Biodegradable Composite Foams of PLA and PHBV Using Subcritical CO<Subscript>2</Subscript>

One key strategy for increasing the application potential for biodegradable plastics lies in improving the physical and mechanical characteristics, which can be attained by inducing a cellular morphology in the pure polymer with the aid of a blowing agent, as well as by blending two or more polymers with the desirable properties. This paper examines the effect that blending two biodegradable polymers has on the thermal properties and morphology of the resultant foams blown with carbon dioxide (CO₂). Polylactic acid (PLA), polyhydroxybutyrate-co-valerate (PHBV) and blends of both were foamed and characterized in terms of thermal characteristics, relative density, cell size, and foam morphology. The results indicate that although PLA and PHBV are immiscible, the presence of small quantities of PHBV (25 wt%) could lead to low density foams with finer, more uniform cells. Furthermore, the crystallinity of PHBV was found to be unaffected by the presence of PLA in the composite, which supports the immiscibility of PLA and PHBV.     

Water Aided Fabrication of Whey and Albumin Plastics

Development of polymeric materials that can reduce the reliance on petroleum derived synthetic polymers involves biopolymers such as proteins, starch, cellulose and lipids which can be obtained as agricultural co-products or by-products. Specifically, bioplastics from protein feedstock may have significant advantages over traditional plastics, especially in areas such as packaging, agriculture, horticulture and medical materials. This article focuses on fabricating plastics from whey and albumin proteins and describing properties of plastics made from them. These protein biomasses were plasticized using water and compression molded into plastic samples. Results indicated the importance of water on plasticization during fabrication and on mechanical performance later due to densification during drying.     

Transfer of Graphene CVD to Surface of Low Density Polyethylene (LDPE) and Poly(butylene adipate-co-terephthalate) (PBAT) Films: Effect on Biodegradation Process

Here, the influence of graphene as a coating on the biodegradation process for two different polymers is investigated, poly(butylene adipate-co-terephthalate) (PBAT) (biodegradable) and low-density polyethylene (LDPE) (non-biodegradable). Chemical vapor deposition graphene was transferred to the surface of two types of polymers using the Direct Dry Transfer technique. Polymer films, coated and uncoated with graphene, were buried in a maturated soil for up to 180 days. The films were analyzed before and after exposure to microorganisms in order to obtain information about the integrity of the graphene (Raman Spectroscopy), the biodegradation mechanism of the polymer (molecular weight and loss of weight), and surface changes of the films (atomic force microscopy and contact angle). The results prove that the graphene coating acted as a material to control the biodegradation process the PBAT underwent, while the LDPE covered by graphene only had changes in the surface properties of the film due to the accumulation of solid particles. Polymer films coated with graphene may allow the production of a material that can control the microbiological degradation, opening new possibilities in biodegradable polymer packaging. Regarding the possibility of graphene functionalization, the coating can also be selective for specific microorganisms attached to the surface.     

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.     

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.     

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.     

Biodegradable Soy-Based Plastics: Opportunities and Challenges

Today's plastics are designed with little consideration for their ultimate disposability or the effect of the resources (feedstocks) used in making them. This has resulted in mounting worldwide concerns over the environmental consequences of such materials when they enter the mainstream after their intended uses. This led to the concept of designing and engineering new biodegradable materials–materials that have the performance characteristics of today's materials but that undergo biodegradation along with other organic waste to soil humic materials. Hence, the production of biodegradable materials from annually renewable agricultural feedstocks has attracted attention in recent years. Agricultural materials such as starches and proteins are biodegradable and environmentally friendly. Soybean is a good candidate for manufacturing a large number of chemicals, including biodegradable plastics, as it is abundantly available and cheap. Soy protein concentrate, isolate, or flakes could be compounded with synthetic biodegradable plastics such as polycaprolactone or poly (lactic acid) to make molded products or edible films or shopping bags and make the environment cleaner and greener.     

Spectral Characterization of Four Kinds of Biodegradable Plastics: Poly (Lactic Acid), Poly (Butylenes Adipate-Co-Terephthalate), Poly (Hydroxybutyrate-Co-Hydroxyvalerate) and Poly (Butylenes Succinate) with FTIR and Raman Spectroscopy

Fourier transform infrared microscope and confocal Raman spectroscope were employed in this study to investigate four kinds of biodegradable plastics: poly(lactic acid),poly(butylenes adipate-co-terephthalate), poly(butylenes succinate) and poly(hydroxybutyrate-co-hydroxyvalerate), which are used more and more popularly in everyday life but can not be identified easily with other instruments. Infrared and Raman spectra of the plastics were tentatively interpreted. The indicative peaks to characterize the four polymers were also summarized. The result in this study can help the forensic scientists discriminate the plastics accurately when they occurred as trace evidences in cases, it also offers the producer and environment scientists an effective, non-invasive and fast method to characterize and identify these four polymers.     

