Effect of Hydrothermal Aging on Injection Molded Short Jute Fiber Reinforced Poly(Lactic Acid) (PLA) Composites

This work focused on the durability of short jute fiber reinforced poly(lactic acid) (PLA) composites in distilled water at different temperatures (23, 37.8 and 60 °C). Morphological, thermal and mechanical properties (tensile, flexural, and impact) of jute/PLA composites were investigated before and after aging. Different from traditional synthetic fiber reinforced polymer composites, the stability of jute/PLA composites in water was significantly influenced by hydrothermal temperature. The mechanical properties of the composites and molecular weight of PLA matrix declined quickly at 60 °C, however, this process was quite slower at temperatures of 23 and 37.8 °C. Impact properties of the composites were hardly decreased, but the tensile and flexural properties suffered a drop though to various degrees with three degradation stages at 23 and 37.8 °C. The poor interface of composites and the degradation of PLA matrix were the main damage mechanism induced by hydrothermal aging. Furthermore, considering the hydrolysis of PLA matrix, the cleavage of PLA molecular chain in different aging time was quantitatively investigated for the first time to illustrate hydrolysis degree of PLA matrix at different aging time.     

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

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

Biodegradation of acrylic acid polymers and oligomers by mixed microbial communities in activated sludge

The biodegradability (mineralization to carbon dioxide) of acrylic acid oligomers and polymers was studied in activated sludge obtained from continuous-flow activated sludge (CAS) systems exposed to mixtures of low molecular weight (Mw < 8000) poly(acrylic acid)s and other watesoluble polymers [poly(ethylene glycol)s] in influent wastewater. Dilute preparations of activated sludge from the CAS units were tested for their ability to mineralize acrylic acid monomer and dimer, as well as a series of model acrylic acid oligomers and polymers (Mw 500, 700, 1000, 2000, and 4500), as sole carbon and energy sources. Complete mineralization of acrylic acid monomer and dimer was observed in low-biomass sludge preparations previously exposed to the polymer mixture, based on carbon dioxide production and residual dissolved organic carbon analyses. Extensive (though incomplete) degradation was also observed for the low molecular weight acrylic acid oligomers (Mw 500 and 700), but degradation dropped off sharply for the 1000, 2000, and 4500 Mw polymers. Radiochemical (¹⁴C) data also confirmed the low degradation potential of the 1000, 2000, and 4500 Mw materials. Degradation of two commercial poly(ethylene glycol)s at 1000 and 3400 Mw was complete and comparable to that of the acrylic acid monomer and dimer. Our results indicate that mixed populations of activated sludge microorganisms can extensively metabolize acrylic acid oligomers of seven units or less. Complete mineralization, however, could be confirmed only for the monomer and dimer material, and carbon mass balance data suggested that the true molecular weight cutoff for complete biodegradation was significantly less than the 500–700 Mw range tested.     

Photodegradation and Biodegradation Study of a Starch and Poly(Lactic Acid) Coextruded Material

To simulate the behavior of agricultural mulch coextruded poly(lactic acid)(PLA)/starch films, two stages were carried out. The first was an ultraviolet treatment (UV) at 315 nm, during which glass transition temperature T_g, weight, and molecular weight (MW) decreased and a separation between PLA and starch phase was observed. For the second stage, the mineralization of the carbon of the material was followed using the ASTM (D 5209–92 and 5338–92) and ISO/CEN (14852 and 14855) standard procedures. To measure the biodegradability of polymer material, the assessment of the carbon balance allowed determination of the distribution between the carbon rate used to the biomass synthesis or the respiration process (released CO₂), as well as the dissolved organic carbon into the culture medium and the carbon in the residual insoluble material. The influence of the nature of the medium and the standardized procedures on the final rate of biodegradation was investigated. Whatever the standardized method, the biodegradation percentage was significantly stronger in liquid medium (92.4–93.4) than on inert medium (80–83%). In the case of the compost process, only released CO₂ was measured and corresponded to 79.1–80.3%.     

