• Clean Technology
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• v.12 no.2
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• pp.62-66
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• 2006

Poly($\small{L}$-Lactide)(PLLA) was prepared by a ring-opening polymerization of $\small{L}$-Lactide with various polydimethylsiloxane(PDMS) based copolymers as a stabilizer in supercritical carbon dioxide($scCO_2$). The block copolymeric stabilizers were synthesized by group transfer polymerization (GTP) by using PDMS macroinitiator. PLLA was found to be produced with fairly low molecular weight distribution as confirmed by gel permeation chromatography(GPC) analysis. Scanning electron microscopy (SEM) results showed that sub-micron size Poly($\small{L}$-lactide)(PLLA) particles were formed by suspension polymerization.

• Journal of Adhesion and Interface
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• v.4 no.1
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• pp.18-27
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• 2003

Interfacial properties and microfailure degradation mechanisms of the oxygen-plasma treated biodegradable poly(p-dioxanone) (PPDO) fiber/poly(L-lactide) (PLLA)composites were investigated for the orthopedic applications as implant materials using micromechanical technique and surface wettability measurement. PPDO fiber reinforced PLLA composite can provide good mechanical performance for long hydrolysis time. The degree of degradation for PPDO fiber and PLLA matrix was measured by thermal analysis and optical observation. IFSS and work of adhesion, $W_a$ between PPDO fiber and PLLA matrix showed the maximum at the plasma treatment time, at 60 seconds. Work of adhesion was lineally proportional to the IFSS. PPDO fiber showed ductile microfailure modes at We initial state, whereas brittle microfailure modes appeared with elapsing hydrolysis time. Interfacial properties and microfailure degradation mechanisms can be important factors to control bioabsorbable composites performance because IFSS changes with hydrolytic degradation.

• Fibers and Polymers
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• v.5 no.4
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• pp.289-296
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• 2004

The kinetic parameters, including the activation energy E, the reaction order n, and the pre-exponential factor Z, of the degradation of the copolymers based on the poly(L-lactide) (PLLA) or poly(p-dioxanone-co-L-lactide) (PDO/PLLA) and diol-terminated poly(ethylene glycol) (PEG) segments have been evaluated by the single heating methods of Friedman and Freeman-Carroll. The experimental results showed that copolymers exhibited two degradation steps under nitrogen that can be ascribed to PLLA or PDO/PLLA and PEG segments, respectively. However, copolymers exhibited almost single degradation step in air. Although the values of initial decomposition temperature were scattered, copolymers showed the lower maximum weight loss rate and degradation-activation energy in air than in nitrogen whereas the higher value of temperature at the maximum rate of weight loss was observed in air.

• Journal of Environmental Science International
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• v.15 no.2
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• pp.177-183
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• 2006

The hydrolytic kinetics of biodegradable poly(l-lactide) (PLLA) have been studied by using two model systems, solution-grown single crystal (SC) and Langmuir monolayer techniques, for elucidating the mechanism for both alkaline and enzymatic degradations. The present study investigated the parameters such as degradation medium and time. The Langmuir mono layers of PLLA showed faster rates of hydrolysis when they were exposed to a basic subphase rather than they did when exposed to neutral subphase. Both degradation mediums had moderate concentrations to show a maximized activity, depending on their sizes. An alkaline degradation of SCs of PLLA showed the decrease of molecular weight of the remained crystals due to the erosion of chain-folding surface. However, the enzymatic degradation of SCs of PLLA occurred in the crystal edges thus the molecular weight of remained crystals was not changed. This behavior might be attributed to the size of enzymes which is much larger than that of alkaline ions; that is, the enzymes need larger contact area with monolayers to be activated.

• Journal of Adhesion and Interface
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• v.3 no.2
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• pp.17-29
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• 2002

Interfacial properties and microfailure degradation mechanisms of the bioabsorbable composites for implant materials were investigated using micromechanical technique and measurement of surface wettability. As hydrolysis time increased, the tensile strength, the modulus and the elongation of poly(ester-amide) (PEA) and bioactive glass fibers decreased, whereas those of chitosan fiber almost did not change. Interfacial shear strength (IFSS) between bioactive glass fiber and poly-L-lactide (PLLA) was much higher than PEA or chitosan fiber/PLLA systems using dual matrix composite (DMC) specimen. The decreasing rate of IFSS was the fastest in bioactive glass fiber/PLLA composites whereas that of chitosan fiber/PLLA composites was the slowest. Work of adhesion, $W_a$ between bioactive glass fiber and PLLA was the highest, and the wettability results were consistent with the IFSS. Interfacial properties and microfailure degradation mechanisms can be important factors to control bioabsorbable composite performance.

