Formulation of a Photosensitized Polyethylene Film; Its Structure and Property Variation Under the Weathering Conditions of Tehran

To develop an environmentally degradable polymer material, a masterbatch pro-oxidant system was blended into low-density polyethylene. The polymer film samples were prepared by compression molding. The prepared films were placed under the natural environment of Tehran for weathering studies and accelerated conditions were also performed for UV aging in UV chamber. At different time intervals, the changes in chemical structure of photosensitized polyethylene samples were studied by FTIR and compared to that of the control polyethylene films. Also the mechanical properties of photosensitized polyethylene films were determined in comparison with the control films by measuring the tensile strength and elongation at break after exposure to the natural environment and UV radiation. Results showed that the overall rate of degradation process is clearly dependent on the polyethylene composition, test conditions (natural or accelerated), season of the year, and the duration of the weathering of the samples.     

Assessment of the Whole Environmental Degradation of Oxo-Biodegradable Linear Low Density Polyethylene (LLDPE) Films Designed for Mulching Applications

The current paper is aimed at understanding the environmental fate of linear low density polyethylenes (LLDPE) films designed for mulching purposes and loaded with different pro-degradant additives. These were analyzed, upon exposure to natural sunlight for a period intended to mimick a general crop season in the mediterranean region. The selected samples underwent a relatively low extent of degradation as monitored by carbonyl index, molecular weight variation, extractability by solvent, changes in the onset of the decomposition temperature and crystallinity. The tendency to biodegradation of outdoor exposed LLDPE was then assessed under different environmental compartments including soil medium, aqueous medium as well as in axenic culture of white-rot fungus Phanerochaete chrysosporium. That fungus is known to be effective in the degradation of recalcitrant organic materials and plastic items. During the soil burial biodegradation test, lasted for 27?months, samples specimen were withdrawn at time intervals and characterized by means of structural and thermal analysis. These analytical assessments allowed to monitor any progress of oxidative degradation as a direct effect of the incubation in an active microbial environment. Analogous characterizations were carried out at the end of the biodegradation tests in aqueous medium and in P. chrysosporium axenic cultures. Data presented here are in keeping with the initial abiotic oxidation via a free radical chain reaction promoted by a pro-degradant additive acting on hydroperoxides and peroxide moieties present initially in the polymer bulk. This step was followed by a free radical cascade reactions leading to degradation once the oxidation started under relatively mild conditions (sunlight exposure). During the incubation step in soil, the abiotically degraded samples underwent significant variation in the level of oxidation and degradation with respect to the detected starting values. Indications were gained on the synergistic effect of a random fashion microbial metabolization coupled to biotically mediated oxidation of the original abiotically fragmented samples. Similar results were obtained in the biodegradation tests carried out in the aqueous media and in presence of P. chrysosporium axenic cultures. These evidences are suggesting the role of natural occurring microorganisms in promoting both partial oxiditation and degradation of LLDPE samples in combination with contextual mineralization process of the oxidized fragments.     

Natural Weathering of Polypropylene and Waste Tire Dust (PP/WTD) Blends

Three series of polypropylene and waste tire dust (PP/WTD) blends using three different WTD sizes were prepared, compression-molded and cut into dumbbells. The specimens were exposed to natural weathering in the northern part of Malaysia for a period of 6 months. The results show that at the same blend composition, blends with fine WTD size exhibit higher mechanical properties than that of blends with coarse WTD after exposure to natural weathering. Regardless of WTD size, the retention of tensile strength and elongation at break, E_b increases with the increase in WTD content. From the exposed surface morphology, it is apparent that the blends with fine WTD and WTD-rich blends were able to withstand weathering better than blends with coarse WTD and PP-rich blends. The DSC thermograms suggest that the overall drop in melting temperature (T_m) of the exposed blends decreases as the WTD content increases.     

