Oxygen Barrier and Thermomechanical Properties of Poly (3-hydroxybutyrate-co-3-hydroxyvalerate) Biocomposites Reinforced with Calcium Carbonate Particles.

This study aimed to prepare poly (3-hydroxybutyrate-co-3-hydroxyvalerate), biocomposites with incorporating various percentages of calcium carbonate using extrusion processing. Calcium carbonate was synthesized in the absence and presence of poly(vinyl sulfonic acid). The polymorph and morphology of calcium carbonate chanced with the introduction of poly(vinyl sulfonic acid). The rhombohedral calcite was obtained in the absence of poly(vinyl sulfonic acid). Rhombohedral calcite transformed into spherical vaterite with the addition of poly(vinyl sulfonic acid). The influence of filler contents on the properties of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) composites was studied. The structure and properties of poly (3-hydroxybutyrate-co-3-hydroxyvalerate)/ calcium carbonate biocomposites were investigated by XRD, FTIR, TGA, DSC, SEM, OTR and DMA. The nucleation effect of the calcium carbonate on the crystallization of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) was observed in the DSC and XRD measurements by increasing crystallinity of poly (3-hydroxybutyrate-co-3-hydroxyvalerate). It was shown that the variation of the barrier properties of biocomposites was influenced by polymorph and morphology of calcium carbonate. The addition of 0.5 wt% of the rhombohedral calcite and spherical vaterite increased the barrier properties by 25% and 12%, respectively compared to neat polymer. The dynamic mechanical properties of composites based on rhombohedral calcite and spherical vaterite in poly (3-hydroxybutyrate-co-3-hydroxyvalerate) matrix were investigated. The storage modulus increases by adding both particles in the composites over a wide range of temperature (-30 to 150 °C) where the reinforcing effect of calcite and vaterite was confirmed. At the same loading level, rhombohedral calcite led to more increase in the storage modulus, while less increase in storage modulus was observed in the presence of spherical vaterite particles.

The Effect of Boron Nitride on the Thermal and Mechanical Properties of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate).

The thermal and mechanical properties of poly(3-hydroxybutyrate-co-3-hydroxyvalerate, PHBV) composites filled with boron nitride (BN) particles with two different sizes and shapes were studied by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), thermal gravimetric analysis (TGA) and mechanical testing. The biocomposites were produced by melt extrusion of PHBV with untreated BN and surface-treated BN particles. Thermogravimetric analysis (TGA) showed that the thermal stability of the composites was higher than that of neat PHBV while the effect of the different shapes and sizes of the particles on the thermal stability was insignificant. DSC analysis showed that the crystallinity of the PHBV was not affected significantly by the change in filler concentration and the type of the BN nanoparticle but decreasing of the crystallinity of PHBV/BN composites was observed at higher loadings. BN particles treated with silane coupling agent yielded nanocomposites characterized by good mechanical performance. The results demonstrate that mechanical properties of the composites were found to increase more for the silanized flake type BN (OSFBN) compared to silanized hexagonal disk type BN (OSBN). The highest Young's modulus was obtained for the nanocomposite sample containing 1 wt.% OSFBN, for which increase of Young's modulus up to 19% was observed in comparison to the neat PHBV. The Halpin⁻Tsai and Hui⁻Shia models were used to evaluate the effect of reinforcement by BN particles on the elastic modulus of the composites. Micromechanical models for initial composite stiffness showed good correlation with experimental values.

Fabrication of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) biocomposites with reinforcement by hydroxyapatite using extrusion processing.

The aim of this study was to prepare poly(3-hydroxybutyrate-co-3-hydroxyvalerate), PHBV, biocomposites with incorporating various percentages of hydroxyapatite (HAP) using extrusion processing. The biocomposites were produced by melt extrusion of PHBV with untreated HAP and surface-treated HAP crystals. The structure of biopolymer/HAP biocomposites was investigated by XRD, FTIR, DSC and SEM. Silane coupling agent was used for HAP surface treatment in PHBV/HAP composites. Silane-treated HAP nanoparticles yielded nanocomposites characterized by good mechanical performance and fine nanofiller dispersion, as shown by SEM investigations. The Halpin-Tsai and Hui-Shia models were used to evaluate the effect of reinforcement by HAP particles on the elastic modulus of the composites. Micromechanical models for initial composite stiffness showed good correlation with experimental values. Disparities in the Halpin-Tsai model were evident for composite with higher HAP loadings.

