This document discusses research on developing polylactic acid (PLA) based materials for durable applications. PLA has high strength but low toughness and heat resistance, limiting its use. The document reviews recent research using various strategies to improve the toughness and heat resistance of PLA blends and composites. These strategies include reactive compatibilization using functional monomers like glycidyl methacrylate to improve compatibility between PLA and other polymers in blends. Reactive blending and compatibilization can produce "super toughened" PLA blends with impact strengths over 35 kJ/m2 by enhancing stress transfer between phases. The document analyzes mechanisms governing toughness and heat resistance and factors affecting morphology of blends
This document summarizes a study on developing supertough poly(lactic acid) (PLA) blends through reactive melt blending of PLA, ethylene-methyl acrylate-glycidyl methacrylate (EMA-GMA) terpolymer, and a series of renewable poly(ether-b-amide) elastomeric copolymer (PEBA). Ternary blends of PLA/EMA-GMA/PEBA were fabricated and their phase morphology, thermal behavior, and mechanical properties were investigated. An optimized blending ratio of 70 wt% PLA, 20 wt% EMA-GMA, and 10 wt% PEBA achieved an impact strength of ~500 J/m
This document summarizes research into improving the impact strength and heat deflection temperature of poly(lactic acid) (PLA) biocomposites. The researchers created biocomposites from a ternary blend of PLA, poly(ether-b-amide), and ethylene-methyl acrylate-glycidyl methacrylate with 10% miscanthus fibers. Adding 1% of the nucleating agent Lak-301 and molding at 110°C resulted in biocomposites with 42% crystallinity, a 4-fold increase in impact strength over neat PLA, and an increased heat deflection temperature from 55°C to 85°C. The presence of the nucleating agent significantly
IRJET- Research and Development of Advanced Polymer Matrix Composite Mate...IRJET Journal
The document summarizes research on advanced polymer matrix composite materials (APMMCs). It discusses how APMMCs are lightweight composite materials composed of polymer matrices reinforced with fibers. The document outlines the two main types of polymer matrices used - thermosetting polymers and thermoplastics. It describes properties and production methods for composites using each type of matrix. Finally, the document discusses applications of APMMCs in industries like aerospace, automotive, and sports equipment due to their strength and lightweight properties.
This document summarizes a research article that analyzed the surface degradation of polypropylene (PP) and high-density polyethylene (HDPE) composites with 5% and 10% banana fiber loads when immersed in distilled water, ethanol, and sodium chloride solutions for up to 200 days. Samples were weighed over time to measure degradation and absorption in different environments. Surface degradation was also evaluated using scanning electron microscopy. The researchers found that longer immersion times led to greater material degradation regardless of environment.
This document discusses Sorona, a new polymer platform developed by DuPont based on 1,3-propanediol. 1,3-propanediol can be produced biologically from corn sugar through fermentation, offering economic and environmental advantages over conventional production methods. Sorona polymer has unique mechanical properties due to its molecular structure, including high elastic recovery. These properties provide benefits for textile applications. The document also describes the development and commercialization of the biological production process for 1,3-propanediol and the manufacturing of Sorona polymer.
Improvement of Tensile Properties of Recycled Low-Density Polyethylene by Inc...Dr. Amarjeet Singh
Plastics are used in versatile applications including
automobile, packaging, piping and house goods, these huge
uses attribute in the consumption of the oil reserves and the
emerged waste harm the environment when it disposed
irregularly. Recycling of plastics is one of the realistic
solutions to the aforementioned problems and to reduce
production cost. However, the reduction in mechanical
properties of recycled plastics limit their use and thus
reinforced plastics become popular because of their high
mechanical, physical and thermal properties. The effects of
calcium carbonate content from 0 to 15 wt.% on the tensile
properties of recycled low-density polyethylene (RLDPE)
were tested, the addition of calcium carbonate particles up to
15 wt.% was found to enhance the tensile strength and
modulus of elasticity of RLDPE samples. Three calcium
carbonate particle sizes (80, 200 and 500 µm) were mixed
with RLDPE to investigate the effect of particles size on the
tensile properties of RLDPE, it was found that the addition of
small filler particles resulted in a noticeable improvement of
tensile strength and modulus of elasticity of RLDPE
compared with large filler particles. It was also observed that
the addition of stearic acid slightly improves tensile
properties of RLDPE which may be related to improvement
of the interfacial adhesion between the filler and RLDPE. The
crystallization temperature and the degree of crystallinity of
RLDPE were increased by the addition of 7.5 wt.% calcium
carbonate particles because they act as nucleating agents.
