Miscibility and crystallization behaviors of poly(trimethylene terephthalate)/poly(ethylene naphthalate) blends

Poly(trimethylene terephthalate) (PTT)/poly(ethylene naphthalate) (PEN) blends of various compositions were prepared by the solution-blending and melt-blending methods. The changes in miscibility and crystallization behaviors of the blends upon thermal treatment above the melting temperature of the blends at 280°C were investigated by using DSC, DMA,¹H NMR, and SAXS analyses. Without any thermal treatment, the blend systems were not miscible, and the thermal transitions, such as glass transition, cold crystallization, and crystal melting of the individual components were observed in the DSC and DMA analyses. With thermal treatment, though, they became miscible as the thermal transitions of each component disappeared and single glass transition peaks were observed in the thermal analysis. The chain randomness determined using¹H NMR spectroscopy revealed that thermal treatment at 280°C for more than 30 min brought about transesterification reactions between the PTT and PEN segments resulting in an increase in their miscibility. These results were confirmed by the small angle X-ray analysis conducted to determine the long period (L), the thickness of the crystalline lamella stack (l _c ), and the thickness of the amorphous region (l _a ). After short thermal treatment, the melt-blended sample followed the values for the individual components. However, with extended thermal treatment, the blend became homogeneous, possessing different crystalline morphologies which resulted in different values ofL, l _c , andl _a .     

Copper metallization of poly(ethylene terephthalate) fabrics via intermediate polyaniline layers

Poly(ethylene terephthalate) fabrics were metallized through electroless plating of copper. The copper plating was performed on palladium-decorated polyaniline surfaces, and polyaniline was present as an intermediate layer on fabrics to facilitate palladium formation. Different oxidation states of polyaniline were tested in their efficacy in Pd (II) reduction and subsequent Cu plating. X-ray photoelectron spectroscopy was used to monitor the surface changes along the metallization procedure, and surface resistance was measure to probe the electrical properties of the metallized fabrics.     

Improvement of mechanical and electrical properties of poly(ethylene glycol) and cyanoresin based polymer electrolytes

Ionic conductivity and mechanical properties of a mixed polymer matrix consisting of poly(ethylene glycol) (PEG) and cyanoresin type M (CRM) with various lithium salts and plasticizer were examined. The CRM used was a copolymer of cyanoethyl pullulan and cyanoethyl poly(vinyl alcohol) with a molar ratio of 1:1, mixed plasticizer was ethylene carbonate (EC) and propylene carbonate (PC) at a volume ratio of 1:1. The conductive behavior of polymer electrolytes in the temperature range of 298∼338 K was investigated. The PEG/LiClO₄ complexes exhibited the highest ionic conductivity of ∼10⁻⁵ S/cm at 25°C with the salt concentration of 1.5 M. In addition, the plasticized PEG/LiClO₄ complexes exhibited improvement of ionic conductivity. However, their complexes showed decreased mechanical properties. The improvement of ionic conductivity and mechanical properties could be obtained from the polymer electrolytes by using CRM. The highest ionic conductivity of PEG/CRM/LiClO₄/(EC-PC) was 5.33×10⁻⁴ S/cm at 25°C.     

The preparation and characterization of conductive poly(ethylene terephthalate)/polyaniline composite fibers using benzoyl peroxide

Conductive polyaniline (PAn)/poly(ethylene terephthalate) (PET) composite fibers were prepared by chemical polymerization of aniline in the presence of PET fibers using benzoyl peroxide (Bz₂O₂) in organic solvent/aqueous hydrochloric acid mixtures. The effects of polymerization conditions such as organic solvent/water ratio, oxidant, aniline and hydrochloric acid concentrations and temperature were investigated on the amount of PAn deposited on PET fiber and the electrical surface resistance of composite fibers. The maximum PAn content and the lowest electrical surface resistance of composite fibers were observed at HCl concentrations of 0.5 mol L⁻¹. The properties of PAn/PET composite fibers such as density, diameter, tensile strength and breaking elongation were also investigated in comparison with those of pure PET. Characterization of conductive composite fibers was carried out by FTIR, TGA, SEM techniques, surface resistance measurements, and cross section images taken by optical microscope.     

