The surface chemistry of water-reducible polymer solutions/dispersions 1. Surface tension behavior

Both static tension and dynamic surface tension of water-reducible (W/R) polymer solutions were carefully examined. It is shown that the cosolvent and its concentration are controlling factors in surface tension behavior for most concentration regions of W/R polymer solutions. This is true for both static and dynamic surface tensions. The polymer and its concentration have a much smaller effect on static surface tension than does the cosolvent. Much of the dynamic surface tension correlates with the bulk shear viscosity of W/R polymer solutions. The examination of cosolvent /water mixtures shows a critical solution concentration (CSC) for most cosolvents, analogous to the critical micelle concentration (CMC) in surfactant solutions. Both CSC and CMC originate from the same structural characteristics, i.e. molecules having a hydrophilic head and hydrophobic tail. Typically cosolvents have a less hydrophobic nature so values of CSC are higher than those typical of CMC for surfactants. This CSC plays a unique role in the surface tension of W/R polymer solutions. Above the CSC, constant surface tension is observed, while below the CSC a rapid increase in surface tension with decrease of cosolvent concentration occurs.     

Relationship between surface chemistry and surface energy of different shape pigment blend coatings

The influence of pigment shapes and pigment blends on the surface energy was investigated and compared with the surface chemistry of pigmented latex coatings. The coatings were made of different volume ratios of two pigments: plate-like kaolin clay pigment and prismatic precipitated calcium carbonate (PCC) pigment. These were mixed together with carboxylated styrene–butadiene–acrylonitrile latex (SBA), and applied over nonabsorbent substrates as well as absorbent substrates. The composition of the surface of the coatings was investigated by X-ray photoelectron spectroscopy (XPS). Two approaches were used to estimate the total surface energy and the components of the coatings: a conventional approach—“the Kaelble approach”—and a more modern approach—“the van Oss approach.” Pigment blends with different shapes and increments caused a change in the surface chemistry and the surface energy of the latex coatings. As the prismatic PCC pigment particles increased in the kaolin/SBA coating system, the SBA latex content at the coating surface increased and the total surface energy of the coating decreased. This is valid for both nonabsorbent as well as absorbent substrates. It was found that there was a strong correlation between the surface energy and the surface composition. The surface energy of the coatings estimated by the Van Oss approach was always lower than that estimated by the Kaelble approach. Colloidal interactions between pigment–pigment and/or pigment–binder were thought to play an essential role in determining the final coating surface energy and its components. Changes in the surface latex content and the surface energy due to the different pigment blends investigated were found to fit straight-line equations.     

Effect of sintering on surface chemistry and surface energy of pigmented latex coatings

Drying in the absence of water (sintering) of pigmented coatings made of styrene–butadiene (SB) latex and kaolin clay at different levels of pigmentation was investigated. As found from X-ray photoelectron spectroscopy, sintered coatings showed a higher SB area percent on the surface than did latex with a high glass-transition temperature (T_g) and dried at room temperature. This was a result of latex spreading at the surface. Sintering the high-T_g coatings that were dried at room temperature caused a decrease in the surface energy. Drying in the presence of water (wet coalescing) was compared to drying in the absence of water (sintering). Even though sintered coatings were more porous and had higher gloss, no significant difference was found in the SB/clay ratio at the surface or in the surface energy above the critical pigment volume concentration (CPVC). However, at and below CPVC, the sintering process yielded a higher SB content at the surface and a lower surface energy than the wet-coalescing process. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 968–975, 2001     

Effect of pigmentation on the surface chemistry and surface free energy of paper coating binders

The effect of the addition of clay and TiO₂ pigments on the surface energy and surface chemistry of films made from polymers used in paper coating formulations was evaluated. The polymers were carboxymethyl cellulose, polyvinyl alcohol and a protein-based polymer - all water-soluble - and two styrene-butadiene latexes of different carboxylation levels. The morphology of the surfaces was characterized by SEM examination, gloss measurement and stylus profilometry. Chemical composition was determined by EDS and XPS techniques. Surface energy and its Lifshitz-van der Waals and acid-base components were obtained from contact angle measurements using the van Oss et al. approach. Even though the addition of pigment increasingly upset the planar surface of the films, their surface chemistry and surface energy were only slightly affected over the pigmentation range studied (up to 40% by volume) and were dominated by the characteristics of the binder polymer.     