This document describes the development of composite polymer scaffolds made of PLGA/PEG particles combined with hydrogel components like Pluronic F127, fibrin, or hyaluronic acid. The scaffolds are formed by mixing the PLGA/PEG particles with a hydrogel at room temperature, then allowing them to solidify at 37°C as the particles sinter together over time. Testing showed the compressive strength of the scaffolds increased between 15 minutes and 2 hours at 37°C. The maximum strengths were 1.2 MPa for PLGA/PEG-Pluronic F127 scaffolds, 2.4 MPa for PLGA/PEG-hyaluronic acid scaffolds, and 0.6 MPa for PLGA
1. The study investigates the effect of adding silicon carbide and calcium sulfate fillers to e-glass/epoxy composites fabricated using hand layup.
2. Results show that calcium sulfate filled composites have higher tensile strength and hardness but lower impact strength compared to neat and silicon carbide filled composites.
3. Composites filled with both calcium sulfate and silicon carbide have lower thermal expansion, longer ignition times, and lower mass loss rates during burning compared to other composites tested.
This document summarizes a study on developing supertough poly(lactic acid) (PLA) blends through reactive melt blending of PLA, ethylene-methyl acrylate-glycidyl methacrylate (EMA-GMA) terpolymer, and a series of renewable poly(ether-b-amide) elastomeric copolymer (PEBA). Ternary blends of PLA/EMA-GMA/PEBA were fabricated and their phase morphology, thermal behavior, and mechanical properties were investigated. An optimized blending ratio of 70 wt% PLA, 20 wt% EMA-GMA, and 10 wt% PEBA achieved an impact strength of ~500 J/m
This document summarizes research into improving the impact strength and heat deflection temperature of poly(lactic acid) (PLA) biocomposites. The researchers created biocomposites from a ternary blend of PLA, poly(ether-b-amide), and ethylene-methyl acrylate-glycidyl methacrylate with 10% miscanthus fibers. Adding 1% of the nucleating agent Lak-301 and molding at 110°C resulted in biocomposites with 42% crystallinity, a 4-fold increase in impact strength over neat PLA, and an increased heat deflection temperature from 55°C to 85°C. The presence of the nucleating agent significantly
IRJET- Research and Development of Advanced Polymer Matrix Composite Mate...IRJET Journal
The document summarizes research on advanced polymer matrix composite materials (APMMCs). It discusses how APMMCs are lightweight composite materials composed of polymer matrices reinforced with fibers. The document outlines the two main types of polymer matrices used - thermosetting polymers and thermoplastics. It describes properties and production methods for composites using each type of matrix. Finally, the document discusses applications of APMMCs in industries like aerospace, automotive, and sports equipment due to their strength and lightweight properties.
This document summarizes a research article that analyzed the surface degradation of polypropylene (PP) and high-density polyethylene (HDPE) composites with 5% and 10% banana fiber loads when immersed in distilled water, ethanol, and sodium chloride solutions for up to 200 days. Samples were weighed over time to measure degradation and absorption in different environments. Surface degradation was also evaluated using scanning electron microscopy. The researchers found that longer immersion times led to greater material degradation regardless of environment.
This document discusses Sorona, a new polymer platform developed by DuPont based on 1,3-propanediol. 1,3-propanediol can be produced biologically from corn sugar through fermentation, offering economic and environmental advantages over conventional production methods. Sorona polymer has unique mechanical properties due to its molecular structure, including high elastic recovery. These properties provide benefits for textile applications. The document also describes the development and commercialization of the biological production process for 1,3-propanediol and the manufacturing of Sorona polymer.
