Poly(propylene)/poly(ethylene terephthalate‐co‐isophthalate) blends and glass bead filled composites: Microstructure and thermomechanical properties

Blends of poly(propylene) (PP) and poly(ethylene terephthalate‐co‐isophthalate) (co‐PET) (95/5) with and without compatibilizing agent (maleic anhydride PP), as well as composites of these blends with glass beads (50 wt%) with and without silane coupling agent surface‐treatment, were prepared and studied on a basis of the material microstructure and thermomechanical properties. Infrared and Raman spectroscopy, as well as transmission electron microscopy, displayed evidence of MAPP compatibilizing action for the blend. Differential scanning calorimetry showed a remarkable effect of nucleation rate increase exerted by co‐PET on the PP crystallization. Moreover, glass beads were found to increase the PP nucleation rate slightly. PP crystallinity hardly varied with the composition. Wide angle X‐ray diffraction allowed determination of differences in the orientation of the poly(propylene) b‐axis, with more homogeneous orientations in the presence of both co‐PET and glass beads. MAPP promoted the PP b‐axis orientation. Differences in PP α′ relaxation could be analyzed through dynamic‐mechanical thermal analysis (DMTA). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1841–1852, 2004     

Improving oxygen barrier properties of poly(ethylene terephthalate) by incorporating isophthalate. II. Effect of crystallization

The present study examined crystallization of poly(ethylene terephthalate) (PET) and a series of random and blocky copolymers in which up to 30% of the terephthalate was replaced with isophthalate. Isothermal crystallization kinetics and direct observation of the spherulitic morphology revealed that the blocky copolymers crystallized more rapidly than PET, at least in part, as the result of enhanced spherulite nucleation. The statistical copolymers with 10 and 20% isophthalate achieved almost the same level of crystallinity as that of the blocky copolymers. The statistical copolymers with 10% isophthalate crystallized almost as fast as PET, although the statistical copolymer with 20% isophthalate crystallized much more slowly. Crystallization substantially reduced the oxygen permeability. Analysis of oxygen‐transport parameters in terms of a two‐phase structural model that considered a dispersion of lower‐permeability spherulites in an amorphous matrix of higher permeability revealed that dedensification of the PET interlamellar amorphous regions was responsible for the unexpectedly high oxygen solubility of crystallized PET. In contrast, copolymerization with isophthalate prevented dedensification of the interlamellar amorphous regions. As a result, crystallization was more effective in reducing the oxygen permeability. It was speculated that segregation of kinked isophthalate units to the amorphous regions of the spherulite relieved constraint on the interlamellar amorphous chain segments. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1629–1642, 2005     

Crystalline and thermal behavior of poly(ethylene terephthalate)/polyphenoxy blends

Poly(ethylene terephthalate) (PET)/polyphenoxy blends were prepared by melt blending. Crystalline and thermal behaviors of PET/polyphenoxy blends were verified by use of DSC. The experiment results show that the initial temperature, peak temperature, and ending temperature of cold crystallization increase with increasing phenoxy content. On the contrary, the onset melting temperature, finishing melting temperature, and peak temperature in the first heating and the secondary heating processes decrease with increasing phenoxy content. The crystallization enthalpy and melting enthalpy, as well as the crystallization rate, decrease with increasing phenoxy content. Avrami exponents of the blends are slightly higher than that of pure PET and almost independent of phenoxy content. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 878–885, 2005     

Poly(ethylene terephthalate‐co‐isophthalate) copolyesters obtained from ethylene terephthalate and isophthalate oligomers

A series of poly(ethylene terephthalate‐co‐isophthalate) copolyesters containing upto 50%‐mole of isophthalic units were prepared by polycondensation from ethylene terephthalate and ethylene isophthalate fractions of linear oligomers containing from 5 to 6 repeating units in average. The polyesters were obtained in good yields and with high‐molecular‐weights. The microstructure of the copolyesters was studied as a function of reaction time by ¹³C‐NMR showing that a random distribution of the comonomers was achieved since the earlier stages of polycondensation. The melting temperature and enthalpy of the copolyesters decreased with the content of isophthalic units so that copolyesters containing more than 25% of these units were amorphous. Isothermal crystallization studies made on crystalline copolyesters revealed that the crystallization rate of copolyesters decreased with the content in isophthalic units. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Blends of poly(ethylene terephthalate) and poly(butylene terephthalate)

