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.     

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.     

Mechanical and thermal properties of recycled poly(ethylene terephthalate) reinforced newspaper fiber composites

This study presents the mechanical and thermal properties of environment-friendly composites made from recycled newspaper fibers reinforced recycled poly(ethylene terephthalate) (rPET) resin with the addition of styrene-ethylene-butylene-styrene grafted maleic anhydride (SEBS-g-MA) as compatibilizer. The effect of SEBS-g-MA addition (i.e., 10 phr) by using a twin-screw extruder to the rPET resin, followed by different fiber content (5, 10 and 15 wt.%) on the tensile, flexural and impact properties of the composites were determined. Stiffness of composites increased significantly compared to those of rPET/SEBS-g-MA blend. Fiber addition resulted in moderate increases in both tensile and flexural strength of the composites. Scanning electron microscope (SEM) photomicrographs of the impact fracture surfaces demonstrate good adhesion at 5 and 10 % fiber content. Differential scanning calorimetry (DSC) showed that the presence of newspaper fibers enhanced the nonisothermal crystallization kinetics and crystallinity. Thermal stability of the composites was improved as indicated by thermogravimetric analysis (TGA).     

Incorporating shape memory properties in poly(ethylene terephthalate) film by isothermal crystallization

In this paper the peculiar shape memory property of semicrystalline PET films is studied. The shape memory samples were prepared through isothermal crystallization of glassy PET films at different temperatures between 120 and 230 °C for 15 and 4 minutes. It was assumed that the incorporated shape memory constitution is due to crystalline and amorphous parts and also third phase i.e. a rigid amorphous fraction (RAF) which rose by increasing the degree of crystallinity. The microstructure of samples was probed by DSC and WAXD analysis, and concluded that isothermal crystallization at temperature which spinodal decomposition mechanism is dominant, brings the formation of secondary crystal lamellas in amorphous regions between pre-existing lamellar stacks, incorporating shape recovery in the samples. As the crystallization proceeds with time or at higher temperatures, the fraction of RAF increases leading to suppression of shape memory effect.     

Structure-properties relationship of poly(ethylene terephthalate) wool-type fibres

Two PET wool-type fibres were studied for this research, i.e. a normal wool-type and a low-pilling modification. The structural morphology and crystalline orientation of the fibres were investigated by means of wide-angle x-ray scattering (WAXS), density measurements and infrared (IR) spectroscopy. The degree of crystallinity, crystallite orientation, apparent crystallite dimensions and micro-void system were determined by x-ray scattering. Birefringence measurements were used to study the average molecular orientation and the orientation of macromolecular chain segments in the amorphous regions. In addition, PET samples were conventionally dyed and the effect of the structure on colour was followed using colorimetry. Significant differences between the two PET wool fibre types were observed; i.e. crystallinity is higher for the standard PET wool fibre type, the crystallites are slightly larger and better oriented, long periods are larger, the orientation of molecular segments in non-crystalline phase is higher, and bigger voids are formed. The observed structure gives rise to fibres higher tenacity and higher bending stiffness.     

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 .     

Thermal and structure properties of biobased cellulose nanowhiskers/poly (lactic acid) nanocomposites

Cellulose nanowhiskers were used to improve the performance of poly (lactic acid) (PLA). The nanocomposites mixed with three different molecular weight of poly (ethylene glycol) (PEG) were characterized by mechanical testing, thermal gravimetry and differential scanning calorimetry. The tensile test showed an increase in tensile strength and elongation at break with the addition of PEG to PLA/CNW nanocomposites, the thermal analysis results showed an increase of crystallization temperature (T _c) and crystallization compatibility (larger crystallization and melting areas), which indicated that the cellulose nanowhiskers (CNW) and PEG or CNW alone should not be considered as nucleating agents for the PLA matrix; The CNW was homo-dispersed which contributed to decreasing mobility of polymer chain segments. The compatibility between hydrophobic PLA matrix and the hydrophilic CNW was improved by the addition of different molecular weight polymeric-PEG. The thermo gravimetric analysis indicated that the thermal stability of the different composites were reflected well in the region between 25 °C and 245 oC. The structure of the PLA/CNW/PEG composites was characterized by AFM, which showed that the CNW dispersed in the PLA matrix evenly.     