Bioabsorbable soy protein plastic composites: Effect of polyphosphate fillers on water absorption and mechanical properties

The use of synthetic and natural bioabsorbable plastics has been severely limited due to their low stiffness and strength properties as well as their strong tendency to absorb moisture. This research focused on the development of bioabsorbable polyphosphate filler/soy protein plastic composites with enhanced stiffness, strength, and water resistance. Bioabsorbable polyphosphate fillers, biodegradable soy protein isolate, plasticizer, and adhesion promoter were homogenized and compression-molded. Physical, mechanical, and water absorption testing was performed on the molded specimens. Results showed improvements in stiffness, strength, and water resistance with increasing polyphosphate filler content up to 20% by weight. Application of a coupling agent produced further mechanical property enhancements and a dramatic improvement in water resistance, interpreted by an interfacial chemical bonding model. Examination of the fracture surfaces of the materials revealed that the addition of the polyphosphate fillers changed the failure mode from brittle to pseudo-ductile. These results suggest that these materials are suitable for many load-bearing applications in both humid and dry environments where current soy protein plastics are not usable.     

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.     

Novel Biodegradable Thermoplastic Elastomer Based on Poly(butylene succinate) and Epoxidized Natural Rubber Simple Blends

Novel biodegradable thermoplastic elastomer based on epoxidized natural rubber (ENR) and poly(butylene succinate) (PBS) blend was prepared by a simple blend technique. Influence of blend ratios of ENR and PBS on morphological, mechanical, thermal and biodegradable properties were investigated. In addition, chemical interaction between ENR and PBS molecules was evaluated by means of the rheological properties and infrared spectroscopy. Furthermore, the phase inversion behavior of ENR/PBS blend was predicted by different empirical and semi-empirical models including Utracki, Paul and Barlow, Steinmann and Gergen models. It was found that the co-continuous phase morphology was observed in the blend with ENR/PBS about 58/42 wt% which is in good agreement with the model of Steinmann. This correlates well to morphological and mechanical properties together with degree of crystallinity of PBS in the blends. In addition, the biodegradability was characterized by soil burial test after 1, 3 and 9 months and found that the biodegradable ENR/PBS blends with optimum mechanical and biodegradability were successfully prepared.     

Biodegradability and biodegradation rate of poly(caprolactone)-starch blend and poly(butylene succinate) biodegradable polymer under aerobic and anaerobic environment

The biodegradability and the biodegradation rate of two kinds biodegradable polymers; poly(caprolactone) (PCL)-starch blend and poly(butylene succinate) (PBS), were investigated under both aerobic and anaerobic conditions. PCL-starch blend was easily degraded, with 88% biodegradability in 44 days under aerobic conditions, and showed a biodegradation rate of 0.07 day⁻¹, whereas the biodegradability of PBS was only 31% in 80 days under the same conditions, with a biodegradation rate of 0.01 day⁻¹. Anaerobic bacteria degraded well PCL-starch blend (i.e., 83% biodegradability for 139 days); however, its biodegradation rate was relatively slow (6.1 mL CH₄/g-VS day) compared to that of cellulose (13.5 mL CH₄/g-VS day), which was used as a reference material. The PBS was barely degraded under anaerobic conditions, with only 2% biodegradability in 100 days. These results were consistent with the visual changes and FE-SEM images of the two biodegradable polymers after the landfill burial test, showing that only PCL-starch blend had various sized pinholes on the surface due to attack by microorganisms. This result may be use in deciding suitable final disposal approaches of different types of biodegradable polymers in the future.     

