Photodegradation of low-density polyethylene with prooxidant and photocatalyst

Low-density polyethylene (LDPE) composite films with trisilver phosphate (Ag₃PO₄) and cadmium selenide (CdSe) particles as photocatalysts and manganese stearate as prooxidant were prepared. The film samples were irradiated under UV and visible light and their photodegradation were evaluated using Fourier-transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, and differential scanning calorimetry. The carbonyl index of the photocatalyst containing samples was very higher than the pure irradiated LDPE and even prooxidant containing film. The morphologies of the irradiated composite films were completely changed and had many cavities and cracks. The thermal stability of the composites was very lower than the pure polyethylene. However the crystallinity of the LDPE films with photocatalysts was enhanced contrarily the LDPE film with manganese stearate. Generally the results showed that the combination of the prooxidant with photocatalyst have synergistic effect on the photodegradation of the LDPE and can be used to accelerate the degradation of the polyethylene films.     

Polyaniline modified mesoporous titanium dioxide that enhances oxo‐biodegradation of polyethylene films for agricultural plastic mulch application

Mesoporous titanium dioxide (M‐TiO₂) nanoparticles were successfully prepared followed by chemical modification with different contents of polyaniline (PANI/M‐TiO₂) and were used to accelerate the photo‐oxidation and biodegradation process of low‐density polyethylene (LDPE) film. The influence of these additives as a pro‐oxidant additive on the accelerated degradation of LDPE was investigated by photocatalytic oxidation under UV light irradiation and biodegradation with fungal strains. It was found that the as‐prepared PANI modified M‐TiO₂ particles exhibited an obvious light response from 400 to 800 nm which can improve the utilization of solar light. Compared with M‐TiO₂, PANI/M‐TiO₂ exhibited better photocatalytic performance when irradiated under UV light and the subsequent biodegradation efficiency was enhanced. Enhancement of the photocatalytic performance of PANI/M‐TiO₂ could be attributed to good dispersibility and compatibility of PANI/M‐TiO₂ in the LDPE matrix, a narrow band gap, effective separation of photogenerated electron–hole pairs and the chromophoric group of PANI which was used as a photosensitizer in the LDPE/PANI/M‐TiO₂ composite film. © 2019 Society of Chemical Industry     

Degradation and biodegradation of polyethylene with pro‐oxidant aditives under compost conditions establishing relationships between physicochemical and rheological parameters

In the present work, an analysis is carried out to provide a relationship between the Molecular Weight (M_w) of degraded LDPE films (containing Mn stearate as pro oxidant (MnSt‐LDPE) and changes in viscosity, elongation at break (EB %) and carbonyl index (CI) occurring during thermal degradation in the thermophilic phase of the compost process. The thermal treatment comprised various temperatures (50°C, 60°C, and 70°C) and exposure times, and was characterized through a so‐called Energy‐Time Factor (the product of thermal energy and exposure time). Changes in viscosity, EB %, and CI were correlated to this factor. A modified Mark‐Houwink equation was used to relate the zero shear‐rate viscosity and M_w of the degraded LDPE films. Results indicate that the EB %, M_w and viscosity decrease simultaneously with an increase in the CI as the Energy‐Time Factor augments, allowing the assessment of the variation of these properties with M_w. Calculations of the percentage abiotic degradation (%D) of LDPE films indicate that a M_w of 6 kg mol^?1 corresponds to a maximum abiotic degradation degree of 91.85%, which is henceforth susceptible to biodegradation. The film treated with Energy‐Time Factor of 2.79E+09 J s mol^?1 reached a 74% of biodegradation in 90 days (average time of the composting process). Results exhibit clearly the correlation between abiotic and biotic degradation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42721.     

