Carbon fibers derived from UV‐assisted stabilization of wet‐spun polyacrylonitrile fibers

A rapid, dual‐stabilization route for the production of carbon fibers from polyacrylonitrile (PAN) precursor fibers is reported. A photoinitiator, 4,4′‐bis(diethylamino)benzophenone, was added to PAN solution before the fiber wet‐spinning step. After a short UV treatment that induced cyclization and crosslinking at a lower temperature, precursor fibers could be rapidly thermo‐oxidatively stabilized and successfully carbonized. Scanning electron microscopy micrographs show no deterioration of the microstructure or hollow‐core formation in the fibers due to UV treatment or presence of photoinitiator. Fast‐thermally stabilized pure PAN‐based carbon fibers show hollow‐core fiber defects due to inadequate thermal stabilization, but such defects were not observed in carbon fibers derived from fast‐thermally stabilized fibers that contained photoinitiator and were UV treated. Tensile testing results confirm that fibers containing 1 wt % photoinitiator and UV treated for 5 min display higher tensile modulus than all other sets of thermally stabilized and carbonized fibers. Wide‐angle X‐ray diffraction results show a higher development of the aromatic structure and molecular orientation in thermally stabilized fibers. No significant increase in interplanar spacing or decrease in crystals size were observed within the UV‐stabilized carbon fibers containing photoinitiator, but such fibers retain a higher extent of molecular orientation when compared with control fibers. These results establish for the first time, the positive effect of the external addition of photoinitiator and UV treatment on the properties of the PAN‐based fibers, and may be used to reduce the precursor stabilization time for faster carbon fiber production rate. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40623.     

Effects of superfine silk protein powders on mechanical properties of wet‐spun polyurethane fibers

Mechanical measurements were employed to investigate the effects of three types of superfine silk protein powder on tensile strength, elongation, and elasticity of wet‐spun Pellethane^® 2363‐80AE polyurethane (PU) fiber. These superfine silk protein powders included undegummed silk (with both native silk fibroin and sericin, water insoluble), native silk fibroin (with native silk fibroin only, water insoluble), and regenerated silk fibroin (with regenerated silk fibroin only, water soluble) in powder form. Experimental data derived from the mechanical measurements illustrated that the miscibility between the PU and regenerated silk fibroin were superior to that between PU and the other two silk proteins. This may be attributed to the similar chemical structure and microphase separation of PU and regenerated silk fibroin with lower molecular weight than native silk fibroin. This preliminary work may provide some information for biomimetic processing of silk‐inspired PU biofibers, which combine elasticity of synthetic PU with biofunction of natural silk fibroin for special biomedical applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Chitin nanocrystal reinforced wet‐spun chitosan fibers

Chitosan (CS) has been extensively studied and found wide applications in the field of biomedicine because of its favorable biological properties. Normal CS fibers are manufactured either by wet‐spinning or by dry‐jet wet‐spinning. However, the poor tensile strength of CS fibers raises much concern. The present study uses chitin nanocrystal (ChiNC), a stiff rod‐like nanofiller, to enhance the mechanical properties of wet‐spun CS fibers. Owing to the good compatibility between CS and ChiNC, the nanoparticles are well distributed in the CS matrix. When the ChiNCs loading is 5 wt %, the optimal mechanical properties of CS fibers are obtained, and the peak stress is 2.2 cN/dtex and modulus is 145.6 cN/dtex, which are increased by 57% and 84.5%, respectively, compared to that of nonfilled CS fibers under the same processing condition. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40852.     

Chitosan‐based wet‐spun scaffolds for bioactive agent delivery

Use of scaffolds both as supporting materials at defect site and delivery vehicles for bioactive agents is a commonly employed strategy to aid in tissue repair and regeneration. In this study, fibrous meshes of chitosan were prepared by wet spinning and coated with alginate. BSA as a model protein and gentamicin as a model antibiotic were incorporated into the scaffolds in multiple loading models and their release kinetics were studied. The effects of structural form of scaffold and properties of bioactive agents on release profiles were evaluated. Our results suggest that, designed scaffolds are potential candidates for tissue engineering with the feature of controlled bioactive agent delivery. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3759–3769, 2013     

Structure and properties of flame‐sprayed poly(ethylene‐co‐vinyl alcohol) copolymer coatings

