Effect of Lignosulfonate on the Thermal and Morphological Behavior of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

The effect of lignosulfonate on poly(3-hydroxybutyrate-co-3-hydroxyvalerate), PHBV, was studied by scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The PHBV/lignosulfonate samples were prepared by melt mixing in an internal mixer. SEM showed that PHBV/lignosulfonate samples present a cracked surface that is more intense in mixtures with high lignosulfonate proportions. According to DSC, melting and glass transition temperatures of the PHBV matrix decrease with lignosulfonate addition. The same effect was observed for melting enthalpies (ΔH_m), which indicates a decrease of crystallinity. TGA showed that thermal stability of PHBV/lignosulfonate samples was shifted to lower temperatures, which indicates the existence of an interaction between the thermal decomposition processes of PHBV and lignosulfonate.     

The Influence of Artificial Photodegradation on Properties of Poly(3-hydroxybutyrate-<Emphasis Type="Italic">co</Emphasis>-3-hydroxyvalerate)(PHBV)/Graphite Nanosheets (GNS) Nanocomposites

The potential use of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/graphite nanosheets (GNS) as a biodegradable nanocomposite has been explored. PHBV/GNS nanocomposites films were prepared by solution casting at various concentrations of GNS—0.25, 0.50 and 1.00 wt% GNS. The films were exposed to artificial ultraviolet radiation (UV) during 52 h. The effect of GNS on PHBV photodegradation was investigated and compared to neat PHBV film. The artificial photodegradation induced changes in physical (weight loss), chemical carbonyl index by Fourier transform infrared spectroscopy, thermal degree of crystallinity and melting temperature by differential scanning calorimetry and morphological scanning electron microscopy characteristics. Based on the results obtained from aforementioned analyzes it was verified that GNS inhibits the oxidative degradation of PHBV matrix.     

The Effect of Chain Extender on Poly(3-hydroxybutyrate-co-3-hydroxyvalerate): Thermal Degradation,Crystallization, and Rheological Behaviours

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), a semi-polycrystalline biopolymer from the polyhydroxyalkanonate family has in recent years become a commercial bioplastic with mechanical properties comparable to isotactic polypropylene and enhanced O₂, CO₂ and H₂O barrier properties. However, its brittleness and sensitivity to thermal and hydrolysis degradations restrict its applications. To overcome the problems associated with degradation during processing blending of PHBV and an epoxy-functionalized chain extender (Joncryl^® ADR-4368 S) was conducted in a twin screw extruder. The effect of concentration of the chain extender on thermal, crystallization and rheological behaviours of PHBV was investigated. Thermal gravimetric analysis results indicated improvement in the resistance to thermal decomposition of PHBV by introducing the chain extender. This was accompanied with calculation of thermal degradation activation energy (E_a) using the Flyn–Walls–Ozawa method which confirmed increase of E_a with the increase in content of the chain extender. The rheological behaviour and crystallization of modified PHBV was characterized by rotational rheometry and differential scanning calorimetry techniques, respectively. The results show that addition of chain extender enhanced viscosity of PHBV and also reduce the rate of crystallization.     

Comparison of the Effect of Plasticizers on PHBV—and Organoclay—Based Biodegradable Polymer Nanocomposites

The aim of this work was to evaluate the effect of different plasticizers on the morphology, crystallization, and mechanical properties of poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV)/organomodified montmorillonite (OMt) nanocomposites. We investigated three different plasticizers: dioctyl phthalate (DOP), a commonly used additive in the polymer industry, and two natural and biodegradable plasticizers: epoxidized soybean oil (ESO) and triethyl citrate (TEC). The nanocomposites with 3 wt% OMt were obtained by melt processing in an internal mixer. The plasticizers were used alone or in combination with clay in a concentration of 10 wt%. X-ray diffraction and scanning electron microscopy results revealed a partially intercalated structure. The degree of crystallinity was higher for all of the samples compared to neat PHBV, although the melting temperature decreased with the use of plasticizers combined with OMt. The impact strength results were dependent on the interaction between the components of the system. Triethyl citrate was the most effective plasticizer due to its more pronounced interaction with the PHBV matrix, which yielded improvements in processing conditions and PHBV’s flexibility and impact properties.     

