Thermal analysis of hydrolysis and degradation of biodegradable polymer and bio-composites

The purpose of this study was to conduct a thermal analysis of the hydrolysis and degradation behavior of biodegradable polymers and bio-composites at 50°C and 90% relative humidity (RH). With increasing hydrolysis time, the thermal stability and degradation temperature of polybutylene succinate (PBS) slightly decreased. The glass transition temperature (T _g) and melting temperature (T _m) of PBS and the anti-hydrolysis agent treated PBS did not vary significantly with increasing hydrolysis time, whereas those of the trimethylolpropane triacrylate (TMPTA)-treated PBS slightly increased. With increasing hydrolysis time, the storage modulus (E’) values of the bio-composites decreased, whereas those of the TMPTA treated bio-composites slightly increased. Also, the tan values of the anti-hydrolysis agent and TMPTA treated PBS-BF bio-composites were slightly lower than those of the non-treated bio-composites, due to the reduction in their degree of hydrolysis. The tanδ_max peak temperature (T _g) of the anti-hydrolysis agent treated bio-composites was not significantly changed, whereas that of the TMPTA treated bio-composites was increased.     

Thermal properties of agro-flour-filled biodegradable polymer bio-composites

In this study, the thermal properties of agro-flour-filled polybutylene succinate (PBS) bio-composites were investigated. PBS is one of the biodegradable polymers made from the condensation reaction of glycols and dicarboxylic acid and is naturally degraded by natural soil burial system. The thermal properties of the bio-composites were analyzed according to the agro-flour content and mesh size. On increasing agro-flour content, the thermal stability, degradation temperature and derivative thermogravimetric curve (DTG_max) temperature of the bio-composites decreased while the ash content increased. The thermal degradation of the bio-composites was not affected by agro-flour mesh size. The glass transition (T_g) and melting (T_m) temperatures of the bio-composites were not significantly changed. The storage modulus (E’) of the bio-composites was higher than that of neat PBS, because the incorporation of agro-flour increased the stiffness of the bio-composites. At higher temperatures, E’ of the bio-composites decreased due to the increasing viscosity and chain mobility of neat PBS. The thermal properties of bio-composites have an important effect on the manufacturing system and application methods.     

Biodegradability of bio-flour filled biodegradable poly(butylene succinate) bio-composites in natural and compost soil

This study investigated the biodegradability of PBS and bio-flour, which is a poly(butylene succinate) (PBS) bio-composite filled with rice-husk flour (RHF) reinforcing, in natural and aerobic compost soil. The percentage weight loss and the reduction in mechanical properties of PBS and the bio-composites in the compost soil burial test were significantly greater than those in the natural soil burial test. These results were supported by degraded surface of PBS and bio-composites observed through morphological study and the total colony count of natural soil was lower than that of compost soil. The biodegradability of the bio-composites was enhanced with increasing bio-flour content because the bio-flour is easily attacked by microorganisms. As the biodegradability test progressed over time up to 80 days, the molecular weight of PBS decreased in the soil burial test. We confirmed by attenuated total reflectance (FTIR-ATR) analyser that the chemical structures of PBS and the bio-composites were changed after the compost burial test. The glass transition temperature (T_g), melting temperature (T_m), crystallization temperature (T_c), heat of fusion (ΔH_f) and heat of crystallization (ΔH_c) of the natural and composted soil tested PBS were investigated using differential scanning calorimetry (DSC). From the results, we concluded that use of these bio-composites will reduce the environmental problems associated with waste pollution and the study findings support the predicted application of bio-composites as “green-composites” or “eco-materials”.     

Thermal properties of bio flour-filled polypropylene bio-composites with different pozzolan contents

In this study, the thermal properties of bio-flour-filled, polypropylene (PP) bio-composites with different pozzolan contents were investigated. With increasing pozzolan content, the thermal stability, 5% mass loss temperature and derivative thermogravimetric curve (DTG_max) temperatures of the bio-composites slightly increased. The coefficient of thermal expansion (CTE) and thermal expansion of the bio-composites decreased as the pozzolan content increased. The glass transition temperature (T _g), melting temperature (T _m) and percentage of crystallinity (X _c) of the bio-composites were not significantly changed. The thermal stability, thermal expansion and X _c of the maleic anhydride-grafted PP (MAPP)-treated bio-composites were much higher than those of non-treated bio-composites at 1% pozzolan content due to enhanced interfacial adhesion. X-ray diffraction (XRD) analysis confirmed the crystallinity of pozzolan-added bio-composites. From these results, we concluded that the addition of pozzolan in the bio-composites was an effective method for enhancing the thermal stability and thermal expansion.     

