Biodegradable Nanocomposites of Poly(butylene adipate-co-terephthalate) (PBAT) and Organically Modified Layered Silicates

The present article summarizes the development of poly(butylene adipate-co-terephthalate) (PBAT) and organically modified layered silicates nanocomposite using a co-rotating twin screw extruder having a blown film unit. Wide angle X-ray diffraction (WAXD) studies indicated an increase in d spacing of the nanoclays in the bio-nanocomposite hybrids revealing formation of intercalated morphology. Transmission Electron Microscopy (TEM) also confirmed presence of partially exfoliated clay galleries as well as layers of intercalated structures within the PBAT matrix in the nanocomposite. Mechanical tests showed that the nanocomposite hybrids prepared using B109 nanoclay exhibited higher tensile modulus. Functionalization of PBAT matrix upon grafting with maleic anhydride (MA) resulted in further improvement in mechanical properties. The existence of interfacial bonds in grafted bio-nanocomposite hybrids are substantiated using FTIR spectroscopy. Thermal properties of nanocomposite hybrids employing DSC, TGA also revealed improved T_g, T_c and thermal stability over the virgin polymer. Dynamic Mechanical Analysis (DMA) indicated an increase of storage modulus (E′) of PBAT biopolymer with incorporation of nanofiller. The biodegradability of PBAT bionanocomposite hybrids showed an increase in the rate of biodegradability with addition of Na⁺MMT due to hydrophilic nature of the nanoclay.     

Mechanical and Physical Properties of Green Biocomposite Based on Medium Density Fiberboard Sanding Powder/Polyethylene/Nanoclay

Medium density fiberboard (MDF) sanding powder is an industrial waste that has not been yet used as a raw material to produce composites. In this study, the influence of nanoclay particles on the flexural and impact strengths and the withdrawal strength of green biocomposites (based on MDF sanding powder/polyethylene/nanoclay) were investigated. For this aim, medium density fiberboard sanding dust and polyethylene were used as the lignocellulosic and thermoplastic material, respectively. In addition, maleic anhydride grafted polyethylene was used in three weight percentages (0, 3 and 6 %) as a coupling agent and compatibilizer, and Cloisite^®15A was used in four weight percentages (0, 2, 4 and 6 %). To prepare samples, wood-plastic granules were produced by using a twin-screw extruder followed by the hot pressing method. The mechanical and physical properties were measured according to the CEN/TS15534:2007 and ASTM-D256 technical specifications. The results showed that the coupling agent improved the mechanical and physical properties of biocomposites; however, its effect might be affected by the nanoclay particles. Furthermore, the ultrastructure of the biocomposites was surveyed with SEM.     

Degradation studies of novel degradable starch-polyethylene plastics containing oxidized polyethylene and prooxidant

Linear low-density polyethylene films were prepared that contained native corn starch (7, 14, or 28%), low or high molecular weight oxidized polyethylene (15%), and a prooxidant mixture (18% POLYCLEAN II) that contains manganese and vegetable oil. For each mixture all components were first mixed at high temperatures in a twin-screw extruder and pelletized. The pellets were cast into films using a single-screw extruder. Oxidized-polyethylene addition did not impair the transparency and thickness of the films and did not reduce the percentage elongation, whereas significant reductions in film mechanical properties were observed. Thermal and photodegradation properties of each film were evaluated by 70°C forced-air oven treatment (20 days), by high-temperature, high-humidity treatment in a steam chamber (20 days), and by exposure to ultraviolet light (365 nm; 4 weeks). Changes in the mechanical properties of the films were determined by an Instron Universal Test Machine; in the carbonyl index, Fourier transform infrared spectroscopy; and in molecular weight, by high-temperature gel-permeation chromatography (HT-GPC). The addition of oxidized polyethylene, especially high molecular weight oxidized polyethylene, and up to 14% starch to the films significantly increased the rate of thermal and photodegradation.Journal Paper No. J-15363 of the Iowa Agriculture and Home Economics Experiment Station, Ames. Project No. 0178 and 2889.     

