Studies of polycarbonate — poly (butylene terephthalate) blends

The composition and microstructure of a blend of bisphenol-A polycarbonate (PC) and poly (butylene terephthalate) (PBT) have been established by a variety of physical methods. The composition was established by solvent extraction and infra-red spectrophotometry, while the microstructure was determined by these and the additional methods of differential scanning calorimetry and dynamic mechanical thermal analysis. The PBT retained its crystallinity in the commercial blend, (Xenoy CL-100), but blending reduced the main glass-rubber transition of the PC from 147°C to approximately 100°C. Conditioning of the blend at high temperatures resulted in progressive transesterification: 3 minutes at 240°C gave a small but significant effect, while 30 minutes at 270°C yielded large changes in the structure. These findings are important in respect of processing the material, and the limitations which might be incurred in plant recycling of scrap.     

The morphology and deformation behavior of poly(butylene terephthalate)/BPA polycarbonate blends

Summary In this communication the results of a series of recent studies of the morphology and deformation behavior of toughened poly(butylene terephthalate) (PBT)/BPA polycarbonate (PC) blends are briefly summarized. Several papers containing a more detailed account are currently in press (1–3). Among the unique morphological features of these blends are the consistent isolation of the core/shell impact modifier (IM) in the PC phase and the crystallization and phase separation of the PBT from the partially miscible PBT/PC melt on slow cooling. DSC studies provide corroborating evidence for melt miscibility of the two resins. The blends deform through a combination of cavitation and shear processes. In all cases cavitation occurs exclusively within the IM particles and is suppressed at higher PC concentrations and elevated temperatures.     

Morphological studies on the blends of poly(butylene terephthalate) and bisphenol-A polycarbonate

The morphology of the blends of poly(butylene terephthalate) (PBT) and bisphenol-A polycarbonate (PC) crystallized from the melt were studied by density measurement and small angle light scattering techniques. Rate of crystallization of these blends was found to be slower with increasing amount of PC. The Avrami exponent n for the blends was calculated and related to the shape of superstructures formed. H_v and V_v scattering patterns as seen by small angle light scattering were analyzed to determine the nature, shape, and size of the superstructures. The changes in the superstructure formation with increasing amount of PC in these blends have been analyzed.     

Hot drawing of partially miscible blends of polycarbonate and poly(butylene terephthalate)

Samples of PC-PBT blends over the entire composition range were drawn at 160°C to high extensions, 2.1–5.8, to study the mechanical reinforcement and the molecular structure development upon deformation. Elastic modulus E' increases with extension ratio for all compositions and temperatures. Blends with 25 and 40 wt% of PC show higher E' at low temperature than pure PBT blends do. Crystallinity increases with extension ratio and is relatively smaller with increasing PC content. The influence of the reversible α to β crystal form transformation was also studied. The second moment of the orientation function f for both crystal forms increases to high values > 0.9 at relatively low extensions. f decreases with PC content for α crystals but decreases for β crystals. The α fraction is high for PBT and decreases with PC content and extension ratio in the blends. Strain recovery experiments show that the α to β transformation is also elastic in nature at high extension ratios and that the reinforcing effect in high PBT content blends is not due to the α/β ratio. © 1996 John Wiley & Sons, Inc.     

Molecular orientation and relaxation in poly(butylene terephthalate)/polycarbonate blends

Rheo-optical Fourier-transform infrared (FTIR) spectroscopy is based on the simultaneous acquisition of stress-strain data and FTIR spectra on-line to the mechanical treatment of polymers and is frequently applied for the characterization of transient structural changes during deformation and stress-relaxation. In the present communication, this technique has been employed in order to investigate the distribution of molecular orientation and its relaxation in uniaxially drawn solution-cast films of semicrystalline partial miscible blends of poly(butylene terephthalate) (PBT) with polycarbonate (PC) containing 10, 30 and 50 wt% PC. The uniaxial deformation of these blend films having a PBT-crystallinity degree ranging from 31 to 12%, in unstretched blends, leads to a appreciable high segmental orientation for the crystalline PBT due to a structural transformation from lamellae to microfibrils. The formation of this fibrillar structure is attributed to non-reversibility of an extended phase with all-trans conformational sequence of the aliphatic segments of PBT, occurring during elongation. The rate of relaxation of this conformational transition, however, increases with increasing amorphous content in the blends. Also it is observed that even with increasing amorphous content in the PBT/PC blends the crystalline PBT shows significant orientation. In such cases, apart from the few lamellae which transform to microfibrils, it is suggested that a stress induced transformation of PBT chains in amorphous PBT-component to irreversible all-trans extended crystalline form also contributes to PBT crystalline orientation. In contrast with this high crystalline orientation, the amorphous PBT located in the interlamellar regions inside the PBT-spherulites show a lower orientation in blends as compared in pure PBT.On the other hand, an overall segmental orientation of PC chains in blends is of lower order which is attributed mainly to low stretching temperature compared to T_g of pure PC. The results are discussed in terms of the resulting spherulitic morphology and the temporary network formed by the elongated PBT and PC chains inside the interlamellar regions, in blends.     