Improvement of Tensile Properties of Recycled Low-Density Polyethylene by Inc...Dr. Amarjeet Singh
Plastics are used in versatile applications including
automobile, packaging, piping and house goods, these huge
uses attribute in the consumption of the oil reserves and the
emerged waste harm the environment when it disposed
irregularly. Recycling of plastics is one of the realistic
solutions to the aforementioned problems and to reduce
production cost. However, the reduction in mechanical
properties of recycled plastics limit their use and thus
reinforced plastics become popular because of their high
mechanical, physical and thermal properties. The effects of
calcium carbonate content from 0 to 15 wt.% on the tensile
properties of recycled low-density polyethylene (RLDPE)
were tested, the addition of calcium carbonate particles up to
15 wt.% was found to enhance the tensile strength and
modulus of elasticity of RLDPE samples. Three calcium
carbonate particle sizes (80, 200 and 500 µm) were mixed
with RLDPE to investigate the effect of particles size on the
tensile properties of RLDPE, it was found that the addition of
small filler particles resulted in a noticeable improvement of
tensile strength and modulus of elasticity of RLDPE
compared with large filler particles. It was also observed that
the addition of stearic acid slightly improves tensile
properties of RLDPE which may be related to improvement
of the interfacial adhesion between the filler and RLDPE. The
crystallization temperature and the degree of crystallinity of
RLDPE were increased by the addition of 7.5 wt.% calcium
carbonate particles because they act as nucleating agents.
This document describes the development of composite polymer scaffolds made of PLGA/PEG particles combined with hydrogel components like Pluronic F127, fibrin, or hyaluronic acid. The scaffolds are formed by mixing the PLGA/PEG particles with a hydrogel at room temperature, then allowing them to solidify at 37°C as the particles sinter together over time. Testing showed the compressive strength of the scaffolds increased between 15 minutes and 2 hours at 37°C. The maximum strengths were 1.2 MPa for PLGA/PEG-Pluronic F127 scaffolds, 2.4 MPa for PLGA/PEG-hyaluronic acid scaffolds, and 0.6 MPa for PLGA
1. The study investigates the effect of adding silicon carbide and calcium sulfate fillers to e-glass/epoxy composites fabricated using hand layup.
2. Results show that calcium sulfate filled composites have higher tensile strength and hardness but lower impact strength compared to neat and silicon carbide filled composites.
3. Composites filled with both calcium sulfate and silicon carbide have lower thermal expansion, longer ignition times, and lower mass loss rates during burning compared to other composites tested.
IRJET- Experimental Investigation of Hybrid Composites using Glass Fiber and ...IRJET Journal
The document describes an experimental investigation of hybrid composites using glass fiber and recycled polyester. Researchers prepared glass fiber reinforced polyester composites using the hand layup process and tested the composites for various mechanical properties including hardness, compression, tensile and impact strength. The composites were made with different fiber volume fractions and tested to evaluate the effect of fiber content on mechanical properties.
Biopolymers for Paperboard Extrusion Coating and Converting - SPE FlexPackCon...C. Carey Yang, Ph.D.
Biopolymers have shown promising options for sustainable packaging applications. This article presents an overview of challenges and opportunities in biopolymers for paperboard extrusion coating and converting processes. Material properties, extrusion coating process and equipment requirements, regulatory compliance, and downstream converting are reviewed. The latest developments and emerging trends in biopolymer technology and innovation are discussed.
Processing, annealing and sterilisation of poly-l-lactide, Biomaterials, 2003Dr Neill Weir
1) The document examines how processing, annealing, and sterilization affect the properties of poly-l-lactide (PLLA), including its crystallinity, molecular weight, and mechanical properties.
2) It finds that compression molding and extrusion significantly reduced the crystallinity of PLLA pellets, but annealing increased crystallinity. Crystallinity further increased after sterilization with ethylene oxide gas.
3) A slight decrease in molecular weight was observed for extruded PLLA after processing, annealing, and sterilization. Mechanical properties like Young's modulus and tensile strength generally increased with higher crystallinity.
Jake Behrens presented on biocontainer materials made from renewable polymers and fillers. Various polymer matrices like PLA and PHA were evaluated along with fillers such as soy polymer, lignin, and DDGS to increase degradation and strength properties. Formulations were processed via extrusion and injection molding, which presented difficulties due to lack of shear thinning and high injection pressures. Results from tensile and crush tests showed that filler content inversely affected strength, and adding 1% colorant improved appearance and strength. The conclusions were to avoid moisture during processing, decrease temperatures with a plasticizer, and that colorant aided properties.
