Mechanical and thermal properties of poly(butylene succinate)/poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) biodegradable blends

Biodegradable polymer blends of poly(butylene succinate) (PBS) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) were prepared with different compositions. The mechanical properties of the blends were studied through tensile testing and dynamic mechanical thermal analysis. The dependence of the elastic modulus and strength data on the blend composition was modeled on the basis of the equivalent box model. The fitting parameters indicated complete immiscibility between PBS and PHBV and a moderate adhesion level between them. The immiscibility of the parent phases was also evidenced by scanning electron observation of the prepared blends. The thermal properties of the blends were studied through differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The DSC results showed an enhancement of the crystallization behavior of PBS after it was blended with PHBV, whereas the thermal stability of PBS was reduced in the blends, as shown by the TGA thermograms. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42815.     

Study on the poly(3‐hydroxybutyrate‐co−4‐hydroxybutyrate)‐based composites toughened by synthesized polyester polyurethane elastomer

In this study, polycaprolactone(PCL)‐based polyurethane (PU) elastomer containing 45 wt % hard segment component was synthesized and characterized by fourier transform infrared spectroscopy, gel permeation chromatography, and X‐ray diffraction. As a toughening agent, the as‐synthesized PU was incorporated into biodegradable poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) [P(3,4)HB] by solution casting to prepare P(3,4)HB/PU composites. The microstructure and properties of P(3,4)HB/PU composites were investigated using transmission electron microscopy, X‐ray diffraction, tensile testing, scanning electron microscopy, differential scanning calorimetry, thermogravimetric analysis, and activated sludge degradation testing. The results show that PU can disperse well in a P(3,4)HB matrix. The elongation at break of P(3,4)HB/PU composites is remarkably increased while the yield strength and elastic modulus are decreased with an increase in PU content. At the same time, it is found that the fracture characteristic of P(3,4)HB is obviously transformed from brittleness into ductility with a gradual increase in PU loading. Moreover, the thermal stability of P(3,4)HB/PU composites is significantly improved compared with that of pure P(3,4)HB. In addition, the biodegradation rate of P(3,4)HB/PU composites is evidently reduced with the increase of PU content in the activated sludge degradation testing. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42740.     

The mechanical properties of β‐Si3N4 whiskers‐reinforced dental resin composites

The surface‐modified β‐Si₃N₄ whiskers were used as inorganic fillers to reinforce dental resin (Bis‐GMA/TEGDMA) matrix with filler level ranging from 0 to 60 wt %. The experimental results indicated that the fracture strength of the composites increased from 79.85 to 139.8 MPa with increasing the whiskers loading. The compressive strength, elastic modulus, and rockwell hardness all increased monotonously with increasing filler level. Furthermore, thermal cycling did not decrease the fracture strength of the composites. Moreover, the composites showed good biocompatibility to support MG63 cells adhesion and proliferation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40692.     

Improvement of the thermal properties of poly(3‐hydroxybutyrate) (PHB) by low molecular weight polypropylene glycol (LMWPPG) addition

In this work, blends of poly(3‐hydroxybutyrate) (PHB) with 5, 10, 15, and 20 wt % low molecular weight poly(propylene glycol) (LMWPPG) have been prepared and characterized by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) with attenuated total reflectance (ATR) accessory and simultaneous thermal analysis (TG/DTA). FTIR and thermal analyses suggested that the presence of LMWPPG led to a maximum crystallinity for the blend PHB/PPG (90/10) blend. The presence of LMWPPG also caused a significant increase of the PHB processability window, i.e., the difference of the melting and degradation temperature, of PHB from 105 to 134°C, which is extremely important for the industrial uses of PHB. This PHB stabilization effect is discussed in terms of an intermolecular interaction of the PHB carbonyl with LMWPPG methyl groups which probably hinders the classical radon β‐scission PHB intramolecular decomposition mechanism. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Plasticization of poly(3-hydroxybutyrate) with triethyl citrate: Thermal and mechanical properties,morphology, and kinetics of crystallization