Degradation in soil behavior of artificially aged polyethylene films with pro‐oxidants

Bio‐based, biodegradable in soil, as well as degradable polyethylene mulching films with pro‐oxidants, have been introduced in the market in an effort to deal with the serious problem of managing plastic waste streams generated from conventional mulching films. In a previous experimental investigation, a series of naturally degraded under water melon cultivation conditions linear low density polyethylene (LLDPE) mulching films with pro‐oxidants, buried in the field for 8.5 years, were recovered intact even though undergoing a continuous slow abiotic degradation in soil. The aim of the present article was to simulate the behavior of the LLDPE mulching films with pro‐oxidants under a much longer time‐scale (e.g. some decades). Toward this purpose, samples of LLDPE with pro‐oxidants film were artificially degraded to simulate severe degradation/fragmentation of these films while been buried in the soil for many years, following the end of the cultivation season. Further degradation of these severely degraded samples was investigated by burying them in the soil over a period of seven years. During this burial period, all degradation parameters and their evolution with time were measured. The artificially degraded LLDPE film samples with pro‐oxidants, in contrast to the naturally degraded film that remained intact for 8.5 years, were gradually transformed into tiny micro‐fragments in the soil. These fragments, through a continuing abiotic degradation process under natural soil conditions are eventually transformed into invisible micro‐fragments. The fate of these micro‐fragments and their long‐term impact to the environment and human health is unpredictable. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42289.     

Manganese stearate initiated photo‐oxidative and thermo‐oxidative degradation of LDPE,LLDPE and their blends

This study is an attempt to investigate the effect of a representative pro‐oxidant (manganese stearate) on the degradation behavior of 70 ± 5 μ thickness films of LDPE, LLDPE and their blends. Films were prepared by film blowing technique in the presence of varying quantities of manganese stearate (0.5–1% w/w) and subsequently subjected to accelerated degradative tests: xenon arc exposure and air‐oven exposure (at 70°C). The physico–chemical changes induced as a result of aging were followed by monitoring the mechanical properties (Tensile strength and Elongation at break), carbonyl index (CI), morphology (SEM), melt flow index (MFI), oxygen content (Elemental analysis), and DSC crystallinity. The results indicate that the degradative effect of pro‐oxidant is more pronounced in LDPE than LLDPE and blends, due to the presence of larger number of weak branches in the former. The degradation was also found to be proportional to the concentration of the pro‐oxidant. Flynn‐Wall‐Ozawa iso‐conversion technique was used to determine the kinetic parameters of degradation, which were used to determine the effect of the pro‐oxidant on the theoretical lifetime of the polymer. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Study of ultraviolet photooxidative degradation of LDPE film containing cerium carboxylate photosensitizer

The carbonyl indices (CI) of photooxidation of low-density polyethylene (LDPE) films containing cerium carboxylate (CeCar₃) with/without aromatic ketones (AK) were determined by infrared (IR) spectroscopy. The effects of these photosensitizers on the rates of ultraviolet (UV) photooxidation of LDPE films and their mechanism in sensitizing photooxidative degradation are studied. Results show that CeCar₃ can cause the accelerated photooxidative degradation of LDPE films, but CeCar₃ in combination with AK may bring about the accelerated or retarded photooxidative degradation of LDPE films to varying degrees. After UV irradiation, followed by long duration storage, LDPE films containing these photosensitizers continued storage oxidative degradation at the storage oxidative rates similar to the past, except for the Michler ketone.     

Photodegradation of some low‐density polyethylene–montmorillonite nanocomposites containing an oligomeric compatibilizer

The photo‐oxidation behavior at the exposed surfaces of maleated low‐density polyethylene [LDPE poly(ethylene‐co‐butylacrylate‐co‐maleic anhydride) (PEBAMA)] and montmorillonite (MMT) composites was studied using attenuated total reflection Fourier transform infrared spectroscopy, X‐ray diffraction (XRD), transmission electron microscopy (TEM), and mechanical testing. Two different MMT clays were used with the maleated polyethylene, an unmodified clay, MMT, and an organically modified montmorillonite (OMMT) clay which was significantly exfoliated in the composite. The morphologies of sample films were examined by XRD and TEM. The results were explained in terms of the effect of the compatibilizing agent PEBAMA on the clay dispersion. It was found that the OMMT particles were exfoliated in the polymer matrix in the presence of the PEBAMA, whereas the MMT clay particles were agglomerated in this matrix. Both mechanical and spectroscopic analyses showed that the rates of photo oxidative degradation of the LDPE‐PEBAMA–OMMT were higher than those for LDPE and LDPE‐PEBAMA–MMT. The acceleration of the photo‐oxidative degradation for LDPE‐PEBAMA–OMMT is attributed to the effects of the compatibilizer and the organic modifier in the composite. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40788.     