New Eco-Sustainable Polyamide-Based Polymers and Compounds for Multipurpose A...RadiciGroup
This document discusses new eco-sustainable polyamide-based polymers and compounds for multipurpose applications. It begins with an overview of sustainability at RadiciGroup and their bio-based polyamides. Properties of bio-polyamides like PA 6.10, PA 10.10 and PA 11 are compared. Case studies show engineering plastic compounds and films made from these polymers have good mechanical properties, thermal stability, and barrier properties. Examples of applications for the compounds include pneumatic pipes, truck air brake lines, and fuel connectors.
Influence of processing and sterilisation on PCL Polymers, Rubber, Composites...Dr Neill Weir
This document discusses how processing and sterilization can affect the properties of poly-e-caprolactone (PCL), a biodegradable polymer. PCL pellets were either injection molded or extruded and then sterilized using ethylene oxide gas. Testing showed that processing and sterilization did not significantly change the polymer's molecular weight. However, crystallinity was affected. Injection molding increased crystallinity by 5%, and sterilization further increased crystallinity in all materials by approximately 10%. While properties like mechanical strength were not influenced by sterilization, the results suggest that sterilization does cause annealing of PCL and increases its crystallinity.
The production of paper is essentially the dewatering of a
paper making slurry, which takes place on a moving wire
(Forming Fabric). This process of uniform drainage and sheet
http://www.wirefabrik.com/snippets/919297664SNIP-OCT10.pdf
George Snow has over 20 years of experience in research and development of dispersion polymers. He has worked at Lubrizol Corporation since 1988, holding several senior roles where he developed new products, conducted manufacturing troubleshooting, provided technical support to customers, and led projects with budgets up to $2 million. Snow has filed several patent applications, received patents, and published papers in his field. He has a Bachelor's degree in Chemistry and additional training in polymer science and business skills.
The document proposes research into synthesizing an interpenetrating polymer network of PDMS-PU-PEGMA to increase the permeability of glucose and oxygen through silicone-based coatings. The goal is to apply this coating to microbial fuel cells to improve their power output and open circuit voltage. The research will involve synthesizing PDMS-PU-PEGMA hydrogels with varying PEGMA content, characterizing their material properties, and measuring permeability. The coating is expected to allow glucose and oxygen transport through the layer to microbial fuel cells for improved performance.
Bin Yang is a polymer scientist pursuing a Ph.D. in Polymer Science and Engineering from the University of Southern Mississippi. He has expertise in polymer synthesis, characterization, formulation, and structure-property relationships. His research focuses on developing (meth)acrylate and epoxy functional polyisobutylene prepolymers for thermosetting adhesives and investigating their curing kinetics and material properties. He has collaborated with Henkel Corporation and the US Army on various polymer projects.
This document describes a new coating technology developed by Sandia National Laboratories and Lockheed Martin that uses a simple, safe, and economical self-assembly process to create multifunctional optical coatings. Some key benefits of this new technology over traditional coating methods are that it can be done at room temperature and ambient pressure, uses non-toxic and inexpensive materials, and is suitable for coating large and irregular surfaces. Potential applications highlighted include anti-reflective coatings for aircraft canopies, windows, and solar panels, as well as uses in electronics, displays, and sensors.
IRJET - Uses of Various Plastic Materials in Bitumious Concrete (Flexible Pav...IRJET Journal
The document discusses using various plastic materials in bituminous concrete or flexible pavement. Waste plastics like polyethylene, polystyrene, and polypropylene are shredded and coated on aggregates which are then mixed with hot bitumen to create a mix used in pavement construction. This strengthens the pavement and increases durability while providing an eco-friendly and economical solution to plastic disposal. The paper reviews literature on previous studies of polymer-modified bitumen and use of waste plastics in roads. It also describes aggregate tests and a process using a central mixing plant to uniformly coat aggregates with plastic and bitumen.
This paper present the state-of-the-art literature review and explore the research guidelines
on natural fibres polymeric composites. Due to the environmental issues, cost reduction and high
performance of engineering applications, the demand of natural fibre is increasing day by day.
Reinforcement with natural fiber in composites has recently gained attention due to low cost, easy
availability, low density, acceptable specific properties, ease of separation, enhanced energy
recovery, bio-degradability and recyclable in nature. To safeguard the environment, efforts are being
made for recycling different wastes and utilise them in value added applications.