The hydrolytic effect of moisture and hygrothermal aging on poly(butylene succinate)/organo-montmorillonite nanocomposites

The study of hydrolysis on biodegradable poly(butylene succinate) (PBS) is essential to predict the materials properties in a humid environment. In this study, PBS nanocomposites were exposed to different conditions of relative humidity (RH) and temperature. The moisture uptake increased with organo-montmorillonite (OMMT) loading and the RH of the testing environment. The exposure of PBS and the nanocomposites to a humid environment caused changes in the mechanical properties. The hydrolytic degradation becomes more pronounced upon hygrothermal aging at high temperature, whereby premature failure occurred. PBS nanocomposites were found to exhibit a better hydrolytic stability than neat PBS. The degradation was evaluated through Fourier transform infrared (FTIR) spectroscopy and gel permeation chromatography (GPC). A drastic reduction in the molecular weight of PBS has revealed the occurrence of degradation after exposure to moisture and heat. This has led to an alteration of the thermal behavior as investigated using differential scanning calorimetry (DSC).     

Thermomechanical degradation of PLA‐based nanobiocomposite

Nanobiocomposites are a new class of biodegradable polymer materials with nanometric dispersion of inert particles in a biodegradable polymer matrix that show very interesting properties often very different from those of conventional‐ filled polymers and also biodegradability. An important issue in the applications of the biodegradable polymers is their easy degradability during processing due to the thermomechanical stress or to the presence of humidity. In this work, the thermomechanical degradation behavior of a nanobiocomposite made by a PLA‐based blend and an organomodified montmorillonite has been investigated. The degradation kinetics has been followed by means of rheological, mechanical and morphological characterization. In particular, the influence of temperature and of the presence of humidity have been considered. The presence of the nanoparticles slightly increases the thermomechanical degradation of the pure matrix and in particular with increasing time and temperature processing. In the more severe conditions, indeed, the organomodifier undergoes some slight decomposition of the organomodifier of the clay because of the Hoffmann elimination. The radicals formed through this decomposition enhance the degradation of the matrix. However, this decomposition is at the first stage, and the evolved CO₂ remains entrapped in the clay increasing the level of intercalation and causing also some exfoliation. Then the morphology of the nanobiocomposite changes because of the processing conditions. Moreover, the thermomechanical degradation remarkably increased if the materials are not pre‐dried because of the hydrolytic degradation of the biodegradable polyesters of the matrix. Copyright © 2015 John Wiley & Sons, Ltd.     

In vitro and in vivo degradation behaviors of thermosensitive poly(organophosphazene) hydrogels

Biodegradable and thermosensitive poly(organophosphazenes) with various substituents were synthesized and their hydrolytic degradation properties were investigated in vitro and in vivo. The aqueous solutions of all polymers showed a sol-gel phase transition behavior depending on temperature changes. The side groups of polymers significantly affected the polymer degradation and accelerated hydrolysis of polymers in the order of carboxylic acid > depsipeptide > without carboxylic acid and depsipeptide. The increased gel strength led to the decreased hydrolysis rate. The polymer hydrogels with 750 Da of α-amino-ω-methoxy poly(ethylene glycol) were rapidly decreased by dissolution. The polymer degradation was also influenced by pH and temperature. The in vivo behaviors of mass decrease of the polymer hydrogels were similar with the in vitro results. These results suggest that the biodegradable and thermosensitive poly(organophosphazenes) hold great potentials as an injectable and biodegradable hydrogel for biomedical applications with controllable degradation rate.     

Thermal and mechanical properties of cassava and pineapple flours-filled PLA bio-composites

The research focused on enhancing the mechanical properties and thermal stability of bio-composites with natural flours and improving the interfacial adhesion between biodegradable polymer and flour. The tensile and flexural strength of the PLA bio-composites decreased with increasing flour addition. However, a 3% loading of the compatibilizer in the PLA bio-composite increased this strength up to that observed with the 10% loading flour. The degradation temperature of PLA was decreased by the flour but destarched cassava flour had higher thermal stability on account of its higher lignin content than pineapple flour. This means that the PLA bio-composites with destarched cassava flour had higher thermal stability than those with the pineapple flour. In addition, the thermal degradation temperature was increased by adding MAPLA. The compatibilizer improved the crystallinity of PLA, which enhanced the mechanical strength of the PLA bio-composites. As the pineapple flour and destarched cassava flour 30% loading was increased, the HDT of the PLA bio-composites increased from 56.8?°C to ~66.3 and 69.7?°C, respectively. The thermal aging test showed no reduction in strength of the neat PLA. However, the PLA bio-composites showed a gradual decrease in tensile strength with increasing number of cycles. Moreover, the shrinkage ratio of the neat PLA was 5% of that found with the PLA resin.     

