Biodegradable Poly(butylene succinate) and Poly(butylene adipate-co-terephthalate) Blends: Reactive Extrusion and Performance Evaluation

Two biodegradable polyesters, poly(butylene adipate-co-terephthalate) (PBAT) and poly(butylene succinate) (PBS) were melt-compounded in a twin screw extruder to fabricate a novel PBS/PBAT blend. The compatibility of the blend was attributed to the transesterification reaction that was confirmed by Fourier transform infrared spectroscopy. The Gibbs free energy equation was applied to explain the miscibility of the resulting blend. Dynamic mechanical analysis of the blends exhibits an intermediate tanδ peak compared to the individual components which suggests that the blend achieved compatibility. One of the key findings is that the tensile strength of the optimized blend is higher than each of the blended partner. Rheological properties revealed a strong shear-thinning tendency of the blend by the addition of PBAT into PBS. The phase morphology of the blends was observed through scanning electron microscopy, which revealed that phase separation occurred in the blends. The spherulite growth in the blends was highly influenced by the crystallization temperature and composition. In addition, the presence of a dispersed amorphous phase was found to be a hindrance to the spherulite growth, which was confirmed by polarizing optical microscopy. Furthermore, the increased crystallization ability of PBAT in the blend systems gives the blend a balanced thermal resistance property.     

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.     

Miscibility and Biodegradability of Poly(Butylene Succinate)/Poly(Butylene Terephthalate) Blends

As one of the biodegradable polymers, the blend of poly(butylene succinate) and poly(butylene terephthalate) is dealt with in this study. In our previous work, it was demonstrated that PBS and PBT are immiscible not only from the changes of T _g but also from logG–log G plots. It is expected that the biodegradability of the blends could be improved by enhancing the miscibility. We tried to induce the transesterification reaction between two polyesters with various time intervals to enhance the miscibility of the blends. The extent of transesterification reaction was examined by ¹H-NMR. We utilized a dynamic mechanical thermal analyzer and a rotational rheometer to investigate the changes in miscibility. We also verified the biodegradability of PBS/PBT blends after the transesterification reaction by the composting method.     

Biodegradable Compatibilized Poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactide)/Thermoplastic Polyurethane Blends: Design,Preparation and Property Testing

Biodegradable blends of poly(l-lactide) (PLL) toughened with a polycaprolactone-based thermoplastic polyurethane (TPU) elastomer and compatibilized with a purpose-designed poly(l-lactide-co-caprolactone) (PLLCL) copolymer were prepared. Both 2-component (PLL/TPU) and 3-component (PLL/TPU/PLLCL) blends of various compositions were prepared by melt mixing, hot-pressed into thin films and their properties tested. The results showed that, although the TPU could toughen the PLL, the blends were immiscible leading to phase separation with the TPU domains distributed in the PLL matrix. However, addition of the PLLCL copolymer could partially compatibilize the blend by improving the interfacial adhesion between the two phases. Biodegradability testing showed that the blends were biodegradable and that the PLLCL copolymer could increase the rate of biodegradation under controlled composting conditions. The 3-component blend of composition PLL/TPU/PLLCL?=?90/10/10 parts by weight was found to exhibit the best all-round properties.     

Preparation and Properties of Biodegradable Poly(lactic acid)/Poly(butylene adipate-co-terephthalate) Blend with Epoxy-Functional Styrene Acrylic Copolymer as Reactive Agent

Poly (lactic acid) (PLA) and poly (butylene adipate-co-terephthalate) (PBAT) are biodegradable polyesters and can be blended by twin-screw extrusion. Epoxy-functional styrene acrylic copolymer (ESA) was used as reactive agent for PLA/PBAT blends and the mechanical properties, phase morphology, thermal properties, melt properties, and melt rheological behaviors of the blends were investigated. During thermal extrusion, ESA was mainly a chain extender for the PLA matrix but had no evident reaction with PBAT. The great improvement in the toughness of PLA based blends was achieved by the addition of PBAT of no less than 15 wt% and that of ESA of no more than 0.5 wt%. Although SEM micrographs and the reduced deviation of the terminal slope of G′ and G″ indicated better compatibility and adhesion between the two phases, the blend with ESA was still a two-phase system as indicated in DSC curves. Rheological results reveal that the addition of ESA increased the storage modulus (G′), loss modulus (G″) and complex viscosity of the blend at nearly all frequencies. The melt strength and melt elasticity of the blend are improved by addition of ESA.     

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.     