Commercial grade poly(ethylene terephthalate), (PET, intrinsic viscosity = 0.80 dL/g) and poly(butylene terephthalate), (PBT, intrinsic viscosity = 1.00 dL/g) were melt blended over the entire composition range using a counterrotating twin‐screw extruder. The mechanical, thermal, electrical, and rheological properties of the blends were studied. All of the blends showed higher impact properties than that of PET or PBT. The 50:50 blend composition exhibited the highest impact value. Other mechanical properties also showed similar trends for blends of this composition. The addition of PBT increased the processability of PET. Differential scanning calorimetry data showed the presence of both phases. For all blends, only a single glass‐transition temperature was observed. The melting characteristics of one phase were influenced by the presence of the other. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 75–82, 2005     

A preliminary study of blends of bisphenol a polycarbonate and poly(ethylene terephthalate)

The microstructure of blends of bisphenol A polycarbonate (PC), and poly(ethylene terepthalate) (PETP) has been studied by solvent extraction, infrared spectrophotometry, differential scanning calorimetry and dynamic mechanical thermal analysis. The blends appear to contain two amorphous phases over the whole composition range. The tensile behaviour and the Charpy impact strength of some of the blends have been determined, before and after heat treatment at 125°C for 18 hours. Improved performance of the blends, compared with that of the homopolymers PC and PETP, has been demonstrated.     

Improvement of compatibility of poly(ethylene terephthalate) and poly(ethylene octene) blends by γ‐irradiation

Blends of poly(ethylene terephthalate) (PET) and poly(ethylene octene) (POE) were prepared by melt blending with various amounts of trimethylolpropane triacylate (TMPTA). The mechanical properties, phase morphologies, and gel fractions at various absorbed doses of γ‐irradiation have been investigated. It was found that the toughness of blends was enhanced effectively after irradiation as well as the tensile properties. The elongation at break for all studied PET/POE blends (POE being up to 15 wt %) with 2 wt % TMPTA reached 250–400% at most absorbed doses of γ‐irradiation, approximately 50–80 times of those of untreated PET/POE blends. The impact strength of PET/POE (85/15 wt/wt) blends with 2 wt % TMPTA irradiated with as little as 30 kGy absorbed dose exceeded 17 kJ/m², being approximately 3.4 times of those of untreated blends. The improvement of the mechanical properties was supported by the morphology changes. Scanning electron microscope images of fracture surfaces showed a smaller dispersed phase and more indistinct inter‐phase boundaries in the irradiated blends. This indicates increased compatibility of PET and POE in the PET/POE blends. The changes of the morphologies and the enhancement of the mechanical properties were ascribed to the enhanced inter‐phase boundaries by the formation of complex graft structures confirmed by the results of the gelation extraction and Fourier Transform Infrared analyses. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Mechanical properties of poly(ethylene terephthalate) modified with functionalized polymers

This study examined the effect of blending poly(ethylene terephthalate) (PET) with 5% of a functionalized polymer. The blends were characterized by particle size and size distribution, unnotched tensile behavior, toughness, and notch sensitivity. The improved properties of blends that incorporated a functionalized elastomer were consistent with in situ formation of a graft copolymer by reaction with PET end groups. Triblock copolymers were examined that had styrene end blocks and an ethylene/butylene midblock (SEBS) with grafted maleic anhydride. The present study extended previous investigations that focused on level of grafting to examine the effects of component molecular weight and PET hydroxyl‐to‐carboxyl end‐group ratio. Increasing the molecular weight of the SEBS and decreasing the hydroxyl‐to‐carboxyl ratio of the PET increased the effectiveness of the SEBS. In addition, a mix of an unfunctionalized SEBS with a functionalized SEBS was more effective than a single SEBS with the same total anhydride content. The same elastomers were the most effective for modifying a lower molecular weight PET (intrinsic viscosity 0.73) and a higher molecular weight PET (intrinsic viscosity 0.95). Some functionalized polypropylenes included in the study did not enhance the properties of PET. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 203–219, 1999     