Synthesis and water absorbency of crosslinked superabsorbent polymers

A series of novel copolymer superabsorbents based on monomer acrylamide (AM), potassium methacrylate (KMA), and 2‐hydroxyethyl methacrylate (HEMA) were prepared by copolymerization using ammonium persulfate (APS) as an initiator and N,N‐methylenebisacrylamide (MBA) as a crosslinking agent. The synthetic variables (the monomer concentration, crosslinker concentration, and initiator concentration) were also studied. The experimental results of superabsorbent polymers (SAPs) show a better absorbency in both water and NaCl solutions. The copolymers were characterized by IR spectroscopy. The water retention in the soil was enhanced using the above superabsorbents. The use of SAPs for the growth of groundnut plants was also investigated. SAPs can be considered for water‐managing materials for agriculture and horticulture purposes in desert and drought‐prone areas. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1795–1801, 2002     

The influence of aluminium surface pretreatment on the corrosion stability and adhesion of powder polyester coating

One of the most important factors in corrosion prevention by protective coatings is the coating adhesion loss under environmental influence. Thus, adhesion strength is often used when characterizing protective properties of organic coatings on a metal substrate. In order to improve the adhesion of organic coating the metal substrate is often pretreated in some way. In this work, the adhesion of polyester coatings on differently pretreated aluminium surface (by anodizing, with and without sealing, by phosphating and by silane film deposition) was examined. The dry and wet adhesion of polyester coatings were measured by a direct pull-off standardized procedure, as well as indirectly by NMP test. It was shown that under dry test conditions all polyester coatings showed very good adhesion, but that aluminium surface pretreated by silane film showed superior adhesion. The overall increase of wet adhesion for polyester coating on aluminium pretreated by silane film was maintained throughout the whole investigated time period. The different trends in the change of adhesion of polyester coatings were observed for different aluminium pretreatments during exposure to the corrosive agent (3% NaCl solution). The highest adhesion reduction was obtained for polyester coating on aluminium pretreated with phosphate coating. The corrosion stability of polyester coated aluminium was investigated by electrochemical impedance spectroscopy in 3% NaCl solution. The results confirmed good protective properties of polyester coating on aluminium pretreated with silane film, i.e. greater values of pore resistance and smaller values of coating capacitance were obtained in respect to other protective systems, whereas charge-transfer resistance and double-layer capacitance were not measurable during 2 months of exposure to a corrosive agent.     

Role of activated carbon structural properties and surface chemistry in mercury adsorption

In this work the performance of activated carbons prepared from raw and demineralised lignite for gas-phase Hg° removal was evaluated. A two-stage activation procedure was used for the production of the activated samples. In order to study the effect of mineral matter on pore structure development and surface functionality of the activated carbons, a demineralisation procedure involving a three-stage acid treatment of coals, was used, prior to activation. Hg° adsorption tests were realized in laboratory-scale unit consisted of a fixed-bed reactor charged with the tested activated samples. The examined adsorbent properties that may affect removal capacity were the pore structure, the surface chemistry and the presence of sulphur on the surface of activated carbons. The obtained results revealed that activated carbons produced from demineralised lignite posses a high-developed micropore structure with increased total pore volume and BET surface area. These samples exhibit enhanced Hg° adsorptive capacity. In all cases, mercury removal efficiency increased by sulphur addition. Finally, the starting material properties and activation conditions affect the concentration and the type of the oxygen groups on activated carbon surface, that have been determined with TPD-MS experiments.     

The influence of zinc surface pretreatment on the adhesion of epoxy coating electrodeposited on hot-dip galvanized steel

The adhesion and electrochemical properties of epoxy coatings electrodeposited on hot-dip galvanized steel with and without passive films were investigated during exposure to 3% NaCl. The passive films were formed in hot air, in boiling water and by chromating. Adhesion was measured both by a standardized pull-off method and by swelling in N-methyl pyrrolidone. Pretreatment of hot-dip galvanized steel with passive film formed in hot air increases both dry and wet adhesion strength of the epoxy coating compared to pretreatment with passive film formed in boiling water and chromate coating. The overall increase of wet adhesion for this sample was maintained throughout the whole investigated time period. It was shown that the change in adhesion of epoxy coating on a chromate coating is smallest of all investigated samples, although the initial value of adhesion on this surface had the lowest value. The corrosion stability of coated Zn samples pretreated by different methods, was investigated by electrochemical impedance spectroscopy and in the initial time of exposure to NaCl the highest values of pore resistance were also obtained for the epoxy coating on Zn pretreated in hot air, whereas the epoxy coating on a HDG steel with a chromate coating showed the smallest change in electrochemical properties (pore resistance, coating capacitance, charge-transfer resistance) during prolonged exposure time.     