Molecular Weight Changes and Polymeric Matrix Changes Correlated with the Formation of Degradation Products in Biodegraded Polyethylene

The molecular weight changes in abiotically and biotically degraded LDPE and LDPE modified with starch and/or prooxidant were compared with the formation of degradation products. The samples were thermooxidized for 6 days at 100°C to initiate degradation and then either inoculated with Arthobacter paraffineus or kept sterile. After 3.5 years homologous series of mono- and dicarboxylic acids and ketoacids were identified by GC-MS in abiotic samples, while complete disappearance of these acids was observed in biotic environments. The molecular weights of the biotically aged samples were slightly higher than the molecular weights of the corresponding abiotically aged samples, which is exemplified by the increase in from 5200 g/mol for a sterile sample with the highest amount of prooxidant to 6000 g/mol for the corresponding biodegraded sample. The higher molecular weight in the biotic environment is explained by the assimilation of carboxylic acids and low molecular weight polyethylene chains by microorganisms. Assimilation of the low molecular weight products is further confirmed by the absence of carboxylic acids in the biotic samples. Fewer carbonyls and more double bonds were seen by FTIR in the biodegraded samples, which is in agreement with the biodegradation mechanism of polyethylene.     

Environmental and Cost Assessment of a Polypropylene Nanocomposite

This paper describes a study on the use of a polypropylene (PP)/layered silicate nanocomposite as packaging film, agricultural film, and automotive panels. The study’s main question was “Are the environmental impacts and costs throughout the life cycle of nanocomposite products lower than those of products manufactured from conventional materials?” The conventional (benchmark) materials studied were pure polypropylene as packaging film, pure polyethylene as agricultural film, and glass fiber-reinforced polypropylene as automotive panels. In all three cases, the use of the PP nanocomposite resulted in a reduction of the amount of material used, while ensuring the same functionality. Material reduction was estimated using Ashby’s material indices and amounted to ?9% for packaging film, ?36.5% for agricultural film, and ?1.25% for automotive panels. It goes without saying that a product’s impact on the environment will decrease when less material is used. The production and incorporation of nanoparticles, however, may have additional impacts. We found clear environmental benefits throughout the entire life cycle when the PP nanocomposite is used in the manufacture of agricultural film. We noted some cost benefits when the nanocomposite is used in the production of agricultural film and automotive panels. If the price of nanoclay is at most €5,000 tonne then the cost of nanocomposite packaging film is also lower than that of the conventionally produced product.     

Bamboo–Fiber Filled High Density Polyethylene Composites: Effect of Coupling Treatment and Nanoclay

High density polyethylene (HDPE)/bamboo composites with different nanoclay and maleated polyethylene (MAPE) contents were fabricated by melt compounding. The compounding characteristics, clay dispersion, HDPE crystallization, and mechanical properties of the composites were studied. The equilibrium torque during compounding decreased with use of clay masterbatch and increased with the addition of MAPE. The X-ray diffraction (XRD) data showed that the clay was exfoliated only when 1% clay was added to pure HDPE without MAPE. For HDPE/bamboo systems, MAPE was necessary to achieve clay exfoliation. For pure HDPE system, both dynamic and static bending moduli increased, while impact strength decreased with increased clay loading. For the HDPE/bamboo fiber composites, tensile strength, bending modulus and strength were improved with the use of MAPE. The use of the clay in the system led to reduced mechanical properties. Techniques such as pre-coating fibers with clay–MAPE mixture are needed to enhance the synergetic effect of the clay and bamboo fiber on the composite properties in the future study.     

Biodegradation of γ Irradiated Poly 3-hydroxybutyrate (PHB) Films Blended with Poly(Ethyleneglycol)

Poly(3-hydroxybutyrate) (PHB) was evaluated in blends with poly(ethyleneglycol) (PEG) of different weight average molecular weight (Mw = 300, 600, 1,000 and 6,000). Irradiation of the PHB/PEG films was carried out to different levels of irradiation doses (5 and 10 kGy) and the effects were investigated talking into consideration: thermal properties by differential scanning calorimetry (DSC), perforation resistance, water vapor transmission rate and biodegradation in simulated soil. The addition of plasticizer alters thermal stability and crystallinity of the blends. The improvement in perforation resistance due to irradiation was regarded to be a result of the crosslinking effect. Also, biodegradation assays resulted in mass retention improvements with increases in PEG molar masses, PEG concentration and irradiation dose. The irradiation process was shown to hamper the biodegradation mechanism.     

