Biodegradation of oxo‐biodegradable polyethylene

Biodegradation of polyethylene and oxo‐biodegradable polyethylene films was studied in this work. Abiotic oxidation, which is the first stage of oxo‐biodegradation, was carried out for a period corresponding to 4 years of thermo‐oxidation at composting temperatures. The oxidation was followed by biodegradation, which was achieved by inoculating the microorganism Pseudomonas aeruginosa on polyethylene film in mineral medium and monitoring its degradation. The changes in the molecular weight of polyethylene and the concentration of oxidation products were monitored by size exclusion chromatography and Fourier transform infrared (FTIR) spectroscopy, respectively. It has been found that the initial abiotic oxidation helps to reduce the molecular weight of oxo‐biodegradable polyethylene and form easily biodegradable product fractions. In the microbial degradation stage, P. aeruginosa is found to form biofilm on polymer film indicating its growth. Molecular weight distribution data for biodegraded oxo‐biodegradable polyethylene have shown that P. aeruginosa is able to utilize the low‐molecular weight fractions produced during oxidation. However, it is not able to perturb the whole of the polymer volume as indicated by the narrowing of the polymer molecular weight distribution curve toward higher molecular fractions. The decrease in the carbonyl index, which indicates the concentration of carbonyl compounds, with time also indicates the progress of biodegradation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Biodegradation studies of LDPE filled with biodegradable additives: Morphological changes. I

Low‐density polyethylene (LDPE) samples filled with three commercial biodegradable additives (Mater‐Bi, Cornplast, and Bioefect) have been subjected to an accelerated soil burial test in a culture oven for 1 year. By means of Differential Scanning Calorimetry (DSC), the effect of the degradation in soil in the samples morphology has been analyzed, in terms of their melting temperature, their crystalline content, and their lamellar thickness distribution. These morphological parameters evolve in different stages, depending on the additive used. It has been found that the LDPE–Mater‐Bi samples are the ones exhibiting faster changes in their crystalline content. However, the LDPE blends with Cornplast and Bioefect display more significant changes in their lamellar thickness distribution. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1683–1691, 2002     

Preparation and characterization of polyethylene‐g‐maleic anhydride–styrene/montmorillonite nanocomposites

It is difficult to prepare polyethylene/montmorillonite by direct melt mixing because of the difference in character between polyethylene and montmorillonite. Therefore, it is necessary to modify polyethylene with polar groups, which can increase the hydrophilicity of polyethylene. At the same time, the inorganic montmorillonite should be modified with long‐chain alkyl ammonium to increase the basing space between the interlayers. Thus, through the grafting of the polar monomer onto the main chain of polyethylene by reactive extrusion, polyethylene/montmorillonite nanocomposites can be prepared by the melt mixing of the grafter and organic montmorillonite. Fourier transform infrared has been used to prove that the monomers are grafted onto polyethylene. X‐ray diffraction and transmission electron microscopy have been employed to characterize the nanocomposites. Furthermore, thermogravimetric analysis measurements show that the thermal stability of the nanocomposites is improved in comparison with that of the virgin materials. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 805–809, 2006     

Ultraviolet weathering of photostabilized wood‐flour‐filled high‐density polyethylene composites

Wood‐plastic composites are being increasingly examined for nonstructural or semistructural building applications. As outdoor applications become more widespread, durability becomes an issue. Ultraviolet exposure can lead to photodegradation, which results in a change in appearance and/or mechanical properties. Photodegradation can be slowed through the addition of photostabilizers. In this study, we examined the performance of wood flour/high‐density polyethylene composites after accelerated weathering. Two 2⁴ factorial experimental designs were used to determine the effects of two hindered amine light stabilizers, an ultraviolet absorber, a colorant, and their interactions on the photostabilization of high‐density polyethyl‐ ene blends and wood flour/high‐density polyethylene composites. Color change and flexural properties were determined after 250, 500, 1000, and 2000 h of accelerated weathering. The results indicate that both the colorant and ultraviolet absorber were more effective photostabilizers for wood flour/high‐density polyethylene composites than the hindered amine light stabilizers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2609–2617, 2003     