A New Respirometric Test Simulating Soil Burial Conditions for the Evaluation of Polymer Biodegradation

A new convenient and reliable method is described for assessing the biodegradation properties of polymeric materials under simulated soil burial conditions, which makes it possible to test with nutrient-rich soils. This method consists of the utilization of a minimum amount of a soil layer, in which the samples to be tested are set in close contact, sandwiched between two layers of perlite, a natural porous aluminosilicate. The biodegradation level is monitored by determining the carbon dioxide evolution derived from the test samples. The limited amount of soil used limits carbon dioxide evolution from the blanks, due to the corresponding limited overall amount of soil carbon. This experimental setup allows for an extremely satisfactory level of confidence in the analytical results, permitting a wider variety of soil types to be tested.     

LDPE/EPDM Multilayer Films Containing Recycled LDPE for Greenhouse Applications

In this paper the reuse of recycled LDPE in combination with the incorporation of EPDM modifier in the production of greenhouse films has been investigated. A three-layer film (60-100-40 micron thickness) containing recycled LDPE in the middle layer and a high UV-stabilized 40-micron outer layer was developed and proven to be commercially successful. Films with 25% and 50% recycled material content were produced. The effect of natural weathering on the film properties over a period of 15 months has been observed. Changes in physical and mechanical property were determined. The addition of EPDM to the raw resin was found to improve the extrudability of the compound and improve the weather resistivity of the film. The EPDM-modified films containing 25% to 50% recycled material retained approximately 95% and 75%, respectively, of their original extensibility after 9 months' exposure to natural weathering. Optimization of EPDM and UV stabilizer concentration was carried out to develop a balanced film with excellent mechanical and physical properties and resistance to weathering conditions. The use of UV stabilizer concentrations slightly higher than commercial practice in the outer layer of the multilayer film can be justified by the cost reduction by the incorporation of recycled LDPE materials.     

Compatibilization Improves Performance of Biodegradable Biopolymer Composites Without Affecting UV Weathering Characteristics

With growing interest in the use of eco-friendly composite materials, biodegradable polymers and composites from renewable resources are gaining popularity for use in commercial applications. However, the long-term performance of these composites and the effect of compatibilization on their weathering characteristics are unknown. In this study, five types of biodegradable biopolymer/wood fiber (WF) composites were compatibilized with maleic anhydride (MA), and the effect of accelerated UV weathering on their performance was evaluated against composites without MA and neat biopolymers. The composite samples were prepared with 30 wt% wood fiber and one of the five biodegradable biobased polymer: poly(lactic) acid (PLA), polyhydroxybutyrate (PHB), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), Bioflex (PLA blend), or Solanyl (starch based). Neat and composite samples were UV weathered for 2000 h (hours), and characterized for morphological, physical, thermal, and mechanical properties before and after weathering. Compared to composites without MA, composites containing MA grafted polymers exhibited improved properties due to increased interfacial adhesion between the fiber and matrix. Upon accelerated weathering, thermal and mechanical properties of 70% of the samples substantially decreased. Surfaces of all the samples were roughened, and drastic color changes were observed. Water absorption of all the samples increased after weathering exposure. Even though the compatibilization is shown to improve composite properties before weathering, it did not affect weathering of samples, as there were no considerable differences in properties exhibited by the composites with MA and without MA after weathering. The results suggest that compatibilization improves properties of biodegradable biobased composites without affecting its UV degradation properties.     

Determining biodegradability of plastic materials under controlled and natural composting environments

With the advent of recently promulgated Government regulations on plastics in Mauritius, a study was initiated to examine the biodegradability of two different types of plastic, namely Willow Ridge Plastics - PDQ-H additive (Plastic A) and Ecosafe Plastic - TDPA additive (Plastic B) under controlled and natural composting environments. The results obtained from the controlled composting environment showed that the cumulative carbon dioxide evolution for Plastic A was much higher than that for Plastic B. Plastic A therefore showed a higher level of biodegradation in terms of CO2 evolution than Plastic B. However, from the regression analysis, it was found that the level of CO2 varying with time fitted the sigmoid type curves with very high correlation coefficients (R2 values: 0.9928, 0.9921 and 0.9816, for reference material, inoculum and Plastic A, respectively). The corresponding F-values obtained from the ANOVA analysis together with significance levels of p<0.05 indicated that the three treatments analysed in the biodegradability experiment were significant. The other experiment was undertaken to observe any physical change of Plastics A and B as compared to a reference plastic, namely, compostable plastic bag (Mater-Bi product-Plastic C), when exposed to a natural composting environment. Thermophilic temperatures were obtained for about 3-5 days of composting and the moisture content was in the range of 60-80% throughout the degradation process. It was observed that after 55 days of composting, Plastic C degraded completely while Plastic A and Plastic B did not undergo any significant degradation. It can be concluded that naturally based plastic made of starch would degrade completely in a time frame of 60 days, whereas plastics with biodegradable additive would require a longer time.     