Biodegradable water-soluble polycarboxylic acid design: Biodegradability and builder performance in detergent formulation of partially dicarboxylated polyuronide containing sugar residues in the backbone

Partially dicarboxylated polyuronide having a variable amount of unreacted sugar blocks as an enzymatically cleavable segment was prepared by the controlled oxidation of pectic acid and alginic acid. It was found that partially dicarboxylated polyuronides containing uronide blocks showed better biodegradability than those having no uronide block in the polycarboxylate chain. The rate of biodegradation varies according to the degree of dicarboxylation. It was confirmed that dicarboxy polyuronides containing more than 70% unreacted uronide residues tended to biodegrade quickly. The biodegradability obtained by the BOD test and the enzymatic degradability are well correlated, suggesting that these polymers are first cleaved at the sugar blocks by carbohydrase with subsequent assimilation of the resultant oligomeric fractions. Detergency was dependent on the content of the carboxylate groups in the polymer. The polymers with high carboxylate contents showed better builder performance. The detergency of dicarboxy pectic acid was better than that of dicarboxy alginic acid when compared on the basis of an equal degree of dicarboxylation.     

The basic properties of poly(lactic acid) produced by the direct condensation polymerization of lactic acid

Poly(lactic acids) with high molecular weights have been synthesized by direct condensation polymerization of lactic acid. These polymers have good mechanical properties and can be processed into products such as cups, film, and fiber, which can be used as compostable materials. This polymerization method can be applied to the synthesis of copolymers of lactic acid and other hydroxyacids. The properties of poly(lactic acid) and copolymers synthesized by the direct process are different from those of polymers obtained by the conventional lactide process.     

Anaerobic Biodegradation of Poly (Lactic Acid) Film in Anaerobic Sludge

The anaerobic biodegradation rates of four different sizes of poly (lactic acid) (PLA) films (thickness 25???m) in anaerobic sludge at 55?°C were examined. The anaerobic biodegradation rates of small pieces of PLA film were slower than for large pieces of PLA film. We also examined whether PLA film could also be used as a reference material in the anaerobic biodegradation test in addition to PLA powder. The anaerobic biodegradation rate of PLA film became slower with lower activity sludge, but the rate of decrease was gradual, and the anaerobic biodegradation rate of PLA film was faster than the PLA powder (125?C250???m). The anaerobic biodegradation rate of the PLA powder (125?C250???m) reflected the plastic anaerobic biodegradation activity of the sludge more accurately than the thin PLA film (thickness 25???m). Consequently, PLA powder (125?C250???m) is more suitable than thin PLA film (thickness?<?25???m) for use as a reference material to assess the plastic anaerobic biodegradation activity of the sludge in an anaerobic biodegradation test at 55?°C.     

Synthesis, Characterization, and Hydrolytic Degradation of Copolymers of 2-Methylene-1,3-dioxepane with Ethylene and with Styrene

2-Methylene-1,3-dioxepane (MDP) was copolymerized with ethylene (E) at a pressure of approximately 1000 psi and a temperature of approximately 70°C with AIBN as the free radical initiator. The copolymers obtained, poly(MDP-co-E), were characterized by elemental analysis, IR, ¹H-NMR and ¹³C-NMR spectroscopy, DSC, and GPC. The copolymers contained 2–15 mol% ester units. MDP was also copolymerized with styrene (S) at 120°C with di-t-butyl peroxide as the initiator to prepare the copolymer, poly(MDP-co-S). The number-average molecular weights of both types of copolymers were in the range of 6000 to 11,000, and the weight-average molecular weights were in the range of 9000 to 17,000. The melting temperatures of poly(MDP-co-E) decreased with increasing ester unit content in the copolymer. For the MDP-S copolymers, the glass transition temperatures decreased with increasing ester unit content. Both poly(MDP-co-E) and poly(MDP-co-S) were degraded by methanolysis, and their molecular weights decreased by the expected amounts based on the ester unit content.     

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.     

Effects of Diisocyanate and Polymeric Epoxidized Chain Extenders on the Properties of Recycled Poly(Lactic Acid)

Increasing demand in the use of poly(lactic acid) (PLA) leads to a debate about using potential foodstuffs for plastic production and a moral issue when starvation problem is taken into account. One of the solutions is recycling of PLA; however, recycling results in property losses during melt processing due to low thermal stability of PLA. This study focuses on using chain extenders to offset thermal degradation of recycled PLA. The effects of a diisocyanate and a polymeric epoxidized chain extender on the properties of the recycled poly(lactic acid) were investigated. In order to mimic the recycling process, PLA was subjected to thermo-mechanical degradation using a laboratory scale compounder. Chain extender type, loading and mixing time were investigated. On-line rheology and intrinsic viscosity measurements of PLA before and after chain extension confirmed that the molecular weight increased. Dynamic mechanical analysis, rheology and tensile tests revealed that the chain extenders led to a significant increase in modulus, strength and melt-viscosity. It was found that diisocyanate had slightly higher and faster chain extension reactivity than polymeric extender. Differential scanning calorimetry results showed an increase in the crystallization temperature due to the branched and extended chain structure.     