Synthesis and hydrophilicity of poly(trimethylene 2,6-naphthalate)/poly(ethylene glycol) copolymers

Poly(trimethylene 2,6-naphthalate) (PTN)/poly(ethylene glycol) (PEG) copolymers were synthesized by the two-step melt copolymerization process of dimethyl-2,6-naphthalenedicarboxylate (2,6-NDC) with 1,3-propanediol (PD) and PEG. The copolymers produced had different PEG molecular weights and contents. The structure, thermal property, and hydrophilicity of these copolymers were studied by proton nuclear magnetic resonance (¹H-NMR) analysis, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and by contact angle, moisture content, and instantaneous elastic recovery measurements. The intrinsic viscosity and the instantaneous elastic recovery of the PTN/PEG copolymers increased with increasing PEG molecular weight and content, whereas the glass transition, melting, and cold crystallization temperatures, and the heat of fusion of the PTN/PEG copolymers all decreased with increasing PEG molecular weight or content. The thermal stability of the copolymers was not affected by PEG molecular weight or content. The hydrophilicity, as determined by contact angle and moisture content measurements of the copolymer films, was significantly improved with increasing PEG molecular weight and content.     

Thermal properties of Poly(trimethylene terephthalate)/Poly(ethylene terephthalate) melt blends

The thermal behavior, morphology, ester-interchange reaction of Poly(trimethylene terephthalate) (PTT)/Poly(ethylene terephthalate) (PET) melt blends were investigated over the whole composition range(xPTT/(1-x)PET) using a twinscrew Brabender. The melt blends were analyzed by differential scanning calorimetry (DSC), nuclear magnetic resonance spectroscopy (¹³C-NMR), and scanning electron microscopy (SEM). Single glass transition temperature (T _g ) and cold crystallization temperature (T _cc ) were observed in all melt blends. Melt blends were found to be due to the ester-interchange reaction in PTT/PET blend. Also the randomness of copolymer increases because transesterification between PTT and PET increases with increasing blending time. This reaction increases homogeneity of the blends and decreases the degree of crystallinity of the melt blends. In PTT-rich blends, mechanical properties decrease with increase of PET content compared with that of pure PTT. And, in PET-rich blends, tensile modulus decreases with increase of PTT content, but tensile strength and elongation is similar to that of pure PET.     

Synthesis and hydrophilicities of Poly(ethylene 2,6-naphthalate)/Poly(ethylene glycol) copolymers

Poly(ethylene 2,6-naphthalate) (PEN)/Poly(ethylene glycol) (PEG) copolymers were synthesized by two step reaction during the melt copolymerization process. The first step was the esterification reaction of dimethyl-2,6-naphthalenedicarboxylate (2,6-NDC) and ethylene glycol (EG). The second step was the condensation polymerization of bishydroxyethylnaphthalate (BHEN) and PEG. The copolymers contained 10 mol% of PEG units with different molecular weights. Structures and thermal properties of the copolymers were studied by using¹H-NMR, DSC, TGA, etc. Especially, while the intrinsic viscosities of PEN/PEG copolymers increased with increasing molecular weights of PEG, but the glass transition temperature, the cold crystallization temperature, and the weight loss temperature of the copolymers decreased with increasing molecular weights of PEG. Consequently, the hydrophilicities by means of contact angle measurement and moisture content of the copolymer films were found to be significantly improved with increasing molecular weights of PEG.     

Helium/oxygen atmospheric pressure plasma treatment on poly(ethylene terephthalate) and poly(trimethylene terephthalate) knitted fabrics: Comparison of low-stress mechanical/surface chemical properties

Helium-oxygen plasma treatments were conducted to modify poly(trimethylene terephthalate)(PTT) and poly(ethylene terephthalate) (PET) warp knitted fabrics under atmospheric pressure. Lubricant and contamination removals by plasma etching effect were examined by weight loss (%) measurements and scanning electron microscopy (SEM) analysis. Surface oxidation by plasma treatments was revealed by x-ray photoelectron spectroscopy (XPS) analyses, resulting in formation of hydrophilic groups and moisture regain (%) enhancement. Low-stress mechanical properties (evaluated by Kawabata evaluation system) and bulk properties (air permeability and bust strength) were enhanced by plasma treatment. Increasing interfiber and interyarn frictions might play important roles in enhancing surface property changes by plasma etching effect, and then changing low-stress mechanical properties and bulk properties for both fabrics.     