Poly(3-hydroxybutyrate) (PHB), is one important biopolymer and a promising alternative to petroleum-based plastics. In this article, formulations of PHB and triethyl citrate (TEC) as plasticizer were prepared by melt extrusion. The effect of TEC on the mechanical, thermal, and morphological properties of PHB was investigated by tensile tests, impact resistance, dynamic-mechanical analysis, differential scanning calorimetry, polarized optical microscopy, and small- and wide-angle X-ray scattering. TEC acted as an efficient plasticizer for PHB, imparting gradual changes in the properties as the mass fraction of TEC increased. A reduction in the elastic modulus, an increase in the intensity of β relaxation indicated a higher capacity of mechanical energy dissipation for the formulations containing higher mass fractions of TEC. TEC reduced its glass transition and melting temperatures, contributing to the increase of the processing window of the temperature and minimizing thermal degradation of PHB. TEC had a strong influence on the kinetics of crystallization, the morphology of the spherulites, and the crystalline structural parameters, such as long period, crystalline lamella, and interlamellar amorphous region thicknesses. Our study clarifies how the morphology of the PHB crystalline phase evolves in the presence of the plasticizer and with the time of crystallization.     

Poly(lactic acid) biocomposites reinforced with ultrafine bamboo‐char: Morphology,mechanical, thermal,and water absorption properties

In this study, ultrafine bamboo‐char (BC) was introduced into poly(lactic acid) (PLA) matrix to improve mechanical and thermal properties of PLA based biodegradable composites. PLA/BC biocomposites were fabricated with different BC contents by weight. Uniform dispersion of BC in the PLA matrix and good interaction via physical and chemical interfacial interlocks were achieved. The maximum tensile strength and tensile modulus values of 14.03 MPa and 557.74 MPa were obtained when 30% BC was used. Impact strength of the biocomposite with 30% BC was increased by 160%, compared to that of pure PLA. DSC analysis illustrated that PLA/BC biocomposites had a better thermal property. Crystallization temperature decreased and maximal crystallinity of 30.30% was observed with 30% BC load. We did not notice significant thermal degradation differences between biocomposites with different BC loadings from TGA. Better water resistance was obtained with the addition of BC. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43425.     

Thermal degradation of poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) in drying treatment

This study examines the isothermal treatment of poly(3‐hydroxybutyrate) (PHB) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) powders and films. The PHB and PHBV crystallinities were determined using X‐ray diffractometry, and shown to increase with temperature (130–150°C) and then decreased from 55% to 45% at 180°C. The crystal morphology of crystal planes (101) and (111) became sharp at a high temperature. The weight average molecular weight (M_w) of PHB decreased from 1,028,000 to 41,800 g/mol when heated at 180°C for 30 min. The molecular weight of PHB decreased more rapidly than that of PHBV with time. No peak signal was observed in gel permeation chromatography after heating at 150°C because the solubility of PHB changed with crystallinity. The thermal behaviors of PHB and PHBV were analyzed by differential scanning calorimetry and thermogravimetric analysis. The roughness, contact angle, and surface morphology of PHB and PHBV films were also measured to determine the surface properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3659–3667, 2013     

Preparation and properties of biocomposites based on jute fibers and blend of plasticized starch and poly(β‐hydroxybutyrate)

In this work, preparation and properties of biocomposites based on jute fibers and blend of plasticized starch and poly(β‐hydroxybutyrate) (PHB) have been investigated. Different amounts of glycerol and aliphatic polyesters (PHB) have been added to native starch to obtain a processable biodegradable matrix. In the same way natural jute fibers up to 30 wt % loading were added to improve the mechanical and thermal stability of the material. Tensile mechanical, thermal, and thermomecahnical analyses have been performed to characterize the ensuing materials. Significant enhancement in the mechanical properties and water sensitivity were noted by the addition of 8 wt % PHB. The fibers incorporation into the biopolymer matrix brings about an increase in both the mechanical strength and modulus as much higher as the fibers loading is important. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Oil‐spill cleanup: The influence of acetylated curaua fibers on the oil‐removal capability of magnetic composites

A magnetic resin based on cardanol, furfural, and curaua fibers was prepared and characterized. The material could be used in oil‐spill cleanup processes, because of its aromatic/aliphatic balance. The resin was prepared through bulk polycondensation of cardanol and furfural in the presence of curaua fibers and maghemite nanoparticles. Hydrophobicity of the curaua fibers was improved by acetylation, increasing the oil‐absorbing capability of the composites. The obtained magnetic composites were studied by Fourier‐transform infrared spectroscopy, X‐ray diffraction, and thermogravimetric analysis. Degree of cure, magnetic force, and oil‐removal capability tests were also performed. The results show that the composites possess an elevated cure degree in addition to a considerable magnetic force. The materials exhibit a good oil removal capability in the presence of a magnetic field, which is improved by the use of acetylated curaua. In the best case, the composite filled with maghemite and curaua can remove 12 parts of oil from water. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41732.     

