Studies on fiber formation of thermotropic copolyesters

Thermotropic copolyesters PET/60 PHB and PET/80 PHB fibers are melt spun at different extrusion temperatures and at different draw-down ratios. The flow behavior of PET/60 PHB is studied at different temperatures and shear rates. The melt of (PET/60 PHB) at temperatures above 265°C exhibit low viscosity and low activation energy of flow. The modulus and strength for both PET/60 PHB and PET/80 PHB fibers increase with the increase in extrusion temperature and draw-down ratio in the ranges studied. High birefringence, indicating the presence of mesophase is observed between 265 and 300°C on a hot stage polarizing microscope. X-ray diffraction patterns show that the molecular orientation increased with increasing draw-down ratio. Scanning electron microscopy of these fibers shows a well-developed highly oriented fibrillar structure. Superior mechanical performance of fibers spun at around 275°C are attributed to the presence of nematic mesophase in the polymer melt. © 1993 John Wiley & Sons, Inc.     

Strain-induced crystallization of poly(ethylene terephthalate)

The fabrication of poly(ethylene terephthalate), PET, into fibers, films, and containers usually involves molecular orientation caused by molecular strain, which may lead to stress- or strain-induced crystallization (SIC). The SIC of PET was studied by the methods of birefringence, density, thermal analysis, light scattering, and wide-angle X-ray. The development of crystallinity is discussed in relation to the rate of crystallization, the residual degree of orientation, and stress relaxation. The experimental procedure involves stretching samples at temperatures above the glass transition temperature, Tg, to a given extension ratio and at a specific strain rate of an Instron machine. At the end of stretching, the sample is annealed in the stretched state and at the stretching temperature for various periods of time, after which the sample is quickly quenched to room temperature for subsequent measurements. During stretching, the stress strain and the stress relaxation curves are recorded. The results indicate that the SIC of annealed, stretched PET can proceed in three different paths depending on the residual degree of orientation. At a low degree of residual orientation, as indicated by the birefringence value, annealing of stretched PET leads only to molecular relaxation, resulting in a decrease of birefringence. At intermediate orientation levels, annealing causes an initial decrease in birefringence followed by a gradual increase and finally a leveling off of birefringence after a fairly long period of time. At higher orientation levels, annealing causes a rapid increase in birefringence before leveling off. The interpretation of the above results is made using the measurements of light scattering, differential scanning calorimetry, and wide-angle X-ray. The rate of the SIC of PET is also discussed in terms of specific data analysis.     

Development of high‐tenacity,high‐modulus poly(ethylene terephthalate) filaments via a next generation wet‐melt‐spinning process

In this study, PET (intrinsic viscosity of 1.05 dl/g) was melt processed with a horizontal isothermal bath (HIB) treatment. Tensile properties of PET fiber samples were highly increased by using the HIB. The process‐structure‐property relationship of control (no HIB) and HIB fiber samples were characterized by tensile testing, differential scanning calorimetry, birefringence measurement, scanning electron microscopy and hot‐air shrinkage measurements. It was found that HIB fiber samples, which had been subjected to post‐drawing process, had a high degree of molecular chain orientation, that is, a high birefringence, high crystallinity and a fibrillar structure. The best tensile property acquired from a HIB‐drawn PET fiber sample was 10.24 g/d in tenacity, 114.17 g/d in modulus, and 13.49% in elongation at break. Applying the HIB in the melt spinning process was simple and required only small process space; hence, it is cost effective. In addition, acquiring HIB fiber samples was successful at a final take‐up speed of 2,500 m/min. Hence, this HIB‐assisted melt spinning technology has a high potential to be used in industries for technical textiles applications. POLYM. ENG. SCI., 57:224–230, 2017. © 2016 Society of Plastics Engineers     

The development of molecular orientation and morphological texture in thermotropic copolyesters