PEN/PET共混物结晶行为研究

用差示扫描量热法(DSC)研究了不同共混比例PEN/PET共混物的熔体结晶行为,并进行了等温结晶动力学测定。结果表明:随着两种组分向中间比例(50/50)靠近,共混物的熔融温度越低,结晶速率也越慢。     

Rheological and thermal properties of blends of modified poly(ethylene terephthalate) with p‐acetoxybenzoic acid and poly(butylene terephthalate)

Blending of thermotropic liquid crystalline polyesters (LCPs) with conventional polymers could result in materials that can be used as an alternative for short fiber‐reinforced thermoplastic composites, because of their low melt viscosity as well as their inherent high stiffness and strength, high use temperature, and excellent chemical resistance and low coefficient of expansion. In most of the blends was used LCP of 40 mol % of poly(ethylene terephthalate) (PET) and 60 mol % of p‐acetoxybenzoic acid (PABA). In this work, blends of several copolyesters having various PABA compositions from 10 to 70 mol % and poly(butylene terephthalate) (PBT) were prepared and their rheological and thermal properties were investigated. For convenience, the copolyesters were designated as PETA‐x, where x is the mol % of PABA. It was found that PET‐60 and PET‐70 copolyesters decreased the melt viscosity of PBT in the blends and those PBT/PETA‐60 and PBT/PETA‐70 blends showed different melt viscosity behaviors with the change in shear rate, while blends of PBT and PET‐x having less than 50 mol % of PABA exhibited totally different rheological behaviors. The blends of PBT with PETA‐50, PETA‐60, and PETA‐70 showed the morphology of multiple layers of fibers. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1797–1806, 1999     

Melting and crystallization behavior of poly(ethylene terephthalate) and poly(m‐xylylene adipamide) blends

The crystallization and melting behaviors as well as the crystalline morphologies of Poly(ethylene terephthalate)/Poly(m‐xylylene adipamide) (PET/MXD6) blends have been examined and characterized with the aid of differential scanning calorimetry (DSC) and wide angle x‐ray diffraction (WAXD). The isothermal and nonisothermal crystallization behaviors of the blends were studied as functions of the contents of MXD6, catalyst concentrations, and the effects of the interchange reactions between PET and MXD6. Wide angle x‐ray scattering has been used to examine the crystalline morphologies of the PET/MXD6 blends, to characterize their crystalline and amorphous phases, and to determine crystallite sizes in the blends. Results indicate that the catalyst has both catalyzing and nucleation effects on the PET/MXD6 blends, with the extents of each effect dependent upon the content of catalyst. In addition the crystalline morphology was found to be dominated by the MXD6 content as well as the crystallization temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Uniaxial orientation and tensile properties of poly(ethylene terephthalate)/poly(ethylene-2,6-naphthalate) blends

Amorphous films of poly(ethylene terephthalate)/poly(ethylene-2,6-naphthalate) (PET/PEN) blends with different blend ratios were uniaxially drawn by solid-state coextrusion and the structure development during solid state deformation was studied. As-prepared blends showed two T_gs. The lower T_g was ∼72 °C, independent of the blend ratio. In contrast, the higher T_g increased with increasing PEN content. Thus, the coextrusion was carried out around the higher T_g of the sample. At a given draw ratio of 5, which was close to the achievable maximum draw ratio, the tensile strength of the drawn samples from the initially amorphous state increased gradually with increasing PEN content. On the other hand, the tensile modulus was found to decrease initially, reaching a minimum at 40-60 wt% PEN, and then increased as the PEN content increased. The results indicate that we can get the drawn films with a moderate tensile modulus and a high tensile strength. The drawn samples from the blends containing 40-60 wt% of PEN showed a maximum elongation at break, and a maximum thermal shrinkage around 100 °C. Also, the degree of stress-induced crystallinity showed a broad minimum around the blend ratio of 50% of PEN. These morphological characteristics explained well the effects of blend ratio on the tensile modulus and strength of drawn PET/PEN blend films.     

