The effect of heat treatment on water sorption in polylactide and polylactide composites via changes in glass‐transition temperature and crystallization kinetics

Water sorption into polylactide (PLA) and polylactide‐montmorillonite (PLLA‐MONT) composites containing 5 wt % of montmorillonite (MONT) under different heat treatment conditions was studied using the quartz crystal microbalance/heat conduction calorimetry (QCM/HCC) technique. Results showed that water sorption in neat polymer films and composite films increased with heat treatment temperature up to 120 °C. Differential scanning calorimetry was used to measure the glass‐transition temperature and isothermal crystallization kinetics of all samples. The mobility of the amorphous domain in all samples increased with heat treatment temperature, indicated by the decrease in glass‐transition temperature. PLA composites crystallized at a much faster rate than neat PLA did because MONT acted as a nucleating agent. Under the same heat treatment condition, water sorption in PLLA‐MONT composites was always higher than that in neat PLA due to the presence of the hydrophilic hydroxyl groups on the surface of MONT particles. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Thermal Degradation of Poly(ε-caprolactone), Poly(L-lactic acid) and their Blends with Poly(3-hydroxy-butyrate) Studied by TGA/FT-IR Spectroscopy

Summary: The thermal degradation behavior of poly(ε-caprolactone) (PCL) and poly(L-lactic acid) (PLA) have been studied in different environment. It was found that these polymers undergo completely different degradation processes in nitrogen and oxygen atmosphere. In oxygen environment PCL and PLA mainly decompose to CO₂, CO, water and short-chain acids. In nitrogen atmosphere PCL releases 5-hexenioc acid, CO₂, CO and ε-caprolactone, whereas PLA decomposes to acetaldehyde, CO₂, CO and lactide. The polymer blends of poly(3-hydroxybutyrate) (PHB) with PCL and PLA decompose similar to the individual homopolymers with crotonic acid as the initial decomposition product of PHB.     

Photochemical transformation of diketone dopants in polyester matrices: Effect of dopants concentration and polyester structure on changes in molecular characteristics and hydrolysis of the matrices

Photochemical transformations of photoactive diketone derivatives, 1,2-diphenylethane-1,2-dione (benzil, BZ) and 1,4-bis(benzoylcarbonyl)benzene (bisbenzil, BIS), and the effects of their transformations on changes in the molecular characteristics and hydrolytic properties of poly(ε-caprolactone) (PCL) and polylactide (PLA) matrices are reported. Studies were performed in a broad dopant concentration range of 0.2–7.5 wt%. Structural changes were observed by FTIR spectroscopy. FTIR spectroscopy proved the progressive transformation of BZ to benzoyl peroxides and, in the case of PCL, the formation of polar groups. Changes in molecular characteristics were observed in GPC traces. Irradiation of the doped polymer films at λ > 400 nm under an air atmosphere resulted mainly in the degradation of the polymer matrices. Additionally, high dopant concentrations in PCL led to partially crosslinked structures with gel contents up to 15%. The photochemical transformation of dopants had a large impact on the PCL matrices compared to that of the PLA matrices. A subsequent hydrolysis process was investigated by determining the extractable products as well as using GPC. Hydrolysis of irradiated PCL samples showed a significant acceleration of hydrolysis compared to that of nonirradiated samples. Furthermore, the hydrolysis rate gradually increased with increasing dopant concentration. The PCL crosslinking and degradation is adjustable by the type of dopant, concentration of dopant and intensity of light during irradiation of PCL. In contrast, a photochemical pretreatment had no observable effect on the hydrolysis of PLA under the investigated conditions.     

Toughening of polylactide by melt blending with a biodegradable poly(ether)urethane elastomer

Melt blending of polylactide (PLA) and a biodegradable poly(ether)urethane (PU) elastomer has been performed in an effort to toughen the polylactide without compromising its biodegradability and biocompatibility. The miscibility, phase morphology, mechanical properties, and toughening mechanism of the blend were investigated. The blend was found by dynamic mechanical analysis to be a partially miscible system with shifted glass transition temperatures. The PU elastomer was dispersed in the PLA matrix with a domain size of sub-micrometer scale. The addition of PU elastomer not only accelerated the crystallization speed, but also decreased the crystallinity of the PLA. With an increase in PU content, the blend shows decreased tensile strength and modulus; however, the elongation at break and the impact strength were significantly increased, indicating the toughening effects of the PU elastomer on the PLA. The brittle fracture of neat PLA was gradually transformed into ductile fracture by the addition of PU elastomer. It was found that the PLA matrix demonstrates large area, plastic deformation (shear yielding) in the blend upon being subjected the tensile and impact tests, which is an important energy-dissipation process and leads to a toughened, biodegradable polymer blend.     

