Utilization of Porous Carbons Derived from Coconut Shell and Wood in Natural Rubber

The porous carbons derived from cellulose are renewable and environmentally friendly. Coconut shell and wood derived porous carbons were characterized with elemental analysis, ash content, X-ray diffraction, infrared absorbance, particle size, surface area, and pore volume. The results were compared with carbon black. Uniaxial deformation of natural rubber (NR) composites indicate the composites reinforced with the porous carbon from coconut shell have higher tensile moduli at the same elongation ratio than the composites reinforced with wood carbon. 40 % coconut shell composite showed a fivefold increase in tensile modulus compared to NR. Polymer–filler interactions were studied with frequency dependent shear modulus, swelling experiments and dynamic strain sweep experiments. Both linear and non-linear viscoelastic properties indicate the polymer–filler interactions are similar between coconut shell carbon and wood carbon reinforced composites. The swelling experiments, however, showed that the polymer–filler interaction is greater in the composites reinforced with coconut shell instead of wood carbon.     

Kinetics of scrap tyre pyrolysis under vacuum conditions

Scrap tyre pyrolysis under vacuum is attractive because it allows easier product condensation and control of composition (gas, liquid and solid). With the aim of determining the effect of vacuum on the pyrolysis kinetics, a study has been carried out in thermobalance. Two data analysis methods have been used in the kinetic study: (i) the treatment of experimental data of weight loss and (ii) the deconvolution of DTG (differential thermogravimetry) curve. The former allows for distinguishing the pyrolysis of the three main components (volatile components, natural rubber and styrene–butadiene rubber) according to three successive steps. The latter method identifies the kinetics for the pyrolysis of individual components by means of DTG curve deconvolution. The effect of vacuum in the process is significant. The values of activation energy for the pyrolysis of individual components of easier devolatilization (volatiles and NR) are lower for pyrolysis under vacuum with a reduction of 12 K in the reaction starting temperature. The kinetic constant at 503 K for devolatilization of volatile additives at 0.25 atm is 1.7 times higher than that at 1 atm, and that corresponding to styrene–butadiene rubber at 723 K is 2.8 times higher. Vacuum enhances the volatilization and internal diffusion of products in the pyrolysis process, which contributes to attenuating the secondary reactions of the repolymerization and carbonization of these products on the surface of the char (carbon black). The higher quality of carbon black is interesting for process viability.The large-scale implementation of this process in continuous mode requires a comparison to be made between the economic advantages of using a vacuum and the energy costs, which will be lower when the technologies used for pyrolysis require a lower ratio between reactor volume and scrap tyre flow rate.     

Rheology of Concentrated Cellulose Solutions in 1-Butyl-3-methylimidazolium Chloride

Rheological behavior of the concentrated cellulose/1-butyl-3-methylimidazolium chloride ([BMIM]Cl) solutions was investigated. As polymeric fluid, solutions of cellulose in [BMIM]Cl display a marked elastic behavior under shear flow. The dependence of the shear viscosity η, and of the dynamic modulus, on concentration, average degree of polymerization (DP) and temperature is discussed. At lower concentrations and degrees of polymerization (DP), cellulose solutions show viscous, inelastic behavior at low frequencies and low shear rate. At higher concentration and DP, cellulose solutions are more elastic at higher frequencies and shear rate. Such solutions also have some usual rheological properties. The dynamic rheological responses revealed that the Cox–Merz rule did not hold for these cellulose solutions at high deformation rate. Plotting storage modulus G′ against loss modulus G″ gave almost a master curve which is independent of temperature and concentration, with the slope of about 1.651 for 10 wt% cellulose solutions. This value indicates the existence of microheterogeneity in the solution system.     

