Thermodynamic properties of poly(butylene terephthalate)

Specific heat of poly(butylene terephthalate) was measured in a Mettler TC 10 differential thermal analyzer. Its glass transition, melting behaviour, as well as its enthalpy, entropy, Gibbs free energy, and the rigidity of the chains are described.     

Electrical properties of poly(butylene terephthalate)

Direct current (dc) and alternating current (ac) electrical properties of semicrystalline poly(butylene terephthalate) (PBT) are investigated as a function of temperature and frequency. Dc electrical conductivity measurements have been performed over the temperature range ?75°C to 130°C and point out an essentially ionic mechanism of charge transport. Charge carriers are identified in protons supplied by ionization of carboxyl end-groups after dissociation of the existing hydrogen bonds. Dielectric constant and loss factor have been measured over the temperature range ?100°C to 130°C and over the frequency range 10^?6 to 10⁶ Hz. Together with de measurements, they allow the detection of the α glass-rubber and the β subglass relaxation processes, as well as an interfacial polarization of the Maxwell–Wagner–Sillars type. Finally, the contour map of loss factor, summarizing the overall dielectric behavior of the polymer, is reported and discussed for electrical applications of PBT.     

Physical properties of oriented poly(butylene terephthalate)

The effect of orientation on the low-strain mechanical properties, dielectric relaxation, and thermal expansivity of poly(butylene terephthalate) has been studied. The α relaxation at 50°C (1 Hz), which involves large-scale chain motion in the amorphous regions, is reduced in magnitude and shifted to higher temperature after drawing. In contrast, the localized motions of the carbonyl and glycol groups associated with the β process at ?90°C (1 Hz) is not much affected by orientation. At low temperature, a large difference along and normal to the draw direction is observed for both Young's modulus and thermal expansivity. The anisotropy, however, diminishes with increasing temperature and becomes nearly zero above the α relaxation. This feature can be understood on the basis of the Takayanagi model.     

Fluorinated poly(butylene terephthalate): Preparation and properties

Fluorinated poly(butylene terephthalate) (PBT) can be easily prepared using a telechelic perfluoropolyether (PFPE) as a comonomer. The functional groups of the PFPE react completely with other monomers, but the distribution of the PFPE blocks is not homogeneous and in the final polymeric material there is a significant fraction of PFPE bonded to very short segments of polyester. Due to the very poor miscibility of PFPE and PBT, the PFPE is present as a separate phase dispersed in an almost pure PBT matrix. Accordingly, both thermal and mechanical properties of PBT are little affected by the PFPE. The presence of PFPE induces a slight improvement on the fracture resistance and on surface properties such as wear resistance and coefficient of friction. © 1994 John Wiley & Sons, Inc.     

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     

Mechanical properties in torsion for poly(butylene terephthalate) and a poly(ether ester) based on poly(ethylene glycol) and poly(butylene terephthalate)

The torsional behavior of poly(ether ester) (PEE) thermoplastic elastomer, based on poly(ethylene glycol) (PEG) and poly(butylene terephthalate) (PBT) was studied and compared with that of PBT itself. Two types of experiments were performed: (1) stress relaxation in torsion, and (2) measurement of intermittent couple-twist responses. It was shown that the relaxation of the torsional couple M could be represented as a sum of several exponential terms in the time, rather than as a simple exponential function. This sum might be called a Prony series on the analogy of the usual stress relaxation which occurs after stretching a sample to a certain deformation and holding it constant. The intermittent couple-twist experiments were carried out by analogy with similar experiments in elongation. For PEE the couple rises steadily with the twist, whereas for PBT it rises abruptly and remains constant within the experimental error for high twists. The residual twist, however, showed a similar trend for both PEE and PBT. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 495–502, 1998     

Crystallization of poly(butylene terephthalate)

This article provides a thorough analysis of the crystallization process of poly(butylene terephthalate) (PBT). Isothermal crystal growth rates have been experimentally measured between 459 and 491 K, and analyzed according to the Hoffman and Lauritzen theory. A II–III regime transition occurs at 484 K, accompanied by a change in crystal morphology. By means of a non‐linear fitting procedure, precise values of the nucleation constant K_g were obtained. The lateral surface free energy σ was calculated and, from this, the α parameter of the Thomas‐Staveley expression was obtained.     

Hydrolysis of poly(butylene terephthalate)

The hydrolytic stability of poly(butylene terephthalate) (PBT) resins and compounds was studied. Rates of reaction were determined by measuring changes in melt flow rate. Hydrolysis was slightly accelerated by contact of PBT with glass containers and reduced by incorporation of some flame retardant additives. Melt flow rates were related to tensile elongation ofunfilled PBT and tensile strength ofthe glass fiber reinforced polymer and used as failure criteria. Reaction rates were used to predict failure times at various conditions.     