Bio-based Polyethylene–Lignin Composites Containing a Pro-oxidant/Pro-degradant Additive: Preparation and Characterization

Formulations of low cost bio-based oxo-biodegradable polyethylene (PE)/Lignin hybrid polymeric composites were prepared by using ethylene/vinyl acetate (EVA) copolymer as compatibilizer and a transition metal salt as oxo-biodegradation promoter. The hybrid composites and relevant Lignin-free blends were formulated by following a statistical mixture design. The effect of Lignin, pro-degradant additive, EVA copolymer and their compatibility with the PE continuous matrix, was evaluated by means of structural features by attenuated total reflectance, morphological by scanning electron microscopy, thermal by differential scanning calorimetry and thermo-gravimetric analysis and mechanical properties by an Instron Machine. The results attained in this study, regarding especially the thermal and mechanical properties, suggest that bio-based oxo-biodegradable hybrid composites offer an interesting way to produce low cost bio-based materials with fairly enhanced properties. The moderate-low cost hybrid materials appear to be attractive for their potential in the mercantile area of commodities including: packaging, personal care products, agricultural mulch films and disposable items. This will constitute a novel added-value contribution aimed at mitigating the environmental burden caused by plastic waste items improperly abandoned in the environment.     

Biodegradability of degradable plastic waste.

Plastic waste constitutes the third largest waste volume in Malaysian municipal solid waste (MSW), next to putrescible waste and paper. The plastic component in MSW from Kuala Lumpur averages 24% (by weight), whereas the national mean is about 15%. The 144 waste dumps in the country receive about 95% of the MSW, including plastic waste. The useful life of the landfills is fast diminishing as the plastic waste stays un-degraded for more than 50 years. In this study the compostability of polyethylene and pro-oxidant additive-based environmentally degradable plastics (EDP) was investigated. Linear low-density polyethylene (LLDPE) samples exposed hydrolytically or oxidatively at 60 degrees C showed that the abiotic degradation path was oxidative rather than hydrolytic. There was a weight loss of 8% and the plastic has been oxidized as shown by the additional carbonyl group exhibited in the Fourier transform infra red (FTIR) Spectrum. Oxidation rate seemed to be influenced by the amount of pro-oxidant additive, the chemical structure and morphology of the plastic samples, and the surface area. Composting studies during a 45-day experiment showed that the percentage elongation (reduction) was 20% for McD samples [high-density polyethylene, (HDPE) with 3% additive] and LL samples (LLDPE with 7% additive) and 18% reduction for totally degradable plastic (TDP) samples (HDPE with 3% additive). Lastly, microbial experiments using Pseudomonas aeroginosa on carbon-free media with degradable plastic samples as the sole carbon source, showed confirmatory results. A positive bacterial growth and a weight loss of 2.2% for degraded polyethylene samples were evident to show that the degradable plastic is biodegradable.     

LCA comparison of container systems in municipal solid waste management

The planning and design of integrated municipal solid waste management (MSWM) systems requires accurate environmental impact evaluation of the systems and their components. This research assessed, quantified and compared the environmental impact of the first stage of the most used MSW container systems. The comparison was based on factors such as the volume of the containers, from small bins of 60–80 l to containers of 2400 l, and on the manufactured materials, steel and high-density polyethylene (HDPE). Also, some parameters such as frequency of collections, waste generation, filling percentage and waste container contents, were established to obtain comparable systems. The methodological framework of the analysis was the life cycle assessment (LCA), and the impact assessment method was based on CML 2 baseline 2000. Results indicated that, for the same volume, the collection systems that use HDPE waste containers had more of an impact than those using steel waste containers, in terms of abiotic depletion, global warming, ozone layer depletion, acidification, eutrophication, photochemical oxidation, human toxicity and terrestrial ecotoxicity. Besides, the collection systems using small HDPE bins (60 l or 80 l) had most impact while systems using big steel containers (2400 l) had less impact. Subsequent sensitivity analysis about the parameters established demonstrated that they could change the ultimate environmental impact of each waste container collection system, but that the comparative relationship between systems was similar.     