The vibration welding of poly(butylene terephthalate) and a polycarbonate/poly(butylene terephthalate) blend to each other and to other resins and blends

Vibration welding is used to assess the weldability of poly(butylene terephthalate) (PBT) and a polycarbonate/poly(butylene terephthalate) blend (PC/PBT) to each other and to other resins and blends: PBT to PC/PBT, PBT to modified poly(phenylene oxide) (M-PPO), PBT to polyetherimide (PEI) and PEI to a 65 wt% mineral-filled polyester blend (65-PF-PEB), PBT to a poly(phenylene oxide)/polyamide blend (PPO/PA), PC/PBT to M-PPO, and PC/PBT to PPO/PA. Based on the tensile strength of the weaker of the two materials in each pair, the following relative weld strengths have been demonstrated: PBT to PC/PBT,98%; PBT to PEI, 95%; 65-PF-PEB to PEI, 92%; and PC/PBT to M-PPO, 73%. PBT neither welds to M-PPO nor to PPO/PA, and PC/PBT does not weld to PPO/PA.     

High-Temperature large-strain behavior of polycarbonate,polyetherimide and poly(butylene terephthalate)

A noncontacting experimental procedure has been used for characterizing the high-temperature large-strain uniaxial behavior of polycarbonate (PC), polyetherimide (PEI), and poly(butylene terephthalate) (PBT), through controlled tests on flat specimens cut from extruded sheet. While each of these polymers exhibits stable necking over a broad temperature range, the transition to the necked state is shown to be more gradual at higher temperatures, resulting in a less sharply defined neck transition region during the drawing process. These trends in necking behavior, and other phenomena such as double necking, which only occur at high temperatures, are illustrated through contour plots of the Cauchy-Green deformation tensor. Elevated temperature true-stress versus stretch data are given for each of these polymers.     

Partial miscibility of poly(butylene terephthalate)/BPA polycarbonate melt blends

Summary Differential scanning calorimetry (DSC) measurements have been carried out on a number of poly(butylene terephthalate) (PBT)/BPA polycarbonate (PC) blends prepared by melt compounding and solution casting from hexafluoroisopropanol (HFIP). The results clearly indicate that appreciable mixing of the two polymers takes place in the melt phase whereas complete separation is observed in cast films. The failure of the casting procedure to mimic the melt blending results is related in part to liquid-liquid phase separation and to crystallization of both polymers from the casting solvent.     

Fibers from poly(ethylene terephthalate) and poly(butylene terephthalate) blends I. Mechanical behavior

Fibers prepared from poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) blends show a sharp decrease in tensile strength and modulus when blends are on the verge of phase segregation. The modulus values differ for homopolymers for their differences in chain configuration and methylene groups and that of the blends are in proportion. The experimental strength values are higher than the predicted values according to Paul's model for incompatible polymers. At 90/10 PET/PBT blend, the modulus is high, which may be a relative factor to the smaller crystal size of the components.     

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.     

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.     

Influence of the morphology on the fire behavior of a polycarbonate/poly(butylene terephthalate) blend

Polycarbonate/Poly(butylene terephthalate) (PC/PBT) blends are used in various industrial sectors, particularly in the cable industry. In this work, the fire behavior of PC/PBT blends was studied for the entire range of blend composition to investigate the relation between fire properties and blend morphology. The morphology of the binary blends used presents a phase inversion point for 25–30 wt % PBT. Various tests have been performed to characterize the fire behavior [limiting oxygen index (LOI), epiradiator test, cone calorimeter, and pyrolysis combustion flow calorimeter (PCFC)]. A change in fire behavior has been observed when the PBT content increases from 20 to 30 wt %, corresponding to the phase inversion, from a continuous rich-PC phase to a continuous rich-PBT phase. Consequently, it can be suggested that the control of the morphology of binary polymer blends is crucial to improve their fire properties. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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.     

Nanocomposites based on poly(butylene adipate‐co‐terephthalate) and montmorillonite

Nanocomposites based on biodegradable poly(butylene adipate‐co‐terephthalate) (PBAT) and layered silicates were prepared by the melt intercalation method. Nonmodified montmorillonite (MMT) and organo‐modified MMTs (DA‐M, ODA‐M, and LEA‐M) by the protonated ammonium cations of dodecylamine, octadecylamine, and N‐lauryldiethanolamine, respectively, were used as the layered silicates. The comparison of interlayer spacing between clay and PBAT composites with inorganic content 3 wt % measured by X‐ray diffraction (XRD) revealed the formation of intercalated nanocomposites in DA‐M and LEA‐M. In case of PBAT/ODA‐M (3 wt %), no clear peak related to interlayer spacing was observed. From morphological studies using transmission electron microscopy, the ODA‐M was found to be finely and homogeneously dispersed in the matrix polymer, indicating the formation of exfoliated nanocomposite. When ODA‐M content was increased, the XRD peak related to intercalated clay increased. Although the exfoliated ODA‐M (3 wt %) nanocomposite showed a lower tensile modulus than the intercalated DA‐M and LEA‐M (3 wt %) composites, the PBAT/ODA‐M composite with inorganic content 5 wt % showed the highest tensile modulus, strength, and elongation at break among the PBAT composites with inorganic content 5 wt %. Their tensile properties are discussed in relation to the degree of crystallinity of the injection molded samples. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 386–392, 2005     

