Experimental observation on multiaxial ratchetting of polycarbonate polymer at room temperature

Multiaxial stress-controlled and mixed stress-strain-controlled cyclic tests were carried out to investigate the multiaxial ratchetting of polycarbonate (PC) polymer at room temperature. The effects of applied mean stress, stress amplitude, loading rate, loading path and loading history on the ratchetting are discussed. The results show that the multiaxial ratchetting mainly occurs in the direction of non-zero mean stress. In the multiaxial stress-controlled cases, the ratchetting strain increases with increasing mean stress and stress amplitude and decreasing stress rate. Different values of ratchetting strain were obtained in the multiaxial cyclic tests with seven different loading paths, and prior cyclic loading with higher stress level resulted in decreased ratchetting in the subsequent cyclic loading with lower stress level. In the multiaxial mixed stress-strain-controlled tests, the ratchetting increased with increasing axial (or equivalent shear) stress and torsional-angle (or axial-displacement) amplitude and decreasing applied deformation rate.     

Sample temperatures during outdoor and laboratory weathering exposures

Effective exposure temperatures (T_eff) in Arizona were calculated from hourly or 10-min parsed irradiation data along with ambient, black panel, and sample temperatures. The T_eff represents a constant temperature that creates the same amount of photodegradation as the naturally varying temperature and provides a benchmark temperature for making lifetime predictions from accelerated laboratory exposures. The annual ambient and black panel T_eff at a Wittmann, Arizona site were 30 °C and 42 °C, respectively, assuming that the photodegradation has an activation energy (E_a) of 21 kJ/mol (5 kcal/mol). T_eff was only weakly dependent on E_a over the range of 10-40 kJ/mol (3-10 kcal/mol). Samples exposed as van sunroofs were found to have T_eff that were offset from the black panel temperatures by a constant amount for the entire year. Thus, measurements of sample and black panel need to be made for only a few weeks to determine the offset and give the annual sample T_eff if the annual black panel T_eff is known. Light-colored samples probably are better compared with the ambient temperatures. Sample temperatures in xenon arc exposures usually are higher than the outdoor T_eff, so Arrhenius temperature corrections need to be carried out to relate accelerated to outdoor exposures. Temperatures in xenon arc exposure tests often correspond more closely to maximum temperatures that samples might encounter for only a few hours per year.     

The effect of different impact modifiers in halogen-free flame retarded polycarbonate blends - II. Fire behaviour

In this second of a series of two papers, the fire behaviour of halogen-free flame retarded polycarbonate (PC) blends with different impact modifiers was studied. The impact modifiers were acrylonitrile-butadiene-styrene (ABS), a poly(n-butyl acrylate) rubber (PBA) with a poly(methyl methacrylate) (PMMA) shell and two silicone-acrylate rubbers consisting of PBA with different amounts of polydimethylsiloxane (PDMS) and different shell materials (PMMA and styrene-acrylonitrile, SAN). The flame retardant was bisphenol A bis(diphenyl phosphate) (BDP). Flammability was determined by LOI and UL 94. The burning behaviour under forced flaming conditions was studied by cone calorimeter under different external irradiations and by pyrolysis combustion flow calorimeter measurements. The exchange of ABS with the pure acrylate rubber worsened flammability, while similar results were obtained in cone calorimeter measurements. The exchange of ABS with the silicone-acrylate rubbers is promising, particularly with higher amounts of PDMS. In flammability tests strongly enhanced LOI values were obtained and therefore silicone-acrylate rubbers look like promising alternatives for ABS.     

Kinetic analysis of thermal degradation of recycled polycarbonate/acrylonitrile-butadiene-styrene mixtures from waste electric and electronic equipment

The study of properties in waste polymeric materials is important for a further recycling and eventual reuse. The determination of thermal properties of PC-ABS mixtures obtained from waste electric and electronic equipment (WEEE) by using thermogravimetric analysis (TGA) has been carried out in this work. Kinetic parameters, such as apparent activation energies, have been calculated by using the autocatalytic model, which has shown a good correlation with experimental data. A good agreement between calculated and experimental results was observed for PC-based mixtures. This is an indication that the addition of a high amount of ABS permits the creation of a network formed by elastomeric domains which leads to a general increase in heterogeneity of the mixture.     