Comparative Biodegradation Studies of Non-poronized and Poronized LDPE Using Indigenous Microbial Consortium

Seventeen bacterial isolates were screened for the utilization of low density polyethylene (LDPE) as the sole carbon source, out of which five potential strains were selected for the development of a consortium. In vitro biodegradation efficiency of the consortium was studied for two differently textured forms of LDPE viz. non-poronized and poronized. Although, both the forms were acted-upon well by the consortium, but the degradation was found to be better in the poronized form. This was substantiated by λ-max shift, FTIR spectra and simultaneous TG-DTG-DTA. The analysis revealed the breakage and formation of chemical bonds in the polymer backbone, as a result of microbial activity. The biodegraded samples of non-poronized and poronized LDPE exhibited similar weight losses at 400 °C (24.12% and 24.48%, respectively) as compared to their controls (4% and 4.5% respectively), but the latter could achieve it with greater ease as reveled by its lower heat of reactions (ΔH values). The study signifies the influence of poronization of polyethylene on its rate of biodegradation.     

Material Properties and Influence of Molecular Weight and Testing Rate on Adhesion Properties of Epoxidized Natural Rubber-Based Adhesives

The effect of molecular weight and testing rate on peel and shear strength of epoxidized natural rubber (ENR-50)-based adhesive was investigated using petro resin as the tackifier. Toluene and polyethylene terephthalate were used as the solvent and substrate respectively. Peel and shear strength were determined by a Llyod Adhesion Tester operating at different rates of testing. Result shows that peel strength and shear strength increases up to an optimum molecular weight of 4.2 × 10⁴ g/mol of ENR-50. This observation is attributed to the combined effects of wettability and mechanical strength of rubber for peel strength. For shear strength, it is ascribed to the optimum cohesive and adhesive strength. Both peel strength and shear strength increases with increasing rate of testing, an observation which is associated to the viscoeslastic response of the adhesive. Thermal study, SEM and FTIR study confirms the miscibility of tackifier with ENR-50.     

Compostability of Poly(lactide): Degradation in an Inert Solid Medium

Commercial poly(lactide) degradation was studied in an inert solid medium simulating compost conditions, with the aim to achieve a complete carbon balance of the polymer degradation. The mineralisation rate at the end of the test was compared to those obtained for poly(lactide) degradation in compost. It was shown that the mineralisation rate after 45 days of degradation was quite lower in inert solid medium than in compost but the standard deviation of data was enhanced. A protocol for both extraction and quantification of the carbon included in the different degradation by-products was proposed and the carbon balance of the polymer degradation was followed during the test with a satisfactory accuracy. The non-degraded PLA material was recovered during the test, hence the evolution of the glass transition temperature and the molecular weight was followed. A two-step degradation mechanism was highlighted in inert solid medium, showing the fundamental role of abiotic reactions for PLA degradation in compost.     

Physical Properties, Photo- and Bio-degradation of Baked Foams Based on Cassava Starch, Sugarcane Bagasse Fibers and Montmorillonite

The objectives of this work were to develop biodegradable trays from cassava starch, sugarcane fibers and Na-montmorillonite (Na-MMT) using a baking process and to study the effects of these components on the physical properties, photo- and bio-degradation of the trays. The sample F20 (produced with 20 g fiber/100 g formulation) showed the maximum yield production (100 %). All formulations resulted in well-shaped trays with densities between 0.1941 and 0.2966 g/cm³. The addition of fibers and Na-MMT resulted in less dense and less rigid trays compared to control samples (only starch). The studied processing conditions resulted in good nanoclay dispersion, leading to the formation of an exfoliated structure. The evaluation of the photo-degradation stability of the trays under UV exposure for 336 h showed that a sample produced with a specific combination of fiber and nanoclay (20 g fiber and 5 g nanoclay/100 g formulation) had the highest loss in stress at break (91 %). Biodegradation assays showed that Control trays (starch) and F20 (20 g fiber/100 g formulation) lost a greater percentage of their weight after 90 days of incubation in soil, with losses of up to 85.50 and 82.70 %, respectively.     