Biodegradability and Mechanical Properties of Poly(vinyl alcohol)-Based Blend Plastics Prepared Through Extrusion Method

Plastic blend materials consisting of poly(vinyl alcohol), glycerol and xanthan or gellan were prepared through laboratory extrusion. Their base mechanical properties were compared with the properties of poly(vinyl alcohol) foil and their biodegradability in soil, compost and both activated and anaerobic sludge were assessed. In samples with lower polysaccharide content (10–21 %w/w) the tensile strength of 15–20 MPa was found; the elongation at break of all blends was relatively close to the parameter of poly(vinyl alcohol) foil. The biodegradability levels of the blends tested corresponded to the content of natural components, and the mineralization of the samples with the highest carbohydrate proportion (42 %) reached 50–78 %, depending on the type of the environment. Complete biodegradation of all samples occurred in activated sludge.     

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.     

Modification of Aliphatic Polyesters and Their Reactive Blends with Starch

Modified polycaprolactone was synthesized by melt reaction of PCL and reactive monomers such as glycidyl methacrylate (GMA) and maleic anhydride (MAH) in the presence of benzoyl peroxide in Brabender mixer. MAH showed a different grafting phenomenon compared to GMA. The reaction mechanism was discussed with different reactive monomers. Reactive blends of the PCL-g-GMA and the gelatinized starch with glycerin were prepared and their mechanical properties and biodegradabilities were investigated. Reactive blends of PCL-g-GMA and starch showed well-dispersed starch domain in the matrix and better mechanical strength than the unmodified PCL/starch blend. However, the reaction between PCL-g-GMA and starch induced a crosslinking during the reactive blending and this crosslinking in the blend lowered the biodegradation of the blend during the composting test. The biodegradability was investigated by the weight loss and surface morphology change of the blend in the composting medium.     

Influence of Technological Process on Biodegradation of PVA/Waxy Starch Blends in an Aerobic and Anaerobic Environment

Improving biodegradability of PVA/starch blends is a reality already documented by a number of works. Admittedly, mechanical properties of products (for example, tensile strength) are somewhat worse, but suitable composition optimizing or chemical modifying of starch may eliminate the problem to a large degree. This work is an attempt to find another potential effect influencing biodegradability, that of technological procedure for producing films from these blends on an extruder. The procedure with a so-called pre-extrusion step (two-stage) and dry-blend (single-stage) produced blends of slightest differences in achieved biodegradability (virtually within limits of experimental error) in aerobic (76 vs. 79%) as well as anaerobic breakdown (48 vs. 52%). Conversely, morphological analysis exhibited superior homogeneity of films prepared by the two-stage process; their tensile strength was also higher.     

Effect of Ionizing Radiation on the Morphological,Thermal and Mechanical Properties of Polyvinyl Alcohol/Polyethylene Glycol Blends

Blends of water—soluble polymers based on Poly vinyl alcohol (PVA) and Polyethylene glycol (PEG) have been prepared by the solution casting technique. The effect of various doses of γ-radiation on the structural properties of PVA/PEG polymer blends with all its compositions has been investigated. From the visual observation of all the blend compositions, it was found that, the best compatibility of the blend is up to 40% PVA/60%PEG. The structure–Property behavior of all the prepared blends before and after γ-irradiation was investigated by IR Spectroscopy, thermogravimetric analysis (TGA), mechanical properties and Scanning electron microscope (SEM). The gel content and the swelling behavior of the PVA/PEG blends were investigated. It was found that the gel content increases with increasing irradiation dose and PVA concentration in the blend. Swelling percent increased as the composition of PEG increased in the blend. The results obtained by FTIR analysis and SEM confirm the existence of possible interaction between PVA and PEG homopolymers. TGA of PVA/PEG blend, before and after γ-irradiation, showed that the unirradiated and irradiated PVA/PEG blends are more stable against thermal decomposition than pure PVA. Improvement in tensile mechanical properties of PVA/PEG blends was occurred.     

