Thermal stability of aromatic polyimides: Factors affecting the oxidative stability of poly-N,N′-(4,4′-diphenyl ether) pyromellitimide

Polyimide samples in the form of powders, films and sintered mouldings were prepared from pyromellitic dianhydride and 4,4′-diaminodiphenyl ether. The effect of environmental variables on the oxidative stability at 400°C of the high molecular weight films was studied, and it was shown that hydrolytic processes could greatly accelerate the degradation. The higher stability of powders was attributed to the presence of low molecular weight fractions which could inhibit these hydrolytic processes. Improvement of the stability of the films by the addition of low molecular weight materials during the casting process and the destabilisation of powders by prolonged solvent extraction gave support to this hypothesis. For comparison of thermal stabilities of polypyromellitimides of differing chemical structure weight loss results should therefore be determined on high molecular weight films under controlled humidity conditions.     

Photochemical aging and processability of life‐time‐controlled polystyrene/high‐impact polystyrene blends

This work investigated the influence of the addition of acetophenone and benzophenone (2.5 and 5%) on the photodegradability of polystyrene/high‐impact polystyrene blends (50/50 w/w) prepared by sheet extrusion, aiming to improve their decomposition during exposure to a natural environment. The modified materials were submitted to photodegradation under controlled conditions, and the extent of degradation was monitored by suitable characterization techniques, such as infrared and ultraviolet–visible spectroscopy, viscosimetry, and measurements of the mechanical properties. The processability of the modified blends was also studied by capillary and oscillatory rheometry. Evidence for the formation of hydroperoxides and carbonyl groups, the occurrence of chain scission, and the loss of mechanical properties was achieved, being greater for samples with benzophenone. It was also observed that for the same ketone level, benzophenone caused greater changes in the mechanical properties, and this was in agreement with the decrease in the molecular weight observed. Thus, the addition of this type of chemical compound could enhance the photodegradability of polystyrene/high‐impact polystyrene blends without a significant effect on their processability and mechanical performance. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Degradation of poly(L‐lactide) films under ultraviolet‐induced photografting and sterilization conditions

The degradation of polymers under ultraviolet (UV) irradiation has been a great concern for biomaterial and agricultural applications. The major objective of this research was to study the effect of UV irradiation on the representative bulk and surface properties of poly (L ‐lactide) (PLA) films. Two UV sources with different spectral outputs and intensities were chosen so that one of them could be used for surface modification and the other could be used for UV sterilization of the PLA films. The results established that the molecular weight of PLA decreased significantly during irradiation from the photografting lamp under atmospheric conditions. Irradiation through a Pyrex container was shown to minimize polymer degradation during UV exposure from the photografting lamp. The PLA films UV‐irradiated under the sterilization lamp for 12 h revealed a similar reduction in the molecular weight and no change in the surface hydrophilicity. However, significantly less photodegradation was observed under the sterilization lamp when the samples were held in a Pyrex container. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

含铁络合物类光敏剂降解塑料性能的研究

合成了以二硫代氨基甲酸为配体的一系列铁络合物以及硬脂酸铁光敏剂。通过人工加速紫外光降解试验和自然暴露试验,研究了含光敏剂的LDPE膜的力学性能、粘均分子量、红外线吸收及羰基指数的变化,比较讨论含上述铁盐光敏剂的LDPE的光降解性能     

光屏蔽剂对聚甲醛耐老化性能的影响

采用炭黑和纳米级氧化锌两种光屏蔽剂对共聚甲醛进行耐老化改性,对比了改性前后聚甲醛耐紫外光、耐热氧及耐热水老化性能的变化。结果表明,紫外光老化对聚甲醛性能影响最显著,两种光屏蔽剂均能减缓聚甲醛的光降解过程。炭黑的光屏蔽效果优于氧化锌,但会加速聚甲醛热氧降解。聚甲醛试样表面层相对分子质量的变化规律基本上与试样断裂伸长率、冲击强度以及色差变化规律保持一致。     

含氨甲酸铁络合物光敏剂的聚乙烯膜光降解性能的研究

合成了以二烷基二硫代氨基甲酸为配体的一系列铁络合物光敏剂,测试了光敏剂的红外和紫外光谱。通过人工加速紫外光降解试验和自然曝露试验,测定了含光敏剂的LDPE膜的力学性能、粘均相对分子质量、红外吸收及羰基指数的变化。结果表明：加入了0．1％二异丙基氨基甲酸铁（FeDIPC)的LDPE膜的光降解效果明显优于含其它敏剂的LDPE膜。     