Influence of copper-phthalocyanine on the photodegradation of polycarbonate

Dyes and pigments are extensively used in polymer materials to confer colour-changing properties. However, these additives can significantly affect polymer stability against degradation. While the mechanism of stabilization of polymers by some pigments, such as carbon black, has been studied and is well known, the action of chromatic colorants, mainly in the sensitization of the degradation process, remains unclear. Cu-phthalocyanine dye can stabilize polymers against degradation as well as accelerate degradation in other situations. Cu-phthalocyanine incorporated into polycarbonate resulted in an acceleration of the degradation when the material was submitted to photochemical aging. The possible mechanism to explain the photodegradative behavior of PC containing Cu-phthalocyanine is based on the hypothesis that specific interactions among excited states of PC and Cu-phthalocyanine take place and enhance the formation of reactive species in polycarbonate. Excited states of Cu-phthalocyanine may abstract hydrogen atoms from methyl groups in polycarbonate, increasing the formation of free radicals P, which are the starting points for the sequential photo-oxidation reactions that lead to the degradation of the polycarbonate. Electron transfer sensitization is also a possible mechanism: the excited state of Cu-Ph abstracts an electron from PC to form the Cu-Ph radical anion and the PC radical cation. These reactive species in the presence of oxygen can cause oxidation of the aromatic ring.     

A new method for detection of alpha particles in 1 mm thick polycarbonate detectors using 50 Hz – HV ECE method

Recent studies in our laboratory have proved that electrochemical etching (ECE) of polycarbonate track detectors (PCTD) under 50 Hz – high voltage (HV) field conditions has potentials for time-integrated heavy charged particle detection and dosimetry applications. The rationale in the study is the ECE process of alpha particle tracks in 1 mm thick PCTDs by a 50 Hz – HV generator at optimized ECE conditions. Tracks of 3.2 MeV alpha particles from a collimated beam of an ²⁴¹Am source degraded in air and background tracks were registered. The effects of HV and ECE duration on alpha track registration efficiency and track diameters were studied for 3 sets of 50 Hz – 4, 5 and 6 kV field conditions in a PEW solution (potassium hydroxide, ethanol and water) at 26 °C. The optimized ECE conditions obtained at this stage of development for 1 mm thick PCTDs are 50 Hz – 4 kV in PEW solution at 26 °C for 10 h. Alpha track registration efficiency at 3.2 MeV is about 30% with 37 ± 6 μm mean track diameter. The mean background track density at the above stated optimized conditions is about 571 ± 16 tracks.cm⁻² with a mean diameter of 65 ± 5 μm. All tracks are observable by the unaided eyes. The mean background track diameter is near two times larger than that of alpha particle tracks at the optimum conditions applied; they are easily distinguished against each other. This high background track density while at this stage of development seems a drawback for low dose and low fluence particle applications, it has minimal effects on high fluence ion detection applications. The simple 50 Hz – HV generator used proved to be convenient for efficient alpha track amplifications. Studies are underway for improvement of the method in particular for reducing background track density.     