Radiation Crosslinking of Poly(Butylene Succinate) in the Presence of Inorganic Material and Its Biodegradability

Three kinds of poly(butylene succinate)s (PBS) with different molecular weight were irradiated with electron beams in the presence of inorganic material. Fourteen kinds of inorganic materials were used in this work. The presence of inorganic material inside cross-linked PBS samples enhances the yield of gel formation. The heat stabilities of PBS samples were checked; it was found that silicon dioxide and carbon black significantly improve these properties. Enzymatic and soil burial tests were performed; the presence of these inorganic materials in cross-linked PBS accelerates the rate of biodegradation.     

Blending Modification of PHBV/PCL and its Biodegradation by <Emphasis Type="Italic">Pseudomonas mendocina</Emphasis>

Poly(3-hydroxybutyrate-co-hydroxyvalerate) (PHBV) is a biodegradable polymer synthesized in microorganisms. The application of PHBV is limited by certain material disadvantages. Poly(ε-caprolactone) (PCL) possesses excellent thermodynamic and mechanical properties and was used to modify PHBV in the presence of triethyl citrate (TEC) and dicumyl peroxide (DCP), which was used as plasticizer and grafting agent, respectively. The effects of PCL and additive agents on the mechanical, thermal, amphipathic and degradability behaviors of the blends were investigated. The results showed that the mechanical properties of the PHBV blends improved by PCL incorporation and improved even further after TEC and DCP addition. The addition of DCP could not induce an increase in crystallization temperature but improved the crystallization degree of the blends. The presence of hydrophilic groups in TEC leads to an apparent increases in the hydrophilicity of the PHBV blends. A PHBV/PCL blend (40/60) with TEC (20 wt.%) and DCP (0.5 wt.%) was chosen for its good mechanical properties and hydrophilicity. The chosen ratio of the blends was also shown a preferable degradation activity by biodegradation assay using Pseudomonas mendocina. The addition of TEC and DCP has no conspicuous negative effect on the biodegradation.     

Processing and Characterization of Recycled Polypropylene and Acrylonitrile Butadiene Rubber Blends

In this paper investigation on thermoplastic elastomers (TPE) and thermoplastic vulcanizates (TPV) derived from waste polypropylene (WPP) of Municipal Solid Waste (MSW) and acrylonitrile-butadiene rubber (NBR) are reported. The WPP was segregated, cleaned, dried and melt processed with NBR at 180 °C in a Brabender Plasticorder at different blend ratios. TPV was prepared by dynamic vulcanization of the TPE with conventional sulfur accelerator curing system. The mechanical properties measured were found to decrease with increase in NBR proportion in the blend; however the dynamic vulcanization of the nitrile rubber phase enhanced the strength properties of the corresponding TPE. The crystallinity of the WPP reduced with increase in NBR ratio. The dynamic modulus decreased with nitrile rubber content in the TPE. Interestingly, the storage modulus of the TPV at higher rubber content enhanced significantly and damping characteristics increased sharply. The rheology studies reveal that the damping of the blend has been reduced with the addition of high storage modulus rubber at melt processing conditions and hence increased viscosity. The amorphous rubber content with higher storage modulus imparts higher viscosity for the polypropylene (PP) matrix at the processing temperature. The SEM study reveals that the dynamic vulcanization of the rubber phase in the blend caused a smoother and finer surface morphology.     