Liquid crystalline polymers can be processed to form high strength/modulus materials. In processing these materials, it is apparent that molecular orientation is an important factor in determining the physical strength of the processed materials. In this study a systematic investigation was carried out to determine how a thermotropic copolyester of parahydroxybenzoic acid (PHB) and polyethylene terephthalate (PET) responds to two basic types of flows: shear and extensional flow. This was accomplished by preparing sheared and extended samples under controlled conditions of temperature and flow history. Sheared disks were prepared using a disk and plate geometry of a Rheometrics Mechanical Spectrometer (RMS model 605), while extended ribbons were prepared using a slit die attached to an Instron capillary rheometer. Two copolymerer compositions of 60 mole percent and 80 mol percent PHB were investigated. The sheared disks and extended ribbons were investigated for molecular orientation and morphological textures using wide angle x-ray scattering (WAXS) and scanning electron microscopy (SEM) analysis, respectively. It was found that extensional flow has a greater capacity for orienting such materials than shear flow. Samples annealed at their softening points for 1 minute (240°C for the 60 mole percent PHB/PET copolymer and 300°C for the 80 mole percent PHB/PET copolymer) showed no significant loss of orientation, indicating that once orientation is produced it may remain in the melt for a long period of time. Sheared samples prepared by shearing the sample while cooling showed significantly higher degrees of orientation than those not cooled while being sheared. This may indicate that a minimum stress level exists for the production of orientation in shear flow.     

PHB/PET/HQ-TPA液晶共聚酯纤维的制备及结构性能研究

对所合成的ＰＨＢ／ＰＥＴ／ＨＱ－ＴＰＡ三元液晶共聚酯进行纺丝实验，制备了初生纤维并对其进行了热处理。利用ＤＳＣ，ＷＡＸＤ，密度，Ｓ－Ｓ曲线等方法对初生纤维及热处理后纤维的结构与性能进行了研究。结果表明：该体系的液晶共聚酯具有较好的可纺性，初生纤维在ＤＳＣ升温过程中有冷结晶峰和熔融双峰现象产生，初生纤维经热处理后，可使其微晶尺寸有较大提高，力学性能得到一定程度改善，但未使其取向性能得到进一步改善。     

Synthesis and characterization of liquid crystalline polymers from p-hydroxybenzoic acid,poly(ethylene terephthalate), and third monomers

Eight new p-hydroxybenzoic acid (PHB) and poly(ethylene terephthalate) (PET) copolymers containing vanillic acid (VA), p-aminobenzoic acid, m-hydroxybenzoic acid, hydroquinone/terephthalic acid (TPA), bisphenol A/TPA, 1,5-naphthalenediol/TPA, 2,7-naphthalenediol/TPA, and 1,4-dihydroxyanthraquinone/TPA as eight third monomers with a variety of structural features were synthesized by melted-state copolycondensation and were characterized through a thermal analyzer, proton nuclear magnetic resonance, wide-angle X-ray diffraction (WAXD), and a scanning electron microscope (SEM). The experimental results show that PHB/PET/VA copolymers exhibit a faster polycondensation rate, lower melting temperature, and higher thermostability than do the other seven copolymers and third monomer-free PHB/PET polymers. The as-spun fibers derived from the PHB/PET/VA copolymers with different VA contents show tensile strengths, Young's moduli, and break elongations of 0.6–1.5 GPa, 28–67 GPa, and 7–9%, respectively. A highly oriented fibrillar structure in the PHB/PET/VA copolymer fibers was observed using WAXD and SEM. The most effective third monomer of the eight third monomers for an enhancing polycondensation rate and molecular weight of the PHB/PET polymers and for improving their thermal and mechanical properties is found to be vanillic acid (VA). © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2129–2138, 1997     