Effect of Hot Drawing on the Mechanical Properties of Biodegradable Fibers

The use of biodegradable polymers is increasingly attracting interest over the last years, since they can reduce the environmental effects related to disposal of traditional plastics and, in general, the use of fossil, non-renewable resources. One of the most promising applications is represented by fibers production. However, the orientation and the crystallinity degrees can significantly affect the mechanical properties. Therefore, it is of interest to investigate on the optimum processing conditions, in order to improve the mechanical properties. In particular, while crystallinity can be slightly modified by the processing, orientation can be significantly improved. In this work, the effects of hot stretching on the mechanical and structural properties of fibers made from two different families of biodegradable blends were investigated. The orientation proved to significantly change the mechanical properties, and it was shown that factors such as the different relaxation times, the different crystallization temperatures and the cooling rate can give opposite effects in the three investigated polymer systems with significant consequences on the mechanical behaviour of the fibers. In particular, the behaviour during fiber production in hot stretching, and the orientation mechanisms were studied and explained on the basis of rheological and thermal properties of the polymers.     

Evaluation of the Biodegradability of Polyvinyl Alcohol/Starch Blends: A Methodological Comparison of Environmentally Friendly Materials

Polyvinyl alcohol (PVA) and starch are both biodegradable polymers. These two polymers can be prepared as biodegradable plastics that are emerging as one of the environmental friendly materials available now. In this study, after reacting with sodium trimetaphosphate (STMP), modified corn starch was blended with PVA in different ratios by a barbender. Test samples were prepared for mechanical and thermal properties measurements. The surface roughness and morphology of fractured surface of the samples were observed by an atomic force microscopy (AFM) and scanning electron microscope (SEM) measurements. Aqueous degradation by enzyme, water absorption and biodegradability behavior were evaluated for the degradability. The biodegradability of these materials was followed by bio-reactivity kinetics models. Results showed that the addition of modified starch could enhance its water uptake. With an addition of 20 wt% of modified starch, the blend had a maximum weight loss during enzymatic degradation. It was found that the degradability was enhanced with the addition of the starch. Analyzing the results of the biodegradability based on the kinetic models, the growth rate of the microorganism was found to be increasing with the increase of the content of starch in the PVA/starch blends in the first order reaction fashion. In our biodegradability analysis, i.e., based on the China national standards (CNS) 14432 regulations, we estimated the decomposition behavior based on the mentioned first order reaction. We found that the PVA/starch blends would take 32.47, 16.20 and 12.47 years to degrade by 70% as their starch content 0, 20 and 40 wt%, respectively.     

Green Synthesis of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/Cellulose/Polyvinyl Alcohol Hybride Aerogel and Its Application for Dye Removal

A novel Fe₃O₄/cellulose–polyvinyl alcohol (PVA) aerogel was successfully synthesized by an eco-friendly and facile method in this work. Cellulose/PVA matrix was prepared through an environmental friendly physical cross-linking process and further in-situ decorated with Fe₃O₄. Series of Fe₃O₄ decorated aerogels were prepared and the effects of Fe₃O₄ nanoparticles (NPs) on the aerogels were systematic investigated. As-prepared aerogels exhibited desirable properties including nanostructure, relatively high porosity, improved mechanical and superparamagnetism. The TEM results showed that Fe₃O₄ NPs were integrated in the three-dimensional matrix of cellulose/PVA with a diameter of 9–12 nm. Furthermore, the mechanical strength of the aerogels was significantly enhanced after the introduction of Fe₃O₄ NPs. Meanwhile, the obtained Fe₃O₄/cellulose/PVA aerogel exhibited excellent adsorption performance toward methyl blue dye, and can be reused through fenton-like catalysts oxidative degradation of organic dye in H₂O₂ solution. Therefore, they will have a great potential application as eco-friendly and economical adsorbents.     

Synthesis,Characterization and NH<Subscript>3</Subscript>/N<Subscript>2</Subscript> Gas Permeation Study of Nanocomposite Membranes

Carbon nanotubes have exceptional mechanical properties which make them very attractive for the development of composite membranes. In this research, NH₃/N₂ gas permeation behavior of flat sheet composite membranes was examined. The cellulose acetate-multiwalled carbon nanotubes composite membranes were synthesized using solution casting method. The morphology and dispersion of carbon nanotubes were observed through SEM. However, the composite membranes were also characterized using several analytical techniques such as X-ray diffraction analysis, tensile testing analysis, and thermal gravimetric analysis. Characterization of these membranes depicted that carboxylic group functionalized MWCNTs are extremely compatible with CA. The permeation experiments were performed with NH₃ and N₂ to explore the host–guest interaction of MWCNTs with chosen gases. The permeability of NH₃ was found pronounced compared to N₂. The NH₃/N₂ selectivity up to 90 was documented.     

