Polylactide. II. Discontinuous dry spinning–hot drawing preparation of fibers

The mechanical properties and morphology of poly(L-lactide) fibers, prepared by the dry spinning–hot drawing process using different nonsolvent/chloroform spinning solutions, were studied in relation to fiber in vitro degradability. Acetone, methanol, ethanol, and cyclohexane were used as nonsolvents in the spinning mixture with as-polymerized PLLA, i.e., PLLA containing 10% of residual L-lactide. The tensile strength, structure, and degradability of obtained fibers were mainly governed by the nonsolvent volatility. Generally, the higher the volatility, the higher the strength, and the faster the degradation. The acetone/chloroform spinning system produced fiber with an increased degradation rate in comparison to the pure chloroform spinning system. © 1994 John Wiley & Sons, Inc.     

Ultra-high strength polyethylene by hot drawing of surface growth fibers

Summary Hot drawing at 150°C has been applied to high molecular weight polyethylene fibers produced by flow induced crystallization in a Couette apparatus, referred to as the surface growth technique. A distinct improvement of the tensile properties of the fibers was noticed upon drawing. A tensile strength at break of 4.7 GPa was reached. Drawability is discussed in relation to fiber morphology. The shish-kebab like structure of the surface growth fiber was transformed into a morphology consisting of smooth fibrils upon drawing.     

Two‐stage drawing process to prepare high‐strength and porous ultrahigh‐molecular‐weight polyethylene fibers: Cold drawing and hot drawing

High‐strength and porous ultrahigh‐molecular‐weight polyethylene (UHMWPE) fibers have been prepared through a two‐stage drawing process. Combined with tensile testing, scanning electron microscopy, and small‐angle X‐ray scattering, the mechanical properties, porosity, and microstructural evolution of the UHMWPE fibers were investigated. The first‐stage cold drawing of the gel‐spun fibers and subsequent extraction process produced fibers with oriented lamellae stacks on the surface and plentiful voids inside but with poor mechanical properties. The second‐stage hot drawing of the extracted fibers significantly improved the mechanical properties of the porous fibers because of the formation of lamellar backbone networks on the surface and microfibrillar networks interwoven inside to support the voids. With various processing conditions, the optimized mechanical properties and porosity of the prepared UHMWPE fibers were obtained a tensile strength of 1.31 GPa, a modulus of 10.1 GPa, and a porosity of 35%. In addition, a molecular schematic diagram is proposed to describe structural development under two‐stage drawing, including void formation and lamellar evolution. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42823.     

The effect of hot drawing on the properties of thermotropic polymer fibers

Thermotropic liquid crystal polymers have been modeled as an array of highly ordered polyhedric nematic domains immersed in a less-ordered, nearly isotropic matrix. A function has been defined that expresses the elastic moduli of drawn fibers as a function of orientation and geometry of the nematic domains. When such a material is hot drawn in extension, the domains orient and elongate to produce an orthotropic fibrous phase. Equations are proposed to relate the elastic moduli of the fibers to the draw ratio and the extrusion conditions. Upon annealing of the hot drawn fibers, shrinkage occurs. It is proposed that the shrinkage is the result of a physical transformation from the fibrous state back to the nematic domain structure present before extrusion and drawing. The Avrami equation is used to describe the nucleation and growth processes controlling the shrinkage at constant annealing temperature. The model is shown to correlate experimental data on the elastic properties and the shrinkage of hot drawn PET/PHB60 liquid crystal polymer with the processing conditions.     

High-strength–high-modulus polyimide fibers I. One-step synthesis of spinnable polyimides

Polyimides with aromatic links are synthesized usually in two steps, but a series of aromatic polyimides with large molecular weights sufficient to produce strong fibers were prepared in one step by the reaction of 3,3′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) with various aromatic diamines. The one-step polycondensation was possible even when BPDA was replaced to some extent by pyromellitic dianhydride, which is a basic component in the conventional two-step method. The copolyimides based on BPDA and mixtures of aromatic diamines were also synthesized in similar manner. For the one-step polycondensation, phenol and some of its derivatives were found to be suitable solvents, while the typical solvent employed in the two-step method, such as N-methyl-2-pyrrolidone, could not be used because of the precipitation of low-molecular weight polyimides. p-Hydroxybenzoic acid proved to be a very efficient accelerator for the conversion of polyamic acids to polyimides.     