This document discusses lactic acid bacteria (LAB) and their potential use as vaccines. It outlines that LAB naturally colonize mucosal membranes and could serve as ideal mucosal vaccine delivery vehicles. Examples are given of LAB like Lactococcus lactis being genetically engineered to express antigens from pathogens like Brucella abortis and Helicobacter pylori. The benefits of LAB vaccines are their safety, ability to survive the stomach, and lack of endotoxicity. Future work aims to develop multi-valent LAB vaccine vectors in clinical trials with biological containment to ensure environmental safety.
This document provides a comprehensive review of literature from 2000 to 2010 on natural fibers and biopolymers that are commonly used as reinforcements in biocomposites. It discusses the most popular natural fiber types used, their sources, structures, properties and modifications. The fiber modification methods covered include physical treatments like corona and plasma treatments as well as chemical treatments such as silane, alkaline, acetylation and enzyme treatments. The review also examines the most common biopolymer matrices used in biocomposites and various processing techniques for manufacturing biocomposites, including their effects on mechanical properties. Finally, it concludes with recent developments and future trends in biocomposites.
The document discusses the lactic acid energy system. It provides the key points that:
1) Glycolysis breaks down glucose into pyruvate to produce energy during the first 10 seconds to 2-3 minutes of exercise when the lactic acid system is dominant.
2) Lactic acid builds up as a byproduct, decreasing pH and affecting muscle contraction.
3) Trained athletes can resist the fatiguing effects of lactic acid accumulation longer due to an increased lactate threshold point.
The document discusses various fiber reinforced plastic (FRP) composite manufacturing processes. It defines FRP composites and describes common matrix materials like thermoset and thermoplastic resins. Manufacturing methods covered include hand lay-up, spray-up, resin transfer molding (RTM), filament winding, pultrusion, matched-die molding, and reaction injection molding (RIM). Each process is explained along with associated materials, equipment, advantages, disadvantages and applications.
Characterization of natural fiber reinforced composites bamboo and sisal a re...eSAT Publishing House
IJRET : International Journal of Research in Engineering and Technology is an international peer reviewed, online journal published by eSAT Publishing House for the enhancement of research in various disciplines of Engineering and Technology. The aim and scope of the journal is to provide an academic medium and an important reference for the advancement and dissemination of research results that support high-level learning, teaching and research in the fields of Engineering and Technology. We bring together Scientists, Academician, Field Engineers, Scholars and Students of related fields of Engineering and Technology.
This document discusses the SERVQUAL model, which is a framework for measuring service quality. It was developed in the 1980s and measures service quality across five dimensions: reliability, assurance, tangibles, empathy, and responsiveness. The document explains the five gaps in service quality as identified by the SERVQUAL model and provides examples. It also discusses criticisms of the model and how organizations can use it to measure customer expectations and perceptions over time to improve service quality.
This document discusses the synthesis of poly(lactic acid) (PLA) biomaterials. There are two main synthetic methods - direct polycondensation and ring-opening polymerization of lactide monomers. Direct polycondensation includes solution and melt polycondensation, but yields PLA with low molecular weight. Ring-opening polymerization using metal catalysts is more common and can produce high molecular weight PLA, but the metal catalysts require removal. Recent research focuses on developing non-toxic catalysts and new polymerization conditions.
Study of Bio-Nano Composite of Poly-Lactic Acid for Food Packaging- A Reviewpaperpublications3
Abstract: The impact of environment, economic and safety challenges have provoked the need to partially substitute petrochemical based polymer with bio degradable ones. [Poly lactic acid] PLA is the leading biodegradable polymer but its applications are limited by its relatively high cost, poor impact strength and barrier properties, which may be improved by adding reinforcing compounds (fillers), forming composites. Most reinforced materials present poor matrix–filler interactions, which tend to improve with decreasing filler dimensions. The use of fillers with at least one nanoscale dimension (nanoparticles) produces nanocomposites. Nanoparticles have proportionally larger surface area than their microscale counterparts, which favors the filler–matrix interactions and the performance of the resulting material.
Applications of nanomaterials in combination with PLA structures for creating new PLA nanocomposite with greater abilities are also covered. These approaches may modify PLA weakness for some food packaging applications. Nanotechnology approaches are being broadened in food science, especially in packaging material science with high performance and low concentrations and prices, so this category of nano-research is estimated to be revolutionary in food packaging science in the near future. The linkage of the 100% bio originated material and nanomaterial opens new windows for becoming independent, primarily, of petrochemical based polymers and, secondarily, for answering environmental and health concerns will undoubtedly be growing with time.
