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.     

Effect of Poly(l-Lactide) and Poly(Butylene Succinate) on the Growth of Red Pepper and Tomato

Seeds of red pepper and tomato were sowed and cultivated in a soil blended with powdery poly(l-lactide) (PLLA), and poly(butylene succinate) (PBS). PBS depressed the growth of the two plants significantly even at a concentration as low as 5%, whereas PLLA up to 35% affected negligibly or even boosted the growth of the two plants. pH and number of microbial cells in the soil after 80 days of cultivation were almost the same independently whether the soil was blended with the two polymers or not. In contrast, the molecular weight of PBS decreased much faster than that of PLLA. Because succinic acid and 1,4-butane diol, from which PBS was synthesized, exhibited toxicity to both plant and animal cells to retard the germination rate of young radish seeds and to deform the morphology of HeLa cells significantly [1], the monomers and the oligomers produced from the PBS degradation should have a detrimental influence on the growth of the two plants.     

Effect of Crystalline and Amorphous Structures on Biodegradability of Poly(Tetramethylene Succinate)

The effect of orientation in the amorphous and crystalline regions on the biodegradability of PTMS [poly(tetramethylene succinate)] was studied using the amorphous orientation function, birefringence, and crystallinity. The crystalline and amorphous intrinsic lateral sonic moduli, E _t,c ⁰ and E _t,am ⁰ , were 2.61 × 10³ and 0.41 × 10³ MPa, respectively. Using the data on birefringence, crystalline and amorphous orientation function (f and f _am), crystallinity, and sonic modulus of the oriented PTMS fibers, the intrinsic birefringence of the crystalline ( _c ⁰ ) and amorphous ( _am ⁰ ) regions were evaluated to be 0.0561 and 0.0634, respectively. The biodegradabilities of oriented PTMS films were reduced as the elongation increased, i.e., the amorphous orientation increased. At low elongation (100 and 150%), however, biodegradabilities remained unchanged when the degradation test was performed in activated sludge, which was attributed to the amorphous orientation occurring even at 100% elongation, though the amorphous orientation direction was perpendicular to the fiber axis.     

Synthesis of a block copolymer of poly(3-hydroxybutyrate) and poly(ethylene glycol) and its application to biodegradable polymer blends

A block copolymer {P[(R,S)-HB-b-EG]} of atactic poly[(R,S)-3-hydroxybutyrate] {P[(R,S)-HB]} and poly(ethylene glycol) (PEG) was prepared by the ring-opening polymerization of -butyrolactone in the presence of a macroinitiator (PEG/ZnEt₂/H₂O) which had been produced by the reaction of ,-dihydroxy PEG ( _n=3000) with ZnEt₂/H₂O (1/0.6) catalyst. The block copolymer ( _n=10,500, _w/ _n=1.2) was an A-B-A triblock copolymer comprising atactic P[(R,S)-HB] (A) and PEG (B) segments. The miscibility, physical properties, and biodegradability of binary blends of microbial poly[(R)-3-hydroxybutyrate] {P[(R)-HB]} with the block copolymer P[(R,S)-HB-b-EG] has been studied. The glass-transition temperature (T _g) data showed that the P[(R)-HB]/P[(R,S)-HB-b-EG] blend was miscible in the amorphous state. The P[(R)-HB] film became flexible and tough by means of blending with P[(R,S)-HB-b-EG] block copolymer. The enzymatic degradation of blend films was carried out at 37°C and pH 7.4 in a 0.1M phosphate solution of an extracellular PHB depolymerase fromAlcaligenes faecalis. The enzymatic degradation took place solely on the surface of the blend films.     

Radiation Crosslinking of Poly(Butylene Succinate) in the Presence of Inorganic Material and Its Biodegradability

Three kinds of poly(butylene succinate)s (PBS) with different molecular weight were irradiated with electron beams in the presence of inorganic material. Fourteen kinds of inorganic materials were used in this work. The presence of inorganic material inside cross-linked PBS samples enhances the yield of gel formation. The heat stabilities of PBS samples were checked; it was found that silicon dioxide and carbon black significantly improve these properties. Enzymatic and soil burial tests were performed; the presence of these inorganic materials in cross-linked PBS accelerates the rate of biodegradation.     