Compatibility and characteristics of poly(butylene succinate) and propylene-co-ethylene copolymer blend

Propylene-co-ethylene elastomer resin (PER) has been blended into biodegradable poly(butylene succinate) copolymer (PBS) by a melt-blending process to develop a novel semi-biodegradable thermoplastic elastomer. The PBS/PER blends displayed good compatibility in the range 70/30 > PBS/PER > 30/70 according to analyses by DSC, DMA and the Couchman method. Although the PBS/PER blends displayed compatibility, SEM analyses of most of the PBS/PER blends revealed two-phase structures including sea-island and irregular fiber-shaped morphologies, except for PBS/PER (70/30). PBS/PER (60/40) and PBS/PER (50/50) display low tensile strength due to large sea-phase and irregular fiber-shaped morphologies, even though they have good compatibility. PBS/PER (70/30) apparently exhibited a single phase by SEM and showed the best compatibility by DSC and DMA. Furthermore, the tan δ, elongation and initial moduli of the PBS/PER blends were seen to increase with increasing PER content, indicating that the toughness and shock resistance of PBS are improved by incorporating PER into the composition.     

Thermal properties of 4,4-oxydiphathalic anhydride chitosan filled chitosan bio-composites

The 4,4,-oxydiphthalic anhydride-chitosan (ODAC) filler at composition of 2–12 wt/v% was selected to reinforce the Cs matrix by solution casting method. The thermal properties of the bio-composites were then evaluated by thermogravimetry analysis, differential scanning calorimetry, and dynamic mechanical analysis. The addition of ODAC filler in Cs matrix up to 10 wt/v% had increased the thermal stability of the bio-composites by increasing the thermal degradation (T _d) and glass transition temperature (T _g) of the bio-composites. Good interfacial bonds of electrostatic interactions and inter-hydrogen bonds of the bio-composite components significantly influenced the thermal properties of the bio-composites.     

Poly(ethylene oxide) induced microstructure and hydrolytic degradation behavior changes of poly(butylene succinate)

Degradable polyesters exhibit wide application in many fields due to the fact that the waste of these polymers can be easily reclaimed, which greatly reduces the environmental risk. In this work, a small quantity of water-soluble poly(ethylene oxide) (PEO) was introduced into biodegradable poly(butylene succinate) (PBS). Crystallization behavior of the PBS matrix was comparatively investigated using polarized optical microscope (POM), differential scanning calorimetry (DSC) and wide angle X-ray diffraction (WAXD). The results demonstrate that PEO affects the crystallization behavior of the PBS matrix, which is greatly dependent upon the PEO content. At relatively low PEO content, accelerated crystallization is achieved for the PBS matrix, while the role of PEO becomes inconspicuous at relatively high PEO content. The sample surface hydrophilicity was evaluated through contact angle measurement of distilled water. The results demonstrate that incorporating PEO into PBS greatly enhances the hydrophilicity of the sample surface. The hydrolytic degradation measurements were carried out under an alkaline condition. The results clearly show that the presence of PEO accelerates the hydrolytic degradation of the PBS matrix. Furthermore, the sample obeys the surface erosion mechanism. The mechanism for the largely enhanced hydrolytic degradation ability is then analyzed.     

Compression-moulded flax fabric-reinforced polyfurfuryl alcohol bio-composites

Bio-composites (FF-PFA-D) were successfully compression moulded by reinforcing polyfurfuryl alcohol (PFA) with 10 layers of woven flax fabric (FF). FF-reinforced PFA-based bio-composites were then immersed in water to get wet bio-composite samples (FF-PFA-W). Mechanical and impact properties of the bio-composites in dry and wet state were determined. Characterisations of the bio-composites were performed by thermogravimetric analysis, thermomechanical behaviour, and cone calorimeter data. Results indicated the increase in α-relaxation temperature for FF-PFA-W. SEM micrograph showed that the flax fibres were completely coated with the resin indicating complete wetting of the fabrics by the matrix. As expected, time of ignition showed an increase for the bio-composites due to the flame retardant characteristics of PFA. This work gives us simple and effective way to prepare bio-composites from 100 % renewable resources.     