CA/聚己内酯-环氧丙烷共混膜的生物降解研究

研究了二醋酸纤维素（CA）与己内酯—环氧丙烷共聚物膜的生物降解过程。发现共混物膜的生物降解性能与其组成密切相关。共混膜的降解速率随着己内酯—环氧丙烷共聚物含量的增加而加快。共混物膜的生物降解是从表面开始进行的，并逐步深入到共混物膜的内部。在降解过程中，分子量较小的部分首先开始降解，而且降解的速度较高。分子量高的部分降解较慢，控制着整个共混膜的降解速率。     

Heat treatment of tetrahedral amorphous carbon films grown by filtered cathodic vacuum-arc technique

Tetrahedral amorphous carbon (ta-C) is a potential low-cost substitute for diamond in certain applications, but little is known of the temperature range over which its desirable properties are retained. The thermal stability of tetrahedral amorphous carbon (ta-C) films has been investigated by heat treatment of the films at temperatures from room temperature to 450°C in high vacuum, low vacuum and oxygen ambient. It was found that heat treatment in oxygen ambient leads to a much more prominent variation in film thickness, stress and hardness than in both low and high vacuum. Raman studies also show an increase of the G-band frequency to higher values, an increase of the integrated intensity ratio and a narrowing of the G bands for films annealed in oxygen ambient with increasing temperature. By contrast, ta-C films exhibit a high resistance to degradation during treatment in low and high vacuum. They sustain their structure, thickness, stress and hardness for temperatures up to 400°C.     

Effect of pro‐oxidants on biodegradation of polyethylene (LDPE) by indigenous fungal isolate,Aspergillus oryzae

Proxidant additives represent a promising solution to the problem of the environment contamination with polyethylene film litter. Pro‐oxidants accelerate photo‐ and thermo‐oxidation and consequent polymer chain cleavage rendering the product apparently more susceptible to biodegradation. In the present study, fungal strain, Aspergillus oryzae isolated from HDPE film (buried in soil for 3 months) utilized abiotically treated polyethylene (LDPE) as a sole carbon source and degraded it. Treatment with pro‐oxidant, manganese stearate followed by UV irradiation and incubation with A. oryzae resulted in maximum decrease in percentage of elongation and tensile strength by 62 and 51%, respectively, compared with other pro‐oxidant treated LDPE films which showed 45% (titanium stearate), 40% (iron stearate), and 39% (cobalt stearate) decrease in tensile strength. Fourier transform infrared (FTIR) analysis of proxidant treated LDPE films revealed generation of more number of carbonyl and carboxylic groups (1630–1840 cm⁻¹ and 1220–1340 cm⁻¹) compared with UV treated film. When these films were incubated with A. oryzae for 3 months complete degradation of carbonyl and carboxylic groups was achieved. Scanning electron microscopy of untreated and treated LDPE films also revealed that polymer has undergone degradation after abiotic and biotic treatments. This concludes proxidant treatment before UV irradiation accelerated photo‐oxidation of LDPE, caused functional groups to be generated in the polyethylene film and this resulted in biodegradation due to the consumption of carbonyl and carboxylic groups by A. oryzae which was evident by reduction in carbonyl peaks. Among the pro‐oxidants, manganese stearate treatment caused maximum degradation of polyethylene. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

High-performance biosensors based on enzyme precipitate coating in gold nanoparticle-conjugated single-walled carbon nanotube network films

Single-walled carbon nanotube (SWCNT) network films with high network density were prepared by vacuum-filtering a suspension of SWCNTs, and used as a host of enzyme precipitate coating of glucose oxidase (EPC-GOx). EPC-GOx was fabricated into the SWCNT network films in a two-step process of enzyme precipitation and crosslinking. High GOx loading in a form of EPC expedited the generation of electrons while the good connectivity of conductive SWCNTs in the network structure increased the electron transfer rate. According to amperometric measurements, the sensitivities of GOx/SWCNT electrodes, governed by both generation and transfer of electrons, were significantly enhanced by filling up the open pores of SWCNT films with the EPC-GOx when compared to the approaches of covalent-attachment (CA) and enzyme coating (EC) with no step of enzyme precipitation. For example, the sensitivities of CA, EC and EPC-GOx were 0.039, 0.140, and 5.72 μA mM⁻¹, respectively. High sensitivity of EPC-GOx was maintained under iterative uses for 10 days. The deposition of gold nanoparticles into SWCNT films has resulted in high-performance glucose sensors with a remarkable sensitivity of 24.5 μA mM⁻¹, which can be explained by further expedited electron transfer due to deposited gold nanoparticles.     

