Deterioration of polypropylene/silicon dioxide nanocomposites before oxidative degradation

The thermal aging of polypropylene (PP)/SiO₂ nanocomposite films was carried out at 130°C. In contrast to the widely accepted thermal oxidation mechanism, the film ruptured far before the carbonyl group was detected and without a noticeable reduction in the molecular weight. Observations with a polarizing optical microscopy and a scanning electron microscopy demonstrated that, instead of oxidative degradation, at least three other factors were responsible for the rapid deterioration of the PP/SiO₂ nanocomposites: (1) recrystallization during the thermal aging, which gave rise to a major volume contraction and, thus, great stress along the spherulite boundaries, which might have induced cracks there (another effect of the recrystallization was the rejection of nanoparticles and defects to the spherulite boundaries, which, therefore, weakened the boundaries); (2) poor interfacial interaction between the matrix and the nanoparticles; and (3) large temperature changes, which created interfacial debonding because of the significant difference in the thermal expansion coefficients of PP and the nanoparticles. The results of this study extend the understanding of the thermal oxidative degradation mechanism of polymer materials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Structure development in processing of polypropylene films with additives

The crystallization behavior, modification of crystalline form, and orientation in polypropylene processed by blow film extrusion was studied as a function of processing parameters as well as different types of additives. The isothermal crystallization rate was greatly enhanced in the presence of certain additives, especially CaCO₃. The crystalline form was predominantly α type in both compression molded or blow extruded films. However, there was an unusually large intensity of the α₀₄₀ peak in the X-ray diffraction of the latter case films. The variation of the peak intensities and the increase of birefringence with increase of take-up speed has been explained on the basis of orientation induced by uniaxial stress in the machine direction. This orientation contained two components, namely the orientation of the b axis of the crystallites and the orientation of loosely bound polymer chains in the amorphous regions. © 1995 John Wiley & Sons, Inc.     

Surface modifications of polypropylene with nonylphenol ethoxylates melt additives

Nonylphenol ethoxylated (NPE) additives were melt blended in polypropylene (PP) films and characteristics of the modified films were investigated. It was found that melt blending of NPE additives improved hydrophilicity of PP films through additive surface segregation. Surface specific techniques, such as X‐ray photoelectron spectroscopy (XPS) and Time‐of‐Flight Secondary Ion Mass Spectrometry (ToF‐SIMS) were used to study surface compositions of samples modified with NPE additives at different aging time after extrusion. We found that surface enrichment of additives lead to hydrophilic surfaces. Hydrophilic chain length in NPE affected surface composition and hydrophilicity of NPE containing PP polymer. The effect of water immersion and aging were also reported. POLYM. ENG. SCI., 52:1920–1927, 2012. © 2012 Society of Plastics Engineers     

A study on the onset surface melt fracture of polypropylene materials with foaming additives

The melt fracture behaviors of linear and branched polypropylene resins with foaming additives were investigated. The effects of branching, processing temperature, additives, and blowing agent on the surface melt fracture of polypropylene materials were thoroughly studied. A CCD camera was installed at the die exit to precisely observe the onset of surface melt fracture of extruded foams. The critical wall shear stress was determined for various linear and branched polypropylene resins using a capillary die. It was found that the branching required to foam polypropylene resins also promotes melt fracture: the critical shear stress was decreased by 0.0175 MPa with an increase of 0.1 n/1000c in long‐chain branching. It was also observed that the dissolved blowing agent (butane) significantly suppressed the melt fracture of both linear and branched polypropylene resins. On the other hand, a noticeable increase in the critical shear stress of branched polypropylene materials was observed with the nucleating agent (talc) and the aging modifier (glycerol mono stearate), whereas almost negligible effect of the additives on the critical shear stress was observed for linear polypropylene materials. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

助剂改性聚丙烯耐候性研究进展

近年来,聚丙烯老化改性的研究引起了广泛的关注,其中包括有机助剂改性和无机助剂改性。综述了聚丙烯老化改性的几种常用方法、国内外发展情况以及老化改性的机理等内容。     

Electrical insulation properties of silicone rubber under accelerated corona and thermal aging