Functionalized graphene nanoplatelets/poly(ethylene oxide) nanocomposites: Correlation between crystallization behavior and mechanical performance

Poly(ethylene oxide) (PEO) nanocomposites containing pristine or functionalized graphene nanoplatelets (FGnP) prepared via solution blending and thermal and mechanical properties of nanocomposites were investigated. Chemical functionalization of graphene nanoplatelets was conducted through an amidation reaction between carboxylic acid groups of acidified graphene and hydroxyl groups of polyethylene glycol (PEG). An interfacial linkage and a good dispersion of FGnP was observed via scanning electron microscope (SEM). Differential scanning calorimetry (DSC) analysis revealed that the degree of crystallinity of samples decreased by addition of graphene nanoplatelets, while the size of spherulites increased as indicated by polarized optical microscope (POM). A lower degree of crystallinity and larger spherulites were detected in the case of FGnP. Filler/matrix interfacial adhesion was also remarkably influenced the mechanical properties of PEO as an effective reinforcement of matrix obtained upon the addition of FGnP nanosheets compared to untreated graphene.     

Thermal performance and flammability of poly(ethylene terephthalate) fabrics grafted with different monomers followed by electron beam irradiation

Electron beam irradiation grafting of acrylic acid (AAc), acrylamide (AAm), and dimethyl vinylphosphonate (DMVP) onto poly(ethylene terephthalate) (PET) fabrics was performed using a high-energy electron accelerator. Parameters affecting the graft polymerization of PET fabrics, including absorbed dose and monomer concentration, were investigated. Fourier transform infrared spectroscopy analysis confirmed that the monomers were grafted onto the PET fabrics. The thermal behavior of the grafted PET fabrics was investigated with thermogravimetric analysis. Findings showed that grafting with AAm could improve the thermal stability of PET. The limiting oxygen index values and vertical flammability test results showed that PET fabric graft-polymerized with AAc could improve the flammability and prevent melt dripping. Grafting with AAm and DMVP could improve the flame retardation property of PET fabric. Scanning electron micrographs showed that the surface morphology of the PET fabric samples was significantly influenced by graft polymerization, and that grafting with AAc could promote the formation of residual char and impart an anti-dripping quality to PET fabrics.     

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.     

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.     

Mechanical and thermal properties of polypropylene (PP) composites filled with CaCO3 and shell waste derived bio-fillers

The clam shell (CS) waste was first modified by furfural and hydrochloric acid to prepare fillers FCS and ACS, which were then used as fillers in polypropylene (PP), as well as the commercial calcium carbonate (CC). These fillers were characterized and analyzed by means of X-ray diffraction (XRD), atomic force microscopy (AFM), particle size analyzer, Fourier transformed infrared spectroscopy (FTIR) and contact angle measurement. The mechanical and thermal properties of PP composites were investigated as well. XRD analysis indicated that the major crystalline phase of CC was calcite; of shell waste derived fillers, calcite and aragonite. The CC was fully hydrophobic, while the shell derived fillers were amphiphilic. Mechanical property studies showed that the incorporation of FCS played the role mainly of toughening the PP; of CC, CS and ACS, that of reinforcing. The optimum filler contents of CS, ACS and FCS could reach 5, 7 and 15 wt.%, respectively, to obtain a good balance between fracture toughness and stiffness of the PP composites. Polarized optical microscopy (POM) observation indicated that the inclusion of these fillers could promote the heterogeneous nucleation of PP.     

A novel eco-friendly colorant and dyeing method for poly(ethylene terephthalate) substrate

Although madder (Rubia tinctorum) has been used as a well-known natural textile dye source for dyeing of natural fibers such as wool, silk and cotton, 100 % polyester dyeing with madder is not common. In this study, polyester samples were dyed with madder at different dyeing temperatures, from 60 °C to 130 °C, in company with 7 chemical and 5 natural mordants. Color properties and rub, light and wash fastness performances were investigated. Different shades of orange, brown, pink and reddish green colors were obtained. Dyeing at 130 °C exhibited the highest color yield, the highest chroma and the lowest lightness values. Overall, chemical mordants exhibited higher color yields than natural mordants. High wash fatness, moderate light and rub fastness levels were observed. The potassium bitartrate and gallnut, a natural mordant, exhibited the best results. The madder dyeing of polyester should be carried out at hot temperature conditions, 130 °C, in order to obtain the highest achievable color yield and chroma with the highest light and wash fastness properties.     

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.     

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.     