Crystallization and Mechanical Properties of Recycled Poly(ethylene terephthalate) Toughened by Styrene–Ethylene/Butylenes–Styrene Elastomer

Recycled poly(ethylene terephthalate) (R-PET) was blended with 15–30 wt% of styrene–ethylene/butylenes–styrene (SEBS) block copolymer and maleic anhydride grafted SEBS (SEBS-g-MA). Effects of nucleation and toughening of the elastomers were evaluated systematically by study of morphology, crystallization, thermal and mechanical properties of the blend. The addition of 30 wt% SEBS promoted the formation of co-continuous structure of the blend and caused the fracture mechanism to change from strain softening to strain hardening. Addition of SEBS-g-MA resulted in significant modification of phase morphology and obviously improved the impact strength. The compatibilization reaction of PET with SEBS-g-MA accelerated the crystallization of PET and increased the crystallinity. The shifts in glass transition temperature of PET towards that of SEBS-g-MA and the higher modulus for R-PET/SEBS-g-MA (70/30) blend found by DMA are also indications of better interactions under the conditions of compatibilization and interpenetrating structure.     

Preparation and Characterization of PVC Matrix Composites with Biochemical Sludge

Biochemical sludge (BS), generated in the waste water treatment of paper mills, was pretreated by enzyme hydrolysis. The effect and action mechanism of the enzymatic treatment on the properties of polyvinyl chloride (PVC) matrix composites with BS were discussed. Results showed that when the filler content was 30 wt%, the tensile strength of the PVC composites filled with BS and its modified products which were pretreated by laccase, cellulase and hemicellulase can be increased by 38.64, 67.4, 63.5 and 66.3% than the PVC composite filled with calcium carbonate. When the dosage of filler was 40 wt%, the elastic modulus of PVC composites filled with BS and its above three modified products decreased by 53.3, 52.3, 50.0 and 46.3%, respectively. Meanwhile, the thermal stability of PVC composites can also be improved at the temperature of over 340 °C. It can be concluded that the enzyme pretreatment can improve the application performance of BS usage in PVC matrix composites.     

Bioabsorbable Soy Protein Plastic Composites: Effect of Polyphosphate Fillers on Biodegradability

The use of biodegradable polymers made from renewable agricultural products such as soy protein isolate has been limited by the tendency of these materials to absorb moisture. A straightforward approach for controlling the inherent water absorbency of the biodegradable polymers involves blending special bioabsorbable polyphosphate fillers, biodegradable soy protein isolate, plasticizer, and adhesion promoter in a high-shear mixer followed by compression molding. The procedure yields a relatively water-resistant, biodegradable soy protein polymer composite, as previously reported. The aim of the present study is to determine the biodegradability of the new polyphosphate filler/soy protein plastic composites by monitoring the carbon dioxide released over a period of 120 days. The results suggest that the composites biodegrade satisfactorily, with the fillers having no significant effect on the depolymerization and mineralization of the soy protein plastic, processes that would otherwise result in nonbiodegradable composites. Further, the results indicate that the biodegradation and useful service life of these biocomposites may be controlled by changing the filler concentration, making the biocomposites useful in applications in which the control of water resistance and biodegradation is critical.     

Processing and Physical Properties of Plastics Made from Soy Protein Polyester Blends

Blending soy protein with polyesters using a polyvinyllactam as a compatibilizer successfully made soy protein-based plastics. The polyesters used to produce blends included polycaprolactone (PCL) and Biomax (a commercial biodegradable polyester). The blends were processed by compounding extrusion and injection molding. Blends containing soy protein/Biomax-poly(vinyl alcohol) had tensile strengths ranging from 16–22 MPa, with samples containing larger percentages of the synthetic polymer exhibiting greater strengths. Blends made from soy protein, Biomax, and PCL had tensile strengths ranging from 27–33 MPa. All the blends had high Young's moduli but demonstrated brittle characteristics as evident from their low elongations at break, ranging from 1.8–3.1%. Plastics made from soy protein/polyester blends exhibited low water absorption and had good stability under ambient conditions relative to the plastics made from soy protein alone. Blends made from soy protein flour produced plastics with the lowest water absorption.     

Injection Molded Biocomposites from Soy Protein Based Bioplastic and Short Industrial Hemp Fiber

Biocomposites from soy based bioplastic and chopped industrial hemp fiber were fabricated using twin-screw extrusion and injection molding process. Soy based bioplastics were prepared through cooking with plasticizer and blending with biodegradable poly(ester amide). Mechanical, thermal properties and fracture surface morphology of the “green”/biocomposites were evaluated with universal testing system (UTS), dynamic mechanical analysis (DMA), Environmental Scanning Electron Microscopy (ESEM). It was found that the tensile strength and modulus, flexural strength and modulus, impact strength and heat deflection temperature of industrial hemp fiber reinforced biocomposites significantly improved. The fracture surfaces showed no signs of matrix on the fiber surface suggesting poor interfacial adhesion.     