The hydrolytic stability of glass fiber reinforced poly(butylene terephthalate), poly(ethylene terephthalate) and polycarbonate

The hydrolytic stability of glass fiber reinforced poly(butylene terephthalate) (PBT), poly(ethylene terephthalate) (PET) and polycarbonate (PC) was studied. The activation energies in kcal/mole for hydrolysis are 26 for PBT and 23 for PET. Both PBT and PET contain 30 percent glass fiber reinforcement. The hydrolysis rates for a series of experimental PC's containing 10, 30 and 40 percent glass were obtained from GPC data. These increase with glass concentration but are lower than that of the unreinforced PC. Melt flow rate changes are a good measure of the hydrolytic degradation of PET. However, in the time scale of these experiments, the tensile properties of glass reinforced PBT and PC do not correlate well with M?_w changes, unlike unreinforced PBT and PC polymers. Consequently, to compare these three glass fiber reinforced polymers, estimates of failure time must be based on changes in tensile strength rather than melt flow rate.     

Polyester–polycarbonate blends. I. Poly(butylene terephthalate)

Melt blends of bisphenol A polycarbonate with poly(butylene terephthalate) were studied by DTA and dynamic mechanical behavior to determine their state of miscibility. Both techniques showed multiple glass transitions indicative of incomplete miscibility in the amorphous phase. However, these transitions in some cases did not correspond to those in the pure components and varied with overall blend composition in some instances. This indicates that there are amorphous phases containing both components, i.e., partial miscibility. This view was supported by the crystallization behavior of the polyester. Two crystallization exotherms were observed for quenched samples, which is interpreted as polyester crystallization from two separate phases, one richer in this component than the other. Other interpretations of these results are discussed.     

Melting and solidification behavior of blends of high density polyethylene with poly(butylene terephthalate)

This study focuses on the effect of various processing and cooling conditions upon the subsequent melting and solidification behavior of blends of poly(butylene terephthalate) (PBT) and high density polyethylene (HDPE). Differential scanning calorimetry (DSC) measurements have shown that the crystallization of reprocessed PBT is different from the crystallization behavior of virgin samples. Two melting endotherms for PBT were observed for reprocessed PBT and for PBT-PE blends. The nature of each PBT peak is discussed in relation to processing history, solidification conditions, and composition. The presence of two crystallization peaks for the PE component in blends of PE and PBT are thought to be associated with the restriction of molecular motion of PE in the presence of the second component. The relative magnitudes of the two exotherms of PE vary with composition and cooling rate during solidification.     

Novel poly(butylene terephthalate)/poly(vinyl butyral) blends prepared by in situ polymerization of cyclic poly(butylene terephthalate) oligomers

Blends of in situ polymerized PBT from cyclic oligomers (c-PBT) and PVB were prepared with varying compositions and compared with mechanical blends of conventional PBT and PVB. The materials were characterized by a variety of techniques including DSC, DMTA, DETA, FTIR, NMR and GPC. It was found that the in situ prepared blend of c-PBT/PVB has one glass transition temperature and shows evidence of miscibility. In contrast, the conventional blend of PBT/PVB shows incompatibility after blending. The cause of miscibility in the in situ prepared PBT/PVB blends is thought to be the formation of a graft copolymer. These results show that there are unique possibilities for in situ processing by combining polymerization of cyclic polyester oligomers with blending.     

Formation and morphology development of poly(butylene terephthalate) nanofibers from poly(butylene terephthalate)/cellulose acetate butyrate immiscible blends

Nano‐scale poly(butylene terephthalate) (PBT) fibers were prepared from PBT/cellulose acetate butyrate (CAB) immiscible polymer blends due to in situ microfibrillar formation during a melt extruding process. The morphological development of the dispersed phase was studied with samples collected at different zones in a twin screw extruder. It was found that the holistic developmental trends of PBT dispersed phase were nearly the same. Fibers began to form even under the shear flow of the twin‐screw extruder. The morphology developmental mechanism of the dispersed phase involved the formation of sheets, holes and network structures, then the size reduction and formation of nanofibers. The effect of viscosity ratio, blend ratio, and shear rate on the morphology evolution was also studied by analyzing the shape and size distribution of the samples. The diameter distribution of the nanofibers could be affected by viscosity ratio, blend ratio, and shear rate. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers