Development of a gel spinning process for high‐strength poly(ethylene oxide) fibers

This article describes a new gel‐spinning process for making high‐strength poly(ethylene oxide) (PEO) fibers. The PEO gel‐spinning process was enabled through an oligomer/polymer blend in place of conventional organic solvents, and the gelation and solvent‐like properties were investigated. A 92/8 wt% poly(ethylene glycol)/PEO gel exhibited a melting temperature around 45°C and was highly stretchable at room temperature. Some salient features of a gel‐spun PEO fiber with a draw ratio of 60 are tensile strength at break = 0.66 ± 0.04 GPa, Young's modulus = 4.3 ± 0.1 GPa, and a toughness corresponding to 117 MJ/m³. These numbers are significantly higher than those previously reported. Wide‐angle x‐ray diffraction of the high‐strength fibers showed good molecular orientation along the fiber direction. The results also demonstrate the potential of further improvement of mechanical properties. POLYM. ENG. SCI., 54:2839–2847, 2014. © 2014 Society of Plastics Engineers     

Gel spinning of UHMWPE fibers with polybutene as a new spin solvent

Gel spinning of UHMWPE fibers using low molecular weight polybutene (PB) as a new spin solvent was investigated. A 98/2 wt% PB/UHMWPE gel exhibits a melting temperature around 115°C and shows large‐scale phase separation upon cooling the solution to room temperature. The resulting precursor fiber from this gel was hot‐drawn to a ratio of 120, yielding a fiber with tensile strength of 4 GPa and Young's modulus of over 150 GPa. Wide‐angle X‐ray diffraction indicates good molecular orientation along the fiber axis. The results also demonstrate the potential to further improve the mechanical properties. With respect to the gel spinning industry, this new solvent has a number of advantages over paraffin oil and decahydronaphthalene, and holds a promise of greatly improving the process efficiency. POLYM. ENG. SCI., 56:697–706, 2016. © 2016 Society of Plastics Engineers     

Wet spinning of aliphatic and aromatic polyamides

Bench-scale equipment for wet spinning was designed and built. An experimental study of the wet spinning of several polyamides has been carried out. The polymers studied include nylon 6, nylon 66, redissolved Nomex, and redissolved Kevlar. The superstructure of the wet-spun fibers were studied by optical and scanning electron microscopy as well as small- and wide-angle x-ray diffraction. Mechanical properties were measured and related to the spinning variables. For nylon 6 and nylon 66, the coagulation bath composition was found to be of major importance in determining fiber superstructure. For the case of the redissolved Kevlar, anisotropic spinning dopes were obtained from redissolved fiber, and the wet-spun filaments produced from such solutions were investigated. These fibers proved to have relatively high modulus and strength as spun. They had even greater strengths after hot drawing.     

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     

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     

Resorbable materials of poly(L-lactide). II. Fibers spun from solutions of poly(L-lactide) in good solvents

Fibers of poly(L -lactide) (PLLA) with a tensile strength up to 1.2 GPa and Young's modulus in the range of 12–15 GPA were obtained by a hot drawing of fibers spun from solution of PLLA in good solvents such as dichloromethane and trichloromethane. The tensile strength of fibers was strongly dependent on the molecular weight of PLLA and on polymer concentrations in the spinning solution. Changing of the polymer concentration in the spinning solution gives rise to formation of fibers with different shape and porosity. Fibers spun from 10–20% solutions at room temperature exhibit a regular structurization, due to the melt fracture. These fibers had knot strengths up to 0.6 GPa, whereas fibers with a smooth surface spun from more dilute solutions had weaker square knots up to 0.3 GPa.     

