Investigation of the thermoformability of various D-Lactide content poly(lactic acid) films by ball burst test

In this article, we investigated the thermoformability of poly(lactic acid) (PLA) films with various D -Lactide contents and therefore different crystallization properties, performing tensile and ball burst tests at various temperatures and testing rates. We found that the behavior of the PLA films tested above the glass transition temperature significantly differs due to the difference in D -Lactide content, and thus crystallinity. During tensile testing, elevated temperatures and mechanical stress caused the crystallization temperature to decrease and thus highly induced crystallization. At the same time, as testing speed was increased, the ability of the polymer to crystallize decreased. In ball burst tests, the PLA films crystallized more than during tensile testing. We described the differences found between tensile testing and ball burst testing, which latter better represents the conditions of thermoforming through inducing biaxial deformation.     

Effect of poly(ε-caprolactone) and titanium (IV) dioxide content on the UV and hydrolytic degradation of poly(lactic acid)/poly(ε-caprolactone) blends

The effect of accelerated weathering degradation on the properties of poly(lactic acid) (PLA)/poly(ε-caprolactone) (PCL) blends and PLA/PCL/titanium (IV) dioxide (TiO₂) nanocomposites are presented in this paper. The results show that both polymers are susceptible to weathering degradation, but their degradation rates are different and are also influenced by the presence of TiO₂ in the samples. Visual, microscopic and atomic force microsocpy observations of the surface after accelerated weathering tests confirmed that degradation occurred faster in the PLA/PCL blends than in the PLA/PCL/TiO₂ nanocomposites. The X-ray diffraction results showed the degradation of PCL in the disappearance of its characteristic peaks over weathering time, and also confirmed that PLA lost its amorphous character and developed crystals from the shorter chains formed as a result of degradative chain scission. It was further observed that the presence of TiO₂ retarded the degradation of both PLA and PCL. These results were supported by the differential scanning calorimetry results. The thermogravimetric analysis results confirmed that that PLA and PCL respectively influenced each other's thermal degradation, and that TiO₂ played a role in the thermal degradation of both PLA and PCL. The tensile properties of both PLA/PCL and PLA/PCL/TiO₂ were significantly reduced through weathering exposure and the incorporation of TiO₂.     

Spectroscopic and thermal analyses of α′ and α crystalline forms of poly(l-lactic acid)

Poly(lactic acid) samples rich in α′ or α crystals have been characterized using spectroscopic and thermal methods. Cryogenic infrared and Raman spectroscopy were used to probe the differences in chain conformation and packing. Compared to the α crystal, the α′ crystal has weakened specific carbonyl and methyl interactions. Experimental spectroscopic analysis in conjunction with simulation studies have shown that the α′ crystal has uniform conformational disorder in the C_α-C torsion angle. This disorder in chain conformation and packing leads to different crystalline forms with different stabilities. The difference in thermal stability was quantified by measuring enthalpic change at melting for both crystalline forms. Significantly different values for the two crystalline forms were obtained ( and ). The transformation from the less stable α′ to the more stable α phase has been characterized. This analysis provides an explanation to the double melting peaks usually found in PLLA samples.     

Synergized poly(lactic acid)–hydroxyapatite composites: Biocompatibility study

In vitro biocompatibility of impact modified composites produced from poly(lactic acid) (PLA) and hydroxyapatite (HA) is reported in this study. Surface modification was previously used to facilitate the dispersion of HA in PLA, whereas impact property of the PLA-HA composites was deliberately enhanced as it was necessary. Herein, osteoblast cell culture assay was used to assess the possible effects of HA surface modification and impact modification on the cell behavior in physiological media. Furthermore, antimicrobial properties of the HA were assessed. Evidence of HA modification was confirmed through elemental and spectroscopic analysis. Incorporation of HA offered better cell attachment and proliferation to the PLA matrix, with significant increase in the cell viability (%). Also, modification of HA did not present obvious cytotoxicity to the PLA-HA composite. Conversely, incorporation of impact modifier slowed down the rate of cell proliferation on the composite surface but facilitates increased wettability. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47400.     

Biodegradation of poly(lactic acid)—cassava bagasse composites produced by injection molding

Neat poly (lactic acid) (PLA) and PLA/cassava bagasse (CB) composites were used to produce seedling tubes by extrusion and injection molding. The tubes were buried in simulated soil, and their biodegradation was investigated by weight loss, scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR). After 180 days, the composites' biodegradation was higher than neat PLA material, and the higher the CB content, the higher the biodegradation, which caused fissures and voids in the material. The biodegradation of PLA/CB composites increased the phosphorus content in the soil after 180 days. Composites of PLA with CB, an abundant agro-industrial residue in Brazil, are promising because they can reduce the environmental impact due to CB's proper destination, and the composites' costs and biodegradation are faster than pure PLA material. Both the faster biodegradation of the tube and the higher P content are advantageous for seedling tubes.     

