The Effect of Masterbatch Addition on the Mechanical, Thermal, Optical and Surface Properties of Poly(lactic acid)

There has been considerable interest in the use of the biodegradable polymer poly(lactic acid) (PLA) as a replacement for petroleum derived polymers due to ease of processability and its high mechanical strength. Other material properties have however limited its wider application. These include its brittle properties, low impact strength and yellow tint. In an attempt to overcome these drawbacks, PLA was blended with four commercially available additives, commonly known as masterbatches. The effect of the addition of 1.5 wt% of the four masterbatches on the mechanical, thermal, optical and surface properties of the polymer was evaluated. All four masterbatches had a slight negative effect on the tensile strength of PLA (3–5% reduction). There was a four fold increase in impact resistance however with the addition of one of the masterbatches. Differential scanning calorimetry demonstrated that this increase corresponded to a decrease in the polymer crystallinity. However there was an associated increase in polymer haze with the addition of this masterbatch. The clarity of PLA was improved through the addition of an optical brightener masterbatch, but the impact resistance remained low. The glass transition and melting temperatures of PLA were not affected by the addition of the masterbatches, and no change was observed in surface energy. Some delay in PLA degradation, in a PBS degradation medium at 50 °C, was observed due to blending with these masterbatches.     

Earthworms and the Degradation of Lactic Acid–Based Stereocopolymers

Two lactic acid–based stereocopolymers, namely 50/50 and 96/4 L/D poly(l-lactic-co-d-lactic acids) and corresponding oligomers, were allowed to age under different conditions in order to investigate their toxicity and that of some potential degradation by-products, namely lactic acid and sodium and calcium lactates, to earthworms. Degradation characteristics in various worm-free and worm-containing media were also investigated under various conditions including direct feeding using impregnated paper or coated tree-leaves, model composting, and vermi composting. Data were compared with abiotic degradation in sterile neutral phosphate buffer. Last but not least, a novel method aimed at assessing the bioassimilation of degradable polymers and oligomers was utilized, which is based on the monitoring of weight changes of a population of starved worms when the worms are given the polymeric or oligomeric compounds as potential nutrients. The work shows that high molar mass poly(lactic acids) can be ingested by earthworms provided they are disintegrated first. However, they cannot be bioassimilated before hydrolytic degradation generates oligomers. The involvement of microorganisms in the bioassimilation is discussed.     

Reactive Blending of Biodegradable Polymers: PLA and Starch

Poly(lactic acid) (PLA) and starch are important biodegradable polymers. Mechanical properties of blends of PLA and starch using conventional processes were very poor because of incompatibility. In this study, PLA and starch were blended with a reactive agent during the extrusion process. The affects of the reactive blending were investigated and significant improvements were confirmed by measuring the tensile strength and elongation at break, IR spectra, and DSC.     

The basic properties of poly(lactic acid) produced by the direct condensation polymerization of lactic acid

Poly(lactic acids) with high molecular weights have been synthesized by direct condensation polymerization of lactic acid. These polymers have good mechanical properties and can be processed into products such as cups, film, and fiber, which can be used as compostable materials. This polymerization method can be applied to the synthesis of copolymers of lactic acid and other hydroxyacids. The properties of poly(lactic acid) and copolymers synthesized by the direct process are different from those of polymers obtained by the conventional lactide process.     

Physical Properties and Fiber Morphology of Poly(lactic acid) Obtained from Continuous Two-Step Melt Spinning

Fibers of poly(lactic acid) (PLA) produced by two-step melt-spinning are studied. The PLA resin used contains a 98:02 ratio of l:d stereochemical centers. A range of processing conditions is explored. The cold-draw ratio is varied from 1 to 8 under conditions of constant heating. In addition, three draw ratios are studied at three different heating rates. The thermal, mechanical, and morphological properties of the resultant fibers are determined. Properties can be widely manipulated through a combination of draw ratio and draw temperature. A maximum tensile strength and modulus of 0.38 GPa and 3.2 GPa, respectively, are obtainable. Using atomic force microscopy, the fiber morphology is found to be highly fibrillar; microfibril diameters are roughly 40 nm in diameter. Very high draw ratios cause the fiber to turn from shiny and translucent to dull and white; this transition is attributed to surface crazing. Significant molecular weight loss is observed upon processing (weight-average molecular weights drops between 27% and 43%).     

