Comparison of the structure-property relationships for PTT and PET fibers spun at various take-up speeds

A comparison of poly(trimethylene terephthalate)(PTT) and poly(ethlene terephthalate)(PET) fibers spun at various take-up speeds was presented. Fiber characterization included tensile and thermal properties, optical birefringence, density, sonic modulus, boil-off shrinkage, and wide-angle X-ray diffraction. The phenomenon of stress-induced crystallization was inferred from the X-ray diffraction diagrams for fibers spun with take-up speeds over 4000 m/min. The tenacity and elongation of PTT and PET fiber showed typical results, but the initial modulus of PTT fiber was nearly unchanged over the entire take-up speed range (2000–7000 m/min), whereas that of PET, as expected, increased monotonically with increasing take-up speed. This divergent behavior could be explained by the different molecular deformations in the c-axis as determined from X-ray diffraction patterns. The fiber crystallinity, density, and heat of fusion of both polymers increased with take-up speed. The boil-off shrinkage decreased with increasing take-up speed. The optical birefringence of the two fiber types showed a maximum level at a take-up speed of ca. 5000 m/min. The melting temperature behavior of PTT fiber was different from that of PET fibers. It was found that PTT is less sensitive to stress induced changes at high spinning speeds than is PET.     

Structure development and dynamic properties in high-speed spinning of high molecular weight PEN/PET copolyester fibers

The structure development and dynamic properties of fibers produced by high-speed spinning of P(EN-ET) random copolymers were investigated. The as-spun fibers were found to remain amorphous up to the spinning speed of 1500 m/min, and subsequent increases in speed resulted in the crystalline domains containing primarilyα crystalline modification of PEN. Theβ modification was not found up to spinning speeds of 4500 m/min. On the other hand, annealing of constrained fibers spun at the 2100 m/min at 180, 200, and 240°C exhibitedβ-form crystalline structure, while the annealed fibers spun in 600–1500 m/min range exhibited dominantlyα-form. Howeverβ-form crystals disappeared above the spinning speed of 3000 m/min. With increasing spinning speeds from 600 to 4500 m/min, the storage modulus of as-spun fibers increased continuously and reached a value of about 10.4 Gpa at room temperature. The tanδ curves showed theα-relaxation peak at about 155–165°C, which is considered to correspond to the glass transition. Theα-relaxation peaks became smaller and broader, and shift to higher temperatures as the spinning speed increases, meaning that molecular mobility in the amorphous region is restricted by increased crystalline domain.     

Air-gap spinning of cellulose/ionic liquid solution and its characterization

In order to study the effects of the spinning conditions on the structure and the properties of the regenerated fiber, cellulose was dissolved in ionic liquid and then spun into fiber using an air-gap spinning process. The solution concentration, the take-up speed and the fixation of the fiber ends during coagulation improved the crystallinity and the tensile strength at the same time. The fiber surface became smooth by addition of DMF (dimethylformamide). However, it decreased the crystallinity and the tensile strength of the fibers. We revealed that the developed structure during coagulation determined the morphology and the properties of the fibers. The co-solvent resulted in smooth surface of the fiber and also changed the mechanical properties.     

Effect of degree of polymerization on the mechanical properties of regenerated cellulose fibers using synthesized 1-allyl-3-methylimidazolium chloride

1-Ally-3-methylimidazolium chloride ([AMIM]Cl) was successfully synthesized and was used as a green spinning solvent for cellulose. The celluloses of various degrees of polymerization (DP) were dissolved in the [AMIM]Cl to obtain 5 % (w/w) cellulose solutions, which were regenerated to cellulose fibers through wet spinning process. Of three different regenerated cellulose fibers with different DPs, a DP of 2,730 was gave the strongest regenerated fiber without drawing having a tensile strength of 177 MPa and an elongation at break of 9.6 % respectively, indicating that celluloses of higher molecular weight can be entangled and oriented more easily. Also maximum draw ratio of the as-spun fibers increased from 1.2 to 1.7 with increasing degree of polymerization leading to a tensile strength and modulus of 207 MPa and 48 GPa, respectively. Particularly the tensile modulus was substantially higher than those of lyocell and high performance viscose fibers of 20 GPa or less. The higher DP of pristine cellulose was critical in increasing the mechanical properties such as tensile strength and elongation at break of the as-spun fibers coupled with higher tensile modulus after drawing.     