The aliphatic oxirane powder coating system: development, crosslinking chemistry and coating properties

Powder paints based on the new aliphatic oxirane binder system (Uranox) do not require hazardous-chemical labelling and meet the most stringent regulations concerning health, safety and the environment. The new system features a complete binder based on a polyester resin and an aliphatic oxirane crosslinker. This unique approach and the new crosslink chemistry of the binder make this system an important innovation in the global powder coating business. The development that has lead to the oxirane binder is described. After the synthesis and screening of several glycidyl compounds, the disubstituted aliphatic epoxides were selected for application in the new system. An extensive study on the crosslinking of the new binder has been carried out. It was found that special catalysis is necessary to obtain good conversion and, concomitantly, good coating properties. Finally the properties, handling characteristics and performance of aliphatic oxirane-based powder coating systems are discussed. In addition, a very efficient matting agent is described which has been specially developed for the aliphatic oxirane binder system. This matting agent enables the gloss of aliphatic oxirane-based powder coatings to be reduced to any desired level.     

Effects of solid substrate on structure and properties of casting waterborne polyurethane/carboxymethylchitin films

We prepared two series of semiinterpenetrating polymer network (semi-IPN) films from cross-linked waterborne polyurethane (WPU) and carboxymethylchitin (CMCH) in the aqueous solution on the glass and Teflon as the hydrophilic and hydrophobic substrates, respectively, by casting method. The chemical compositions, structure and morphologies of the films were examined by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and scanning electron microscopy (SEM). The miscibility, thermal stability and mechanical properties of the films were investigated by density measurement, dynamic mechanical analysis (DMA), ultraviolet (UV) spectroscopy, thermogravimetric analysis (TGA), tensile testing and solvent swelling testing. The results revealed that the semi-IPN films exhibited good miscibility when CMCH content was lower than 35 and 65 wt% for the films prepared on the glass and Teflon, respectively, resulting in higher light transmittance, thermal stability and tensile strength than the WPU film. Interestingly, the films prepared with the Teflon as the substrate possessed better miscibility and higher storage modulus, thermal stability, tensile strength and solvent-resistance than that with the glass as the substrate over the entire composition range studied here. This difference can be attributed that a strong intermolecular interaction occurred between WPU and CMCH to form a dense architecture, owing to that two kinds of macromolecules all were repulsed from the Teflon surface and forced to concentrate into inner surface. It has been confirmed that the hydrophility and hydrophobility of the solid substrate significantly influenced the structures and properties of the casting films, and using Teflon solid substrate can more effectively improve the miscibility and properties of the semi-IPN materials with hydrophilic character than glass one. We proposed a model describing the formation of WPU/CMCH semi-IPN films cast on the hydrophilic and hydrophobic substrates to illustrate the different structures of two types of films.     

影响悬浮树脂表观密度和吸油率的因素

阐述了高表观密度和适中吸油率PVC树脂在化学建材业的使用效果。分析了在生产过程中影响高表观密度和适中吸油率PVC树脂生产的因素,提出了解决方法。     

Role of microporosity and surface chemistry in adsorption of 4,6-dimethyldibenzothiophene on polymer-derived activated carbons

Two carbon samples derived from poly(4-styrenesulfonic acid-co-maleic acid) based polymer by carbonization between 700 and 800 °C were oxidized to two different levels of surface acidity. The surfaces of resulting adsorbents were characterized by potentiometric titration, adsorption of nitrogen, FTIR, SEM/EDAX and thermal analysis. The materials were used as adsorbents of 4,6-dimethyldibenzothiophene (4,6-DMDBT) from hexadecane with initial concentration of sulfur between 10-150 ppmw. Although it was found that pores with diameter less than 10 Å govern the amount of 4,6-DMDBT adsorbed, that amount is enhanced when acidic groups are present in the larger pores owing to the contributions of specific interactions. Surface chemistry plays an important role in reactive adsorption and deposition of the products of surface reactions in the pore system.     

Probing substrate influence on graphene by analyzing Raman lineshapes

We provide a new approach to identify the substrate influence on graphene surface. Distinguishing the substrate influences or the doping effects of charged impurities on graphene can be realized by optically probing the graphene surfaces, included the suspended and supported graphene. In this work, the line scan of Raman spectroscopy was performed across the graphene surface on the ordered square hole. Then, the bandwidths of G-band and 2D-band were fitted into the Voigt profile, a convolution of Gaussian and Lorentzian profiles. The bandwidths of Lorentzian parts were kept as constant whether it is the suspended and supported graphene. For the Gaussian part, the suspended graphene exhibits much greater Gaussian bandwidths than those of the supported graphene. It reveals that the doping effect on supported graphene is stronger than that of suspended graphene. Compared with the previous studies, we also used the peak positions of G bands, and I_2D/I_G ratios to confirm that our method really works. For the suspended graphene, the peak positions of G band are downshifted with respect to supported graphene, and the I_2D/I_G ratios of suspended graphene are larger than those of supported graphene. With data fitting into Voigt profile, one can find out the information behind the lineshapes.     