Bulk and surface modifications of polylactide

This article reviews various methods of modifying the bulk and surface properties of poly(lactic acid) (PLA) so that the polymer may be used as a drug carrier in a drug delivery system (DDS) and as a cell scaffold in tissue engineering. Copolymerization of lactide with other lactone-type monomers or monomers with functional groups such as malic acid, copolymerization of lactide with macromolecular monomer such as poly(ethylene glycol) (PEG) or dextran, as well as blending polylactide and natural derivatives and other methods of bulk modification are discussed. Surface modifications of PLA-type copolymers, such as surface coating, chemical modification, and plasma treatment are described. Cell culture technology proves the efficiency of bulk and surface modification and the potential application of PLA in tissue engineering.     

Improving polylactide/starch biocomposites by grafting polylactide with acrylic acid--characterization and biodegradability assessment

In this article, the properties of a polylactide and starch composite (PLA/starch) and an acrylic acid grafted polylactide and starch composite (PLA-g-AA/starch) were compared. The composite containing PLA-g-AA was found to have much better dispersion and homogeneity of starch in the polymer matrix than the composite containing PLA, indicating better compatibility between the two phases. Better mechanical and thermal properties of the PLA-g-AA/starch composite, notably an increase in tensile strength and elongation at breakpoint, evidenced its superiority to the PLA/starch composite. Furthermore, the lower viscosity of PLA-g-AA/starch makes it easier to process than PLA/starch. Weight loss on exposure to a soil environment over a period of three months showed that the starch in the composites was almost completely biodegradable, even at a high degree of substitution (60 wt.-% starch). After three months in soil, a reduction in the mechanical properties of the blends was observed, especially in those with higher starch contents.     

PLA maleation: an easy and effective method to modify the properties of PLA/PCL immiscible blends

In this study, maleic-anhydride-grafted polylactide (PLA-g-MA) was investigated as a potential compatibilizing agent for the polylactide (PLA)/poly(ε-caprolactone) (PCL) system, with the aim of enhancing the final properties of the two polymer blends. Indeed, PLA-g-MA was prepared via reactive blending through a free radical process and characterized by means of ¹H-NMR and titration measurements, which demonstrated that the employed procedure allows grafting 0.7 wt% of MA onto the polymer backbone, while avoiding a dramatic reduction of PLA molecular mass. The specific effect of the MA-grafted PLA on the features of the PLA/PCL system was highlighted by adding different amounts of PLA-g-MA to 70:30 (w/w) PLA/PCL blends, where the 70 % PLA component was progressively substituted by its maleated modification. The efficiency of PLA-g-MA as a compatibilizer for the PLA/PCL blends was assessed through SEM analysis, which showed that the dimensions of PCL domains decrease and their adhesion to PLA improves by increasing the amount of PLA-g-MA in the blends. The peculiar microstructure promoted by the presence of PLA-g-MA was found to enhance the mechanical properties of the blend, improving the elongation at break without decreasing its Young’s modulus. Our study demonstrated that not only the microstructure but also the thermal properties of the blends were significantly affected by the replacement of PLA with PLA-g-MA.     

Effect of natural weather on the structure and properties of polylactide/Cloisite 30B nanocomposites

The degradation of polylactide (PLA)/Cloisite 30B nanocomposites under natural weathering was investigated as a function of clay loadings (1, 3 and 5 wt.%) for up to 130 days using Fourier transform infrared (FT-IR) spectroscopy, size exclusion chromatography (SEC), nanoindentation measurements, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). For comparative purposes, the neat PLA was also considered. The FT-IR results showed that the photo-oxidation mechanism of PLA was not modified in the presence of Cloisite 30B, but only the degradation rates were accelerated. Moreover, the photo-oxidative degradation of PLA nanocomposite samples led to the formation of vinyl unsaturation, carbonyls, anhydrides and hydroperoxides groups as a result of the occurrence of several chemical mechanisms simultaneously. The decrease of the weight-average molecular weight, and the number-average molecular weight associated with an enhanced polydispersity of the nanocomposite samples indicated that chain scission was the most prominent phenomenon in natural weathering. The thermal degradation of the PLA was faster in the presence of clay. Modulus and hardness measured by nanoindentation increased slightly with exposure time for both neat PLA and PLA nanocomposite samples; the increase is also a function of the clay content. Finally, the weathering effect on the morphology of exposed samples observed by SEM revealed that the fractured surfaces exhibited many voids and cracks. These defects were much more pronounced for the PLA nanocomposites.     