TiO2‐kaolin‐PE composite film: A study based on photocatalytic degradation and biodegradation

A novel photodegradable and biodegradable polyethylene (PE) film was prepared through a melt blending technique, where nano‐TiO₂ and common kaolin were used as the photocatalyst and biodegradable promoter showing improved degradable efficiency of the waste PE. The photo‐degradation of the composite film was investigated by weight loss monitoring, attenuated total reflection–fourier transformed infrared spectroscopy (ATR–FTIR), and scanning electron microscopy. The aerobic biodegradation of the residue films after photodegradation was investigated by analysis of evolved carbon dioxide of films in aquatic test systems according to the international standards (ISO 14852, 1999). The results showed that the weight loss of as‐prepared photo‐ and biodegradable composite film reached 26.8% after 240 h of UV light irradiation. The big cavities formed not only on the film surface but also inside the bulk film, together with the chalking phenomenon taking place. The biodegradation results revealed that the addition of kaolin enhanced the degradation of UV‐light treated TiO₂‐PE films. The prepared PE based composite films showed promising application as novel photo‐biodegradable environment‐harmless materials. In addition, a degradation mechanism for this composite film was also discussed. POLYM. COMPOS., 37:2353–2359, 2016. © 2015 Society of Plastics Engineers     

Comparative effects of cobalt carboxylates on the thermo‐oxidative degradation of LDPE films

This article reports the effect of three cobalt carboxylates—cobalt stearate (CoSt₃), cobalt palmitate (CoPal₃), and cobalt laurate (CoLau₃)—on the thermo‐oxidative degradation of low‐density polyethylene (LDPE) films prepared by sheeting process. The carboxylates were blended with LDPE in the concentration range of 0.05–0.2% (w/w). The degradation was monitored by techniques such as FTIR spectroscopy, change in the mechanical properties (tensile strength and elongation at break), viscometry, surface electron microscopy, melt flow index measurements, and apparent density measurements. Studies indicate that films containing these additives are highly susceptible to thermo‐oxidative degradation. Oxygen containing functionalities such as carbonyl and vinyl species are generated on the surface of polyethylene because of thermo‐oxidation, as indicated by FTIR studies. This oxidative process is accelerated in the presence of cobalt carboxylates. The degradation of LDPE was found to increase proportionally with concentration as well as with increasing chain length of the cobalt carboxylate, and follow the order CoSt₃ > CoPal₃ > CoLau₃. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3758–3765, 2007     

硬脂酸铁加速LDPE膜光降解作用的研究

本文合成了硬脂酸铁(FeSt_s),用等离子体发射光谱、热分析仪、紫外光谱、红外光谱等分析手段进行了表征,研究了它对光氧化低密度聚乙烯(LDPE)薄膜羰基指数和粘均分子量的影响,并探讨了它的作用机理.结果表明:在LDPE膜中加入0.1%～0.3?St_s,即可控制可分解LDPE膜的使用寿命;羧酸铁在光解LDPE膜中的敏化活性依次递减如下:硬脂酸铁>月桂酸铁>辛酸铁;月桂酸铁和辛酸铁的光敏催化活性较低;二苯甲酮不是LDPE的有效光敏剂,能阻滞LDPE的光降解作用;高温下UV光降解LDPE膜的光降解速率高于低温下的光降解速率.     

