Direct fiber formation and fiber properties of aromatic polyoxadiazoles

A novel and simple fiber formation process has been developed to fabricate aromatic polyoxadiazoles. The aromatic copolyoxadiazole solution prepared from terephthalic acid, isophthalic acid, and hydrazine sulfate in fuming sulfuric acid was utilized directly as spinning solution and was successfully wet-spun to form fiber into a coagulating bath containing sulfuric acid. In the wet-spinning process, selection of the coagulating bath was the most important factor, and the best results were obtained by the use of approximately 50 wt-% aqueous sulfuric acid. It was easy to prepare a polyoxadiazole fiber having a tenacity of more than 4 g/den. and an elongation of more than 10%. In addition, the fiber properties reached to a tenacity of 6 g/den. and an elongation of 12% under optimum spinning conditions. The wet-spun polyoxadiazole fiber showed an almost round cross section and a clear skin-core structure by microscopic observation. The fiber had a high level of thermal and dimensional stability and a high proportion of property retention at elevated temperatures, as well as all-round general fiber properties.     

Effect of air-gap distance on the morphology and thermal properties of polyethersulfone hollow fibers

By using 30/70 polyethersulfone/NMP (N-methyl-2-pyrrolidone) solutions as an example, we have determined the role of air-gap distance on nascent fiber morphology, performance, and thermal properties. An increase in air-gap distance results in a hollow fiber with a less layer of fingerlike voids and a significant lower permeance. For the first time we have reported that the T_g of a dry-jet wet-spun fiber prepared from one-polymer/one-solvent systems is lower than that of a wet-spun fiber, and T_g decreases with an increase in air-gap distance. These interesting phenomena arise from the fact that different precipitation paths take place during the wet-spinning and dry-jet wet-spinning processes. Wet-spun fibers experience vigorous and almost instantaneous coagulations; it results in hollow fiber skins with a long-range random, unoriented chain entanglement, but loose structure. Dry-jet wet-spun fibers first go through a moisture-induced phase separation process and then a wet-phase inversion process; it results in external fiber skins with a short-range random, compact, and slightly oriented or stretched structure. As a result, the outskin of wet-spun fibers have a greater free volume and a higher first T_g than that of the dry-jet wet-spun ones. Both SEM (scanning electronic microscope) photomicrographs and DSC (differential scanning calorimeter) analyses support our conclusion. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1067–1077, 1997     

Processing and properties of phthalic anhydride modified soy protein/glycerol plasticized soy protein composite films

Phthalic anhydride modified soy protein (PAS)/glycerol plasticized soy protein (GPS) composite films were fabricated by using extrusion and compression‐molding. Modified with phthalic anhydride, the soy protein lost its thermoplastic ability and was used as a filler to reinforce the GPS matrix. Fourier transform infrared spectra, optical transmittance, scanning electron microscope, mechanical tests, water resistance tests, as well as thermo‐gravimetric analysis were carried out to investigate the structure and properties of PAS and the plastic composites. The similar chemical structure of PAS and GPS led to compatibility of the two components resulting in high transparency and enhanced tensile properties of the composites. The water resistance of GPS was also improved by the incorporation of PAS. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42221.     

Preparation and properties of alginate superabsorbent filament fibers crosslinked with glutaraldehyde

Superabsorbent filament fibers based on sodium alginate were prepared using glutaraldehyde as a crosslinking agent. Alginate was extruded into an aqueous hydrochloric acid coagulation bath to form continuous alginic acid gel fibers via a wet‐spinning method. The alginic acid gel fibers were dehydrated by exchanging water with dioxane, crosslinked, then neutralized for better absorbency. Crosslinked alginate filaments exhibited a high saline solution and synthetic urine absorbencies, maintaining the integrity of the fiber structure. Maximum synthetic urine absorbency was obtained with the fiber crosslinked at a lower glutaraldehyde concentration compared with that required for maximum saline solution absorbency. This appears to be due to the crosslinking effect of calcium ions in the synthetic urine solution being absorbed. Strain and tenacity of the crosslinked alginate fibers decreased with an increasing amount of glutaraldehyde used in the crosslinking reaction. The decrease in tenacity was not significant while the strain showed an extensive decrease. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1797–1804, 2000     

