12‐crown‐4–ether and tri(ethylene glycol) dimethyl–ether plasma‐coated stainless steel surfaces and their ability to reduce bacterial biofilm deposition

It has been demonstrated that surfaces coated with poly(ethylene glycol) (PEG) are capable of reducing protein adsorption, bacterial attachment, and biofilm formation. In this communication cold‐plasma–enhanced processes were employed for the deposition of PEG‐like structures onto stainless steel surfaces. Stainless steel samples were coated under 1,4,7,10‐tetraoxacyclododecane (12‐crown‐4)–ether and tri(ethylene glycol) dimethyl ether (triglyme)–radio frequency (RF)–plasma conditions. The chemistry and characteristics of plasma‐coated samples and biofilms were investigated using electron spectroscopy for chemical analysis (ESCA), atomic force microscopy (AFM), and water contact angle analysis. ESCA analysis indicated that the plasma modification resulted in the deposition of PEG‐like structures, built up mainly of –CH₂? CH₂? O– linkages. Plasma‐coated stainless steel surfaces were more hydrophilic and had lower surface roughness values compared to those of unmodified substrates. Compared to the unmodified surfaces, they not only significantly reduced bacterial attachment and biofilm formation in the presence of a mixed culture of Salmonella typhimurium, Staphylococcus epidermidis, and Pseudomonas fluorescens but also influenced the chemical characteristics of the biofilm. Thus, plasma deposition of PEG‐like structures will be of use to the food‐processing and medical industries searching for new technologies to reduce bacterial contamination. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3425–3438, 2001     

Raman spectroscopic analysis of L‐phenylalanine and hydrolyzed eggwhite protein penetration into keratin fibers

To investigate the penetration of amino acids and hydrolyzed protein derived from eggwhites (HEWP) into keratin fibers, the structure of cross‐sectional samples at various depths of virgin white human hair treated with L ‐phenylalanine (Phe) and bleached black human hair treated with HEWP was directly analyzed without isolating the cuticle and cortex using Raman spectroscopy. The hydrophobic amino acids clearly penetrated into the virgin white human hair, while hydrophilic amino acids did not penetrate at all. The Phe hydrophobic amino acid content at various depths of the virgin white hair increased by performing the Phe treatment (at 50°C for 16 h), indicating that Phe deeply penetrated into the virgin human hair. Also, the disulfide (? SS? ) and random coil contents at various depths of the bleached human hair increased by performing the HEWP treatment, indicating that HEWP also deeply penetrated into the bleached human hair. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Novel surface modification of high‐density polyethylene films by using enzymatic catalysis

The surface of high‐density polyethylene (HDPE) films was modified by an enzyme, soybean peroxidase (SBP). The enzymatic surface modification was performed using a peroxidase as catalyst and hydrogen peroxide as oxidizing agent. The chemical composition and morphology of HDPE surfaces were characterized by X‐ray photoelectron spectroscopy, infrared spectroscopy, and scanning electron microscopy. Results showed that after enzymatic treatment, the O/C atomic ratio of HDPE surfaces increased, and new functional groups such as –CO– appeared. Moreover, the surface of treated HDPE films became rougher than untreated surfaces. The hydrophilicity of treated and untreated HDPE films was analyzed by UV–vis spectroscopy and contact angle measurements. The decreased contact angle of the HDPE with water and increased adsorption ability of the surface to a water‐soluble dye clearly indicated that enzymatic treatment can significantly increase the hydrophilicity of the surfaces of HDPE films. The catalytic mechanism of SBP was also discussed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3673–3678, 2004     

Enhanced Proton Conductivity of Sulfonated Poly(ether ether ketone) Membrane Embedded by Dopamine‐Modified Nanotubes for Proton Exchange Membrane Fuel Cell