Thermophysical properties of bacterial poly(3‐hydroxybutyrate): Characterized by TMA,DSC, and TMDSC

The melting, isothermal and nonisothermal crystallization behaviors of poly(3‐hydroxybutyrate) (PHB) have been studied by means of temperature modulated differential scanning calorimetry (TMDSC) and conventional DSC. Various experimental conditions including isothermal/annealing temperatures (80, 90, 100, 105, 110, 120, 130, and 140°C), cooling rates (2, 5, 10, 20, and 50°C/min) and heating rates (5, 10, 20, 30, 40, and 50°C/min) have been investigated. The lower endothermic peak (T_m1) representing the original crystals prior to DSC scan, while the higher one (T_m2) is attributed to the melting of the crystals formed by recrystallization. Thermomechanical analysis (TMA) was used to evaluate the original melting temperature (T_melt) and glass transition temperature (T_g) as comparison to DSC analysis. The multiple melting phenomenon was ascribed to the melting‐recrystallization‐remelting mechanism of the crystallites with lower thermal stability showing at T_m1. Different models (Avrami, Jeziorny‐modified‐Avrami, Liu and Mo, and Ozawa model) were utilized to describe the crystallization kinetics. It was found that Liu and Mo's analysis and Jeziorny‐modified‐Avrami model were successful to explain the nonisothermal crystallization kinetic of PHB. The activation energies were estimated in both isothermal and nonisothermal crystallization process, which were 102 and 116 kJ/mol in respective condition. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42412.     

Plasticized poly(3‐hydroxybutyrate) with improved melt processing and balanced properties

The widespread application of poly(3‐hydroxybutyrate) (PHB) in the food packaging and biomedical fields has been hindered by its high brittleness, slow crystallization, poor thermal stability, and narrow processing window. To overcome these limitations, a mixture of biodegradable and biocompatible plasticizers was used to modify PHB. Epoxidized soybean oil (ESO), acetyl tributyl citrate, poly(ethylene glycol) 4000 (PEG4000), and poly(ethylene glycol) 6000 (PEG6000) were tested to improve PHB melt processing and to achieve balanced thermal and mechanical properties. These plasticizers increased the flexibility and decreased the melt viscosity, improving the processability. The tensile strength was maintained within the limit of experimental error for ESO and decreased slightly (6–7%) for the other plasticizers. PEG6000 and ESO delayed the decomposition process of PHB. The plasticizers did not hinder the crystallization, and poly(ethylene glycol)s increased the crystallinity. The change in the interplanar distance and crystallite size, correlated with lamellar stack dimensions, gave more information on the plasticizers' effects in PHB. The blend with 5 wt % ESO was considered suitable for the fabrication of marketable PHB films. This study showed that it is possible to tailor the rheological, thermal, and mechanical behavior of a commercial PHB through the addition of a second plasticizer. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44810.     

Design of highly tough poly(l‐lactide)‐based ternary blends for automotive applications

Technical renewable poly(l ‐lactide) (PLA)‐based blends represent an elegant way to achieve attractive properties for engineering applications. Recently, the miscibility between PLA and poly(methyl methacrylate) (PMMA) gave rise to new formulations with enhanced thermo‐mechanical properties but their high brittleness still remains a challenge to be overcome. This work here focuses on rubber‐toughened PLA/PMMA formulations for injection‐molding processes upon the addition of a commercially available ethylene‐acrylate impact modifier (BS). The miscibility between PLA and PMMA is not altered by the presence of BS but the incorporation of BS (17% by weight) into a PLA/PMMA matrix could enhance both ductility and toughness of PLA/PMMA blends for PMMA content up to 50 wt %. An optimum range of particle sizes (d_n ～0.5 µm) of the dispersed domains for high impact toughness is identified. These bio‐based ternary blends appear as promising alternatives to petro‐sourced blends such as ABS‐based blends in engineering injection‐molding parts. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43402.     

