Mechanical,thermal, and dielectric properties of poly(lactic acid)/chitosan nanocomposites

Poly(lactic acid) (PLA) loaded with various levels of chitosan nanoparticles (CsNP) (0–5.0%) were prepared by twin‐screw extrusion. The nanocomposites were investigated based on their morphology, thermal, mechanical and dielectric properties. The SEM morphology showed that CsNP was dispersed uniformly in the PLA matrix. Thermal analysis through DSC revealed that the cold crystallization temperature of PLA in the case of nanocomposites slightly decreased with increasing content of CsNP; indicating a limit nucleating effect of CsNP. TGA analysis revealed that the incorporation CsNP slightly decreased the thermal stability of the PLA matrix. The mechanical analysis indicated that the incorporation of the CsNP in the PLA matrix improved the elongation and the impact strength, but decreased the tensile strength. The dielectric properties of these materials have been investigated for the α‐relaxation process as a function of the temperature and frequency. The α‐relaxation process was analyzed with Vogel–Fulcher–Tamman and Havriliak–Negami models and fitting parameters and their evolution were obtained. POLYM. ENG. SCI. 56:987–994, 2016. © 2016 Society of Plastics Engineers     

Synthesis and characterization of poly(lactic acid) based graft copolymers

This review summarizes recent developments in the preparation and characterization of grafting of poly(lactic acid) or polylactide (PLA). PLA is the most expansively researched and utilized biodegradable, biocompatible, compostable, recyclable and renewable thermoplastic polyester. The graft copolymers of PLA have been synthesized and characterized by different spectroscopic techniques, including FTIR spectra and NMR data. The graft copolymers of PLA have been analyzed critically by taking different monomers/polymers; such as chitosan, cellulose, starch, polyethylene glycol, vinyl based polymers, lignin, dextran, methyl methacrylate, maleic anhydride and graphene oxide. In the first part of this review, the grafting of PLA and applications of grafted PLA has been discussed briefly. The second part, the major objective of this paper, focuses on the synthesis and characterization of different PLA based graft copolymers. For few cases, where useful properties, such as high molecular weight, narrow PDI, or stereocontrol, have been observed, a more detailed examination of the graft copolymers is provided.     

Fabrication and characterization of sucrose palmitate reinforced poly(lactic acid) bionanocomposite films

Environmental issues concerning petroleum‐based polymers have begun a growing emphasis to utilize sustainable poly(lactic acid) (PLA) based packaging. However, PLA has its own limitations such as brittleness, high gas permeabilities and slow crystallization rate. With the aim to alleviate these limitations, we made a maiden effort to use a food additive, sucrose palmitate (SP) as eco‐friendly filler for fabrication of PLA based bionanocomposites. FTIR analysis elucidated the presence of hydrogen bonding and intermolecular interaction between PLA and reinforcement. Ordered orientation of the SP in the PLA matrix visualized by TEM analysis revealed uniform dispersion of SP filler into PLA matrix. DSC and XRD results confirmed that the incorporated bio‐filler acted as a nucleating agent and thus partially contributed towards the crystallinity of PLA‐SP bionanocomposites. Enhancement in the tensile strength and elongation at break up to 83 and 56% respectively is obtained. The best positive influence for the oxygen barrier was confirmed for the PLA‐SP bionanocomposite film where the reduction in oxygen permeability by 69% is achieved in comparison to pure PLA. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41320.     

Processing and characterization of poly(lactic acid) films plasticized with commercial adipates

The high brittleness of Poly(lactic acid) is a major drawback for flexible food packaging applications. The aim of this work is to evaluate the potential use of commercial adipates as PLA plasticizers to obtain transparent films with enhanced mechanical properties. Processing conditions were optimized. The effect of plasticizers was characterized by a decrease on the glass transition temperature and an increase in PLA chains mobility, which induced crystallization on heating. Thermal stability was not significantly affected, and mechanical properties showed an increase in ductility with the plasticizer content. Oxygen transmission rate was also measured to evaluate the effect of the microstructures generated by the presence of these additives in PLA‐based films. The monomeric adipate presented lack of homogeneity that makes films plasticized with this additive not useful for the intended application. Good compatibility was observed between polyadipates (up to 20 wt %) and the matrix, making them promising materials for biodegradable films manufacturing. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Biodegradable antimicrobial films based on poly(lactic acid) matrices and active azo compounds

Using solvent casting and melt compounding methods, we realized antibacterial and antifungal poly(lactic acid)‐based films by introducing different percentages of antimicrobial azo dyes into polymer matrices. Concentration up to 0.01% (w/w) of azo compounds permitted the preparation of antimicrobial and transparent films. The thin films retained the properties of the pure PLA matrices, such as glass transition temperature, flexibility, and amorphous nature. The films exhibited antimicrobial activity and the capability to inhibit biofilms formation of Staphylococcus aureus and Candida albicans. Spectrophotometric investigation of azo compounds release from the polymer matrices confirmed that the materials might have applications in fields where an intrinsic antimicrobial ability of the material is required, such as biomedical tools, biodegradable antibacterial coatings, and films for active packaging. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42357.     

