Miscibility of natural polyhydroxyalkanoate blend with controllable material properties

Polyhydroxyalkanoate (PHA) copolyesters were synthesized by Cupriavidus necator cells in continuous feeding of cosubstrates. During the PHA accumulation phase, the composition of 3‐hydroxybutyrate (3HB), 3‐hydroxyvalerate (3HV), and 4‐hydroxyvalerate (4HV) of the copolyesters changed with time, resulting in a change in their miscibility. The as‐produced PHA finally became a miscible blend of copolymers with a broad chemical composition distribution. The good miscibility and low crystallinity of the natural P(3HB‐co‐3HV‐co‐4HV) blend lead to a remarkable increase in ductility and elongation at break. It indicates that the material properties of copolyesters can be tailored via feeding control of cosubstrates. It was also found that the fractions of natural PHA blend exhibited distinctive thermal behavior and the overall behavior of the as‐produced PHA blend was primarily dependent on a fraction of high 3HB content. The material properties of a PHA blend are therefore not determined by its overall chemical composition but more likely by the combined effect of individual copolyesters or fractions. Moreover, the degree of X‐ray crystallinity of random P(3HB‐co‐3HV‐co‐4HV) blend declined significantly with the increase of 3HV and 4HV content, in contrast to the high crystallinity of well‐known P(3HB‐co‐3HV) copolyesters. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Characterization of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) biosynthesized by mixed microbial consortia fed fermented dairy manure

The bioplastic poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV), was isolated from a bioreactor using mixed microbial consortia fed volatile fatty acids (VFA), from fermented dairy manure, as the carbon source. The molar fraction of 3‐hydroxyvalerate (3HV) amounted to 0.33 mol mol^?1 for two isolated PHBV samples as determined by GC‐MS and ¹H‐NMR spectroscopy. The chemical, thermal, and mechanical properties were determined. The PHBVs had relatively high M_w (～790,000 g mol^?1). Only a single glass transition temperature (T_g) and melting point (T_m) were observed. Isolated PHBVs exhibited good flexibility and elongation to break as compared with commercial PHBVs with lower HV. The diad and triad sequence distributions of the monomeric units were determined by ¹³C‐NMR spectroscopy and followed Bernoullian statistics suggesting that the PHBVs were random. The PHBV sequence distribution was also characterized by electrospray ionization‐mass spectrometry (ESI‐MSⁿ) after partial alkaline hydrolysis to oligomers showing a random 3HV distribution. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40333.     

Thermal stability and degradation of biological terpolyesters over a broad temperature range

Because of high susceptibility to thermal degradation during conventional melt processing of poly(3‐hydroxybutyrate) (P3HB) homopolymer, incorporation of a second or third monomer unit in the polyester backbones is expected to reduce the melting temperature and crystallinity, resulting in a controlled thermal degradation with improved stability. In this work, random poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate‐co‐4‐hydroxyvalerate) (P3HB3HV4HV) terpolyesters biologically synthesized by Cupriavidus necator were investigated for the thermal stability and degradation over a broad temperature range (100–300°C) in comparison with P3HB homopolyester. The work revealed that below the complete melting point (around 150°C), the terpolyester exhibited a high thermal stability and became an amorphous semisolid suitable for conventional thermal processing. Size exclusion chromatography plus nuclear magnetic resonance analysis was used to examine the thermal degradation products and the vulnerability of different monomer units at high temperatures (240–290°C). We found that 3HV unit in P3HB3HV4HV copolymers was more vulnerable to thermal degradation than 3HB unit under air. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41715.     

Lignin valorization by forming thermally stimulated shape memory copolymeric elastomers—Partially crystalline hyperbranched polymer as crosslinks

Lignin based thermal‐responsive elastomers were produced by a melt polycondensation reaction with a long alkyl chain hyperbranched poly(ester‐amine‐amide) (B₃‐A₂‐CB₃¹). The effect of lignin content on elastomers properties was investigated. The thermal and mechanical properties of the copolymers were characterized by DMA, DSC, and TGA. The morphology of the copolymer was examined by SEM. Tensile properties were dominated by HBP <25% lignin content while lignin dominated >25% content. The copolymers glass transition temperature (T_g) increased with lignin content. The elastomer with 30% lignin content demonstrated optimal mechanical properties (tensile strength 5.3 MPa, Young's modulus 8.9 MPa, strain at break 301%, and toughness 1.03 GPa). Thermally stimulated dual shape memory effects (SME) of the copolymers were quantified by cyclic thermomechanical tests. The transition temperature (T_trans) of the polymer was able to be controlled (room to body temperature) by varying the amount of lignin added which broadens the range to medical applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41103.     