A contactless method based on energy shift of high-energy cut-off of the x-ray bremsstrahlung, the so-called Duane Hunt Limit and a conventional low voltage electrical technique (three-probes technique) is applied on thermal and corona aged silicone rubber (SiR) to measure, respectively, the surface potential, V_s, and the surface resistivity, ρ_s. The effect of aging on these quantities, representing the dielectric properties, is studied. The results are highly reproducible and highlight a good correlation between V_s and ρ_s. It was observed that thermal aging combined with electrical aging deteriorates more the electrical properties of the polymer than thermal aging alone. Explanations for electrical characteristics (V_s, ρ_s) change with aging are supported by attenuated total reflection Fourier transform infrared spectroscopy spectra analysis and a chemical mechanism of aging in three steps (i.e., oxidation-polycondensation, degradation, and thermal cracking). The surface degradation of the polymer is revealed by images of surface morphology obtained by using scanning electron microscopy (SEM). Roughness is greater for combined thermal and corona aging mode compared to thermal aging alone. In addition, the surface degradation of SiR polymer is confirmed by the loss of its hydrophobicity.     

Determination of antioxidants in polypropylene by liquid chromatography

Polyolefins, such as polypropylene, are subject to thermal and oxidative degradation and are not used in practical applications unless protected by several antioxidants. Liquid exclusion (LEC) and liquid adsorption (LAC) chromatography have been used to determine the antioxidants in commercial polypropylenes and molded parts. Although a LEC analysis takes as long as 3 hr, LAC separations can be obtained in less than 15 min. Prior to the chromatographic measurements, the antioxidants were extracted from the talc-filled polypropylene using tetrahydrofuran (THF) and Methylene chloride (CH₂Cl₂) for the LEC and LAC separations, respectively. Room-temperature extraction of the additives as a function of time showed that 24 hr was sufficient for THF. A comparison of the LEC chromatogram for a freshly molded part to that for a part which was heat treated showed not only the depletion of certain antloxidants but also showed that the antioxidant distearyl 3,3′-thiodipropionate (DSTDP) thermally decomposed to give stearyl propionate. Mass spectrometry was used to confirm the identity of the additives in the polypropylene without extraction. The “life” af several polypropylenes was also measured by thermogravimetric analysis and compared to the concentration of DSTDP.     

MnSt2–kaolin–polyethylene film: An eco‐friendly polyethylene composite film and its thermo‐ and biodegradable research

A novel thermo‐ and biodegradable MnSt₂–kaolin–polyethylene (signed as MKPE) composite film was prepared through a melt blending technique. Manganese stearate and common kaolin were employed as thermo‐degradable additives and biodegradable promoter to improve the degradable efficiency of the waste PE. Thermo‐oxidative testing was carried out in an air oven maintained at 70°C simulating a compost temperature. The biodegradation of the aging films was also investigated by analysis of evolved carbon dioxide of films in aquatic test systems according to the International Standards ISO 14852 (1999). The composite film was characterized by electronic universal testing machine, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, attenuated total reflection‐flourier transformed infrared spectroscopy and thermo gravimetric analysis. These results showed that the MKPE film exhibited a high degree of susceptibility to thermo‐oxidation and biodegradation. After thermal aging for 30 days, the mechanical properties of MKPE films reduced quickly and oxygen groups were introduced into the polymer chains. The kaolin particles wrapped in polymers were exposed gradually because of the rupture of polymer chains by thermal aging. The biodegradation degree reached 24.26% after incubation in an aqueous medium for 60 days. A possible mechanism for thermal oxidative degradation and biodegradation was also discussed. POLYM. COMPOS., 36:939–945, 2015. © 2014 Society of Plastics Engineers     

Aging behavior of polyarylsulfone films

The aging behavior of two experimental polyarylsulfone films is discussed. The mechanical and electrical properties of the films were measured as a function of time at temperatures of 300°, 275°, and 250°C. The effect of “reprocessing” the material is also reported. DTA and TGA analysis, coupled with other aging test results, point out the excellent thermal stability of the polyarylsulfones. However, some peculiar behavior is exhibited by the unrefined polymer. Free film aging of this material showed no signs of discoloration or deterioration in properties after 1000 hr at 300°C. Film aged wrapped on metal and glass rods discolors badly, is subject to stress cracking, and embrittles. The reprocessed'' film is superior to its predecessor and exhibits none of the disadvantages that characterize the unrefined polymer. Solubility studies, coupled with the other aging tests, provided some insight into the degradation phenomenon of this polymer. Resistance to ultraviolet light is extremely poor. Reprocessing of the material provided for a much superior film material with a higher level of mechanical, electrical, optical, and thermal properties.     