Powder coatings formed by flame spraying are being used in industrial applications. The resistance of plastics and their composite materials to chemicals, solvents, and atmospheric conditions and their high impact strength even at low service temperatures increase the importance of plastic and plastic‐based coatings. In this study, an ethylene vinyl alcohol copolymer powder was coated via flame spraying with gases of oxygen and acetylene. The bond strengths and microstructures of the coatings were determined with tensile testing, scanning electron microscopy, and Fourier transform infrared. The bond strengths of the coatings were determined according to ASTM C 633. Oxidizing, carburizing, and neutral flames were used. The bond strengths were lower for the oxidizing and carburizing coatings than for the neutral flame coatings. The results indicated that during the flame‐spraying process, the composition, gas, spraying distance, and coating thickness were important factors in the coating bond strength. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1357–1364, 2004     

Structural and emission properties of Eu3+‐doped alkaline earth zinc‐phosphate glasses for white LED applications

Quaternary alkaline earth zinc‐phosphate glasses in molar composition (40 ? x)ZnO – 35P₂O₅ – 20RO – 5TiO₂ – xEu₂O₃ (where x=1 and R=Mg, Ca, Sr, and Ba) were prepared by melt quenching technique. These glasses were studied with respect to their thermal, structural, and photoluminescent properties. The maximum value of the glass transition temperature (T_g) was observed for BaO network modifier mixed glass and minimum was observed for MgO network modifier glass. All the glasses were found to be amorphous in nature. The FT‐IR suggested the glasses to be in pyrophosphate structure, which matches with the theoretical estimation of O/P atomic ratio and the maximum depolymerization was observed for glass mixed with BaO network modifier. The intense emission peak was observed at 613 nm (⁵D₀→⁷F₂) under excitation of 392 nm, which matches well with excitation of commercial n‐UV LED chips. The highest emission intensity and quantum efficiency was observed for the glass mixed with BaO network modifier. Based on these results, another set of glass samples was prepared with molar composition (40 ? x)ZnO – 35P₂O₅ – 20BaO – 5TiO₂ – xEu₂O₃ (x=3, 5, 7, and 9) to investigate the optimized emission intensity in these glasses. The glasses exhibited crystalline features along with amorphous nature and a drastic variation in asymmetric ratio at higher concentration (7 and 9 mol%) of Eu₂O₃. The color of emission also shifted from red to reddish orange with increase in the concentration of Eu₂O₃. These glasses are potential candidates to use as a red photoluminsecent component in the field of solid‐state lighting devices.     

Towards improving wet‐adhesion in a metal oxide‐polymer coating system

An investigation using a variable radius roll adhesion test (VaRRAT) revealed an irreversible increase in the wet‐adhesion in a metal–oxide–polymer system, under specific experimental conditions. This observation is further confirmed by the T_g measurements and the ATR‐FTIR studies. The increase in wet‐adhesion is attributed to late H₂O‐catalyzed curing of the previously partially cured polymers (epoxy ring opening), as well as the formation of nanocomposite layer within the epoxy primer matrix, because of precipitation of the nanocrystals including zinc ammine complexes formed as a result of dissolution of the zinc/aluminum alloy as well as the metal oxide pigments by the amine crosslinker. High activation energy of ～100 kJ mol^?1 indicated a chemical process to be responsible for the adhesion gain. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3318–3327, 2006     

Characteristics of wet‐spun and thermally treated poly acrylonitrile fibers

The performance of carbon fibers depends on the quality of the precursor and the conditions of the thermal treatment. In detail, for a PAN precursor fiber the viscosity of a spinning dope and the draw ratio during the spinning process needs to be considered. Through wet spinning, different types of PAN precursor fibers with defined spinning parameters, including solid content, solvent content in a bath, and especially draw ratio resulting in defined cross section diameters, were fabricated and analyzed with tensile tests, density investigations, SEM, TGA‐MS, FTIR, and XRD. The results show that the mechanical properties of the fibers correlate to crystallinity. The cross section diameter is strongly related to the morphology of the fibers after thermal treatment. By extending the postdrawing of PAN fibers high tenacities were obtained at the cost of the cross section shape. In addition, TGA measurements reveal trapped residues of the wet spinning process as well as show several chemical reactions takes place at the same time at different temperatures. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43698.     