Effects of Compatibilizer and Thermoplastic Starch (TPS) Concentration on Morphological,Rheological, Tensile,Thermal and Moisture Sorption Properties of Plasticized Polylactic Acid/TPS Blends

The blends of polylactic acid plasticized with acetyl tributyl citrate (P-PLA) and thermoplastic wheat starch (TPS) were prepared by a co-rotating twin screw extruder and the effect of maleic anhydride grafted PLA (PLA-g-MA) content as reactive compatibilizer on blends compatibility through morphological, rheological and tensile properties of the blends was investigated. Considerable improvement in properties of P-PLA/TPS (70/30 w/w) blend with incorporating the optimum PLA-g-MA content of 4 phr was achieved as this blend exhibited better morphological and rheological properties with an increase by 158 and 276% in tensile strength and elongation at break, respectively, compared to the uncompatibilized blend. Also the thermal stability and moisture sorption properties of the blends as effected by TPS content were studied. Decreasing in thermal stability and increasing in equilibrium moisture content of the blends were observed with progressively increasing of TPS content. For prediction the moisture sorption behaviour of blends with various TPS contents at different relative humidity, the moisture sorption isotherm data were modeled by GAB (Guggenheim–Anderson–de Boer) model.     

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

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

Processing and Thermal Behaviors of Poly (Butylene Succinate) Blends with Highly-Filled Starch and Glycerol

Fully-biodegradable and highly-filled thermoplastic starch plasticized with glycerol (GTPS)/poly (butylene succinate) (PBS) blends were prepared by Haake Mixer. Processing properties, thermal behaviors including melting and crystallization behavior, crystal structure, and compatibility of the blends were investigated using differential scanning calorimeter (DSC), wide angle X-ray diffractometer (WAXD), scanning electron microscopy (SEM) and dynamic mechanical analysis (DMA). The maximum and equilibrium torques decreased with the rising of glycerol contents and the dropping of PBS contents. GTPS30/PBS blends exhibited double melting endothermic peaks in the DSC thermograms, which related to the crystallization behavior and compatibility of the blends, but no double peaks for GTPS40/PBS. The addition of starch and glycerol could lead to higher crystallinity and lower crystallization rate of PBS, but would not change the crystal types and crystallite sizes of PBS according to DSC and WAXD analysis. SEM and DMA results gave the evidence to confirm the better compatibility of GTPS40/PBS. Besides, higher storage modulus in glassy state of GTPS/PBS blends than PBS could be seen from DMA analysis, which was the contrary in rubbery state.     

Starch, Poly(lactic acid), and Poly(vinyl alcohol) Blends

Research on biodegradable materials has been stimulated due to concern regarding the persistence of plastic wastes. Blending starch with poly(lactic acid) (PLA) is one of the most promising efforts because starch is an abundant and cheap biopolymer and PLA is biodegradable with good mechanical properties. Poly(vinyl alcohol) (PVOH) contains unhydrolytic residual groups of poly(vinyl acetate) and also has good compatibility with starch. It was added to a starch and PLA blend (50:50, w/w) to enhance compatibility and improve mechanical properties. PVOH (M_W 6,000) at 10%, 20%, 30%, 40%, 50% (by weight) based on the total weight of starch and PLA, and 30% PVOH at various molecular weights (M_W 6,000, 25,000, 78,000, and 125,000 dalton) were added to starch/PLA blends. PVOH interacted with starch. At proportions greater than 30%, PVOH form a continuous phase with starch. Tensile strength of the starch/PLA blends increased as PVOH concentration increased up to 40% and decreased as PVOH molecular weight increased. The increasing molecular weight of PVOH slightly affected water absorption, but increasing PVOH concentration to 40% or 50% increased water absorption. Effects of moisture content on the starch/PLA/PVOH blend also were explored. The blend containing gelatinized starch had higher tensile strength. However, gelatinized starch also resulted in increased water absorption.     

Physical properties and biodegradability of blends containing poly(ε-caprolactone) and tropical starches

In order to assess feasibility of tropical starches (sago and cassava starches) as biodegradable plastic materials, blending with poly(-caprolactone) (PCL), a biodegradable polymer, was carried out. It was confirmed that the physical properties (tensile strength and elongation) of PCL/sago and PCL/cassava blends were similar to those of PCL/corn blend, suggesting that sago and cassava starches can also be blended with PCL for production of biodegradable plastic. However, the properties of all PCL/starch blends were still low compared with those of polyethylene. Enzymatic degradability evaluation showed that lipase degradation of PCL and-amylase degradation of starch increased as the starch content in the blend increased. Burial test of the blends for 1, 3, and 5 months was carried out and the rate of degradation of the PCL/sago blend was confirmed to be slower than those of PCL/corn and PCL/cassava blends. Observation of the film blends structure by scanning electron microscope revealed that the starch was dispersed in a PCL continuous phase. Furthermore, changes in the film surface before and after enyzme treatments were observed.     

