Crystallization of bisphenol‐A polycarbonate by a vacuum process

The surface of bisphenol‐A‐polycarbonate (BAPC) showing a stable amorphous state can be crystallized by the “vapor transportation method”. Crystallized BAPC was employed as the novel simple storage medium and bit patterns were recorded on its surface by laser irradiation. Copyright © 2004 John Wiley & Sons, Ltd.     

Effect of supercritical carbon dioxide on the crystallization and melting behavior of linear bisphenol A polycarbonate

The crystallization and melting behavior of bisphenol A polycarbonate treated with supercritical carbon dioxide (CO₂) has been investigated with differential scanning calorimetry. Supercritical CO₂ depresses the crystallization temperature (T_c) of polycarbonate (PC). The lower melting point of PC crystals increase nonlinearly with increasing treatment temperature. This indicates that the depression of T_c is not a constant at the same pressure. T_c decreases faster at a higher treatment temperature than at a lower temperature. The leveling off of the depression in T_c at higher pressures is due to the antiplasticization effect of the hydrostatic pressure of CO₂. The melting curves of PC show two melting endotherms. The lower melting peak moves to a higher temperature with increasing treatment temperature, pressure, and time. The higher temperature peak moves toward a higher temperature as the treatment temperature is increased, whereas this peak is independent of the treatment pressure, time, and heating rate. The double melting peaks observed for PC can be attributed to the melting of crystals with different stability mechanisms. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 280–285, 2004     

Effect of ionic additives on deformation behavior of bisphenol a polycarbonate

The deformation behavior of bisphenol A polycarbonate containing only a small amount of oligoionomeric additives in the range of a few parts per hundred parts of resin was examined. The impact strength of polycarbonate markedly decreased as the content of additive increased, and brittle fracture of polycarbonate was observed in tensile tests when the concentration of additive was above 2.5 phr. The ductile‐to‐brittle transition that was determined using a comparison of the critical shear yield stress and the critical craze stress appeared to exist in the range of 2.5–3.5 phr of additive. The measured entanglement density was also found to decrease significantly with the addition of a few parts per hundred parts of resin of additives, and the change of the dominant deformation mechanism from ductile to brittle failure was recognized as a result of the change of the entanglement density of polycarbonate. Therefore, it was concluded that the presence of a small amount of ionomeric additives caused the loss of entanglement density that induced transition of the deformation mechanism of polycarbonate from ductile to brittle failure and led to the corresponding deterioration of impact strength. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2635–2643, 2001     

Thermal properties of polycarbonate grade bisphenol A

Thermal properties of 4,4(2,2-propylidene)-diphenol, referred to as bisphenol A, or BPA, are discussed. Parameters of thermal transitions were measured by DSC. The commercial product crystallizes in -form crystals which melt at 157°C (onset) and 161°C (peak) with a heat of fusion 134.37 J g^–1. Supercooled BPA shows a glass transition at about 40°C. Almost identical results were obtained for samples recovered by different methods: flakes, pastilles and prills. Two new polymorphs, the and -forms were identified. The -form melts at 131°C with a heat of fusion of 104.9 J g^–1. The melting point of the -form was measured to be 138°C and its heat of fusion is 118.3 J g^–1. Thermal conductivity of crystalline BPA was measured.Dedicated to Professor Bernhard Wunderlich on the occasion of his 65th birthdayThe author wishes to acknowledge helpful discussions with Dr. C. W. Uzelmeier and Dr. R. L. June during the course of this work. Many thanks go to J. M. Olvera for her help in gathering the experimental data.     

Crystallization of bisphenol a polycarbonate induced by supercritical carbon dioxide

Supercritical carbon dioxide readily induces crystallization in bisphenol A polycarbonate. Crystallization begins within one h of exposure to the CO₂ at temperatures and pressures as low as 75°C and 100 atm. The degree of crystallinity increases sharply as the CO₂ pressure is raised from 100 to 300 atm but levels off thereafter. This behavior is likely due to a minimum in the T_g of the polycarbonate/CO₂ mixture owing to the opposite effects of the pressure on the T_g of the polymer and on the equilibrium weight fraction of CO₂ absorbed. Percent crystallinities of over 20%, comparable to that achieved using acetone or other organic liquids, have been obtained after 2 h exposure to supercritical CO₂. Since polycarbonate degasses quickly and quantitatively at ambient temperature and pressure, the high T_g of bisphenol A polycarbonate can be regained in the crystallized material without further vacuum treatment.     

