

Some Advances in the Inorganic Chemistry of Bromine

Recent advances in the chemistry of bromine and its inorganic compounds are covered under the headings of technology, properties and reactions, liquid bromine as an inorganic solvent, analysis, and new or newly studied compounds. Much of what is new is bromine chemistry is characteristic also of what is new in inorganic chemistry as a whole. That is, more detailed information about compounds and reactions is becoming available from the application of new instrumental and theoretical techniques.