Processability and Biodegradability Evaluation of Composites from Poly(butylene succinate) (PBS) Bioplastic and Biofuel Co-products from Ontario

This study investigates the processability and biodegradability of composite bioplastic materials. Biocomposites were processed using twin-screw compounding of the bioplastic poly(butylene succinate) (PBS) with bio-based fillers derived from co-products of biofuel production. An extensive biodegradability evaluation was conducted on each biocomposite material, as well as the base materials, using respirometric testing to analyze the conversion of organic carbon into carbon dioxide. This evaluation revealed that the presence of meal-based fillers in the biocomposites increased the rate of biodegradation of the matrix polymer, degrading at a faster pace than both the pure PBS polymer and the switchgrass (SG) composite. This degradation was further confirmed using FT-IR and thermal analysis of the material structure before and after biodegradation. The increased biodegradation rate is attributed to the high concentration of proteins in the meal-based composites, which enhanced the hydrolytic biodegradation of the material and facilitated micro-organism growth. The SG-based composite degraded slower than the pure polymer due to its lignin content, which degrades via a different mechanism than the polymer, and slowed the biodegradation process.     

Biodegradation Behaviors of Poly(p-dioxanone) in Different Environment Media

This work was aimed at researching the aerobic biodegradation of poly(p-dioxanone) (PPDO), a novel kind of degradable polymer material, by simulating real-life conditions in a laboratory-scale test, specified by the standard methods based on two biodegradation environments, composting and aqueous media. To measure and describe the biodegradability of PPDO, not only had carbon dioxide produced by respiratory metabolism of microorganism been measured, which determines the ultimate aerobic biodegradability of chemical compounds, but also the detailed results of biodegradation were further characterized by monitoring physical, chemical and thermal properties changes of test materials at different incubation times in the two media, confirmed by using the appropriate analytical techniques. Scanning electron microscopy was used to observe the surface morphology, and the thermal performance of PPDO was characterized by differential scanning calorimetry. The changes of molecular weight were detected by intrinsic viscosity ([η]) and gel permeation chromatography, and the variations of the molecular structure were monitored by the nuclear magnetic resonance and FT-IR. The results show that PPDO has outstanding character of biodegradation and may be more adapted for biodegrading in liquid medium than in composting.     

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.     

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.     

The Effect of Composite Nucleating Agent on the Crystallization Behavior of Branched Poly (Lactic Acid)

Composite nucleating agent (CNA) consisting of zinc oxide as a crystallization promoter and phenylphosphonic acid zinc salt (PPZn) as an heterogeneous nucleation agent was employed to improve the crystallization behaviors of branched poly (lactic acid) (B-PLA) which was prepared by use of multi-functional epoxy-based chain extender (CE). The differential scanning calorimeter results showed that the crystallinity and crystallization temperature of prepared B-PLA/CNA were higher than that of linear poly (lactic acid) (L-PLA) and B-PLA at a high cooling rate. The corresponding phenomena of heterogeneous nucleation of B-PLA/CNA were observed by means of polarized optical microscope. The crystalline mechanism research results show that the degradation reaction and chain extending reaction were occurred simultaneously after the addition of CE and CNA into the PLA, PPZn as an effective nucleation points could increase the nucleation density and the degraded short molecular chains with higher chain mobility would improve crystal growth during the crystallization of the branched PLA. Non-isothermal cold crystallization kinetics of various B-PLA with different content of CNA was studied. The corresponding result showed that the crystallinity and crystallization rate increased obviously with the CNA content greater than or equal to 5phr, as well as the crystallization time decreased. The similar experimental results of non-isothermal and isothermal melt crystallization kinetics also showed that CNA had a significant impact on crystallization behavior of B-PLA.     