Macrostructure and mechanical behavior of fibers of poly-p-phenylene benzobisthiazole

Morphology and tensile behavior of wet-spun fibers of poly-p-phenylene benzobisthiazole have been investigated. The as-spun fibers contain a large number of voids, which result in void-localized tensile failure. The stress–strain behavior is elastic–plastic with strain hardening. This behavior is shown to be the result of residual stresses which arise during the wet-spinning process.     

Functionalization of Crosslinked Sodium Alginate/Gelatin Wet-Spun Porous Fibers with Nisin Z for the Inhibition of Staphylococcus aureus-Induced Infections

Nisin Z, an amphipathic peptide, with a significant antibacterial activity against Gram-positive bacteria and low toxicity in humans, has been studied for food preservation applications. Thus far, very little research has been done to explore its potential in biomedicine. Here, we report the modification of sodium alginate (SA) and gelatin (GN) blended microfibers, produced via the wet-spinning technique, with Nisin Z, with the purpose of eradicating Staphylococcus aureus-induced infections. Wet-spun SAGN microfibers were successfully produced at a 70/30% v/v of SA (2 wt%)/GN (1 wt%) polymer ratio by extrusion within a calcium chloride (CaCl₂) coagulation bath. Modifications to the biodegradable fibers’ chemical stability and structure were then introduced via crosslinking with CaCl₂ and glutaraldehyde (SAGNCL). Regardless of the chemical modification employed, all microfibers were labelled as homogeneous both in size (≈246.79 µm) and shape (cylindrical and defect-free). SA-free microfibers, with an increased surface area for peptide immobilization, originated from the action of phosphate buffer saline solution on SAGN fibers, were also produced (GNCL). Their durability in physiological conditions (simulated body fluid) was, however, compromised very early in the experiment (day 1 and 3, with and without Nisin Z, respectively). Only the crosslinked SAGNCL fibers remained intact for the 28 day-testing period. Their thermal resilience in comparison with the unmodified and SA-free fibers was also demonstrated. Nisin Z was functionalized onto the unmodified and chemically altered fibers at an average concentration of 178 µg/mL. Nisin Z did not impact on the fiber’s morphology nor on their chemical/thermal stability. However, the peptide improved the SA fibers (control) structural integrity, guaranteeing its stability for longer, in physiological conditions. Its main effect was detected on the time-kill kinetics of the bacteria S. aureus. SAGNCL and GNCL loaded with Nisin Z were capable of progressively eliminating the bacteria, reaching an inhibition superior to 99% after 24 h of culture. The peptide-modified SA and SAGN were not as effective, losing their antimicrobial action after 6 h of incubation. Bacteria elimination was consistent with the release kinetics of Nisin Z from the fibers. In general, data revealed the increased potential and durable effect of Nisin Z (significantly superior to its free, unloaded form) against S. aureus-induced infections, while loaded onto prospective biomedical wet-spun scaffolds.     

甘油合成环氧氯丙烷氯化阶段催化剂选择研究

针对甘油法合成环氧氯丙烷第一阶段——氯化阶段的工作,对催化剂进行筛选与复配实验,确定了具有较好催化活性且环境友好的二元催化剂配方——己二酸与乙酸酐。该催化剂在反应温度为115℃,反应时间为5 h,原料甘油40 g,氯化氢通气量200 m L/min,催化剂总量为甘油的7.5%(m/m),m(己二酸)∶m(乙酸酐)=3∶2时,二氯丙醇收率69.5%,甘油转化率达99%。     