Rheology and interdiffusion in miscible blends of a low molar mass liquid crystal and bisphenol A–polycarbonate

The melt rheology of blends of a low molar mass liquid crystal (LC) blended with bisphenol A–polycarbonate (PC), and the self‐diffusion of the polycarbonate in the blends are reported. Results of small angle light scattering indicate that the LC is miscible in the mixture for weight fraction of LC less than 6%. The rheological properties of the blended sample within the miscible regime of the blends vary significantly with LC content. Although at low shear rates, the viscosity is similar to that of the pure polycarbonate, at high shear rates the curves show three regions of behavior, as has been described previously for pure LCs. The diffusion coefficient was obtained from interdiffusion studies using nuclear reaction analysis of bilayer films. An addition of only 1 wt % LC to the polycarbonate significantly increased the diffusion coefficient, but at higher concentration the converse was found. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2187–2195, 2007     

Blends of polycarbonate and acrylic polymers: Crystallization of polycarbonate

The microstructure of amorphous polymer blends has been extensively studied in the past, but now there is a growing interest for polymer blends where one or more of the components can crystallize. In this study we investigate such blends, namely miscible polycarbonate (PC)/acrylic blends. Using small angle X-ray scattering (SAXS) measurements, combined with atomic force microscopy (AFM), electron microscopy (SEM), and optical microscopy, we demonstrate that the amorphous acrylic component mostly segregates inside the spherulites between the lamellar bundles (interfibrillar segregation). Varying the PC molecular weight or the mobility of the amorphous component (by changing its molecular weight and T_g) does not change the mode of segregation. So far qualitative predictions of the mode of segregation in semicrystalline polymer blends have been proposed using the δ parameter (the ratio between the diffusion coefficient D of the amorphous component in the blend and the linear crystallization rate G), introduced by Keith and Padden. Our results suggest that other parameters have to be considered to fully understand the segregation process. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2197–2210, 1998     

High‐rate crystallization of polycarbonate in spincast thin film

Surface morphology of bisphenol‐A polycarbonate (BAPC) thin films, with thickness ranging from 30 to 1000 nm on silicon substrates was studied by atomic force microscopy. The films were prepared by spincasting from 1,2‐dichloroethane solutions of 0.25–5.0 wt % BAPC. Even though longer annealing than 250 h was necessary for complete crystallization for bulk BAPC, high crystallinity was observed for 30 nm thick film after annealing at 200 °C for 48 h in vacuum. Positron annihilation lifetime spectroscopy measurements showed that the free volume hole size in 30 nm thick film was larger than that of bulk at 200 °C. Comparison of the BAPC concentration in the precursor solution with the overlap concentration suggests that the high crystallinity of the 30 nm BAPC film is due to less entangled chains caused by rapid removal of the solvent from the dilute solution. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Relationships between the molecular architecture,crystallization capacity,and miscibility in poly(butylene terephthalate)/polycarbonate blends: A comparison with poly(ethylene terephthalate)/polycarbonate blends

Poly(butylene terephthalate) (PBT)/polycarbonate (PC) samples, prepared via reactive blending in the presence of Ti‐ and Sm‐based catalysts, resulted in block copolymers whose block length decreased as the mixing time increased. A single homogeneous amorphous phase occurred when the blocks had monomeric sequences shorter than 10 units. Otherwise, a crystalline phase of PBT developed. Also, in poly(ethylene terephthalate) (PET)/PC blends previously studied, the miscibility was strictly correlated with the crystallizability of the system. Therefore, the miscibility of the PBT/PC and PET/PC blends was compared with respect to the tendency of the PBT and PET blocks to crystallize under isothermal conditions. The crystallization rate of the PBT/PC copolymers was faster than that of the PET/PC copolymers with similar block lengths. Accordingly, the minimum crystallizable sequence length of the PBT blocks was shorter than that of the PET blocks (18 vs 31 monomeric unit sequences). This behavior was interpreted as an effect of the more flexible PBT units, which had a greater tendency to fold and crystallize than the PET units. Therefore, PBT, the blocks of which tended to crystallize even if they were very short and phase‐separated, was characterized by a poorer compatibility with PC than that of PET. As a result, the block size had a fundamental role in determining the crystallizability and, therefore, phase behavior of the semicrystalline block copolymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2821–2832, 2004     