Preparation of high-modulus poly(ethylene terephthalate) fibers by vibrating hot drawing

A novel drawing method, vibrating hot drawing, was successfully applied to poly(ethylene terephthalate) fiber, which has a normal molecular weight (IV = 0.7 dL/g) and was prepared by melt spinning. The process was divided into three steps, with differing conditions in drawing temperature, applied tension, vibrating frequency, and amplitude. The drawing temperature and vibration frequency were decided by considering the α_a dispersion of the polymer. In spite of a low draw ratio (7.7) and a low crystallinity (0.55), the birefringence and dynamic storage modulus at room temperature of the 3rd-step fiber reached 0.260 and 36 GPa, respectively. The modulus remains at a high level at elevated temperatures, for example, 29 GPa at 100°C and 17 GPa at 200°C. Further, it was found from temperature and intensity of the α_a dispersion peak that the movements of amorphous chains are strongly inhibited. © 1996 John Wiley & Sons, Inc.     

Preparation of high-modulus nylon 6 fibers by vibrating hot drawing and zone annealing

To prepare high-modulus fibers, the vibrating hot-drawing and zone-annealing methods have been applied to nylon 6. The vibrating hot drawing was repeated two times, increasing the applied tension; further, the zone annealing was superposed on the vibrating hot-drawn fibers. The superstructure and mechanical properties of each step fiber were investigated. The vibration under a cooperation of heating and tension was very useful for increasing the draw ratio, birefringence, and orientation factor of the amorphous chains. Consequently, the obtained fiber indicated high moduli, namely, Young's modulus of 23 GPa and the dynamic storage modulus at room temperature of 25.3 GPa. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1993–2000, 1998     

Copolyester studies. III. Melt-spinning,drawing, and mechanical properties of tetramethylene terephthalate–tetramethylene sebacate copolymer fibers

Fibers have been prepared from tetramethylene terephthalate–tetramethylene sebacate copolymers, containing up to 20 mol % of the latter, using a conventional melt-spinning technique. The mechanical properties of these undrawn fibers and of highly oriented fibers prepared from them have been evaluated. The changes in mechanical properties brought about by the introduction of sebacate groups in poly(tetramethylene terephthalate) have been related to the glass-transition temperatures of the copolymers and to the flexible nature of the sebacate unit. The formation of voids during a continuous drawing process and during mechanical testing is discussed.     

Thermoplasticization of bagasse. I. preparation and characterization of esterified bagasse fibers

This research was to investigate the conversion of bagasse into a thermoformable material through esterification of the fiber matrix. For this purpose, bagasse was esterified in the absence of solvent using succinic anhydride (SA). The reaction parameters of temperature reaction, time, and amount of succinic anhydride added were studied. Ester content, Fourier transform infrared (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic mechanical thermal analysis (DMTA) were used to characterize the chemical and thermal properties of the esterified fibers. The results showed that on reacting bagasse with SA in the absence of solvent, ester content up to about 48% could be obtained. Diester formation increased with increasing reaction time and temperature at high levels of ester content. Ester content determination of the esterified fibers and their corresponding holocelluloses showed that the reaction took place in the lignin and holocellulose components of bagasse. The IR results showed that the crystallinity index of different esterified bagasse samples did not decrease as a result of increasing the ester content. DSC and TGA results showed that esterified‐bagasse fibers were less thermally stable than the untreated fibers. DMTA results showed that esterification of the fibers resulted in a decrease in the tan δ peak temperature of the esterified fibers compared to the untreated fiber. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 561–574, 2000     

Polylactide. III. Fiber preparation by spinning in precipitant vapor

The mechanical properties and morphologies of poly(L-lactide) (PLLA) fibers, prepared by spinning in different vapor precipitants and hot drawing afterward, were studied in relation to fiber in vitro degradability. Petrolether, methanol, and ethanol were employed as precipitants. PLLA was used as-polymerized, i.e., with 10% of residual L-lactide. The tensile strength, structure, and degradability of obtained fibers were mainly governed by the nonsolvent concentration in the vapor phase. Using methanol as the precipitant for the fiber preparation, total tensile strength loss was achieved during 12 wk of in vitro degradation. © 1994 John Wiley & Sons, Inc.     