Fabrication and Characterization of PLA/PHBV-Chitin Nanocomposites and Their Foams

This paper examines the effect of biobased chitin nanowhisker fillers on the thermal, rheological, physical, mechanical and morphological properties of biobased polylactic acid (PLA) and PLA/polyhydroxybutyrate-co-valerate (PHBV) blended nanocomposites as well as the physical, mechanical and morphological properties of porous PLA and PLA/PHBV nanocomposite foams. Solid nanocomposites of PLA, PLA/PHBV and chitin nanowhiskers were manufactured through melt blending while porous nanocomposites foams were fabricated through a batch foaming process with the aid of CO₂ as blowing agent. It was found that by incorporating small quantities of chitin nanowhiskers (<2 wt%) the mechanical properties of solid specimens are improved while strength and expandability of the foam can be significantly improved, yielding a homogenously distributed cell morphology with average cell size of 1.5 μm.     

Recovery of indium from used LCD panel by a time efficient and environmentally sound method assisted HEBM

In this study, a method which is environmentally sound, time and energy efficient has been used for recovery of indium from used liquid crystal display (LCD) panels. In this method, indium tin oxide (ITO) glass was crushed to micron size particles in seconds via high energy ball milling (HEBM). The parameters affecting the amount of dissolved indium such as milling time, particle size, effect time of acid solution, amount of HCl in the acid solution were tried to be optimized. The results show that by crushing ITO glass to micron size particles by HEBM, it is possible to extract higher amount of indium at room temperature than that by conventional methods using only conventional shredding machines. In this study, 86% of indium which exists in raw materials was recovered about in a very short time.     

Study of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV)/Bamboo Pulp Fiber Composites: Effects of Nucleation Agent and Compatibilizer

In this study, poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV)/bamboo pulp fiber (BPF) composites were prepared by melt compounding and injection molding. The crystallization ability, tensile strength and modulus, flexural strength and modulus, and impact strength were found substantially increased by the addition of BPF. Tensile and flexural elongations were also moderately increased at low fiber contents (<20%). BPF demonstrated not only higher strength and modulus, but also higher failure strain than the PHBV8 matrix. Boron nitride (BN) was also investigated as a nucleation agent for PHBV8 and maleic anhydride grafted PHBV8 (MA-PHBV8) as a compatibilizer for the composite system. BN was found to increase the overall properties of the neat polymer and the composites due to refined crystalline structures. MA-PHBV8 improved polymer/fiber interactions and therefore resulted in increased strength and modulus. However, the toughness of the composites was substantially reduced due to the hindrance to fiber pullout, a major energy dissipation source during the composite deformation.     

Thermal Properties and Biodegradability Studies of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

For investigating the relationship between thermal properties and biodegradability of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), several films of PHBV containing different polyhydroxyvalerate (HV) fractions were subjected to degradation in different conditions for up to 49 days. Differential scanning calorimetry (DSC), thermogravimetry (TG), specimen weight loss and scanning electron microscopy (SEM) were performed to characterize the thermal properties and enzymatic biodegradability of PHBV. The experimental results suggest that the degradation rates of PHBV films increase with decreasing crystallinity; the degradability of PHBV occurring from the surface is very significant under enzymatic hydrolysis; the crystallinity of PHBV decreased with the increase of HV fraction in PHBV; and no decrease in molecular weight was observed in the partially-degraded polymer.     