Design and fabrication of alternative proton exchange membrane (PEM) with high proton conductivity is crucial to the commercial application of PEM fuel cell. Inspired by the bioadhesion principle, dopamine‐modified halloysite nanotubes (DHNTs) bearing –NH₂ and –NH– groups are facilely synthesized by directly immersing natural halloysite nanotubes (HNTs) into dopamine aqueous solution under mild conditions. DHNTs are then embedded into sulfonated poly(ether ether ketone) (SPEEK) matrix to prepare hybrid membranes. HNTs‐filled hybrid membranes are prepared for comparison. The microstructure and physicochemical properties of the membranes are extensively investigated. Fourier transform infrared analysis implies that ordered acid–base pairs (e.g., –S–O^–…⁺H–HN–, –S–O^–…⁺H–N–) are formed at SPEEK–DHNT interface through strong electrostatic interaction. In such a way, continuous surface‐induced ion‐channels emerge along DHNTs. Although the incorporation of DHNTs reduces the channel size, water uptake, and area swelling of the hybrid membranes, which in turn would reduce the vehicle‐type proton transfer, the acid–base pairs create continuous pathways for fast proton transfer with low energy barrier via Grotthuss mechanism. Consequently, DHNT‐filled hybrid membrane with 15% DHNTs achieves a 30% increase in proton conductivity and a 52% increase in peak power density of single cell when compared with SPEEK control membrane, particularly.     

Preparation and properties of keratin–poly(vinyl alcohol) blend fiber

Keratin–poly(vinyl alcohol) (PVA) blend fibers containing 13–46 wt % of –SSONa⁺ (S‐sulfo) keratin were prepared by the wet‐spinning technique. They were formed by dehydration of an aqueous solution of S‐sulfo keratin and PVA (spinning dope) in a coagulation bath of sodium sulfate–saturated solution and subsequently drawn. Keratin–PVA fibers showed higher tenacity than that of wool, presumably originating from the high mechanical strength of the PVA component. The heat treatment at about 200°C improved the waterproof characteristics such as shrinkage of keratin–PVA fibers more conspicuously than did PVA fibers. That is, after heat treatment at 195°C for 10 min, keratin–PVA blend fiber shrank 20% in water at 60°C, whereas PVA fiber shrank 56%. Differential thermal analysis suggested the crosslinking of disulfide bonds between keratin molecules during the heat treatment, whereas the additional crystallization of PVA component was not observed. Adsorption of heavy metal and toxic gas to keratin–PVA fibers was also investigated. Keratin–PVA fiber was found to adsorb Ag⁺ and formaldehyde gas more efficiently than PVA. Thus, blends of keratin and PVA were advantageous for both polymer fibers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 756–762, 2004     

Photoactive behavior of polyacrylonitrile fibers based on silver and zirconium co‐doped titania nanocomposites: Synthesis,characterization, and comparative study of solid‐phase photocatalytic self‐cleaning

Silver and zirconium co‐doped and mono‐doped titania nanocomposites were synthesized and deposited onto polyacrylonitrile fibers via sol–gel dip‐coating method. The resulted coated‐fibers were characterized by X‐ray diffraction (XRD), scanning electron microscopy, energy dispersive spectroscopy, transmission electron microscopy, diffuse reflectance spectroscopy, thermogravimetric analysis, and BET surface area measurement. Photocatalytic activity of the TiO₂‐coated and TiO₂‐doped coated fibers were determined by photomineralization of methylene blue and Eosin Y under UV–vis light. The progress of photodegradation of dyes was monitored by diffuse reflectance spectroscopy. The XRD results of samples indicate that the TiO₂, Ag‐TiO₂, Zr‐TiO₂, and Ag‐Zr‐TiO₂ consist of anatase phase. All samples demonstrated photo‐assisted self‐cleaning properties when exposed to UV–vis irradiation. Evaluated by decomposing dyes, photocatalytic activity of Ag–Zr co‐doped TiO₂ coated fiber was obviously higher than that of pure TiO₂ and mono‐doped TiO₂. Our results showed that the synergistic action between the silver and zirconium species in the Ag‐Zr TiO₂ nanocomposite is due to both the structural and electronic properties of the photoactive anatase phase. These results clearly indicate that modification of semiconductor photocatalyst by co‐doping process is an effective method for increasing the photocatalytic activity. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

