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.     

Study of Fatigue Life and Filler Interaction of Paper Sludge Filled Epoxidized Natural Rubber (ENR) and Maleated Natural Rubber (MNR) Composites

An investigation on the effect of epoxidation and maleated natural rubber (MNR) on fatigue and rubber-filler interaction properties of paper sludge filled natural rubber composites was elucidated. Paper sludge loading was varied from 0 to 40 phr and conventional vulcanisation system was used while compounding was carried out on a laboratory sized two roll mill. Two different types of natural rubber, SMR L and ENR 50 having 0 and 50 mole% of epoxidation were used in order to investigate the effect of epoxidation on the composites. Results indicate that, at a fixed filler loading, ENR 50 vulcanizates exhibit higher fatigue life than SMR L vulcanizates especially at filler loading below 20 phr which might be associated with better rubber-filler interaction. In the case of composites with the addition of maleated natural rubber (MNR), a higher fatigue life was observed due to presence of physical and/or chemical linkages, which increases the interfacial adhesion. Scanning electron microscopy (SEM) micrographs of fatigue fracture surfaces and rubber-filler interaction study supported the observed result on fatigue life.     

Characterization of Biodegradable Polymer Blends of Acetylated and Hydroxypropylated Sago Starch and Natural Rubber

Development of biodegradable polymers from absolute environmental friendly materials has attracted increasing research interest due to public awareness of waste disposal problems caused by low degradable conventional plastics. In this study, the potential of incorporating natural rubber latex (NRL) into chemically modified sago starch for the making biodegradable polymer blends was assessed. Native sago starch was acetylated and hydroxypropylated before gelatinization in preparing starch thermoplastic using glycerol. They were than casted with NRL into biopolymer films according to the ratios of 100.00/0.00, 99.75/1.25, 98.50/2.50, 95.00/5.00, 90.00/10.00 and 80.00/20.00 wt/wt, via solution spreading technique. Water absorption, thermal, mechanical, morphological and biodegradable properties of the product films were evaluated by differential scanning calorimetry (DSC), universal testing machine (UTM), scanning electron microscopy (SEM) and fourier transform infrared spectroscopy. Results showed that acetylation promoted the incorporating behavior of NRL in sago starch by demonstrating a good adhesion characteristic and giving a uniform, homogenous micro-structured surface under SEM observation. However, the thin biopolymer films did not exhibit any remarkable trend in their DSC thermal profile and UTM mechanical properties. The occurrence of NRL suppressed water adsorption capacity and delayed the biodegradability of the biopolymer films in the natural environment. Despite the depletion in water adsorption capacity, all of the product films degraded 50 % within 12 weeks. This study concluded that biopolymers with desirable properties could be formulated by choosing an appropriate casting ratio of the sago starch to NRL with suitable chemical substitution modes.     

Preparation of Liquid Epoxidized Natural Rubber by Oxidative Degradations Using Periodic Acid,Potassium Permanganate and UV-Irradiation

Epoxidized natural rubber (ENR) needs to be degraded into shorter chain lengths, to form liquid epoxidized natural rubber (LENR), for applications such as coating and adhesives. Since ENR contains both C=C and epoxide groups as reactive sites for degradation reactions, thus, LENR could be prepared by different methods through cleavages of C=C or epoxide groups, or a combination of both sites. Different mechanisms would produce different terminals on the LENR. This paper reports the oxidative degradation by (a) periodic acid, (b) potassium permanganate and (c) ultra violet (UV) irradiation. The degraded rubbers were characterized by gel permeation chromatography (GPC), nuclear magnetic resonance (NMR) and Fourier transform infra-red spectroscopy (FTIR). Ester and ketone terminals were formed in all the three methods, but lactone and hydrofuranic structures were observed only in degradation by UV irradiation. NMR spectrum reveals that cyclization of ENR has occurred during degradation by periodic acid. At lower periodic acid concentration, degradation takes place only via C=C cleavage, but at higher concentration, the attack to the epoxide groups becomes more prominent. Potassium permanganate has attacked both the double bonds and epoxide groups. On the other hands, epoxide group was not affected during degradation by UV irradiation, which cleaved only the C=C bonds.     