Graft copolymer modification of polyethylene–polystyrene blends. I. Graft preparation and characterization

The preparation and characterization of styrene–low-density polyethylene graft copolymers for addition to blends of polyethylene and polystyrene to improve blend mechanical properties is described. The direct method of grafting with ⁶⁰Co radiation was employed using the polyethylene in pellet form. This approach gave good grafting efficiency with maximum yields limited to about 1 g of styrene reacted per gram of polyethylene. Excessive crosslinking at radiation doses beyond about 1 mrad was detrimental to the melt processibility of the graft. Crystallinity, dynamic mechanical properties, morphology, and stress–strain behavior of the grafts were examined and compared with melt blends of similar composition in order to better characterize the material produced.     

Polylactide toughening with epoxy‐functionalized grafted acrylonitrile–butadiene–styrene particles

Glycidyl methacrylate functionalized acrylonitrile–butadiene–styrene (ABS‐g‐GMA) particles were prepared and used to toughen polylactide (PLA). The characteristic absorption at 1728 cm^?1 of the Fourier transform infrared spectra indicated that glycidyl methacrylate (GMA) was grafted onto the polybutadiene phase of acrylonitrile–butadiene–styrene (ABS). Chemical reactions analysis indicated that compatibilization and crosslinking reactions took place simultaneously between the epoxy groups of ABS‐g‐GMA and the end carboxyl or hydroxyl groups of PLA and that the increase of GMA content improved the reaction degree. Scanning electron microscopy results showed that 1 wt % GMA was sufficient to satisfy the compatibilization and that ABS‐g‐GMA particles with 1 wt % GMA dispersed in PLA uniformly. A further increase of GMA content induced the agglomeration of ABS‐g‐GMA particles because of crosslinking reactions. Dynamic mechanical analysis testing showed that the miscibility between PLA and ABS improved with the introduction of GMA onto ABS particles because of compatibilization reactions. The storage modulus decreased for the PLA blends with increasing GMA content. The decrease in the storage modulus was due to the chemical reactions in the PLA/ABS‐g‐GMA blends, which improved the viscosity and decreased the crystallization of PLA. A notched impact strength of 540 J/m was achieved for the PLA/ABS‐g‐GMA blend with 1 wt % GMA, which was 27 times than the impact strength of pure PLA, and a further increase in the GMA content in the ABS‐g‐GMA particles was not beneficial to the toughness improvement. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Ionomer studies of polyethylene–acrylic acid copolymer. I. Fiber preparation and properties

Two EAA (Ethylene/acrylic acid) copolymers from Dow Chemical Company have been studied. Primacor resin (5980), having a mol wt of about 30,000 and an acrylic acid content of 19.2%, was converted into 10 and 20 denier per filament fibers to create a high surface area. Cold drawing and use of a fiber lubricant helped prevent sticking and blocking during spinning. The fiber was optimally swollen in a 0.5 N caustic at 55°C to produce an ion exchange fiber. Primacor resin (5980) in pellet form was reacted with alkali and was subsequently hammermilled into an ion exchange porous particulate. Physical and chemical properties, such as thermal properties, swelling, cation exchange activity and selectivity, tensile and elongation properties, among others, were determined on the fiber before and after conversion to specific metal (cationic) forms. The swollen fibers appeared to have more cation binding capacity than hammermilled pellets. The EAA polymers were colored by some metal cations. Some metal cations could be preferentially removed from solutions of mixed cations. Most fibers were weak, even after exchanging with multivalent ions, and did not have a precise melting point. Fiber tension and solution pH during the cationic exchange had an effect on the cation uptake, as well as on the physical properties obtained. © 1993 John Wiley & Sons, Inc.     

