Examination of the role of oxygen in the photografting of methacrylic acid on a polyethylene film with a mixed solvent consisting of water and organic solvents

The photografting of methacrylic acid (MAA) on a linear low‐density polyethylene film (thickness = 30 μm) under air and nitrogen atmospheres was investigated at 60°C in mixed solvents consisting of water and an organic solvent, with xanthone as a photoinitiator. The organic solvents used were acetone, methanol, tetrahydrofuran, and dioxane. A maximum percentage of grafting occurred at a certain concentration of the organic solvent in the mixed solvent. This was observed for the systems under both air and nitrogen. The grafting reaction under air exhibited an induction period, but the rate of grafting after the period was greater than that under nitrogen. The formation of poly(ethylene peroxide)s by photoirradiation seemed to be a factor for the accelerated photografting under air. On the basis of attenuated total reflection infrared spectroscopy and scanning electron microscopy of the grafted film, the MAA‐grafted chains of the sample prepared under air tended to penetrate more deeply inside the film than those of the sample prepared under nitrogen. The resulting grafted films exhibited a pH‐responsive character: the grafted films shrank in an acidic medium but swelled in alkaline medium. This was evaluated from measurements of dimensional changes in the grafted films. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 992–998, 2003     

Characterization of alternative plasticizers in poly(vinyl chloride) sheets for blood containers

This study aimed to optimize the ratio of dioctyl 4‐cyclohexene‐1,2‐dicarboxylate (DOTH) and di‐isononyl‐cyclohexane‐1,2‐dicarboxylate (DINCH^®) for use as plasticizers in poly(vinyl chloride) (PVC) sheets. We also evaluated the biological safety of DOTH for its potential to be part of a safe PVC‐based blood container. The suppression of hemolysis in mannitol‐adenine‐phosphate / red cell concentrates (MAP/RCC) with DOTH/(DINCH^®‐PVC) sheets and the elution of plasticizers from the sheets increased with higher DOTH compositions. The properties of the PVC sheet containing DOTH and DINCH^® in the ratio of 25:33 parts against PVC 100 parts as a weight were almost identical to the PVC sheet made of di(2‐ethylhexyl) phthalate. From a subchronic toxicity test, DOTH did not show any adverse effects on all organs, including the testes, epididymis, liver, and kidneys. The no‐observed‐adverse‐effect level was 300 mg/kg body weight/day in a rat. These results suggest that DOTH/DINCH^® (25:33) is a promising candidate for the replacement of di(2‐ethylhexyl) phthalate in blood containers. J. VINYL ADDIT. TECHNOL., 22:520–528, 2016. © 2015 Society of Plastics Engineers     

Synthesis and polymerization of maleimide-type new macromonomer with polystyrene having controlled chain length

A new reactive and functionalized polystyrene with a maleimide moiety at the one polymer end was synthesized with N-(4-(1-chloroethyl)pheyl)maleimide (CEPMI)/SnCl₄/tetra-butylammonium chloride (TBAC) initiating system. The polymer obtained with the CEPMI/SnCl₄/TBAC initiating system under the condition of [TBAC]/[SnCl₄] = 1 was to be maleimide-type macromonomer with polystyrene having controlled molecular weight of polystyrene (VI). VI could be polymerized with anionic and radical initiators to give new type graft polymer (poly[N-(4-ethylphenyl)maleimide]-graft-polystyrene) with controlled chain length with respect to side chains.     

Preparation of raspberry‐like poly(methyl methacrylate) particles by seeded dispersion polymerization

The facile preparation of nonspherical raspberry‐like poly(methyl methacrylate) (PMMA) particles by seeded dispersion polymerization of methyl methacrylate (MMA) on micron‐sized PMMA seed particles was described. Various polymerization parameters influencing the particle morphology, as well as the polymerization kinetic and morphological stability, were investigated in detail. It was found that the following polymerization conditions were necessary to prepare this kind of nonspherical particles: a relatively low temperature, an appropriate ratio of seed/MMA, an initiator with a relatively low decomposition rate, and a relatively low initiator concentration. These particles showed very good morphological stability at room temperature, but they changed to the spherical ones when heat treated at 60°C in methanol solution of MMA. The experimental results suggest that the prepared PMMA particles were kinetically favored and the localized polymerization of the MMA monomer on PMMA seed particle surface was responsible for the formation of the raspberry‐like particles. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Polymer electrolyte membrane with nanomatrix channel prepared by sulfonation of natural rubber grafted with polystyrene