Behaviour of Rice-Byproducts and Optimizing the Conditions for Production of High Performance Natural Fiber Polymer Composites

This present study deals with evaluating some available rice by-products, such as rice straw and rice husks, as a fiber component in manufacturing of high performance natural fiber polymer composites (NFPC). The utilization of these undesirable wastes will contribute to the reduction of the environmental impact of waste disposal by burning. Two matrices (thermoset and thermoplastic) were used. Optimization of manufacture conditions of polyester-based thermosetting polymer composites was carried out through examine the effects of fibers to polymer ratio, amounts of catalyzed and initiator, fraction size of fibers and substituting one fibers by another, as well as time, temperature and pressure of pressing. The possibility of styrene containing polyester solution on improving the fiber interface via in situ grafting and enhancing the strength and water resistance of the produced NFPC was also evaluated, in comparison with that produced from using thermoplastic matrix (polypropylene) in presence of coupling agent. The production of this valuable product (NFPC) by this simple procedure, which not needs special devices (twin extrusion with heater), and chemicals to improve the compatibility between fibers and polymer matrix, will ensure reasonable profits and direct impacts on the Egyptian economy in general and rice growers in particular.     

Man-Made and Natural Fibres as a Reinforcement in Fully Biodegradable Polymer Composites: A Concise Study

Biodegradable and ecologically friendly polymer materials attract great attention of many scientific groups in the world as they fit well in the sustainable development policy and are considered to be “a right thing to do” by the general public. Such polymers can be modified by the addition of different fillers, favorably of natural origin. In the paper we provide a comparison between composites based on two biodegradable polymers: poly(lactic acid)—biodegradable, natural stock polymer and poly(butylene succinate)—biodegradable polymer produced from fossil based materials. For each polymer we have prepared a series of composites with different fibres (natural: hemp and flax, and manmade: Cordenka) and different filler loadings. To fully characterize obtained materials thermal, mechanical and surface free energy measurements were performed, completed with morphology observations and an attempt to compare the experimental data for tensile measurements with values obtained using the modified rule of mixtures. The tensile results calculated using the modified rule of mixture for below 30% fibre loading are found to be fitting the experimental data. Composites mechanical properties and morphology were strongly affected by the type of fibre used and its loading, however thermal properties remained almost unchanged. In specific, Cordenka fibres tend to form bunches which presence greatly influences the mechanical properties but still our studies have shown clear advantage of manmade Cordenka fibres over the hemp and flax fibres when considering distribution and fibre–polymer interaction.     

Preparation and Properties of Starch/Nanosilicate Layer/Polycaprolactone Composites

Starch nanocomposites have been prepared using mineral clay. Montmorillonite, kaolin and a surface-modified montmorillonite by dimethyl (hydrogenated tallow alkyl) ammonium cation were used. Starch-g-PCL nanocomposites have been prepared with graft polymerization through in situ ring-opening polymerization of ε-caprolactone in the presence of starch, Sn(Oct)₂ (Tin(II) 2-ethyl hexanoate) as an initiator/catalyst and silicate layers. In fact, the related composites were prepared in solution method, bulk polymerization and in situ polymerization methods with introducing the mineral clay. The effect of kind of clay on d-spacing of silicate layers was investigated and the obtained nanocomposites were analyzed using X-ray diffraction. The obtained compounds were characterized by Fourier transform infrared (FT-IR). Morphology of the prepared nanocomposites was investigated using scanning electron microscopy and DSC enhanced the study of thermal behaviour of the prepared composite compounds.     

Biomass Carbon Ratio of Polymer Composites Measured by Accelerator Mass Spectrometry

The evaluation method of biomass carbon ratio of polymer composite samples including organic and inorganic carbons individually was investigated. Biodegradable plastics and biobased plastics can have their mechanical properties improved by combining with inorganic fillers. Polymer composites consisting of biodegradable plastics and carbonate were prepared by two different methods. Poly(lactic acid) (PLA) composite was prepared by synthesis from l-lactide with catalyst and calcium carbonate (CaCO₃) powders from lime. Poly(butylene succinate) (PBS) composite was prepared by hot-pressing the mixture of PBS powder and CaCO₃ powders from oyster shells. The mechanical properties of composite samples were investigated by a tensile test and a compression test using an Instron type mechanical tester. Tensile test with a dumbbell shape specimen was performed for PBS composite samples and compression test with a column shape specimen for PLA composite samples. Strength, elastic modulus and fracture strain were obtained from the above tests. Biomass carbon ratio is regulated in the American Standards for Testing and Materials (ASTM). In ASTM standards on biomass carbon ratio, it is required that carbon atoms from carbonates, such as CaCO₃, are omitted. Biomass carbon ratio was evaluated by ratio of ¹⁴C to ¹²C in the samples using Accelerator Mass Spectrometry (AMS). The effect of pretreatment, such as oxidation temperature and reaction by acid, on results of biomass carbon ratio was investigated. Mechanical properties decrease with increasing CaCO₃ content. The possibility of an evaluation method of biomass carbon ratio of materials including organic and inorganic carbons was shown.     