The effect of clay catalyst on the chemical composition of bio-oil obtained by co-pyrolysis of cellulose and polyethylene

Cellulose/polyethylene (CPE) mixture 3:1, w/w with and without three clay catalysts (K10 – montmorillonite K10, KSF – montmorillonite KSF, B – Bentonite) addition were subjected to pyrolysis at temperatures 400, 450 and 500 °C with heating rate of 100 °C/s to produce bio-oil with high yield. The pyrolytic oil yield was in the range of 41.3–79.5 wt% depending on the temperature, the type and the amount of catalyst. The non-catalytic fast pyrolysis at 500 °C gives the highest yield of bio-oil (79.5 wt%). The higher temperature of catalytic pyrolysis of cellulose/polyethylene mixture the higher yield of bio-oil is. Contrarily, increasing amount of montmorillonite results in significant, almost linear decrease in bio-oil yield followed by a significant increase of gas yield. The addition of clay catalysts to CPE mixture has a various influence on the distribution of bio-oil components. The addition of montmorillonite K10 to cellulose/polyethylene mixture promotes the deepest conversion of polyethylene and cellulose. Additionally, more saturated than unsaturated hydrocarbons are present in resultant bio-oils. The proportion of liquid hydrocarbons is the highest when a montmorillonite K10 is acting as a catalyst.     

Structure and Morphology of Microbial Degraded Poly(ε-caprolactone)/Graphite Oxide Composite

Biodegradation of poly(ε-caprolactone) composite with graphite oxide (GO) by the action of Bacillus subtilis (BS) was studied in this work. Nanocomposite produced in a form of thin film was exposed to nutrient cultivation medium with BS as well as to abiotic nutrient medium (control run) at 30 °C. The matrix itself was exposed to the same conditions for comparison. Biodegradation was demonstrated by the weight loss and the decrease of molecular weight during 21 days of the experiment as well as by changes in the surface morphology and structure. Both degraded and control materials were characterized by confocal laser scanning microscopy, differential scanning calorimetry, thermogravimetry, and Fourier transform infrared spectroscopy with attenuated total reflectance. The bacterial growth expressed as the measure of the optical density/turbidity in McFarland units and pH of medium were measured in situ during the experiment. Lipolytic activity of BS was determined by spectrophotometric assay. Degradation process was accompanied by the increase of matrix crystallinity degree. GO served as nucleating agent and facilitated absorption of cultivation media into the composite which led to the increase of the crystallinity degree also for control nanocomposite specimens. It was not evaluated to be promoter of biodegradation. The surface cracks formation was initiated by BS action. Large surface cracks were formed on BS-degraded composite surfaces while surface erosion was more significant on BS-degraded matrix.     

Wood Modification Effects on Weathering of HDPE-Based Wood Plastic Composites

The effects of weathering on the constituents of wood and polymer matrix behavior in wood plastic composites (WPCs) were investigated. WPCs were produced from pine, extractives-free pine, and pine holocellulose fibers (60%) together with HDPE (40%). These composites were subjected to xenon-arc accelerated and outside weathering for a total of 1200 h and 120 days, respectively. The color and chemical changes that occurred on the surface of the WPCs were analyzed using a set of analytical techniques. For pine and extractive-free pine filled composites, the results showed that the total color change, lightness, and oxidation increased, while the lignin content decreased. In addition, the weight average molecular weight (Mw) and number average molecular weight (Mn) of extracted HDPE decreased with an increase in exposure time of the composites. However, HDPE crystallinity increased with longer exposure time. Lightness of holocellulose-based WPC changed the least while the change in its HDPE crystallinity was not significant compared to the other composite types. Therefore, holocellulose-based WPC may be preferred for applications where color stability is of high priority.     