• Korean Journal of Environmental Biology
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• v.25 no.3
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• pp.260-266
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• 2007

A thermophilic bacterium capable of poly (L-lactide)(PLLA) degradation was isolated from cultivating soil in Korea. The isolate was Gram positive rod-shaped bacterium, and was identified as Geobacillus caldoxylosilyticus based on the 16S rDNA sequence analysis. The strain proved to be a new PLLA degrading bacterium which has not been reported in the open literatures yet. The degradation activity of the strain was assessed in a sterilized compost inoculated with the strain under controlled compost condition at $58^{\circ}C$ for 40 days. The strain mineralized 66%, 57%, 41% and 40% of PLLA5000, PLLA11000, PLLA34000 and PLLA256000 whose weight average molecular weights were 5000, 11000, 34000 and 256000, respectively. Incorporation of 0.1% each of gelatin, yeast extract and ammonium sulfate in the compost containing PLLA256000 as a nutritional supplement raised the biodegradation activity by 27%, 13% and 10%, respectively. Increase of the inoculum size from $10^9cfu\;g^{-1}\;to\;10^{10}cfu\;g^{-1}\;and\;10^{11}cfu\;g^{-1}$ also enhanced the biodegradation activity by 14% and 20%, respectively.

• Polymer(Korea)
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• v.33 no.1
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• pp.13-18
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• 2009

To increase mechanical properties of the hydroxyapatite/poly (L-lactide) (HA/PLLA) composite which was a potential bone substitute material, HA was modified by the surface grafting with D-lactide (DLA) and the formation of stereocomplexes between components was introduced. The composite films were prepared by the solvent-nonsolvent technique to minimize the precipitation of HA during drying. The structure and properties of the composites were investigated by thermal gravimetric analysis (TGA), differential scanning calorimeter, and scanning electron microscopy, and mechanical property measurements. TGA results showed that the amount of DLA grafted on the HA surfaces (g-HA) was 6 wt%. The obtained g-HA exhibited better dispersity in an organic solvent than HA. The formation of stereocomplexes in the composites was confirmed by the change in melting temperature. The mechanical properties of g-HA/PLLA composites were increased, compared to the HA/PLLA composites.

• Polymer(Korea)
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• v.35 no.4
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• pp.284-288
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• 2011

For the purpose of the pre-industry production of poly(L-lactide) (PLLA) and full understanding of the supercritical polymerization system, large scale polymerization of L-iactide initiated by 1-dodecano/stannous 2-ethyl-hexanoate (DoOH/Sn(Oct)$_2$) was carried out in supercritical chlorodifluoromethane under various reaction conditions (time, temperature and pressure)and reactants (monomer and supercritical solvent) concentrations. A 3 L sized-reactor system was used throughout this study. The monomer conversion increased to 72% on increasing reaction time to 5 h. The molecular weight of PLLA product also increased to 68000 g/moi over the same period. An increase in monomer concentration resulted in a higher molecular weight, up to 144000 g/mol and 97% of monomer conversion. Raising the reaction pressure from 130 to 240 bar also resulted in an increased monomer conversion and molecular weight. To increase heat resistivity of PLLA, methanol treatment and heat-vacuum methods were evaluated. Both of them successfully improved the heat resistivity property of PLLA.

• Polymer(Korea)
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• v.25 no.3
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• pp.385-390
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• 2001

The A-B-A type block copoly(ester-ether)s consisting of poly(L-lactic acid) (PLLA)(A) and poly(oxyethylene-co-oxypropylene)(B) were prepared to improve the mechanical properties and hydrolyzability of PLLA. The block copolymers showed an improved flexibility due to the incorporation of the soft segments. Then, the same copolymer has an improved anti-thrombogenicity probably due to the specific microphase separation structure in the surface. The AFM of the film of the block copolymer revealed that the surface was quite flat in comparison with that of PLLA. Therefore, the flatness of the surface may be related with the increased anti-thrombogenicity of the copolymer film.

• Advanced Composite Materials
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• v.18 no.3
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• pp.287-295
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• 2009

$\beta$-Tricalcium phosphate ($\beta$-TCP) particles reinforced bioresorbable plastics poly-L-lactide (PLLA) composites were prepared by injection molding. The nominal weight ratio of $\beta$-TCP was selected as 5, 10 and 15%. In order to clarify effects of the PLLA crystallinity on the mechanical properties, the specimens were heat treated isothermally. Results of differential scanning calorimetry indicated that the PLLA crystallinity increased with increasing heat treatment temperature. Bending and compressive tests were conducted on the specimen with different $\beta$-TCP contents and crystallinities. The results show that the bending and compressive moduli increased with increasing $\beta$-TCP contents and crystallinity. On the other hand, bending strength decreased with increasing $\beta$-TCP contents. Maximum bending strength was obtained at the heat treatment of $70^{\circ}C$ for 24 h, whereas compressive 0.2% proof strength increased with increasing heat treatment temperature. This difference is attributed to the difference in the microscopic damages.