Preparation of polybenzoxazole fibers via electrospinning and postspun thermal cyclization of polyhydroxyamide

Polybenzoxazole (PBO) fibers with a submicron diameter were successfully prepared by electrospinning its precursor, polyhydroxyamide (PHA), solutions to obtain the PHA fibers first, followed by appropriate thermal treatments for cyclization reaction. BisAPAF‐IC PHA with two different molecular weights (MWs) were synthesized from a low temperature polymerization of 2,2′‐bis(3‐amino‐4‐hydroxyphenyl) hexafluoropropane (BisAPAF) and isophthaloyl chloride (IC). Using dimethylacetamide (DMAc) and tetrahydrofuran (THF), solvent effects on the electrospinnability of PHA solutions were investigated. For balancing the solution properties, it was found that DMAc/THF mixture with a weight ratio of 1/9 was the best cosolvent to prepare smooth PHA fibers; uniform PHA fibers with a diameter of 325–720 nm were obtained by using 20 wt % PHA/(DMAc/THF) solutions. For a fixed PHA concentration, solutions with a lower MW of PHA yielded thinner electrospun fibers under the same electrospinning condition. After obtaining the electrospun BisAPAF‐IC PHA fibers, subsequent thermal cyclization up to 350 °C produced the corresponding thermally stable BisAPAF‐IC PBO fibers with a diameter of 305–645 nm. The structure of the precursor fibers and the fully cyclized fibers were characterized by FTIR. For the cyclized BisAPAF‐IC PBO fibers, thermogravimetric analysis showed a 5% weight loss temperature at 523 °C in nitrogen atmosphere. The interconnected fiber structure in the BisAPAF‐IC PBO fiber mats was irrelevant to the curing process, but resulted from the jet merging during the whipping process as revealed by the high speed camera images. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 8159–8169, 2008     

Enzymatic and chemical hydrolysis of poly(ethylene terephthalate) fabrics

Alkaline and enzymatic hydrolyzes of poly(ethylene terephthalate) fabrics (PET) were mechanistically compared based on released degradation products (HPLC‐UV‐RI) and changes in surface properties [hydrophilicity, cationic dyeing, X‐ray photoelectron spectroscopy (XPS)]. Enzymatic hydrolysis led to an increase in the amount of hydroxyl and carboxyl groups on the surface resulting in an enhanced water absorption and dyeability. Enzymes partially adsorbed to PET fabrics during hydrolysis were completely removed by subsequent extraction according to XPS analysis. In contrast to the enzyme treatment, alkaline hydrolysis did not lead to an increase of hydroxyl and acid groups according to XPS while both treatments caused a substantial increase in hydrophilicity and were more effective on amorphous fibers. Alkaline hydrolysis led to a greater increase in the K/S value after cationic dyeing due to enlarged surface area. Consequently, ESEM‐images demonstrated that alkaline treatment drastically affected the surface morphology of the polymer resulting in crater‐like structures of the fibers, whereas after enzymatic treatment the morphology of the fibers remained unchanged. To reach similar benefits in hydrophilicity, drastically higher amounts of degradation products were released during alkaline hydrolysis as also indicated by >6% weight loss compared to <1% after enzyme treatment. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6435–6443, 2008     

Properties of partially hydrolyzed PAN fibers

The properties of base PAN (polyacrylonitrile) fibers and their partially hydrolyzed PAN-COOH fibers were characterized by means of a Fourier transform infrared spectrophotometer, elemental analyzer, specific surface area analyzer etc. The main factors that can affect the strength of the base PAN fibers and how the hydrolysis reaction happens in alkaline conditions are discussed. Acidic hydrolyzed PAN-COOH fibers, having a strength of 9.6 cN/dtex, capacity of 0.26 mmol/g, BET area of 0.58 m²/g (calculated on dry basis) were prepared. The conversion rate from -CN to -COOH, the ways that groups of -COOH array on the surface of the fibers and the possible maximum amounts of -COOH are discussed in detail. __________ Translated from Transactions of Beijing Institute of Technology, 2008, 28(2) (in Chinese)     

Effects of take‐up speed on the structure and properties of melt‐spun poly(L‐lactic acid) fibers