Morphology and Structure of Constituent Fibres in Thermally Bonded Nonwovens

Summary: A new process has been developed to produce three‐dimensional nonwovens directly from staple fibres. In order to establish suitable windows of the process parameters to achieve high‐quality nonwoven products, the effects of thermal bonding temperature, dwell time and mould material on the morphology and structure of the fibre have been investigated using PP/PET bi‐component fibres. It was evident from both scanning electron microscope images and Raman spectra that thermal‐induced shrinkage of the PP sheath fibre occurred in the thermal bonding process, leading to deformation and cracking of the PP sheath and exposure of the PET core. X‐ray diffraction results revealed crystal imperfection and/or less ordered polymer chains, more γ‐form and thermal contraction of the crystal lattice for the PP sheath fibre, while birefringence measurements indicated that both the birefringence and the orientation factor for the PP fibre decreased after the thermal bonding process. The degrees of the thermal‐induced shrinkage increased, and the crystallinity, birefringence and orientation factor of the PP sheath fibre decreased with increasing thermal bonding temperature, dwell time and thermal conductivity of the mould material. All these can be attributed to the different levels of modification of chemical composition caused by thermal oxidative degradation and thermal‐induced relaxation of the orientation during the thermal bonding process.

Changes of morphology and crystalline features of PP/PET fibre after thermal bonding process.     

Strong orientation correlation and optical anisotropy in blend of cellulose ester and poly(ethylene 2,6‐naphthalate) oligomer

Molecular orientation of two aromatic additives in cellulose acetate propionate (CAP) matrix was investigated from orientation birefringence data and an intermolecular orientation correlation represented by nematic interaction (NI) was evaluated. Poly(ethylene terephthalate) (PET) and poly(ethylene naphthalate) (PEN) oligomers with low molecular weight (ca. 400 g mol^?1) were used as the additives. The NI strengths of CAP‐PET and CAP‐PEN were determined to be 0.28 ± 0.05 and 0.96 ± 0.15, respectively. In particular, compared with other polymer/polymer and polymer/small additive blends, the NI value in CAP/PEN blend is much stronger and represents the perfect orientation correlation. The strong orientation correlation is possibly due to the rigid naphtalate structure in PEN. Contrary, a relation between birefringence and orientation function for CAP in bulk and blend showed the same trend, suggesting that the orientation behavior of CAP determines the orientation birefringence. As two ester groups in CAP are responsible for birefringence, the alignment of the ester groups is affected by only the main chain orientation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40570.     

Computer Simulation of Polyester High‐Speed Thermal Channel Spinning

A mathematical model to describe the thermal channel spinning (TCS) process in PET high‐speed melt‐spinning has been developed. This model, which is based on the spinning process kinematics, includes the effects of acceleration, gravity, and surfacial air friction. It incorporates the constitutive equation of PET polymer, the heat transfer related to the transverse air blowing and, in particular, to a convection and radiation combining procedure in the thermal channel, while taking into account the nonisothermal crystallization kinetics related to temperature and molecular orientation as well as the elongational viscosity of PET polymer connected with temperature, intrinsic viscosity and crystallinity. The developments of crystallinity, molecular orientation and morphological features of high‐speed‐spun PET fiber in the TCS process are investigated at take‐up speeds ranging from 3 600–4 400 m/min and thermal channel temperatures ranging from 160–200°C. The simulated results of this model are compared with the measured crystallinity, diameter, and birefringence of the spun yarn. The “necking point” in the TCS spinline can be predicted by this model.     

Preparation and properties of blends from poly(3‐hydroxybutyrate) with poly(vinyl acetate)‐modified starch

This research used the ceric ion to initiate the graft‐polymerization of vinyl acetate (VAc) to a soluble potato starch. Fourier transform infrared spectra confirmed the formation of starch graft copolymer. After 4 h of reaction at 50°C, total monomer conversion, grafting efficiency, and grafting ratio were measured as 91%, 12.5%, and 0.223, respectively. The synthesized PVAc‐modified starch was then blended with poly(3‐hydroxybutyrate) (PHB). Structures, thermal and mechanical properties of the prepared blends were examined. The results showed the PHB and PVAc‐modified starch were miscible in all compositions. In addition, thermal gravimetric analysis revealed that the addition of PVAc‐modified starch increased the thermal stability of the PHB component. Further evidence also showed that the addition of PVAc‐modified starch reduced the extent of decrease in molecular weight of PHB in a melt‐mixer. PHB/PVAc‐modified starch blends exhibit higher toughness than pure PHB because of increased compatibility and the leathery PVAc‐modified starch. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Analysis of the tensile modulus of poly(p‐hydroxybenzoate)/poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) ternary polyester composite fibers