Effect of blend ratio and nanofiller localization on the thermal degradation of graphite nanoplatelets-modified PLA/PCL

A variety of poly(lactic acid) (PLA)-poly(ε-caprolactone) (PCL) samples with different PLA:PCL ratios, containing different contents of graphite nanoplatelets (GrP), were analysed in a thermogravimetric analyser (TG) under, respectively, nitrogen and oxygen atmospheres, and in a differential scanning calorimeter (DSC) in a nitrogen atmosphere. Their respective morphologies were determined through scanning electron microscopy. The TG analyses in nitrogen gave fairly predictable results, but the analyses in oxygen gave complex results that seemed to be dependent on the respective morphologies of the blend samples and on the presence and amount of GrP in the respective samples. It was observed that, depending on the blend or nanocomposite morphologies, the GrP could have played the role of catalysing the degradation process, or inhibiting the onset of degradation by immobilizing the polymer or free radical chains and by delaying the evolution of the degradation products from the respective samples. The DSC results clearly showed the influence of the respective components in the blends and composites on the crystallization behaviour and crystallinities of the two polymers.

     

Melt rheology of polylactide/montmorillonite nanocomposites

In this article, the linear and nonlinear shear rheological behaviors of polylactide (PLA)/clay (organophilic‐montmorillonite) nanocomposites (PLACNs) were investigated by an Advanced Rheology Expanded System rheometer. The nanocomposites were prepared by master batch method using a twin‐screw extruder with poly(ε‐caprolactone) (PCL) as a compatibilizer. The presence of org‐MMT leads to obvious pseudo‐solid‐like behaviors of nanocomposite melts. The behaviors caused by the formation of a “percolating network” derived from the reciprocity among the strong related sheet particles. Therefore, the storage moduli, loss moduli, and dynamic viscosities of PLACNs show a monotonic increase with MMT content. Nonterminal behaviors exists in PLACNs nanocomposites. Besides the PLACNs melts show a greater shear thinning tendency than pure PLA melt because of the preferential orientation of the MMT layers. Therefore, PLACNs have higher moduli but better processibility compared with pure PLA. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3189–3196, 2007     

Morphology and thermal degradation studies of melt-mixed poly(lactic acid) (PLA)/poly(ε-caprolactone) (PCL) biodegradable polymer blend nanocomposites with TiO2 as filler

The morphology and thermal stability of melt-mixed poly(lactic acid) (PLA)/poly(ε-caprolactone) (PCL) blend nanocomposites with small amounts of TiO₂ nanoparticles were investigated. The nanoparticles were mostly located in the PLA phase, with good dispersion of individual particles, although significant aggregation was also visible. The thermal stability and degradation behaviour of the different samples were studied using thermogravimetric analysis (TGA) and TGA-Fourier-transform infrared (FTIR) spectroscopy. Neat PCL showed better thermal stability than PLA, but the degradation kinetics revealed that PLA had a higher activation energy of degradation than PCL, indicating its degradation rate more strongly depends on temperature, probably because of a more complex degradation mechanism based on chain scission and re-formation. Blending of PLA and PCL reduced the thermal stabilities of both polymers, but the presence of TiO₂ nanoparticles improved their thermal stability. The nanoparticles also influenced the volatilization of the degradation products from the blend, acted as degradation catalyst and/or retarded the escape of volatile degradation products.     