Poly(L ‐lactic acid) (PLLA) filament fibers were prepared by one‐step melt spinning process and the effects of variations in take‐up speed on their thermal properties, mechanical properties, and crystalline structures were investigated. Differential scanning calorimetry (DSC) results revealed that the PLLA fibers showed multiple melting peaks and that the melting peak appearing at a lower temperature moved lower while that at a higher temperature moved higher with increasing take‐up speed. The glass transition temperature (T_g) obtained from dynamic mechanical analysis (DMA) increased with increasing take‐up speed. The tenacity increased and the boiling water shrinkage (BWS) decreased with increasing take‐up speed. However, these mechanical and thermal properties were stabilized at take‐up speeds over 3500 m/min. The melt‐spun PLLA fibers of this study showed an α‐form crystal structure which was not affected by the take‐up speed. The change in the tendency of the thermal and mechanical properties at around 3500 m/min did not appear to result from the change in crystal form but rather from the change in crystallite size and crystallite orientation. Copyright © 2008 John Wiley & Sons, Ltd.     

Preparation of porous ultrafine polyacrylonitrile (PAN) fibers by electrospinning

A facile method for the preparation of porous ultrafine nanofibers was demonstrated. The PAN/NaHCO₃ composite nanofibers were electrospun, and then NaHCO₃ was removed by a selective dissolution and reaction with the solution of hydrochloric acid (10 wt%). The obtained PAN fibers showed highly porous surfaces after the extraction of NaHCO₃. The structure and properties of ultrafine PAN nanofibers were characterized by Fourier transform infrared (FT‐IR), X‐ray diffraction (XRD), and thermogravimetry (TG). The results indicated that NaHCO₃ could be introduced into the PAN solution and successfully electrospun. CO₂ is released and pores are formed on the fibers. The morphology image of the fibers was detected by scanning electron microscope (SEM) and showed that many pores aligned the nanofibers. Copyright © 2008 John Wiley & Sons, Ltd.     

固相微萃取涂层的制备及其在水体和气态基质中的应用

采用物理涂渍的方法制备了γ-Al2O3固相微萃取涂层。通过γ-Al2O3固相微萃取（SPME）-气相色谱（GC）联用技术,对水中痕量苯系物苯、甲苯、乙苯、二甲苯异构体(BTEXs)进行萃取分析,结果表明该涂层具有热稳定性强(最高使用温度可达350 ℃)、灵敏度高(检测限为1~10 μg/L)以及制备重复性好（相对标准偏差为8.3%）的特点;同时该涂层对气态基质中的污染物亦可进行萃取分析。     

Functionalization of carbon nanofibers (CNFs) through atom transfer radical polymerization for the preparation of poly(tert‐butyl acrylate)/CNF materials: Spectroscopic,thermal, morphological,and physical characterizations

Vapor‐grown carbon nanofibers (CNFs) were oxidized and functionalized for atom transfer radical polymerization (ATRP) of tert‐butyl acrylate (t‐BA) from the surface of the CNFs. The materials were characterized by solubility tests, Fourier‐transform infrared (FTIR) spectroscopy, Raman spectroscopy, thermogravimetric analysis (TGA), X‐ray diffraction (XRD), and scanning electron microscopy. The FTIR and electron microscopy results suggest that ATRP process was successfully used to graft poly(tert‐butyl acrylate) (poly(t‐BA)) chains from the surface of the fibers. Raman results strongly indicate the partial degradation of the graphitic layer of CNFs because of the chemical treatments. TGA results suggest that the presence of poly(t‐BA) leads to a decrease of the initial degradation temperature of the fibers. XRD and electron microscopy results indicate that the microstructure of fibers was not destroyed because of the oxidation and functionalization processes. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3326–3335, 2008     

一次性固相微萃取-高效液相色谱法测定环境水样中的3种多环芳烃

以涂有聚二甲基硅氧烷(PDMS)的石英光导纤维作为固相微萃取纤维,建立了一次性固相微萃取与高效液相色谱联用测定环境水样中的菲、荧蒽和屈3种多环芳烃(PAHs)的方法。实验考察了解吸时间、萃取时间、搅拌速度、盐效应以及样品溶液pH值对萃取效率的影响,优化得到的萃取和解吸条件为: 于60 mL样品溶液中放入两段萃取纤维(1.5 cm)和1.2 g氯化钠,在1200 r/min搅拌速度下萃取60 min,取出萃取纤维并转入120 μL甲醇中密封静置解吸24 h后,取20 μL解吸液进行液相色谱测定。该方法对于菲、荧蒽和屈的检出限分别为0.17、0.17和0.08 μg/L;精密度(以测定0.5 μg/L PAHs标准溶液6次的相对标准偏差计)小于8%;实际样品中3种PAHs的加标回收率为80.0%～107%。该方法快速简便,纤维一次性使用,克服了污染物在纤维上残留的问题。     