Biodegradable soy protein–polyester blends by reactive extrusion process

Blends of soy protein concentrate and biodegradable polyester (Eastar Bio Copolyester, EPE) were prepared by using glycerol as a compatibilizing agent. Good miscibility was obtained only when the soy protein was initially combined with glycerol under high shear and at elevated temperatures in an extruder. Under these conditions, partial denaturing of the soy protein led to specific interactions between functional groups of the protein with the glycerol. The extrusion conditions and appropriate screw configuration were the critical factors affecting the reactivity of the protein and hence, the properties of the blends. Screws with large kneading blocks that produced high shear mixing were preferred and led to thermoplastic blends characterized by high elongation and high tensile strength. The morphology of these soy protein/polyester blends was studied by using environmental scanning electron microscopy (ESEM) and indicated good wetting of the soy protein particles within the polyester matrix. The thermal properties were studied by differential scanning calorimetry (DSC) and showed a lower degree of crystallinity and a continuous depression of the melting point of the polyester as the concentration of protein was increased. The possibility of using soy protein concentrate instead of the more expensive (higher purity) soy protein isolate in the preparation of biodegradable resins should lead to new commercial opportunities based on renewable, agricultural byproducts. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3231–3239, 2004     

A new crosslinked protein fiber from gliadin and the effect of crosslinking parameters on its mechanical properties and water stability

BACKGROUND: Although several cereal proteins have been used to develop fibers and films, it has not been possible to obtain protein materials with good mechanical properties and water stability, even after crosslinking. Previously, high concentrations of glutaraldehyde were used to improve the mechanical properties of protein fibers but the effect of crosslinking conditions on the properties of the crosslinked materials has not been studied in detail. RESULTS: Low concentrations of glutaraldehyde can be used to improve the mechanical properties and water stability of gliadin fibers. Quantitative relationships that can predict the breaking tenacity of the fibers at various crosslinking conditions are developed. Glutaraldehyde crosslinking is more resistant to hydrolysis in neutral pH than under acidic conditions in terms of increasing and retaining the breaking tenacity. The crosslinked fibers show improved resistance to hydrolysis over poly(lactic acid) fibers in aqueous dispersions at pH = 4 and 7 at 50 and 90 °C, respectively. CONCLUSIONS: This study shows that low concentrations of glutaraldehyde can impart excellent mechanical properties to gliadin fibers. The quantitative relationships developed can be used to select the crosslinking conditions such low glutaraldehyde concentration and high temperature or vice versa to obtain the desired improvement in mechanical properties or water stability. Copyright © 2008 Society of Chemical Industry     

Exploring the effects of non-solvent concentration, jet-stretching and hot-drawing on microstructure formation of poly(acrylonitrile) fibers during wet-spinning

The simultaneous effects of non-solvent concentration in the spinning dope, jet-stretching and hot-drawing on porosity, morphology development and mechanical properties of wet-spun poly(acrylonitrile) fibers were studied. Addition of non-solvent to the spinning dope increased dope viscosity, the entanglement density of the polymeric solution and the number of entanglements per chain. Drawability of the as-spun fiber depended on the number of entanglements per polymer chain. Therefore, addition of non-solvent improved or spoiled drawability of the wet-spun fibers based on the concentration of the initial spinning dope. Hot-drawing and jet-stretching did not affect the fraction of nanovoids but shifted their size distribution towards smaller values. However, hot-drawing was more effective in reducing the overall porosity of the fibers in comparison with jet-stretching. Fiber tenacity increased when overall porosity decreased. Finally, strength-diameter correlation showed good agreement with the Griffith’s theory.     