Microbial Desulfurization of Ground Tire Rubber by Sphingomonas sp.: A Novel Technology for Crumb Rubber Composites

This study focused on the microbial desulfurization of ground tire rubber (GTR) by Sphingomonas sp. that was selected from coal mine soil and had sulphur oxidizing capacity. GTR was immersed in the medium co-cultured with the Sphingomonas sp. for 20?days. The growth curve of Sphingomonas sp. during co-cultured desulfurization with GTR was measured and the surface chemical groups of GTR before and after desulfurization were analyzed. The crosslink density, mechanical properties, dynamic mechanical properties, and morphology of fracture surface of SBR composites filled with GTR or DGTR were studied to evaluate the microbial desulfurization effect. The results showed that GTR had low toxicity to Sphingomonas sp., so Sphingomonas sp. was able to maintain a high biomass. After desulfurization, not only a rupture of conjugated C=C bonds, but also a reduction of sulfur content had happened to GTR. The sol fraction of GTR increased from its original 4.69?C8.68% after desulfurization. Desulfurated ground tire rubber (DGTR) sheets had better physical properties, and higher swelling values than GTR sheets. The DMA results showed that SBR/DGTR composite had a reduction of molecular chain friction resistance during glass transition region and a decrease of glass transition temperature. SEM photograph further indicated a good coherency interface between DGTR and the rubber matrix.     

New Route for Devulcanization of Natural Rubber and the Properties of Devulcanized Rubber

Devulcanization of natural rubber (NR) compound was carried out by means of benzoyl peroxide as a devulcanizing agent by two different techniques namely (a) chemical process and (b) mechano-chemical process. Furthermore, the effects of time and concentration of devulcanizing agent on the devulcanization process were investigated. The extent of devulcanization of natural rubber was studied by estimation of percent devulcanization, volume fraction of rubber after swelling, Mooney viscosity and crosslinked density. The devulcanized natural rubber obtained from mechano-chemical process was blended with virgin natural rubber in different proportions. The mechanical properties and morphology of the revulcanized blends were examined and found to be interesting. Thus, waste rubber could be reused successfully by this technique.     

Use of Nutshells as Fillers in Polymer Composites

Nutshells are agricultural waste products that can be procured at relatively low cost. In this work we examined the possibility of using these biodegradable materials as fillers in poly(lactic acid) and low density polyethylene. The nutshells were ground into powder, blended with the polymer, and then injection molded with final weight varying from 10 to 40 weight %. The mechanical and thermal properties of the composites were then studied. In general, the addition of fillers caused reductions in mechanical properties to varying extents, but thermal properties were only slightly affected. The use of maleic anhydride and peroxide with the fillers had a negative effect on poly(lactic acid) but a slightly positive effect on the stiffness of polyethylene. The results suggested that polymer-nutshell composites may be usable in applications where cost is a concern and where some reductions in mechanical properties are acceptable.     

Characterization of Sorghum Bran/Recycled Low Density Polyethylene for the Manufacturing of Polymer Composites

The objective of the study was to investigate the suitability of using sorghum bran in recycled low density polyethylene (R-LDPE) composites manufacturing. In response to the disposal of environmental problematic agricultural and polymer waste, composite sheets using recycled low density polyethylene and sorghum bran of different loadings (5, 10, 15 and 20 wt%) were prepared by melt compounding and compression molding. The effects of sorghum bran loadings on the mechanical, thermal, water absorption, swelling and crystalline properties of the composites were determined. Characterization of composites was carried out using X-ray diffraction (XRD), differential scanning calorimetry (DSC), thermo gravimetric (TGA/DTG) and mechanical analyses. It was found that increasing fiber loadings resulted to increased moduli and tensile strength while hardness was decreased. XRD indicated that fiber addition to R-LDPE did not change characteristic peak position. DSC results showed that the R-LDPE had significantly larger peak heat flow during cooling run than the blank R-LDPE, showing higher crystallization rates for R-LDPE. The results obtained confirmed that sorghum bran particles showed some potential as a good reinforcement in polymer matrix composites and indicate its thermal stability for possibly future composite applications.     

Biodegradable Green Glove Containing Ascorbic Acid from Maleated Epoxidized Natural Rubber/Poly(vinyl alcohol) Blend: Preparation and Physical Properties

Journal of Polymers and the Environment - The objective of this work was to prepare a maleate epoxidized natural rubber (MENR) and poly(vinyl alcohol) (PVA) (MENR/PVA) blend in the presence of...     