Water‐Soluble Polypeptides at Aqueous Interface Produce Extensible Silk‐Like Fiber

A silk‐like extensible poly(α,L ‐amino acid) fiber is created by self‐assembly of poly(α,L ‐lysine) and poly(α,L ‐glutamic acid) at their aqueous solutions' interface. Distinguishing features of the PLL/PLG fiber are the high extensibility and good stretch. Stretching after spinning changes this fiber to a rigid and strong one. The concept and the poly(α,L ‐amino acid) fibers themselves open doors for the production of new protein fibers which are more silk‐ and wool‐like.     

Polypyrrole/graphene composite-coated fiber for the solid-phase microextraction of phenols

A polypyrrole (Ppy)/graphene (G) composite was developed and applied as a novel coating for use in solid-phase microextraction (SPME) coupled with gas chromatography (GC). The Ppy/G-coated fiber was prepared by electrochemically polymerizing pyrrole and G on a stainless-steel wire. The extraction efficiency of Ppy/G-coated fiber for five phenols was the highest compared with the fibers coated with either Ppy or Ppy/graphene oxide (GO) using the same method preparation. Significantly, compared with various commercial fibers, the extraction efficiency of Ppy/G-coated fiber is better than or comparable to 85 μm CAR/PDMS fiber (best extraction efficiency of phenol, o-cresol, and m-cresol in commercial fibers) and 85 μm polyacrylate (PA) fiber (best extraction efficiency of 2,4-dichlorophenol and p-bromophenol in commercial fibers). The effects of extraction and desorption parameters such as extraction time, stirring rate, and desorption temperature and time on the extraction/desorption efficiency were investigated and optimized. The calibration curves were linear from 10 to 1000 μg/L for o-cresol, m-cresol, p-bromophenol, and 2,4-dichlorophenol, and from 50 to 1000 μg/L for phenol. The detection limits were within the range 0.34-3.4 μg/L. The single fiber and fiber-to-fiber reproducibilities were <8.3 (n=7) and 13.3% (n=4), respectively. The recovery of the phenols spiked in natural water samples at 200 μg/L ranged from 74.1 to 103.9% and the relative standard deviations were <3.7%.     

Novel hollow fiber immobilization techniques for whole cells and advanced bioreactors

A novel microporous hollow fiber membrane-based immobilization technique for whole cells has been developed. Yeast cells (Saccharomyces cerevisiae) were grown on chopped hydrophobic microporous hollow fibers as well as on hydrophilic hollow fibers. This immobilization support was used to carry out fermentation in a tubular bioreactor. Air was passed from time to time to facilitate cell growth. The microbial culture reached a very high cell density level of around 10¹⁰/mL of fiber lumen volume. An ethanol concentration of 45 g/L and productivity of 41 g/L-h were obtained with an initial glucose concentration of 100 g/L. The present technique does not have the shortcomings of conventional immobilization methods.     

Self‐assembly and morphology of polydimethylsiloxane supramolecular thermoplastic elastomers

Functionalization of polydimethylsiloxanes (PDMS) polymers with hydrogen‐bonding ureidopyrimidinone (UPy) groups leads to supramolecular thermoplastic elastomers. In previous studies, no lateral stacking of UPy dimers was observed in UPy‐functionalized polymers, unless additional urethane or urea groups were built into the hard block. However, we have shown that when PDMS is used as the soft block, this lateral aggregation of UPy dimers does take place, since long fibers could be observed in the atomic force microscopy (AFM) phase image. Also in bulk, the presence of these interactions was proven by oscillatory shear experiments. We attribute this aggregation to the incompatibility of soft block and hard block, leading to phase separation. Moreover, we have shown that additional urethane or urea groups in the hard block do lead to materials with more fibers and higher melting points. For the UPy‐urea functionalized PDMS even single fibers are observed with AFM when dropcasted from a very diluted solution. When the length of the soft block is increased, the morphology changes from fibrous to spherical. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3877–3885, 2008     

Solvent and concentration effects on the properties of electrospun poly(ethylene terephthalate) nanofiber mats