淀粉／硬脂酸铈配合体系的降解LDPE包装薄膜的研究

研究了淀粉／硬脂酸铈配合体系的组成，讨论了铝酸酯对淀粉的疏水处理，氧化聚乙烯对淀粉／ＬＤＰＥ共混体系的增容，硬脂酸铈对光氧降解ＬＤＰＥ羰基指数的影响，并对含２０％淀粉，０。４％硬脂酸铈的ＬＤＰＥ包装薄膜进行性能测试和应用试验。     

Physicochemical properties of irradiated and loaded LDPE films with polyfunctional monomers

Polyfunctional monomers (PFMs), namely, trimethylol propane trimethacrylate (TMPTMA), trimethylol propane triacrylate, ethylene glycol dimethacrylate, and diethylene glycol diacrylate were blended with low‐density polyethylene (LDPE) and exposed to different doses of EB irradiation. Fourier transform infrared and ultraviolet and UV–vis spectroscopy of the unirradiated, irradiated, unloaded, and PFMs‐loaded LDPE films were studied under various irradiation doses up to 300 kGy. The degree of crosslinking and oxidative degradation, as measured by the spectroscopic parameters, were dependent on both the irradiation dose and the type of loaded PFMs. For all of the loaded monomers, the extent of crosslinking increased at different rates as a function of irradiation dose. TMPTMA monomer was the most efficient in enhancing the crosslinking of LDPE films compared to the other loaded monomers. However, the unloaded LDPE film showed the least extent of crosslinking. In addition, the EB‐radiation‐induced changes, such as trans‐vinylene formation, a decrease in vinyl and vinylidene unsaturation; and carbonyl double‐bond formation and change in crystallinity were correlated. The importance of these results on the prediction of the role of polyfunctional monomers in the production of crosslinked polymers is discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2025–2035, 2003     

Rice bran‐filled biodegradable low‐density polyethylene films: Development and characterization for packaging applications

Rice bran was incorporated into low‐density polyethylene (LDPE) at different concentrations by compounding in a twin‐screw extruder and blown into films of uniform thickness. The rice bran incorporation influenced physical, mechanical, barrier, optical, thermal properties, and biodegradation of LDPE. The mechanical and optical properties decreased as the percentage of rice bran increased. The effect of rice bran on the morphology of LDPE blends was examined using scanning electron microscopy. Oxygen transmission rate and water vapor transmission rate increased with the increased content of rice bran. Addition of rice bran did not alter the melting temperature (T_m) of the blends; however the thermal stability decreased, while glass transition temperature (T_g) increased. Kinetics of thermal degradation was also investigated and the activation energy for thermal degradation indicated that for up to 10% filler addition, the dispersion and interfacial adhesion of rice bran particles in LDPE was good. Aerobic biodegradation tests using municipal sewage sludge and biodegradation studies using specific microorganism (Streptomyces species) revealed that the films are biodegradable. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4514–4522, 2006     

Effect of soil environment on the photo‐degradation of polyethylene films

Outdoor weathering field trials performed with oxo‐degradable polyethylene (PE) thin films were conducted across temperate, grassland, and subtropical sites around Australia. It was found that a site factor, that was apparently independent of total solar dose and temperature, significantly impacted the rate and extent of photo‐oxidation. Controlled laboratory‐based accelerated aging trials of both PE film with no prodegradant and oxo‐degradable PE films (containing iron stearate) revealed that the rate and extent of PE photo‐oxidation did not correlate with temperature under the film or UV exposure, but was soil dependent. Under accelerated photo‐oxidative conditions, the time to reach embrittlement for a PE film aged over the soil from the temperate site (OM 8.4) was half (24.5 days) the time taken when aged over air (48 days). Further investigation revealed that humic acids and fulvic acids within soil organic matter may contribute to an increased rate of PE photo‐oxidation, possibly through the formation of volatile reactive oxygen species that may form under photo‐oxidative conditions. The presence of water also had a significant impact on the rate of photo‐oxidation. Overall, the impact of soil on PE photo‐oxidation was found to be complex and likely dependent at least in part on soil components that varied between different soil types, consequently influencing their photo‐chemistry. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42558.     