Biodegradable self-reporting nanocomposite films of poly(lactic acid) nanoparticles engineered by layer-by-layer assembly

We designed and fabricated multilayer assemblies of biodegradable poly(lactic acid) (PLA) nanoparticles based on hydrogen-bonding or electrostatic interactions. The PLA nanoparticles were prepared by precipitation method and their surface charge was switched by modified precipitation in the presence of poly(ethylene imine) (PEI). Moreover, gold nanoparticles were grown within the PLA nanoparticle assemblies either through UV-irradiation or under mild reducing conditions to create biodegradable nanocomposites with distinct optical response which allows monitoring biodegradation of the films. The nanocomposite coatings of PLA nanoparticles were enzymatically degraded by α-chymotrypsin. We demonstrated that the biodegradation process can be colorimetrically monitored with UV-vis spectroscopy thus opening the way for facile and real-time monitoring useful for biotechnology applications.     

Morphology,thermal, mechanical,and barrier properties of graphene oxide/poly(lactic acid) nanocomposite films

To improve the physical and gas barrier properties of biodegradable poly(lactic acid) (PLA) film, two graphene nanosheets of highly functionalized graphene oxide (0.3 wt% to 0.7 wt%) and low-functionalized graphene oxide (0.5 wt%) were incorporated into PLA resin via solution blending method. Subsequently, we investigated the effects of material parameters such as loading level and degree of functionalization for the graphene nanosheets on the morphology and properties of the resultant nanocomposites. The highly functionalized graphene oxide (GO) caused more exfoliation and homogeneous dispersion in PLA matrix as well as more sustainable suspensions in THF, compared to low-functionalized graphene oxide (LFGO). When loaded with GO from 0.3 wt% to 0.7 wt%, the glass transition temperature, degree of crystallinity, tensile strength and modulus increased steadily. The GO gave rise to more pronounced effect in the thermal and mechanical reinforcement, relative to LFGO. In addition, the preparation of fairly transparent PLA-based nanocomposite film with noticeably improved barrier performance achieved only when incorporated with GO up to 0.7wt%. As a result, GO may be more compatible with hydrophilic PLA resin, compared to LFGO, resulting in more prominent enhancement of nanocomposites properties.     

Degradation kinetics of photopolymerizable poly(lactic acid) films

A series of acrylic poly(lactic acid) (PLA) films were produced via photopolymerization. Enzymatic degradation of the films was investigated by submerging or spraying the films with a solution of proteinase K, Chromobacterium viscosum (CvL), Rhizomucor miehei (RmL), or Candida cylindracea (CcL). Degradation was monitored by titration of the carboxylic acid groups, MS, and MS/MS. It was found that the degradation rate of the films was dependent on the water uptake of the film and enzyme solution used. The highest degradation rates, for both systems, were obtained by use of a proteinase K solution. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40475.     

Chitosan from Muga silkworms (Antheraea assamensis) and its influence on thermal degradation behavior of poly(lactic acid) based biocomposite films

The research work is focused on extraction of chitin from Muga silkworms (MS) and its conversion into chitosan by chemical treatment process. The extracted amount of chitin and chitosan from MS were obtained ～8 wt % and ～7 wt %, respectively. Potentiometric titrations, conductometric titrations, elemental analysis, ¹H‐NMR and FTIR analyses were employed to calculate the degree of deacetylation of chitosan (extracted at 80 ºC after 10 h) and found as 77% ± 2, 81% ± 1.8, 82% ± 2.4, 97.77% ± 0.3, and 82% ± 1.8, respectively. The deacetylation process of chitin showed pseudo‐first order reaction kinetics and activation energy was estimated as ～15.5 kJ/mole. The extracted chitosan (at 80 ºC after 10 h) showed higher crystallinity and improved thermal stability with respect to chitosan extracted from other marine sources. Subsequently, poly(lactic acid) (PLA) and extracted chitosan dispersed biocomposite films were prepared by solution casting method. Significant dispersion of chitosan (extracted at 80 ºC after 10 h) micro‐particles were observed in biocomposite films using FESEM analysis. Due to chitosan interaction with PLA, significant reduction in thermal degradation and activation energy was observed during nonisothermal degradation scan of such films using Flynn‐Wall‐Ozawa and Kissinger‐Akahira‐Sunose models. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43710.     