A Novel Packaging Film from Cassava Starch and Natural Rubber

Currently, there is an environmental pollution problem generated in part by packaging materials produced from non-biodegradable synthetic polymers made from petroleum. However, these can be replaced with biodegradable materials made from cassava starch (CS) and natural rubber (NR). In the work described, a novel biopolymer film was obtained from the CS and NR using glycerol (GE) as a plasticizer in a water-based system. The physical properties of an 95/5 CS/NR blend films with the addition of NR and with varying GE contents were studied based on their swelling ratio, moisture content, moisture absorption, mechanical properties and biodegradability in soil. The results showed that the moisture content and moisture absorption tended to be directly proportional to the GE content, while the moisture content and moisture absorption of the sample decreased as a function of the NR content. The swelling ratio of the 95/5 CS/NR blend slightly decreased as a function of the NR and GE content. Surprisingly, the best swelling ratio of 350% was found at 10% NR. The elongation at break of the CS/NR blend was improved by the addition of GE. The contact angle of the 95/5 CS/NR blend decreased as a function of the GE. With increased NR in the composite, an increasing, trend in the contact angle was found. Further, the 95/5 CS/NR blend exhibited good transparency when it was applied as a coating to delay the ripening of bananas, the results were positive. Moreover, the film showed decomposition well in natural soil.     

Aromatic/Aliphatic Polyester Blends

Blends of poly(3-hydroxybutyrate) (PHB) and poly(ethylene terephthalate-co-1,4-cyclohexenedimethanol terephthalate) (PETG) were prepared in a batch mixer and in a twin screw extruder and characterized by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), field emission scanning electron microscopy (FE SEM), flexural tests, biodegradation tests in soil compost and in an enzymatic medium. The torque data showed that the addition of PETG to PHB improved its processability. DSC, DMA and FE SEM showed that the polymers are immiscible with morphology dependent on the processing conditions. A fine dispersion of PETG in the PHB matrix was observed for extruded and injection molded blends. Flexural modulus for blends was higher for blends in comparison with PHB, while the impact resistance of blends containing 20 wt% and 30 wt% of PETG is comparable to the value for PHB. PHB is biodegradable, while PETG did not degrade either in simulated soil or in the α-amylase medium. On the other hand, the PHB phase of the blends degrades under these aging conditions. Thus, the addition of PETG to PHB results in advantage such as improving of processability and Young′s modulus without significant changes in the impact resistance while keeping the biodegradability of PHB.     

Biodegradation of Polylactide and Gelatinized Starch Blend Films Under Controlled Soil Burial Conditions

The biodegradability of polylactide (PLA) and gelatinized starches (GS) blend films in the presence of compatibilizer was investigated under controlled soil burial conditions. Various contents (0–40 wt%) of corn and tapioca starches were added as fillers; whereas, different amounts of methylenediphenyl diisocyanate (MDI) (0–2.5 wt%) and 10 wt% based on PLA content of polyethylene glycol 400 (PEG400) were used as a compatibilizer and a plasticizer, respectively. The biodegradation process was followed by measuring changes in the physical appearance, weight loss, morphological studies, and tensile properties of the blend films. The results showed that the presence of small amount of MDI significantly increased the tensile properties of the blends compared with the uncompatibilized blends. This is attributed to an improvement of the interfacial interaction between PLA and GS phases, as evidenced by the morphological results. For soil burial testing, PLA/GS films with lower levels (1.25 wt%) of MDI had less degradation; in contrast, at high level of MDI, their changes of physical appearance and weight loss tended to increase. These effects are in agreement with their water absorption results. Furthermore, biodegradation rates of the films were enhanced with increasing starch contents, while mechanical performances were decreased.     

Utilization of Waste Lignin and Hydrolysate From Chromium Tanned Waste in Blends of Hot-Melt Extruded PVA-Starch

The demand for biodegradable plastic material is increasing worldwide. However, the cost remains high in comparison with common forms of plastic. Requirements comprise low cost, good UV-stability and mechanical properties, as well as solubility and water uptake lead to the preparation of multi-component polymer blends based on polyvinyl alcohol and starch in combination with waste products that are hard to utilize—waste lignin and hydrolysate extracted from chromium tanned waste. Surprisingly the addition of such waste products into PVA gives rise to blends with better biodegradability than commercial PVA in an aquatic aerobic environment with non-adapted activated sludge. These blends also exhibited greater solubility in the water and UV stability than commercial PVA. Tests on the processing properties of the blends (melt flow index, tensile strength and elongation at break of the films) as well as their mechanical properties showed that materials based on these blends might be applied in agriculture (for example as the systems for controlled-release pesticide or fertilizer) and, somewhat, in the packaging sector.