Liquid crystalline polymer reinforced plastics were prepared by compounding (PHB/PEN/PET) blends. A fibrillar PHB structure was formed in situ in the PEN/PET matrix under a high elongational flow field during melt‐spinning of the composite fibers. The formation of PHB microfibrils in the composite fiber with different PHB contents and winding speeds was observed. The PHB microfibril reinforced PEN/PET composite fibers exhibited an unexpectedly low tensile modulus. We have evaluated the tensile modulus of the fibers using the non‐modified 22 and a modified 23 Halpin–Tsai model. From the analysis of both models, large differences were found between the theoretical and experimental values of the tensile modulus, and the low value of the tensile modulus of the composite fiber could not adequately be explained by either model. Thus, we analyzed the observed modulus values using the Takayanagi model, 24 which describes the concept of mechanical discontinuities in semi‐crystalline polymers. Using the Takayanagi model, the effective fraction of continuous or discontinuous microfibrils was evaluated. Consequently, we could successfully explain the very low modulus of the PHB/PEN/PET composite fiber, having a large number of PHB microfibrils, using the Takayanagi model. Copyright © 2003 Society of Chemical Industry     

Birefringence prediction of optical media

The flow and thermally induced birefringence of injection‐compression molded optical media such as compact discs and digital video discs is predicted by applying a stress‐optical rule to the flow and thermally induced stresses, which are estimated with a viscoelastic material model integrated into a non‐isothermal compressible flow simulation. The resulting model considers flow and cooling induced molecular orientation, and the transient effect of thermal stress and pressure. Contrary to previous research for polystyrene, the validated results indicate that, for polycarbonate, the magnitude of the thermally induced birefringence is comparable to the flow induced birefringence. Simulation results of the flow and thermally induced in‐plane birefringence for compact‐disc‐recordable moldings with an optical grade of polycarbonate compared well with experimental observations at different mold and melt temperatures. Both simulation and experiments indicate that mold and melt temperatures have a significant effect on the level of birefringence; increasing mold or melt temperature significantly reduces the birefringence. Polym. Eng. Sci. 44:814–824, 2004. © 2004 Society of Plastics Engineers.     

Processability modifications of poly(3‐hydroxybutyrate) by plasticizing,blending, and stabilizing

Poly(3‐hydroxybutyrate) (PHB) was plasticized with dioctyl (o‐)phthalate, dioctyl sebacate, and acetyl tributyl citrate (ATBC). The thermal properties, mechanical properties, and melt flow ability were studied with differential scanning calorimetry, thermogravimetric analysis, a universal material testing machine, and a melt flow indexer. ATBC was revealed to be an efficient plasticizer, reducing the glass‐transition temperature and increasing the thermoplasticization ability of PHB. We also blended poly(3‐hydroxybutyrate‐co‐hydroxyhexanoate) (PHBHHx) and poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) [P(3/4HB)] with PHB, ATBC, and antioxidant 1010 to overcome the brittleness of PHB and improve the melt flow stability of the materials. PHBHHx did little to improve the thermal processing but increased the fluidity of PHB, and P(3/4HB) toned the toughness of PHB. The addition of antioxidant 1010 enhanced the thermal stabilization of PHB. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Processing–structure–property relationships in poly(ethylene terephthalate) blown film

An investigation was undertaken to establish processing–structure–property relationships in poly(ethylene terephthalate) (PET) blown film. For the study, a commercial grade of PET was used to fabricate the film specimens by means of a tubular film blowing process. In this process, the stretch temperature was accurately controlled by an oven. The annealing treatment of the oriented specimens involved clamping the sample in an aluminum frame and then putting the clamped sample in an oven, controlled at a temperature between the glass transition temperature (70°C) and the melting point (255°C) of PET, for a specified annealing period. The structure of the blown film samples was characterized by density, bulk birefringence, flat plate wide-angle X-ray scattering, and pole figure analysis. The processing variables, namely, takeup ratio, blowup ratio, and stretch temperature were found to significantly affect the bulk birefringence and density of the oriented PET blown film samples. It was found that both the bulk birefringence and density of the specimens increased upon annealing at an elevated temperature. Both the crystalline and amorphous orientation functions were calculated from the data of bulk birefringence, density, and the pole figure analysis. Compared to the amorphous orientation functions, the crystalline orientation functions were found to be relatively insensitive to the processing variables. It was concluded that equibiaxially oriented PET films can be produced via a tubular film blowing process by judiciously controlling the processing and annealing conditions. It has also been observed that the tensile stress-at-break of equibiaxially oriented PET film increases with decreasing stretch temperature and increasing annealing temperature.     