Mechanical,barrier, and thermal properties of poly(lactic acid)/poly(trimethylene carbonate)/talc composite films

Poly(l ‐lactic acid) (PLA) is now a very attractive polymer for food packaging applications. In this study, PLA/poly(trimethylene carbonate) (PTMC)/talc composite films were prepared by solvent casting. The influence of the talc loading (0, 1, 2, and 3 wt %) on the phase morphology of the PLA/PTMC/talc composites and the improvement in the resulting properties are reported in this article. The scanning electron microscopy images of the composite films demonstrated good compatibility between the PLA and PTMC, whereas talc was not thoroughly distributed in the PLA matrix at talc contents exceeding 3 wt %. The tensile strength and elongation at break of the composite films significantly improved (p < 0.05). On the contrary, the water vapor permeability and oxygen properties of the composite films decreased by 24.7 and 39.2%, respectively, at the 2 wt % talc loading. Differential scanning calorimetry showed that the crystallinity of the PLA phase increased with the presence of talc filler in the PLA/PTMC/talc composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40016.     

In vitro nifedipine release from poly(lactic acid)/chitosan nanoparticles loaded with nifedipine

In this study, nanoparticles based on poly(lactic acid) (PLA), chitosan (CS), and nifedipine (NIF) were prepared by an emulsion method with poly(ethylene oxide) (PEO) as an emulsifier. We investigated the most suitable conditions for preparing the poly(lactic acid)/chitosan/nifedipine nanoparticles (PCNs) by changing the distilled water volume, PEO content, and PLA/CS ratio. NIFs with different contents were loaded into poly(lactic acid)/chitosan nanoparticles (PCs) to study in vitro drug‐delivery systems. The PCNs were characterized with a Zetasizer particle size analyzer, field emission scanning electron microscopy, Fourier transform infrared (FTIR) spectroscopy, and X‐ray diffraction (XRD) methods. From the obtained results of the particle size parameters of the PCNs, the most suitable conditions for the preparation of the PCNs were found. The FTIR spectroscopy and XRD results show that NIF was loaded into the PCs. The PCNs had major basic particle sizes in the range 20–40 nm. NIF release from the PCNs was studied as a function of the pH of the immersed solution, the immersion time, and the NIF content. The kinetics of drug release were investigated and are reported to determine the type of release mechanism. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43330.     

Biocomposite foams from poly(lactic acid) and rubber wood sawdust: Mechanical properties,cytotoxicity, and in vitro degradation

The objectives of this work were to seek a simple method for preparation of poly(lactic acid) (PLA) foams and evaluate properties of these foams for scaffold application. Using a typical blowing agent and compression molding, biocomposite foams were successfully prepared from a PLA/rubber wood sawdust (PLA/RWS) blend. Selection of RWS for the biocomposites was based on particle size. RWS particles in two size ranges were used: 212–600 μm and ≤75 μm. Alkaline and silane treatments were applied to the RWS before blending with PLA. The tensile properties, Izod impact strength, foam morphology, and thermal degradation of the biocomposite foams were evaluated. Cytotoxicity and in vitro degradation were tested to determine the potential of the biocomposite foam for use as a scaffold in tissue engineering. Silane treatment improved mechanical properties by increasing the interfacial adhesion between PLA and RWS. The density and void fraction of the foam samples had a greater effect on mechanical properties than pore size. Proliferation of MG-63 cells increased with culture time, indicating that the foam samples were not cytotoxic. Promising samples were tested for degradation in a lysozyme/phosphate-buffered saline and showed a slow rate of in vitro degradation. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48259.     

Melt processing of biodegradable poly(lactic acid)/functionalized chitosan nanocomposite films: mechanical modeling with improved oxygen barrier and thermal properties