New method of dyeing keratin fibers using poly(ethylene imine) and its coloring mechanism

To improve the colorability of keratin fibers at lower temperatures, we developed a novel coloring method using poly(ethylene imine) (PEI) as a counterion reagent (human hair was treated beforehand with a PEI solution and then was colored with an acid dye). As a result of this new method, the coloring and color fastness to shampooing clearly improved with respect to the usual method. Next, to study the coloring mechanism with PEI, we investigated the penetration of PEI and Orange II into bleached human hair by optical microscopy. The results showed that the penetration of PEI and Orange II into bleached human hair increased with an increasing PEI treatment time and with a decreasing PEI molecular weight. With these experiments, we demonstrated that PEI, which penetrated the cortex region, exerted counterionization on Orange II, thereby increasing the penetration of Orange II into bleached human hair. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3806–3810, 2003     

Reduction mechanism of tioglycolic acid on keratin fibers using microspectrophotometry and FT-Raman spectroscopy

In order to investigate the reduction mechanism of thioglycolic acid (TG) on the keratin fibers, cross-sectional samples of white human hair treated with TG were prepared. The heterogeneous reaction between TG and keratin fibers involving the diffusion of TG into human hair was analyzed at the molecular level using microspectrophotometry and FT-Raman spectroscopy. The diffusion of TG into human hair clearly increased by increasing the treatment time and by raising pH. The TG relative concentration and the disconnected relative concentration of disulfide (–SS–) groups at various depths of the hair samples with pH 9.0 were in good agreement, indicating that the reaction rate (the disconnection of –SS– groups) was faster than the diffusion rate of TG into human hair. From these experiments, we demonstrated that TG diffuses gradually beyond the cuticle region, and toward the inside of the cortex region along with the disconnection of –SS– groups.     

Cover: Macromol. Mater. Eng. 3/2005

Summary: A novel human hair protein hybrid fiber was developed by combining (i) the high‐efficiency extraction technique for preparing human hair proteins and (ii) the watery hybridization spinning method using gellan and chitosan. The resulting human hair protein‐gellan‐chitosan hybrid fibers are conveniently produced by simply mixing the 7–35 wt.‐% human hair protein‐1.0 wt.‐% gellan aqueous solution and the 1.0 wt.‐% chitosan‐0.15 M acetic acid solution at 50 °C, followed by pulling out to spin the human hair protein‐gellan‐chitosan ternary complex thus formed at the aqueous solution interface. By use of this simple procedure and ambient spinning condition, the human hair proteins were successfully incorporated into the fiber matrix of gellan‐chitosan, without any denaturation and degradation. The hybrid fiber can also be recognized as a new type of the regenerated human hair keratin fiber, because of its high purity and content of human hair keratin types I and II. Mechanical strength of the human hair protein‐gellan‐chitosan fiber varies from 108 to 153 MPa, depending on the contents of the human hair proteins. SEM observation revealed that the incorporated human hair proteins were found as the particles (1–10 μm) on the fiber surface. The type I and II keratins in the fiber matrices were rapidly biodegraded by chymotrypsin within 30 min, and the digested fragments slowly released from the fiber matrices. Thus, the human hair hybrid fiber is a very promising material to have a broad spectrum of applications as the engineering fibers, particularly for the medical uses, because the human hair proteins are easily available, biocompatible, and bioresorbable materials.

Gellan‐chitosan hybrid fiber (a), human hair protein‐gellan‐chitosan hybrid fiber (b).     