Synthesis and properties of carboxymethyl cellulose‐graft‐poly(acrylic acid‐co‐acrylamide) as a novel cellulose‐based superabsorbent

A new cellulose‐based superabsorbent polymer, carboxymethyl cellulose‐graft‐poly(acrylic acid‐co‐acrylamide), was prepared by the free‐radical grafting solution polymerization of acrylic acid (AA) and acrylamide (AM) monomers onto carboxymethyl cellulose (CMC) in the presence of N,N′‐methylenebisacrylamide as a crosslinker with a redox couple of potassium persulfate and sodium metabisulfite as an initiator. The influences of reaction variables such as the initiator content, crosslinker content, bath temperature, molar ratio of AA to AM, and weight ratio of the monomers to CMC on the water absorbency of the carboxymethylcellulose‐graft‐poly(acrylic acid‐co‐acrylamide) copolymer were investigated. The copolymer's structures were characterized with Fourier transform infrared spectroscopy. The optimum reaction conditions were obtained as follows: the bath temperature was 50°C; the molar ratio of AA to AM was 3 : 1; the mass ratio of the monomers to CMC was 4 : 1; and the weight percentages of the crosslinker and initiator with respect to the monomers were 0.75 and 1%, respectively. The maximum water absorbency of the optimized product was 920 g/g for distilled water and 85 g/g for a 0.9 wt % aqueous NaCl solution. In addition, the superabsorbent possessed good water retention and salt resistance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1382–1388, 2007     

Thermal and morphological studies of chemically prepared emeraldine‐base‐form polyaniline powder

In this study, emeraldine base (EB)‐form polyaniline (PANI) powder was chemically prepared in 1M HNO₃ aqueous solution. The thermal characteristics and chemical structures of this powder were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), and X‐ray diffraction (XRD). A polarizing optical microscope was also used to examine the crystalline morphology of this sample. The results indicated that the EB‐form PANI powder had a discernible moisture content. Moreover, in the first run of DSC thermal analysis, the exothermic peak at 170–340°C was due to the crosslinking reaction occurring among the EB‐form PANI molecular chains. FTIR and XRD examinations further confirmed the chemical crosslinking reaction during thermal treatment. TGA results illustrated that there were two major stages for weight loss of the EB‐form PANI powder sample. The first weight loss, at the lower temperature, resulted from the evaporation of moisture. The second weight loss, at the higher temperature, was due to the chemical structure degradation of the sample. The degradation temperature of the EB‐form PANI powder was around 420–450°C. The degradation temperature of emeraldine salt (ES)‐form PANI powder was lower (around 360–410°C) than that of the EB form (around 420–450°C). From the TGA results, I roughly estimated that 2.74 aniline repeat units, on average, were doped with 1 HNO₃ molecule in the ES‐form PANI. I found a single crystalline morphology of EB‐form PANI, mostly like a conifer leaf. More complex, multilayered dendritic structures were also found. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2142–2148, 2003     

Dry‐jet‐wet spun polyurethane fibers. I. Optimization of the spinning parameters

This study examined the spinning of polyurethane‐based elastomeric fibers with the dry‐jet‐wet spinning method. The three important spinning variables that were chosen were the coagulation bath ratio (dimethylformamide/water), the bath temperature, and the stretch ratio. A three‐variable factorial design method, proposed by Box and Behnken, was used to optimize these process parameters. The spinning process was further fine‐tuned by the variation of the stretch ratio and the dope solid content. The effect of the dry‐jet length on the fiber properties was also studied. The tenacity and elastic recovery properties of the fibers were found to be optimum at a bath ratio (dimethylformamide/water) of 60 : 40, a bath temperature of 15°C, and a stretch ratio of 2.5. The density and sonic modulus were measured to determine the effect of varying the process variables on structural parameters such as the density and orientation. The surface morphological features, as revealed by scanning electron microscopy, were correlated to the fiber properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influence of laser irradiation on the optical and the mechanical properties of Makrofol‐DE polycarbonate

The effect of IR laser irradiation on the optical and the mechanical properties of Makrofol‐DE 1‐1 CC polycarbonate films were investigated. Three hundred microns‐thick films of Makrofol‐DE 1‐1 CC polycarbonate were irradiated with 0.00–10.40 J/cm² of Ga‐As laser pulses, 904 nm, 5 W, and 200‐ns pulse duration. Fourier transform infrared spectroscopy measurements showed that (C?O) groups degrade under laser irradiation at the studied fluence range. The aliphatic and aromatic (C? H) groups exhibited the same behavior, which can be attributed to nature of laser interaction with matter. The Makrofol samples exhibited degradation under the effect of laser irradiation up to 0.94 J/cm², where crosslinking mechanism started and continued until 7.07 J/cm². The refractive index had a minimum value at 0.94 J/cm² and maximum value at 7.07 J/cm² due to the degradation and crosslinking formation inside the sample, respectively. The decrease in elastic modulus, E, of Makrofol irradiated with 0.47–0.94 and 7.07–10.40 J/cm² indicates that the sample becomes more flexible, which results from the decrease in interatomic force constants. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The skin‐core structure of poly(acrylonitrile‐itaconic acid) precursor fibers in wet‐spinning