Fe-Sr2Bi2O5光催化降解低密度聚乙烯膜

采用共沉淀法合成的新型光催化剂(Fe-Sr₂Bi₂O₅)与低密度聚乙烯(LDPE)通过熔融共混制备了一种新型光催化降解复合膜(Fe-Sr₂Bi₂O₅/PE)。通过力学性能、接触角、傅里叶变换红外光谱(FT-IR)和场发射扫描电镜(FESEM)等表征手段研究了该催化剂在室温条件下固相光催化降解LDPE复合膜的性能变化。结果表明:Fe-Sr₂Bi₂O₅在紫外光和可见光条件下对LDPE均具有较好的光催化降解能力,其中,紫外灯照射10 d后,Fe-Sr₂Bi₂O₅/PE复合膜断裂伸长保留率低于5%,拉伸强度保留率低于40%,接触角降低22.52°,已完全脆化;同时,LDPE复合膜中出现明显的羰基等降解特征吸收峰和降解孔洞;与Sr₂Bi₂O₅和TiO₂相比,Fe-Sr₂Bi₂O₅对LDPE具有更好的降解效果。综上所述,在紫外光和可见光条件下,Fe-Sr₂Bi₂O₅对LDPE具有明显的光催化降解作用,为未来光催化降解聚乙烯(PE)提供了一定的新依据。     

Photodegradation and biodegradation by bacteria of mulching films based on ethylene‐vinyl acetate copolymer: Effect of pro‐oxidant additives

The photodegradation (432 h under irradiation of Xe‐Lamp‐solar filter) of an ethylene vinyl acetate (EVA) copolymer with vinyl acetate content of 9% was studied, and the effect of iron and calcium stearates was evaluated using different techniques such us attenuated total reflectance‐Fourier transform infrared spectroscopy (ATR‐FTIR), gel permeation chromatography (GPC), and thermal analysis methods (DSC and TGA). A re‐arrangement in crystallization and consequent decrease in thermal stability were found through differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), which were in agreement with the chain scission tendency. The presence of Ca and Fe pro‐oxidants additives in EVA films increased the ketone carbonyl formation and decreased the ester absorption band of the acetate respect to the pure EVA, as it was evidenced by the significant changes in Carbonyl Indexes found by FTIR. The activity of stearates has been also evaluated by chemiluminescence, where the temperature‐ramping tests under nitrogen showed the formation of a peroxide peak at lower temperature. The lower stability of the films containing pro‐oxidants was evidenced by the values of oxidation induction time (OIT) determined by DSC. The results were supported by GC‐MS, where the concentration of extracted products identified in the EVA containing pro‐oxidants was significant and a much greater decrease in molecular weight was determined by GPC, which confirmed the development of degradation for EVA with Ca and Fe stearates in comparison to pure EVA. Biodegradation of photodegraded EVA films were studied at 45°C during 90 days using a mixture of Bacillus (MIX) (B. cereus, B. megaterium, and B. subtilis) and, in parallel, by Brevibacillus borstelensis as reference strain. Biodegradation of EVA‐films was studied by Chemiluminescence, ATR‐FTIR and GC‐product analysis and the data confirm more efficient biodegradation on the materials containing pro‐oxidants. The chemiluminescence emissions due to decomposition of oxidation species was observed at lower temperatures on the biodegraded samples. Also, the drastic decrease of carbonyl index and the disappearance of photogenerated low molecular products with biodegradation were more efficient on the biodegraded films containing pro‐oxidants. EVA mineralization was evaluated by carbon dioxide measurement using indirect impedance technique. Biodegradation by B. borstelensis and MIX at 45°C was similar and exhibited a pronounced difference between the pure photodegraded EVA film (around 15% of mineralization) and the corresponding photodegraded films containing Ca and Fe stearates where biodegradation extent reached values of 23‐26% of biodegradation after 90 days. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Enhancement of pro‐degradant performance in polyethylene/starch blends as a function of distribution