Effect of halloysite nanotubes on the thermal degradation behaviour of poly(ε-caprolactone)/poly(lactic acid) microfibrillar composites

This paper reports on the thermal degradation behaviour and kinetics of halloysite nanotubes containing microfibrillated poly(ε-caprolactone) (PCL)/poly(lactic acid) (PLA) blends. It was found that the nanotubes probably catalyzed the PLA degradation, and that the free radicals formed during the PLA degradation initiated PCL degradation at lower temperatures, maybe in combination with halloysite nanotubes (HNT) catalysis. Drawing to form microfibrillated nanocomposites had little influence on the degradation behaviour of these materials, but pre-mixing of the HNT with PLA or PCL prior to melt-mixing and extrusion-drawing of the blends did influence the degradation behaviour, but in different ways. No evidence could be found that the presence and amount of HNT, or the mode of preparation, had an influence on the degradation mechanism, as evidenced through a Fourier-transform infrared (FTIR) analysis of the degradation products.     

Biodegradable polymer matrix nanocomposites for tissue engineering: A review

Nanocomposites have emerged in the last two decades as an efficient strategy to upgrade the structural and functional properties of synthetic polymers. Aliphatic polyesters as polylactide (PLA), poly(glycolides) (PGA), poly(?-caprolactone) (PCL) have attracted wide attention for their biodegradability and biocompatibility in the human body. A logic consequence has been the introduction of organic and inorganic nanofillers into biodegradable polymers to produce nanocomposites based on hydroxyapatite, metal nanoparticles or carbon nanotructures, in order to prepare new biomaterials with enhanced properties. Consequently, the improvement of interfacial adhesion between the polymer and the nanostructures has become the key technique in the nanocomposite process. In this review, different results on the fabrication of nanocomposites based on biodegradable polymers for specific field of tissue engineering are presented. The combination of bioresorbable polymers and nanostructures open new perspectives in the self-assembly of nanomaterials for biomedical applications with tuneable mechanical, thermal and electrical properties.     

Pyrolysis-GC-MS reveals important differences in hydrolytic degradation process of wood flour and rice bran filled polylactide composites

Pyrolysis-GC-MS of polylactide (PLA) biocomposites before and after hydrolytic degradation revealed prominent differences in the hydrolytic degradation process of rice bran and wood flour filled biocomposites. The water uptake and mass loss for polylactide/wood flour composites were similar to that of plain PLA. Pyrolysis-GC-MS, however, showed that on prolonged ageing the hydrolysis of PLA led to increased wood flour concentration in the remaining biocomposite matrices. In contrast, the polylactide/rice bran composites exhibited larger water uptake and higher mass loss. Pyrolysis-GC-MS and FTIR analysis proved that the higher mass loss was caused by migration of rice bran from the composites. The type of natural filler could thus greatly influence the degradation process and/or the stability of the materials in aqueous or humid environments.     

Thermal analysis applied to the characterization of degradation in soil of polylactide: I. Calorimetric and viscoelastic analyses

An accelerated soil burial test has been performed on a commercial polylactide (PLA) for simulating non-controlled disposal. Degradation in soil promotes physical and chemical changes in polylactide properties, which can be characterized by Thermal Analysis techniques. Physical changes occurred in polylactide due to the degradation in soil were evaluated by correlating their calorimetric and viscoelastic properties. It is highly remarkable that each calorimetric scan offers specific and enlightening information. Degradation in soil affects the polylactide chains reorganization. A multimodal melting behavior is observed for buried PLA, degradation in soil also promotes the enlarging the lamellar thickness distribution of the population with bigger average size. Morphological changes due to degradation in soil lead to an increase in the free volume of the polylactide chains in the amorphous phase that highly affected the bulk properties. Thermal Analysis techniques provide reliable indicators of the degradation stage of polylactide induced by degradation in soil, as corroborated by molecular weight analysis.     

Synthesis and barrier properties of poly(ε-caprolactone)-layered silicate nanocomposites

A new polymer-ceramic nanocomposite has been synthesized consisting of well-dispersed, two-dimensional layers of an organically modified mica-type silicate (MTS) within a degradable poly(ε-caprolactone) matrix. A protonated amino acid derivative of MTS was used to promote delamination/dispersion of the host layers and initiate ring-opening polymerization of ε-caprolactone monomer, resulting in poly(ε-caprolactone) chains that are ionically bound to the silicate layers. The polymer chains can be released from the silicate surface by a reverse ion-exchange reaction and were shown to be spectroscopically similar to pure poly(ε-caprolactone). Thick films of the polymer nanocomposite exhibit a significant reduction in water vapor permeability that shows a linear dependence on silicate content. The permeability of nanocomposite containing as low as 4.8% silicate by volume was reduced by nearly an order of magnitude compared to pure poly(ε-caprolactone). © 1995 John Wiley & Sons, Inc.     