Photodegradation of bisphenol A polycarbonate

When bisphenol A polycarbonate is subjected to weathering conditions this polymer shows two different degradation mechanisms depending on the used irradiation wavelengths, i.e. photo-oxidation and photo-Fries rearrangement. The relative importance of these mechanisms in outdoor exposure conditions is still unknown. In this study bisphenol A polycarbonate is exposed to simulated weathering conditions. Different analysing techniques show that photo-oxidation is the most dominant degradation reaction. However, fluorescence spectroscopy shows that small amounts of photo-Fries rearrangement products are formed. With model compounds blended in polypropylene it is shown that the photo-Fries reaction increases the photo-oxidation rate, thus in PP the photo-Fries reaction can proceed through radical intermediates. However, this is not the case in PC, ageing at condition causing an increased photo-Fries reaction rate did not result in a higher oxidation rate. This implies that in PC the photo-Fries reaction does not initiate its oxidation and thus does not proceed through radicals.     

Crystallization behavior of polypropylene/polycarbonate blends

Crystallization behavior and morphology of polypropylene (PP)/polycarbonate (PC) blends have been studied by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). In the study of non-isothermal crystallization of the blends, the phenomenon of multiple crystallization peaks of PP/PC blends was related to the blend morphology in which PP was the dispersed phase as small droplets in the PC matrix. The phenomenon of a single crystallization peak of the PP/PC blends was related to the blend morphology in which PP was a continuous phase; in that case the crystallization peak temperatures of the blends were higher than that of the PP. The isothermal crystallization kinetics of the PP and PP/PC (80/20) blend were described by the Avrami equation. The results showed that the Avrami exponent of the PP/PC (80/20) blend was higher than that of the PP, and the crystallization rate of the PP/PC (80/20) blend was faster than that of the PP. The crystallization rate of the PP and PP/PC (80/20) blend were calculated according to the Hoffmann theory. Both the PP and PP/PC (80/20) blend had maximum crystallization rates. The temperature at the maximum crystallization rate for the PP/PC (80/20) blend was higher than that of the PP.     

Dielectric studies of tetraaryl and triaryl polycarbonates and comparisons with bisphenol A‐polycarbonate

The relative permittivity, loss, and breakdown strength are reported for a commercial sample of bisphenol A‐polycarbonate (comm‐BPA‐PC) and a purified sample of the same polymer (rp‐BPA‐PC) as well as for two new polycarbonates having low molecular cross‐sectional areas, namely a copolymer of tetraaryl polycarbonate and BPA‐PC (TABPA‐BPA‐PC) and a triaryl polycarbonate homopolymer (TriBPA‐PC). The glass transition temperatures of the new polymers are higher than the T_g of BPA‐PC (187 and 191 °C vs. 148 °C). Relative permittivity and loss measurements were carried out from 10 to 10⁵ Hz over a wide temperature range, and results for the α‐ and γ‐relaxation regions are discussed in detail. For the α‐relaxation, the isochronal peak position, T_α, scales approximately with T_g. On the other hand, the peak temperature for the γ‐relaxation is approximately constant, independent of T_g. Also, in contrast to what is observed for α, γ exhibits a strong increase in peak height as temperature/frequency increases and a significant difference is found between Arrhenius plots determined from isochronal and isothermal data analyses. Next, the γ‐relaxation region for comm‐BPA‐PC and associated activation parameters show strong history/purity effects. The activation parameters also depend on the method of data analysis. The results shed light on discrepancies that exist in the literature for BPA‐PC. The shapes of the γ loss peaks and hence glassy‐state motions for all the polymers are very similar. However, the intensities of the TriBPA‐PC and TABPA‐BPA‐PC γ peaks are reduced by an amount that closely matches the reduced volume fraction of carbonate units in the two new polymers. Finally, for comm‐BPA‐PC, the breakdown strength is strongly affected by sample history and this is assumed to be related to volatile components in the material. It is found that the breakdown strengths for TriBPA‐PC and TABPA‐BPA‐PC are relatively close to that for rp‐BPA‐PC with the value for TriBPA‐PC being slightly larger than that for rp‐BPA‐PC or the value usually reported for typical capacitor grade polycarbonate. Finally, it is shown that the real part of the relative permittivity remains relatively constant from low temperatures to T_g. Consequently, based on the dielectric properties, TriBPA‐PC and TABPA‐BPA‐PC should be usable in capacitors to at least 50 °C higher than BPA‐PC. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Effect of prepolymer molecular weight on solid state polymerization of poly(bisphenol a carbonate) with nitrogen as a sweep fluid