<Emphasis Type="Italic">Mesua ferrea</Emphasis> L. Seed Oil Based Highly Branched Environment Friendly Polyester Resin/Clay Nanocomposites

To develop a high performance environment friendly material, highly branched polyester/clay nanocomposites have been prepared from Mesua ferrea Linn seed oil-based polyester resin and hydrophilic bentonite nanoclay. The prepared nanocomposites were characterized by Fourier transform infra-red spectroscopy, X-ray diffractometer, scanning electron microscope, transmission electron microscope and rheological studies. Partial exfoliation of clay layers by the polymer chains with good interfacial interactions was observed in the nanocomposites. The formation of delaminated nanocomposites was manifested through the enhancement of tensile strength, scratch hardness, chemical resistance, impact resistance, thermostability, etc. The results show enhancement of three times in tensile strength and 18 °C in thermostability by inclusion of 5 wt% nanoclay as compared to the pristine polymer. By the influence of 5 wt% nanoclay four times enhancement in elongation at break as compared to the pristine polymer was noticed. Thus these nanocomposites have the potential to be used in many advanced applications.     

Degradation Study of Biobased Polyester–Polyurethane and its Nanocomposite Under Natural Soil Burial,UV Radiation and Hydrolytic-Salt Water Circumstances

The current study focuses on the development of a formulation of polyester polyurethane (PEPU) samples using castor oil (CO) modified polyester polyol and partially biobased aliphatic isocyanate. The CO modified polyester polyol was synthesized employing transesterification reaction between CO and diethylene glycol in the presence litharge (PbO) catalyst. Subsequently, the modification of CO was confirmed using proton nuclear magnetic resonance (¹HNMR) spectra analysis. In the next stage, the biobased polyester polyurethane nanocomposites (PEPUNC) were prepared by incorporating 3 wt% OMMT nanoclay within PEPU through in situ polymerization technique. The produced PEPU was confirmed by Fourier transform infrared spectroscopy (FTIR) and ¹HNMR spectra analysis. Further, the degradation properties of developed PEPU subjected to soil-burial, UV exposure and hydrolytic-salt water medium were noted by FTIR spectroscopy. Corresponding weight loss, mechanical measurements and morphological studies through scanning electron microscopy (SEM) analysis were studied. The results showed that the addition of OMMT nanoclay within the PEPU matrix produces significant improvement in the degradation rate which indicated the susceptibility of OMMT nanoclay to humidity upon exposure to soil burial. The produced microorganisms from the soil resulted in significant chemical and morphological changes in the entire structure of the PEPU. Additionally, the highest degradation and percentage of weight loss was observed under soil burial as compared to UV exposure and hydrolytic-salt water medium.     

A Review of the Fate and Effects of Silicones in the Environment

Silicones are well-known useful materials varying in structure, reactivity, and chemical and physical properties, but they all contain a covalent bond between the silicon atom and an organic group. Most common of these polymers are those based on polydimethylsiloxane (PDMS) having a siloxane (Si–O–Si) repeat unit and two methyl groups on each silicon atom. All these polymers are manmade, and the organosilicon linkage is not found in nature. It was therefore erroneously assumed that these polymers do not degrade naturally in the environment. It is the purpose of this review to refute this myth and to describe the degradation processes of PDMS in the environment and any potential ecological impact on the terrestrial, aquatic, and atmospheric compartments. Although it was found that minor degradation takes place by hydrolysis of PDMS to dimethylsilandiol followed by oxidation of the methyl group to aldehyde and ultimately to CO₂ by Arthobacter and Fusarium oxysporium schlechtendahl, the major degradation processes are abiotic. High molecular weight PDMS are initially depolymerized by soil hydrolysis of the siloxane bonds to yield organosilanol terminated oligomers. These organosilanols and low molecular weight linear PDMS and cyclics are evaporated into the atmosphere and are oxidized there by hydroxyl radicals to benign silica, water, and CO₂.