Borassus powder-reinforced poly(lactic acid) composites with improved crystallization and mechanical properties

This article reports on the development of biocomposites based on polylactic acid (PLA) and borassus powder. Borassus powder was treated with alkali to remove hemicelluloses and lignin. The treated borassus improved the homogeneous mixing with PLA and increased the crystallinity of PLA. Dispersibility of the borassus was studied by scanning electron microscopy (SEM) and X-ray MicroCT. PLA/borassus composites were prepared by melt mixing of PLA with 5, 10, and 15 wt % treated/untreated borassus. Composites were examined for mechanical properties and crystallization. Composites showed enhanced tensile strength compared to neat PLA. The PLA/treated borassus powder composites displayed higher crystallinity than PLA. The isothermal cold crystallization study showed increase in the crystallization rate of PLA in the presence of treated borassus. The spherulitic growth was studied using polarized optical microscopy. The enhanced performance of the PLA-borassus composites was observed in the presence of borassus. This study demonstrates that the PLA-borassus composites show great promise for bioplastics applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47440.     

Biobased blends of poly(propylene carbonate) and poly(hydroxybutyrate‐co‐hydroxyvalerate): Fabrication and characterization

Poly(propylene carbonate) (PPC), a CO₂‐based bioplastic and poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV) were melt blended followed by injection molding. Fourier transform infrared spectroscopy detected an interaction between the macromolecules from the reduction in the OH peak and a shift in the C?O peak. The onset degradation temperature of the polymer blends was improved by 5% and 19% in comparison to PHBV and PPC, respectively. Blending PPC with PHBV reduced the melting and crystallization temperatures and crystallinity of the latter as observed through differential scanning calorimetry. The amorphous nature of PPC affected the thermal properties of PHBV by hindering the spherulitic growth and diluting the crystalline region. Scanning electron micrographs presented a uniform dispersion and morphology of the blends, which lead to balanced mechanical properties. Incorporating PHBV, a stiff semi‐crystalline polymer improved the dimensional stability of PPC by restricting the motion of its polymer chains. © 2016 The Authors Journal of Applied Polymer Science Published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44420.     

Effect of two different plasticizers on the properties of poly(3‐hydroxybutyrate) binary and ternary blends

Plasticized poly(3‐hydroxybutyrate) (PHB) films were obtained by solvent casting. The effects of two different additives on several properties of PHB have been examined, utilizing tributyrin and poly[di(ethyleneglycol) adipate] (A). Based on changes in the glass transition temperature (T_g) and cold crystallization temperature of host PHB, the two components are miscible with PHB and they can act as plasticizers. Binary and ternary blends were obtained by adding both plasticizers separately or together, respectively. The effect of plasticizer addition on the optical transparency, water vapor permeability, and tensile properties of the films was studied. It was found that the blends remain transparent and water vapor permeability was maintained constant until a 20 wt % of plasticizer content. Plasticizing effect was corroborated and it depended on the plasticizer percentage. Binary blends had an increased plasticity, in concordance with T_g diminution of PHB. Although ternary blends presented T_g diminution, mechanical properties were not improved probaby due to strong interactions between plasticizers. Finally, binary and ternary blends presented enhanced properties, causing an increment on processability. A correct knowledge between the formulation of the film and the role played by each component could allow getting custom films. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46016.     

Peroxide induced cross‐linking by reactive melt processing of two biopolyesters: Poly(3‐hydroxybutyrate) and poly(l‐lactic acid) to improve their melting processability

Poly(3‐hydroxybutyrate) (PHB) and poly(l ‐lactic acid) (PLLA) were individually cross‐linked with dicumyl peroxide (DCP) (0.25–1 wt %) by reactive melt processing. The cross‐linked structures of the polymer gel were investigated by nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectroscopies. The size of the polymer crystal spherulites, glass transition temperature (T_g), melting transition temperature (T_m), and crystallinity were all decreased as a result of cross‐linking. Cross‐linking density (ν_e) was shown to increase with DCP concentration. Based on parallel plate rheological study (dynamic and steady shear), elastic and viscous modulus (G″ and G′), complex viscosity (η^*) and steady shear viscosity (η) were all shown to increase with cross‐linking. Cross‐linked PHB and PLLA showed broader molar mass distribution and formation of long chain branching (LCB) as estimated by RheoMWD. Improvements in melt strength offer bioplastic processors improved material properties and processing options, such as foaming and thermoforming, for new applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41724.     

