Sonocrystallization Yields Monoclinic Paracetamol with Significantly Improved Compaction Behavior

Ultrasound‐assisted crystallization (sonocrystallization) was used to prepare a mixture of nano‐ and micrometer‐sized crystals of the monoclinic form of paracetamol—a widely used analgesic known for its particularly problematic mechanical behavior under compression (i.e. poor tabletability). The nano‐ and micrometer‐sized crystals yielded a powder which exhibits elastic moduli and bulk cohesions that are significantly higher than those observed in samples consisting of macrometer‐sized crystals, thus leading to enhanced tabletability without the use of excipients, particle coating, salt, or cocrystal formation. Experimental compaction and finite element analysis were utilized to rationalize the significantly improved compaction behavior of the monoclinic form of paracetamol.     

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     

Synthesis of AB and ABA block copolymers as compatibilizers in nylon 6/polycarbonate blends

Nylon 6 (Ny6) and Bisphenol A polycarbonate (PC) are immiscible and form biphasic blends. To improve the compatibility of Ny6 and PC several ABA and AB Ny6/PC block copolymers were synthesized, and their compatibilizing behavior on the blends were tested. Block copolymers were prepared by reacting monoamino- or diamino-terminated Ny6 homopolymers with high molecular weight PC at 130°C in anhydrous DMSO. The reaction of diamino- and monoamino-terminated Ny6 with polycarbonate produces block copolymers of the type PC-Ny6-PC (ABA) and PC-Ny6 (AB), respectively, plus a certain amount of unconverted PC degradated to lower molecular weights. To separate the block copolymer from the unconverted PC, a selective fractionation with tetrahydrofuran (THF) and trifluoroethanol (TFE) was carried out. Three different fractions were obtained: THF-soluble fraction, TFE-soluble fraction, and the TFE-insoluble fraction. The scanning electron microscopy (SEM) analysis of a 75/25 (wt/wt) Ny6/PC blend added with 2% of ABA or AB block copolymers, showed the presence of smaller PC particles more adherent to the polyamide matrix, with respect to the same blend nonadded, which is clearly biphasic. The size of the PC particles decreases from ABA to AB compatibilized blends and the adhesion with the matrix is increases in the same way. © 1996 John Wiley & Sons, Inc.     

Phenylene motion in polycarbonate and polycarbonate/additive mixtures

Pulsed deuteron NMR line shapes have been analysed to characterize type and time scale of the phenylene group motion in glassy bisphenol-A polycarbonate. The motional mechanism involves-flips about theC ₁ C ₄ axis augmented by small angle fulctuations about the same axis, reaching a rms amplitude of ±35 at 380 K. The distribution of correlation times for the-flips is heterogeneous in nature and can be described either by a log-Gaussian or an asymmetric distribution with a more rapid decay at high correlation times comparable to the Williams-Watts distribution. From both distributions essentailly the same mean activation energy of 37 kJ/mol is obtained, whereas the temperature dependent width of the highly asymmetric distribution is somewhat smaller compared to the log-Gaussian distribution. Time scale and activation energy of the-flip motion are correlated to secondary mechanical relaxations. Low molecular mass additives, which suppress the mechanical relaxation, also hinder the phenylene motion for a substantial fraction of phenylene groups. The effect of additives is not only to shift the mean value of the distribution of correlation times to higher values but also to increase drastically the width of the distribution. The results of this work strongly suggest that the secondary mechanical relaxation and the large amplitude motions of the phenylene groups in polycarbonate are related.     

Carbon tetrachloride-induced crack healing in polycarbonate

Crack healing induced by carbon tetrachloride in polycarbonate has been studied at temperatures in the range of 40–60°C. The carbon tetrachloride treatment reduces the glass transition temperature of polycarbonate. Crack healing is observed because the effective glass transition temperature in polycarbonate is reduced to below the test temperature by the carbon tetrachloride treatment. Two distinctive stages of crack healing are divided based on the recovery of mechanical strength and fractograph. The first stage corresponds to the progressive healing due to the convolution of wetting and self-diffusion, which has a constant crack closure rate. Immediately following the first stage, the second stage, corresponding to the self-diffusion of polymer chain, enhances the quality of healing behavior. The transport of carbon tetrachloride in polycarbonate consists of case I (concentration gradient controlled) and case II (relaxation controlled) behaviors. The direction of case II is opposite to that of case I. The solubility decreases with increasing temperature, but diffusivity and velocity for mass transfer, crack closure rate, and diffusion coefficient for the diffusion front have the opposite trend. The first stage of crack healing is controlled by case II transport. The transport of carbon tetrachloride changes the fracture behavior of polycarbonate from ductile to brittle. A comparison of crack healing in polycarbonate and poly (methyl methacrylate) is made. © 1994 John Wiley & Sons, Inc.     