Utilization of Sunflower Stalk in Manufacture of Thermoplastic Composite

Dimensional stability and mechanical performance of polypropylene thermoplastic composites filled with sunflower stalk (SS) flour at 30, 40, 50, and 60 wt% contents of the SS flour were investigated. The thickness swelling and water absorption of the specimens increased with increasing SS flour content. The modulus in the flexural and tensile improved with increasing SS flour content while the tensile and flexural strengths of the specimens decreased. The use of maleic anhydride polypropylene (3 wt%) had a positive effect on the dimensional stability and mechanical properties of the polypropylene thermoplastic composites filled with SS flour. The melting temperature of polypropylene decreased with increasing content of the SS flour. The degree of crystallinity of filled polypropylene composites between fibre loading of 0–30 % by weight was higher than that of unfilled polypropylene composites. However, further increment in the filler content decreased the degree of crystallinity. The obtained results showed that SS flour could be potentially suitable raw material in the manufacture of polypropylene composites.     

Rheological Investigation of Wood-Polypropylene Composites in Rotational Plate Rheometer

In this research work, the rheological properties of Wood-Plastic Composites (WPC) with some selected compositions are investigated. WPC is being recognized as a green composite that, in the past 20?years, has emerged to a commercial product. A study on rheological properties of these materials can give insight into the proper selection of composition and processing condition. Two grades of polypropylene (PP) with two different melt flow indexes (MFI) were selected to prepare WPCs with three different wood contents (50, 60 and 70?% wt.). Four types of rheological experiments were performed utilizing a rotational plate rheometer: (1) strain sweep, (2) frequency sweep, (3) temperature sweep and (4) steady shear rate sweep. The independent variables were chosen as wood content, MFI of polymer (two types), melt temperature, frequency or shear rate, the gap between the plates, and strain percentage. The strain sweep tests specified the linear and non-linear viscoelastic zones of each experiment. The results of frequency sweep experiments indicated that increasing the wood content and frequency and also decreasing the strain percentage and the gap distance, lead to an increase in the storage modulus. Regarding the loss modulus, wood percentage and the gap distance presented positive effects and strain percentage showed a negative effect. The behavior of complex viscosity was almost similar to that of the storage modulus but increasing the frequency caused a decrease in the complex viscosity. In case of temperature sweep experiments, it was observed that the rheological properties exhibit a rapid change near to a temperature of 160?°C. The results also showed that beyond this point, increasing the wood content and also MFI of polypropylene caused an increase in the storage modulus. The results of steady shear rate sweep experiments specified that increasing wood content and also decreasing the MFI of PP, the gap distance and shear rate lead to an increase in both viscosity and shear stress.     

Fabrication and Properties of Acid Treated Carbon Nanotubes Reinforced Soy Protein Nanocomposites

Acid treated multiwalled carbon nanotubes (MWNTs) were incorporated into glycerol plasticized soy protein to form MWNTs/soy protein nanocomposite plastics. The influence of the polar groups grafted on carbon nanotubes by acid treatment on the compatibility would be studied. The results showed that aggregation of carbon nanotubes was reduced by acid treatment and some polar groups were grafted on the nanotubes. The modified MWNTs were dispersed in soy protein matrix homogeneously and exhibited good compatibility with soy protein matrix. The crystalline structure of soy protein was not changed by MWNTs. The mechanical properties were dramatically enhanced through MWNTs incorporation due to the strong hydrogen bonding between them and the homogeneously dispersion of MWNTs in protein matrix, indicating the reinforcing effect of MWNTs in soy protein matrix. The water uptake was reduced and the thermal stability was enhanced by MWNTs incorporation.     