Thermal and Rheological Properties of Commercial-Grade Poly(Lactic Acid)s

Poly(lactic acid) is the subject of considerable commercial development by a variety of organizations around the world. In this work, the thermal and rheological properties of two commercial-grade poly(lactic acid)s (PLAs) are investigated. A comparison of the commercial samples to a series of well-defined linear and star architecture PLAs provides considerable insight into their flow properties. Such insights are valuable in deciding processing strategies for these newly emerging, commercially significant, biodegradable plastics. Both a branched and linear grade of PLA are investigated. The crystallization kinetics of the branched polymer are inferred to be faster than the linear analog. Longer relaxation times in the terminal region for the branched material compared to the linear material manifests itself as a higher zero shear rate viscosity. However, the branched material shear thins more strongly, resulting in a lower value of viscosity at high shear rates. Comparison of the linear viscoelastic spectra of the branched material with the spectra for star PLAs suggests that the branched architecture is characterized by a span molecular weight of approximately 63,000 g/mol. The present study conclusively demonstrates that a wide spectrum of flow properties are available through simple architectural modification of PLA, thus allowing the utilization of this important degradable thermoplastic in a variety of processing operations.     

The Effect of Nanoclays on the Properties of PLLA-modified Polymers Part 1: Mechanical and Thermal Properties

Organically modified montmorillonite clays were incorporated at a 5% loading level into film grade of poly-L-lactic acid (PLLA) using a variety of masterbatches based on either semi-crystalline or amorphous poly-(lactic acid), as well as biodegradable aromatic aliphatic polyester. The PLLA masterbatches and compounded formulations were prepared using a twin screw compounding extruder, while the films were prepared using a single screw cast film extruder. The thermal and mechanical properties of the films were examined in order to determine the effect of the clay and different carriers on the polymer–clay interactions. In the optimal case, when a PLLA-based masterbatch was used, the tensile modulus increased by 30%, elongation increased by 40%, and the cold crystallization temperature decreased by 15 °C, compared to neat PLLA. The properties improvement of PLLA films containing nano clays demonstrated the possibility to extend the range of biodegradable film applications, especially in the field of packaging.     

Thermal and mechanical properties of poly(lactic Acid) and poly(ethylene/butylene Succinate) blends

In this study, blends of poly (lactic acid) (PLA) with poly(ethylene/butylene succinate) (Bionolle) have been investigated for their thermal and mechanical properties as a function of the concentration of Bionolle. Differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and tensile tests were used to characterize the blends. From the results of the DMA and DSC, it was found that this blend system was not miscible within the compositions studied. DSC results showed that adding Bionolle aids in crystallization of PLA. It was observed that increasing the Bionolle concentration led to a slight increase in the strain-at-break of the blends but a decrease in the Young’s modulus and ultimate tensile strength. Biaxially oriented films showed an increase in tensile strength, modulus, and strain-at-break.     

Evaluation of Poly(lactic acid) and Sugar Beet Pulp Green Composites

Poly(lactic acid) (PLA) and sugar beet pulp (SBP) were compounded by twin-screw extrusion and injection molded into composite forms. Specific mechanical energy decreased with the addition of SBP during processing. PLA–SBP composites retained more tensile strength than expected based on the Nicolais–Narkis model especially at high levels of SBP suggesting adhesion between SBP and PLA. The thermal characteristics of PLA were not affected by thermo-mechanical processing or by the incorporation of SBP up to 30% weight basis. PLA and PLA–SBP composites had similar tensile properties to other thermoplastic resins and may be used as a cost-competitive replacement.

A Literature Review of Poly(Lactic Acid)

A literature review is presented regarding the synthesis, and physicochemical, chemical, and mechanical properties of poly(lactic acid)(PLA). Poly(lactic acid) exists as a polymeric helix, with an orthorhombic unit cell. The tensile properties of PLA can vary widely, depending on whether or not it is annealed or oriented or what its degree of crystallinity is. Also discussed are the effects of processing on PLA. Crystallization and crystallization kinetics of PLA are also investigated. Solution and melt rheology of PLA is also discussed. Four different power-law equations and 14 different Mark–Houwink equations are presented for PLA. Nuclear magnetic resonance, UV–VIS, and FTIR spectroscopy of PLA are briefly discussed. Finally, research conducted on starch–PLA composites is introduced.     