How the biaxially stretching mode influence dielectric and energy storage properties of polypropylene films

The most important polymer film used in commercial capacitors is biaxially oriented polypropylene (BOPP), which could be produced by sequentially or simultaneously biaxial orientation after the melt-extrusion. In order to disclose the influence of the stretching technique on the properties of films, the BOPP films with varied thickness were fabricated by sequential and simultaneous orientation, respectively. Compared to the sequentially biaxially stretched films, the crystal grains in the simultaneously biaxially stretched films are more isotropically dispersed. As temperature increases, all the BOPP films exhibit similar dielectric constant, and the simultaneous films have much lower dielectric loss thanks to the finer blended crystalline and amorphous phases. When the film thickness is smaller than 5 μm, the breakdown field strength, energy density and discharging time of the simultaneous films can be increased by at least 10% comparing to the sequential ones, which is very important for reducing the volume of the film capacitors. All the results suggest the simultaneously biaxial orientation mode shows significant advantages in producing thin BOPP films with better mechanical and electrical properties.     

An organic bioactive pro-oxidant behavior in thermal degradation kinetics of polypropylene films

Due to its versatility and low cost, polypropylene (PP) is one of the most widely used polymers in the world. However, since it does not easily degrade in natural environment, various methods have been studied to reduce its lifetime. The pro-degrading additives promote the polymer degradation process by accelerating the polymer degradation under heat and/or UV. Eco-one is an organic bioactive pro-oxidant additive that induces biodegradation when it is incorporated into a polymeric matrix by attracting microorganisms in the biotic phase. The aim of this work was to investigate the abiotic degradability of this organic bioactive pro-oxidant additive in PP films. Thermal oxidation studies of the specimens were carried out to investigate the abiotic degradability. We analyzed compositions of PP films containing 1, 3, and 5% Eco-one by mass. These films were characterized by thermogravimetric analysis to calculate the activation energy (E _α) and to estimate their lifetime. Differential scanning calorimetry was conducted to provide oxidative induction time. The samples were then aged at 80 °C and characterized by Fourier transform infrared spectroscopy to obtain the carbonyl index (CI). Compositions containing 1% Eco-one additive showed the optimal composition with lower activation energy, and shorter predicted lifetime, suggesting easier thermal degradation. Furthermore, high CI was also observed in samples containing 1% additive, indicating thermodegradation for this composition.     

Radiation-induced graft polymerization of acrylonitrile onto isotactic polypropylene and poly(tetrafluoroethylene–ethylene) copolymer films

Direct radiation-induced grafting of acrylonitrile (AN) onto both isotactic polypropylene (IPP) and (tetrafluoroethylene–ethylene) copolymer (ET) films has been studied. The effect of grafting conditions such as inhibitor and monomer concentrations and irradiation dose on the grafting yield was investigated. Homopolymerization of acrylonitrile was reduced to a minimum using ferric chloride (FeCl₃), and the suitable optimum concentration of the inhibitor was found to be 0.1 wt%. The higher the monomer concentration, the higher the degree of grafting obtained. It was observed that the degree of grafting onto IPP was higher than onto ET, at given grafting conditions. The effect of aging on IPP was also examined. IR spectroscopy showed that IPP was susceptible to photooxidation by aging. The swelling behaviour and electrical conductivity of the graft and hydrolysed graft films were investigated. The electrical conductivity was improved by hydrolysis of polyacrylonitrile in the graft chains.     

Calcium carbonate and ammonium polyphosphate‐based flame retardant composition for polypropylene

The chemical mode of action as a flame retardant of calcium carbonate nanoparticles combined with ammonium polyphosphate in polypropylene was investigated. Reduction in burning rates for 0.5 mm thick samples were observed without appreciable char formation up to 30 wt % loading of additives. Thermogravimetric analysis (TGA) of the mixture of CaCO₃ and ammonium polyphosphate (APP) showed that calcium carbonate nanoparticles react with ammonium polyphosphate before the degradation of the phosphate chains. TGA–FTIR studies of the polymer composite samples and powder mixtures of the additives confirmed the evolution of ammonia and carbon dioxide due to interaction between the additives. X‐ray diffraction (XRD) analysis of chars, obtained after burning the films, showed definite diffraction peaks corresponding to that of calcium metaphosphate. The inert gasses produced by the interaction of the additives hindered the advancing flame and, thus, reduces the burning rates, at times even without char formation. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Biaxially oriented polypropylene film in power capacitors