Polyethylene composite fibers. I. Composite fibers of high‐density polyethylene

Polymer matrix composites are generally studied in the form of bulk solids, and very few works have examined composite fibers. The research described here extended such bulk studies to fibers. The question is whether or not what has been reported for bulk polymers will be the same in fibers. In this article are reported studies of high‐density polyethylene (HDPE), whereas those of linear low‐density polyethylene are reported in part II of this article series. Two types of filler were used, that is, organically modified montmorillonite (OMMT), in which the nanosized filler particles had a high aspect ratio, and microsized calcium carbonate (CaCO₃), with an aspect ratio nearer to unity. Composite fibers of both as‐spun and highly drawn forms were prepared, and their structures, morphology, and mechanical properties were studied. It was found that the microsized particles gave HDPE composite fibers with mechanical properties that were the same as those of the neat polymer. In the case of clay composite fibers, the clay interfered with the yield process, and the usual yield point could not be observed. The particle shape did not affect the mechanical properties. The fibers showed different deformation morphologies at low draw ratios. The CaCO₃ composite fibers showed cavities, which were indicative of low interaction between the polymer and the filler. The OMMT composite fibers showed platelets aligned along the fibers and good polymer–filler interaction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

High-strength–high-modulus polyimide fibers II. Spinning and properties of fibers

The polyimides based on 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) described in Part I of this series were dissolved in p-chlorophenol and spun into fibers using a coagulating bath of ethanol. The fibers as spun had in general low tenacities and low moduli, but a heat treatment at 300–500°C under tension produced a remarkable increase in strength and modulus, and fibers with a tensile strength of 26 g/den (3.1 GPa) and an initial modulus higher than 1,000 g/den (120 GPa) could be obtained. Thus, the annealed fibers of polyimides are comparable to aramid fibers in mechanical properties. To heating in air and in the saturated steam, the polyimide fibers showed higher resistance than the aramid fibers. The polyimide fibers surpassed the aramid fibers in resistance to acid treatment and ultraviolet (UV) irradiation, but were inferior in resistance to alkali treatment. The annealed fibers of polyimides displayed distinct X-ray diffraction patterns. The chain repeat distance of 20.5 Å determined on the fibers of polyimide prepared from BPDA and o-tolidine, and 20.6 Å determined on the fibers of polyimide derived from BPDA and 3,4′-diaminodiphenyl ether are reasonable when the dimensions of monomeric units and the shapes of the molecular chains are considered. The X-ray reflections of both polyimide fibers were indexed satisfactorily on the basis of postulated unit cells.     

Effect of hot drawing on properties of wet‐spun poly(L,D‐lactide) copolymer multifilament fibers

Polylactide stereocopolymer multifilament fibers were prepared by wet spinning and subsequent hot drawing. The stereocopolymers were poly‐(L,D ‐lactide) [P(L,D )LA], L/D ratio 96/4, and poly‐(L,DL ‐lactide) [P(L,DL )LA], L/DL ratio 70/30. They were dissolved in dichloromethane and coagulated in a spin bath containing ethanol. The hot‐drawing temperature was 65°C. The draw ratios (DR) were upto 4.5 to the P(L,D )LA 96/4 filaments and upto 3 to the P(L,DL )LA 70/30 filaments. Wet spinning decreased crystallinities of both copolymers. Hot drawing increased the crystallinity of the P(L,D )LA 96/4 filament but not to the level of the original copolymer, whereas the as‐spun and the hot‐drawn P(L,DL )LA 70/30 filaments were amorphous. The filament diameter, tenacity, Young's modulus, and elongation at break were dependent on the DR. The maximum tenacity (285 MPa) and Young's modulus (2.0 GPa) were achieved with the P(L,D )LA 96/4 filament at the DR of 4.5. Respectively, the maximum tenacity of the hot‐drawn P(L,DL )LA 70/30 filament was 175 MPa and Young's modulus 1.3 GPa at the DR of 3. Hot drawing slowed down in vitro degradation rate of both stereocopolymer filaments. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polylactide,nanoclay, and core–shell rubber composites