Cellulose Fiber/Bentonite Clay/Biodegradable Thermoplastic Composites

Adding cellulose fiber reinforcement can improve mechanical properties of biodegradable plastics, but fiber must be well dispersed to achieve any benefit. The approach to dispersing fiber in this study was to use aqueous gels of sodium bentonite clay. These clay-fiber gels were combined with powdered compostable thermoplastics and calcium carbonate filler. The composite was dried, twin-screw extruded, and injection molded to make thin parts for tensile testing. An experimental design was used to determine the effect of fiber concentration, fiber length, and clay concentration. Polybutylene adipate/terephthalate copolymer (PBAT) and 70/30 polylactic acid (PLA)/PBAT blend were the biodegradable plastics studied. The composite strength decreased compared to the thermoplastics (13 vs. 19 MPa for PBAT, 27 vs. 38 MPa for the PLA/PBAT blend). The composite elongation to break decreased compared to the thermoplastics (170% vs. 831% for PBAT, 4.9% vs. 8.7% for the PLA/PBAT blend). The modulus increased for the composites compared to the thermoplastic standards (149 vs. 61 MPa for PBAT, 1328 vs. 965 MPa for the PLA/PBAT blend). All composite samples had good water resistance.     

Preparation and Optimization of Starch/Poly Vinyl Alcohol/ZnO Nanocomposite Films Applicable for Food Packaging

Pollution and destruction of the environment due to the accumulation of non-degradable plastics are some of the most important concerns in the world. A significant amount of this waste is related to the polymers used in food packaging. Therefore, experts in the food industry have been looking for suitable biodegradable alternatives to synthetic polymers. Preparing biocompatible and biodegradable films based on starch is a good choice. In this study, various factors affecting films of starch/polyvinyl alcohol (PVA)/containing ZnO nanoparticles such as the amount of starch, PVA, glycerol, and ZnO were evaluated by response surface methodology (RSM). Film formation by solvent casting method, mechanical properties, swelling, solubility, and water vapor permeability (WVP) were selected as responses of RSM. The results showed that hydrogen bonding interactions between polyvinyl alcohol and starch improved the film formation. The effect of glycerol and PVA content on the mechanical strength was contrary to each other. As the amount of PVA increased, the tensile strength first decreased and then increased. The value of WVP was for all Runs from 0 to 6.77?×?10^??8 g m^??1 s^??1 Pa^??1. Finally, films with high film formation, maximum tensile strength, and high elongation at break, minimum solubility, permeability, and swelling were optimized.

     

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.     

Effect of Nanoscale SiO<Subscript>2</Subscript> and TiO<Subscript>2</Subscript> as the Fillers on the Mechanical Properties and Aging Behavior of Linear Low-Density Polyethylene/Low-Density Polyethylene Blends

Linear low-density polyethylene (LLDPE) was blended with low-density polyethylene (LDPE) at a fixed ratio (80 wt LLDPE and 20 wt %LDPE) and filled with nanoparticles of SiO₂ and TiO₂ at a ratio up to wt 5%, so as to develop the polymeric composites suitable to preparing the agricultural micro-irrigation pipes having good environmental adaptability. These compounds were blended using calcium stearate, polyethylene wax, and titanate coupling agent as the auxiliary dispersants, and ethylene-vinyl acetate copolymer (EVA) as the toughness improver. The LLDPE/LDPE composites filled with the nanoparticles were extruded and injected to prepare the composites specimens for the performance evaluations and micro-irrigation pipe field test. The mechanical properties, thermostability, and processibility of the injected composites were investigated. The effect of heating in an oven and irradiating by ultraviolet on the mechanical properties of the composites was explored. The environmental adaptability of the micro-irrigation pipes made of the filled LLDPE/LDPE composites was evaluated making use of long-term outdoor field test in northwest China where the arid and harsh natural conditions are of great concerns. It was found that the LLDPE/LDPE blend with the LLDPE mass fraction fixed as 80% showed balanced mechanical and thermal properties and flexibility, and was suitable to be used as the basic resin matrix. The incorporation of nano-TiO₂ contributed to effectively improving the resistance to heating and ultraviolet irradiation of the composites. The composite made from 91% basic resin matrix, 6% EVA, and 3% mixed nano-SiO₂ and TiO₂, showed balanced comprehensive properties. The micro-irrigation pipes made of this filled LLDPE/LDPE composite had good environmental adaptability and service behavior in a three-year field test and were suitable to be used in arid area.