The effect of pro‐degradant distribution in polyethylene (PE)/starch blends on ultraviolet (UV) photo‐oxidative degradation was investigated. Two kinds of pro‐degradants, Fe and Co‐based, were used in this study. The distribution of pro‐degradants in the different phases was varied by a dual step process using a side‐feed on a reactive extruder. The variation in mechanical properties and evaluation of carbonyl groups by FTIR were conducted to investigate the effect of degradation following exposure to UV photo‐oxidative degradation. It was found that the variation in mechanical properties was higher when the pro‐degradants were distributed in the PE phase. The concentration of carbonyl groups increased as a function of UV exposure, and the concentration of carbonyl groups was higher when the pro‐degradants were distributed in the PE phase. Micro‐cracking was observed on the interface between starch and PE after adding the pro‐degradants. When the pro‐degradants were distributed in high‐density polyethylene (HDPE) phase, the micro‐cracks mainly appeared in HDPE matrix, and the density of micro‐crack was higher. In general, the function of the pro‐degradants in PE/starch blends was enhanced when their distribution was varied within HDPE phase. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of ferric salt of orange peel solid fraction on photo-oxidation and biodegradability of LDPE films

The present study is concerned with accelerating photo-oxidation and biodegradability of low-density polyethylene (LDPE) film in the presence of orange peel solid fraction (OPS), especially its ferric salt (OPSFe). Orange peel was made free from essential oils and pigments and then turned into a fine powder. The rate of photo-oxidative degradation of pure LDPE film and the blend samples, containing OPS/OPSFe at 0?C5?wt% in combination with PE-g-MA as a compatibilizer at 1?wt% of LDPE, in exposure to artificial sunlight was monitored by determination of carbonyl index derived from FTIR spectroscopy and the variations in mechanical properties in terms of UV-irradiation time. The original and irradiated samples (300?h) were buried in agricultural soil simultaneously and their biodegradation was evaluated by weight loss measurement, optical microscopy, and also calculation of carbonyl index derived from FTIR spectroscopy. The results obtained revealed that OPSFe acts as a significant accelerator in photo-oxidation and subsequent biodegradation of LDPE in soil enviornment. It is concluded that by incorporating small amount of Fe³⁺ ions into the polymer blend, photo-oxidative degradation of LDPE film is much more developed. Increase in OPSFe loading contributes to enhance the rate of photo- and biodegradability of LDPE films.     

Photobiodegradation of low‐density polyethylene/banana starch films

The effects of the starch content, photosensitizer content, and compatibilizer on the photobiodegradability of low‐density polyethylene (LDPE) and banana starch polymer blend films were investigated. The compatibilizer and photosensitizer used in the films were PE‐graft‐maleic anhydride (PE‐g‐MA) and benzophenone, respectively. Dried banana starch at 0–20% (w/w) of LDPE, benzophenone at 0–1% (w/w) of LDPE, and PE‐g‐MA at 10% (w/w) of banana starch were added to LDPE. The photodegradation of the blend films was performed with outdoor exposure. The progress of the photodegradation was followed by determining the carbonyl index derived from Fourier transform IR measurements and the changes in tensile properties. Biodegradation of the blend films was investigated by a soil burial test. The biodegradation process was followed by measuring the changes in the physical appearance, weight loss, and tensile properties of the films. The results showed that both photo‐ and biodegradation rates increased with increasing amounts of banana starch, whereas the tensile properties of the films decreased. The blends with higher amounts of benzophenone showed higher rates of photodegradation, although their biodegradation rates were reduced with an increase in benzophenone content. The addition of PE‐g‐MA into polymer blends led to an increase in the tensile properties whereas the photobiodegradation was slightly decreased compared to the films without PE‐g‐MA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2725–2736, 2006     

A New Synthesized of Ferrous Ricinoleate Mixed with Maleic Dextrose Additive to Enhance Photo and Biodegradation Characteristics of LDPE

Low density polyethylene films blended (LDPE) with mixed Ferrous ricinoleate maleic dextrose additive have been exposed to accelerated UV and biotic environments. The films were accelerated UV light for 70 h before being mixed with water and municipal solid compost. The photo degraded and biodegraded LDPE films were examined by infrared spectroscopy and also to study the photodegraded film attacked by mitochondria β oxidation process of microorganism and its morphological study by SEM analysis and degree of crystallinity behaviour by XRD analysis.