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.     

On the use of ball milling to develop PHBV–graphene nanocomposites (I)—Morphology,thermal properties,and thermal stability

In the first part of this work, novel nanocomposites based on poly (3‐hydroxybutyrate co‐3‐hydroxyvalerate) (PHBV) and functionalized graphene nanosheets (FGS) were prepared through ball milling. As revealed by morphological characterization, this blending methodology was able to allow proper nanofiller dispersion and distribution into the matrix. Thermal properties were studied under non‐isothermal and isothermal conditions and the addition of FGS into PHBV matrix, although no changes in crystallization mechanism were observed, it modified the crystallization kinetics leading to increased crystallinity. Thermal stability analysis revealed that FGS affected the mechanism of oxidative thermal degradation and had no effect on thermal degradation by pyrolysis. Furthermore, an analysis of isothermal degradation kinetics showed that FGS speeded up the degradation rate. The Sestak‐Berggren model was used as a model to explain the isothermal degradation behavior of the obtained materials in good agreement with the experimental data. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42101.     

Influence of amorphous alkaline lignin on the crystallization behavior and thermal properties of bacterial polyester

Bacterial polyester poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) and alkaline lignin composites were prepared via melt processing method, and the influence of amorphous lignin on the crystallization behavior and thermal properties of PHBV were investigated. It was found that dual melting peaks appeared in DSC curves of PHBV/lignin composites, while only one single peak existed in PHBV. The non‐isothermal crystallization process analyzed by Jeziorny method suggested that lignin changed the nucleation mode of composites and hindered the crystallization rate of PHBV. Data calculated from the results of WAXD demonstrated that lignin did not change the basic crystal structure of PHBV, but decreased the average size of the lamellar stacks. POM results confirmed that the effect of lignin on the crystallization behavior of PHBV carried out in two opposite way, namely the enhanced effect of nucleation and the hindered effect of growth. Besides, the thermal stability of composites was also decreased significantly. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41325.     

Synthesis and characterization of poly(ethylene terephthalate‐co‐isophthalate)s with low content of isophthalate units

The objective of this work was to study the effect of the introduction of low amounts of isophthalate units on the mechanical properties, crystallization rates, and thermal parameters of poly(ethylene terephthalate). For this reason a series of five random poly(ethylene terephthalate‐co‐isophthalate) copolymers, containing 0.5, 1, 1.5, 2, and 4 mol % isophthalic acid, were prepared by the melt polycondensation process. The intrinsic viscosity of copolymers ranged between 0.7 and 0.8 dL/g. The increase of isophthalate content resulted in a significant decrease of the crystallization rates, but in a small decline of tensile strength, Young's modulus, and elongation at break, whereas tensile strength at yield point remained almost unaffected. Also, a decrease in the melting point was recorded, whereas the glass‐transition temperature was only very slightly affected. The higher decrease for the aforementioned parameters was noted for the copolymer with 4 mol % isophthalate units content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1931–1941, 2002     

Metallocene ethylene‐co‐(5,7‐dimethylocta‐1, 6‐diene) copolymers crosslinked using electron beam irradiation: a tunable alternative

Ethylene‐co‐(5,7‐dimethylocta‐1,6‐diene) copolymers with various 5,7‐dimethylocta‐1,6‐diene contents incorporate double bonds in the lateral chains that facilitate the development of crosslinkings in the resulting polymeric material after electron beam irradiation. As an effect of such irradiation, crystallization is delayed but crystallinity remains practically constant after melting and further cooling of irradiated specimens. Crystallinity, crystallite thickness and gel content are key parameters in the mechanical performance of these copolymers. Consequently, the controlled incorporation of non‐conjugated dienes into the polyethylene structure appears as an alternative strategy for tuning the mechanical response in crosslinked polyolefins. Moreover, the resulting materials exhibit good thermal stability. Copyright © 2011 Society of Chemical Industry     