This study seeks to overcome PLA limitations by reinforcing PLA with nanoparticles and low-cost agricultural residues. The work presented in this thesis focuses on exploration of following relevant aspects:
• Preparation of PLA nanocomposite from LA [lactic acid].
• Reinforcement of various fillers during preparation.
• Testing of the formed nanomaterial to study the enhanced properties for sustainable green food packaging.
• Comparative study of the newly formed nanocomposites with respect to its properties
Nanotechnology has demonstrated a great potential to provide important changes in food packaging sector.
Nanocomposites are promising to expand the use of bio-degradable polymer, since the addition of nanoreinforcement has been related to improvement in overall performance of biopolymers, making them more competitive in a market dominated by non-biodegradable materials.
IRJET- Experimental Investigation of Hybrid Composites using Glass Fiber and ...IRJET Journal
The document describes an experimental investigation of hybrid composites using glass fiber and recycled polyester. Researchers prepared glass fiber reinforced polyester composites using the hand layup process and tested the composites for various mechanical properties including hardness, compression, tensile and impact strength. The composites were made with different fiber volume fractions and tested to evaluate the effect of fiber content on mechanical properties.
Biopolymers for Paperboard Extrusion Coating and Converting - SPE FlexPackCon...C. Carey Yang, Ph.D.
Biopolymers have shown promising options for sustainable packaging applications. This article presents an overview of challenges and opportunities in biopolymers for paperboard extrusion coating and converting processes. Material properties, extrusion coating process and equipment requirements, regulatory compliance, and downstream converting are reviewed. The latest developments and emerging trends in biopolymer technology and innovation are discussed.
Processing, annealing and sterilisation of poly-l-lactide, Biomaterials, 2003Dr Neill Weir
1) The document examines how processing, annealing, and sterilization affect the properties of poly-l-lactide (PLLA), including its crystallinity, molecular weight, and mechanical properties.
2) It finds that compression molding and extrusion significantly reduced the crystallinity of PLLA pellets, but annealing increased crystallinity. Crystallinity further increased after sterilization with ethylene oxide gas.
3) A slight decrease in molecular weight was observed for extruded PLLA after processing, annealing, and sterilization. Mechanical properties like Young's modulus and tensile strength generally increased with higher crystallinity.
Jake Behrens presented on biocontainer materials made from renewable polymers and fillers. Various polymer matrices like PLA and PHA were evaluated along with fillers such as soy polymer, lignin, and DDGS to increase degradation and strength properties. Formulations were processed via extrusion and injection molding, which presented difficulties due to lack of shear thinning and high injection pressures. Results from tensile and crush tests showed that filler content inversely affected strength, and adding 1% colorant improved appearance and strength. The conclusions were to avoid moisture during processing, decrease temperatures with a plasticizer, and that colorant aided properties.
New Eco-Sustainable Polyamide-Based Polymers and Compounds for Multipurpose A...RadiciGroup
This document discusses new eco-sustainable polyamide-based polymers and compounds for multipurpose applications. It begins with an overview of sustainability at RadiciGroup and their bio-based polyamides. Properties of bio-polyamides like PA 6.10, PA 10.10 and PA 11 are compared. Case studies show engineering plastic compounds and films made from these polymers have good mechanical properties, thermal stability, and barrier properties. Examples of applications for the compounds include pneumatic pipes, truck air brake lines, and fuel connectors.
Influence of processing and sterilisation on PCL Polymers, Rubber, Composites...Dr Neill Weir
This document discusses how processing and sterilization can affect the properties of poly-e-caprolactone (PCL), a biodegradable polymer. PCL pellets were either injection molded or extruded and then sterilized using ethylene oxide gas. Testing showed that processing and sterilization did not significantly change the polymer's molecular weight. However, crystallinity was affected. Injection molding increased crystallinity by 5%, and sterilization further increased crystallinity in all materials by approximately 10%. While properties like mechanical strength were not influenced by sterilization, the results suggest that sterilization does cause annealing of PCL and increases its crystallinity.