Investigation on the gelation behavior of biodegradable poly(butylene succinate) during isothermal crystallization process

The early stage of polymer crystallization may be viewed as physical gelation process,i.e.,the phase transition of polymer from liquid to solid.Determination of the gel point is of significance in polymer processing.In this work,the gelation behavior of poly(butylene succinate)(PBS) at different temperatures has been investigated by rheological method.It was found that during the isothermal crystallization process of PBS,both the storage modulus(G′) and the loss modulus(G″) increase with time,and the rheological response of the system varies from viscous-dominated(G′G″),meaning the phase transition from liquid to solid.The physical gel point was determined by the intersection point of loss tangent curves measured under different frequencies.The gel time(t_c) for PBS was found to increase with increasing crystallization temperature.The relative crystallinity of PBS at the gel point is very low(2.5%-8.5%) and increases with increasing the crystallization temperature.The low crystallinity of PBS at the gel point suggests that only a few junctions are necessary to form a spanning network,indicating that the network is"loosely"connected,in another word,the critical gel is soft.Due to the elevated crystallinity at gel point under higher crystallization temperature,the gel strength S_g increases, while the relaxation exponent n decreases with increasing the crystallization temperature.These experimental results suggest that rheological method is an effective tool for verifying the gel point of biodegradable semi-crystalline polymers.     

Storage Stability Study of Salicylate-based Poly(anhydride-esters)

Storage stability was evaluated on a biodegradable salicylate-based poly(anhydride-ester) to elucidate the effects of storage conditions over time. The hydrolytically labile polymer samples were stored in powdered form at five relevant storage temperatures (−12 °C, 4 °C, 27 °C, 37 °C, 50 °C) and monitored over four weeks for changes in color, glass transition temperature, molecular weight, and extent of hydrolysis. Samples stored at lower temperatures remained relatively constant with respect to bond hydrolysis and molecular weight. Whereas, samples stored at higher temperatures displayed significant hydrolysis. For hydrolytically degradable polymers, such as these poly(anhydride-esters), samples are best stored at low temperatures under an inert atmosphere.     

Biodegradable Cellulose Block Copolymers

Biodegradable polymers can be prepared by the incorporation of cellulose oligomeric blocks into the polymer backbone. Block copolymers prepared by reacting equimolar amounts of depolymerized cellulose triacetate (CTA) with MDI or TDI and block terpolymers prepared by reacting the CTA oligomer with poly (propylene glycol) capped with MDI or TDI were deacetylated and incubated with cellulysin at pH 5 and 50 °C. The intrinsic viscosity of each copolymer decreased substantially even after 10 hr incubation time. There was negligible acid hydrolysis. Cellulose showed a smaller decrease at the same incubation time-probably due to its lower accessibility. Methods for incorporating cellulose oligomeric blocks and other biodegradable blocks into different types of polymers are discussed.     

Morphology control of poly(lactic) acid/polypropylene blend composite by using silanized cellulose fibers extracted from coir fibers

The objective of this work is the use of cellulose fibers extracted from coir fibers as Janus nanocylinders to suppress the phase retraction and coalescence in poly(lactic) acid/polypropylene bio-blend polymers via prompting the selective localization of cellulose fibers at the interface using chemical modification. The untreated and modified cellulose fibers extracted from coir fibers using a silane molecule (tetraethoxysilane) were used as reinforcement and as Janus nanocylinder at two weight contents (2.5 wt% and 5 wt%) to manipulate the morphology of the bio-blends. Their bio-composites with PLA-PP matrix were prepared via melt compounding (at PLA/PP: 50/50). The treatment effect on component interaction and the bio-composites properties have been studied via Scanning electron microscopy, infrared spectroscopy, and differential calorimetry analysis. The mechanical and rheological properties of nanocomposites were similarly assessed. Young's modulus and tensile strength of PLA-PP nanocomposites reinforced by silanized cellulose fibers show a great enhancement as compared to a neat matrix. In particular, there was a gain of 18.5% in Young's modulus and 11.21% in tensile strength for silanized cellulose fiber-based bio-blend composites at 5 wt%. From the rheological point of view, it was found that the silanized cellulose fibers in PLA-PP at both fibers loading enhances the adhesion between both polymers leading to tuning their morphology from sea-island to the continuous structures with the appearance of PLA microfibrillar inside of bio-composites. This change was reflected in the relaxation of the chain mobility of the bio-blend composites.