Biodegradable Blends Based on Starch and Poly(Lactic Acid): Comparison of Different Strategies and Estimate of Compatibilization

Finding plastic substitutes based on sustainability, especially for short-term packaging and disposable applications has aroused scientific interest for many years. Starch may be a substitute for petroleum based plastics but it shows severe limitations due to its water sensitivity and rather low mechanical properties. To overcome these weaknesses and to maintain the material biodegradability, one option is to blend plasticized starch with another biodegradable polymer. To improve both the compatibility between the main phases and the performance of the final blend, different compatibilization strategies are reported in literature. However, the relative efficiency of each strategy is not widely reported. This paper presents three different strategies: in situ (i) formation of urethane linkages; (ii) coupling with peroxide between starch and PLA, and (iiii) the addition of PLA-grafted amylose (A-g-PLA) which has been elaborated ex situ and carefully analyzed before blending. This study compares the effect of each compatibilization strategy by investigating mechanical and thermal properties of each blend. Compatibilizing behavior of the A-g-PLA is demonstrated, with a significant increase (up to 60%) in tensile strength of starch/PLA blend with no decrease in elongation at failure.     

Mechanical and Barrier Properties of Biodegradable Films Made from Chitosan and Poly (Lactic Acid) Blends

Biodegradable film blends of chitosan with poly(lactic acid) (PLA) were prepared by solution mixing and film casting. The main goal of these blends is to improve the water vapor barrier of chitosan by blending it with a hydrophobic biodegradable polymer from renewable resources. Mechanical properties of obtained films were assessed by tensile test. Thermal properties, water barrier properties, and water sensitivity were studied by differential scanning calorimeter analysis, water vapor permeability measurements, and surface-angle contact tests, respectively. The incorporation of PLA to chitosan improved the water barrier properties and decreased the water sensitivity of chitosan film. However, the tensile strength and elastic modulus of chitosan decreased with the addition of PLA. Mechanical and thermal properties revealed that chitosan and PLA blends are incompatible, consistent with the results of Fourier transform infrared (FTIR) analysis that showed the absence of specific interaction between chitosan and PLA.     

Mechanical Property Characterization of Plasticized Sugar Beet Pulp and Poly(Lactic Acid) Green Composites Using Acoustic Emission and Confocal Microscopy

Sorbitol and glycerol were used to plasticize sugar beet pulp-poly(lactic acid) green composites. The plasticizer was incorporated into sugar beet pulp (SBP) at 0%, 10%, 20%, 30% and 40% w/w at low temperature and shear and then compounded with poly(lactic acid) (PLA) using twin-screw extrusion and injection molding. The SBP:PLA ratio was maintained at 30:70. As expected, tensile strength decreased by 25% and the elongation increased. Acoustic emission (AE) showed correlated debonding and fracture mechanisms for up to 20% w/w plasticizer and uncorrelated debonding and fracture for 30–40% sorbitol and 30% glycerol content in SBP–PLA composites. All samples had a well dispersed SBP phase with some aggregation in the PLA matrix. However, at 40% glycerol plasticized SBP–PLA composites exhibited unique AE behavior and confocal microscopy revealed the plasticized SBP and PLA formed a co-continuous two phase system.

Effects of Starch Moisture on Properties of Wheat Starch/Poly(Lactic Acid) Blend Containing Methylenediphenyl Diisocyanate

Methylenediphenyl diisocyanate was found to improve the interfacial interaction between poly(lactic acid)(PLA) and granular starch. The objective of this research was to study the effect of starch moisture content on the interfacial interaction of an equal-weight blend of wheat starch and PLA containing 0.5% methylenediphenyl diisocyanate by weight. Starch moisture (10% to 20%) had a negative effect on the interfacial binding between starch and PLA. The tensile strength and elongation of the blend both decreased as starch moisture content increased. At 20% moisture level, the starch granules embedded in the PLA matrix were observed to be swollen, resulting in poor strength properties and high water absorption by the blend.     

Method of Producing Biodegradable Reference Material and its Biodegradability Based on International Standard Evaluation Method (ISO 14855-2)

Returnable cups made of poly(lactic acid) (PLA) are employed as an example of products made of biodegradable plastics. Two kinds of PLA samples plates and powders with different shapes were prepared from PLA cups. The plates were cut from a cup using nippers. Powders were prepared using a rotation mechanical mixer for 45 min. PLA powders were separated by sieves with 60 meshes (250 μm) into a size ranging from 0 to 250 μm. An average diameter of powders separated by a sieve is 169 μm. Biodegradation tests of PLA plates, PLA powders and cellulose powders in controlled compost at 58 °C were performed using a Microbial Oxidative Degradation Analyzer (MODA) instrument according to ISO 14855-2. PLA powders showed almost the same biodegradation curve as that of cellulose powders. PLA plates biodegraded at a slower rate than PLA powders.     