Structure and properties of syndiotactic polystyrene fibers prepared in high-speed melt spinning process

High-speed melt spinning of syndiotactic polystyrene was carried out using high and low molecular weight polymers, HMs-PS and LMs-PS, at the throughput rates of 3 and 6 g/min. The effect of take-up velocity on the structure and properties of as-spun fibers was investigated. Wide angle X-ray diffraction (WAXD) patterns of the as-spun fibers revealed that the orientation-induced crystallization started to occur at the take-up velocities of 2–3 km/min. The crystal modification wasα-form. Birefringence of as-spun fibers showed negative value, and the absolute value of birefringence increased with an increase in the take-up velocity. The cold crystallization temperature analyzed through the differential scanning calorimetry (DSC) decreased with an increase in the take-up velocity in the low speed region, whereas as the melting temperature increased after the on-set of orientation-induced crystallization. It was found that the fiber structure development proceeded from lower take-up velocities when the spinning conditions of higher molecular weight and lower throughput rate were adopted. The highest tensile modulus of 6.5 GPa was obtained for the fibers prepared at the spinning conditions of LMs-PS, 6 g/min and 5 km/min, whereas the highest tensile strength of 160 MPa was obtained for the HMs-PS fibers at the take-up velocity of 2 km/min. Elongation at break of as-spun fibers showed an abrupt increase, which was regarded as the brittle-ductile transition, in the low speed region, and subsequently decreased with an increase in the take-up velocity. There was a universal relation between the thermal and mechanical properties of as-spun fibers and the birefringence of as-spun fibers when the fibers were still amorphous. The orientation-induced crystallization was found to start when the birefringence reached — 0.02. After the starting of the orientation-induced crystallization, thermal and mechanical properties of as-spun fibers with similar level of birefringence varied significantly depending on the processing conditions.     

Novel fibers prepared from cellulose in NaOH/thiourea/urea aqueous solution

The regenerated cellulose fibers were prepared by wet-spinning from NaOH/thiourea/urea aqueous solvent system for the first time. The effects of coagulation and stretch conditions on the structure, morphology, and mechanical properties of the prepared fibers were investigated by wide-angle X-ray diffraction (WAXD), scanning electron microscope (SEM), and tensile tester, respectively. When the cellulose spinning dope was coagulated in 10% H₂SO₄/12.5% Na₂SO₄ aqueous solution at 15 °C, the prepared fibers had a typical crystalline structure of cellulose II and circular cross-sectional shapes with smooth surface and slightly high tensile properties to viscose fibers.     

Preparation of carbon fiber from heavy oil residue through bromination

A pitch precursor for a general purpose carbon fiber was prepared by condensation of pyrolized fuel oil (petroleum residual oil) with bromine under nitrogen blowing. Such a condensation raised the softening point of the pitch from 40°C to 265°C with a yield of 43%. The pitch precursor showed an enhanced aromaticity and enlarged molecular size, which led to a reduction in molecular mobility and optical isotropy. The precursor was spun into fibers of 20 μm diameter at a take-up speed of 700 m/min. The fiber was stepwise stabilized in air and carbonized in Ar gas to obtain an isotropic carbon fiber. The carbon fiber exhibited tensile strengths of 500–800 MPa though the fiber was formed via a crude method. The electric conductivity of the carbon fiber was relatively high, 2.2×10² S/cm, sufficient to be used as electrode materials.     

Spinnability in pre-gelled gel spinning of polyacrylonitrile precursor fibers

The spinnability in pre-gelled gel spinning of polyacrylonitrile (PAN) precursor fibers was investigated. The spinning solutions were aged at 25 °C for different times prior to fiber spinning. The pre-gelled spinning solution aged for 2.5 h was much more strain hardening than the ungelled one, which can increase the spinnability of the solution. The maximum take-up velocity of the first winding roller V _1m, which reflects the spinnability of the spinning solutions, was found to be largest when the aging time was 1.5 h. The spinnability increased with the increase of the air gap length and the lengthdiameter ratio L/D of the spinnerette. Once the L/D increased beyond 15, the spinnability hardly changed. The fibers spun from the spinning solution aged for 1.5 h had the best mechanical properties and favorable structure, showing that good spinnability favors the performance increase of resultant PAN precursor fibers.     