     

热塑性淀粉/PBS共混物的微生物降解性研究

以甘油作为增塑剂,采用玉米淀粉与改性后的聚丁二酸丁二醇酯(PBS)熔融共混制备出淀粉/PBS共混材料.对这种改善了两相相容性的共混材料在特定微生物条件下的降解行为进行了研究.结果显示,共混物降解28天后,含有30%PBS的共混物质量损失达到35%左右,其力学性能只有降解前的20%,甘油含量减小和PBS含量增加均能减缓材料的降解.且随着降解时间的延长,PBS的结晶度和熔点有所提高.     

Synthesis,characterization and isothermal crystallization behavior of poly(butylene succinate)‐b‐poly(diethylene glycol succinate) multiblock copolymers

In order to modify the properties of poly(butylene succinate), poly(diethylene glycol succinate) (PDGS) segment was incorporated by chain‐extension reaction of dihydroxyl‐terminated PBS and PDGS precursors using hexamethylene diisocyanate as a chain extender to form PBS‐b‐PDGS multiblock copolymers. The chemical structure and basic physical properties of the multiblock copolyesters were characterized by nuclear magnetic resonance spectroscopy, differential scanning calorimeter (DSC), wide angle X‐ray diffraction, and tensile testing. The results suggested that the incorporation of PDGS segments would increase the elongation at break of PBS significantly while decrease its melting temperature and crystallization temperature slightly. The isothermal crystallization kinetics studied by DSC and polarized optical microscopy indicated that the crystallization rate of the multiblock polymers decreased gradually with increasing PDGS segment content while the crystallization mechanism kept unchanged and the spherulitic growth rate of the multiblock copolymers decreased gradually with increase in PDGS content due to its diluent effect to the crystallization of PBS segments. Copyright © 2015 John Wiley & Sons, Ltd.     

Erosion of multilayered films fabricated from degradable polyamines: Characterization and evidence in support of a mechanism that involves polymer hydrolysis

Multilayered polyelectrolyte assemblies fabricated using hydrolytically degradable polyamines ( 1 – 3 ) erode gradually when incubated in physiologically relevant media. This investigation sought to characterize physically and chemically the erosion of films fabricated from these polymers and sodium poly(styrene sulfonate) (SPS) and to investigate specifically the potential role of polymer hydrolysis in governing film erosion. The characterization of erosion using reflective infrared spectroscopy revealed changes in the carbonyl region of the spectrum that were consistent with the generation of polymer hydrolysis products. To evaluate the role of the esters in these materials more directly, we also synthesized a structural analogue of polymer 2 containing amide functionality rather than ester functionality. Assemblies fabricated from this amide-containing polymer did not erode significantly or release SPS into solution when incubated in phosphate-buffered saline (PBS). Finally, we characterized the erosion of assemblies fabricated from polymer 1 in PBS buffer prepared with D₂O rather than H₂O. These assemblies eroded significantly more slowly in deuterated media than in buffer prepared with H₂O. These results, when combined, provide support for the view that polymer hydrolysis plays an important role in governing the erosion of assemblies fabricated from these degradable polymers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5161–5173, 2006     

Aroma scalping characteristics of polybutylene succinate based films

The removal of aroma compounds from packaged food items - aroma scalping – can be primarily controlled by the choice of packaging materials. Although the utilization of biodegradable polymers as packaging materials can greatly contribute to the sustainability of the packaging industry, only limited data on their aroma scalping properties are available. In this work, the aroma scalping characteristics of a series of films made from biodegradable polybutylene succinate (PBS) and polybutylene succinate-co-addipate (PBSA) for common aroma compounds in foods (ethyl acetate, ethyl butyrate, ethyl hexanoate, hexan-1-ol, heptanal and (R)-(+)-limonene) are reported. The aroma scalping characteristics of a film made from poorly biodegradable low density polyethylene (LDPE) are reported for comparison.The aroma scalping characteristics, namely sorption and diffusion coefficients, of the tested aroma compounds were determined at 23 °C by means of sorption microgravimetry, and the permeability coefficients were estimated using the solution-diffusion model. The permeability coefficients for the films made from PBS, PBSA and LDPE were comparable for the more polar compounds: hexan-1-ol, ethyl acetate and ethyl butyrate. Conversely, the permeability coefficients of the less polar aroma compounds (ethyl hexanoate, heptanal and (R)-(+)-limonene) in PBS and PBSA-based films were by one to two orders of magnitude lower than those of the LDPE. In addition, a new mathematical model was proposed for the kinetics of the transient sorption of aroma compounds of low volatility (p^sat < 1 kPa).