N-羟甲基丙烯酰胺对纸张涂层剂性能的影响

研究了 N-羟甲基丙烯酰胺 ( NMA)对 VAc-BA-NMA三元共聚物乳液用作纸张涂层剂性能的影响。     

Influence of substrate treatment temperatures and bias potential on capacitive manganese–cobalt–zinc oxide thin films deposited by radio frequency sputtering

Manganese–cobalt–zinc oxide films are deposited on graphite foils by a dry process, simpler one-step radio frequency sputtering with different substrate treatment temperatures and bias potential. The best long-term operational stability (only reduce about 7% specific capacitance at the 8000th cycle of potential cycling) and good specific capacitance are obtained at a substrate treatment temperature of 200 °C and without substrate bias potential. Furthermore, the lower the substrate treatment temperature, the better the stability. Moreover, the specific capacitance of the manganese–cobalt–zinc oxide electrode decreases with increasing substrate bias potential.     

The performance of surfactant on the surface characteristics of electroless nickel coating on magnesium alloy

Magnesium and its alloys corrode rapidly in the electrolyte bath. Surfactants while used extensively as surface active agents in the electrolyte bath, have been little studied on magnesium surfaces. The influence of surfactants cetyltrimethyl ammonium bromide (CTAB) and sodium lauryl sulfate (SLS) on the surface properties such as roughness, morphology and topography of electroless Ni–P deposits on magnesium alloy was researched. The research reveals that the surfactant solutions has significant influence on the composition of coating, surface roughness and surface morphology. In addition, it has marginal effect on the microhardness. Electroless coatings with addition of surfactants produce a smooth surface and average roughness value of 1.412 μm for CTAB and 1.789 μm for SLS, which are less than the value (2.98 μm) without surfactant addition. There was a significant improvement in the rate of deposition. However, the surfactants influence reached maximum at critical micelle concentration and above this value it gets stabilized. The initial structure appears to be dependent upon the percent occluded surfactants. The surface microstructures are discussed in line with the experimental observations.     

Surface chemistry of galvanized steel sheets relevant to adhesion performance

A review is presented on the recent development of surface treatment technologies for hot-dip galvanized steels relevant to adhesion of organic coatings. Applications of surface analytical techniques have elucidated that the surface layers of the nanometer scale dramatically govern the adhesion performance of painting or adhesive bonding. Surface enrichment of aluminium in the zinc layer deteriorates paint adhesion due to the reduction in phosphatability on the galvanized steel sheets and decreases the adhesive strength of the epoxy/dicyandiamide-bonded sheets due to the loss of acid-base interaction at the adhesive-substrate interface. In addition, the co-segregation of Al and Pb into the surface layer is responsible for the intergranular corrosion of zinc and facilitates the formation of a weak boundary layer, resulting in poor bond durability in a wet atmosphere. Improved adhesion performance has been established by developing new technologies that reduce the surface enrichment of minor elements or impurities in the zinc layer on the galvanizing line or that adopt a surface conditioning process prior to pretreatment in subsequent coil coating lines.     

高分子化学教学改革初探

简要介绍了高分子化学教学过程中的一些特点,通过对高分子化学与其他化学的对比,探讨了高分子化学教学与学习中的辩证关系,并由此提出了高分子化学教学改革的初步设想.     

Combinatorial materials research applied to the development of new surface coatings: II. Process capability analysis of the coating formulation workflow

A combinatorial process has been developed for the high throughput production and evaluation of surface coatings. The workflow designed for the production of arrays of liquid coatings involves the robotic transfer of aliquots of solutions of raw materials to an array of glass vials and mixing of the coatings using an unconventional magnetic stirring process. An investigation of the capability of the workflow to accurately and repeatedly prepare coating arrays was conducted as a function of solution viscosity and aliquot size. In addition, mixing capability was evaluated as a function of solution viscosity, total solution volume, and mechanism of stirring. Overall, the results of the study indicated that adequate accuracy and repeatability of the coating preparation process can be achieved as long as raw material solutions are designed such that viscosity is below about 250 cP and aliquot sizes are above about 75 μl. With regard to mixing capability, total solution volume was found to have a profound affect as did the stirring mechanism.