The use of polymer dielectrics, particularly biaxially oriented polypropylene (BOPP), has revolutionized power distribution around the world. BOPP film of sub mil thickness has displaced impregnated Kraft paper because of superior dielectric performance, lower cost, and small volume. The polypropylene molecule has a unique set of properties which combine stable dielectric properties in the operating temperature and frequency range along with an adequate dielectric constant. High levels of orientation and a small unbalance of orientation are required to produce films of high dielectric strength over large areas of film. Control of thickness uniformities to approximately ± 5 percent are critical to the reliable operation of the capacitor under load and to control of capacitance in the product. A special fibrillated surface is required which promotes complete impregnation by the dielectric fluid. This surface is acquired by the development of a specific crystal morphology at one surface of the film. No additives are used to promote this crystalline structure since most additives effect dissipation factor and generate unwanted heat. Similarly, control of contamination (ppm and ppb) is a key factor in the manufacture of film power capacitors.     

聚丙烯防老化的研究进展

分析了聚丙烯老化的过程和机理,综述了近十几年来国内外关于聚丙烯老化的研究手段和方法,主要包括自然老化试验和人工老化试验;以及提高聚丙烯防老化能力的研究进展,主要包括改善晶体结构、分子改性或制备、添加助剂和添加填料等,最后对聚丙烯防老化的研究发展进行了展望.     

聚丙烯热氧老化机理的研究

利用熔体流动速率法和红外光谱法研究了纯聚丙烯（PP）粉料的热氧老化机理。结果表明,纯PP粉料的热氧老化降解机理服从指数函数,且函数的拟合度高,说明在热氧老化降解前期,需要聚集一定的能量,这个过程中PP只发生微弱降解,出现“诱导期阶段”,而当能量积聚到一定程度后,PP开始大幅度降解,这时会出现热氧老化降解的“加速阶段”。     

Photosensitized degradation of polyolefins. II

The oxydative photodegradation of polyethylene sensitized by aromatically substituted dienes such as 1,6-diphenyl-1,3,5-hexatriene (DPH) and 1,4-diphenyl-1,3-butadiene (DPB) has been investigated. The rate of degradation has been monitored by following the change of the mechanical properties of the polymer during accelerated indoor aging tests. It was found that both additives are efficient sensitizers of the photodegradation of polyethylene. The mechanism of photo-oxidation has been investigated by ESR and IR spectroscopy and it has been interpreted on the basis of a complex mechanism which includes excited singlet oxygen (¹O₂) and the products of photodegradation of the additives. Singlet oxygen, produced by DPB and DPH and/or by impurities present in the polymer, reacts with the additives themselves and, directly, with polyethylene. In turn, the products of photodegradation of the additives react with the polymer via hydrogen atom abstraction, further promoting the photodegradation. Irradiation carried out in absence of air seems to rule out the possibility of direct hydrogen atom abstraction by DPB and DPH.     

The Structural,Optical and Electrical Properties of Spin Coated WO<Subscript><Emphasis Type="Bold">3</Emphasis></Subscript> Thin Films Using Organic Acids

Tungsten trioxide (WO₃) thin films were prepared incorporating various organic acid additives by the sol-gel spin coating technique. They were characterized by X-ray diffraction (XRD), UV-Visible analysis, scanning electron microscopy (SEM) and dc electrical conductivity. From XRD, the crystal phase, average grain size and structural parameters of WO₃ thin films were found to vary owing to different water dissolved organic acid additives. The variation of optical conductivity and band gap energy was calculated from the UV-Visible analysis. The SEM studies revealed that the organic acids influenced the surface morphology of the microsized plates of tungsten oxides. The electrical conductivity at various temperatures correlated with the average grain size of the nanocrystallites of WO₃ thin films.     

Thermal and morphological studies on γ‐Fe2O3 polystyrene composites and the affect of additives

γ‐Fe₂O₃polystyrene (PS) composite films were prepared by a gel‐casting technique to obtain monodisperse composite films. To understand the effect of additives on the prepared composite films, additives such as rice husk ash and thiourea were made to disperse into the PS matrix. The as‐prepared γ‐Fe₂O₃ PS composite films, along with their additives, were subjected to characterization and study by X‐ray diffraction, scanning electron microscopy, thermal, IR, and dielectric measurement techniques. These studies showed monodisperse and chemically homogenous composite films with an increase in thermal behavior. An interesting self‐assembly of rod‐like nanoparticles of γ‐Fe₂O₃ particles into the polymer matrix, which formed spherical packets, was observed for the γ‐Fe₂O₃PS composite film. The electrical behavior of these films was interesting, as some showed conduction whereas others showed an increase in dielectric behavior. This nature was explained by the dielectric measurements. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 778–788, 2004