Influence of morphology on photo‐degradation of low density polyethylene films

The effect of the morphology on photo‐degradation was investigated for low‐density polyethylene materials. For this purpose, films with different degrees of crystallinity and different degrees of orientation were prepared. For all the films, photodegradation was promoted at 336K for 12 days using a weather meter. The following results were obtained. There existed an induction period before degradation or chain scission. The induction period was longer for stretched films than for un‐stretched ones. Also, the rate of degradation became lower for stretched films. However, both the induction period and the rate of degradation hardly changed with heat‐treatment condition, that is, the degree of crystallinity. In the induction period, the density changed in a complicated manner. This complicated change must be due to the change in the molecular aggregation state of the amorphous phase. The rheological and GPC measurements indicated that photo‐degradation causes the lowering of molecular weight and the increase in higher molecular weight fraction, and consequently the broadening of molecular weight distribution. The lowering of molecular weight may be caused by chain scission and the increase in higher molecular weight fraction by the formation of crosslinks.     

Properties of poly(ethylene glycol)‐based bioelastomers

In this article, a series of poly(ether ester) bioelastomers, poly(PEG‐co‐CA)s (PECs), were synthesized by the melt polycondensation of citric acid (CA) and poly(ethylene glycol) (PEG) with molecular weights of 150, 200, 300, and 400. The measurements of the mechanical properties of the PEC series testified that these polymers were elastomers with a low hardness and high elongation, and the hydrolytic degradation of polymer films in a buffer of pH 7.4 at 37°C showed that the PECs had excellent degradability. The molecular weight of PEG had a strong influence on the degradation rates, water absorption rates, and mechanical performance of the PECs. The materials are expected to be useful for pressure hemostasis implementation in lacuna and other biomedical applications. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of uniaxial drawing of soy protein isolate biopolymer film on structure and mechanical properties

The effect of uniaxial drawing of biodegradable soy protein isolate (SPI) polymer film on mechanical properties was investigated to accelerate the efforts to develop SPI films with improved properties. The films containing 0–30 wt% glycerol were drawn uniaxially up to a draw ratio of 2.5. The mechanical properties of the SPI film increased significantly after uniaxial drawing. The tensile strength of the undrawn film (49.7 MPa) was approximately doubled by subjecting the film to uniaxial drawing to a D.R. of 2.5. Wide‐angle X‐ray diffraction and differential scanning calorimetry measurements did not show evidence of generation of a crystal phase in the drawn SPI films. ATR‐FTIR revealed that the protein film contained mainly α‐helix and β‐sheets secondary structures. Microwave molecular orientation analysis showed that birefringence increased with increasing draw ratios. Mechanical anisotropy of the SPI film via orientation of α‐helix and β‐sheets structure is thought to be responsible for the enhancement of mechanical properties with uniaxial drawing of the SPI films. POLYM. ENG. SCI., 47:374–380, 2007. © 2007 Society of Plastics Engineers.     

Synthesis and characterization of azo‐based acrylate polymers for use as nonlinear optical materials

In this work, high molecular weight azo polymers were synthesized by incorporating the azo monomer into a base polymer through their reactive functional groups. Copolymers of methyl methacrylate and methacrylic acid (with varying concentrations of carboxylic acid group) were synthesized. These were then reacted with epoxy‐terminated azo molecule by carboxylic acid–epoxy reaction. The functionalized systems show excellent film homogeneity and optical clarity. The series of copolymers were characterized using FTIR, NMR, UV–vis spectrometry, gel permeation chromatography, elemental analysis, thermogravimetric analysis, and differential scanning calorimetry. The polymer films coated on ITO glass slides were poled and their order parameters were calculated to check the stability of oriented dipoles. Temporal stability, checked up to 120 h under ambient conditions, was found to be excellent. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 425–431, 2007     

光敏剂对mLLDPE薄膜光氧化降解性能的影响

将不同光敏剂硬脂酸铁(FeSt)、硬脂酸钴(CoSt)和二乙基二硫代氨基甲酸铁(FeDEC)加入茂金属线型低密度聚乙烯(mLLDPE)中,分别吹塑成膜,将薄膜放入老化箱中考察其在紫外光下的降解规律。结果表明:mLLDPE的降解速度随着紫外光照射时间的延长而提高,光敏剂CoSt对mLLDPE薄膜的降解作用比FeSt和FeDEC效果好而,CoSt含量为0.3%时是降解速度最佳点。     

Modification of tribological performance of DLC films by means of some elements addition

The elements added diamond-like carbon films (hydrogen, fluorine, and sulfur) fabricated from C₂H₂:H₂, C₂H₂:CF₄ and C₂H₂:SF₆ mixtures were used to compare and study the effects of element contents on the deposition and tribological properties of films prepared by plasma-based ion implantation (PBII). The structure of the films was analyzed by Raman spectroscopy. Hardness and elastic modulus of films were measured by nano-indentation hardness testing. Contact angle and surface energy of films were measured by contact angle measurement. Tribological characteristics of films were performed using a ball-on-disk friction tester. The results indicate that with the increasing element contents, the hardness and elastic modulus, and surface energy of all films decreases, while the surface angle tends to increase. Additionally, H-DLC films at C:H flow rate ratio of 1:4 shows a friction coefficient of 0.08 under ambient air, which are considerable improvement in the tribological properties. This is due to the formation of a transfer films on the interface and high hydrogen contents. For F-DLC films and S-DLC films, does not show a significant decrease in the friction coefficient with the fluorine and sulfur contents under ambient air. The decrease in the friction coefficient is greater under high vacuum than under ambient air.     