The effect of prepolymer molecular weight on the solid‐state polymerization (SSP) of poly(bisphenol A carbonate) was investigated using nitrogen (N₂) as a sweep fluid. Prepolymers with different number–average molecular weights, 3800 and 2400 g/mol, were synthesized using melt transesterification. SSP of the two prepolymers then was carried out at reaction temperatures in the range 120–190 °C, with a prepolymer particle size in the range 20–45 μm and a N₂ flow rate of 1600 mL/min. The glass transition temperature (T_g), number–average molecular weight (M_n), and percent crystallinity were measured at various times during each SSP. The phenyl‐to‐phenolic end‐group ratio of the prepolymers and the solid‐state synthesized polymers was determined using 125.76 MHz ¹³C and 500.13 MHz ¹H nuclear magnetic resonance (NMR) spectroscopy. At each reaction temperature, SSP of the higher‐molecular‐weight prepolymer (M_n = 3800 g/mol) always resulted in higher‐molecular‐weight polymers, compared with the polymers synthesized using the lower molecular weight prepolymer (M_n = 2400 g/mol). Both the crystallinity and the lamellar thickness of the polymers synthesized from the lower‐molecular‐weight prepolymer were significantly higher than for those synthesized from the higher‐molecular‐weight prepolymer. Higher crystallinity and lamellar thickness may lower the reaction rate by reducing chain‐end mobility, effectively reducing the rate constant for the reaction of end groups. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4959–4969, 2008     

Thermal degradation of bisphenol a polycarbonate

Bisphenol A polycarbonate (Makrolon 3000) has been purified and fractionated. Thin films of these samples have been degraded by heating at 200° under continuous evacuation (pressure less than 0- 1 Pa) for periods of several hours. The molecular weight is observed (by gel permeation chromatography) to increase with time at 200°. Eventually gel is formed. The variation of the number- and weight-average molecular weights with heating time and the effect of the initial molecular weights of the polycarbonate samples are consistent, in the main, with the Davis-Golden mechanism of thermal degradation of bisphenol A polycarbonate; i.e. the principal reactions are condensation and trifunctional branching. Chain scission due to hydrolysis of the carbonate linkage is absent under our conditions.     

Polycarbonate Crystallization by Vapor‐Grown Carbon Fiber with and without Magnetic Field

Polycarbonate (PC)/vapor‐grown carbon fiber (VGCF™) composite was prepared through melt compounding. It was unexpectedly found from differential scanning calorimetry (DSC) and wide angle X‐ray diffraction (WAXD) that the crystallization of PC was substantially accelerated in the presence of the ordered graphite surface of VGCF™. To make an aligned structure of PC crystallization together with the orientation of VGCF™, a magnetic field of 2.4 T was applied to the composite under several temperature profiles. The WAXD pattern revealed that not only dispersed VGCF™ but also matrix PC crystallization was magnetically aligned through the optimization of processes. The evidence for PC crystallization by VGCF™ with and without magnetic force is described.

Optical micrograph (a) and WAXD pattern (b) of PC/VGCF™ (95:5 wt. ratio) composite which was treated under a magnetic field (vertical direction) of 2.4 T under an optimized heating profile.     

Photodegradation of bisphenol A polycarbonate with different types of stabilizers

When unstabilized bisphenol A polycarbonate is exposed to outdoor weathering conditions, it degrades due to irradiation, humidity and other parameters. To overcome this undesired degradation process BPA-PC can be stabilized. In this study the influence of different types of stabilizers (i.e. UV-absorbers and hindered amine stabilizers) on the photodegradation of BPA-PC were compared. It is shown that the best way to stabilize BPA-PC is to keep the harmful UV light out. Almost all stabilizers caused a decreased degradation rate. The UVAs showed the best results, although radical scavengers cause a decrease in degradation too. By applying a layer of UVA-stabilized BPA-PC on top of unstabilized BPA-PC led to a decreased degradation rate of the unstabilized BPA-PC, which can quantitatively be explained by a reduction of the irradiation intensity.     