Crystallization and melting behaviour of poly(butylene terephthalate) in poly(butylene terephthalate)/polyarylate blends

Summary The crystallization and melting behaviour of poly(butylene terephthalate) has been studied in the pure state and in its blends with a polyarylate of bisphenol A and isophthalic/terephthalic acids. Differential scanning calorimetry has been used as experimental technique and the effects of different thermal treatments have been analyzed. Results show the hindrance for the crystallization of poly(butylene terephthalate) imposed by the presence of polyarylate, as well as the existence of multiple melting after isothermal crystallization. Explanations are given for the observed behaviours.     

Crystallization in blends of poly(ethylene terephthalate) and poly(butylene terephthalate)

Blends composed of poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) were melt-mixed in a Brabender cam mixer at different mixing speeds. The glass transition (T_g) and the crystallization behavior of the blends from glassy state were studied using DSC. It was found that although the blends had the same composition and exhibited the similar T_g, their properties of crystallization could be different; some exhibited a single crystallization peak and some exhibited multiple crystallization peaks depending upon experimental conditions. Results indicated that the behavior of crystallization from glassy state were influenced by entanglement and transesterification of chains. The crystallization time values were obtained over a wide range of crystallization temperature. From curve fitting, the crystallization time values and the temperature, at which the crystallization rate reaches the maximum, were found.     

Fracture surface characteristics and impact properties of poly(butylene terephthalate)

In this article, the relationship between fracture surface feature and impact properties of poly(butylene terephthalate) (PBT) was investigated. The results indicated that the fracture surface morphology of notched impact specimens tested in the temperature range from 196 to 180 °C could be differentiated into brittle (T ≤ 20 °C) and ductile appearances (T > 20 °C). The fracture surface roughness was characterized by surface roughness ratio (R _s) and fractal dimension (D _b). The fracture mode significantly influenced the relationship between impact strength and fracture surface roughness. When PBT fractured in a brittle mode, both the measured values of R _s and D _b could correspond to impact strength appropriately. On the contrary, when PBT fractured in a ductile mode, their relationship became not statistically significant because the area of the plastic deformation zone instead of fracture surface roughness might be the major factor influencing impact strength.     

Morphology and strength of polycarbonate to poly(butylene terephthalate) vibration-welded butt joints

Under the right conditions, the strength of vibration-welded butt joints of amorphous polycarbonate (PC) to semicrystalline poly(butylene terephthalate) (PBT) are shown to be as high as the strength of PBT, the weaker of the two materials. Optical, scanning and transmission electron microscopy are used to examine the morphology of the weld zone. Acoustic microscopy is used to visualize poorly bonded regions. The effects of the weld parameters on weld strength and weld morphology are considered in detail.     

Sequence distribution and thermal properties of poly(butylene naphthalate terephthalate)

Poly(butylene naphthalate terephthalate) (PBNT) copolyesters were synthesized from bis(4-hydroxybutyl) terephthalate (BHBT) and bis(4-hydroxybutyl) naphthalate (BHBN) as starting materials. BHBT and BHBN were either homopolymerized or copolymerized at 260∼270 °C in the presence of titanium tetrabutoxide (TBT) as a catalyst to provide PBNT with various compositions. The copolyesters were characterized using inherent viscosity, X-ray, d.s.c., t.g.a. and ¹H NMR. The composition and sequence distribution of the copolyesters was determined from ¹H NMR spectra. The copolyesters exhibited a degree of randomness of about 1, indicating that the reactivity of BHBT and BHBN was almost the same. X-ray and d.s.c. showed PBNT copolyesters to be crystalline polymers. T.g.a. kinetics showed PBNT copolyesters to exhibit higher degradation activation energy, that is, better thermal stability, than PBTs.     

Crystallization of poly(ethylene terephthalate) and poly (butylene terephthalate) modified by diamides

Poly(ethylene terephthalate) (PET) and poly (butylene terephthalate) have been modified by diamide units (0.1–1 mol%) in an extrusion process and the crystallization behavior studied. The diamides used were: for PET, T2T‐dimethyl (N, N′‐bis(p‐carbomethoxybenzoyl)ethanediamine) and for PBT, T4T‐dimethyl (N, N′‐bis(p‐carbomethoxybenzoyl)butanediamine). The above materials were compared to talc (0.5 wt%), this being a standard heterogeneous nucleator, and to diamide modified copolymers obtained by a reactor process. Two PET materials were used: a slowly crystallizing recycled grade obtained from soft drink bottles and a rapidly crystallizing injection molding grade. The crystallization was studied by differential scanning calometry (DSC) and under injection molding conditions using wedge shaped specimens; the thermal properties were studied by dynamic mechanical analysis. T2T‐dimethyl is effective in increasing the crystallization of PET in both of the extrusion compounds as well as in the reactor materials. It was also found that the crystallization temperature of poly(butylene terephthalate) could be slightly increased by the addition of nucleators.     

Fracture toughness of poly(butylene terephthalate)

The overall fracture toughness of poly(butylene terephthalate) as well as plane stress and plane strain contributions have been measured as a function of rate from 5 × 10^?2 to 5 × 10³ in/min. A pronounced sample thickness dependence in K_c is observed over this range. Poly(butylene terephthalate) appears to exhibit excellent resistance to low speed crack propagation with internal voiding providing an effective crack blunting mechanism.     

Thermal degradation of poly(butylene terephthalate)

The thermal degradation of poly(butylene terephthalate) between 240° and 280°C has been studied by measurements of intrinsic viscosity, carboxyl end groups and weight loss. A first-order mechanism of fission, followed by elimination of butadiene, is proposed. The values of the kinetic constant and activation energy are in good agreement with those obtained for simple esters and poly(ethylene terephthalate).     

Effects of amorphous nylon on the properties of poly(butylene terephthalate) and 70/30 poly(butylene terephthalate)/nylon 6 blends

In this work, the effects of adding small amounts of amorphous nylon (a-nylon) on the properties of poly(butylene terephthalate)(PBT) have been studied. Miscibility and properties of PBT/a-nylon blends were compared with those of PBT/nylon 6 blends. Blends were prepared in a twin-screw extruder. The compositions of a-nylon or nylon 6 were varied from 0 to 20 phr. Rheological, thermal, mechanical, and dynamic mechanical properties of the blends were examined using a capillary rheometer, a differential scanning calorimeter (DSC), a universal testing machine (UTM), and a Rheometrics Mechanical Spectrometer(RMS), respectively. The PBT showed a single endotherm around 225.4°C on the DSC thermogram at the first heating scan but exhibited a second endotherm at a temperature below that of the original endotherm at the second heating scan. When a-nylon was added, the original endotherm was remarkably affected, but the second endotherm was not appreciably changed; i.e., the heat of fusion at the original endotherm decreased linearly with increasing a-nylon content, meaning that the addition of a-nylon affects significantly only the higher-melting crystals of PBT. The impact strength of PBT was decreased with nylon 6 content but was increased with increasing content of a-nylon. With an increase in the a-nylon content, the tensile modulus and the flexural modulus of PBT were decreased. Of interest is, however, that the tensile strength was significantly increased with a-nylon up to 15 phr. The melt viscosity of PBT was decreased with increasing a-nylon content, whereas it was not significantly changed with nylon 6 addition; i.e. the addition of a-nylon acted as a lubricant or a processing aid for PBT. The dynamic mechanical and the morphological studies showed that PBT was more miscible with a-nylon than with nylon 6. It was also found that a-nylon exhibited a compatibilizing effect for the PBT/nylon 6 blend of 70/30 wt% composition.     

Structure and properties of high-speed melt-spun filaments of poly(butylene terephthalate)

Filaments of poly(butylene terephthalate) were prepared by melt spinning with take-up velocities in the range 1000–5600 m/min. Two polymers with different molecular weights were used (intrinsic viscosities of 0.75 and 1.0 dL/g). The filaments were characterized using measurements of density, birefringence, shrinkage, thermal properties (differential scanning calorimetry), crystal size, crystalline orientation and phases present (wide angle X-ray diffraction), and tensile mechanical properties. Filaments spun from the 0.75 IV polymer with a mass throughput of 6 g/min at 1000 m/min have essentially amorphous structures, while higher take-up velocities result in α-form crystals or, at the highest take-up velocity, a mixture of α-form and β-form crystals. Only α-form crystals were detected in the higher IV polymer. Crystal size varied with crystallographic direction but generally increased as take-up velocity increased. At the lowest take-up velocities the filaments increased in length during thermal shrinkage measurements. With increasing take-up velocity the shrinkage became positive and continued to increase until reaching a maximum in the range of the highest sprinning speeds. This behavior correlates with the variation of the orientation factors of the amorphous phase. A plateau was observed in stress versus strain curves corresponding to strain-induced transformation from α-form to β-form crystals. The length of this plateau increased with increase of take-up velocity and the α-form crystal content in the sample. Both morphology and physical properties varied with polymer molecular weight and melt spinning conditions.     

Miscibilities and rheological properties of poly(butylene succinate)–Poly(butylene terephthalate) blends

An aliphatic/aromatic polyester blend has been dealt with in this study. As an aliphatic polyester, poly(butylene succinate) (PBS) was used, which is thought to possess biodegradability, but it is relatively expensive. It has been blended with poly(butylene terephthalate) (PBT) in order to obtain a biodegradable blend with better mechanical properties and lower cost. The miscibilities of PBS–PBT blends were examined not only from the changes of T_g but also from log G′–log G" plots. Dynamic mechanical thermal analyzer (DMTA) was an appropriate, sensitive method to obtain the glass transitions properly. Thermal stabilities of PBS and PBT were also verified at the temperature of 240°C. A transesterification reaction between two polyesters at 240°C was hardly detectable so that it did not affect the miscibilities and properties of the blends. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 945–951, 1999