Crystallization behavior of poly(lactide)/poly(β‐hydroxybutyrate)/talc composites

The morphology and miscibility of commercial poly(lactide) (PLA)/poly(β‐hydroxybutyrate) (PHB, from 5 to 20 wt %) blends prepared by melt extrusion method, were investigated using differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR) observations. The results show that for all the studied blend contents, PLA/PHB blends are immiscible. The effects of PHB and talc on the nonisothermal cold crystallization kinetics of PLA were examined using a differential scanning calorimetry (DSC) at different heating rates. PHB acted as a nucleating agent on PLA and the addition of talc to the blend yielded further improvement, since significant increase in the enthalpy peak was observed for samples containing 10 wt % PHB and talc (from 0.5 to 5 phr). The crystallization kinetics were then examined using the Avrami–Jeziorny and Liu–Mo approach. The simultaneous presence of PHB and talc induced a decrease of the crystallization half time. The evolution of activation energies determined with Kissinger's equation suggests that blending with PHB and incorporating talc promote nonisothermal cold crystallization of PLA. The synergistic nucleating effect of PHB and talc was also observed on isothermal crystallization of PLA from the melt. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Dynamic mechanical thermal analysis of biocomposites based on PLA and PHBV—A comparative study to PP counterparts

The primary objective of this study was the investigation of thermo‐mechanical behavior of cellulosic fiber reinforced polylactid (PLA) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) biopolymers. Both PLA and PHBV were processed with 30 wt % of cellulosic fibers; moreover, to improve the processability and mechanical performance, PHBV was previously blended with 30% by weight poly(butylene adipate‐co‐butylene terephthalate) (PBAT). Secondary target was the comparison of the obtained results to natural fiber reinforced polypropylene (PP) composites reinforced with exact the same fibers and processed by using identical techniques. For validation the thermo‐mechanical properties, a dynamic mechanical thermal analysis (DMTA) was applied. Storage modulus (E′), loss modulus (E″), and loss factor (tan δ) were determined. The DMTA results indicate decreased polymer chain motion with resulting improvement of stiffness expressed by the storage modulus. Finally, the effectiveness of fiber on the moduli was investigated. The C coefficient differs in dependence on fiber type, use of coupling agent, and the reference temperature in glassy state. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3175–3183, 2013     

Comparison of covalent and noncovalent interactions of carbon nanotubes on the crystallization behavior and thermal properties of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)

In this study, multiwalled carbon nanotubes (MWCNTs) were dispersed into a poly(3‐hydroxybutyrate‐co?3‐hydroxyvalerate) (PHBV) matrix, in which PHBV was either covalently attached to the nanotubes through an esterification reaction between the carboxylic groups of functionalized MWCNTs and the hydroxyl groups of PHBV with toluene diisocyanate as a coupling agent or physically mixed to result in only noncovalent interactions. The structure, crystallization behavior, and thermal properties of the resulting nanocomposites were studied. We found that the crystallization of PHBV grafted onto the MWCNTs (PHBV‐g‐MWCNTs) was markedly hindered and exhibited an exothermic peak caused by cold crystallization, whereas the nonisothermal crystallization of PHBV was enhanced because a heterogeneous nucleation effect appeared in the PHBV/MWCNTs. Moreover, the maximum decomposition temperature of the PHBV‐g‐MWCNTs was improved by about 14.4°C compared with that of the PHBV/MWCNTs and by about 23.7°C compared with that of the original PHBV. Furthermore, the PHBV‐g‐MWCNTs exhibited the wider melt‐processing window than the PHBV/MWCNTs and original PHBV. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4299–4307, 2013     

Effects of the shapes and addition amounts of crosslinking reagents on the properties of poly-3-hydroxybutyrate/poly(caprolactone) blends

The effects of the shapes and addition amount of crosslinking reagents on the expression mechanisms of polymer properties of poly(3-hydroxybutyrate) (PHB) and poly(caprolactone) (PCL) blends are investigated. A static tensile test is carried out on 60%PHB/40%PCL blends by adding liquid and solid crosslinking reagents, showing that the Young's modulus of the blends decrease with increasing effective peroxide value of the crosslinking reagent. In addition, the elasticity of the blends increases only when the liquid crosslinker is added, even though T₁H analysis and scanning electron microscopy observation reveal that both crosslinking reagents improve the miscibility of the blend. Furthermore, the ¹H and ¹³C PST-MAS NMR spectra related to the molecular motions of polymer main chains in the blends increase with increasing effective peroxide value of the crosslinking reagents. However, the local molecular motions of substituents in the blends matched with the T₁C values reveal an opposite trend between the rigid PHB and flexible PCL with the addition of the solid crosslinker. The solid-state NMR spectral and relaxation time analyses suggest the possibility of the polymer chain scission as a side reaction, as well as the occurrence of intra-domain crosslinking, both of which reduce the toughness of the blends containing the solid crosslinker.