SFG and DFG investigation of Au(111), Au(210), polycrystalline Au,Au–Cu and Au–Ag–Cu electrodes in contact with aqueous solutions containing KCN and 4-cyanopyridine

We report on potential-dependent in situ SFG and DFG spectroscopy carried out at Au(111), Au(210), polycrystalline Au, Au–Cu and Au–Ag–Cu electrodes in contact with aqueous solutions containing CN⁻ and 4-cyanopyridine (4CP). Spectroelectrochemical work was complemented by cyclic voltammetry. The chief stress has been placed on systematising and quantifying the interaction between 4CP and CN⁻ and the attending effects on the vibrational and electronic structures of the interface. The voltammetric behaviour of the investigated electrodes, modified by the addition of 4CP to the CN⁻ electrolyte, denote changes in the CN⁻ adsorption characteristics and effects of the adsorbed CN⁻ layer on the electrodic reactivity of 4CP. The differences among the investigated electrodes can be explained in terms of their respective degrees of atomic packing or with alloying effects on the stability of adsorbed CN⁻. The potential-dependent spectra have been analysed quantitatively with a model for the second order non linear susceptibility accounting for vibrational and electronic effects. The spectral changes induced by addition of 4CP denote interaction of the aromatic with the electrode through the CN⁻ monolayer. The non-resonant contribution yields information on the effects of 4CP on the fine structure of the bound electron density of states.     

A positive‐working photosensitive polyimide based on thermal cross‐linking and acidolytic cleavage

A novel positive‐working photosensitive polyimide (PSPI) based on a poly(hydroxyimide) (PHI), a crosslinking agent having vinyl ether groups, and a photoacid generator (PAG) was prepared. The PHI as a base resin of the three‐component PSPI was synthesized from 4,4′‐oxydiphthalic anhydride and 2,2′‐bis(3‐amino‐4‐hydroxyphenyl)hexafluoropropane through ring‐opening polymerization and subsequent thermal cyclization. 2,2′‐bis(4‐(2‐(vinyloxy)ethoxy)phenyl)propane (BPA‐DEVE) was used as a vinylether compound and diphenyliodonium 5‐hydroxynaphthalene‐1‐sulfonate was used as a PAG. The phenolic hydroxyl groups of the PHI and the vinyl ether groups of BPA‐DEVE are thermally crosslinked with acetal structures during prebake step, and the crosslinked PHI becomes completely insoluble in an aqueous basic solution. Upon exposure to UV light (365 nm) and subsequent postexposure bake (PEB), a strong acid generated from the PAG cleaves the crosslinked structures, and the exposed area is effectively solubilized in the alkaline developer. The dissolution behavior of the PSPI containing each 11.5 wt % of BPA‐DEVE and of the PAG was studied after UV exposure (365 nm) and PEB. It was found that the difference in dissolution rates between exposed and unexposed areas was enough to get high resolution. A fine positive pattern with a resolution of 5 μm in a 3.7‐μm‐thick film was obtained from the three‐component PSPI. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Organic‐acid‐catalyzed sol–gel route for preparing poly(methyl methacrylate)–silica hybrid materials

In this study, a series of organic–inorganic hybrid sol–gel materials consisting of a poly(methyl methacrylate) (PMMA) matrix and dispersed silica (SiO₂) particles were successfully prepared through an organic‐acid‐catalyzed sol–gel route with N‐methyl‐2‐pyrrolidone as the mixing solvent. The as‐synthesized PMMA–SiO₂ nanocomposites were subsequently characterized with Fourier transform infrared spectroscopy and transmission electron microscopy. The solid phase of organic camphor sulfonic acid was employed to catalyze the hydrolysis and condensation (i.e., sol–gel reactions) of tetraethyl orthosilicate in the PMMA matrix. The formation of the hybrid membranes was beneficial for the physical properties at low SiO₂ loadings, especially for enhanced mechanical strength and gas barrier properties, in comparison with the neat PMMA. The effects of material composition on the thermal stability, thermal conductivity, mechanical strength, molecular permeability, optical clarity, and surface morphology of the as‐prepared hybrid PMMA–SiO₂ nanocomposites in the form of membranes were investigated with thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, gas permeability analysis, ultraviolet–visible transmission spectroscopy, and atomic force microscopy, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Motor oil classification by base stock and viscosity based on near infrared (NIR) spectroscopy data

In this paper we have tried to build effective model for classification of motor oils by base stock and viscosity class. Three (3) sets of near infrared (NIR) spectra (1125, 1010, and 1050 spectra) were used for classification of motor oils into 3 or 4 classes according to their base stock (synthetic, semi-synthetic, and mineral), kinematic viscosity at low temperature (SAE 0W, 5W, 10W, and 15W) and kinematic viscosity at high temperature (SAE 20, 30, 40, and 50). The abilities of three (3) different classification methods: regularized discriminant analysis (RDA), soft independent modelling of class analogy (SIMCA), and multilayer perceptron (MLP) - were also compared. In all cases NIR spectroscopy was found to be quite effective for motor oil classification. MLP classification technique was found to be the most effective one.     