Solid-phase photocatalytic degradation of polystyrene with modified nano-TiO2 catalyst

A novel photodegradable polystyrene-grafted-TiO₂ (PS-g-TiO₂) nanocomposite was prepared by embedding the grafted-TiO₂ into the commercial polystyrene. Solid-phase photocatalytic degradation of the PS-g-TiO₂ nanocomposite was carried out in ambient air at room temperature under ultraviolet lamp and/or sunlight irradiation. The properties of composite film were compared with those of the pure PS film by methods such as weight loss measurement, scanning electron microscope (SEM), gel permeation chromatogram (GPC), X-ray photoelectron spectroscopy (XPS), FT-IR spectroscopy, and UV-vis spectroscopy. The results show that the photo-induced degradation of PS-g-TiO₂ composite film is significantly higher than that of pure PS film. The weight loss of composite film reached 31.9%, average molecular weight (M_w) of composite film decreased by 53.1%, and the number average molecular weight (M_n) decreased by 73.2% after 396 h of UV-light irradiation. FT-IR analysis and weight loss indicated that the benzene rings in PS-matrix of composite film were cleaved during UV-light irradiation. The photocatalytic degradation mechanism of the films is briefly discussed.     

Shear rheological properties of acrylic copolymers and terpolymers suitable for potentially melt processable carbon fiber precursors

In an effort to generate melt processable polyacrylonitrile (PAN) precursor fibers suitable for conversion to carbon fibers, an acrylonitrile/methyl acrylate (AN/MA) copolymer and two acrylonitrile/methyl acrylate/acryloyl benzophenone (AN/MA/ABP) terpolymers were synthesized at molar ratios of 85/15 and 85/14/1, respectively. The termonomer (ABP) was incorporated to accelerate crosslinking via UV irradiation, which serves to prevent relaxation of orientation and flow as the temperature of the fiber is raised during thermooxidative stabilization. Two molecular weights of the terpolymer and one molecular weight of the copolymer were studied to determine the effect of the termonomer, and the effect of molecular weight (MW), on the steady shear viscosity (η) and magnitude of the complex viscosity (η*). A higher rate of increase of η as a function of time was observed for the high MW terpolymer relative to that of the copolymer over the temperature range used. Using a temperature sweep and monitoring levels of η*, a minimum was observed at lower temperatures for both terpolymers. These results suggest that copolymerization with ABP significantly increased the thermally induced kinetics of crosslinking. Comparison of the η and η* data for the low and high MW terpolymers suggested that molecular weight also significantly reduced the melt stability (increased the kinetics of crosslinking). A chemorhelogical correlation was then used to quantify the effects of the termonomer and of molecular weight on the kinetics of crosslinking of the AN terpolymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2856–2865, 2004     

Surface free energy analysis of poly(vinyl alcohol) films having various molecular parameters

The molecular parameters of poly(vinyl alcohol) have enormous effects on its physical and chemical properties. Therefore, the surface characteristics of poly(vinyl alcohol) films are also determined by the molecular parameters. In this study, the dependence of the surface free energy on the molecular weight, degree of saponification, and stereoregularity of poly(vinyl alcohol) films has been evaluated with contact‐angle measurements. The surface free energy of poly(vinyl alcohol) films increases with decreases in the syndiotactic dyad content, molecular weight, and degree of saponification. The polar component of the surface energy is not affected by the deviation of the molecular weight and degree of saponification very much. However, it decreases with increases in the syndiotactic dyad content and ranges from 11.64 to 4.35 dyn/cm. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Study on Curing Kinetics and Thermal Degradation Kinetics of Hyperbranched Poly(Trimellitic Anhydride Ethylene Glycol) Epoxy (HTME)/Diglycidyl Ether of Bisphenol-A Epoxy Hybrid Resin

Hyperbranched poly(trimellitic anhydride ethylene glycol) epoxy (HTME) not only has relatively low viscosity and high molecular weight but also is a functional additive of enhancement and toughness and is used in the thermosetting resin field widely. The curing kinetics and thermal degradation kinetics of HTME/diglycidyl ether of bisphenol-A epoxy hybrid resin were studied in detail using differential scanning calorimetry and thermogravimetric analysis technique, respectively, by the Coats-Redfern model. The effect of molecular weight or generation and content of HTME on activation energy, reaction order, curing time, and curing reaction were discussed and analyzed, and the results indicated that HTME could accelerate curing reaction and reduce activation energy and reaction order of the curing reaction.