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A composite of 70/30 poly(lactic acid)/hydroxyapatite was systematically prepared using various amounts of glycidyl methacrylate as reactive compatibilizer or Joncryl ADR®-4368 containing nine glycidyl methacrylate functions as a chain extension/branching agent to improve the mechanical and biological properties for suitable usage as internal bone fixation devices. The effect of glycidyl methacrylate/Joncryl on mechanical properties of poly(lactic acid)/hydroxyapatite was investigated through flexural strength. Cell proliferation and differentiation of osteoblast-like MC3T3-E1 cells cultured on the composite samples were determined by Alamar Blue assay and alkaline phosphatase expression, respectively. Result shows that flexural strength tends to decrease, as glycidyl methacrylate content increases except for 1 wt.% glycidyl methacrylate. With an addition of dicumyl peroxide, the flexural strength shows an improvement than that of without dicumyl peroxide probably due to the chemical bonding of the hydroxyapatite and poly(lactic acid) as revealed by FTIR and NMR, whereas the composite with 5 wt.% Joncryl shows the best result, as the flexural strength increases getting close to pure poly(lactic acid). The significant morphology change could be seen in composite with Joncryl where the uniform agglomeration of hydroxyapatite particles oriented in poly(lactic acid) matrix. Addition of the epoxy functional compatibilizers at suitable percentages could also have benefits to cellular attachment, proliferation, differentiation and mineralization. So that, this poly(lactic acid)/hydroxyapatite composite could be a promising material to be used as internal bone fixation devices such as screws, pins and plates.

Summary A method for preparation of silica particles from rice husk ash (RHA) is developed for use as fillers in an enhancement of gas permeability of polylactic acid (PLA) resin. Silica particles are produced in a one-step process by employing PLA-grafted-chitosan copolymer (PCT) as a polymeric surfactant. Particles with an average size of ca. 30 micron, which are smaller than those obtained from a conventional method, are obtained. The major advantage of this technique is its ease of operation, in which mechanical grinding is not required. The resulting particles are then used in preparation of PLA/silica composites by varying the silica contents from 0–2.0 wt %. The PCT copolymer is present as a coating layer on the particles surface, which promotes compatibility with the PLA matrix. Gas permeability (water vapor, carbon dioxide, and oxygen) and mechanical properties of the composite films are examined. Enhancements in gas permeability and selectivity are achieved, with slight drops in mechanical properties. The materials have high potential for use as degradable packaging films with tunable gas permeability.

Multi-branched poly(D-lactide)s (mbPDLAs) with various structures are synthesized via ring-opening polymer- ization by using polyglycidol (PG) macro-initiators. Their chemical structures and thermal properties are controlled by adjusting feed ratios of D-lactide (DLA) and PG. The materials are blended with commercial linear poly(L-lactide) (l-PLLA) to form a stereocomplex structure. Effects of mbPDLAs structures and l-PLLA/mbPDLA ratios on the blends' thermal, mechanical, and rheological properties are evaluated. Mechanical properties of the stereocomplex blends, espe- cially elongation at break and toughness, are dependent on the blend compositions, in which a 90:10 ratio exhibits the most desirable properties. The material also exhibits the lowest complex viscosity, which provides easy processing conditions. This is achieved by the incorporation of copolymers with multi-branched structures and an ability to form a much stronger stereocomplex structure.

Glycolyzed polylactic acid (GPLA)-cured epoxidized natural rubber (ENR) is developed for use as a toughening agent for PLA resin. GPLA is obtained from chemical recycling of PLA resin by a glycolysis reaction. GPLA-cured ENR is then prepared by the crosslinking reaction of ENR with GPLA in an internal mixer. Chemical structures of the cured products are characterized by solvent fractionation and thermogravimetric analysis (TGA). The cured ENR products are blended with PLA resin, by varying the cured ENR contents from 5 to 15% wt. Mechanical properties of the blends, and their toughening mechanisms are examined. The cured ENR materials has higher efficiency in improving toughness of PLA resin, compared to uncured ENR, likely due to their rubbery network nature and higher compatibility with the PLA matrix. The incorporation of 5% wt. GPLA-cured ENR also improves elongation at break with no adverse effect on tensile strength and modulus of PLA.