Role of metal oxides in the thermal degradation of bisphenol a polycarbonate

Thermal degradation of poly(2,2,-propane-bis-4-phenyl carbonate) or bisphenol A polycarbonate (PC) alone and in presence of metal oxide as additives have been discussed. Thermal degradation of PC in presence of metal oxide additives may be surface induced catalytic thermo-oxidative degradation. Some metal oxides retard thermo-oxidative degradation of PC.Thanks are due to RSIC, Nagpur University for recording TG curves, Mr. S. S. Umare for his help during the work and the Director, Laxminarayan Institute of Technology for providing computer facilities.     

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.     

Effect of polycarbonate structure and reduction time on graphene oxide dispersion

Polycarbonate (PC)/graphene oxide (GO) composites with different GO reduction time and PC types were prepared by using a twin screw extruder at 260 °C after solution mixing with chloroform. The chemical reaction degree of PC/GO composites with GO reduction time was confirmed by C–H stretching peak at 3000 cm ^?1, and the chemical reaction degree decreased with GO reduction time. The slope for storage (G′) versus loss (G″) modulus plot decreases with an increase in heterogeneous property of the polymer melts. So we can check the GO dispersion of the PC/GO composites using by the slop for G′–G″ plot. According to the G′–G″ slopes for PC/GO composite with GO reduction time, GO was well dispersed within PC matrix when the reduction time decreased. It was re‐confirmed by atomic force microscope (AFM) results. Based on the degradation temperature by Thermogravimetric analysis, G′–G″ slopes, and surface roughness by AFM, the branched PC was better than linear PC for the GO dispersion within PC matrix. The fact was also confirmed by tensile test results that the Young's modulus increased with the improvement of GO dispersion. Copyright © 2015 John Wiley & Sons, Ltd.     

Light scattering of bisphenol-A polycarbonate in the amorphous state and at the beginning of thermal crystallization

Summary Depolarized light scattering of amorphous polycarbonate (PC) is angular independent. The amount of scattering did not give any evidence for the existence of a liquid crystal type of phase, consisting of regions with a strong orientation correlation between chain segments. Annealing of PC belowT _g does not affect its scattering behaviour. Therefore, observed changes in physical properties such as the mechanical behaviour cannot be interpreted by an appreciable increase of intermolecular orientation correlation. If PC is heated at 190 °C for several days, an angular dependent scattering component appears. This component arises from the formation of spherulites with a sheaf-like structure.With 4 figures and 1 table     

Electrical conductivities of carbon nanotube-filled polycarbonate/polyester blends

Carbon nanotube (CNT)-filled polycarbonate (PC)/poly(butylene terephthalate) (PBT) and polycarbonate (PC)/poly(ethylene terephthalate) (PET) blends containing 1 wt% CNTs over a wide range of blend compositions were prepared by melt mixing in a torque rheometer to investigate the structure-electrical conductivity relationship. Field emission scanning electron microscopy was used to observe the blend morphology and the distribution of CNTs. The latter was compared with the thermodynamic predictions through the calculation of wetting coefficients. It was found that CNTs are selectively localized in the polyester phase and conductive blends can be obtained over the whole composition range (20 wt%, 50 wt% and 80 wt% PBT) for CNT-filled PC/PBT blends, while conductive CNT-filled PC/PET blends can only be obtained when PET is the continuous phase (50 wt%, 80 wt% PET). The dramatic difference in the electrical conductivity between the two types of CNT-filled PC/polyester blends at a low polyester content (20 wt%) was explained by the size difference of the dispersed phases on the basis of the transmission electron microscope micrographs.     