Effects of blend ratio and heat treatment on the properties of the electrospun poly(ethylene terephthlate) nonwovens

Semicrystalline poly(ethylene terephthalate) (cPET)/amorphous poly(ethylene terephthalate) with isophthalic acid (aPET) blends with 100/0, 75/25, 50/50, 25/75, and 0/100 by weight ratios were dissolved in a mixture of trifluoroacetic acid (TFA)/methylene chloride (MC) (50/50, v/v) and electrospun via the electrospinning technique. Solution properties such as solution viscosity, surface tension and electric conductivity were determined. The solution viscosity slightly decreased as aPET content increased, while there was no difference in surface tension with respect to aPET composition. The characteristics of the electrospun cPET/aPET blend nonwovens were investigated in terms of their morphology, pore size and gas permeability. All these measurements were carried out before and after heat treatment for various blend weight ratios. The average diameter of the fibers decreased with increasing aPET composition due to the decrease in viscosity. Also, the morphology of the electrospun cPET/aPET blend nonwovens was changed by heat treatment. The pore size and pore size distribution varied greatly from a few nanometers to a few microns. The gas permeability after heat treatment was lower than that before heat treatment because of the change of the morphology.     

Poly(trimethylene terephthalate) fiber melt-spinning: Material parameters and computer simulation

In this work, the method, in principle of the box complex algorithm was adopted to obtain stress-induced crystallization coefficient C and the strain-optical coefficientA _op with the value of 295 and 1.5×10⁻⁹, respectively, and some parametersA ₁=0.27,A ₂=5.06,a=3.5,b=1.8 relative to the elongational viscosity of poly(trimethylene terephthalate)(PTT) fiber. The vitrification distance as a function of the take-up velocity and mass throughput was also gotten. The effects of spinning conditions on filament temperature, velocity gradient, spinning tension, birefringence and crystallinity, and effect of viscoelasticity on take-up velocity had been discussed.     

Thermal degradation and cyclodepolymerization of poly(ethylene terephthalate-co-isophthalate)s

The thermal degradation of poly(ethylene terephthalate-co-isophthalate)s (PETIs) is investigated by using isothermal thermogravimetric analysis at the temperature range of 280–310°C. The degradation rate of PETIs is increased as the mole ratio of ethylene isophthaloyl (EI) units in PETIs increases. The activation energies for the thermal degradation of poly(ethylene terephthalate), PETI(5/5), and poly(ethylene isophthalate) are 33.4, 16.6, and 8.9 kcal/mole, respectively. The degradation rate of PETIs is influenced by their volatile cyclic oligomer components formed during the polymerization and the thermal degradation. It is simulated by the rotational isomeric state model that the content of cyclic dimer in PETIs, which is the most volatile cyclic oligomer component, increases with the EI units in PETIs.     

Crystallization and molecular relaxation of poly(ethylene terephthalate) annealed in supercritical carbon dioxide

Poly(ethylene terephthalate) was annealed at different temperature and pressure of supercritical carbon dioxide (CO₂) using samples quenched from the melt. Crystallization and molecular relaxation behavior due to CO₂-annealing of samples were investigated using differential scanning calorimetric and dynamic mechanical measurements. The glass transition and crystallization temperatures significantly decreased with increasing temperature and pressure of CO₂. The dynamic mechanical measurement of samples annealed at 150 °C in supercritical CO₂ showed three relaxation peaks, corresponding to existence of different amorphous regimes such as rigid, intermediate, and mobile domains. As a result, the mobile chains were likely to facilitate crystallization in supercritical state. It also led to the decreased modulus of CO₂-annealed samples with increasing pressure.     

Preparation and characterization of nanoscaled poly(vinyl alcohol) fibers via electrospinning

Nanoscaled PVA fibers were prepared by electrospinning. This paper described the electrospinning process, the processing conditions, fiber morphology, and some potential applications of the PVA nano-fibers. PVA fibers with various diameters (50–250 nm) were obtained by changing solution concentration, voltage and tip to collector distance (TCD). The major factor was the concentration of PVA solution which affected the fiber diameter evidently. Increasing the concentration, the fiber diameter was increased, and the amount of beads was reduced even to 0%. The fibers were found be efficiently crosslinked by glyoxal during the curing process. Phosphoric acid was used as a catalyst activator to reduce strength losses during crosslinking. Scanning electron micrograph (SEM) and differential scanning calorimetric (DSC) techniques were employed to characterize the morphology and crosslinking of PVA fibers. It was found that the primary factor which affected the crosslinking density was the content of chemical crosslinking agent.     