The production of paper is essentially the dewatering of a
paper making slurry, which takes place on a moving wire
(Forming Fabric). This process of uniform drainage and sheet
http://www.wirefabrik.com/snippets/919297664SNIP-OCT10.pdf
George Snow has over 20 years of experience in research and development of dispersion polymers. He has worked at Lubrizol Corporation since 1988, holding several senior roles where he developed new products, conducted manufacturing troubleshooting, provided technical support to customers, and led projects with budgets up to $2 million. Snow has filed several patent applications, received patents, and published papers in his field. He has a Bachelor's degree in Chemistry and additional training in polymer science and business skills.
The document proposes research into synthesizing an interpenetrating polymer network of PDMS-PU-PEGMA to increase the permeability of glucose and oxygen through silicone-based coatings. The goal is to apply this coating to microbial fuel cells to improve their power output and open circuit voltage. The research will involve synthesizing PDMS-PU-PEGMA hydrogels with varying PEGMA content, characterizing their material properties, and measuring permeability. The coating is expected to allow glucose and oxygen transport through the layer to microbial fuel cells for improved performance.
Bin Yang is a polymer scientist pursuing a Ph.D. in Polymer Science and Engineering from the University of Southern Mississippi. He has expertise in polymer synthesis, characterization, formulation, and structure-property relationships. His research focuses on developing (meth)acrylate and epoxy functional polyisobutylene prepolymers for thermosetting adhesives and investigating their curing kinetics and material properties. He has collaborated with Henkel Corporation and the US Army on various polymer projects.
This document describes a new coating technology developed by Sandia National Laboratories and Lockheed Martin that uses a simple, safe, and economical self-assembly process to create multifunctional optical coatings. Some key benefits of this new technology over traditional coating methods are that it can be done at room temperature and ambient pressure, uses non-toxic and inexpensive materials, and is suitable for coating large and irregular surfaces. Potential applications highlighted include anti-reflective coatings for aircraft canopies, windows, and solar panels, as well as uses in electronics, displays, and sensors.
IRJET - Uses of Various Plastic Materials in Bitumious Concrete (Flexible Pav...IRJET Journal
The document discusses using various plastic materials in bituminous concrete or flexible pavement. Waste plastics like polyethylene, polystyrene, and polypropylene are shredded and coated on aggregates which are then mixed with hot bitumen to create a mix used in pavement construction. This strengthens the pavement and increases durability while providing an eco-friendly and economical solution to plastic disposal. The paper reviews literature on previous studies of polymer-modified bitumen and use of waste plastics in roads. It also describes aggregate tests and a process using a central mixing plant to uniformly coat aggregates with plastic and bitumen.
This paper present the state-of-the-art literature review and explore the research guidelines
on natural fibres polymeric composites. Due to the environmental issues, cost reduction and high
performance of engineering applications, the demand of natural fibre is increasing day by day.
Reinforcement with natural fiber in composites has recently gained attention due to low cost, easy
availability, low density, acceptable specific properties, ease of separation, enhanced energy
recovery, bio-degradability and recyclable in nature. To safeguard the environment, efforts are being
made for recycling different wastes and utilise them in value added applications.
This document discusses lactic acid bacteria (LAB) and their potential use as vaccines. It outlines that LAB naturally colonize mucosal membranes and could serve as ideal mucosal vaccine delivery vehicles. Examples are given of LAB like Lactococcus lactis being genetically engineered to express antigens from pathogens like Brucella abortis and Helicobacter pylori. The benefits of LAB vaccines are their safety, ability to survive the stomach, and lack of endotoxicity. Future work aims to develop multi-valent LAB vaccine vectors in clinical trials with biological containment to ensure environmental safety.
This document provides a comprehensive review of literature from 2000 to 2010 on natural fibers and biopolymers that are commonly used as reinforcements in biocomposites. It discusses the most popular natural fiber types used, their sources, structures, properties and modifications. The fiber modification methods covered include physical treatments like corona and plasma treatments as well as chemical treatments such as silane, alkaline, acetylation and enzyme treatments. The review also examines the most common biopolymer matrices used in biocomposites and various processing techniques for manufacturing biocomposites, including their effects on mechanical properties. Finally, it concludes with recent developments and future trends in biocomposites.