Structure development in melt spinning of poly(ethylene‐co‐octene) filaments with various comonomer contents

An experimental study of the spinnability and the variation in crystallinity and orientation of melt spinning of poly(ethylene‐co‐octene) with different contents of comonomers was carried out. The spinning behavior of these polymers was investigated under different draw‐down ratios and temperatures and correlated to spinline stress. The melt‐spun filaments were characterized by wide‐angle X‐ray diffraction birefringence, and differential scanning calorimetry. S‐1 is a high‐density polyethylene and S‐2, S‐3, and S‐4 have 16, 22, and 38 wt % octene. An orthorhombic unit cell was found in all four polymers, but a dominant hexagonal structure (perhaps mesophase) was found for the highest octene level (S‐4). The orientation factors for the a‐, b‐, and c‐axis of the orthorhombic crystal structure and a‐axis of the hexagonal phase were then calculated. The crystalline orientation behavior of the lower octene copolymers (S‐1, S‐2, and S‐3) are similar and can be represented as a “row‐nucleated“ structure. However, the orientation behavior of S‐4 was different. The uniaxial mechanical properties were also measured. The Young's modulus and tensile strength generally increased with birefringence for all polymers. With increasing content of octene, the Young's modulus showed a decrease from semicrystalline thermoplastic toward an elastomer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 9–22, 2004     

Preparation and characterization of biodegradable polymer blends from poly(3‐hydroxybutyrate)/poly(vinyl acetate)‐modified corn starch

Biodegradable polymer blends prepared by blending poly(3‐hydroxybutyrate) (PHB) and corn starch do not form intact films due to their incompatibility and brittle behavior. For improving their compatibility and flexibility, poly(vinyl acetate) (PVAc) was grafted from the corn starch to prepare the PVAc‐modified corn starch (CSV). The resulting CSV consisted of 47.2 wt% starch‐g‐PVAc copolymer and 52.8 wt% PVAc homopolymer and its structure was verified by FT‐IR analysis. In comparison with 35°C of the neat PVAc, the glass transition temperature (T_g) of the grafted PVAc chains on starch‐g‐PVAc was higher at 44°C because of the hindered molecular mobility imposed from starch on the grafted PVAc. After blending PHB with the CSV, structure and thermal properties of the blends were investigated. Only a single T_g was found for all the PHB/CSV blends and increased with increasing the CSV content. The T_g‐composition dependence of the PHB/CSV blends was well‐fitted with the Gordon‐Taylor equation, indicating that the CSV was compatible with the PHB. In addition, the presence of the CSV could raise the thermal stability of the PHB component. It was also found that the presence of the PHB and PVAc components would not hinder the enzymatic degradation of the corn starch by α‐amylase. POLYM. ENG. SCI., 55:1321–1329, 2015. © 2015 Society of Plastics Engineers     

Fine structure and physical properties of polyethylene/poly(ethylene terephthalate) bicomponent fibers in high‐speed spinning. I. Polyethylene sheath/poly(ethylene terephthalate) core fibers