Thermal and Rheological Properties of Commercial-Grade Poly(Lactic Acid)s

Poly(lactic acid) is the subject of considerable commercial development by a variety of organizations around the world. In this work, the thermal and rheological properties of two commercial-grade poly(lactic acid)s (PLAs) are investigated. A comparison of the commercial samples to a series of well-defined linear and star architecture PLAs provides considerable insight into their flow properties. Such insights are valuable in deciding processing strategies for these newly emerging, commercially significant, biodegradable plastics. Both a branched and linear grade of PLA are investigated. The crystallization kinetics of the branched polymer are inferred to be faster than the linear analog. Longer relaxation times in the terminal region for the branched material compared to the linear material manifests itself as a higher zero shear rate viscosity. However, the branched material shear thins more strongly, resulting in a lower value of viscosity at high shear rates. Comparison of the linear viscoelastic spectra of the branched material with the spectra for star PLAs suggests that the branched architecture is characterized by a span molecular weight of approximately 63,000 g/mol. The present study conclusively demonstrates that a wide spectrum of flow properties are available through simple architectural modification of PLA, thus allowing the utilization of this important degradable thermoplastic in a variety of processing operations.     

Degradation in an Inert Solid Medium of Poly(Lactic Acid) Polymeric Material by Kibdelosporangium aridum

The aim of this work was to estimate the biodegradation of a poly(lactic acid) polymeric material by the actinomycetes Kibdelosporangium aridum using a vermiculite based inert solid medium which could simulate compost medium and enable us to achieve complete carbon balances. The mineralisation rate at the end of the test was compared to those obtained for two basal media. It was shown that cumulative mineralisation after 45 days of degradation was greater (70%) in vermiculite with a basal medium containing gelatin than in vermiculite with a basal medium containing glucose (20%).     

Molecular Structure and Crystallization Dynamics of Poly(3-hydroxyl alkanoate) with Medium-Chain Length Biosynthesized from <Emphasis Type="Italic">Pseudomonas putida</Emphasis>

The molecular structure of poly(3-hydroxyalkanoate) (P3HA) with medium-chain length, biosynthesized from Psuedomonas putida (P. putida), was investigated by thermal analysis, X-ray diffraction, and infrared spectrum. Cultivation in a medium of nonanoic acid and a mixed substrate of nonanoic acid and glycerin as carbon sources provided P3HA with monomer units of 7 and 9 carbons (P3HA_n) and 5, 6, 7, 8, 9, and 10 carbons (P3HA_mix). Since these P3HA has comparatively long side chains, the crystallinity was as low as about 10%. It was suggested that the hydrogen bonding plays an important role in constructing the crystal. The lamellar thickness was 1.20 nm, estimated from the melting temperature depression. This lamellar thickness corresponds to two repeating units. Crystallinity depending on time was observed by the CO stretching mode in the infrared spectrum, and then Avrami’s theory was applied to analyze the crystallization mechanism. The crystallization rate of P3HA_n was very low, on the order of a few hours. An Avrami exponent of 1.45 was estimated from the slope of the Avrami plot. This shows that the conformational arrangement is presumably promoted along the chain axis. The slow crystallization is attributed to the long side chain, which prevents aggregation of the polymer chains.     

Soybean Oil-Based Photo-Crosslinked Polymer Networks

Novel soybean oil-based crosslinked polymer networks were prepared by UV photopolymerization and their mechanical properties were evaluated. Poly(ethylene glycol) diacrylate (PEGDA) and biodegradable poly(ε-caprolactone) diacrylate (PCLDA) were synthesized and used as crosslinking agent to form crosslinked polymer networks by UV-initiated free-radical polymerization with acrylated epoxidized soybean oil (AESO). The synthesis of acrylate end-capped macromers was confirmed using FT-IR and ¹H NMR spectroscopic techniques. Photopolymerization time, the composition of reaction mixture, and the type and length of crosslinking agent were changed to obtain crosslinked polymer networks with various mechanical properties. Polymers prepared from AESO and PCL degraded 6% of the initial weight in 24 days in phosphate buffer solution (pH 7.2) containing lipase enzyme. These potentially biodegradable and biocompatible polymers can be used as ecofriendly materials for biomedical and other applications to replace the existing petroleum-based polymers currently used.     

Studies of Novel Chain Linked Biodegradable Polymers

The synthesis of high-molecular-weight lactic acid based polymers by chain linked polymerization was investigated. Lactic acid based hydroxyl terminated telechelic prepolymer was synthesized and then the molecular weight was increased by chain linked polymerization using methylene diphenyldiisocyanate. All polymerizations were carried out in the melt, using tin octoate as catalyst. The products were characterized by Differential scanning calorimetry, nuclear magnetic resonance spectroscopy and size exclusion chromatography. With the increase in diisocyanate concentration, an increase in the glass transition temperature, molecular weight and molecular weight distribution was observed.