X-ray diffraction studies of poly(aryl ether ether ketone) fibers with different degrees of crystallinity and orientation

A selection of commercially available poly(ethylene terephthalate) fibers with different degrees of molecular alignment and crystallinity have been investigated utilizing a wide range of techniques including optical microscopy, infrared spectroscopy together with thermal and wide-angle X-ray diffraction techniques. Annealing experiments showed increased molecular alignment and crystallinity as shown by the increased values of birefringence and melting enthalpies. Crystallinity values determined from thermal analysis, density, unpolarized infrared spectroscopy and X-ray diffraction are compared and discussed in terms of the inherent capabilities and limitations of each measurement technique. The birefringence and refractive index values obtained from optical microscopy are found to decrease with increasing wavelength of light used in the experiments. The wide-angle X-ray diffraction analysis shows that the samples with relatively low orientation possess oriented non-crystalline array of chains whereas those with high molecular orientation possess well defined and oriented crystalline array of chains along the fiber axis direction. X-ray analysis showed increasing crystallite size trend with increasing molecular orientation. SEM images showed micro-cracks on low oriented fiber surfaces becoming smooth on highly oriented fiber surfaces. Excellent bending characteristics were observed with knotted fibers implying relatively easy fabric formation.     

Fine structure and physical properties of poly(buthylene terephthalate) sheets prepared by roller drawing method

Poly(butylene terephthalate) sheets were prepared by roller-drawing method with various draw ratio. The drawing temperature is 100 °C and draw ratios were varied 2, 2.5, 3, 3.5 and 4. The effect of draw ratio on the crystal structure, the molecular orientation, dynamic viscoelastic properties, sonic modulus and tensile properties of the roller-drawn PBT sheets were investigated. In WAXD results, with increasing of the draw ratio, (010) and (100) planes of preferred orientation have the strongest intensity on the equator. In the meridional scans, it was confirmed that α and β crystal co-existed in the roller drawn PBT sheets with various draw ratio. Uniaxially roller-drawn PBT sheets clearly increased orientation along the stretched direction at high draw ratio. And the four-methylene groups of PBT orient along the surface of the sheet. The mechanical properties of PBT sheets were improved by orientation-induced crystallization during roller drawing process at 100 °C.     

Synthesis,structure, and thermal property of poly(trimethylene terephthalate-<Emphasis Type="Italic">co</Emphasis>-trimethylene 2,6-naphthalate) copolymers

Poly(trimethylene terephthalate-co-trimethylene 2,6-naphthalate)s (P(TT-co-TN)s) with various copolymer composition were synthesized, and their chain structure, thermal property and crystalline structure were investigated by using¹H-NMR spectroscopy, differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD), respectively. It was found from sequence analysis that all the P(TT-co-TN) copolymers synthesized have a statistical random distribution of TT and TN units. It was also observed from DSC thermograms that the glass transition temperature increases linearly with increasing the TN comonomer content, whereas the melting temperature of copolymer decreases with increasing the corresponding comonomer content in respective PTT- and PTN-based copolymer, showing pseudo-eutectic melting behavior. All the samples melt-crystallized isothermally except for P(TT-co-66 mol % TN) exhibit multiple melting endotherms and clear X-ray diffraction patterns. The multiple melting behavior originates from the dual lamellar population and/or the melting-recrystallization-remelting. The X-ray diffraction patterns are largely divided into two classes depending on the copolymer composition, i.e., PTT and PTNβ-form diffraction patterns, without exhibiting cocrystallization.     

Preparation and properties of waterborne poly(urethane-urea) ionomers effect of the type of neutralizing agent

A series of waterborne poly(urethane-urea) anionomers were prepared from isophorone diisocyanate (IPDI), polycaprolactone diol (PCL), dimethylol propionic acid (DMPA), ethylene diamine (EDA), and triethylamine (TEA), NaOH, or Cu(COOCH₃)₂ as neutralizing agent. This study was performed to decide the effect of neutralizing agent type on the particle size, viscosity, hydrogen bonding index, adhesive strength, antistaticity, antibacterial and mechanical properties. The particle size of the dispersions decreased in the following order: TEA based samples (T-sample), NaOH based samples(N-sample), and Cu(COOCH₃)₂ based sample (C-sample). The viscosity of the dispersions increased in the order of C-sample, N-sample, and T-sample. Metal salt based film samples (N and C-sample) had much higher antistaticity than TEA based sample. By infrared spectroscopy, it was found that the hydrogen bonding index (or fraction) of samples decreased in the order of T-sample, N-sample, and C-sample. The adhesive strength and tensile modulus/strength decreased in the order of T-sample, N-sample, and C-sample. The C-sample had strong antibacterial halo, however, T- and N-samples did not.     

