Green and self-lubricating polyoxymethylene composites filled with low-density polyethylene and rice husk flour

Polyoxymethylene (POM) composites filled with low-density polyethylene (LDPE) and rice husk flour (RHF) were prepared by injection molding. The POM/5 wt % LDPE/7.5 wt % RHF composite exhibited the lowest wear rate, whereas the coefficient of friction remained low, and the POM/5 wt % LDPE/5 wt % RHF composite had the best mechanical properties. X-ray diffraction analysis was carried out, and the worn surfaces were examined with scanning electron microscopy. The results showed that the addition of the filler reduced the crystallinity degree of the POM composites. The main wear mechanism for unfilled POM was adhesion, whereas for the POM composites, wear seemed to occur mainly by fatigue and abrasion. It was experimentally confirmed that the POM composite filled with LDPE and RHF, which is well-performing, low-cost, and environmentally friendly, could be a potential material for tribological applications. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of poly(N‐vinyl‐2‐pyrrolidone) grafted sodium alginate hydrogel beads for the controlled release of indomethacin

Graft copolymers of sodium alginate (NaAlg) with N‐vinyl‐2‐pyrrolidone were prepared using azobisisobutyronitrile as initiator. The graft copolymers (NaAlg‐g‐PVP) were characterized with Fourier transform infrared spectroscopy, elemental analysis, and differential scanning calorimetry. Polymeric hydrogel beads of NaAlg and NaAlg‐g‐PVP were prepared by crosslinking method using glutaraldehyde (GA) as a crosslinker in the hydrochloric acid catalyst (HCl) and these beads were used to deliver anti‐inflammatory drug, indomethacin (IM). Chemical stability of the IM after encapsulation into beads was confirmed by FTIR. Preparation conditions of the NaAlg‐g‐PVP beads were optimized by considering the percentage entrapment efficiency, particle size, swelling capacity and their release data. In vitro release studies were performed in simulated gastric fluid (pH 1.2) for the initial 2 h, followed by simulated intestinal fluid (pH 7.4) for 4 h. Effects of GA concentration, exposure time to GA, drug/polymer (d/p) ratio, and concentration of HCl on the release of IM were discussed. It was observed that IM release from the beads decreased with increasing GA concentration and exposure time. IM release also decreases with increasing d/p ratio and HCl concentration. The highest IM release was obtained to be 77% for beads crosslinked with 0.027M GA. Swelling experiments were also performed to compute molecular mass between crosslinks of the beads. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and magnetic properties of novel fully conjugated polymeric complexes containing 1,10‐phenanthroline

A novel fully conjugated polymer containing 1,10‐phenanthroline (DAPcDOD) was first synthesized by the polycondensation of 2,7‐dimethyl‐2,4,6‐octatriene‐1,8‐dial with 5,6‐diamine‐1,10‐phenanthroline. Three polymeric complexes were first prepared by the reaction of DAPcDOD with NiSO₄, CoCl₂, and FeSO₄, respectively. The structures of the polymer and the complexes were characterized by IR, ¹H‐NMR, and elemental analysis. The magnetic behaviors of these complexes were measured as a function of magnetic field strength (0–50 kOe) at 5 K and as a function of temperature (5–300 K) at a magnetic field strength of 30 kOe. The results show that DAPcDOD–Ni²⁺ and DAPcDOD–Co²⁺ were soft ferromagnets, whereas DAPcDOD–Fe²⁺ exhibited the features of an antiferromagnet. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Characterization of poly(vinyl alcohol)/sodium bromide polymer electrolytes for electrochemical cell applications

Sodium‐ion conducting polymer electrolytes based on poly(vinyl alcohol) complexed with sodium bromide were prepared with a solution‐casting technique. The structure of these films was determined with X‐ray diffraction, and the complexation of the salt with the polymer was confirmed with Fourier transform infrared spectroscopy studies. Electrical conductivity was measured with an alternating‐current impedance analyzer in the frequency range of 100 Hz to 1 MHz and in the temperature range of 303–373 K. It was observed that the magnitude of conductivity increased with the increase in the salt concentration as well as the temperature. The nature of the charge transport in these polymer electrolyte films was determined with both Wagner's polarization technique and the Watanabe technique. The dominant conducting species were found to be ions, particularly anions. Optical absorption studies were performed in the wavelength range of 200–600 nm, and the absorption edge, direct band gap, and indirect band gap values were evaluated. Electrochemical cells were fabricated, and their discharge characteristics were studied. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Potentiometric studies of oxidation–reduction reactions with redox copolymers

Polymeric oxidants in the bead form that were macroporous styrene/divinylbenzene copolymers containing N‐chlorosulfonamide functional groups (in sodium or hydrogen form) or N‐bromosulfonamide groups (in sodium form) were synthesized and investigated to determine their oxidizing powers. The redox potentials of the N‐chlorosulfonamide/sulfonamide and N‐bromosulfonamide/sulfonamide systems were determined by potentiometric studies at different pH values with aqueous solutions of Na₂SO₃, KCN, and KSCN as reducers. The formal redox potentials of the N‐chlorosulfonamide copolymers were 0.79, 0.44, and ?0.12 V at pH's of 1.8, 8.45, and 13.6, respectively. The formal redox potential of the N‐bromosulfonamide copolymer was about 100 mV higher in comparable conditions and in solutions over pH = 5 (e.g., 0.56 V at pH = 8.56). The comparatively higher oxidizing power of the N‐bromosulfonamide copolymer was particularly evident in a strong alkaline medium (in which the N‐chlorosulfonamide copolymer was not reactive). In contrast, the N‐chlorosulfonamide copolymer showed strong oxidative properties in acidic media (in which the N‐bromosulfonamide copolymer decomposed itself). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Nondegradative microextrusion of resorbable polyesters for pharmaceutical and biomedical applications: The cases of poly‐lactic‐acid and poly‐caprolactone