Segmented copolymers of uniform tetra‐amide units and poly(phenylene oxide) by direct coupling

Segmented copolymers with telechelic poly(2,6‐dimethyl‐1,4‐phenylene ether) (PPE) segments and crystallizable bisester tetra‐amide units (two‐and‐a‐half repeating unit of nylon‐6,T) were studied. The copolymers were synthesized by reacting bifunctional PPE with hydroxylic end groups with an average molecular weight of 3500 g/mol and bisester tetra‐amide units via an ester polycondensation reaction. The bisester tetra‐amide units had phenolic ester groups. By replacing part of the bisester tetra‐amide units with diphenyl terephthalate units (DPT), the concentration of tetra‐amide units in the copolymer was varied from 0 to 11 wt%. Polymers were also prepared from bifunctional PPE, DPT, and a diaminediamide (6T6‐diamine). The thermal and thermal mechanical properties were studied by DSC and DMA and compared with a copolymer with flexible spacer groups between the PPE and the T6T6T. The copolymers had a high T_g of 180–200°C and a melting temperature that increased with amide content of 220–265°C. The melting temperature was sharp with monodisperse amide segments. The T_m – T_c was 39°C, which suggests a fast, but not very fast, crystallization. The crystallinity of the amide was ～ 20%. The copolymers are semicrystalline materials with a high T_g and a high T_g/T_m ratio (> 0.8). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 512–518, 2007     

Hydroxyapatite as a filler for biosynthetic PHB homopolymer and P(HB–HV) copolymers

This paper deals with some of the fundamental problems encountered when using a semicrystalline polymer as the matrix phase for a particulate‐filled composite. As our model system we adopted poly‐(R)‐3‐hydroxybutyrate, PHB, and two copolymers of (R)‐3‐hydroxybutyrate and (R)‐3‐hydroxyvalerate, P(HB–HV), for the matrix phase, and the mineral calcium hydroxyapatite as a particulate filler. The structure and properties of compression‐moulded films of various compositions were investigated by polarized light microscopy, wide‐angle X‐ray scattering and mechanical testing. It was found that the degree of crystallinity of the matrix was lower in filled samples, and that the spherulitic crystallization of the matrix appeared to cause the filler particles to form agglomerates, which would not be as effective a reinforcement as finely dispersed primary filler particles. The tensile strength, strain‐to‐break and tensile modulus of samples of different compositions were analysed using well‐known theories for composite behaviour. Copyright © 2003 Society of Chemical Industry     

Effect of graft modification with poly(N‐vinylpyrrolidone) on thermal and mechanical properties of poly (3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)

Poly(N‐vinylpyrrolidone) (PVP) groups were grafted onto poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) backbone to modify the properties of PHBV and synthesize a new novel biocompatible graft copolymer. The effect of graft modification with PVP on the thermal and mechanical properties of PHBV was investigated. The thermal stability of grafted PHBV was remarkably improved while the melting temperature (T_m) was almost not affected by graft modification. The isothermal crystallization behavior of samples was observed by polarized optical microscopy and the results showed that the spherulitic radial growth rates (G) of grafted PHBV at the same crystallization temperature (T_c) decreased with increasing graft yield (graft%) of samples. Analysis of isothermal crystallization kinetics showed that both the surface free energy (σ_e) and the work of chain‐folding per molecular fold (q) of grafted PHBV increased with increasing graft%, implying that the chains of grafted PHBV are less flexible than ungrafted PHBV. This conclusion was in agreement with the mechanical testing results. The Young's modulus of grafted PHBV increased while the elongation decreased with increasing graft%. The hydrophilicity of polymer films was also investigated by the water contact angle measurement and the results revealed that the hydrophilicity of grafted PHBV was enhanced. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Morphology and thermal behavior of poly (3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/poly(butylene adipate‐co‐terephthalate)/clay nanocomposites