The biodegradation of lactic acid-based poly(ester-urethanes)

The biodegradability of lactic acid based poly(ester-urethanes) was studied using the headspace test method, which was performed at several elevated temperatures. The poly(ester-urethanes) were prepared using a straight two-step lactic acid polymerization process. The lactic acid is first condensation polymerized to a low molecular weight hydroxyl-terminated telechelic prepolymer and then the molecular weight is increased with a chain extender such as diisocyanate. In the biodegradation studies the effect of different stereostructures (different amounts of D-units in the polymer chain), the length of ester units, and the effect of crosslinking on the biodegradation rate were studied. The results indicate that poly(ester-urethanes) do not biodegrade at 25‡C, but at elevated temperatures they biodegrade well. The different stereostructures and crosslinking have a strong influence on the biodegradation rate. The length of ester units in the polymer chain also affects the biodegradation rate, but much less than crosslinking and stereostructure.     

Degradation of Poly(acrylic acid)s with Phenolic Side-Chains by Manganese Peroxidase from White Rot Fungi

Poly(acrylic acid)s (PAAs) with various functional groups, such as phenolic hydroxyl, amino, and aldehyde groups, in the side-chains were treated with manganese peroxidase (MnP) prepared from the culture of lignin-degrading white rot fungi. While no change in the M_w of PAA without a functional group was observed after a 24-h MnP treatment, the M_w␣of␣PAA␣with p-aminophenol as side-chains decreased from 90,000 to 59,000, and that with␣o-aminophenol from 70,000 to 26,000. MnP treatment also decreased the M_w of PAA with a p-aminoaniline or aldehyde group. Furthermore, the MnP treatment generated a significant depolymerization of the cross-linked PAA with p-aminophenol from an insoluble polymer to water soluble products. These results suggest that functional groups generating radicals can act as elemental devices and induce degradation of the PAA main chain.     

Starch, Poly(lactic acid), and Poly(vinyl alcohol) Blends

Research on biodegradable materials has been stimulated due to concern regarding the persistence of plastic wastes. Blending starch with poly(lactic acid) (PLA) is one of the most promising efforts because starch is an abundant and cheap biopolymer and PLA is biodegradable with good mechanical properties. Poly(vinyl alcohol) (PVOH) contains unhydrolytic residual groups of poly(vinyl acetate) and also has good compatibility with starch. It was added to a starch and PLA blend (50:50, w/w) to enhance compatibility and improve mechanical properties. PVOH (M_W 6,000) at 10%, 20%, 30%, 40%, 50% (by weight) based on the total weight of starch and PLA, and 30% PVOH at various molecular weights (M_W 6,000, 25,000, 78,000, and 125,000 dalton) were added to starch/PLA blends. PVOH interacted with starch. At proportions greater than 30%, PVOH form a continuous phase with starch. Tensile strength of the starch/PLA blends increased as PVOH concentration increased up to 40% and decreased as PVOH molecular weight increased. The increasing molecular weight of PVOH slightly affected water absorption, but increasing PVOH concentration to 40% or 50% increased water absorption. Effects of moisture content on the starch/PLA/PVOH blend also were explored. The blend containing gelatinized starch had higher tensile strength. However, gelatinized starch also resulted in increased water absorption.     

Synthesis of poly(hydroxyalkanoate) from hydrolyzed linseed oil

Pseudomonas putida was grown on a mixture of long-chain fatty acids obtained by hydrolysis of linseed oil. A poly(3-hydroxyalkanoate) containing 51.2% of unsaturated monomers was obtained. A considerable percentage (13.6%) was constituted by C₁₄ and C₁₆ monomers containing three double-bonds in the side chains. The polymer showed a high tendency to crosslink when it was kept in presence of air. In the crosslinked polymer no polyunsaturated monomers could be detected.     

Organic–Inorganic Hybrid Coatings for the Modification of Barrier Properties of Poly(lactic acid) Films for Food Packaging Applications

Organic–inorganic hybrid coatings based on poly(ε-caprolactone), poly(ethylene oxide) or poly(lactic acid) as organic phase and silica from tetraethoxysilane as inorganic phase were prepared by the sol–gel approach. Coatings were applied onto poly(lactic acid) films for food packaging in order to improve its barrier properties towards oxygen and water vapour. All the prepared coatings were dense, homogeneous layers characterized by a good adhesion to the substrate. The permeance of the coating layers resulted one order of magnitude lower than that of the uncoated poly(lactic acid) (PLA) film. The hydrophilic character of the coating did not permit to gain a significant decrease in the water vapour permeance. The perfect visual transparency of the coatings allows their application without worsening of the esthetical properties of the substrate PLA film.