Biodegradation and swelling studies of gelatin‐grafted polyethylene

In this article, we report on biodegradation studies and the swelling/solubility behavior of gelatin‐grafted polyethylene (PE). The successful synthesis of graft copolymers of PE with gelatin was carried out with benzoyl peroxide as the radical initiator. Biodegradation studies of the grafted PE were carried out via a soil burial test (with and without the addition of urea). Percentage weight loss was studied as a function of time, and we observed that the percentage weight loss increased with time and was higher for urea‐enriched soil samples. Microanalysis of the soil containing the samples was carried out after a specified number of days. An increase in the colonies of microorganisms with increasing number of days was observed. This revealed that the microorganisms fed upon the grafted material, which led to an increase in the percentage weight loss. Hydrolysis of the samples, taken out from the soil after a specified number of days, revealed a continuous loss of weight with increasing number of days. The effect of the degradation of the grafted samples buried in soil and urea‐enriched soil on the growth of plants was studied, and we found that the plants grew normally in the soil containing the grafted material. Swelling studies were made in binary and ternary solvent systems comprising water–ethanol and water–ethanol–dimethyl sulfoxide, respectively, to study the maximum swelling and solubility of the grafted PE. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Properties of recycled polycaprolactone‐based thermoplastic polyurethane filled with montmorillonites

The properties of recycled low temperature biodegradable polycaprolactone‐based thermoplastic polyurethane (rTPU), filled with different types of organically modified montmorillonite (MMT) prepared by two‐roll milling, were studied. The dependence of rTPU properties on the mastication time and clays content was determined by various structural and physical testing methods. Results show that the melt flow and mechanical properties of rTPU deteriorate with increasing of mastication time, but thermal properties were affected only slightly. rTPU/MMT composites show exfoliated or intercalated structures depending on the nature of organic modifier of clay. MMT reduces slightly rTPU tensile and melt flow properties, but accelerates hydrolytic degradation process. During degradation the weight loss and polydispersity increase significantly in the presence of MMT, but it does not accelerate crystallinity changes. The degradation of rTPU composites with higher hydrophilicity organoclays proceeds faster than that with hydrophobic ones due to the relatively higher interaction with polymer matrix. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Photochemistry of low‐density polyethylene–montmorillonite composites

Photo‐oxidation at the exposed surfaces of low‐density polyethylene/montmorillonite composites was analyzed with attenuated total reflection/Fourier transform infrared spectroscopy. It was found that the clay particles were dispersed but not exfoliated in the polymer matrix. The extent of oxidative degradation of the low‐density polyethylene matrix was slightly greater when montmorillonite was present and was greatest for the blend of low‐density polyethylene and organically modified montmorillonite. The Fourier transform infrared measurements demonstrated that the rate of photo‐oxidation in the bulk was lower than that observed at the surface, but the oxidation chemistry was similar at the surface and in the bulk. The distribution of the photo‐oxidation products was somewhat modified in the presence of montmorillonite and organically modified montmorillonite in comparison with pure low‐density polyethylene, with the yield of acidic products higher and the yield of double bonds lower. These observations were attributed to a slightly higher yield of radicals and some modification of the quantum yield for the processes leading to the formation of double bonds when the clay filler was present. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Biodegradation potential of some barrier‐coated boards in different soil environments

Three pilot barrier‐coated boards that were recently produced at the Tampere University of Technology were tested for biodegradation potential using the soil‐burial test method. The tests were conducted in the field as well as in the laboratory. We found that the baseboards degraded regardless of differences in coating; however, the degradation rate was different. The laboratory conditions as well as the addition of inoculum accelerated the degradation process. The coated layer of the boards was isolated by laminating with black polyethylene; then their biodegradation rate was compared to the biodegradation rate of the control, boards coated with low‐density polyethylene. It was observed that paperboards coated with polyester‐based polymers were biodegradable but at different rates. The differences in the biodegradation rates of the boards were attributed to their coating formulations. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3193–3202, 2006     

Nanocomposites from fluoro‐oxygenated polyethylene: A novel route to organoclay exfoliation

We present a novel approach to improving organoclay exfoliation in a nonpolar matrix, polyethylene. High‐density polyethylene (HDPE) particles were modified by exposure to a reactive gas atmosphere containing F₂ and O₂. This treatment was aimed at increasing the polarity of the polymer with the formation of carboxyl, hydroxy, and ketone functionalities on the particle surface. The surface‐treated high‐density polyethylene (ST‐HDPE) particles were then melt‐mixed with an appropriate organoclay to form nanocomposites. Transmission electron microscopy (TEM), wide‐angle X‐ray scattering, stress–strain analysis, and Izod impact measurements were used to evaluate the nanocomposite morphology and physical properties. These data were compared to those of equivalent nanocomposites prepared from unmodified HDPE and high‐density polyethylene grafted with maleic anhydride (HDPE‐g‐MA). The nanocomposites prepared from the ST‐HDPE particles exhibited much better properties and organoclay dispersion than those prepared from unmodified HDPE. The level of reinforcement observed in ST‐HDPE‐based nanocomposites was comparable to, if not better than, that seen in HDPE‐g‐MA‐based nanocomposites. However, a comparison of the TEM micrographs suggested better organoclay exfoliation in HDPE‐g‐MA than the current version of ST‐HDPE. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2980–2989, 2006     

Processing characteristics of low‐density polyethylene filled with calcium carbonate of different size distributions