High‐proton‐conductive polymer electrolyte with a nanomatrix channel was prepared by graft copolymerization of styrene onto deproteinized natural rubber followed by sulfonation with chlorosulfonic acid. First, natural rubber latex was purified with urea in the presence of surfactant to remove almost all proteins present in the rubber. Second, graft copolymerization of styrene onto deproteinized natural rubber was carried out with tert‐butyl hydroperoxide/tetraethylenepentamine as an initiator at 30°C in latex stage. The graft‐copolymerized natural rubber (DPNR‐graft‐PS) was sulfonated with chlorosulfonic acid in chloroform solution at an ambient temperature. The resulting sulfonated DPNR‐graft‐PS was characterized by FTIR spectroscopy, solid state ¹³C CP/MAS NMR spectroscopy, elemental analysis, and transmission electron microscopy. High proton conductivity of about 0.1 S/cm, less water uptake of 24 wt % and comparatively good stress at break of 9 MPa were accomplished at suitable contents of styrene units and sulfur, i.e., 32 wt % and 75 mol %, respectively. The high proton conductivity, excellent stability, and good mechanical properties were associated with not only the formation of the nanomatrix channel but also a specific concentration of sulfuric acid group. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Phase Relations and Volume Changes of Hafnia under High Pressure and High Temperature

Using multi-anvil high-pressure devices and synchrotron radiation, X-ray in situ observations of HfO₂ under high pressure and high temperature have been performed to investigate its phase relations and compression behavior. An orthorhombic phase (orthoI) is stable from 4 to 14.5 GPa below 1250°–1400°C and transforms to a tetragonal phase, which is one of the high-temperature forms of HfO₂, above these temperatures. Another orthorhombic phase (orthoII) with a cotunnite-type structure appears above 14.5 GPa. OrthoII is stable up to 1800°C at 21 GPa. OrthoII is quenchable to ambient conditions. The orthoI-to-orthoII transition is accompanied by ∼8 vol% decrease. The bulk moduli of orthoI and orthoII at room temperature are 220 and 312 GPa, respectively. This low compressibility of orthoII indicates that it is a potential candidate for very hard materials.     

Effect of Talc Size on Surface Roughness and Glossiness of Polypropylene Injection Molding Application to Automotive Plastics

Talc-containing polypropylene (PP) resin is extensively employed in automobiles. Herein, considering the microstructure transfer process in injection molding, the effect of the talc's dispersibility and particle size on this process and its impact on the gloss level of the product were investigated. Results show that a fine unevenness of about several micrometers was self-formed by the shrinkage of PP in nontransferred areas due to the blending of talc. Additionally, the amount of self-formed unevenness tended with an increase in the average particle size of talc. Furthermore, due to PP shrinkage and different densities of talc, it was observed that a fine tiger-stripe pattern was self-formed using special molds with modified microstructure. This self-formed fine unevenness changes the gloss level owing to the diffused light reflection effect. This study proposes controlling this change by controlling the average particle size of talc and structure of the mold. POLYM. ENG. SCI., 60:132–139, 2020. © 2019 Society of Plastics Engineers     

Chemical transformation of chiral monolayer-protected gold clusters: observation of ligand size effects on optical and chiroptical responses

Versatile functionalization of metal clusters is a key step in understanding the reactivity of protective monolayers. We here demonstrate that reaction of the outermost amino groups on (S)-/(R)-penicillamine-protected gold clusters with ethyl isocyanate readily modifies the chiral surface structure through carbamoylation. Interestingly, the clusters are electrophoretically separated by the size of the surface ligand, not by the size of the gold core, which is revealed by UV-vis, IR, and energy dispersive X-ray (EDX) spectroscopy as well as SAXS measurements. The ligand size (or length) is extended through additional reactions of the carbamoylated amino groups with isocyanate, while the chemical similarity in ligand structures is realized by their IR spectral similarity. Optical and chiroptical responses of the separated cluster compounds are thus overall similar to each other, but a close inspection reveals that the ligand size has a small but distinct influence on the chiroptical response of the gold clusters.     

Modified tensile adhesion test for evaluation of interfacial toughness of HVOF sprayed coatings

Tensile adhesion test is widely used to evaluate the adhesion strength of coatings sprayed by High Velocity Oxy-Fuel (HVOF) technique. But there are two issues to be improved. Firstly, when the coatings have high adhesion strength, failure occurs in an adhesive layer, and secondary, the edge of a substrate is heavily deformed and rounded due to the high impact energy of sprayed particles. This deformation causes large scatter of adhesion test results. In this paper, a new technique to evaluate the interfacial fracture toughness has been proposed by introducing pre-crack at the interface of a conventional tensile adhesion test specimen. The asymptotic analytical formula was derived for interfacial toughness evaluation. Numerical analysis was also carried out for comparison. The difference between the numerical and the theoretical data was less than 5%. The developed procedure was applied for the SUS316 L steel coatings and the significant effects of the surface roughness and preheating temperature on adhesion strength were reconfirmed quantitatively.