Preparation of poly(3,3′-dialkynyl-2,2′-bithiophene-5,5′-diyl) with high coplanarity and effective π-conjugation system

New head-to-head type polythiophenes with acetylenic -CCR side groups, HH-P3(CCR)Th (R=n-C₁₀H₂₁, n-C₆H₁₃, n-C₄H₉), were prepared by palladium-catalyzed polycondensation of the corresponding dibromo-monomers by using Me₃SnSnMe₃ as the polycondensing agent. The single crystal structure of the monomer revealed high coplanarity of the bithiophene unit, and the derived polymer showed a UV-vis absorption peak at approximately 520 nm. The λ_max position was red-shifted from those of regioregular poly(3-alkylthiophene)s (385 and 430 nm for HH- and HT-type polymers, respectively). These data indicate that the newly synthesized polythiophene with the -CCR group has a highly coplanar structure with a large effective π-conjugation system.     

Synthesis of poly(lactic acid)–poly(ethylene glycol) copolymers using multi-SO3H-functionalized ionic liquid as the efficient and reusable catalyst

Poly(lactic acid)–poly(ethylene glycol) copolymers were synthesized under the catalysis of multi-SO₃H-functionalized ionic liquid. Compared to the ordinary ionic liquids and the traditional Lewis acid catalysts, the ionic liquids with multi-sulfonic acid groups were more catalytically active, and the reaction conversion rate reached up to 97.8 %. The molecular weight of the resulting copolymer was 5.69 × 10⁴ g mol^?1 and the degree of crystallinity was 42.9 %. The copolymers were also of higher hydrophilicity and better mechanical properties. The reaction kinetics of copolymerization was analyzed. The intrinsically high catalytic activity of multi-SO₃H groups originated from the lower activation energy and the higher free acidity. The recovering catalytic activity of the multi-SO₃H ionic liquid catalyst was higher, suggesting that it is a recyclable, environmentally friendly catalyst.     

Investigating the effects of processing parameters on poly(lactic acid) properties – a central composite design approach

ABSTRACT

This study attempts to optimise poly(lactic acid) processing parameters using central composite design approach which is well known statistical tool in design of experiments. Three factors and five levels were chosen for carrying out the analysis. The parameters include mixing temperature (180–210°C), screw speed (50–100?rev min^?1) and mixing time (5–10?min), which were varied independently. The results were evaluated based on maximum stress, tensile modulus, and impact strength under different conditions and the significant factors were determined using variance analysis (ANOVA). An optimum balance between the mechanical properties was obtained when the samples were blend at 180°C at 100?rev min^?1 rotor speed for 10?min. Moreover, validation of the predicted results confirmed the optimised parameters, which were further complemented by morphological and thermal studies.     

Effect of immobilization of poly(γ-glutamic acid) on the biocompatibility of electrospun poly (L-lactide) mats

In this study, poly(L-lactide) (PLLA) non-woven mats were prepared by electrospinning technique, followed by treating with oxygen plasma and grafting with 3-aminopropyl triethoxysilane (APTES), then immersed in poly(γ-glutamic acid) (γ-PGA) solution to form a layer of γ-PGA on the surface. In so doing, hydrophobic PLLA would become highly hydrophilic. Through characterization of hydrophilicity and biocompatibility, the feasibility of these modified mats for wound dressing was evaluated. The results show that after the grafting of γ-PGA, the swelling ratio increased greatly from 7% for pristine PLLA mat to 321% for γ-PGA-grafted PLLA mat, and the contact angle decreased from 112° to 25°. In vitro cytocompatibility tests against L929 fibroblast show that γ-PGA-grafted PLLA was non-cytotoxic. In addition, the proliferation of fibroblasts was higher on γ-PGA-grafted PLLA than on pristine PLLA.     