Low‐density polyethylene (LDPE) was filled with blends of different proportions of two sizes of calcium carbonate (CaCO₃; 600 and 2500 mesh). The torque of the LDPE/CaCO₃ samples was measured with a torque rheometer. The results showed that the process torque values of the LDPE/CaCO₃ samples obviously decreased when LDPE was filled with a blend of two sizes of CaCO₃ (600‐ and 2500‐mesh CaCO₃ blend) in comparison with samples filled with CaCO₃ of a single size (600 or 2500 mesh). When the ratio of 600‐mesh CaCO₃ to the total CaCO₃ was in the range of 40–60 wt %, the lowest torque value of the LDPE/CaCO₃ samples was achieved. When the content of CaCO₃ in a sample was 30 wt %, LDPE filled with CaCO₃ of different size distributions showed the largest decrease in the torque ratio in comparison with the samples filled with CaCO₃ of a single size. The torques of LDPE samples filled with CaCO₃ of a single size and those filled with CaCO₃ of different size distributions at different temperatures were also studied. The results showed that the flow activation energy and flow activation entropy of LDPE samples filled with CaCO₃ of different size distributions increased obviously. The increase in the flow activation entropy was used to explain the phenomenon of the process torque decreasing for LDPE samples filled with CaCO₃ of different size distributions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Modification of properties of CaCO3‐polymerization‐filled polyethylene

CaCO₃–polyethylene (PE) compositions, containing an ultrahigh molecular polyethylene (UHMPE) interlayer between the filler surface and the PE matrix, were synthesized by two‐step polymerization of ethylene on a filler surface activated with a suitable catalyst. The properties of the compositions were studied depending on the molecular weight of the PE matrix and the thickness of the UHMPE intermediate layer at the filler particles. It was shown that the presence of UHMPE as an interlayer in chalk–UHMPE–PE compositions leads to an increase of plastic deformation of the materials as long as the M_w value of the PE matrix is higher than is the brittleness threshold for PE. Chalk–UHMPE–PE compositions exhibit a higher ability for plastic deformation compared to chalk–PE compositions based on a PE matrix of a molecular weight equal to the molecular weight of the total polymer phase (UHMPE–PE) in the first case. There is no improvment of the mechanical properties when the UHMPE is dispersed in the compositions and not as an interlayer between a filler and a matrix. This means that the method of polymerization filling allows one to incorporate the polymer interlayer with a desired nature and properties between a filler surface and polymer matrix in filled polyolefin compositions. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 577–583, 2003     

Modeling the oxidative degradation of ultra‐high‐molecular‐weight polyethylene

Understanding the sequence of reactions that occur in ultra‐high‐molecular‐weight polyethylene (UHMWPE) following ⁶⁰Co γ irradiation has been the focus of numerous experimental studies. In the study reported here, we have incorporated recent experimental findings into a mathematical model for UHMWPE oxidation. Simulation results for shelf aging and accelerated aging are presented. It is shown that very reasonable simulations of shelf‐aging and accelerated‐aging data can be obtained. It is also shown that simulations of shelf aging in reduced oxygen environments predict that the subsurface peaks of ketones will be shifted to the exterior surface. In vivo aging can be simulated if we assume that the oxygen level in the synovial fluid is about one‐eighth that of atmospheric levels. Some reduced irradiation doses are predicted to significantly reduce the ketone formation for shelf‐aging periods of up to 10 years. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 814–826, 2003     

Study of the biodegradation behavior of soy protein‐grafted polyethylene by the soil burial method

In this article, we report on the biodegradation of soy‐protein‐grafted polyethylene, which was successfully synthesized by a graft copolymerization method with benzoyl peroxide as the radical initiator. The biodegradation behavior of the grafted polyethylene was ascertained by a soil burial test. The weight‐loss percentage was measured as a function of the number of days, and it was observed that the percentage weight loss increased with increasing number of days. To further substantiate the degradation, microanalysis of the soil containing the samples was carried out. An increase in microorganism colonies was observed with increasing number of days. The hydrolysis of the samples taken from the soil after a specified number of days also corroborated the findings and revealed a continuous loss of weight. The effect of the degradation of the grafted samples on the growth of plants (wheat and soybean) was studied, and we observed that the products of degradation were not harmful to the growth of the plants. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Morphology‐related packetlike space‐charge behavior in linear low‐density polyethylene doped with Al2O3 nanoparticles