The high‐speed melt spinning of sheath/core type bicomponent fibers was performed and the change of fiber structure with increasing take‐up velocity was investigated. Two kinds of polyethylene, high density and linear low density (HDPE, LLDPE) with melt flow rates (MFR) of 11 and 50, [HDPE(11), LLDPE(50)], and poly(ethylene terephthalate) (PET) were selected and two sets of sheath/core combinations [HDPE(11)/PET and LLDPE(50)/PET bicomponent fibers] were studied. The fiber structure formation and physical property effects on the take‐up velocities were investigated with birefringence, wide‐angle X‐ray diffraction, thermal analysis, tensile tests, and so forth. In the fiber structure formation of PE/PET, the PET component was developed but the PE components were suppressed in high‐speed spinning. The different kinds of PE had little affect on the fine structure formation of bicomponent fibers. The difference in the mechanical properties of the bicomponent fiber with the MFR was very small. The instability of the interface was shown above a take‐up velocity of 4 km/min, where the orientation‐induced crystallization of PET started. LLDPE(50)/PET has a larger difference in intrinsic viscosity and a higher stability of the interface compared to the HDPE(11)/PET bicomponent fibers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2254–2266, 2000     

Miscibility,thermal behaviour,morphology and mechanical properties of binary blends of poly[(R)‐3‐hydroxybutyrate] with poly(γ‐benzyl‐L‐glutamate)+

The miscibility, thermal behaviour, morphology and mechanical properties of poly[(R)‐3‐hydroxybutyrate] (PHB) with poly(γ‐benzyl‐L ‐glutamate) (PBLG) are investigated by means of differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and tensile tests. The DSC results show that PHB and PBLG are immiscible in the melt state. Such immiscibility also exists in the amorphous state due to a clear two‐phase separated structure observed by SEM measurements. The blend samples with different thermal history, namely as original and melt samples separately, display differences in thermal behaviour such as the DSC scan profile, the crystallinity and the melting temperature of PHB. The crystallization of PHB both from the molten state and the amorphous state is retarded on addition of the second component. The SEM measurements reveal that a phase inversion occurs between the PHB/PBLG (60/40) and PHB/PBLG (40/60) blends. Except for the PHB/PBLG (40/60) blend, a microphase separated structure is observed for all blend compositions. The mechanical properties vary considerably with blend composition. Compared with pure components, the PHB/PBLG (20/80) blend shows a certain improvement in mechanical properties. © 2001 Society of Chemical Industry     

高分子量PET／60PHB热致性液晶共聚酯的结构与性能

研究了固相缩聚过程中PET/60PHB共聚酯结构性能的变化。随着反应的进行,分子量增大,分子量分布宽度指数变小;玻璃化温度略增,熔融温度增加幅度较大;热稳定性明显提高。预聚体中主要存在PET的低共熔物或部分同二质晶,固相缩聚反应使PET结晶消失,PHB结晶形成并完善。固相缩聚大大改善了共聚酯的可纺性,用[η]为0.95dL/g的共聚酯制得断裂强度达到高强范围(1GPa)的初生纤维。     

Effect of lignin particles as a nucleating agent on crystallization of poly(3‐hydroxybutyrate)

The effect of lignin fine powder, as a new kind of nucleating agent, on the crystallization process of poly(3‐hydroxybutyrate) (PHB) was studied. The kinetics of both isothermal and nonisothermal crystallization processes from the melt for both pure PHB and PHB/lignin blend was studied by means of differential scanning calorimetry. Lignin shortened the crystallization half‐time t_1/2 for isothermal crystallization. The activation energy ΔE for PHB/lignin and pure PHB in the isothermal crystallization process was ?237.40 and ?131.22 kJ/mol, respectively, clearly indicating that the crystallization of the PHB/lignin blend was more favorable than that of pure PHB from a thermodynamic perspective. At the same time, according to polarized optical microscopy, the rate of spherulitic growth from the melt increased with the addition of lignin, which is ascribed to the reduction of surface fold energy σ_e, that is, σ_e is 59.2 × 10^?3 and 41.6 × 10^?3 J m^?2 for pure PHB and PHB/lignin, respectively. Polarized optical microscopy also showed that the spherulites found in PHB with lignin were smaller in size and greater in number than those found in pure PHB. The wide‐angle X‐ray diffraction indicated that an addition of lignin caused no change in the crystal structure and degree of crystallinity. These results indicated that lignin is a good nucleating agent for the crystallization of PHB. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2466–2474, 2004