Synthesis and environmental degradation of polyesters based on poly (ε-caprolactone)

Poly (-caprolactone) (PCL), poly (-valerolactone) (PVL), poly (-caprolactone-co--valerolactone) [P(CL-co-VL)], and poly (-caprolactone-co-ethylene oxide-co--caprolactone) (PCL-PEO-PCL) were synthesized by ring-opening and diol-initiated polymerization of -caprolactone and -valerolactone. The degradation of the samples by chemical hydrolysis and in a soil burial test was evaluated. It was found that PCL, PVL, and P(CL-co-VL) degrade mainly enzymatically. The rate of degradation depends on their molecular weight, chemical structure, composition, and morphology. PCL-PEO-PCL block copolymers exhibit a repelling effect to the microorganisms in the soil, which depends on the molecular weight and relative amount of PEO block in the copolymer.     

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.     

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.     

Evaluation of biodegradability of poly(ε-caprolactone)/poly(ethylene terephthalate) blends

The results of an investigation aimed at evaluation of the biodegradability of blends of poly(-caprolactone) (PCL) with poly(ethylene terephthalate) (PET) as the major component are reported. Specimens of the blends, as melt extruded films and/or powders, were submitted to degradation tests under different environmental conditions including full-scale composting, soil burial, bench-scale accelerated aerobic degradation, and exposure to axenic cultures and esterolytic enzymes. Indications have been gained that blending in the melt gives rise to insertion of PCL segments in the PET chain. Copolymers thus attained acted as macromolecular compatibilizers, allowing for a complete miscibility of PCL and PET. The biodegradation detected on the blend samples was, however, well below the values expected from chemical composition and behavior of individual homopolymers under the same environmental conditions. The presence of PET as the major component in PET/PCL blends apparently reduces the propensity of PCL to be degraded, at least in the investigated composition range. The degradation data collected under different environmental conditions indicate that the full-scale composting system is the most efficient among the tested degradation procedures.     

A carbon-13 method for evaluating degradation of starch-based polymers

A new method for evaluating biodegradability of starch-based and certain other polymer blends uses the pre- and postexposure stable carbon isotope composition of material coupled with weight loss data to determine which components have degraded. The naturally occurring stable isotope of carbon.¹³C, is enriched in corn starch (¹³C, approx. –11) compared to petroleum-derived synthetic polymers (¹³C, approx. –32). Results on starch-synthetic polymer blends indicate that the ¹³C signatures of these blends are near-linear mixtures of their component ¹³C. Values of a ¹³C for starch-synthetic polymer blends exposed to biologically active laboratory soil and artificial seawater conditions are depleted in¹³C compared to unexposed samples, suggesting loss of the starch component. Combined with weight loss data for the exposed samples, the ¹³C values are statistically consistent with models requiring loss of the soluble component glycerin, followed by loss of starch, then petrochemical polymer, or simultaneous loss of starch and petrochemical polymer. Replicate ¹³C analyses of starch-synthetic polymer blends increase the statistical power of this relatively inexpensive, accessible technique to discriminate between degrading components.     

The degradation of gel-spun poly(β-hydroxybutyrate) “wool”

The apparent biodegradability and biocompatibility of the microbially produced polyester, poly(-hydroxybutyrate) (PHB), has been the focus of much research by a number of authors with regard to its potential for use in packaging and medical implantation devices. PHB has recently been produced by gel-spinning into a novel form, with one possible application being as a wound scaffolding device, designed to support and protect a wound against further damage while promoting healing by encouraging cellular growth on and within the device from the wound surface. This new nonwoven form combines a large volume with a low mass, has an appearance similar to that of cotton wool, and has been called wool because of this similarity. The hydrolytic degradation of this wool was investigated in an accelerated model of pH 10.6 and temperature 70°C. It was determined that the PHB wool gradually collapsed during degradation. The surface area-to-volume ratio was concluded to be a primary influencing factor. Degradation was characterized by a reduction in the glass transition temperatures and melting points and a fusion enthalpy peak of maximum crystallinity, (88%), which coincided with the point of matrix collapse.     

Novel synthesis blends between bacterial polyesters and acrylic rubber: A study on enzymatic biodegradation

The biodegradability of a multicomponent system based on biotechnological occurring polyester (poly(-hydroxybutyrate-co--hydroxyvalerate) (PHBV)) with inclusion of acrylate elastomer (polybutylacrylate) (PBA) was investigated. A bacterium which produced extracellular enzymes that degrades PHBV even when blended with PBA was isolated and tentatively designated asAureobacterium saperdae. It was observed, by morphological investigation, that, while the bacterial degradation was permitted for PBA content of 20% by weight, it was inhibited for PBA content of 30%, owing to the occurrence of a rubbery layer that prevents to the bacteria an easy accessibility in the PHBV-rich regions. In fact, owing the bacterial growth, only PHBV was metabolized, whereas no degradation of PBA was detected for blend samples. It was confirmed that the degradation proceeded via surface erosion of PHBV also in the blends. Finally, mechanical tests on PHBV/PBA specimens as a function of degradation extent have shown different behavior of the blends at different the PBA content. Thermal analysis of blends and PHBV has been reported, too     