Recycled polypropylene reinforced with curaua fibers by extrusion

Curaua fibers were studied as reinforcing agents for postconsumer polypropylene. The composites were processed by extrusion. The composite properties were investigated by mechanical tests, thermal methods, melt flow index, surface morphology, and water uptake. The variables studied were as follows: fiber contents (10 to 40 wt %), fiber surface treatment, initial fiber length, and modification of the polypropylene matrix. The treatment of the fiber with 5 wt % NaOH aqueous solution did not improve fiber‐matrix adhesion and the composites using 20 wt % of untreated curaua fibers presented the better mechanical properties. Feeding the extruder with fibers having shorter lengths (0.01–0.4 mm) produced better fiber dispersion, improving the mechanical properties of the composites. Composites prepared using fibers without surface treatment with postconsumer polypropylene and with polypropylene modified with maleic anhydride showed mechanical properties and water uptake similar to composites using the same polymer reinforced with other lignocellulosic fibers. The extrusion process caused also partial fibrillation of the fibers, improving their aspect ratio. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

硬脂酸对大豆蛋白质塑料性能的影响

对水的敏感性是阻碍大豆蛋白质降解塑料广泛应用的不利因素,为了克服这一缺点,实验固定甘油和大豆蛋白质的比例,通过添加硬脂酸与大豆蛋白质共混,研究了其添加量对机械性能和吸水率的影响。同时拉伸和红外、扫描电镜等实验表明甘油、硬脂酸对膜的力学性能、吸水率、断面形态、红外图谱均有影响。     

Flaking and extrusion as mechanical treatments for enzyme-assisted aqueous extraction of oil from soybeans

Flaking and extruding dehulled soybeans were evaluated as a means of enhancing oil extraction efficiency during enzyme-assisted aqueous processing of soybeans. Cellulase, protease, and their combination were evaluated for effectiveness in achieving high oil extraction recovery from extruded flakes. Aqueous extraction of extruded full-fat soy flakes gave 68% recovery of the total available oil without using enzymes. A 0.5% wt/wt protease treatment after flaking and extruding dehulled soybeans increased oil extraction recovery to 88% of the total available oil. Flaking and extruding enhanced protease hydrolysis of proteins freeing more oil. Treating extruded flakes with cellulase, however, did not enhance oil extraction either alone or in combination with protease. Discrepancies in oil extraction recoveries were encountered when merely considering crude free fat because some oil became bound to denatured protein during extrusion and/or sample drying. Bound fat was unavailable for determination by using the hexane extraction method, but was accounted for by using the acid hydrolysis method for total oil determination. Oil extraction recovery from extruded soybean flakes was affected by oil determination methods, which was not the case for unextruded full-fat soy flour.     

Investigation of wet-spun acrylic fiber morphology by membrane technology techniques

The as-formed structure of wet-spun acrylic fiber from the sodium thiocyanate system has been probed, exploiting a number of techniques developed in the membrane industry. The use of flat membrane geometry in the study of wet-spun fibers has been proven to be valid. The calculation of average pore dimensions in the surface of acrylic membrances by a hydraulic permeability method has agreed well with microscopic examination. The skin layer present on both fibers and membrances has been shown to be structurally isotropic for the extruded fiber by a novel polarized infrared microspectroscopy technique. The consequences of this in downstream processing are discussed. © 1996 John Wiley & Sons, Inc.     

Effect of dope extrusion rate on the formation and characterization of polyacrylonitrile nascent fibers during wet-spinning

Polyacrylonitrile nascent fibers were prepared via the wet-spinning technique and a dimethyl sulphoxide/H₂O coagulation bath system was adopted. The objective of this study was to investigate the influence of dope extrusion rates on formation and characterization of nascent fibers. Nine different dope extrusion rates were adopted when other technique parameters were kept steady. The surface morphology of nascent fibers was observed by field emission scanning electron microscopy. The results showed that the dope extrusion rates played significant effects on the cross-section structure, surface morphology, degree of crystallization, and sound velocity of the nascent fibers. With an increase of dope extrusion rate, the surface roughness increased, and the sound velocity had a point of inflexion. Moreover, the degree of crystallization had a maximum when the dope extrusion rate was 5.92 m/min.     