Direct drawing of gel fibers enabled by twist‐gel spinning process

A new twist‐gel spinning process for ultrahigh molecular weight polyethylene fibers is demonstrated which significantly increases the extraction rate of nonvolatile spin solvent while simultaneously reducing the consumption of extraction solvent by more than 75%. Applying twist to the gel fiber enables it to be directly hot‐drawn, allowing conventional solvent extraction to proceed significantly faster. While solvent extraction effectiveness is largely enhanced, the new process does not show reduced fiber properties. The tensile strength, Young's modulus, surface morphology, and geometry are relatively unaffected when compared to fibers produced using the conventional gel‐spinning process. The new twist‐gel spinning process is expected to improve the processing efficiency of gel‐spun high‐strength fibers, promoting broad expansion of these high performance fibers into applications that were previously prohibitive due to extremely slow production. POLYM. ENG. SCI., 55:1389–1395, 2015. © 2015 Society of Plastics Engineers     

High performance cellulose fibers regenerated from 1-butyl-3-methylimidazolium chloride solution: Effects of viscosity and molecular weight

In the present study, we focused on several factors affecting the utility of 1-butyl-3-methylimidazolium chloride (BMIMCl) for obtaining higher performance fibers. The dependence of the spinnability and tensile strength of the fibers on the zero-shear viscosity of the spinning solutions was investigated based on differences in the molecular weight of the cellulose, pulp concentration, and the pH of BMIMCl. We demonstrated an appropriate viscosity range of 2000–4000 Pa s⁻¹ (100 °C) for spinning dopes to obtain good spinnability and high tensile strength. The pH of the BMIMCl and the molecular weight of the cellulose clearly impacted tensile strength. The high molecular weight of cellulose contributed to high mechanical properties of the regenerated cellulose fibers. Optimizing the molecular weight and concentration of the cellulose based on the appropriate viscosity allowed us to prepare high performance cellulose fibers with a tensile strength of 1.15 GPa and a Young's modulus of 42.9 GPa. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48681.     

High‐strength regenerated cellulose fibers spun from 1‐butyl‐3‐methylimidazolium chloride solutions

High‐performance regenerated cellulose fibers were prepared from cellulose/1‐butyl‐3‐methylimidazolium chloride (BMIMCl) solutions via dry‐jet wet spinning. The spinnability of the solution was initially evaluated using the maximum winding speed of the solution spinning line under various ambient temperatures and relative humidities in the air gap. The subsequent spinning trials were conducted under various air gap conditions in a water coagulation bath. It was found that low temperature and low relative humidity in the air gap were important to obtain fibers with high tensile strength at a high draw ratio. From a 10 wt % cellulose/BMIMCl solution, regenerated fibers with tensile strength up to 886 MPa were prepared below 22 °C and relative humidity of 50%. High strengthening was also strongly linked with the fixation effect on fibers during washing and drying processes. Furthermore, an effective attempt to prepare higher performance fibers was conducted from a higher polymer concentration solution using a high molecular weight dissolving pulp. Eventually, fibers with a tensile strength of ～1 GPa and Young's modulus over 35 GPa were prepared. These tensile properties were ranked at the highest level for regenerated cellulose fibers prepared by an ionic liquid–based process. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45551.     

Predictions of young's modulus of inorganic fibrous particulate‐reinforced polymer composites

In this study, the factors affecting the Young's modulus of inorganic fibrous particulate‐reinforced polymer composites were analyzed, and a new expression of the Young's modulus was derived and was based on a simplified mechanical model. This equation was used to estimate the composite Young's modulus. The estimated relative Young's modulus increased nonlinearly with increasing filler volume fraction. Finally, we verified the equation preliminarily by quoting the measured Young's modulus values of poly(butylene terephthalate)/wollastonite, polypropylene/wollastonite, and nylon 6/wollastonite composites reported in the literature. Good agreement was shown between the predictions and the experimental data of the relative Young's modulus values for these three composite systems. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2957–2961, 2013     

Characterization of jute fibers treated with soap–glycerol micelles

A tossa variety of jute fiber (Corchorus olitorious) treated with soap–glycerol micelles is characterized by infrared (IR) spectroscopy, X‐ray diffraction method, and tensilometry. The IR spectra for jute fibers treated with soap–glycerol micelles show a reduced absorption band due to O H stretching at a frequency of 3420 cm⁻¹ with almost absent OH bending frequencies, prominent CH₂ stretching and bending frequencies at 2915 and 1440 cm⁻¹ and reduced skeletal vibration at 1060 cm⁻¹. The percentage crystallinity measured by the X‐ray diffraction method increases from 45 to 53% on treated jute fibers. The tensile strength and strain percent at maximum load, Young's modulus, and work done per unit volume within an elastic limit (resilience) for treated fibers increased from 1.8 ± 0.2 to 3.43 ± 0.2 GPa, from 3.98 ± 0.1 to 4.75 ± 0.1, from 75 ± 2 to 113 ± 5 GPa, and from 26 ± 2 to 74 ± 3 MJ m⁻³, respectively. Using a stabilizing agent (2%) and a swelling agent (2% KOH), the tensile strength, strain percent, Young's modulus, and resilience increase to 4.02 ± 0.2 GPa, 4.85 ± 0.3, 154 ± 5 GPa, and 95 ± 4 MJ m⁻³, respectively. Under natural weathering at 12–30°C and 30–80% relative humidity over a prolonged period of 8 weeks, all the tensile properties for micelle‐treated fibers increase during the first 2 weeks of exposure and then decrease exponentially to the starting values. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 852–856, 2000     

Properties of bio‐based polymer nylon 11 reinforced with short carbon fiber composites

In this work, micro‐composite materials were produced by incorporating 3‐mm long reclaimed short carbon fibers into bio‐based nylon 11 via melt compounding. A systematic fiber length distribution analysis was performed after the masterbatching, compounding and an injection moulding processes using optical microscopy images. It was found that the large majority of the fibers were within the 200–300 μm in length range after the injection moulding process. The mechanical (flexural and tensile), thermo‐mechanical, and creep properties of the injection moulded materials are reported. We found that an enhancement in flexural and Young's modulus of 25% and 14%, respectively, could be attained with 2 wt% carbon fiber loading whilst no significant drawback on the ductility and toughness of the matrix was observed. The creep resistance and recovery of the nylon 11, tested using dynamic mechanical thermal analysis at room temperature and 65°C, was significantly improved by up to 30% and 14%, respectively, after loading with carbon fiber. This work provides an insight into the property improvement of the bio‐based polymer nylon 11 using a small amount of a reclaimed engineered material. POLYM. COMPOS., 36:668–674, 2015. © 2014 Society of Plastics Engineers     

Preparation and properties of polyimide fibers

Polyimides were synthesized from 4,4′-diamino diphenyl methane and pyromellitic dianhydride using low-temperature solution polycondensation. Solutions of these polyamic acids in dimethyl-formamide (DMF) were spun into fibers by the wet spinning technique using a mixture of DMF and water as coagulants. Various spinning parameters such as dope concentration, bath composition, and jet stretch were standardized to get polyimide fibers with optimum properties. It was observed that fibers spun at higher jet stretch did not cyclize satisfactorily. Higher dope concentrations gave fibers with better properties. Cyclodehydrated fibers were hot-drawn at 300°C. Fibers with a tenacity of 380 mN/tex, an extension at break of 10%, and initial modulus of 4060 mN/tex were obtained. Mechanical properties of fibers at elevated temperatures, i.e., 100 and 200°C were also measured. Heat aging at 100, 200, and 300°C was carried out for 10 hr. This resulted in an increase in the initial modulus of fibers. However, a 28% decrease in tenacity was observed when the fibers were heat-aged at 300°C. The dynamic thermogravimetry in air showed that fibers were stable up to 400°C. The activation energy of decomposition, calculated from these thermograms in the temperature range 540–610°C was 101 kJ/mole.     

Properties of isocyanate‐reactive waterborne polyurethane adhesives: Effect of cure reaction with various polyol and chain extender content

Three series of isocyanate‐reactive waterborne polyurethane adhesives were prepared with various contents of chain extender (4.25/8.25/12.50 mol %) and polyol (20.75/16.75/12.50 mol %). Each series had a fixed amount of excess (residual) NCO group (0.50–2.00 mol %). FTIR and ¹H‐NMR spectroscopy identified the formation of urea crosslink structure mainly above 80°C of various cure temperatures (20–120°C) with excess diisocyanate. The molecular weight, tensile strength, Young's modulus, and adhesive strength depend on excess NCO content and cure temperature and also varied with polyol and chain extender content. The optimum cure temperature was 100°C for all the samples. The tensile strength, Young's modulus, and adhesive strength increased with increasing cure temperature above 60°C up to the optimum temperature) (100°C) and then almost leveled off. Among all the samples, the maximum values of tensile strength, Young's modulus, and adhesive strength were found with 63.22 wt % polyol, 0.93 wt % chain extender, and 1.50 mol % excess (residual) NCO content at 100°C optimum cure temperature. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Microstructural characterization of short glass fiber and PAN based carbon fiber reinforced nylon 6 polymer composites

Microstructural characterization of nylon 6/short glass fiber (SGF) and nylon 6/polyacrolonitrile based carbon fibers (PAN‐CFs) of 10 to 40 wt% has been performed by positron lifetime technique (PLT). The positron lifetime parameters viz., o‐Ps lifetime (τ₃), o‐Ps intensity (I₃), and fractional free volume (F_v) of nylon 6/SGF and nylon 6/PAN‐CF composites are correlated with the mechanical properties viz., tensile strength and Young's modulus. The F_v shows negative deviation with the reinforcement of 10 to 40 wt% of PAN‐CF and show positive deviation in nylon 6/SGF from the linear additivity relation. The negative deviation in nylon 6/PAN‐CF composite suggests the induced molecular packing due to the chemical interaction between the polymeric chains of nylon 6 and PAN‐CF. The positive deviation in nylon 6/SGF composite indicates the formation of interface between the polymeric chains of nylon 6 and SGF. The increased crystallinity of nylon 6/SGF and nylon 6/PAN‐CF composites shows the improved mechanical properties of the composites. The hydrodynamic interaction parameter (h), which shows more negative values in nylon 6/SGF than nylon 6/PAN‐CF composites. However, the extent of chemical interaction in nylon 6/SGF is less compare to nylon 6/PAN‐CF composites. This is evident from Fourier transform infrared spectrometry studies. POLYM. ENG. SCI., 58:1428–1437, 2018. © 2017 Society of Plastics Engineers     

Young's Modulus of Elasticity of Carbon‐Bonded Alumina Materials up to 1450°C

Investigating Young's modulus at elevated temperatures supports the understanding of microstructural changes as a function of application temperature. A sintered alumina and three carbon‐bonded alumina materials with carbon contents of 20 and 30 wt% and alumina grain size of 0.6–3 mm were investigated. Young's modulus was measured in a temperature range from 25°C to 1450°C by the impulse excitation technique. The Young's modulus of carbon‐bonded materials increases up to 140% at 1450°C. After one cycle, a decrease of the Young's modulus up to 50% is registered at room temperature. There is a strong hysteresis behavior during one cycle. Thermal expansion measurements show highest expansion for the highest graphite content material. The expansion of alumina grains and graphite flakes, resulting in microcrack generation during cooling and microcrack healing during heating, is reflected in the registered values of the Young's modulus as a function of the temperature. It is assumed, that higher graphite amounts as well as coarse grains lead to lower sintering effects of the microstructure at elevated temperatures and as a result lower values of the Young's modulus have been registered.     