In Vitro Biodegradation of Polyester-Based Plastic Materials by Selected Bacterial Cultures

A simple and rapid in vitro test was designed for the assessment of the biodegradation of polyester-based plastics by selected biodegrading bacterial strains. Variovorax paradoxus LMG 16137 was used for the degradation of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and Acidovorax avenae subsp. avenae LMG 17238 fo the synthetic-based polyesters poly(-caprolactone) (PCL), poly(butylene succinate-co-butylene adipate), and a starch-PCL blend. Degradation by the bacteria was studied in liquid medium with the plastics (films, granules, and injection-molded test bars) as sole sources of carbon. Degradation was followed through gravimetry, growth of the culture, and tensile testing. The effects of incubation time, inoculum density, aeration, incubation temperature, and pH of the medium on the mass loss were investigated and conditions optimized. The test allowed to obtain reproducible results on the mass loss of plastic samples in less than 3 weeks and yielded excellent partially degraded samples for further analysis.     

Degradation of poly(β-hydroxyalkanoates) and polyolefin blends in a municipal wastewater treatment facility

Six types of plastics and plastic blends, the latter composed at least partially of biodegradable material, were exposed to aerobically treated wastewater (activated sludge) to ascertain their biodegradability. In one study, duplicate samples of 6% starch in polypropylene, 12% starch in linear low-density polyethylene, 30% polycaprolactone in linear low-density polyethylene, and poly(-hydroxybutyrate-co-hydroxyvalerate) (PHB/V), a microbially produced polyester, were exposed to activated sludge for 5 months, and changes in mass, molecular weight average, and tensile properties were measured. None of the blended material showed any sign of degradation. PHB/V, however, showed a considerable loss of mass and a significant loss of tensile strength. In a second study, PHB/V degraded rapidly, but another type of microbial polymer which forms a thermoplastic elastomer, poly(-hydroxyoctanoate), did not degrade. These results illustrate the potential for disposal and degradation of PHB/V in municipal wastewater.     

Correlating the Spatial Distribution of Atmospheric Ammonia with δ15N Values at an Ammonia Release Site

A field ammonia (NH₃) release experiment and open top chambers containing moorland monoliths continuously fumigated with NH₃ or sprayed with NH₄Cl were used to assess the potential for using ¹⁵N values in determining the area of influence around a point NH₃ emission source. ¹⁵N values are being increasingly used as environmental tracers and we tested the hypothesis that the ¹⁵N signal from an NH₃ emission source is observable in nearby vegetation. Using modified monitoring devices, atmospheric NH₃ concentrations were found to decrease with distance from source, with ¹⁵N values also reflecting this trend, producing a signal shift with changing concentration. Open top chamber studies of ¹⁵N values of Calluna vulgaris (L.) Hull indicated a correlation with deposition treatments in current year shoots. Analysis of Calluna shoots from the NH₃ release showed a similar trend of ¹⁵N enrichment. Significant linear correlations between ¹⁵N and percent N in plant material were found, both in the controlled conditions of the open top chambers and at the NH₃ release site, illustrating the possible use of this technique in N deposition biomonitoring.     

Enzymatic Degradation of Cellulose-Based Materials

The biodegradability of cellulose-based materials was compared in the standard Sturm test and by enzymatic hydrolysis. Trichoderma reesei culture filtrate, the purified enzymes endoglucanase I and II from T. reesei, and -glucosidase from Aspergillus niger were used in the experiments. The unpurified Trichoderma reesei culture filtrate was found to contain a mixture of enzymes suitable for cellulose degradation. However, when purified enzymes were used the right balance of the individual enzymes was necessary. The addition of -glucosidase enhanced the enzymatic hydrolysis of cellulose materials when both culture filtrate and purified enzymes were used. In the Sturm test the biodegradability of most of the cellulose materials exceeded 70% carbon dioxide generation, but, in contrast, the biodegradability of the highly substituted aminated cellulose and cellulose acetate was below 10%. The results concerning enzymatic hydrolysis and biodegradability were in good agreement for kraft paper, sausage casing, aminated cellulose, and cellulose acetate. However, diverging results were obtained with cotton fabric, probably as a result of its high crystallinity.     