Dispersing Bacterial Cellulose Nanowhiskers in Polylactides via Electrohydrodynamic Processing

In the present study, hybrid electrospun polylactide (PLA) fibers reinforced with highly dispersed crystalline bacterial cellulose nanowhiskers (BCNW) in solution concentrations up to 15 wt% were developed and characterized. The overall aim was to encapsulate dispersed BCNW in fibers to be later re-dispersed in virgin PLA by melt compounding. Initially, the suitability of three different solvents [1,1,1,3,3,3-hexafluoro-2-propanol (HFP), acetone–chloroform and chloroform/polyethylene glycol (PEG)] for fiber production was evaluated and solutions containing 5 wt% BCNW were used to generate electrospun hybrid PLA fibers. These fibers presented a homogeneous morphology, as assessed by scanning electron microscopy, and transmission electron microscopy images demonstrated that BCNW were well distributed along the fibers. Differential scanning calorimetry analyses showed that the incorporation of PEG into the fibers resulted in a T_g drop due to a plasticization effect and decreased thermal stability as a result of low interactions between the matrix and the BCNW. Subsequently, fibers were produced from the selected solutions (HFP and acetone–chloroform) containing up to 15 wt% BCNW. As a result of the great increase in the viscosity of the solutions, lower solids contents were required, leading to a better dispersion and incorporation degree of BCNW within the fibers. HFP was found to be a more suitable solvent, since higher incorporation levels were estimated by X-ray diffraction and improved matrix–filler interactions were suggested by a slight increase in the T_g of the fibers.     

Solid state dehalogenation of PCBs in contaminated soil using NaBH4

In this work we present the results of an experimental study on the abatement of polychlorinated biphenyl (PCBs) in contaminated soil using a high energy milling technique, that promotes a reaction only by impact between milling bodies. A sample of soil from a controlled landfill was treated with powdered NaBH(4) using two different hydride/soil ratios (5 and 2.5% w/w). The efficiency of the dehalogenation/hydrogenation reaction was studied as a function of the milling time (3.5 up to 30 h). After each run, the total PCBs content and the production of inorganic chloride were measured. The complete abatement was obtained with a starting PCBs concentration of about 2600 mg/kg. The residual PCBs concentration resulted to be <0.2 mg/kg. The final products of the treatment were biphenyl and NaCl. Other toxic or hazardous organic by-products were not generated. Boron was found as boric acid.     

Environmental Degradation of Blends of Atactic Poly[(R,S)-3-hydroxybutyrate] with Natural PHBV in Baltic Sea Water and Compost with Activated Sludge

Degradation of atactic poly[(R,S)-3-hydroxybutyrate] (a-PHB) binary blends with natural poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV, 12 mol% of 3HV units), has been investigated and compared with plain PHBV in the compost containing activated sludge and under marine exposure conditions in the dynamic water of the Baltic Sea. Characteristic parameters of compost and the Baltic Sea water were monitored during the incubation period (6 weeks) and their influence on the degree of biodegradation is discussed. After specified degradation times of the experiments the weight loss of the samples, surface changes, changes in molecular weight and polydispersity as well as changes of the composition and thermo-mechanical properties of the blends have been evaluated. Macroscopic observations of the samples were accompanied by investigations using optical microscopy, size-exclusion chromatography (SEC), nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC) and tensile testing. The degree of degradation of blends of a-PHB with PHBV depends on the blend composition and environmental conditions. In both environments studied the weight loss of plain PHBV was more significant than changes the molecular weight. In both environments only enzymatic degradation of the blends, which proceeds via surface erosion mechanisms, was observed during the incubation period.     

Poly(3-Hydroxybutyrate-co-3-Hydroxyvalerate)/Polylactide Blends: Thermal Stability,Flammability and Thermo-Mechanical Behavior

Blends of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and polylactide (PLA) with different PHBV/PLA weight ratios (100/0, 75/25, 50/50, 25/75, 0/100) were prepared by melt compounding. Their mutual contributions in terms of thermal stability, flammability resistance, mechanical properties and rheological behavior were investigated. The study showed that the increase in PLA content in PHBV/PLA blends leads to enhanced properties. Consequently, thermal stability and flammability resistance were improved. Further, the rheological measurements indicated an increase in storage modulus and loss modulus of PHBV matrix by addition of PLA.     