Disclosing the role of surface and bulk erosion on the viscoelastic behavior of biodegradable poly(ε-caprolactone)/poly(lactic acid)/hydroxyapatite nanocomposites

In this study, biodegradable polymer blends and their nanocomposites were prepared using poly(ε-caprolactone) (PCL) and poly(lactic acid) (PLA) as blending components and hydroxyapatite (HA) nanoparticles as reinforcement. X-ray diffraction spectra showed that the presence of HA nanoparticles enhanced the intensity of the peaks (100) and (200) corresponding to the PCL's crystalline planes. The transmission electron microscopy images confirmed the high tendency of HA nanoparticles to locate in the PLA phase. The water uptake values of samples measured at pH 4 were more than those measured at other pH values. The weight loss behavior of blends in acidic medium was completely different from that in basic and neutral media. The Williams–Landel–Ferry equation and time–temperature superposition principle were applied to the creep compliance of the samples and their master curves were determined at reference temperature of 30 °C, and the mechanical properties of samples were predicted in other conditions. The effect of pH on the creep–recovery response of studied samples was analyzed. From this analysis, it could be found that at pH 4, the creep stain increased, while, at pH 7, there was no a significant change in the viscoelastic property. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47151.     

Surface texture and barrier performance of poly(lactic acid)–cellulose nanocrystal extruded-cast films

In this study, we assessed the influence of cellulose nanocrystal (CNC) addition level (0.5–2 wt %) on the surface texture, thickness, and barrier properties of poly(lactic acid) (PLA) extruded-cast films. Regardless of the CNC content, the addition of CNC increased the surface average roughness and maximum roughness of the PLA films in both the machine and cross-machine directions because of the presence of CNC agglomerates. The increased roughness resulted in films with uneven thicknesses; this affected their accurate measurements with a conventional micrometer. Rather, accurate thickness measurements were obtained through the density method, a more appropriate thickness measurement method for films with rough surfaces. The permeability values were negatively correlated with the increased crystallinity. Both the water vapor permeability and oxygen permeability (OP) values decreased significantly by approximately 26–45 and 25–50%, respectively, as the CNC content increased from 0.5 to 2 wt % because of the tortuosity effect. The OP values of the neat PLA and composite films remained insensitive to changes in the relative humidity (from 0 to 75%) when they were tested at 23 °C. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47594.     

Double yielding behavior of in situ microfibrillar polyolefin elastomer/poly(lactic acid) composites: Effect of microfibrillar morphology

In situ microfibrillar composites (MFCs), with polyolefin elastomer as matrix and poly(lactic acid) (PLA) as dispersed phase, were successfully prepared using multistage stretching extrusion system. Interestingly, a peculiar phenomenon of double yielding was observed on the stress-strain curves of MFCs under tensile loading for the first time. The MFCs with 20 wt% PLA microfibrils exhibited two distinct yield points, and a pronounced hump appeared on the stress-strain curve of PLA-20. Two-dimensional small-angle X-ray scattering analyses showed that the equatorial streak scattering became stronger with increase in PLA microfibrillar content; the meridional scattering trace became stronger with increase in tensile strain for PLA-20. The rheological analysis showed that the G′ of PLA-20 had a plateau in the low frequency region and did not depend on frequency changes.     

Cellulose nanofibre–poly(lactic acid) microcellular foams exhibiting high tensile toughness

We report here the morphology and tensile properties of polylactic acid–cellulose nanofibre (PLA–CNF) microcellular nanocomposites. Two types of CNF were used for the nanocomposite preparation, native and surface acetylated CNF (ac-CNF). Samples were foamed in a mould to enable tensile testing. The effect of the mould use on the foam morphology was first assessed by comparison with free foamed samples. We found that the mould affected the cell growth stage of the foaming process in neat PLA foam while its effect was less important in nanocomposites. Stiffening and strengthening effect of CNF was greatly enhanced by foaming when compared to their solid counterparts. The most notable change in tensile properties was however the large increase in strain at break resulting in the high tensile toughness of microcellular PLA–CNF nanocomposites. Strain at break increased up to 7.5 times in neat PLA and up to 31.5 times in the foam containing 3% of CNF. Surface acetylation of CNF significantly affected the properties of foams with 9% of CNF loading: while foams with ac-CNF were stiffer, foams with native CNF exhibited higher strain at break and so higher overall toughness.     

Novel biodegradable low-density polyethylene–poly(lactic acid)–starch ternary blends

The ternary powder blends based on low-density polyethylene (LDPE) and two polymers of natural origin poly(lactic acid) (PLA) and starch are obtained in a rotor disperser under conditions of shear deformations. The dependence of the final powder dispersity on the composition is explored. A comparative analysis of the mechanical properties of the ternary blends with those of the LDPE–PLA and PLA–starch binary blends previously obtained has revealed that the presence of two rigid polymers PLA and starch leads to an increase in the elastic modulus and a decrease in the tensile strength and elongation at break. In the study of the blend biodegradability, it is found that the presence of two polymers of natural origin in the system with a total mass fraction of 60% promotes intensive biodegradation.     