This study describes the preparation and characterization of nanofibrous mats obtained by electrospinning poly(ethylene terephthalate) (PET) solutions in trifluoroacetic acid/dichloromethane (TFA/DCM). Special attention was paid to the effect of polymer concentration and solvent properties on the morphology, structure, and mechanical and thermal properties of the electrospun nonwovens. The results show that the spinnable concentration of PET solution in TFA/DCM solvents is above 10 wt %. Mats have nanofibrous morphology with fibers having an average diameter in the range of 200–700 nm (depending on polymer concentration and solvent composition) and an interconnected pore structure. Higher solution concentration favors the formation of uniform fibers without beads and with higher diameter. Morphology and fiber assembly changed with the solvent properties. Solvent mixtures rich in TFA, i.e., those with higher dielectric constant and lower surface tension, originated fibers with small diameter. However, due to the lower volatility, those solvent mixtures also produced more branched and crosslinking fibers, with less morphologic uniformity. Mechanical properties (Young's modulus, ultimate strength, and elongation at break) and thermal properties (glass transition, crystallization, and melting) have been studied for the PET electrospun nanomats and compared with those of the original polymer. Solvent effect on fiber crystallinity was not significant, but a complex effect was observed on the mechanical properties of the electrospun mats, as a consequence of the different structural organization of the fibers within the mat network. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 460–471, 2008     

Valorization of Byproducts of Hemp Multipurpose Crop: Short Non-Aligned Bast Fibers as a Source of Nanocellulose

Nanocellulose was extracted from short bast fibers, from hemp (Cannabis sativa L.) plants harvested at seed maturity, non-retted, and mechanically decorticated in a defibering apparatus, giving non-aligned fibers. A chemical pretreatment with NaOH and HCl allowed the removal of most of the non-cellulosic components of the fibers. No bleaching was performed. The chemically pretreated fibers were then refined in a beater and treated with a cellulase enzyme, followed by mechanical defibrillation in an ultrafine friction grinder. The fibers were characterized by microscopy, infrared spectroscopy, thermogravimetric analysis and X-ray diffraction after each step of the process to understand the evolution of their morphology and composition. The obtained nanocellulose suspension was composed of short nanofibrils with widths of 5–12 nm, stacks of nanofibrils with widths of 20–200 nm, and some larger fibers. The crystallinity index was found to increase from 74% for the raw fibers to 80% for the nanocellulose. The nanocellulose retained a yellowish color, indicating the presence of some residual lignin. The properties of the nanopaper prepared with the hemp nanocellulose were similar to those of nanopapers prepared with wood pulp-derived rod-like nanofibrils.     

Microstructural evolution in polyacrylonitrile fibers during oxidative stabilization

Microstructural evolution in polyacrylonitrile fibers during oxidative stabilization was investigated by high‐resolution transmission electron microscopy and wide‐angle X‐ray diffraction. Nanocrystallites and two types of amorphous structures, that is, onion‐like spheres and maze‐like matrix, are observed not only in the precursor fibers but also in the fibers stabilized at 230, 255, and 275 °C. During oxidative stabilization, changes take place earlier in the amorphous onion‐like spheres than in the ordered regions. With increasing temperature, the outer layers of the onion‐like spheres gradually interlace with each other, microscopically demonstrating crosslinking reactions among neighboring macromolecules. The interplanar spacing in crystalline regions increases and the crystallite size decreases as a result of an order–disorder transition. The transition in large crystallites is not completed even in the fibers that are stabilized at 275 °C, suggesting that uniform microstructure and fine crystallites are conducive to homogenous stabilization. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 759–765, 2008     

Synthesis of a new organogelator based on block structures of co‐oligoamide‐6

A series of new bisurea derivatives having in common two co‐oligoamide arms have been synthesized and characterized by NMR, SEC, DSC, SEM, and optical microscopy. These compounds are only soluble at high temperature in aprotic polar solvent. By cooling the solutions, gelation occurs if the concentration of these bisurea derivatives is higher than 3% (w/w). Comparisons with derivatives devoid of oligoamide arms leading no gelation suggest that two kinds of interaction are necessary to get the self‐assembling, namely intermolecular hydrogen‐bonding between urea groups and between oligoamide arms. As these interactions induce interconnections in several directions, the possibility of building the long classical fibrous structures is limited. Accordingly, the ultrastructure of the gel consists only of short interconnected fibers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4122–4129, 2008     

Aging behavior of PBO fibers and PBO‐fiber‐reinforced PPESK composite after oxygen plasma treatment