The skin‐core structure of poly(acrylonitrile‐itaconic acid) [P(AN‐IA)] precursor fibers in wet‐spinning has been analyzed by the means of electron probe microanalyser (EPMA), scanning electron microscope (SEM), and transmission electron microscope. The numerical solution of Fick's second law equations for diffusion in the nascent fiber was obtained by using the Method of Lines. It has been found that [P(AN‐IA)] precursor fiber composed of four parts had remarkable skin‐core structure. The sheet‐like skin, which was compact and homogeneous, had high crystallization and highly oriented structure. However, the core with low crystallization and some voids was loose, somewhat disorderly and unsystematic. Moreover, the precursor fiber had a pillar‐like layered structure along the fiber axis. The average thickness of each layer increased gradually from the skin to the endothecium. Meanwhile, a structural model of PAN precursor fiber has been built. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mechanical properties and morphology of polylactide,linear low‐density polyethylene,and their blends

Melt blending of linear low density polyethylene (LLDPE) and polylactide (PLA) was performed in an extrusion mixer with post extrusion blown film attachment with and without compatibilizer‐grafted low density polyethylene maleic anhydride. The blend compositions were optimized for tensile properties as per ASTM D 882‐91. On the basis of this, LLDPE 80 [80 wt % LLDPE and 20 wt % poly(L ‐lactic acid) (PLLA)] and MA‐g‐low‐density polyethylene 80/4 (80 wt % LLDPE, 20 wt % PLLA, and 4 phr compatibilizer) were found to be an optimum composition. The blends were characterized according to their mechanical, thermal, and morphological behavior. Fourier transform infrared spectroscopy revealed that the presence of compatibilizer enhanced the blend compatibility to some extent. The morphological characteristics of the blends with and without compatibilizer were examined by scanning electron microscopy. The dispersion of PLLA in the LLDPE matrix increased with the addition of compatibilizer. This blend may be used for packaging applications. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of hydrazine‐modified polyacrylonitrile nanofibers for the extraction of metal ions from aqueous media

Polyacrylonitrile (PAN) nanofibers (prepared by an electrospinning technique) were chemically modified with hydrazine. The Fourier transform infrared spectrum of the hydrazine‐modified polyacrylonitrile (HM–PAN) showed that the intensity of the nitrile peak (2250 cm⁻¹) of the PAN nanofibers decreased significantly after treatment with hydrazine. New peaks at about 3400–3100 cm⁻¹ (N H stretching vibration) also appeared, which showed that the hydrazine was chemically attached to the PAN nanofibers. HM–PAN had a smooth surface (as confirmed by a scanning electron microscopy) and was a suitable material for the adsorption of metal ions from aqueous solutions. The adsorption capacity of HM–PAN increased as the adsorption time increased and became constant at 114 and 217 mg/g for Cu(II) and Pb(II) ions, respectively, after 24 h. In addition, more than 90% of the adsorbed Cu(II) and Pb(II) ions were recovered in a 1M HNO₃ solution after 1 h. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

On the structure‐properties relationship in montmorillonite‐filled polyamide 6 nanocomposites

Polyamide 6/montmorillonite (MMT) nanocomposites were prepared by melt compounding method comprising 1–7.5 wt % of Nanomer I.24 TL or 5 and 10 wt % of Cloisite 15A organically modified nanoclays. The composite samples were characterized by synchrotron X‐ray, thermal and FT‐IR spectroscopy methods looking for changes in the micro‐ and nanostructure of both PA6 matrix and MMT reinforcement as a function of the clay content and type. These data were discussed in conjunction with the mechanical properties of the respective nanocomposites. Generally, the Young's modulus was found to increase proportionally to the clay content being the highest in samples with strong aggregation of MMT at micron length scale. The tensile strength passed through a maximum at 2.5 wt % clay load presenting a homogeneous microstructure with almost no agglomeration. Increasing the amount of MMT produced less crystalline PA6 matrices, richer in γ‐PA6 polymorph and resulted in larger long spacings of PA6 due to expansion of both crystalline and amorphous domains. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Surface chemistry and mechanical property changes of wood‐flour/high‐density‐polyethylene composites after accelerated weathering