熔融酯交换法合成聚碳酸酯的研究

采用熔融酯交换法,以碳酸二苯酯(DPC)和双酚A(BPA)为原料合成聚碳酸酯(PC).考察了乙酰丙酮(HACAC)类金属配合物催化剂的活性,以及催化剂活性与相应金属离子螯合配位作用的关系.以不同乙酰丙酮金属配合物为催化剂合成的PC的特性黏数([η])对相应金属离子二苯甲酰甲烷(DBM)配合物的稳定常数的对数值(lgβ1)作图,得到1个双火山型曲线,证明DPC与BPA的熔融酯交换缩聚反应是受乙酰丙酮阴离子的碱性作用和金属离子的螯合配位作用共同影响的.通过比较用各种催化剂合成的PC的性质,发现乙酰丙酮锂(LiACAC)是一种优良的催化剂,可以用来合成分子量超过40000([η]=0.710 dL.g-1)、低支化物(Fries产物)含量、低分散(PDI=2.12)的PC.以LiACAC为催化剂,考察了催化剂用量、反应物配比、酯交换阶段压力以及温度等条件对反应的影响.最佳反应条件为,LiACAC的用量为1.5×10-4mol/mol BPA、原料配比nDPC∶nBPA=1.08、酯交换阶段压力设在4000 Pa、缩聚反应阶段反应温度为260℃.     

Effects of organoclay modifiers on the flammability, thermal and mechanical properties of polycarbonate nanocomposites filled with a phosphate and organoclays

Polycarbonate was melt blended with solid bisphenol A bis(diphenyl phosphate), and a series of organoclays. Effects of the organoclay modifiers on the flammability, thermal and mechanical properties of the nanocomposites were studied by limiting oxygen index, UL-94 burning test, thermogravimetric analysis, differential scanning calorimetry, tensile test and dynamic mechanical analysis. Although all the nanocomposites exhibit an intercalated-exfoliated morphology, they vary in the magnitude of intercalation revealed by X-ray diffraction and transmission electron microscopy. Flammability of the nanocomposites is strongly related to the thermal stability rather than the morphology. Glass transition temperature (T_g) and mechanical properties are controlled by both the morphology and the affinity of the organoclays with the matrix. The modifier containing hydroxyl moiety has stronger interactions with the matrix but it can promote its degradation, thus the corresponding nanocomposite exhibits a better intercalated morphology, higher T_g, superior strength and modulus however a worse thermal stability and flame retardancy. An additional silane within the organoclays would make the organoclays more compatible with the matrix but be a steric obstacle to the intercalation of the matrix chains; however, flame retardancy of the corresponding nanocomposite is enhanced due to the flame retardant nature of the silane. Similarly, the modifier bearing two long alkyl tails shows stronger affinity with the matrix than the one bearing a single tail, but it would hinder the intercalation due to the steric effect. These establishments between organoclay modifiers and the properties of nanocomposites might be guidance for developing materials with practical applications.     

Ionizing particles may create shockwaves

To find a model that describes the gas diffusion on irradiated polymers (Makrofol KG polycarbonate) the diffusion constants have been measured with argon as diffusion gas. The polymers were irradiated with uranium, gold and lead ions of about 10 MeV/u and ion fluences between 1×10¹⁰ and 4×10¹¹ ions/cm². The ion irradiated probes show two quite different dependencies of the diffusion constant on the ion energy loss. These effects are strongly related to the fluence of the irradiation. In case of low ion fluences, the diffusion constant is up to 8 times higher than that of pristine material. In the probes with high ion fluences we observe a decrease of diffusion constant to half the value of the pristine material. To understand the dependence of the diffusion constant on ion fluences we apply a model of compacting. This model describes the compacting ability of shockwaves arising from latent tracks. A track formation model is suggested. When an ion penetrates the foil it creates shockwaves around its path. These shockwaves put compacting forces on earlier created latent tracks in the same foil.     

聚碳酸亚丙酯聚氨酯的合成与性能

用ＣＯ２与环氧丙烷共聚产物聚碳酸亚丙酯制备出聚氨酯（ＰＰＣＰＵ）．同时探讨了ＰＰＣＰＵ最佳合成方法,考察了异氰酸酯基与羟基的比值、扩链交联剂用量等因素对其力学性能的影响．研究了ＰＰＣＰＵ的形态结构及其性能对配比的依赖关系．发现聚碳酸亚丙酯的耐热性因聚氨酯的形成而得到较大的改善,并发现该类材料具有优异的耐水性能．