Effects of Natural and Artificial Weathering on the Physical Properties of Recycled Poly(ethylene terephthalate)

In accelerated weathering tests, specimens are exposed to higher radiation intensity, temperature and humidity than is likely under natural weathering in order to achieve rapid degradation of the polymer in a convenient short time. In the current work, a correlation between the two environments is attempted so that a prediction of lifetimes in the natural environment can be achieved. During aging, surface flaws are created due to the chain scission process. This is initiated by the absorption of ultra-violet light and directly affects visual appearance and impact strength. After natural weathering, the material shows only plastic deformation in an impact test. However, after artificial weathering to 5000 h of UV exposure, there is a decrease of 85% in impact strength. Colour change occurs at a high rate in the early stages of UV exposure. Beyond 2000 h of exposure, the colour change approaches a steady state and a correlation between the changes under natural and artificial weathering becomes apparent for a potential prediction of lifetimes. From the analysis including the specular component (SCI), taking surface roughening into account, 1 year under natural weathering was found to be equivalent to 25 days under accelerated weathering.     

Biodegradation of Epoxy and MF Modified Polyurethane Films Derived from a Sustainable Resource

Mesua ferrea L. seed oil (MFLSO) modified polyurethanes blends with epoxy and melamine formaldehyde (MF) resins have been studied for biodegradation with two techniques, namely microbial degradation (broth culture technique) and natural soil burial degradation. In the former technique, rate of increase in bacterial growth in polymer matrix was monitored for 12 days via a visible spectrophotometer at the wavelength of 600 nm using McFarland turbidity as the standard. The soil burial method was performed using three different soils under ambient conditions over a period of 6 months to correlate with natural degradation. Microorganism attack after the soil burial biodegradation of 180 days was realized by the measurement of loss of weight and mechanical properties. Biodegradation of the films was also evidenced by SEM, TGA and FTIR spectroscopic studies. The loss in intensity of the bands at ca. 1735 cm⁻¹ and ca. 1050 cm⁻¹ for ester linkages indicates biodegradation of the blends through degradation of ester group. Both microbial and soil burial studies showed polyurethane/epoxy blends to be more biodegradable than polyurethane/MF blends. Further almost one step degradation in TG analysis suggests degradation for both the blends to occur by breakage of ester links. The biodegradation of the blends were further confirmed by SEM analyses. The study reveals that the modified MFLSO based polyurethane blends deserve the potential to be applicable as “green binders” for polymer composite and surface coating applications.     

Biodegradability of Thermally Aged PHB,PHB-V,and PCL in Soil Compostage

The biodegradability of poly--hydroxybutyrate (PHB), poly--hydroxybutyrate-co-valerate (PHB-V) and poly--caprolactone (PCL) were examined following thermal aging in an oven for 192, 425 and 600 h. Different temperatures, 100, 120 and 140°C for PHB and PHB-V and 30, 40 and 50^oC for PCL were used to assess the influence of this parameter on biodegradation. The biodegradability tests were done in soil compostage at pH 11.0 and involved measuring the residual mass of polymer. Thermal analysis of the polymers was done using a differential scanning calorimeter (DSC). The melting temperature and crystallinity were also determined. Thermal ageing increased the biodegradability only for PHB at 120 and 140^oC, and there was no correlation between crystallinity and the biodegradation of the polymers.     

Anaerobic Biodegradation of Polymer Composites Filled with Natural Fibers

Polymer composites with natural fibers prepared by melt blending were investigated. Synthetic and natural macromolecules were used, including poly(lactic acid), polyhydroxybutyrate-co-polyhydroxyvalerate and low density polyethylene. These polymers were filled with flax fibers. Mechanical properties of the composites, biogas production and mass loss under anaerobic digestion have been presented. It has been shown that the mechanical properties sustain after 28 days of biodegradation. Such materials can be found in applications as packaging, as well as in medicine as polymeric scaffolds, and drug delivery systems etc.     