Thermal and Mechanical Properties of Plastics Molded from Sodium Dodecyl Sulfate-Modified Soy Protein Isolates

Soybean protein is a potential material for manufacturing of biodegradable plastics. The objective of this investigation was to characterize the thermal and mechanical properties of plastics made from sodium dodecyl sulfate (SDS)-modified soy proteins. Soy protein isolate (SPI) was prepared from defatted soy flour, modified with various concentrations of SDS, and then molded into plastics. The temperatures of denaturation of the modified soy protein increased at low SDS concentration and then decreased at high SDS concentration. At the same SDS concentration, the plastics molded from the modified soy proteins showed a similar temperature of denaturation, but a lower enthalpy of denaturation compared to the modified soy protein. Young's modulus of the plastics decreased as SDS concentration increased, and the tensile strength and strain at break of the plastics reached a maximum value at 1% SDS modification. Two glass transition temperatures were identified corresponding to the 7S and 11S globulins in SPI by dynamic mechanical analysis, and they decreased as SDS concentration increased. The SDS modification increased the water absorption of the plastics.     

Microbial Degradation of the Natural Rubber in Tire Tread Compound by a Strain of Nocardia

Tread compound of truck tires is based primarily on natural rubber or blends of natural rubber (NR) and synthetic polymers in combination with high grade carbon black. When the tread compound is attacked by a strain of Nocardia capable of degrading NR, part of the NR in the compound is mineralized, and part is disintegrated to very small black particles. The small black particles consist of the residual rubber and inorganic fillers. At higher NR content, large and deep cavities are formed on the surface of the pieces of the tread compound after microbial disintegration. At lower content of NR, large but very shallow cavities or very small pits can be seen on the tread surface. During microbial growth on the tread compound, isoprene oligomers with molecular weight of about two thousand are produced. Not only the isoprene oligomers, but also butadiene oligomers are produced during microbial disintegration of the tread compound of NR/synthetic rubber blend.     

Preliminary Studies on Converting Agricultural Waste into Biodegradable Plastics – Part III: Sawdust

Summary Hardwood sawdust was derivatized either by carboxymethylation, glutaration, maleiation, phthallation, or succination in order to produce anionic materials suitable for complexation with soy protein isolate. Blending each derivative with soy protein isolate resulted in instant precipitation of gels. Infrared spectroscopy and differential scanning calorimetry suggested that each derivative formed a complex with protein. Reaction products could be dried into pellets exhibiting tensile strengths between 0.9–2.4 MPa, suggested that these materials could be promising candidates for biodegradable structural materials.     

Bacteria Degrading PCBs and CBs Isolated from Long-Term PCB Contaminated Soil

Bacteria able to degrade polychlorinated biphenyls (PCBs) and chlorobenzoic acids (CBs) were isolated from soil that had been contaminated with PCBs for 15–30 years. Contaminated soil in which PCB content ranged between 10–470 mg/kg was naturally vegetated with different plants including ash (Fraxinus excelsior), birch (Betula pendula), black locust (Robinia pseudoacacia), Austrian pine (Pinus nigra) and goat willow (Salix caprea) trees as well as a variety of grasses and forbs. Bacteria able to use biphenyl as a sole source of carbon and energy were found in the root zone of all plants, but occurred in the largest numbers beneath pine and black locust. Bacteria able to degrade chlorobenzoic acids were isolated from the same location contaminated with PCBs. Strains that were taxonomically identified by 16S rDNA as Pandoraea were able to use 2-CB, 3-CB, 2,3-CB, 2,5-CB as sole carbon sources, and the strain Arthrobacter utilised 4-CB.     

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.     

Viscosity of Soy Protein Plastics Determined by Screw-Driven Capillary Rheometry

Soy protein plastics are a renewable, biodegradable alternative to fossil fuel-based plastic resins. Processing of soy protein plastics using conventional methods (injection molding, extrusion) has met with some success. Viscosities of processable formulations that contain soy protein along with the necessary additives, such as glycerol and cornstarch, have not been reported, but are necessary for extrusion modeling and the design of extrusion dies. Resins consisting of soy protein isolate-cornstarch ratios of 4:1, 3:2, and 2:3 were plasticized with glycerol and soy oil, compounded in a twin screw extruder and adjusted to 10% moisture. The effects on viscosity of added sodium sulfite, a titanate coupling agent and recycling were evaluated using a screw-driven capillary rheometer at shear rates of 100–800/s. The viscosities fit a power-law model and were found to be shear thinning with power-law indices, n, of 0.18–0.46 and consistency indices, m, of 1.1 × 10⁴–1.0 × 10⁵. Power-law indices decreased and consistency indices increased with increasing soy protein-to-cornstarch ratio and in the absence of sodium sulfite. Addition of the titanate coupling agent resulted in increased power-law index and decreased consistency index. Viscosities at a shear rate of 400/s decreased with recycling, except for the 4:1 soy protein isolate to cornstarch formulation, which displayed evidence of wall slip. Power-law indices were unaffected by recycling. Viscosities in the tested shear rate range were comparable to polystyrene and low-density polyethylene indicating soy protein plastics are potential drop-in replacements for commodity resins on conventional plastics processing equipment.     

