PHBV Content Research Articles

Preparation of porous ultra-fine poly(vinyl cinnamate) fibers

In this study, a new method of preparing porous ultra-fine fibers via photo-crosslinking was developed. Ultra-fine poly(vinyl cinnamate)/poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PVCi/PHBV) blend fibers were electrospun and then the PVCi was photo-crosslinked by UV irradiation. PVCi and PHBV were immiscible and the phase separation proceeded during the electrospinning process. After the photo-crosslinking of PVCi, PHBV was extracted from the blend fibers with chloroform. The average pore sizes in the remaining ultra-fine PVCi fibers were increased with increasing the content of PHBV in the ultra-fine PVCi/PHBV fibers.

Melt reaction in blends of poly(3-hydroxybutyrate- co-3-hydroxyvalerate) and epoxidized natural rubber

Poly(3-hydroxybutyrate- co-3-hydroxyvalerate) (PHBV) with hydroxyvalerate content of 12 mol % is a natural aliphatic polyester. At temperatures above its melting point, thermal decomposition occurs leading to shorter chains with carboxyl end groups. In blends with epoxidized natural rubber (ENR), 50% epoxidation level, these carboxyl chain ends may trigger reactions between the constituents since the epoxidized groups provide reactive sites. Glass transition temperature studies reveal immiscibility of the polymers over the entire composition range. Hence, any reaction between the constituents is restricted to the interfacial region between the components. We report here on studies on melt reactions between the components at elevated temperatures. DSC traces display an exothermic peak when the blends are annealed at temperatures ranging from 220 up to 234 °C. The kinetics of the reaction are discussed in terms of a serial reaction scheme. It turns out that the reaction rate increases with annealing temperature ( T a) and with descending PHBV content in the blends when PHBV is the minor component. Morphological studies by optical microscopy reveal that PHBV is still capable of crystallizing at 50 °C after melt reaction at 234 °C. Either ring-banded or fibrillar spherulites can be seen in blends with PHBV in excess. We note, however, that the rate of crystallization is dramatically reduced after melt reaction at T a=234 °C.

Biodegradation of starch-poly(β-hydroxybutyrate-co-valerate) composites in municipal activated sludge

Injection-molded composites were prepared by blending PHBV5 with native cornstarch (30% and 50%) and with cornstarch precoated with PEO as a binding agent. These composites were evaluated for their biodegradability in municipal activated sludge by measuring changes in their physical and chemical properties over a period of 35 days. All composites lost weight, ranging from 45 to 78% within 35 days. Interestingly, the extent and rate of weight loss were quite similar in PHBV composites with no starch, with 30% starch, and with 50% starch. Weight loss was slowest in PHBV blends prepared with PEO-coated starch. For all samples, the weight loss was accompanied by a rapid deterioration in tensile strength and percentage elongation. The deterioration of these mechanical properties exhibited a relative rate of PHBV>starch-PHBV>PEO-coated starch-PHBV. Changes in starch/PHBV composition after biodegradation were quantified by FTIR spectroscopy. Increasing the starch content resulted in more extensive starch degradation, while the PHBV content in the blends became less susceptible to hydrolytic enzymes.

Biodegradability of blends of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with cellulose acetate esters in activated sludge

Blends of the bacterially produced polyester poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) with cellulose acetate esters (CAE) further substituted with propionyl or butyryl groups (degree of substitution: 2.60 propionyl and 0.36 acetyl or 2.59 butyryl and 0.36 acetyl, respectively) were exposed for 4 months to activated sludge to determine their biodegradability. Samples of such blends made by solution-mixing and solvent-casting had complex morphologies in which both individual components as well as a miscible blend phase were present. Additionally, the two opposite surfaces of solvent-cast films showed both physical and chemical differences. After 2 months, samples of pure PHBV had degraded by more than 98% (15 mg/cm2 of surface area), whereas a pure CAE sample had degraded less than 1% (<0.2 mg/cm2). Samples containing 25% CAE lost less than 40% of their initial weights (6 mg/cm2) over the total 4-month period. Samples with 50% CAE lost up to 16% weight (2 mg/cm2), whereas those containing 75% CAE lost only slightly more weight than corresponding sterile control samples (1 mg/cm2). NMR results confirm that weight loss from samples containing 25% CAE resulted only from degradation of PHBV and that the surface of samples became enriched in CAE. Solvent-cast film samples containing equal amounts of PHBV and CAE degraded preferentially on the surface which formed at the polymer-air interface. Scanning electron microscopy and attenuated total reflectance infrared spectroscopy revealed this surface to have a rougher texture and a greater PHBV content.