Thermodynamic study of poly(vinyl chloride)/polyester blends by inverse-phase gas chromatography at 120°C

Polymer/polymer interaction parameters χ′₂₃ have been measured at 120°C as a function of polymer concentration for six different poly(vinyl chloride)/linear aliphatic polyester blends. The technique used is inverse-phase gas chromatography with several molecular probes. The polymers investigated are poly(DL-lactide), poly(ethylene succinate), poly(ethylene adipate), poly(butylene adipate), poly(δ-valerolactone), poly(ε-caprolactone) and poly(hexamethylene sebacate). Probe/polymer interaction parameters χ₁₂ and polymer/polymer interaction parameters χ′₂₃ values are dependent upon the methylene to carbonyl ratio of the polyester, reaching a minimum for a value of 5, this ratio corresponding to poly(ε-caprolactone) blends. Results are interpreted in terms of pairwise interactions between carbonyl, methylene, and [CHCl] groups.     

Plasticized polylactide/clay nanocomposites. II. The effect of aging on structure and properties in relation to the filler content and the nature of its organo‐modification

Plasticized polylactide (PLA) – layered silicate nanocomposites were obtained by melt blending PLA with polyethylene glycol as plasticizer (20 wt %) and with different montmorillonite fillers: Cloisite® 20A, Cloisite® 25A, and Cloisite® 30B (from 1 to 10 wt %). Comparative samples of melt‐blended polylactide (without filler) and plasticized PLA with 20 wt % PEG were considered as well. Samples have been aged for 1 and 4 years and their chemical and physical characteristics were compared with not aged reference ones. It was found that molecular weight of the PLA decreased upon melt‐processing and aging, particularly when the Cloisite content increased, without a clear relation to the nature of the organo‐modifier. On the contrary, the PEG plasticizer was practically undegraded upon melt processing and aging. Structural studies revealed that plasticized PLA and plasticized PLA‐based nanocomposites are unstable in time of aging and undergo deplasticization. They showed, after aging, the presence of a thin PEG crystalline layer at the surface of the samples and improved the order in the PLA matrix to a higher extent in plasticized polylactide than in plasticized nanocomposite (due to clay stabilization effect). The amount of PEG diffusing toward sample surface was correlated with aging time, molecular weight of PLA matrix, and Cloisite® type, in clear relation to the extent of intercalation with PLA and PEG. Some modifications of the viscoelastic properties of PLA matrix, induced by the presence of both the nanoparticlate filler and the plasticizer, as well as a deterioration of the mechanical properties upon aging were observed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 312–325, 2006     

Moisture sorption, transport, and hydrolytic degradation in polylactide

Management of moisture penetration and hydrolytic degradation of polylactide (PLA) is extremely important during the manufacturing, shipping, storage, and end-use of PLA products. Moisture transport, crystallization, and degradation, in PLA have been measured through a variety of experimental techniques including size-exclusion chromatography, differential scanning calorimetry, and X-ray diffraction. Quartz crystal microbalance and dynamic vapor sorption experiments have also been used to measure moisture sorption isotherms in PLA films with varying crystallinity. A surprising result is that, within the accuracy of the experiments, crystalline and amorphous PLA films exhibit identical sorption isotherms.     

Characterizing polymorphism and crystal transformation of polylactide by terahertz time-domain spectroscopy

Terahertz time-domain spectroscopy (THz-TDS), which has been proved to show promising application in complex polymer systems, was employed to investigate the polymorphism phenomenon and crystal transformation of polylactide (PLA) in this study. The THz-TDS shows sensitive response on the crystal structure. The α'-form, α-form and stereocomplex crystals exhibit absorption peaks of lattice vibration at 1.82, 2.01 and 2.09 THz, respectively. THz-TDS has no direct chirality identification on the difference between poly (d-lactide) (PDLA) and poly(l-lactide) (PLLA). However, the PLA stereocomplex shows an extra and distinctive absorption peak at 1.43 THz compared with homo-PLA, and the peak was proved to be stemmed from the collective vibration of L-lactic unit and D-lactic unit pairs connecting by hydrogen bonds. This is the first time that THz-TDS has been proved to be of great potential in identification of polymer stereocomplex crystal. Also, the α'→α crystal transformation of PLA were intuitively investigated at 120 °C using THz-TDS, while the transformation rate was quite slow.