Biopolymers are gaining increasing interest because of decline of mineral oil reserves, increasing waste problem, and increasing consciousness of society for environmental problems. However, competitiveness of biopolymers compared with conventional plastics is still limited due to partly insufficient properties and high prices. This study investigates the influence of blending of poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV) with poly(butylene adipate‐co‐terephthalate) (PBAT) as well as the influence of addition of functionalized montmorillonite (OMMT) to the blends on morphology and thermal behavior. Dispersion state and morphology of the nanocomposites are studied by X‐ray diffraction as well as scanning electron microscopy. Thermal stability is studied by thermogravimetric analysis and crystallization behavior is studied by differential scanning calorimetry and polarized optical microscopy. With respect to the morphology for the blends it can be seen that the immiscible biopolymers PHBV and PBAT are distributed in interlocking zones. There is a good dispersion and homogeneous distribution of OMMT within the biopolymer blends. The addition of 50% or more PBAT to PHBV as well as the insertion of OMMT enhances thermal stability of PHBV. In the blends, the addition of PBAT retards crystallization of PHBV. The OMMT acts as nucleating agent leading in total to more but less perfect crystals in the blends, and the crystallization slows further due to constraint in the movement of polymer chains. These results contribute to the understanding of the structure–properties relationship of bionanocomposite materials for packaging applications. POLYM. COMPOS., 36:2051–2058, 2015. © 2014 Society of Plastics Engineer     

Thermal stability of polyhydroxyalkanoates

In this study, we examined the thermal decomposition of polyhydroxyalkanoates (PHAs) such as the homopolymer poly(3‐hydroxybutyrate) and the copolymer poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate). They are biodegradable polymers that can replace plastics produced from nonrenewable resources, such as polypropylene. The biopolymers we analyzed were commercial PHAs [obtained by means of pure cultures, with hydroxyvalerate (HV) contents of 0 and 10.4 mol %] and biopolymers produced in our laboratories (by means of an enriched activated sludge at two different organic loads, 8.5 and 20 gCOD/L, with a HV content of 20 mol %). To process these biopolymers, it is important to know their thermal stability. For this reason, thermal degradation in air by means of dynamic thermogravimetry (TG) was carried out. The TG data were adjusted to the nth‐order general analytical equation to evaluate the best order of the reaction, the temperatures of the onset and end of thermal decomposition, and the kinetic parameters. The latter were also calculated by means of other integral and differential methods and compared to those obtained by the general analytical solution. Finally, the influence of the preparation method (pure and mixed cultures and HV content within the biopolymer) on thermal stability was analyzed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2111–2121, 2006     

Effects of fumed silica on the crystallization behavior and thermal properties of poly(hydroxybutyrate‐co‐hydroxyvalerate)

The effects of fumed silica on the crystallization behavior and thermal properties of poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV) were investigated. The PHBV/silica composites were prepared by a melt‐blending method. The nonisothermal crystallization, melting process, and isothermal crystallization kinetics of PHBV and PHBV/silica composites were characterized with differential scanning calorimetry. The spherulite development and morphology were observed by polarized optical microscopy. In addition, the thermal degradation properties were determined via thermogravimetric analysis. The results indicated that the melting and crystallization kinetics of PHBV were greatly affected by fumed silica, and this was due to the effective nucleation function of silica, which enhanced the crystallization process. The thermal onset degradation temperature of PHBV increased with the addition of fumed silica. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Biodegradable composites: Morphological,chemical, thermal,and mechanical properties of composites of poly(hydroxybutyrate‐co‐hydroxyvalerate) with curaua fibers after exposure to simulated soil

Composites produced from biodegradable polymeric matrixes reinforced with vegetable fibers have attractive mechanical properties and are environmentally friendly. This work is directed to the biodegradation of a composite made of a poly(hydroxybutyrate‐co‐hydroxyvalerate) matrix reinforced with curaua fibers (with and without alkaline treatment) in simulated soil. The composites were developed by extrusion and injection and were later buried in simulated soil according to the ASTM G160‐03 method. Scanning electron microscopy showed evidence of microbial attack on the samples surfaces. Infrared spectra showed that the composites biodegradation was mainly caused by erosion of the surface layer resulting from microorganisms activity. Thermogravimetric analysis pointed out reduced thermal stability of the samples, and results of differential scanning calorimetry showed that the degree of crystallinity increases and then decreases progressively throughout the degradation period, indicating that enzymatic degradation primarily occurs in the amorphous phase material and thereafter in the crystalline phase. For curaua composite fibers, reductions in tensile strength and elastic modulus are more significant, indicating that the presence of fibers promotes biodegradation of the curaua fiber. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40712.     