Synthesis of copolyesters containing poly(ethylene terephthalate) and poly(ε-caprolactone) units and their susceptibility toPseudomonas sp. lipase

Copolyesters containing poly(ethylene terephthalate) (PET) and poly(-caprolactone) (PCL) were synthesized from PET and PCL homopolymers by transesterification reaction at 270°C in the presence of catalyst. The copolyesters were characterized by¹³C-NMR and differential scanning calorimetry (DSC). The degradation behavior of PCL byPseudomonas sp. lipase in buffer solution (pH 7) and tetrahydrofuran (THF) was investigated by gel permeation chromatography (GPC) and¹H-NMR. From these experiments, it was found thatPseudomonas sp. lipase acted endoenzymatically on PCL. Using this lipase, degradation tests for PET/PCL copolyesters whose PCL content was below 50% by weight were also performed in buffer solution (pH 7). However, evenPseudomonas sp. lipase with high degradation activity on PCL did not easily degrade the PCL unit in PET/PCL copolyesters.     

Thermal and mechanical properties of poly(lactic Acid) and poly(ethylene/butylene Succinate) blends

In this study, blends of poly (lactic acid) (PLA) with poly(ethylene/butylene succinate) (Bionolle) have been investigated for their thermal and mechanical properties as a function of the concentration of Bionolle. Differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and tensile tests were used to characterize the blends. From the results of the DMA and DSC, it was found that this blend system was not miscible within the compositions studied. DSC results showed that adding Bionolle aids in crystallization of PLA. It was observed that increasing the Bionolle concentration led to a slight increase in the strain-at-break of the blends but a decrease in the Young’s modulus and ultimate tensile strength. Biaxially oriented films showed an increase in tensile strength, modulus, and strain-at-break.     

In situ bioremediation of a hydrocarbon polluted site with cyclodextrin as a coadjuvant to increase bioavailability

Bioavailability is one main factor that influences the extent of biodegradation of hydrocarbons. They are very poorly soluble in water and easily adsorbed to clay or humus fractions, so they pass very slowly to the aqueous phase where they are metabolised by microorganisms. Cyclodextrins are natural compounds that form soluble inclusion complexes with hydrophobic molecules and increase degradation rate of hydrocarbons in vitro. In the perspective of an in situ application, we previously checked that -cyclodextrin does not increase eluviation of hydrocarbons through the soil and consequently does not increase the risk of groundwater pollution. The results of an in situ application of -cyclodextrin for bioremediation of a hydrocarbon polluted site are presented. We stated that the combination of bioaugmentation and enhanced bioavailability due to -cyclodextrin was effective for a full degradation.     

Mechanical, Thermal and Water Absorption Properties of Kenaf-Fiber-Based Polypropylene and Poly(Butylene Succinate) Composites

The use of composites made from non-biodegradable conventional plastic materials (e.g., polypropylene, PP) is creating global environmental concern. Biodegradable plastics such as poly(butylene succinate) (PBS) are sought after to reduce plastic waste accumulation. Unfortunately, these types of plastics are very costly; therefore, natural lignocellulosic fibers are incorporated to reduce the cost. Kenaf fibers are also incorporated into PP and PBS for reinforcing purposes and they have low densities, high specific properties and renewable sourcing. However without good compatibilization, the interfacial adhesion between the matrix and the fibers is poor due to differences in polarity between the two materials. Maleic anhydride-grafted compatibilizers may be introduced into the system to improve the matrix-fiber interactions. The overall mechanical, thermal and water absorption properties of PP and PBS composites prepared with 30 vol.% short kenaf fibers (KFs) using a twin-screw extruder were being investigated in this study. The flexural properties for both types of composites were enhanced by the addition of compatibilizer, with improvements of 56 and 16 % in flexural strength for the PP/KF and PBS/KF composites, respectively. Good matrix-fiber adhesion was also observed by scanning electron microscopy. However, the thermal stability of the PBS/KF composites was lower than that of the PP/KF composites. This result was confirmed by both DSC and TGA thermal analysis tests. The water absorption at equilibrium of a PBS composite filled with KFs is inherently lower than of a PP/KF composite because the water molecules more readily penetrate the PP composites through existing voids between the fibers and the matrix. Based on this research, it can be concluded that PBS/KF composites are good candidates for replacing PP/KF composites in applications whereby biodegradability is essential and no extreme thermal and moisture exposures are required.