Comparison of the Effect of Plasticizers on PHBV—and Organoclay—Based Biodegradable Polymer Nanocomposites

The aim of this work was to evaluate the effect of different plasticizers on the morphology, crystallization, and mechanical properties of poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV)/organomodified montmorillonite (OMt) nanocomposites. We investigated three different plasticizers: dioctyl phthalate (DOP), a commonly used additive in the polymer industry, and two natural and biodegradable plasticizers: epoxidized soybean oil (ESO) and triethyl citrate (TEC). The nanocomposites with 3 wt% OMt were obtained by melt processing in an internal mixer. The plasticizers were used alone or in combination with clay in a concentration of 10 wt%. X-ray diffraction and scanning electron microscopy results revealed a partially intercalated structure. The degree of crystallinity was higher for all of the samples compared to neat PHBV, although the melting temperature decreased with the use of plasticizers combined with OMt. The impact strength results were dependent on the interaction between the components of the system. Triethyl citrate was the most effective plasticizer due to its more pronounced interaction with the PHBV matrix, which yielded improvements in processing conditions and PHBV’s flexibility and impact properties.     

A Processing,Characterization and Marine Biodegradation Study of Melt-Extruded Polyhydroxyalkanoate (PHA) Films

A series of polyhydroxyalkanoates (PHA), all containing 1% nucleating agent but varying in structure, were melt-processed into films through single screw extrusion techniques. This series consisted of three polyhydroxybutyrate (PHB) and three polyhydroxybutyrate-valerate (PHBV) resins with varying valerate content. Processing parameters of temperature in the barrel (165–173 °C) and chill rolls (60 °C) were optimized to obtain cast films. The gel-permeation chromatography (GPC) results showed a loss of 8–19% of the polymer’s initial molecular weight due to extrusion processing. Modulated differential scanning calorimetry (MDSC) displayed glass transition temperatures of the films ranging from −4.6 to 6.7 °C depending on the amount of crystallinity in the film. DSC data were also used to calculate the percent crystallinity of each sample and slightly higher crystallinity was observed in the PHBV series of samples. X-ray diffraction patterns did not vary significantly for any of the samples and crystallinity was confirmed with X-ray data. Dynamic mechanical analysis (DMA) verified the glass transition trends for the films from DSC while loss modulus (E′) reported at 20 °C showed that the PHBV (3,950–3,600 MPa) had the higher E′ values than the PHB (3,500–2,698 MPa) samples. The Young’s modulus values of the PHB and PHBV samples ranged from 700 to 900 MPa and 900 to 1,500 MPa, respectively. Polarized light microscopy images revealed gel particles in the films processed through single-screw extrusion, which may have caused diminished Young’s modulus and tensile strength of these films. The PHBV film samples exhibited the greatest barrier properties to oxygen and water vapor when compared to the PHB film samples. The average oxygen transmission rate (OTR) and water vapor transmission rate (WVTR) for the PHBV samples was 247 (cc-mil/m²-day) and 118 (g-mil/m²-day), respectively; while the average OTR and WVTR for the PHB samples was 350 (cc-mil/m²-day) and 178 (g-mil/m²-day), respectively. Biodegradation data of the films in the marine environment demonstrated that all PHA film samples achieved a minimum of 70% mineralization in 40 days when run in accordance with ASTM 6691. For static and dynamic incubation experiments in seawater, microbial action resulting in weight loss as a function of time showed all samples to be highly biodegradable and correlated with the ASTM 6691 biodegradation data.     

Kinetic Study of Naphthalene Biodegradation in Aerobic Slurry Phase Microcosms for the Optimisation of the Process

The research was focused on the slurry-phase biodegradation of naphthalene. The biodegradation process was optimised with preliminary experiments in slurry aerobic microcosms. From soil samples collected on a contaminated site, a Pseudomonas putida strain, called M8, capable to degrade naphthalene was selected. Microcosms were prepared with M8 strain by mixing non-contaminated soil and mineral M9 medium. Different experimental conditions were tested varying naphthalene concentration, soil:water ratio and inoculum density. The disappearance of hydrocarbon, the production of carbon dioxide, and the ratio of total heterotrophic and naphthalene-degrading bacteria were monitored at different incubation times. The kinetic equation that best fitted the disappearance of contaminant with time was determined. The results showed that the isolated strain enhanced the biodegradation rate with respect to the natural biodegradation.     

Technical and environmental long-term properties of industrial residues--summary of field and laboratory investigations

In Sweden, use of industrial residues is still hindered by concern for their long-term properties. A three-year research project was therefore initiated aiming to (1) identify the crucial processes of ageing related to the usefulness of residues in roads; (2) investigate the consequences of these processes for technical and environmental properties of the residues, and (3) propose a method for accelerated ageing to predict the long-term properties. This paper gives an overview of the project methodology, a summary of the test results and references to papers where further details are given.The project, running through 2006-2008, compared naturally aged samples of two residues used as sub-bases in existing asphalt paved roads with samples of fresh residues from producers’ piles. Steel slag of electric arc furnace (EAF) type and municipal solid waste incinerator (MSWI) bottom ash were chosen. The samples were thoroughly characterised in order to identify which ageing processes had been crucial.The results showed that:

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Bottom ash from the pavement edge was more aged than bottom ash from the road centre. However, no difference in pH was found, instead the differences were caused by differences in water exposure.

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Steel slag from the pavement edge showed traces of carbonation and leaching processes, whereas slag from the road centre was identical to fresh slag.

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Water exposure to the subbase materials after ten years in an asphalt paved road was calculated to less than 0.1-0.5 litres per kg.

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Ageing reactions in steel slag and MSWI bottom ash, ready for use, were too small to be verified by laboratory measurement of deformation properties under loaded conditions.

An accelerated ageing test for steel slag was set up to achieve the carbonation (decrease in pH) and leaching that was observed in the pavement edge material.An accelerated ageing test for bottom ash was set up to achieve the pozzolan reactions that were observed in SEM analyses of in situ specimens.It is recommended to use uncrushed particles when properties of aged material are studied, in order to preserve the original particle surfaces.     

Biodegradation of LDPE/Modified Starch Blends Sterilized with Gamma Radiation

Blends of LDPE/modified starch were prepared, sterilized by gamma radiation and investigated with respect to their microbial degradation by a mixture of fungal strains in liquid medium after 90 days, was analyzed by carbon dioxide (CO₂) production (Sturm test). Biodegradation of blends was evaluated by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction; mechanical testing, scanning electron microscopy (SEM). The biodegradation of LDPE/modified starch blends was attributed to microbiological attack, with alterations in the chemical structure of the blend with an increase in the carbonyl and vinyl indices and the appearance of new crystalline symmetry generating a crystalline domain not existing before in the blend and decrease in the mechanical properties.     

Evolution of biodegradation of deinking by-products used as alternative cover material

Deinking by-products (DBP) have been used as alternative cover material for landfills and mine tailings. Since DBP is biodegradable because of its high cellulose and hemicellulose content, a laboratory experimental program was performed to monitor the evolution of biodegradation and changes in the physico-chemical and geotechnical properties of DBP samples submitted to accelerated biodegradation for 1460 days at 38 degrees C. The evolution of gas and leachate production was monitored in terms of both quality and quantity, which allowed for the calculation of mass loss with time. Under the conditions of the tests (no load applied), 19.6% of the mass was lost as gas, whereas 6.1% was leached out. The results show that biodegradation did not significantly alter the compaction behavior of DBP. The void ratio and water content increased significantly, while the volume of the samples slightly decreased. This seem to indicate that the porous structure of the samples was no longer the same after 1460 d of accelerated biodegradation. A slight increase in the relative density indicates that the organic/inorganic matter ratio increased. The results of permeability tests performed with samples at various stages of biodegradation and at various confining stresses show that the saturated hydraulic conductivity of recompacted biodegraded DBP decreased from 7 x 10(-7)cm/s to approximately 2 x 10(-7)cm/s, as biodegradation advanced.