Biodegradation of Natural Rubber and Natural Rubber Products by <Emphasis Type="Italic">Streptomyces</Emphasis> sp. Strain CFMR 7

The rubber degrading activity of Streptomyces sp. CFMR 7 whose whole genome sequence was recently determined was tested with non-vulcanized fresh latex and common vulcanized rubber products such as latex glove, latex condom and latex car tyre. The degradation activity was unequivocally demonstrated by scanning electron microscopy with respect to microbial colonization efficiency, disintegration of rubber material and biofilm formation after 3, 6 and 9 months of inoculation. Fourier transform infrared spectroscopy comprising the attenuated total reflectance analysis on these inoculated products revealed insights into the biodegradation mechanism of this strain whereby, a decrease in the number of cis -1,4 double bonds in the polyisoprene chain, the appearance of ketone and aldehyde groups formation indicating an oxidative attack at the double bond of rubber hydrocarbon. In the presence of strain Streptomyces sp. CFMR 7, gel permeation chromatography analysis revealed a significant shift of the molecular weight distribution to lower values. Clear decrease in the molecular weight was observed over 3, 6 and 9 months of cultivation on fresh latex samples compared to other vulcanized products. No shift in the molecular weight distribution was observed for non-inoculated control. These results clearly showed that Streptomyces sp. CFMR 7 was able to cleave the carbon backbone of poly (cis -1,4-isoprene). Although this strain was able to degrade both non-vulcanized and vulcanized rubber products, faster degradation was obtained with natural rubber and rubber products with low complexity.     

Effect of Lignocellulosic Type on Long-Term Hygroscopic Behavior of Natural Filler/HDPE Composites

Natural filler/high density polyethylene (HDPE) injection-molded composites of flour from different lignocellulosic sources were prepared, and their long-term water absorption and thickness swelling were studied. Filler samples from wheat straw, hybrid Euro-American poplar, and loblolly pine were mixed with the matrix at 35 wt% lignocellulosics content and either zero or 2% maleic anhydride grafted polyethylene (MAPE) as compatibilizer. Results indicated water absorption of all the composites followed the kinetics of a Fickian diffusion process. The water diffusion coefficient of the composites was clearly dependent upon the lignocellulosic type. The wheat straw composites showed the highest and the pine composites exhibited the lowest water absorption coefficients. The highest thickness swelling took place in the wheat straw composites, followed by the poplar and pine composites, respectively. Adding MAPE to the composites decreased the water diffusion coefficient and thickness swelling by improving the adhesion between natural filler and the HDPE.     

Fabrication of Admicelled Natural Rubber by Polycaprolactone for Toughening Poly(lactic acid)

Natural rubber (NR) with polycaprolactone (PCL) core–shell (NR-ad-PCL), synthesized by admicellar polymerization, was acted as an impact modifier for poly(lactic acid) (PLA). PLA and NR-ad-PCL were melt-blended using a co-rotating twin screw extruder. The morphology of PLA/NR-ad-PCL blends showed good adhesion as smooth boundary around rubber particles and PLA matrix. Only 5 wt% of rubber phase, NR-ad-PCL was more effective than NR to enhance toughness and mechanical properties of PLA. The contents of the NR-ad-PCL were varied from 5, 10, 15 and 20 wt%. From thermal results, the incorporation of the NR-ad-PCL decreased the glass transition temperature and slightly increased degree of crystallinity of PLA. Mechanical properties of the PLA/NR-ad-PCL blends were investigated by dynamic mechanical analyser, pendulum impact tester and universal testing machine for tension and flexural properties. The increasing NR-ad-PCL contents led to decreasing Young’s and storage moduli but increasing loss modulus. Impact strength and elongation at break of the PLA/NR-ad-PCL blends increased with increasing NR-ad-PCL content up to 15 wt% where the maximum impact strength was about three times higher than that of pure PLA and the elongation at break increased to 79%.     

Biodegradability and Thermal Properties of Novel Natural Rubber/Linear Low Density Polyethylene/Thermoplastic Starch Ternary Blends

This work aimed to prepare biodegradable thermoplastic elastomers based on NR/LLDPE/TPS ternary simple blends to achieve some exclusive properties, i.e., good biodegradability in terms of water absorption and weight loss after burial, together with reasonable mechanical and thermal properties. A comparative study on biodegradability and other related properties of NR/LLDPE binary and NR/LLDPE/TPS ternary blends was performed. It was found that increasing the TPS proportion decreased storage modulus and complex viscosity. In addition, the size of dispersed TPS domains in the NR/LLDPE co-continuous matrix increased with TPS proportion, while the mechanical properties in terms of 100% moduli, tensile strength, elongation at break, and hardness decreased. This might be attributed to decreased interfacial adhesion with increasing size of TPS domains. Furthermore, increasing the TPS loading in the blend reduced the temperatures for 5 or 50% mass loss (T₅ or T₅₀) and the degradation temperature (T _d ). However, the biodegradability improved, in terms of increased water absorption and weight loss after burial in soil, with the loading level of TPS.