The present work demonstrates about the formulation of functionalized chitosan (CH-g-OLLA) through the transformation of hydrophilic nature of chitosan into hydrophobic by grafting with oligo(L-lactic acid) (OLLA). The developed CH-g-OLLA is easily soluble in poly(lactic acid) (PLA) matrix, which provides an opportunity towards producing industrially viable nanocomposite films for stringent food packaging and beverages applications. The grafting of OLLA chains is confirmed at NH₂ group of chitosan through the presence of two new peaks at 4.2 and 5.1 ppm in ¹H–NMR spectra. Various parameters like yield (%), grafting efficiency (%) and percent grafting (%) are calculated as ~51.6, ~40 and ~150%, respectively. Functionalized chitosan has been utilized as nano-filler in PLA matrix to fabricate PLA/CH-g-OLLA nanocomposite films which have compounded successfully by co-rotating twin screw compounder cum cast film extrusion technique (distinctly advantageous over conventional solution casting) at bench scale as well as semi-pilot scale and further demonstrated for its application in the area of food packaging with tailored oxygen barrier properties. Uniform dispersion of spherical aggregates of functionalized chitosan is observed in PLA/CH-g-OLLA nanocomposite films using TEM analysis. A significant reduction up to ~11 °C in glass transition temperature of PLA is observed by adding 5 wt% of nano-filler as a result of plasticization effect, which is an essential property in designing of flexible packages. Mechanical modeling of extruded PLA/CH-g-OLLA films has been performed to compare the experimental values with theoretical results using various mathematical models in which modified foam model, Nielsen model and modified Mitsuishi model demonstrate the best match for Young’s modulus (±0.08), tensile strength (±0.06) and percentage elongation (±0.03), respectively. This may be a significant contribution towards commercialization of such formulation where elegant melt extrusion process of PLA with functionalized chitosan is capable of reducing oxygen permeability up to ~10 folds due to a drastic reduction (~96%) in oxygen solubility.     

Biocomposites of poly(lactic acid) and lactic acid oligomer-grafted bacterial cellulose: It's preparation and characterization

This work demonstrates the synthesis of lactic acid oligomer-grafted-untreated bacterial cellulose (OLLA-g-BC) by in situ condensation polymerization which increased compatibilization between hydrophobic poly(lactic acid) (PLA) and hydrophilic BC, thus enhancing various properties of PLA-based bionanocomposites, indispensable for stringent food-packaging applications. During the synthesis of OLLA-g-BC, hydrophilic BC is converted into hydrophobic due to structural grafting of OLLA chains with BC molecules. Subsequently, bionanocomposites films are fabricated using solution casting technique and characterized for structural, thermal, mechanical, optical, and gas-barrier properties. Morphological images showed uniform dispersion of BC nanospheres in the PLA matrix, which shows strong filler–matrix interaction. The degradation temperatures for bionanocomposites films were above PLA processing temperature indicating that bionanocomposite processing can be industrially viable. Bionanocomposites films displayed decrease in glass transition (T_g) and ~20% improvement in elongation with 10 wt % fillers indicating towards plasticization of PLA. PLA/OLLA-g-BC films showed a slight reduction in optical transparency but had excellent UV-blocking characteristics. Moreover, dispersed BC act as blocking agents within PLA matrix, reducing the diffusion through the bionanocomposite films which showed ~40% improvement in water-vapor barrier by 5 wt % filler addition, which is significant. The reduced T_g, improved elongation combined with improved hydrophobicity and water-vapor barrier make them suitable candidate for flexible food-packaging applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47903.     

Preparation and characterization of poly(ethylene glycol) crosslinked chitosan films

Poly(ethylene glycol) (PEG) crosslinked chitosan films with various PEG to chitosan ratio and PEG molecular weight were successfully prepared via the epoxy‐amine reaction between chitosan and PEG‐epoxy. The thermal and mechanical properties and swelling behavior were studied for the PEG crosslinked chitosan films. The mechanical strength of chitosan films were greatly enforced by the introduction of PEG‐epoxy, achieving an elongation of about 80%. It was found that the crosslinked chitosan films form hydrogel in water, achieving a swelling ratio higher than 20 times of original weight. The swelling behavior of chitosan films relied greatly on the molecular weight of the crosslinker PEG‐epoxy and the weight percent of PEG‐epoxy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Synergistic reinforcing of poly(lactic acid) by poly(butylene adipate-co-terephthalate) and alumina nanoparticles

Biodegradable poly(lactic acid) (PLA)/poly(butylene adipate-co-terephthalate) (PBAT) blends and PLA/PBAT/Al₂O₃ nanocomposites were fabricated via solution blending. The influence of PBAT and Al₂O₃ content on the thermal stability, flexural properties, impact strength, and morphology of both the PLA/PBAT blends and the PLA/PBAT/Al₂O₃ nanocomposites were investigated. The impact strength of the PLA/PBAT/Al₂O₃ nanocomposites containing 5 wt% PBAT increased from 4.3 to 5.2 kJ/m² when the Al₂O₃ content increased from 0 to 1 wt%. This represents a 62% increase compared to the impact strength of pristine PLA and a 20% increase compared to the impact strength of PLA/PBAT blends containing 5 wt% PBAT. Scanning electron microscopy imaging revealed that the Al₂O₃ nanoparticles in the PLA/PBAT/Al₂O₃ nanocomposites function as a compatibilizer to improve the interfacial interaction between the PBAT and the PLA matrix.     