Crystallization behavior and morphology of PE-g-LCP copolymers

 This study presents DSC and optical microscopy investigations on copolymers of semiflexible liquid crystalline polymer SBH 112 grafted to functionalized low molecular mass polyethylene (PEox) obtained by melt polycondensation or reactive blending procedures. The crystallization behavior of the PE-g-SBH copolymers has been studied under non-isothermal measurement conditions carried out at different cooling rates. The crystallization temperature (T _cr) of the PE component of the copolymers decreases steadily upon increasing the concentration of the SBH grafts. It was found that the copolymers prepared by reactive blending crystallize at slightly higher T _cr than those prepared by polycondensation and with a higher rate, confirmed by the determination of the crystallization rate coefficients (CRC). The results have been interpreted by the fact that the PE crystallizable segments and SBH grafts of the copolymers obtained by reactive blending are longer than those of the copolymers prepared by polycondensation. The overall nonisothermal crystallization kinetics has been studied by the Harnisch and Muschik equation. The results show that the mechanism of the crystallization of the PE phase changes only when the SBH content overruns ca.50%, due to the decrease of both nucleation and crystal growth rates. The morphology of the copolymers crystallized nonisothermally from melt has been examined by polarization microscopy. Fairly homogeneous morphology with tiny PE spherulites is observed for PE-g-SBH copolymers prepared by polycondensation with SBH as the minor phase. No sign of the dispersed LCP domains can be recognized. On the contrary, the morphology of the copolymers prepared by reactive blending is distinctly biphasic. The allegedly longer PE segments crystallize into tiny spherulites too, but the LC domains formed by the long SBH branches present in this type of copolymers appear clearly in the micrographs at room temperature. It is concluded that the copolymers prepared by reactive blending would be more effective as compatibilizers for PE/SBH blends than those prepared by polycondensation. Received: 9 October 1996 Accepted: 13 January 1997     

Crystallization behavior of polypropylene with or without sodium benzoate as a nucleating agent

The crystallization kinetics of polypropylene (PP) with or without sodium benzoate as a nucleating agent were investigated by means of DSC and polarized optical microscopy in isothermal and nonisothermal modes. A modified Avrami equation was applied to the kinetic analysis of isothermal crystallization. The addition of the nucleating agent up to its saturation concentration increased the crystallization temperature by 15 °C and shortened both the isothermal and nonisothermal crystallization half‐times. It was concluded that the sodium benzoate acted as a good nucleating agent for α‐form PP. By adding the nuclefier to PP, adequately controlled spherulites increased the mechanical properties including especially the Izod impact strength and shortened cycle time of PP. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 1001–1016, 2001     

Crystallization behavior of a propylene/ethylene copolymer: Nucleation and a clarifying additive

The isothermal crystallization behavior of a propylene/ethylene copolymer containing a clarifying additive has been studied in detail and compared with the equivalent unclarified grade. Differential scanning calorimetry was used to obtain crystallization exotherms for both the unclarified system and the clarified analogue. Avrami analysis of these data was then performed, using both linear and nonlinear data‐fitting techniques. Linear analysis revealed a change from a primary to a secondary crystallization process in the clarified system at about 50% relative crystallinity. Nonlinear techniques, however, led to more reliable estimates of the Avrami parameters and provided estimates of crystallization‐induction times. By combining the preceding with isothermal crystal‐growth‐rate data, the nucleation density in each material was obtained as a function of crystallization temperature. In the unclarified case, this fell exponentially with temperature. The nucleation density in the sorbitol‐clarified copolymer was 10³–10⁶ times greater than in the unclarified material, but decreased only slowly with increasing crystallization temperature throughout the temperature range investigated here. This final result appears entirely contradictory to previous morphological work in which a distinct morphological transition was observed at 128 °C and associated with a marked reduction in the nucleating efficiency of the sorbitol. Possible explanations for this apparent contradiction are considered. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2178–2189, 2002     

Crystallization and melting behavior of a main-chain thermotropic copolyester

The crystallization and melting behavior of a main-chain thermotropic copolyester has been investigated by differential scanning calormetry (DSC). The effect of annealing time and temperature on the transition temperatures and enthalpies has been evidenced. Two melting peaks are observed and the first one clearly develops on annealing. Hypotheses are suggested about the crystallization mechanism.