Preparation and properties of fibers produced from a cellulose/complex PA solvent system precipitating in diverse coagulants

Ethanol, as the first coagulation bath, and several common organic solvents, as well as aqueous solutions of NH₄Cl, NaHCO₃ and NaOH were explored and demonstrated to be adopted as the second coagulation bath for cellulose/phosphoric acid/tetraphosphoric acid (cellulose/complex PA solvent) solution to produce novel cellulose fibers by two-stage dry-wet spinning in a laboratory scale, and effect of coagulants, cellulose concentration, solvent concentration (P₂O₅ concentration) and coagulation temperature on crystal structure and properties of corresponding fibers were investigated. Surface morphology of regenerated fibers as-spun from different coagulants was observed by scanning electronic microscope (SEM), indicating that methanol and 8 wt% NaOH aqueous solution all rendered cellulose fibers relatively dense and smooth surface. X-ray diffraction (XRD) analysis showed that cellulose fiber precipitated from 8 wt% NaOH aqueous solution had pronounced characteristic peak of cellulose II than those of fibers precipitated from other coagulants, and highest crystallinity and orientation. Meanwhile, those two coagulants referred above also gave cellulose fibers relatively higher tensile strength under the same prerequisite. TGA curves exhibited that fibers were thermally stable produced from two salt aqueous solutions (8 wt% NH₄Cl and NaHCO₃) since they had the relatively higher onset decomposition temperatures. By evaluating the effect of cellulose concentration, P₂O₅ concentration and coagulation temperature on the structure and properties of asprepared fibers, it was preferable to produce cellulose fiber from a solution at 20 wt% cellulose concentration, 73 % P₂O₅ concentration, and coagulating in methanol at coagulation temperature of 60 °C at the second-stage.     

Structure and performance of fibers prepared from liquefied wood in phenol

The fibers from liquefied wood in phenol (WPFs) were spun by adding hexamethylenetetramine as synthetics and cured by soaking in solution containing hydrochloric acid and formaldehyde as main components. The chemical structure of WPFs remarkably changed from that of liquefied wood was identified by FT-IR spectrometer. WPFs with the average diameter of 27∼42 μm, tensile strength of 230∼356 MPa, and modulus of 15∼31 GPa were obtained using spinning speed of 0.72 μm min⁻¹, hydrochloric acid concentration of 18.5 %, heating rate of 10 °C h⁻¹, and curing time of 4 h. These WPFs showed a high thermal stability and a complex thermal decomposition process by TG(thermogravimetric) analysis. It was also found that the two obvious weight loss temperatures of WPFs were 510°C and 748°C.     

Microstructure and mechanical properties of apocynum venetum fibers extracted by alkali-assisted ultrasound with different frequencies

Apocynum venetum (AV) fibers were extracted by the combination of low (28 kHz) and high frequency (53 kHz) ultrasonic treatment after aqueous alkali maceration. The surface impurities and cementing components between fibers in the range of 10–50 μm were removed by low frequency ultrasound. The surface impurities in the range of 2–8 μm, as well as the residuals in the surface depression and inner cavum of fibers were further eliminated by high frequency ultrasonic irradiation. The treatment did not change crystal structure of cellulose I of AV fibers and could lead to a higher degree of crystallinity. Meanwhile, the examination of mechanical properties showed that the AV fibers could be used for textile industry. It is demonstrated that the combination of low and high frequency ultrasound after alkali treatment is simpler, more controllable and more environment-friendly and is a promising degumming method for textile industry.     

Preparation of regenerated cellulose fiber via carbonation. I. Carbonation and dissolution in an aqueous NaOH solution

Cellulose carbonate was prepared by the reaction of cellulose pulp and CO₂ with treatment reagents, such as aqueous ZnCl₂ (20–40 wt%) solution, acetone or ethyl acetate, at −5–0°C and 30–40 bar (CO₂) for 2 hr. Among the treatment reagents, ethyl acetate was the most effective. Cellulose carbonate was dissolved in 10% sodium hydroxide solution containing zinc oxide up to 3 wt% at −5–0°C. Intrinsic viscosities of raw cellulose and cellulose carbonate were measured with an Ubbelohde viscometer using 0.5 M cupriethylenediamine hydroxide (cuen) as a solvent at 20°C according to ASTM D1795 method. The molecular weight of cellulose was rarely changed by carbonation. Solubility of cellulose carbonate was tested by optical microscopic observation, UV absorbance and viscosity measurement. Phase diagram of cellulose carbonate was obtained by combining the results of solubility evaluation. Maximum concentration of cellulose carbonate for soluble zone was increased with increasing zinc oxide content. Cellulose carbonate solution in good soluble zone was transparent and showed the lowest absorbance and the highest viscosity. The cellulose carbonate and its solution were stable in refrigerator (−5°C and atmospheric pressure).     