Packetlike space‐charge behavior and the isothermal decay processes of the injected charge in neat linear low‐density polyethylene (LLDPE) and LLDPE doped with Al₂O₃ nanoparticles were investigated by the pressure wave propagation method. The 1‐mm sheet samples, sandwiched by semiconductive electrodes, were submitted to 40 kV/mm of direct current field at various temperatures for 3 h. The charge‐injecting rate and the apparent mobility of packetlike space charge under direct‐current stress were compared among the samples subjected to different blending processes with or without nanoparticles. The slight doping concentration showed a significant influence on the space‐charge dynamics, with a lower injecting rate and apparent mobility for higher doped samples. The isothermal decay processes of the injected charge indicated trap‐modulated features. The phenomena were considered to be related to the changing morphology of the matrix material. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of exfoliation and dispersion on the yield behavior of melt‐compounded polyethylene–montmorillonite nanocomposites

The yield behavior of melt‐mixed nanocomposites containing 5 wt % organically modified montmorillonite in matrices of a linear low‐density polyethylene (LLDPE) or a modified polyethylene was studied as a function of the temperature and strain rate. In the melt‐mixed LLDPE nanocomposite, the montmorillonite showed a slight increase in the clay spacing, which suggested that the clay was at best intercalated. Transmission electron microscopy (TEM) images showed that the dispersion in this nanocomposite was poor. The use of the modified polyethylene promoted exfoliation of the clay tactoids in the nanocomposite, as assessed by X‐ray diffraction and TEM. In both nanocomposites, the yield mechanisms were insensitive to the addition of the organoclay, even though modest increases in the modulus were produced. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3044–3049, 2006     

Preparation of polyethylene–clay nanocomposites directly from Na+ montmorillonite by a melt intercalation method

Polyethylene (PE)/clay nanocomposites were prepared directly from Na⁺ montmorillonite by a melt intercalation technique, using hexadecyl trimethyl ammonium bromide (C16) as a reactive compatibilizer. Three other polymer–clay nanocomposites were also prepared by this new technique. Their structures were characterized by X‐ray diffraction and transmission electron microscopy. The mechanism of this new method was studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2583–2585, 2003     

Thermal analysis of high‐density polyethylene and low‐density polyethylene with enhanced biodegradability

The thermal properties of high‐density polyethylene (HDPE) and low‐density polyethylene (LDPE) filled with different biodegradable additives (Mater‐Bi AF05H, Cornplast, and Bioefect 72000) were investigated with thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The DSC traces of the additives indicated that they did not undergo any significant phase change or transition in the temperature region typically encountered by a commercial composting system. The TGA results showed that the presence of the additive led to a thermally less stable matrix and higher residue percentages. The products obtained during the thermodegradation of these degradable polyolefins were similar to those from pure polyethylenes. The LDPE blends were thermally less stable than the HDPE blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 764–772, 2002     

Effects of ultraviolet absorbers on the ultraviolet degradation of rice‐hull/high‐density polyethylene composites

In China, rice‐hull powder is widely used as a fiber component to reinforce polymers because of its ready availability and lower cost compared to wood fibers. However, an issue concerning these composites is their weathering durability. In this study, the effects of two ultraviolet absorbers (UVAs), UV‐326 and UV‐531, on the durability of rice‐hull/high‐density polyethylene (HDPE) composites were evaluated after the samples were exposed to UV‐accelerated weathering tests for up to 2000 h. All of the samples showed significant fading and color changes in exposed areas. X‐ray photoelectron spectroscopy and Fourier transform infrared spectroscopy were used to detect surface chemical changes. The results indicate that surface oxidation commenced immediately within the first 500 h of exposure for all of the samples. However, the control rice‐hull/HDPE composites underwent a greater degree of oxidation than those with the UVAs. Scanning electron microscopy revealed that the rice‐hull/HDPE composites degraded significantly upon accelerated UV aging, with dense cracking on the exposed surface. The UVAs provided effective protection for the rice‐hull/HDPE composites, and UV‐326 had a more positive effect on the color stability than UV‐531. The results reported herein serve to enhance our understanding of the efficiency of UV stabilizers in the protection of rice‐hull/HDPE composites against UV radiation, with a view toward improving their formulation. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and characterization of polyethylene–clay nanocomposites by using chlorosilane‐modified clay

Clay was modified by trimethylchlorosilane; after modification, hydroxyl groups at the edge of layers were reacted and CEC value was drastically decreased. Polyethylene–clay composites were prepared by melt compounding. Wide angle X‐ray diffraction (WAXD) and transmission electron microscopy (TEM) showed that intercalated nanocomposites were formed using organoclay ion‐exchanged from chlorosilane‐modified clay, but conventional composites formed using organoclay directly ion‐exchanged from crude clay. Dynamic mechanical analysis (DMA) of PE and PE–clay composites was conducted; the results demonstrated that nanocomposites were more effective than conventional composites in reinforcement and addition of organoclay resulted in the increase of glass transition temperature (T_g), but crude clay had no effect on T_g of PE–clay composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 676–680, 2004