Although wood–plastic composites have become more accepted and used in recent years and are promoted as low‐maintenance, high‐durability building products, they do experience a color change and a loss in mechanical properties with accelerated weathering. In this study, we attempted to characterize the modulus‐of‐elasticity (MOE) loss of photostabilized high‐density polyethylene (HDPE) and composites of wood flour and high‐density polyethylene (WF/HDPE) with accelerated weathering. We then examined how weathering changed the surface chemistry of the composites and looked at whether or not the surface changes were related to the MOE loss. By examining surface chemistry changes, we hoped to begin to understand what caused the weathering changes. The materials were left unstabilized or were stabilized with either an ultraviolet absorber or pigment. After 1000 and 2000 h of accelerated weathering, the samples were tested for MOE loss. Fourier transform infrared (FTIR) spectroscopy was employed to monitor carbonyl and vinyl group formation at the surface. Changes in the HDPE crystallinity were also determined with FTIR techniques. It was determined that structural changes in the samples (carbonyl group formation, terminal vinyl group formation, and crystallinity changes) could not be reliably used to predict changes in MOE with a simple linear relationship. This indicated that the effects of crosslinking, chain scission, and crystallinity changes due to ultraviolet exposure and interfacial degradation due to moisture exposure were interrelated factors for the weathering of HDPE and WF/HDPE composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2263–2273, 2004     

Molecular structure and orientation of gel‐spun polyethylene fibers

Characterization of molecular structure and orientation of six commercially available gel‐spun polyethylene fibers have been carried out using infra‐red and Raman spectroscopy, thermal and X‐ray diffraction analysis, together with optical microscopy techniques. Thermal and X‐ray diffraction analysis revealed the existence of highly oriented orthorhombic and monoclinic crystallites together with a highly oriented intermediate phase known as pseudohexagonal mesophase structure. The results suggest the existence of a three‐phase structure consisting, at room temperature, of orthorhombic and monoclinic polymorphic crystallites, oriented noncrystalline and un‐oriented noncrystalline (amorphous) phases, respectively. The crystallinity measurements have been carried out using density, thermal and X‐ray diffraction analysis together with infra‐red and Raman spectroscopy techniques whereas the molecular orientation measurements have been carried out using birefringence and polarized IR spectroscopy, respectively. The results obtained from density, thermal analysis, and Raman spectroscopy based on a simple two‐phase modeling approach lead to the overestimated amorphous fractions and appears to ignore the presence of an intermediate phase known as oriented noncrystalline structure. X‐ray analysis has also been used for the measurement of the apparent crystallite sizes. The birefringence values have been used to determine the overall orientation parameters whereas the dichroic measurements of IR bands have been used to determine the crystalline and oriented noncrystalline orientation parameters. The results show that the orthorhombic and monoclinic phases are more highly oriented than the oriented pseudohexagonally packed noncrystalline chains. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1317–1333, 2006     

Silver‐nanoparticle‐loaded chitosan lactate films with fair antibacterial properties

Food quality and safety are major concerns in the food industry. Antimicrobial packaging can be considered an emerging technology that could have a significant impact on life and food safety. Antimicrobial agents in food packaging can control the microbial population and target specific microorganisms to provide greater safety and higher quality products. In this work, a lactic acid grafted chitosan film was synthesized. Silver nanoparticles were loaded into the chitosan lactate (CL) film by equilibration in a silver nitrate solution, which was followed by citrate reduction. The presence of silver nanoparticles was confirmed with transmission electron microscopy, X‐ray diffraction, Fourier transform infrared spectroscopy, and thermogravimetric analysis of the film. The silver‐nanoparticle‐loaded CL film was investigated for its antimicrobial properties against Escherichia coli. This newly developed material showed strong antibacterial properties and thus has potential for use as an antibacterial food‐packaging material. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Optimization of the reaction conditions and characterization of L‐lactic acid direct polycondensation products catalyzed by a non‐metal‐based compound

In this article, we deal with the investigation into a poly(lactic acid) (PLA) preparation process catalyzed by a non‐metal‐based compound. Low‐molecular‐weight PLA was synthesized by the direct melt polycondensation of L ‐lactic acid catalyzed by methanesulfonic acid (MSA). This study was focused on the investigation into optimal MSA concentration determination and into the temperature (130, 145, 160, 175, and 190°C) and time (6, 12, 18, and 24 h) influence on the structure (Fourier transform infrared spectroscopy), molecular weight (viscometric measurements and gel permeation chromatography), and thermal properties (differential scanning calorimetry) of the samples. The results show an optimal MSA content of 0.5 wt %. The highest molecular weight of PLA prepared by this method was reached after 18 h of reaction at 175°C (weight‐average molar mass = 17.2 × 10³ g/mol). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010