Molecular ordering and α′-form formation of poly(l-lactide) during the hydrolytic degradation

Hydrolytic degradation ability is an intriguing characteristic of poly(l-lactide) (PLLA) and it has been intensively investigated recently. However, the microstructure evolution of PLLA during the early stage of the hydrolytic degradation process is neglected. In this work, amorphous PLLA was hydrolyzed in alkaline media at temperatures from 40 to 60 °C. The variations of weight loss and molecular weight were measured to study the degree of the hydrolytic degradation of PLLA. The effect of hydrolytic degradation on microstructure of the amorphous PLLA was investigated by differential scanning calorimetry (DSC), Fourier transform infrared spectroscope (FTIR), wide angle X-ray diffraction (WAXD) and scanning electron microscope (SEM). The results clearly proves the occurrence of molecular ordering and the formation of α′-form PLLA, which is greatly related to the hydrolytic degradation conditions. At relatively low hydrolytic degradation temperature (40 and 50 °C), locally ordered structure is provoked, while a large number of α′-form crystallites are induced at relatively high temperature (60 °C). This work is very significant in understanding the microstructure evolution of PLLA during the hydrolytic degradation process.     

Mathematical Modeling of the Poly(lactic acid) Ring–Opening Polymerization Kinetics

The modeling of ring-opening polymerization of (D,L)-lactide to poly(lactic acid) (PLA) has been performed. Except some reported data on the apparent rate constant, there is lack of data in the literature on the rate constants for initiation, propagation and termination steps of PLA polymerization. Using a simple numerical technique, the individual rate constants are evaluated theoretically and the results are compared with the available experimental data for ring-opening polymerization of PLA. The proposed method works well without requiring a polymer chain length independent rate constant. It is also shown that presence of even small amount of impurity (e.g., water) in the reaction kettle can greatly limit the polymer molecular weight.     

X-ray microtomographic analysis of α-tricalcium phosphate-poly(lactic-co-glycolic) acid nanocomposite degradation

The degradation characteristics of αTCP-PLGA(50:50) nanocomposites containing varying ceramic weight loadings in an aqueous medium have been assessed using X-ray microtomography (XμT). Also measured were bulk density changes, pharmaceutic drug release and medium acidification for the degrading materials.     

The effect of silk fibroin nanoparticles on the morphology,rheology, dynamic mechanical properties,and toughness of poly(lactic acid)/poly(ε-caprolactone) nanocomposite

The silk fibroin nanoparticles (SFNPs) were extracted from silkworm cocoons and used as a nanofiller in poly(lactic acid) (PLA)/poly(ε-caprolactone) (PCL) blend. The nanoparticle localization was studied theoretically and experimentally and the effects of SFNP on the morphology, rheology, toughness, and dynamic mechanical properties of the blend were investigated. According to the calculated wetting coefficient, SFNP should be thermodynamically located in the PLA matrix during the melting process. The results of SEM illustrated a common sea-island structure for the PLA/PCL blend and the incorporation of SFNP reduced the PCL domain sizes from 1.170 ± 92 μm to 794 ± 46 nm. The atomic force microscopy results showed that the nanoparticles are mainly located in the PLA matrix and also, partially at the phase interface with a thickness of layers around 80 nm. The rheological tests displayed the network formation of SFNP in the prepared nanocomposites. The dynamic mechanical analysis revealed that by the addition of SFNP, the storage modulus of neat PLA and PLA/PCL blend were increased by around 57 and 50%, respectively and the glass transition temperatures (Tg) values of PLA and PCL shifted toward each other. Additionally, using SFNP caused a lower water uptake and higher impact strength (~64%) of the blend.     

Effects of processing conditions on hybrid filler selective localization,rheological, and thermal properties of poly(ε-caprolactone)/poly(lactic acid) blends

In this study, the effects of processing conditions through different mixing sequences were used to analyze the factors, which could influence the hybrid filler selective localization in an immiscible polymer blend and how localization can influence the rheological and thermal properties. Different selective localizations were observed depending on the mixing sequence used when the hybrid filler was added. Notably, nanoparticles can interact with each other, which favor a synergy between them and alters, besides the localization, the dispersion state, or can interact with one polymer phase, and also alter the nanoparticles' selective localization. An improvement in rheological properties was observed in the hybrid nanocomposite in which there was interaction between the nanoparticles, favoring the hexagonal boron nitride exfoliation. On the other hand, for the storage modulus and degree of crystallinity, the sharpest increase occurred in the hybrid nanocomposite in which the nanoparticles could interact preferably with one polymer phase. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48711.