Synthetic organofluoromica/poly(lactic acid) nanocomposites: Structure,rheological and thermal properties

Organically modified fluoromica/poly(lactic acid) (PLA) nanocomposites were prepared by melt processing at different compositions in an internal mixer at the same conditions. Gel permeation chromatography (GPC) was used to measure the molar masses of PLA alone, before and after processing. The results indicated that PLA presented some degradation during melt mixing. With the addition of the organically-modified fluoromica, higher reduction in the polymer molar masses was found. The structure of the synthetic mica and of the clay polymer nanocomposites (CPN) was studied by small-angle X-ray scattering (SAXS), which revealed the presence of nanometer-sized clay mineral aggregates. Dynamical rheological measurements were carried out in the linear viscoelastic region for both PLA and CPN molten samples. A predominantly viscous behavior was obtained for the polymer samples, whereas the CPN presented a pronounced elastic behavior. Addition of mica to PLA also had a significant effect on the complex viscosity of PLA, imparting an increasing shear thinning behavior with increasing mica composition. Below T_g, dynamical mechanical analysis results showed a substantial decrease of rigidity of the CPN in relation to PLA alone, attributed to the presence of high content of organic intercalant in the synthetic fluoromica. Lower cold crystallization rate was detected for the CPN in comparison with processed PLA alone.     

Pd nanoparticles deposited on poly(lactic acid) grafted carbon nanotubes: synthesis, characterization and application in Heck C-C coupling reaction

Herein we described the synthesis of a novel f-CNTs-Pd nanocatalyst by covalent grafting of poly(lactic acid) (PLA) onto carbon nanotubes (CNTs) and subsequent deposition of Pd nanoparticles. Prior to grafting of PLA, CNTs were oxidized with a mixture of HNO(3)/H(2)SO(4) and successively activated with thionyl chloride. The PLA grafted CNTs (f-CNTs) were then used as platform for in-situ deposition of Pd nanoparticles. The formation of f-CNTs-Pd nanocatalyst was analyzed by UV-vis, FTIR and Raman spectroscopy, powder XRD, energy dispersive spectroscopy and thermogravimetric analysis. The morphologies of the nanocatalyst were characterized using scanning and transmission electron microscopes. The f-CNTs stabilized Pd nanoparticles are found to be more effective in the promotion of Heck cross-coupling reaction between aryl halides and n-butyl acrylate. The f-CNTs-Pd nanocatalyst was regenerated for three cycles of reaction without any significant loss in its activity.     

Plasticized poly(lactic acid) with low molecular weight poly(ethylene glycol): Mechanical,thermal, and morphology properties

Poly(lactic acid) PLA was plasticized with low molecular weight poly(ethylene glycol) PEG‐200 to improve the ductility of PLA, while maintaining the plasticizer content at maximum 10 wt%. Low molecular weight of PEG enables increased miscibility with PLA and more efficient reduction of glass transition temperature (T_g). This effect is enhanced not only by the low molecular weight but also by its higher content. The tensile properties demonstrated that the addition of PEG‐200 to PLA led to an increase of elongation at break (>7000%), but a decrease of both tensile strength and tensile modulus. The plasticization of the PLA with PEG‐200 effectively lowers T_g as well as cold‐crystallization temperature, increasing with plasticizer content. SEM micrographs reveal plastic deformation and few long threads of a deformed material are discernible on the fracture surface. The use of low molecular weight PEG‐200 reduces the intermolecular force and increases the mobility of the polymeric chains, thereby improving the flexibility and plastic deformation of PLA. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4576–4580, 2013     

Synthesis and thermal properties of telechelic poly(lactic acid) ionomers

Telechelic poly(lactic acid) (PLA) ionomers were synthesized using a chemical recycling process. A transesterification reaction between a commercial PLA and 2-hydroxyethyl methacrylate or ethylene glycol was used to produce a hydroxy-terminated PLA. The hydroxy-terminated PLA was then reacted with itaconic anhydride to produce terminal carboxylic acid groups, which were neutralized with appropriate metal acetates to produce Na-, Li-, K-, Zn-, Ca- and Y-ω- and α,ω-telechelic PLA ionomers. ¹H NMR spectroscopy was used to confirm the presence of the itaconic acid end-groups and FTIR spectroscopy was used to quantify the extent of neutralization. The addition of the ionic groups increased the glass transition (T_g), and T_g increased as the strength of the ion-pair increased. The ionic groups suppressed crystallinity, especially when multivalent cations were used.