Influence of urea on the coloring ability of a low‐temperature coloring method of keratin fibers using polyethyleneimine

For the purpose of improving the coloring ability of keratin fibers at a lower temperature, we investigated the influence of urea on the coloring ability of a low‐temperature coloring method using polyethyleneimine (PEI) as a counter ion reagent (the human hair was previously treated with a PEI solution, and then was colored with acid dye). The coloring and color fastness to shampooing of the hair pretreated with a PEI solution containing urea clearly improved compared with those pretreated with a PEI solution not containing urea. Also, we prepared cross‐sectional samples of the treated hair and investigated the penetration of PEI and Orange II into human hair by optical microscopy. The results showed that the penetration of PEI and Orange II into human hair pretreated with a PEI solution that contained urea clearly increased compared with those pretreated with a PEI solution that did not contain urea. From these experiments, we concluded that urea acts as a penetration accelerator for PEI; and PEI, which penetrates deeper into human hair by adding urea, exerts counter ionization on Orange II, thus increasing the penetration of Orange II into human hair and thereby improving the coloring ability. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3827–3834, 2004     

Synthesis and characterization of hybrid fluoro‐emulsion based on silica/copolymer composite particles

BACKGROUND: To create a hydrophobic surface, a commonly used two‐step process is the formation of a rough surface and its subsequent modification with materials of low surface energy. Here, a new method for making a hydrophobic surface is proposed using emulsion copolymerization with a low‐surface‐energy fluoropolymer in the presence of a high percentage of silica particles creating a well‐spread roughness. RESULTS: Irregular core–shell structural composite particles such as of snowman shape and sandwich shape were obtained and characterized. The hydrophobicity and chemical structure of the hybrid film were investigated. It was found that strong inter‐ and intramolecular chemical bonding in the composite film may improve the properties of the hybrid film. Enrichment of fluorine on the film surface and well‐distributed roughness due to the silica particles covered by the fluoropolymer contribute to the increased hydrophobicity of the film. The water contact angle on the film increased from 106 ± 2° to 135 ± 2°. CONCLUSION: The stable core–shell hybrid latex synthesized in this work will be of use in preparing high‐performance hydrophobic aqueous coatings. Copyright © 2008 Society of Chemical Industry     

High‐speed melt spinning of various grades of polylactides

Five kinds of polylactides (PLAs), with different D ‐lactide contents and tacticities, were subjected to high‐speed melt‐spinning experiments. In addition to stereochemical purity, the PLA types differed in molecular mass and molecular mass distribution. The properties of the different PLA materials were characterized by thermogravimetry, differential scanning calorimetry, dynamic mechanical analysis, size exclusion chromatography, and ¹H‐NMR and ¹³C‐NMR spectroscopy. The material was spun with a high‐speed spinning process within the range 2000–5000 m/min. The physical and tensile properties of the fibers were determined. The maximum tensile properties of the fibers were a 300 MPa tenacity at an elongation at break of 30% and a tensile modulus of 6.8 GPa. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 800–806, 2004     

Concentrated emulsion polymerization for preparation of β‐cyclodextrin‐supported chromatography columns

Concentrated inverse emulsion polymerization was used for making chromatography columns (based on crosslinked polystyrene divinylbenzene (PS‐DVB)) with pore sizes less than 10 μm. According to DSC‐thermal gravimetry thermograms, it was confirmed that the residual monomer concentration after polymerization process is negligible. For application of these columns in chiral chromatography, the β‐cyclodextrin is chemically fixed on the PS‐DVB resin pore surface. The presence of hydroxyl groups in the PS‐DVB resin after chemical modification was confirmed by FTIR spectroscopy. By chemical modification of the PS‐DVB resin, thermal stability increased up to 446°C. The structure of columns was analyzed by scanning electron microscopy (SEM). SEM evaluations showed that the porous structure of PS‐DVB resin was maintained intact after the chemical modification with β‐cyclodextrin. According to X‐ray data, presence of the crystalline domain that is related to β‐cyclodextrin is confirmed.© 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 857–863, 2006     

Poly(ethylene terephthalate)–poly(caprolactone) block copolymer. I. Synthesis,reactive extrusion,and fiber morphology