Mechanical properties of flax-g-poly(methyl acrylate) reinforced phenolic composites

In order to develop composites with better mechanical properties and environmental performance, it becomes necessary to increase the hydrophobicity of the natural fibers and to improve the interface between matrix and natural fibers. Graft copolymerization of natural fibers is one of the best methods to attain these improvements. Only few workers have reported the use of graft copolymers as reinforcing material in the preparation of composites. So in the present paper, we report the preparation of graft copolymers of flax fibers with methyl acrylate (MA) using Fenton’s reagent (FAS-H₂O₂) as redox system. Synthesized flax-g-poly(MA) was characterized with FTIR, TGA/DTA, scanning electron microscopy (SEM), and X-ray diffraction (XRD) techniques. Composites were prepared using flax-g-poly(MA) as a reinforcement and phenolformaldehyde (PF) as the binding material. Mechanical properties of phenol-formaldehyde composites were compared and it has been found that composites reinforced with flax-g-poly(MA) showed improvement in mechanical properties. Composites reinforced with flax-g-poly(MA) showed better tensile strength (235 N) and compressive strength (814 N) in comparison to composites reinforced with original flax fiber which showed lesser tensile strength (162 N) and compressive strength (372 N). Composites reinforced with flax-g-poly(MA) shows the improved MOR, MOE, and SP.     

Mechanical properties of semi-interpenetrating polymer network hydrogels based on poly(2-hydroxyethyl methacrylate) copolymer and chitosan

Semi-interpenetrating polymeric network (semi-IPN) hydrogels based on poly(2-hydroxyethyl methacrylate) (PHEMA) and poly(2-hydroxyethyl methacrylate-co-sodium methacrylate) [P(HEMA-co-SMA)], and chitosan with different molecular weights were prepared by crosslinking with ethylene glycol dimethacrylate (EGDMA) and poly(ethylene glycol) diacrylate (PEGDA) and their gelation time, water content, mechanical properties, and morphology were investigated. In consideration of the influence of the molecular weight of chitosan, there is no big difference in the water content, while tensile properties and compressive modulus increased as the molecular weight of chitosan increased. The water content increased and tensile properties and compressive modulus decreased with increasing SMA concentration. Considering the effect of the crosslinking agent, PEGDA had higher water content and lower tensile and compressive moduli than EGDMA. It is suggested that PHEMA/chitosan and P(HEMA-co-SMA)/chitosan semi-IPN hydrogels with different structures and physical properties can be prepared depending on the molecular weight of chitosan, the copolymerization with SMA, and the crosslinking agent type.     

Interchange reaction kinetics and sequence distribution of liquid crystalline poly(ethylene terephthalate-co-2(3)-chloro-1,4-phenylene terephthalate)

Liquid crystalline (LC) poly(ethylene terephthalate-co-2(3)-chloro-1,4-phenylene terephthalate) [copoly(ET/CPT)] was prepared using poly(ethylene terephthalate) (PET) as a flexible spacer, terephthalic acid (TPA), and chlorohydroquinone diacetate (CHQDA). All reactions involved in the copolymerization were investigated using some model compounds: TPA was used for acidolysis, diphenylethyl terephthalate (DPET) for interchange reaction between PET chains, and di-o-chlorophenyl terephthalate (DOCT) and di-m-chlorophenyl terephthalate (DMCT) for interchange reaction between PET and rigid rodlike segments. Activation energies obtained for the acidolysis of PET with TPA and for interchange reaction of PET with DPET, DOCT, and DMCT were 19.8 kcal/mole, 26.5 kcal/mole, 60.2 kcal/mole, and 45.9 kcal/mole, respectively. This result supports that the copolymerization proceeds through the acidolysis of PET with TPA first and subsequent polycondensation between carboxyl end group and CHQDA or acetyl end group, which is formed from the reaction of CHQDA and TPA. Also, it was found that ester-interchange reaction can be influenced by the steric hindrance. Copoly(ET/CPT)s obtained had ethylene acetate end groups formed from acetic acid and hydroxy ethylene end groups and showed almost the random sequence distribution for all compositions.