Prediction of environmental stress cracking in polycarbonate by molecular modeling

Environmental stress cracking (ESC) is a premature failure of a polymer exposed to a fluid, under stress which is much less than its yield stress. Many experimental works were done before in an effort to predict experimentally the ESC potential of a fluid in different polymers. None of the previous works applied molecular modeling techniques to predict this potential so this work is a pioneering work. This study's goal was to apply atomistic molecular modeling techniques to gain a better understanding of the ESC mechanism and to predict the ESC potential of different fluids in polymers. Our model experimental system was amorphous polycarbonate (PC) with water as an ESC fluid. The computational study was expanded to include a high level ESC fluid for PC–toluene and a non ESC fluid–BD, together with the moderate ESC fluid–water. A clear distinction between ESC fluids and non ESC fluids for PC was achieved by means of molecular modeling. The experimental work approved that water is an ESC fluid for PC as predicted in the computational part. Copyright © 2014 John Wiley & Sons, Ltd.     

Thermal characterization of polycarbonate/polycaprolactone blends

In this work, we prepared blends of bisphenol A polycarbonate (PC) and poly(ϵ‐caprolactone) (PCL) in a wide composition range by melt mixing and solution mixing. Two different molecular weights of PCL were used (nominally, 10.000 g/mol, PCL10, and 80.000 g/mol, PCL80). The thermal behavior of both systems was studied via differential scanning calorimetry under dynamic and isothermal conditions. The blends were miscible in the entire composition range in the liquid and amorphous states, as indicated by the single glass‐transition temperature (T_g) exhibited by both the PC/PCL10 and PC/PCL80 blends. The compositional variation of the T_g was accurately described by the Fox equation for the PC/PCL80 blends, whereas slight deviations from this equation were exhibited by the PC/PCL10 blends. For blend compositions containing 40% or more PCL, either one or both blend components crystallized. Crystallization occurred during cooling from the melt or during subsequent heating in the form of cold crystallization. Although PCL crystallization was reduced and its crystallization rate decreased with the addition of PC, PCL was a very effective macromolecular plasticizer for PC, to the extent that crystallization during the scan was detected for some blend compositions. Isothermal crystallization experiments allowed the determination of equilibrium melting points (T) by the Hoffman–Weeks extrapolation method. A T depression was found for both PCL and PC components as the content of the other blend component was increased. The Avrami equation was closely obeyed by both blend components during the isothermal overall crystallization kinetics up to crystalline conversion degrees of 60–70% and with values of Avrami indices ranging from 3 to 4, depending on the crystallization temperature employed. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 771–785, 2001     

阿特拉津在聚碳酸酯膜中的迁移性能研究

采用紫外分光光度法研究不同条件下阿特拉津在孔径为100 nm的聚碳酸酯膜上的迁移性能的差异,考察黑壤腐植酸与阿特拉津的结合情况.实验结果表明:溶液pH值范围为5.3 ～7.4时,阿特拉津吸光度相对稳定;不同浓度阿特拉津在聚碳酸酯膜上的迁移量与浓度呈线性关系,线性方程为γ=0.0792x-0.0016,R2=0.9999;溶液pH为6.4,阿特拉津与腐植酸的结合效果最好;离子强度逐渐增加对阿特拉津与腐植酸的结合有一定的抑制作用.     

Rheology of polycarbonate reinforcedwith functionalized and unfunctionalized single-walled carbon nanotubes

Nanocomposites of polycarbonate (PC) containing low concentrations of pristine and COOH and OH functionalized single-walled carbon nanotubes (SWNTs, COOH-SWNTs and OH-SWNTs) were prepared by melt-mixing and analyzed using rheology and scanning electron microscopy (SEM). The steady state and linear viscoelastic behavior of each nanocomposite material is presented and compared to that of the neat PC. SEM analysis revealed that samples containing functionalized SWNTs were more dispersible than samples containing the pristine SWNTs.     