Rheological behavior and spinnability of ethylamine hydroxyethyl chitosan/cellulose co-solution in N-methylmorpholine-N-oxide system

In this work, the novel chitosan derivative ethylamine hydroxyethyl chitosan (EHC) was synthesized and blended with cellulose in an aqueous N-methylmorpholine-N-oxide (NMMO) solution in order to fabricate antibacterial chitosan/cellulose fiber. The rheological behaviors of the obtained co-solution in both steady and dynamic states were carefully investigated to determine the spinnability of the co-solution. In steady state, the addition of EHC was found to preserve the power-law flow characteristics of cellulose in the aqueous NMMO solution, while broadening the first Newtonian fluid-flow area. Under dynamic conditions, both Han-plot and viscoelastic analyses indicated the homogeneity of the co-solution. EHC/cellulose antibacterial fibers were successfully spun via the lyocell process using aqueous NMMO as the solvent, confirming the excellent spinnability of the EHC/cellulose co-solution. Scanning electron microscopy was used to observe the morphology of the obtained EHC/cellulose fibers; they were also investigated for antibacterial activity. The obtained EHC/cellulose fiber exhibited good spinning consistency and strong antibacterial activity against Escherichia coli, demonstrating potential applications for the material in antibacterial textiles.     

Effect of polystyrene mixing on mechanical properties and structural changes in melt spinning

To increase the spinning speed of poly(trimethylene terephthalate) (PTT) fibers, polystyrene (PS) was selected as an additive polymer in the PTT matrix. Mixing of the immiscible PS with PTT led to an increase in spinning speed up to 5,500 m/min. PS was employed to improve the extensibility of the matrix PTT in the spinning process as it can prevent PTT molecular orientation. Experimental results show that the mixing of PS achieved this. The elongation at break of spun fibers increased with the amount of PS. PS addition prevented fiber orientation, especially amorphous orientation, and improved drawability, and as such, increased spinning speed up to 5,500 m/min.     

Studies on melt spinning of sea-island fibers. I. morphology evolution of polypropylene/polystyrene blend fibers

Isotactic polypropylene/atactic polystyrene (iPP/aPS) immiscible polymer blends are prepared and are melt-spun to prepare blend fibers with matrix-fibril morphologies. The running fibers are captured at different positions of the spinning line, and the morphologies including dispersions of aPS droplets in iPP matrix fibers, droplets diameter and their distributions, as well as the radial gradients on counts and diameter of droplets are analyzed. The effect of take-up velocity on the morphology of take-up fibers is discussed by comparing with that of extrudate fibers. At low take-up velocities, the enhanced radial gradients are attributed to shrinking of matrix fibers on the elongation of spinning stress. While the effects of non-uniform deformation, coalescence and migration of droplets play a role to resist the effects of shrinking of matrix fibers at high take-up velocities. Based on morphology analysis, the mechanisms of compression from the shrinking of matrix fibers, non-uniform deformation, coalescence and migration of droplets are presented to explain why and how the radial gradients form.     

Electrospinning PVA solution-rheology and morphology analyses

This study investigates the electrospinning (ES) of poly(vinyl alcohol) (PVA). All of the electrospinning process or property parameters, including the concentration effect, the molecular weight effect, the pH effect, the salt effect, electrode voltage, surface tension, shear viscosity and extensional viscosity were examined. The pH variation had an insignificant effect on the formation of fibers. An increase in electrode voltage and salt concentration negatively affects the ES process. The salt concentration that yields an acceptable ES membrane without droplets was below 0.001 N. Also, the decrease in elongation viscosity rather than the variation in electric conductivity or surface tension was the main cause of the negative effect on the fiber formation when the salt was added to a PVA solution. The salt negative effects follow the order CaCl₂ < NaCl < NaI < KBr < KI. Experimental results show that the ES processability of PVA solution depends mainly on the concentration and secondly on the molecular weight of the dissolved polymer. The PVA solution prepared with a larger molecular weight had a lower concentration window in the ES process. The concentration window of PVA solution with an MW of 88,000 in the ES process ranged between 6 and 14 wt%. Additionally, experimental results demonstrated that the upper limitation on PVA concentration depends strongly on the extension viscosity of the spun solution. Whenever the power law index n determined by extension test exceeds one, spinning is unfeasible, regardless of whether the index of the power law for shearing is within the normal range. Briefly, this work indicates that the extension viscosity can be adopted as a good indicator for predicting ES processability.     