Sequence analysis of poly(ethylene terephthalate)/poly(butylene terephthalate) copolymer prepared by ester-interchange reactions

The molecular structure of the copolyester formed through the interchange reaction in poly(ethylene terephthalate)/poly(butylene terephthalate) blends was investigated with ¹³C-NMR spectroscopy. The molar fractions of heterolinkage triads in the copolyesters were lower than the values calculated by Bernoullian statistics; this indicates that the sequence of heterolinkages was far from a random distribution at the initial stage of the interchange reaction. However, the randomness increased and the number-average sequence length decreased with reaction time. The solubility of the blend decreased with increasing sequence length, resulting from the formation of block copolymers with long sequence lengths at the initial stage of the interchange reaction. The solubility of the copolyester formed by a dibutyltin dilaurate (DBTDL)-catalyzed reaction was higher than that of the copolyester formed by a titanium tetrabutoxide-catalyzed reaction; this is related to the fact that alcoholysis prevailed in the DBTDL-catalyzed reaction. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 159–168, 2001     

Effect of shearing on crystallization behavior of poly(ethylene terephthalate)

The shear‐induced crystallization behavior of PET was investigated by measuring the time‐dependent storage modulus (G′) and dynamic viscosity (η′) with a parallel‐plate rheometer at different temperatures and shear rate. The morphology of shear‐induced crystallized PET was measured by DSC, X‐ray, and polarizing optical microscopy. When a constant shear rate was added to the molten polymer, the shear stress increased with the time as a result of the orientation of molecular chains. The induction time of crystallization is decreased with frequency. Moreover, the rate of isothermal crystallization of PET was notably decreased with increasing temperature. The shape of spherulites is changed to ellipsoid in the direction of shear. In addition, aggregation of spherulites is increased with increasing frequency. Particularly, the row nucleation morphology could be observed under polarized light for ω = 1. From the results of DSC, the melting point and enthalpy have a tendency to decrease slightly with increasing frequency. The crystallite size and perfectness decreased with frequency, which was confirmed with X‐ray data. The unit length of the crystallographic unit cell of the PET increased and the (1 0 3) plane peak increased with increasing frequency. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2640–2646, 2001     

Morphology and crystallization of poly(ethylene terephthalate)

The melting behaviour and the morphology of poly(ethylene terephthalate) crystallized from the melt are reported. In general, dual or triple melting endotherms are seen, and single endotherms are seen when the samples are crystallized above 215°C for long times. The location of the uppermost endotherm was found to be constant below T_c = 230°C, and above that temperature the location depends on T_c. Therefore, we have shown that samples of PET which are crystallized above T_c = 230°C contain perfect crystals only; below T_c = 230°C, they contain perfect and imperfect crystals. Scanning electron microscopy showed that the perfect crystals are the dominant lamellae in the spherulitic structure, while the imperfect crystals are the subsidiary lamellae in the spherulitic structure, The amorphous regions are located between individual lamellae.     

Recycled poly(ethylene terephthalate)/linear low‐density polyethylene blends through physical processing

Poly(styrene‐ethylene/butylene‐styrene) (SEBS) was used as a compatibilizer to improve the thermal and mechanical properties of recycled poly(ethylene terephthalate)/linear low‐density polyethylene (R‐PET/LLDPE) blends. The blends compatibilized with 0–20 wt % SEBS were prepared by low‐temperature solid‐state extrusion. The effect of SEBS content was investigated using scanning electron microscope, differential scanning calorimeter, dynamic mechanical analysis (DMA), and mechanical property testing. Morphology observation showed that the addition of 10 wt % SEBS led to the deformation of dispersed phase from spherical to fibrous structure, and microfibrils were formed at the interface between two phases in the compatibilized blends. Both differential scanning calorimeter and DMA results revealed that the blend with 20 wt % SEBS showed better compatibility between PET and LLDPE than other blends studied. The addition of 20 wt % of SEBS obviously improved the crystallizibility of PET as well as the modulus of the blends. DMA analysis also showed that the interaction between SEBS and two other components enhanced at high temperature above 130°C. The impact strength of the blend with 20 wt % SEBS increased of 93.2% with respect to the blend without SEBS, accompanied by only a 28.7% tensile strength decrease. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Phase structure and properties of poly(ethylene terephthalate)/high‐density polyethylene based on recycled materials