Effect of the graft yield of maleic anhydride on the rheological behaviors,mechanical properties,thermal properties,and free volumes of maleic anhydride grafted high‐density polyethylene

The rheological behavior, thermal properties, and molecular mobility of a series of maleic anhydride (MA) grafted high‐density polyethylenes were characterized and evaluated. The rheological behavior was studied with a Haake minilaboratory. The viscosity of the samples in their melt state decreased with an increase in the graft yield, and this could be attributed to the higher molecular mobility for samples with a higher degree of grafting. The thermal properties were investigated with dynamic mechanical analysis and differential scanning calorimetry. Positron annihilation lifetime measurements were used to study the effect of the degree of grafting on the chemical environment and the atomic‐scale free‐volume properties. It was found that the grafted MA group played a significant chemical inhibition role in positronium formation when the graft yield was low. The results also indicated that the higher the degree of grafting was, the broader the free‐volume distribution was. The relationship between the microstructure and rheological behavior is discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Grafting of maleic anhydride onto polyethylene through a green chemistry approach

The grafting of a polymer can lead to the improvement and modification of the polymer and thus expand its applications. Grafting methods include solution grafting in organic solvents, melt grafting at high temperatures, and light grafting with radioactive sources. These methods have their advantages and disadvantages. The disadvantages include waste treatment, consumption of energy, and so on. In this study, a hydrothermal process which is called the green approach, was developed to prepare graft copolymers. The effect of various factors on the grafting degree was investigated in detail. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Epoxidation of high trans‐1,4‐polyisoprene and its properties

A new organic‐solvent‐free water‐phase suspension method was used to synthesize partially epoxidized high trans‐1,4‐polyisoprene (TPI) to improve its properties, including oil resistance and wet‐skid resistance. The epoxidation was conducted in an aqueous peracetic acid solution and on the TPI granules prepared by a bulk precipitation method with supported titanium catalyst. The effects of the synthesis conditions, including reaction temperature, reaction time, and pH value, on the epoxy content were investigated. Epoxidized trans‐1,4‐polyisoprene (ETPI) with epoxy contents between 10 and 80% were obtained within 4 h. Both the amorphous and crystalline regions of TPI were epoxidized. The crystallization properties decreased with increasing epoxy content. ETPIs possessed lower mechanical properties than TPI but could be enhanced by vulcanization. The oil resistance and wet‐skid resistance were significantly improved after epoxidation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Kinetics study of Ti[O(CH2)4OCHCH2]4 initiated ring‐opening polymerization of ε‐caprolactone by differential scanning calorimetry

Chemical shrinkage was used for the in situ measurement of the progressing chemical stabilization reactions and the influence of ozone during the stabilization of polyacrylonitrile. A method for evaluating the activation energy through the sensitivity temperature is presented. The calculated results show that the activation energies were 161.57 kJ/mol in air and 181.23 kJ/mol in ozone-enriched air. Therefore, the chemical reactions were postponed during stabilization in ozone-enriched air. Ozone seemed to act in three ways: first, ozone promoted the formation of the serious skin–core structure. Second, ozone accelerated the chemical reactions and shortened the stabilization time at lower heating rates. Third, ozone postponed the chemical reactions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Novel approach in investigation of the poly(acrylic acid) hydrogel swelling kinetics in water

The swelling kinetics curves of structurally defined poly(acrylic acid) hydrogel in bidistilled water at temperatures: 25, 30, 35, 40, and 45°C were determined. The possibility of kinetically explaining the isothermal swelling process by applying the following models: reaction controlled by diffusion, first order chemical reaction kinetics, and second order chemical reaction kinetics, was investigated. It was found that kinetically explaining the swelling process using these methods was limited to only certain parts of the process. The swelling process in bidistilled water was described in full range assuming that the hydrogel's swelling rate was a kinetically controlled reaction by the rate of the movement of reactive interface of hydrogel. Based on that model, the kinetic parameters, activation energy (E_a) and preexponential factor (A), of the swelling process were determined to be E_a = 35 kJ/mol and lnA = 8.6. A possible mechanism of the investigated swelling process was discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Microwave heating of poly(ethylene terephthalate) bottle preforms used in the thermoforming process

Thermoforming (free blowing) of poly(ethylene terephthalate) preforms was successfully and quickly performed in a rotating system designed for dielectric hysteresis heating. Temperature profile modeling was carried out with the amorphous poly(ethylene terephthalate) permittivity at different temperatures. The Maxwell and heat equations were used to determine the best profile and power tuning. The determination of the theoretical boundary conditions was accomplished by the adjustment of the numerical transient external surface wall temperature with experimental infrared pyrometry results. In comparison with infrared, microwaves allowed high power density absorption inside the perform wall without a dramatic temperature gradient. Consequently, the heat blowing stage could be accelerated, and the process took at least 5 times less energy than infrared heating. Industrial applications involve the integration of the molding step and the design of the overall process. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008