Production and Purification of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Degrading Enzyme from Streptomyces sp. AF-111

A poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) degrading bacterial strain designated as AF-111 was isolated from sewage sludge sample. The bacterium was identified by 16S rRNA gene sequencing. The results revealed that strain AF-111 showed 99 % similarity with Streptomyces althioticus strain NRRL B-3981 and designated as Streptomyces sp. strain AF-111. An extracellular PHBV depolymerase enzyme was produced under optimized conditions and purified through ammonium sulphate fractionation and column chromatography. The enzyme was purified to homogeneity, indicated by sodium dodecyl sulfate–polyacrylamide gel electrophoresis and molecular weight was found to be approximately 51 kDa. Effect of temperature, pH, metal ions and inhibitors on the PHBV depolymerase activity was determined. The enzyme was stable at wide range of temperature (35–55 °C) and pH (6–8). PHBV depolymerase was stable in the presence of different metal ions except iron and zinc which had inhibitory effect on depolymerase activity. Both ethylenediamine teteracetic acid and phenylmethyl sulphonyl fluoride strongly inhibited enzyme activity which indicates that this enzyme belongs to the serine hydrolase family like other polyhydroxyalkanoate depolymerases. The results show that a depolymerase from strain AF-111 can effectively degrade PHBV, therefore, it can be applied in the process of biochemical monomer recycling.     

Biodegradation of Injection Molded Starch-Poly (3-hydroxybutyrate-co-3-hydroxyvalerate) Blends in a Natural Compost Environment

Injection molded specimens were prepared by blending poly (hydroxybutyrate-co-valerate) (PHBV) with cornstarch. Blended formulations incorporated 30% or 50% starch in the presence or absence of poly-(ethylene oxide) (PEO), which enhances the adherence of starch granules to PHBV. These formulations were evaluated for their biodegradability in natural compost by measuring changes in physical and chemical properties over a period of 125 days. The degradation of plastic material, as evidenced by weight loss and deterioration in tensile properties, correlated with the amount of starch present in the blends (neat PHBV < 30% starch < 50% starch). Incorporation of PEO into starch-PHBV blends had little or no effect on the rate of weight loss. Starch in blends degraded faster than PHBV and it accelerated PHBV degradation. Also, PHBV did not retard starch degradation. After 125 days of exposure to compost, neat PHBV lost 7% of its weight (0.056% weight loss/day), while the PHBV component of a 50% starch blend lost 41% of its weight (0.328% weight loss/day). PHB and PHV moieties within the copolymer degraded at similar rates, regardless of the presence of starch, as determined by ¹H-NMR spectroscopy. GPC analyses revealed that, while the number average molecular weight (Mn) of PHBV in all exposed samples decreased, there was no significant difference in this decrease between neat PHBV as opposed to PHBV blended with starch. SEM showed homogeneously distributed starch granules embedded in a PHBV matrix, typical of a filler material. Starch granules were rapidly depleted during exposure to compost, increasing the surface area of the PHBV matrix.     

Systematic comparison of mechanical and thermal sludge disintegration technologies

This study presents a systematic comparison and evaluation of sewage sludge pre-treatment by mechanical and thermal techniques. Waste activated sludge (WAS) was pre-treated by separate full scale Thermo-Pressure-Hydrolysis (TDH) and ball milling facilities. Then the sludge was processed in pilot-scale digestion experiments. The results indicated that a significant increase in soluble organic matter could be achieved. TDH and ball milling pre-treatment could offer a feasible treatment method to efficiently disintegrate sludge and enhance biogas yield of digestion. The TDH increased biogas production by ca. 75% whereas ball milling allowed for an approximately 41% increase. The mechanisms of pre-treatment were investigated by numerical modeling based on Anaerobic Digestion Model No. 1 (ADM1) in the MatLab/SIMBA environment. TDH process induced advanced COD-solubilisation (COD_soluble/COD_total = 43%) and specifically complete destruction of cell mass which is hardly degradable in conventional digestion. While the ball mill technique achieved a lower solubilisation rate (COD_soluble/COD_total = 28%) and only a partial destruction of microbial decay products. From a whole-plant prospective relevant release of ammonia and formation of soluble inerts have been observed especially from thermal hydrolysis.     