Viscoelastic properties of ultrathin polycarbonate films by liquid dewetting

A liquid dewetting method for the determination of the viscoelastic properties of ultrathin polymer films has been extended to study thickness effects on the properties of ultrathin polycarbonate (PC) films. PC films with film thicknesses ranging from 4 to 299 nm were placed on glycerol at temperatures from below the macroscopic glass transition temperature (T_g) to above it with the dewetting responses being monitored. It is found that the isothermal creep results for films of the same thickness, but dewetted at different temperatures can be superposed into one master curve, which is consistent with the fact of PC being a thermorheologically simple material. Furthermore, the results show that the T_g of PC thin films is thickness dependent, but the dependence is weaker than the results for freely standing films and similar to literature data for PC films supported on rigid substrates. It was also found that the rubbery plateau region for the PC films stiffens dramatically, but still less than what has been observed for freely standing polycarbonate films. The rubbery stiffening is discussed in terms of a recently reported model that relates macroscopic segmental dynamics with the stiffening. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1559–1566     

Outdoor and accelerated weathering studies of bisphenol A polycarbonate

The influence of outdoor weathering on the degradation rate of unstabilized bisphenol A polycarbonate (BPA-PC) films is investigated and compared to the results found for indoor accelerated weathering conditions, using UV and IR spectroscopy. At the same dosage, changes in UV and IR were larger for the accelerated than for the outdoor weathered samples, this could be explained by the lower degradation temperature during outdoor exposures. The difference between outdoor and accelerated weathering is according to the IR measurement larger than according to the UV measurement. This difference is ascribed to difference in wavelength distribution between the spectra of the light emitted in the accelerated test and from the terrestrial sunlight. The larger difference for the IR results than for the UV results suggests a difference in ratio between photo-Fries rearrangements and photo-oxidation reaction between both exposures.     

Wavelength sensitivity of the photoinduced reaction in polycarbonate

Bisphenol A polycarbonate (PC) was irradiated with monochromatic light of wavelengths 260, 280, 300, 320, 340, 400, and 500 nm by use of the Okazaki large spectrograph (OLS). The quantum yield of main-chain scission (?_cs), efficiency of photo-Fries rearrangement (E_r), and effects of wavelength on ?_cs and E_r were investigated. It was found that photodegradation and photo-Fries rearrangement of PC took place by the irradiation of 260–300 nm light, but did not by the irradiation at λ ≧ 320 nm. The ?_cs has a maximum value in the case of the irradiation with 260 nm light, while E_r was found to have a maximum value by the irradiation of 280 nm light. © 1993 John Wiley & Sons, Inc.     

Gold polycarbonate microchannels for electrochemical applications

In this paper, we present gold-plating polycarbonate (PC) microchannels. The fabrication of the gold microfluidic channels is achieved by tuning the sequence of reagent insertion into milled and closed submillimeter PC system channels. The resulting gold surface can be utilized in many applications where the benefits of microfluidics, (bio)chemistry of surfaces, and electrochemistry can be combined. Here, we combine the advantages of electrochemistry with microfluidics by mixing the gold sensor with microfluidics. This approach differs from the classic one – the sensor will undergo modifications (e. g., shape and size) depending on the specific scientific problem and will be designed individually; hence its characteristics will be changed. Our goal in this work is to indicate new possibilities for combining two methodologies – electrochemistry and microfluidics. In our work, we emphasize that it confirms the validity of our chosen concept (proof-of-concept). In this work, we present one such application, the use of a gold microfluidic channel as a working electrode (WE). We describe the microchip‘s construction and electrochemical characterization, including the gold flow-through WE, the Ag/AgCl wire pseudo-reference, and the Pt auxiliary electrode. The measured current is the result of the flow through a rectangular duct of the gold microchannel electrode embedded in the four walls of the chip.     

Diffusion of camphorquinone in uniaxially drawn polycarbonate films

Employing the laser-induced holographic grating relaxation technique, we have measured tracer diffusion coefficients of a phtochromous dye, camphorquinone, in uniaxially drawn polycarbonate films as a function of stretch ratio. Anisotropy in the tracer diffusion coefficient has been observed with D_∥ greater than D_⟂ by at least a factor of 4 for the film stretched to the stretch ratio δ = 2.3. The diffusion coefficient along the direction of stretch D_∥ increases significantly with increasing δ, whereas D_⟂ decreases slightly with increasing δ. The stretch ratio dependence of D_∥ and D_⟂ is interpreted according to a modified free volume theory. The strain rate and stretch temperature dependence of the anisotropic tracer diffusion coefficient has also been investigated. © 1992 John Wiley & Sons, Inc.