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     

Influence of the synthesis conditions on the structural and thermal properties of poly(l‐lactide)‐b‐poly(ethylene glycol)‐b‐poly(l‐lactide)

The poly(l ‐lactide)‐b‐poly(ethylene glycol)‐b‐poly(l ‐lactide) block copolymers (PLLA‐b‐PEG‐b‐PLLA) were synthesized in a toluene solution by the ring‐opening polymerization of 3,6‐dimethyl‐1,4‐dioxan‐2,5‐dione (LLA) with PEG as a macroinitiator or by transterification from the homopolymers [polylactide and PEG]. Two polymerization conditions were adopted: method A, which used an equimolar catalyst/initiator molar ratio (1–5 wt %), and method B, which used a catalyst content commonly reported in the literature (<0.05 wt %). Method A was more efficient in producing copolymers with a higher yield and monomer conversion, whereas method B resulted in a mixture of the copolymer and homopolymers. The copolymers achieved high molar masses and even presenting similar global compositions, the molar mass distribution and thermal properties depends on the polymerization method. For instance, the suppression of the PEG block crystallization was more noticeable for copolymer A. An experimental design was used to qualify the influence of the catalyst and homopolymer amounts on the transreactions. The catalyst concentration was shown to be the most important factor. Therefore, the effectiveness of method A to produce copolymers was partly due to the transreactions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40419.     

Tensile and elastic properties of triblock copolymer based on aramide end‐segments and polyether mid‐segments

The tensile and elastic behavior of triblock copolymers containing uniform aramide (TΦB) hard end‐segments (HS) and poly(tetramethylene oxide) (PTMO, M_n = 2900 g/mol) soft segments (SSs) was studied. The molecular weight of the copolymer was varied by changing the length of the soft mid‐segment; by extending the PTMO₂₉₀₀ with terephthalate units, the SS length was increased from 2900 g/mol to 21,000 g/mol and concurrently the aramide concentration decreased from 18 to 3 wt %. The mechanical properties were investigated by means of tensile testing, stress relaxation (SR) experiments, and cyclic tensile set (TS) tests. The E‐modulus was found to increase with increasing aramide content. The low molecular weight copolymers were brittle whereas the high molecular weight copolymers displayed large fracture strain values. The transition from brittle to ductile seemed to occur at a triblock copolymer molecular weight of 6600 g/mol. A strain‐induced crystallization was observed at strains above 250%, and both the fracture strain and stress were found to be highly dependant on the molecular weight of the copolymer. Cyclic tensile experiments showed that the materials had low TS values up to the strain hardening point. On the other hand, the SR data at 10% strain seemed to be little dependant on the molecular weight. The higher molecular weight copolymers did not display lower SR values than their low molecular weight counterparts. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Crystallization of poly(ethylene terephthalate) and poly (butylene terephthalate) modified by diamides

Poly(ethylene terephthalate) (PET) and poly (butylene terephthalate) have been modified by diamide units (0.1–1 mol%) in an extrusion process and the crystallization behavior studied. The diamides used were: for PET, T2T‐dimethyl (N, N′‐bis(p‐carbomethoxybenzoyl)ethanediamine) and for PBT, T4T‐dimethyl (N, N′‐bis(p‐carbomethoxybenzoyl)butanediamine). The above materials were compared to talc (0.5 wt%), this being a standard heterogeneous nucleator, and to diamide modified copolymers obtained by a reactor process. Two PET materials were used: a slowly crystallizing recycled grade obtained from soft drink bottles and a rapidly crystallizing injection molding grade. The crystallization was studied by differential scanning calometry (DSC) and under injection molding conditions using wedge shaped specimens; the thermal properties were studied by dynamic mechanical analysis. T2T‐dimethyl is effective in increasing the crystallization of PET in both of the extrusion compounds as well as in the reactor materials. It was also found that the crystallization temperature of poly(butylene terephthalate) could be slightly increased by the addition of nucleators.