Nanofibers of poly(L-lactide-co-DL-Lactide) (PDLLAx) copolymers with DL-lactate (DLLA) contents of 0, 2.5, 7.5, and 50%, which exhibit strong structure/properties correlation, were fabricated by electrospinning. Effect of the copolymer structure and electrospinning conditions on morphology and properties of the fibers were examined by SEM, DSC, XRD, and tensile measurements. Bead-free fibers of PDLLAx prepared from a DMF/CHCl3 mixed solvent are roughly 10-times smaller in size (600–800 nm), with lower degree of surface porosity, compared to those of CHCl3. When CHCl3 is employed, an increase in size (2.4–5.5 μm) and surface porosity (0–45%) with relative humidity value is observed in crystallizable copolymers, whereas an amorphous copolymer shows a reverse trend. Thermal properties and chain arrangements of the electrospun fibers are critically affected by DLLA content of the copolymers and electrospinning conditions, as a result from interplay between intermolecular and intramolecular hydrogen bonding. Contents of crystalline domains and “physical crosslinks” generated from DL lactate segments are proposed as the origin of this phenomenon. Fiber mats of PDLLA with 50% DLLA content show a large improvement in all aspects of mechanical properties, which are suitable for various biomedical applications. POLYM. ENG. SCI., 54:472–480, 2014. © 2013 Society of Plastics Engineers

A series of 0–3 composites of lead zirconate titanate (PZT)/ferroelectric odd–odd nylons was prepared with variations in the size of PZT powder and in the dipole density of ferroelectric odd–odd nylons. The as-formed PZT powder prepared by a spray-drying technique consists of spherical granules composed of large numbers of interconnected fine particles. Electrical properties of the composites as a function of the size of this particular PZT powder and the dipole density of ferroelectric odd–odd nylons were studied. With the PZT powder sintered at 1100°C, the relative permittivity, polarization, and piezoelectric strain coefficient (d33) of the PZT/nylon composites increased with increasing powder size of PZT. The electrical properties of the composites also increased as the dipole density of the polymer increased. The PZT/nylon 57 composite exhibited a high-relative permittivity and piezoelectric strain coefficient d33 due to an increase in its dipole density. The optimum relative permittivity and polarization of this composite were obtained by the PZT with an average granule size of 95 μm. The highest piezoelectric strain coefficient d33 of the 0–3 composite was found at 28 pC/N whereas the relative permittivity was approximately 73.

A series of 0-3 composites of lead zirconate titanate (PZT) and nylon77 was prepared with PZT volume fractions between 0.1 and 0.6 using the combined method of solvent casting and hot pressing. Depending upon the volume fraction of PZT, the relative permittivities of the composites were found to be in the range of 200–2000 when measured at the highest practically possible temperature of 200°C. As PZT volume fraction increases, both the relative permittivity and the piezoelectric constant d33 increase. The best combination of electrical properties and flexibility was obtained in 0.5 PZT volume fraction composites. At this composition, the remanent polarization Pr of composites was up to 1000 mC/m2 at the applied electric field of 40 MV/m and it increased with an increase in temperature. The highest piezoelectric strain coefficient d33 was obtained at 17 pC/N in 0.6 PZT volume fraction composites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

This paper discusses a new ferroelectric polymer with high dielectric constant (>50 at 1K-1M Hz) and large electrostrictive response (~5%) at ambient temperature, which is based on a processable semicrystalline terpolymer comprising vinylidene difluoride (VDF), trifluoroethylene (TrFE), and chlorotrifluoroethylene (CTFE). This VDF/TrFE/CTFE terpolymer was prepared by a combination of a borane/oxygen initiator and bulk polymerization process at ambient temperature. The control of monomer addition afforts the terpolymers with high molecular weight and relatively narrow molecular weight and composition distributions. The incorporated bulky CTFE units homogeneously distributed along the polymer chain seem to reduce the thickness of ferroelectric crystalline domains without destroying the overall crystallinity. This nano-size semicrystalline morphology results in the reduction of ferroelectric-paraelectric (F-P) phase transition to near ambient temperature with a very small energy barrier. Some terpolymers exhibited common ferroelectric relaxor behaviors with a broad dielectric peak that shifted toward higher temperatures as the frequency increased, and a slim polarization hysteresis loop at near the dielectric peak (around ambient temperature) that gradually evolved into a normal ferroelectric polarization hysteresis loop with reduced temperature.