Synthesis and characterization of acrylic fibers-<Emphasis Type="Italic">g</Emphasis>-polyacrylamide

Graft copolymerization of acrylamide onto commercial acrylic fibers was carried out using benzoyl peroxide as a free-radical initiator in aqueous medium within the 75–95 °C temperature range. In this study, the effects of initiator and monomer concentration, the amount of fiber, polymerization time, and temperature on the graft yield were investigated. The optimum concentration for initiator was found to be 2.0×10⁻³ mol/l and the optimum temperature of 85 °C. The activation energy of the reaction was calculated to as 35.81 kJ/mol at the temperature interval of 75–95 °C. The structures and morphologies characterization of grafted fibers was investigated by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The thermogravimetric analysis data showed that the thermal stability of the acrylic fibers increased with graft yield. The scanning electron photographs showed that the homogeneous appearance of the fiber surface changed and a shell-like heterogeneous structure occurred at the surface with an increasing degree of grafting. The moisture content, water absorption, dyeability, and antimicrobial activity of grafted acrylic fibers were also reported. The results showed that grafting of polyAAm improved the moisture contain, water absorption, dyeability, and antimicrobial activity of fiber.     

Preparation and properties of 2-(2-aminoethoxy) ethyl chitosan/cellulose fiber using N-methylmorpholine-N-oxide process

N-methylmorpholine-N-oxide (NMMO) is used widely in the manufacturing of man-made cellulose fibers and functional lyocell fibers due to its environment-friendly advantage. Although chitosan is known as a natural antibacterial polymer it has poor solubility in neutral to basic medium and the antibacterial activity is shown only in acidic medium. Chitosan’s poor solubility in NMMO is the disadvantage for the production of antibacterial lyocell fibers. This paper investigates a more “NMMO soluble” derivative of chitosan, 2-(2-aminoethoxy) ethyl chitosan (AECS). AECS has greatly improved solubility in NMMO hydrate, and stronger antibacterial activity than chitosan. AECS was introduced to modify the lyocell fiber spun in a co-solution of cellulose and AECS in NMMO hydrate. The physical properties and antibacterial activity of the fibers were examined and the results indicated that the modified lyocell fiber, containing more than 2 wt% of AECS, exhibits good antibacterial activity against E. coli and slightly decreased tensile strength compared with unmodified fibers.     

Study on the matrix-fibril morphologies of polypropylene/polystyrene blends under non-isothermal uniaxial elongational flow

Polypropylene/polystyrene blends with different viscosity ratios, p, ranging from 1.6×10^?2 to 10.8, were prepared by using textile-grade isotactic polypropylene (iPP) and five kinds of atactic polystyrene (aPS), named PS1, PS2, PS3, PS31 and PS46 with different molecular weight, and then melt-spun into composite fibers with matrix-fibril morphology at different take-up velocities, v _L , ranging from 125 to 1000 m/min. The effects of p on the diameters and quantities of dispersed droplets in extrudate fibers, and the effects of p and v _L on the size and quantities of fibrils in take-up fibers were discussed, respectively. Based on a quantitatively characterization for the coalescence and deformation of droplets during melt spinning, a theoretical analysis based on Newtonian fluids simplification and the deformation theory was presented to predict the deformation and breakup of droplets during melt spinning. It is found that there is a good fit between theoretical and observed experimental results at most discussed take-up velocities. Furthermore, the uncertainties of Newtonian fluids simplification and a hypothesis of local energy dissipation from migration and coalescence were noted to explain the deviations between predicted and experimental data.     

Probing of an environmentally friendly regenerated cellulose material having bimorphic behavior

Novel regenerated cellulose material which was prepared from cellulose acetate fiber through the hydrolysis of acetyl groups have been developed by an environmentally friendly process without emitting toxic substances in addition to be at low production cost. They have composite crystalline structure constituted of cellulose II and cellulose IV. Also, they show a lamellar morphology with an increased amorphous region, as compared to conventional regenerated cellulose such as viscose rayon and cupra rayon. Our data obtained by several independent methods demonstrated that the adsorption properties of cellulose fibers depend predominantly on the amorphous region.