Effects of Storage Time on Properties of Soybean Protein-Based Plastics

Soybean protein has been considered as a potential biodegradable polymer in the manufacture of plastics. The purpose of this investigation was to characterize the effect of storage time on thermal and mechanical properties of soybean protein isolate (SPI) plastics. SPI was separated from defatted soy flour, modified with 1M or 2M urea, or plasticized with glycerol, and compression molded into plastics. Plastic made from SPI alone was used as a control. For all SPI plastics, glass transition temperatures and dynamic storage modulus increased and loss tangent decreased during storage. Excess enthalpy of relaxation of all SPI plastics had an exponential relationship with storage time, indicating a fast aging rate at the beginning of storage. All SPI plastics tended to be stiff and brittle during storage. The plastics with glycerol had the slowest aging rate and were fairly stable after 60 days, with about 8.8 MPa tensile strength and 168% strain at break. Plastics with the 2M urea-modification SPI also had a slow aging rate and became relative stable after 60 days, with about 10 MPa tensile strength and 72% elongation.     

Processing and Characterization of Short-Fiber Reinforced Jute/Poly Butylene Succinate Biodegradable Composites: The Effect of Weld-Line

Fabrication of complex injection molded parts often involves the use of multiple gates. In such situations, polymer melts from different gates meld to form the molded part (weld line). This paper reports on the fabrication and characterization of the mechanical and morphological properties of short fiber reinforced jute/poly butylene succinate (PBS) biodegradable composites. The effect of a dual gated mold in the fabrication of welded specimens was a key focus of the investigation. It was observed that incorporation of jute fiber (10 wt%) conferred drastic changes on the stress–strain properties of the matrix as the elongation at break (EB), dropped from 160% in the matrix to just 10% in the composite. The tensile strength of the composite was lower than that of the matrix. However, it is noteworthy that the tensile modulus of the composite increased. Bending test also revealed that both bending strength and modulus increased with the incorporation of jute. Morphological studies of the tensile fracture surface using SEM revealed two types of failure mode. Ductile failure was indicated by plastic deformation at the initiation of fracture followed by brittle failure. The good interfacial bonding indicated between jute and PBS was attributed to positive interaction between the two polar polymers. A comparison of the non-weld and weld-line samples revealed that the weld-line composites have better mechanical integrity than the corresponding polymer matrix with weld line. The results also revealed that elongation at break and toughness are most sensitive to the presence of the weld-line whereas flexural properties are least sensitive.     

Lignocellulosic Fiber-Reinforced Keratin Polymer Composites

Short fiber reinforced polymer composites were prepared from lignocellulose fibers and feather keratin polymer (FKP). The FKP matrix was prepared from the reactive processing of poultry feather keratin, glycerol, water, and sodium sulfite. Lignocellulose fibers of varying source, length, and mass fraction were used and it was found that positive reinforcement of FKP was affected by all three. Positive reinforcement was defined as an increase in elastic modulus when normalized by FKP with the same amount of glycerol but no fibers. Positive reinforcement was only able to occur for modulus but not stress at break indicating that the composites were of high physical properties only under small deformations. At large deformations, fiber pull-out was observed in the composites using scanning electron microscopy. The most likely origin of this behavior appeared to be from weak fiber–polymer interactions dominated by friction and rationalized by a force balance across the fiber–polymer interface. High fiber loadings were shown to be reinforcing because of the formation of a network of lignocellulose fibers. The addition of lignocellulose fibers increased the thermal stability of the material.