In recent years biodegradable polymers, particularly polyesters such as the poly(lactic acid) (PLA) and polycaprolactone (PCL), have gained high interests for their applicability in the biomedical and pharmaceutical fields where they're used for manufacturing various different resorbable devices, from tissue engineering scaffolds to controlled drug release systems. Despite many positive characteristics, processability of these materials still remains a critical issue as they easily tend to degrade during manufacturing. In this article we aimed to assess microextrusion as a nondegradative process for manufacturing PLA and PCL. The results we experimentally obtained, that are hereby presented, set a new point in the on‐going debate on degradation during processing of resorbable polymers as they allow to affirm that microextrusion leaves unmodified molecular weight distributions without producing any evident reductions in mean molecular weight. Microextrusion thus represents a risk‐free high molecular weight polymer processing solution for obtaining nondegraded products within pharmaceutical and biomedical production lines, such as for scaffolds for tissue engineering applications or drug delivery. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and adsorption behavior of a cellulose‐based,mixed‐mode adsorbent with a benzylamine ligand for expanded bed applications

A novel mixed‐mode expanded bed adsorbent with anion‐exchange properties was explored with benzylamine as the functional ligand. The cellulose composite matrix, densified with stainless steel powder, was prepared with the method of water‐in‐oil suspension thermal regeneration. High activation levels of the cellulose matrix were obtained with allyl bromide because of the relative inertness of the allyl group under the conditions of the activation reaction. After the formation of the bromohydrin with N‐bromosuccinimide and coupling with benzylamine, the activated matrix was derived to function as a mixed‐mode adsorbent containing both hydrophobic and ionic groups. The protein adsorption capacity was investigated with bovine serum albumin as a model protein. The results indicated that the prepared adsorbent could bind bovine serum albumin with a high adsorption capacity, and it showed salt tolerance. Effective desorption was achieved by a pH adjustment across the isoelectric point of the protein. The interactions between the cell and adsorbent were studied, and the bioadhesion was shielded by the adjustment of the salt concentration above 0.1M. Stable fluidization in the expanded bed was obtained even in a 2% (dry weight) yeast suspension. The direct capture of target proteins from a biomass‐containing feedstock without extra dilution steps could be expected with the mixed‐mode adsorbent prepared in this work, and this would be especially appropriate for expanded bed adsorption applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Semiflexible random thermotropic copolymers from 8‐(3‐hydroxy phenyl) octanoic acid and 3‐chloro‐4‐hydroxy benzoic acid/3,5‐dibromo‐4‐hydroxy benzoic acid

Two series of semiflexible random thermotropic copolymers containing 8‐(3‐hydroxy phenyl) octanoic acid (HPOA) with either 3‐chloro‐4‐hydroxy benzoic acid or 3,5‐dibromo‐4‐hydroxy benzoic acid were prepared by melt polycondensation techniques. The copolyesters were characterized with Fourier transform infrared spectroscopy, dilute solution viscometry, hot‐stage polarized light microscopy, differential scanning calorimetry, thermogravimetric analysis, and wide‐angle X‐ray diffraction. Studies revealed that the amount of HPOA as a disruptor incorporated into the backbone of substituted 4‐hydroxy benzoic acids had a detrimental effect on the liquid‐crystalline behavior. Mesophase‐transition temperatures were observed between 210 and 250°C, and the optical textures were of typical nematic phases. The degree of crystallinity decreased with an increase in the HPOA content. The thermal stability of the copolymers was in the range of 310–370°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Synthesis,characterization, and redox and electrochromic behaviors of poly(3-n-octyloxythiophene)

Poly(3-n-octyloxythiophene), a conjugated polymer, which possessed solubility in common organic solvents, was synthesized by electrochemical polymerization in the presence of lithium perchlorate as the supporting electrolyte and sodium dodecyl sulfate as the surfactant in an aqueous medium. Characterizations of the intermediate, monomer, and polymer were performed by NMR spectroscopy, Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, and gel permeation chromatography. The process of electrochemical polymerization and the electrochemical redox behaviors were investigated by cyclic voltammetry and the potentiostatic method. A poly(3-n-octyloxythiophene) film that was deposited on a platinum electrode was found to exhibit electrochromic behaviors, and it switched electrochemically between blue–green oxidized and dark red reduced states. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mixtures of tertiary amine functionalized azo-containing mesogens with acid-functionalized polymers

A tertiary amine functionalized 4-nitro-4′-alkoxy azobenzene mesogen with a 10 or 12 carbon spacer (azo-nN) was synthesized and complexed in equimolar proportions with poly(acrylic acid) (PA-H) and poly(sulfonic acid) (PSS-H), and investigated by thermogravimetric analysis, differential scanning calorimetry, polarizing optical microscopy, Fourier transform infrared spectroscopy and X-ray diffraction. The neat azo-nN is characterized by a partial bilayer S_A mesophase at higher temperatures, and a highly ordered phase, in which the molecules are stacked orthogonally in bilayers, at lower temperatures. As supported by infrared analysis, for the azo-nN/PA-H mixture, the complexation is partial while for the same azo-nN/PSS-H mixture, complete proton transfer occurs. When the azo-nN is blended with the PA-H, regarded as a weak acid, a biphasic system is generated and the thermotropic behavior of neat mesogen is not significantly affected. In contrast, by mixing the same mesogen with a PSS-H (regarded as a strong acid), the thermotropic behavior is significantly influenced: the complexation generated a partial or interdigitated smectic A or tilted smectic C lamellar phase.