Aging behavior of poly(p‐phenylene benzobisoxazole) (PBO) fibers and PBO‐fiber‐reinforced poly(phthalazinone ether sulfone ketone) (PPESK) composites after oxygen plasma treatment was investigated. Surface chemical composition, surface roughness and surface morphologies of oxygen‐plasma‐treated PBO fibers before and after aging in air for 1, 3, 5 and 10 days were analyzed by XPS and atomic force microscopy (AFM). The effects of aging on the material were examined by interlaminar shear strength (ILSS) and water absorption measurements. The results indicate that the major aging behavior of the fibers and the composite appeared in the first few days after oxygen plasma treatment, whereas minor aging effects were observed with prolonged aging. Copyright © 2008 John Wiley & Sons, Ltd.     

Modeling the mechanical properties of highly oriented polymer films: A fiber/gel composite theory approach

Controlling the extent of orientation is of great interest in polymer processing and is effected by the choice of polymer, the fabrication technique and the processing conditions. Understanding the crystalline transitions that form highly oriented fibrils is necessary for modeling the changes in physical properties, relative to degree of orientation. A model is proposed to describe the mechanical properties of drawn semicrystalline polymer films based on structural transitions. With a minimal amount of experimental data (requiring testing on only two drawn films samples), this model can be used to predict film properties. These properties include the critical and maximum draw ratios, the moduli at the maximum draw ratio, the moduli of the fiber, the modulus of the nonfibrous gel relative to draw ratio, the volume fraction of fibers, and the rate of fibrillation. Where high degrees of uniaxial orientation are required, the polymer is typically drawn in the solid state, meaning the polymer is stretched in a single direction at temperatures below the melting point. During this process, pre‐existing crystallites are transformed into fiber‐like structures with large aspect ratios. The presence of these rigid asymmetric structures significantly enhances the moduli and break strength of the polymer. This work presents a model that describes the formation of fiber‐like structures. The volume fraction of fibers is predicted to be linear in draw ratio. The derived relationship between volume fraction of fibers and draw ratio can then be used for the prediction of the various properties of the oriented film. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 607–618, 2008     

Synthesis of polypeptides from activated urethane derivatives of α‐amino acids

A series of activated urethane‐type derivatives of α‐amino acids were synthesized and applied to polypeptide synthesis. The urethane used herein, N‐(4‐nitrophenoxycarbonyl)‐α‐amino acids 1 , were synthesized by N‐carbamoylation of γ‐benzyl‐L ‐glutamate, β‐benzyl‐L ‐aspartate, L ‐leucine, L ‐phenylalanine, and L ‐proline, with 4‐nitrophenyl chloroformate. When 1 was dissolved in N,N‐dimethylacetamide (DMAc) and heated at 60 °C, it was smoothly converted into the corresponding polypeptides with releasing 4‐nitrophenol and carbon dioxide. Spectroscopic analyses of the obtained polypeptides revealed that they were comparable with the authentic polypeptides synthesized by the ring‐opening polymerizations of amino acid N‐carboxyanhydrides (NCAs). Besides the successful polycondensations of a series of 1 , their polycondensations of 1a and other 1 were also successfully carried out to obtain the corresponding statistic copolypeptides. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2525–2535, 2008     

Determination of Trace Bisphenol A in Leachate by Solid Phase Microextraction Coupled with High Performance Liquid Chromatography

Abstract

A rapid determination method for trace bisphenol A in leachate by solid phase microextraction (SPME) coupled with high performance liquid chromatography (HPLC) was developed. The experimental condition of SPME, such as select operation, solid phase microextraction fibers, pH, extraction time, extraction temperature, desorption time, desorption solution, mode, and the analytical conditions of HPLC were optimized. As compared with the graph that was produced by HPLC alone, the graph by only HPLC couldn't analyze bisphenol A and compared to the results of three solid‐phase microextraction fibers. The linear range was between 0.0128 mg/L and 0.192 mg/L in this method, and the correlative coefficient was 0.9975. Limits of detection, repeatability, and reproducibility were also determined. The limit of detection of this method was 3.25 µg/L (3σ, n=11). The relative standard deviation (RSD, n=3) was 4.4%. The method was used for the determination of trace bisphenol A in leachate of Qingshan landfill and leachate of Liufang landfill. The recoveries were between 94.5% and 103.3%. This method is fast, convenient, sensitive, solvent free, and suitable for the determination of trace bisphenol A in leachate.