锌粉对聚氯乙烯的机械化学还原脱氯

以锌粉为还原剂进行了聚氯乙烯（PVC）的机械化学还原脱氯（简称脱氯）探索研究，考察了球磨转速、球料比（磨球与试样的质量比）、锌粉与PVC质量比等对脱氯率的影响，并对脱氯产物进行了X射线衍射、红外光谱等分析。实验结果表明，最佳工艺条件为球料比33、球磨转速528r／min、锌粉与PVC质量比9；产物中未形成结晶性氯化锌，且锌粉被氧化成ZnO；行星球磨比搅拌球磨对PVC的脱氯效果好，球磨时间超过3h，PVC的脱氯率可接近100％。     

Determination of Kinetic Parameters for the Degradation of Chitosan/Silica Hybrid Nano Composites

The thermal degradation behavior of chitosan (CS) and chitosan–silica (CS–Si) nanocomposites were studied using a differential kinetic model. The influence of the heating rate in the non-isothermal degradation kinetics of CS and CS–Si nanocomposites are presented. Kinetic parameters, such as the activation energy (E) and pre-exponential factor (A), and thermodynamic parameters, such as the Gibbs free energy (ΔG), enthalpy (ΔH) and entropy (ΔS), were determined using the modified Arrhenius equation. It was shown that the rate constant for degradation (k), activation energy and pre-exponential factor depend on the heating rates. The order of reaction was found to be one. The isothermal stability of CS and CS–Si was determined from non-isothermal kinetics and was also found to be dependent on the heating rate. Thermogravimetric studies revealed that neat CS was less thermally stable than the CS–Si nanocomposites.     

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.     

Blending Modification of PHBV/PCL and its Biodegradation by <Emphasis Type="Italic">Pseudomonas mendocina</Emphasis>

Poly(3-hydroxybutyrate-co-hydroxyvalerate) (PHBV) is a biodegradable polymer synthesized in microorganisms. The application of PHBV is limited by certain material disadvantages. Poly(ε-caprolactone) (PCL) possesses excellent thermodynamic and mechanical properties and was used to modify PHBV in the presence of triethyl citrate (TEC) and dicumyl peroxide (DCP), which was used as plasticizer and grafting agent, respectively. The effects of PCL and additive agents on the mechanical, thermal, amphipathic and degradability behaviors of the blends were investigated. The results showed that the mechanical properties of the PHBV blends improved by PCL incorporation and improved even further after TEC and DCP addition. The addition of DCP could not induce an increase in crystallization temperature but improved the crystallization degree of the blends. The presence of hydrophilic groups in TEC leads to an apparent increases in the hydrophilicity of the PHBV blends. A PHBV/PCL blend (40/60) with TEC (20 wt.%) and DCP (0.5 wt.%) was chosen for its good mechanical properties and hydrophilicity. The chosen ratio of the blends was also shown a preferable degradation activity by biodegradation assay using Pseudomonas mendocina. The addition of TEC and DCP has no conspicuous negative effect on the biodegradation.     

The Investigation of the Toughening Mechanism of PHBV/PBAT with a Novel Hyperbranched Ethylenediamine Triazine Polymer Based Modifier: The Formation of the Transition Layer and the Microcrosslinking Structure

A new type of designed hyperbranched ethylenediamine trazine polymer (HBETP) is successfully synthesized and characterized based upon NMR and GPC. The prepared HBETP is used to modify the poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV)/poly(butylene adipate-co-terephthalate) (PBAT) blends. The effect of HBETP on the microstructure, mechanical properties and thermal properties of the blends is studied. The results indicate that upon addition of 1.0 wt% of HBETP, the impact strength of the PHBV/PBAT blends is increased by 47.1%; ?T_g of the blends decreases from 53.2 to 49.9 °C. These results, together with the morphology analysis of the fractured surface of the blends, conclude the formation of the transition layer between PHBV and PBAT. Also, the XRD result shows that the addition of HBETP can limit the growth of the PHBV crystals and causes the decrease of both the crystallinity and the grain crystalline size. The DSC result demonstrates that the addition of HBETP mainly affects the crystallization of the HB-HV binary eutectic region within PHBV. The mechanism of PHBV/PBAT toughening is due to the formation of the strong physical hydrogen bonding and the chemical micro-crosslinking between HBETP and PHBV/PBAT, which is proposed based on XPS characterization.