Synthesis of hydroxyapatite crystals using carboxymethyl inulin for use as a delivery of ibuprofen.

In the present study biodegradable, environmentally friendly polysaccharide-based polycarboxylate, carboxymethyl inulin (CMI), was used to produce hydroxyapatite (HAP) particles by wet chemical synthesis under controlled temperature, pH, and atmospheric conditions. The morphology and microstructure of the HAP nanoparticles were investigated by XRD, SEM, DTA-TGA and FTIR. CMI affects morphology, surface area, dimension and particle size distribution of the crystals. The reduction in size is greater in the direction of the c-axis. The increase in the polymer concentration to 7.5 g/L resulted in the mixture of nanoparticles with particle sizes of less than 100nm. The SEM micrograph shows the formation of well-crystallized, agglomerated small particles of HAP. X-ray analysis has shown that the resulting particles have high thermal stability. The obtained crystals were used to produce tablets by direct compression of HAP. The influence of sample's CMI concentration on drug release profiles was investigated by using ibuprofen (C13H18O2) as a model drug. The model was used to determine the effective diffusion coefficient of the drug from the tablets. A good agreement between experimental data and model predictions was obtained as calculated in the present work. The values of the diffusion coefficients range from 1.62×10(-7) to 4.72×10(-7) m(2) h(-1).

The inhibitory effects of carboxymethyl inulin on the seeded growth of calcium carbonate.

Kinetics of precipitation of calcite (CaCO(3)) from aqueous solution in the presence of carboxymethyl inulin (CMI) was investigated under strictly controlled temperature, pH, supersaturation ratio (S=4.8) and ionic strength (I=0.1M). The highly reproducible constant composition technique was used to study the influence of biopolymers of crystal growth of CaCO(3), on CaCO(3) seed crystals at pH 8.5 and 25°C. The crystal growth of calcium carbonate (CaCO(3)) was inhibited in the presence of CMI at low concentration (2.5×10(-9) to 25×10(-9)mol/L). The larger number of negatively charged functional groups exhibited a 95% growth rate inhibition at a concentration of 15×10(-9)mol/L. The higher inhibition efficiency is related to the maximum surface charge density due to adsorbed polymer.

The role of vinyl sulfonic acid homopolymer in calcium oxalate crystallization.

In this study, the effect of water soluble homopolymer of vinylsulfonic acid on spontaneous crystallization of calcium oxalate (CaOx) was investigated. CaOx crystals exhibiting different shapes and phase structures were produced in the presence of polymer. While the crystal growth of calcium oxalate was inhibited by homopolymer, the morphology of calcium oxalate transformed from monohydrate to dihydrate. Inhibition of calcium oxalate crystallization was provided by adsorption of homopolymer onto the active growth sites of crystals on account of the charge and hydrophilic effects. Polyelectrolyte effects were interpreted in terms of the adsorption of inhibitors onto the active growth sites on the crystal surface.

The influence of polymer architecture on nanosized hydroxyapatite precipitation.

In this work we present a facile way to produce hydroxyapatite (HAP) nanoparticles by wet chemical synthesis in the presence of polyelectrolytes under controlled temperature, pH, and atmospheric conditions. The resulting calcium rich carbonated HAP is sintered in an air atmosphere to investigate the thermal stability of the synthesized powders. The morphology and microstructure of the HAP nanoparticles were investigated by XRD, SEM, FTIR spectroscopy, thermal analysis, and particle size analyzer. Polyelectrolytes affect the coherent length of the crystalline domain, the dimension and particle size distribution of the crystals. The reduction in size is greater in the direction of the c-axis. The SEM micrograph shows the formation of well-crystallized, agglomerated small particles of HAP. The mean size of the subunit is smaller than that of the surface of the grain observed in SEM. X-ray analysis have shown that the resulting particles have high thermal stability.

Biomimetic mineralization of hydroxyapatite crystals on the copolymers of vinylphosphonic acid and 4-vinilyimidazole.

In the present work, copolymers of vinylphosphonic acid and 4-vinilyimidazole (poly(4-VIm-co-VPA)) were found to be substrates favoring the precipitation of nanohydroxyapatite (HAP) crystals from stable supersaturated solutions at pH 7.4 and 37 degrees C. Deposition kinetics were studied by the constant composition technique. The rates of crystallization both on HAP seed crystals as reference and on the copolymer in powder form were investigated at constant supersaturation conditions. The rates of HAP crystal growth on the polymeric substrate were found to depend on the amount of seed material and on the phosphate content of the copolymer.