A novel poly(ethylene terephthalate)–poly(caprolactone) block copolymer (PET–PCL) is synthesized in a reactive twin‐screw extrusion process. In the presence of stannous octoate, ring‐opening polymerization of ϵ‐caprolactone is initiated by the hydroxyl end groups of molten PET to form polycaprolactone blocks. A block copolymer with minimal transesterification is obtained in a twin‐screw extruder as a consequence of the fast distributive mixing of ϵ‐caprolactone into high melt viscosity PET and the short reaction time. The PET–PCL structure is characterized by IV, GPC, ¹H‐NMR, and DSC. Fully drawn and partially relaxed fibers spun from PET–PCL are characterized by WAXD and SAXS. A substantial decrease in the oriented amorphous fraction appears to be the major structural change in the relaxed fiber that provides the fiber with the desired stress–strain characteristics. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1858–1867, 1999     

Polyimides containing s‐triazine rings

A series of new polyimides containing s‐triazine rings have been synthesized via Diels–Alder intermolecular polymerization of 2,6‐bis(2‐furanylmethylimino)‐4‐isopropoxy‐1,3,5‐triazine with various bis(maleimide)s. All the poly(imino‐s‐triazine imide)s were characterized by elemental analyses, FTIR spectral studies, number average molecular weight ( M _n) by non‐aqueous conductometric titration and thermogravimetry. Glass‐fibre reinforced composites were prepared via an in situ Diels–Alder intermolecular reaction between 2,6‐bis(2‐furanylmethylimino)‐4‐isopropoxy‐1,3,5‐triazine and various bis(maleimide)s. The composites were characterized for chemical resistivity and mechanical properties. © 2003 Society of Chemical Industry     

X‐ray photoelectron,infrared, and Raman spectroscopy studies of novel submicrometric poly[(methacrylato)aluminum(III)]

Poly[(methacrylato)aluminum(III)] was prepared by applying γ‐radiation to the corresponding aluminum(III) methacrylate monomer. Scanning electron microscopy images show pellets of ～ 500 nm for the aluminum(III) methacrylate monomer, and submicrometric fibers‐made granules for the aluminum‐containing polymers. X‐ray photoelectron spectroscopy measurements reveal two peaks in the Al 2p core‐level spectra of the monomer and of the poly[(methacrylato)aluminum(III)], which means that two different coordination modes for the Al(III) ions might be present in these compounds. Infrared and Raman spectroscopy studies confirmed that the structure for this novel coordination polymer consists of hexa‐coordinated Al(III) ions linked by the carboxylate groups of methacrylate ligands, along with hydroxyl groups and coordinated water, in a combination of monodentate and bridging bidentate coordination modes. Hence, combination of spectroscopic methods is a helpful tool to get valuable information on the structure of nonmacrocrystalline coordination polymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5212–5223, 2006     

Synthesis and characterization of side‐chain liquid‐crystalline ionomers containing quaternary ammonium salt groups

A series of thermotropic side‐chain liquid‐crystalline ionomers (LCIs) containing 4‐(4‐alkoxybenzyloxy)‐4′‐allyloxybiphenyl (M) as mesogenic units and allyl triethylammonium bromide (ATAB) as nonmesogenic units were synthesized by graft copolymerization upon polymethylhydrosiloxane. The chemical structures of the polymers were confirmed by IR spectroscopy. DSC was used to measure the thermal properties of these polymers. The mesogenic properties were characterized by polarizing optical microscopy, DSC, and X‐ray diffraction. Homopolymers without ionic groups exhibit smectic and nematic mesophases. The nematic mesophases of the ionomers disappear and the mesomorphic temperature ranges decrease with increasing concentration of ionic units. The influence of the alkoxy chain length on clearing temperature (T_c) values of ionomers clearly shows an odd‐even effect, similar to that of other side‐chain liquid‐crystalline polymers. The mesomorphic temperature ranges increase with increasing alkoxy chain length when the number of alkoxy carbon is over 3. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2879–2886, 2003     