Three types of composites, namely, polylactide (PLA)/nanoclay, PLA/core–shell rubber, and PLA/nanoclay/core–shell rubber, were melt compounded via a corotating twin‐screw extruder. The effects of two types of organically modified montmorillonite nanoclays (i.e., Cloisite®30B and 20A), two types of core (polybutylacrylate)–shell (polymethylmethacrylate) rubbers (i.e., Paraloid EXL2330 and EXL2314), and the combination of nanoclay and rubber on the mechanical and thermal properties of the composites were investigated. According to X‐ray diffraction and transmission electron microscopy analyses, both types of PLA/5 wt% nanoclay composites had an intercalated morphology. In comparison with pure PLA, both types of PLA/5 wt% nanoclay composites had an increased modulus, similar impact strength, slightly reduced tensile strength, and significantly reduced strain at break. On the other hand, PLA/EXL2330 composites with a rubber loading level of 10 wt% or higher had a much higher impact strength and strain at break, but a lower modulus and strength when compared with pure PLA. The simultaneous addition of 5 wt% nanoclay (Cloisite®30B) and 20 wt% EXL2330 resulted in a PLA composite with a 134% increase in impact strength, a 6% increase in strain at break, a similar modulus, and a 28% reduction in tensile strength in comparison with pure PLA. POLYM. ENG. SCI. 46:1419–1427, 2006. © 2006 Society of Plastics Engineers     

Reactive extrusion vs. batch preparation of starch–g–polyacrylonitrile

Acrylonitrile (AN) was graft polymerized onto unmodified cornstarch by a continuous reactive extrusion process and, for comparison, by a typical batch reaction process. The effect of AN/starch weight ratios, level of ceric ammonium nitrate (CAN) initiator, starch in water concentration, reaction temperature, reaction time, and extruder screw speed in the reactive extrusion process was studied. Add-on, reaction efficiency, grafting frequency, weight average molecular weight (MW) and MW distribution of polyacrylonitrile (PAN), and water absorbency of the saponified copolymers were determined. Processing times in the twin-screw extruder (ZSK) were 2–3 min, and total reaction time was about 7 min before reaction of the extruded material was terminated, compared to a reaction time of 2 h used in the typical batch procedure. The continuous reactive extrusion process was found to be a rapid and efficient means of preparing St-g-PAN with high add-on (% PAN of the grafted product). For example, 42% add-on was achieved within the 7-min reaction period using an AN/starch weight ratio of 1.0 (3.5% CAN, starch weight basis), as compared to 38–49% for the 2-h batch process (0.75–1.5 AN/starch ratio). Percentages of homopolymer of the copolymers were low for both extrusion and batch processes. Grafting frequencies were substantially higher while MWs were significantly lower for grafts from the extrusion process. Water absorbency of the saponified St–g–PAN products was somewhat greater for the products prepared by the batch process.     

The drawing behavior of polyvinylalcohol fibers

The solid-state drawing behavior and properties of solution-spun polyvinylalcohol fibers were investigated. A comparsion was made with solution-spun, ultra-drawn polyethylene fibers. The maximum attainable draw ratio of polyvinylalcohol fibers is low (～ 20), even at optimized conditions with respect to polymer concentration in solution. In contrast to polyethylene, the maximum attainable draw ratio hardly increases with increasing molecular weight. However, high modulus (～ 70 GPa) and strength (～ 2.3 GPa) polyvinylalcohol fibers can be produced, despite the low maximum attainable draw ratio. It is suggested that the observed phenomena, with respect to both the drawing behavior and properties of polyvinylalcohol fibers, originate from intermolecular hydrogen bonds in the polymer.