Effect of CaCO3 contents on the properties of polyethylene nanocomposites sheets

Nanocomposites of high-density polyethylene/linear low-density polyethylene (HDPE/LLDPE) filled with untreated and surface treated nano-calcium carbonate (nCC) were prepared. The influence of isopropyl tri-(dioctylpyrophosphato) titanate (JN114) treatment of nCC on the morphology, mechanical, crystallization and flow properties of the nanocomposites were studied. The results of scanning electron microscopy (SEM) showed that JN114 treated nCC was better dispersion in the matrix than the untreated one. A fine dispersion of the treated nanoparticles in the nanocomposites was observed by transmission electron microscopy (TEM). The FTIR spectrum analysis revealed that the JN114 could change the surface properties of nCC, resulting in greater hydrophobicity of the surface and enhanced compatibility with nonpolar matrices. The tensile elastic modulus (E _c ) and Izod impact strength (SIC) of nanocomposites increased with the increasing of nCC content while tensile fracture strength (σ _b ) decreased. The JN114 treated nanocomposites had superior mechanical properties to those of the untreated ones. The compatibility of these nanocomposites was examined by DSC to estimate melting point (T _m ) and crystallization temperature (T _c ). Furthermore, the melt flow index (MFI) of the nanocomposite materials were measured. It was found that the MFI decreased with the addition of weight fraction of the nCC particles.     

Thermotropic liquid crystal polymer reinforced poly(butylene terephthalate) composites to improve heat distortion temperature and mechanical properties

Thermotropic liquid crystal polymer (TLCP)-reinforced poly(butylene terephthalate) (PBT) composites were prepared by melt processing. The improvement in the mechanical properties and the processability of the PBT/TLCP composites was attributed to the reinforcing effect by TLCP phase and its well distribution in the PBT matrix. X-ray diffraction results demonstrated that a slow cooling process leads to the thicker lamellar structures and the formation of more regular crystallites in the composites. The incorporation of TLCP improves not only the tensile strength and flexural modulus but also the heat distortion temperature (HDT) of the PBT/TLCP composites. The HDT values of the composites were dependent on TLCP content. The improvement in the HDT values of the PBT/TLCP composites may be explained in terms with the increased flexural modulus, the development of more regular crystalline structures, and the enhancement of the ability of the composites to sustain the storage modulus by TLCP phase. In addition, the simple additivity rule makes it possible to predict the HDT values of the PBT/TLCP composites.     

Crystallization behavior,rheology, mechanical properties,and enzymatic degradation of poly(L-lactide)/poly(D-lactide)/glycidyl methacrylate grafted poly(ethylene octane) blends

Poly(L-lactide) (PLLA)/poly(D-lactide) (PDLA)/poly(ethylene octene) grafted with glycidyl methacrylate (GPOE) were prepared by simple melt blending method at PDLA loadings from 1 to 5 wt%. Differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) demonstrated the formation of the stereocomplex in the blends. The addition of PDLA led to the increase of nucleation density from polarized microscope (POM) observations. Rheological measurements indicated that the blends exhibited a rheological fluid-solid transition and an enhanced elastic behavior in that ternary system as the PDLA loadings reached up to 5 wt%. By adding 1-2 wt% PDLA, the ternary system has better tensile and impact properties. Dynamic Mechanical Analysis (DMA) results showed that SC crystal formation and its effect on the enhancement of thermal stability at higher temperature. It is interesting that the enzymatic degradation rates have been enhanced clearly in the PLLA/PDLA/GPOE blends than in the PLLA/GPOE blend, which may be of great use and significance for the wider practical application of PLLA/GPOE blends.     

The effect of molecular weight and the linear velocity of drum surface on the properties of electrospun poly(ethylene terephthalate) nonwovens

In this study, we evaluated the effect of the molecular weight of the polymer on electrospun poly(ethylene terephthalate) (PET) nonwovens, and their mechanical properties as a function of the linear velocity of drum surface. Polymer solutions and electrospun PET nonwovens were characterized by means of viscometer, tensiometer, scanning electron microscope (SEM), wide angle X-ray diffraction measurement (WAXD) and universal testing machine (UTM). By keeping the uniform solution viscosity, regardless of molecular weight differences, electrospun PET nonwovens with similar average diameter could be obtained. In addition, the mechanical properties of the electrospun PET nonwovens were strongly dependent on the linear velocity of drum surface. From the results of the WAXD scan, it was found that the polymer took on a particular molecular orientation when the linear velocity of drum surface was increased. The peaks became more definite and apparent, evolving from an amorphous pattern at 0 m/min to peaks and signifying the presence of crystallinity at 45 m/min.