Diffusion behavior of reducing agents into keratin fibers using microspectrophotometry

To investigate the penetration of thioglycolic acid (TG), thiolactic acid (TL), and L ‐cysteine (CYS), into keratin fibers, cross‐sectional samples of virgin white human hair treated with TG, TL, and CYS were prepared. A new method for analyzing the diffusion behavior of reducing agents into human hair was developed. The diffusion pattern of reducing agents into human hair, which cannot be determined by optical microscopy, can be determined by the method developed. The method involves treating virgin hair fibers with TG, TL, and CYS. After the treatment, the cross‐sectioned hair samples were dyed with methylene blue and the cross‐sectional intensity scans were measured at a wavelength of 664 nm (λ_max of methylene blue) with a microspectrophotometer. The three different diffusion patterns from the three reducing agents were obtained. The penetration of TG and TL into virgin human hair clearly increased by increasing the treatment time and pH. On the other hand, the penetration of CYS was less than TG and TL (CYS could not penetrate into the cortex region of the virgin human hair). Also, the diffusion pattern of TG showed Fickian type characteristics. The apparent diffusion coefficient of TG into human hair at pH 9.0 determined from the TG concentration profile was found to be 10^?9 cm²/s. On the other hand, the apparent diffusion coefficient of TG into human hair at pH 7.0 was 10^?10 cm²/s, and thus, the apparent diffusion coefficient of TG depended on the pH of the TG solution. From these experiments, we have concluded that the diffusion patterns of the three reducing agents in this study depended on the electrostatic interaction between the human hair and the reducing agents. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1131–1138, 2004     

Preparation and characterization of core–shell polystyrene–polydimethylsiloxane particles by seeded polymerization

Nanometer scale particles of seed latex were successfully prepared by polymerization induced by gamma rays. By modification of the coupling agent 3‐methacryloxylpropyltrimethoxylsilane (MPS) at the surface of polystyrene (PSt) particles, polydimethylsiloxane (PDMS) was introduced outside the PSt particles and composite latex particles with a core–shell (PSt–PDMS) structure were successfully prepared. Because of the chemical bond linkage between the core and the shell, such a structure is stable. Direct evidence of the core–shell structure was observed by transmission electron microscopy (TEM). In addition the chemical bond linkage was confirmed by Fourier‐transfer infrared (FT‐IR) spectroscopy. An indirect proof of the core–shell structure was given by water absorption ratio determination of the different samples. Copyright © 2004 Society of Chemical Industry     

Preparation and oil–water separation evaluations of polypropylene/low‐melt‐point polyester composites reinforced by thermal bonding and one‐step solution immersion

Nonwoven fabrics have been fabricated for oil–water separation, but simplifying the manufacturing processes is still a challenge. In this work, a facile and easily scaled up approach based on thermal bonding and one‐step solution immersion has been successfully developed to prepare nonwoven fabrics with high separation efficiency and flux of oil. Here, polypropylene (PP) and low‐melt‐point polyester (LPET) fibers with a unique sheath–core structure are employed to form PP/LPET nonwoven fabrics. Thermal bonding by hot press and hydrophobic treatment with 1H,1H,2H,2H‐perfluorodecyl‐1‐thiol (PFDT) are used to manufacture oil–water separation nonwoven fabrics. Effects of the ratio of LPET fibers and the concentration of PFDT are discussed in terms of mechanical properties, morphology, surface chemical composition, water contact angle and performance of oil–water separation and flux of the nonwoven fabrics. The results show that the strength of the nonwoven fabrics gradually increases with increasing ratio of LPET fibers. After immersion in PFDT, the nonwoven fabrics show high hydrophobicity with a water contact angle of 143°. They can be used to separate oil–water mixtures. The separation efficiency is 97–99% and the oil flux is 62 364.92 L m^?2 h^?1. This study provides a new prospect for simple introduction of a hydrophobic agent on a nonwoven fabric to achieve various functional oil–water separation materials. © 2020 Society of Chemical Industry