Mechanical and thermal properties of glass bead–filled nylon‐6

The mechanical and thermal properties of glass bead–filled nylon‐6 were studied by dynamic mechanical analysis (DMA), tensile testing, Izod impact, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) tests. DMA results showed that the incorporation of glass beads could lead to a substantial increase of the glass‐transition temperature (T_g) of the blend, indicating that there existed strong interaction between glass beads and the nylon‐6 matrix. Results of further calculation revealed that the average interaction between glass beads and the nylon‐6 matrix deceased with increasing glass bead content as a result of the coalescence of glass beads. This conclusion was supported by SEM observations. Impact testing revealed that the notch Izod impact strength of nylon‐6/glass bead blends substantially decreased with increasing glass bead content. Moreover, static tensile measurements implied that the Young's modulus of the nylon‐6/glass bead blends increased considerably, whereas the tensile strength clearly decreased with increasing glass bead content. Finally, TGA and DSC measurements indicated that the thermal stability of the blend was obviously improved by incorporation of glass beads, whereas the melting behavior of the nylon‐6 remained relatively unchanged with increasing glass bead content. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1885–1890, 2004     

Mechanical properties of tussah silk fibers treated with methacrylamide

Tussah silk fibers were treated with methacrylamide (MAA). The polymerization of MAA onto tussah silk fibers and the mechanical properties of the MAA-treated tussah silk fibers were investigated. The tanning agent contained in tussah silk fibers acted as an inhibitor to the radical polymerization of MAA. The alkali treatment enhanced the swelling of noncrystalline regions of the tussah silk fibers and promoted the polymerization of MAA onto the tussah silk fibers. The cross-sectional area of the MAA-treated tussah silk fiber was given by the sum of the cross-sectional area of the original silk fiber and that of the MAA polymer. Breaking load of the fibers was almost unchanged by the MAA treatment, while rigidity was markedly increased. Young's modulus of the MAA-treated tussah silk fibers decreased with decreasing volume fractions of the fiber in the MAA-treated tussah silk fibers. Young's modulus of the MAA polymer in the MAA-treated tussah silk fibers was estimated by extrapolating the relation between Young's moduli and the volume fractions of the fiber to zero volume fraction. Young's modulus of the MAA polymer in the MAA-treated tussah silk fibers was significantly larger than the modulus of a MAA polymer plate. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2051–2057, 1997     

Mechanical and dynamic mechanical properties of nylon 66/montmorillonite nanocomposites fabricated by melt compounding

Nylon 66 nanocomposites were prepared by melt compounding of nylon 66 with organically modified montmorillonite (MMT). The organic MMT was pre‐modified with about 14 wt% of ammonium surfactant, much lower than the 35–46 wt% in most commercial organic MMT powders. Transmission electron microscope observation indicated that the MMT layers were well exfoliated in nylon 66 matrix. Dynamic mechanical analysis confirmed the constraint effect of exfoliated MMT layers on nylon 66 chains, which benefited the increased storage modulus, increased glass transition temperature and reduced magnitude of alpha relaxation peak. The effects of organic MMT loading levels on reinforcement and fracture behaviour of the nanocomposites were evaluated using tensile and three‐point bending tests. The addition of the organic MMT clearly increased Young's modulus and tensile strength but decreased ductility and fracture toughness of nylon 66. Copyright © 2004 Society of Chemical Industry     

Properties of syndiotactic-rich poly(vinyl alcohol) thin film in water. VII. Elastic behavior of swollen film in water through heating/cooling or cooling/heating cycles

The thermoelastic behavior for highly swollen films of syndiotactic-rich poly(vinyl alcohol) (s-PVA) was ascertained under loads in water through heating/cooling or cooling/heating cycles (in the range of 25–70°C). The s-PVA films kept at the high temperature of 70°C behaved as a perfect elastomer through the cooling/heating cycle and had very low Young's modulus, 2–3.5 × 10⁶ dyn/cm². When highly swollen s-PVA films were kept at lower temperatures below about 50°C for a long time, microcrystals were formed or propagated in the s-PVA films and plastic deformation occurred in addition to elastic deformation through heating process. The microcrystalline growth and propagation at lower temperatures were supported by an increase in Young's modulus and a decrease in the molecular weight between junctions.