Fibers from urea–formaldehyde resins

The preparation of fibers from aqueous urea–formaldehyde resins has been investigated; a dry spinning process has been developed based on the extrusion of catalyzed resin into a drying chamber at 180–220°C, producing a multifilament yarn at spinning speeds of up to 600 m/min. A range of UF filaments was produced with diameters between 10–70 μm; the tenacities of spun filaments were 6–10 cN/tex, initial moduli were 220–340 cN/tex, and elongation at break was 4–10%. The best tensile properties resulted from conditions that produced the smallest diameter fibers. Postspin heat treatment improved the tenacity to 14 cN/tex and the elongation to 20%. Spinnability improved with increased viscosity of the spinning solution and increased cell temperature, while tenacity and elongation increased with increasing cell temperature and spinning stretch. A correlation was found between TGA weight loss (between 105 and 200°C) and fiber tenacity. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 64–74, 2000     

三醋酸甘油酯绿色合成工艺

用甘油与醋酸、醋酐或醋酸与醋酐混合物作反应物,以五水四氯化锡(SnCl4.5H2O)和磷钨酸(H3O40-PW1.2xH2O)作催化剂,合成三醋酸甘油酯。研究了不同工艺条件对反应产率的影响。结果证明,用醋酐或醋酐加醋酸混合物优于仅用醋酸,适宜的物料比为:甘油∶醋酸∶醋酐=1∶2∶1(摩尔比)。用SnCl4.5H2O催化,优于杂多酸。以甲苯作带水剂适宜的反应温度为105~120℃,脱溶温度为120~140℃,产率达85%~90%。反应与精馏单釜完成。工艺简单,污染少。     

Influence of drawing speed on some properties of acrylic fibers

The effect of drawing speed on several properties of acrylic fibers has been examined. The acrylic fibers were prepared by the wet-spinning process. The coagulation bath contained 30–70% DMF and was held at a temperature varying from 10–45°C. From x-ray diffraction measurement, the orientation of finished fibers increased with an increase in drawing speed, and became constant when the drawing speed exceeded 40–50 m/min. The tenacity and stability to repetitive deformation also increased to a drawing speed of 40–50 m/min, but then decreased. The spinning conditions (spin-bath composition and temperature) influenced the most attainable properties of the finished fibers. The results are discussed from the point of view of structural changes in fibers during drawing.     

Tensile properties of chemically modified ring- and rotor-spun cotton yarns

The effects of chemical treatments and modifications on the tensile properties of ring-and rotor-spun cotton yarns is discussed. The rotor-spun yarns treated with zinc chloride show a higher tenacity at low stretch levels compared to sodium hydroxide, whereas with sodium hydroxide, the rotor-spun yarns show higher tenacity at higher stretch levels compared with zinc chloride. The aqueous-treated rotor-spun yarns show a higher change in tenacity compared to ring-spun yarns. Sodium hydroxide-treated yarns before resin treatment show a higher retained tenacity compared to zinc chloride-treated yarns. The substitution treatment after swelling and stretching to 100% shows a higher tenacity than that of the slack substituted yarns. © 1995 John Wiley & Sons, Inc.     

Extrusion of polypropylene/chitosan/poly(lactic-acid) films: Chemical,mechanical, and thermal properties

Development of extruded films composed of biopolymers blended with synthetic polymers aims to minimize the environmental impact of plastic waste-materials and lead to the sustainable plastic industry. To produce biodegradable polymeric blends, the weight content of biopolymers must be maximum without compromising the performance properties of the extruded films. Using a solvent-free extrusion method, films composed of polypropylene, poly(lactic-acid), and Chitosan, can be obtained with the use of polypropylene-graft-maleic anhydride and glycerol as compatibilizer and plasticizer, respectively. Extruded films with up to a 50 wt% content of biopolymers show acceptable thermal and mechanical properties, where the use of compatibilizer improves the processing characteristics and homogeneous distribution of chitosan throughout the films. Therefore, the extruded films can be considered as alternatives to conventional synthetic-polymer films, due to their acceptable mechanical and thermal properties with direct potential applications in extrusion-method mass production of biodegradable polymers.