Blends based on recycled high density polyethylene (R‐HDPE) and recycled poly(ethylene terephthalate) (R‐PET) were made through reactive extrusion. The effects of maleated polyethylene (PE‐g‐MA), triblock copolymer of styrene and ethylene/butylene (SEBS), and 4,4′‐methylenedi(phenyl isocyanate) (MDI) on blend properties were studied. The 2% PE‐g‐MA improved the compatibility of R‐HDPE and R‐PET in all blends toughened by SEBS. For the R‐HDPE/R‐PET (70/30 w/w) blend toughened by SEBS, the dispersed PET domain size was significantly reduced with use of 2% PE‐g‐MA, and the impact strength of the resultant blend doubled. For blends with R‐PET matrix, all strengths were improved by adding MDI through extending the PET molecular chains. The crystalline behaviors of R‐HDPE and R‐PET in one‐phase rich systems influenced each other. The addition of PE‐g‐MA and SEBS consistently reduced the crystalline level (χ_c) of either the R‐PET or the R‐HDPE phase and lowered the crystallization peak temperature (T_c) of R‐PET. Further addition of MDI did not influence R‐HDPE crystallization behavior but lowered the χ_c of R‐PET in R‐PET rich blends. The thermal stability of R‐HDPE/R‐PET 70/30 and 50/50 (w/w) blends were improved by chain‐extension when 0.5% MDI was added. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Chain extension of poly(ethylene terephthalate) with bisphenol‐A dicyanate

Chain extension of poly(ethylene terephthalate) (PET) with bisphenol‐A dicyanate (BADCy) was studied using an internal mixer under reactive blending conditions. The reaction between PET and BADCy was confirmed by Fourier transform infrared (FTIR) and chemical titration. With increasing amount of BADCy introduced, the modified PET gave rise to higher torque during stirred in an internal mixer, higher viscosity (η′), and higher storage modulus (G′). Measurement of intrinsic viscosity showed that BADCy indeed extended the molecular weight of PET. DSC analysis represented that T_m and T_c of the modified PET were shifted to low temperatures. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Miscibility and crystallization of poly(ethylene succinate)/poly(vinyl phenol) blends

Miscibility of biodegradable poly(ethylene succinate) (PES)/poly(vinyl phenol) (PVPh) blends has been studied by differential scanning calorimetry (DSC) in this work. PES is found to be miscible with PVPh as shown by the existence of single composition dependent glass transition temperature over the entire composition range. Spherulitic morphology and the growth rates of neat and blended PES were investigated by optical microscopy (OM). Both neat and blended PES show a maximum growth rate value in the crystallization temperature range of 45-65 °C, with the growth rate of neat PES being higher than that of blended PES at the same crystallization temperature. The overall crystallization kinetics of neat and blended PES was also studied by DSC and analyzed by the Avrami equation at 60 and 65 °C. The crystallization rate decreases with increasing the temperature for both neat and blended PES. The crystallization rate of blended PES is lower than that of neat PES at the same crystallization temperature. However, the Avrami exponent n is almost the same despite the blend composition and crystallization temperature, indicating that the addition of PVPh does not change the crystallization mechanism of PES but only lowers the crystallization rate.     

Study of the miscibility and crystallization behavior of poly(ethylene oxide)/poly(vinyl alcohol) blends

The miscibility and crystallization behavior of poly(ethylene oxide)/poly(vinyl alcohol) (PEO/PVA) blends were investigated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and polarizing optical microscopy. Because the glass‐transition temperature of PVA was near the melting point of PEO crystalline, an uncommon DSC procedure was used to determine the glass‐transition temperature of the PVA‐rich phase. From the DSC and DMA results, two glass‐transition temperatures, which corresponded to the PEO‐rich phase and the PVA‐rich phase, were observed. It was an important criterion to indicate that a blend was immiscible. It was also found that the preparation method of samples influenced the morphology and crystallization behaviors of PEO/PVA blends. The domain size of the disperse phase (PVA‐rich) for the solution‐cast blends was much larger than that for the coprecipitated blends. The crystallinity, spherulitic morphology, and isothermal crystallization behavior of PEO in the solution‐cast blends were similar to those of the neat PEO. On the contrary, these properties in the coprecipitated blends were different from those of the neat PEO. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1562–1568, 2004