The document discusses the lactic acid energy system. It provides the key points that:
1) Glycolysis breaks down glucose into pyruvate to produce energy during the first 10 seconds to 2-3 minutes of exercise when the lactic acid system is dominant.
2) Lactic acid builds up as a byproduct, decreasing pH and affecting muscle contraction.
3) Trained athletes can resist the fatiguing effects of lactic acid accumulation longer due to an increased lactate threshold point.
The document discusses various fiber reinforced plastic (FRP) composite manufacturing processes. It defines FRP composites and describes common matrix materials like thermoset and thermoplastic resins. Manufacturing methods covered include hand lay-up, spray-up, resin transfer molding (RTM), filament winding, pultrusion, matched-die molding, and reaction injection molding (RIM). Each process is explained along with associated materials, equipment, advantages, disadvantages and applications.
Characterization of natural fiber reinforced composites bamboo and sisal a re...eSAT Publishing House
IJRET : International Journal of Research in Engineering and Technology is an international peer reviewed, online journal published by eSAT Publishing House for the enhancement of research in various disciplines of Engineering and Technology. The aim and scope of the journal is to provide an academic medium and an important reference for the advancement and dissemination of research results that support high-level learning, teaching and research in the fields of Engineering and Technology. We bring together Scientists, Academician, Field Engineers, Scholars and Students of related fields of Engineering and Technology.
This document discusses the SERVQUAL model, which is a framework for measuring service quality. It was developed in the 1980s and measures service quality across five dimensions: reliability, assurance, tangibles, empathy, and responsiveness. The document explains the five gaps in service quality as identified by the SERVQUAL model and provides examples. It also discusses criticisms of the model and how organizations can use it to measure customer expectations and perceptions over time to improve service quality.
This document discusses the synthesis of poly(lactic acid) (PLA) biomaterials. There are two main synthetic methods - direct polycondensation and ring-opening polymerization of lactide monomers. Direct polycondensation includes solution and melt polycondensation, but yields PLA with low molecular weight. Ring-opening polymerization using metal catalysts is more common and can produce high molecular weight PLA, but the metal catalysts require removal. Recent research focuses on developing non-toxic catalysts and new polymerization conditions.
Study of Bio-Nano Composite of Poly-Lactic Acid for Food Packaging- A Reviewpaperpublications3
Abstract: The impact of environment, economic and safety challenges have provoked the need to partially substitute petrochemical based polymer with bio degradable ones. [Poly lactic acid] PLA is the leading biodegradable polymer but its applications are limited by its relatively high cost, poor impact strength and barrier properties, which may be improved by adding reinforcing compounds (fillers), forming composites. Most reinforced materials present poor matrix–filler interactions, which tend to improve with decreasing filler dimensions. The use of fillers with at least one nanoscale dimension (nanoparticles) produces nanocomposites. Nanoparticles have proportionally larger surface area than their microscale counterparts, which favors the filler–matrix interactions and the performance of the resulting material.
Applications of nanomaterials in combination with PLA structures for creating new PLA nanocomposite with greater abilities are also covered. These approaches may modify PLA weakness for some food packaging applications. Nanotechnology approaches are being broadened in food science, especially in packaging material science with high performance and low concentrations and prices, so this category of nano-research is estimated to be revolutionary in food packaging science in the near future. The linkage of the 100% bio originated material and nanomaterial opens new windows for becoming independent, primarily, of petrochemical based polymers and, secondarily, for answering environmental and health concerns will undoubtedly be growing with time.
This study seeks to overcome PLA limitations by reinforcing PLA with nanoparticles and low-cost agricultural residues. The work presented in this thesis focuses on exploration of following relevant aspects:
• Preparation of PLA nanocomposite from LA [lactic acid].
• Reinforcement of various fillers during preparation.
• Testing of the formed nanomaterial to study the enhanced properties for sustainable green food packaging.
• Comparative study of the newly formed nanocomposites with respect to its properties
Nanotechnology has demonstrated a great potential to provide important changes in food packaging sector.
Nanocomposites are promising to expand the use of bio-degradable polymer, since the addition of nanoreinforcement has been related to improvement in overall performance of biopolymers, making them more competitive in a market dominated by non-biodegradable materials.
This document summarizes a study investigating the effect of size-fractionated biocarbon particles on the microstructure and macroscopic properties of biocomposites made from poly(trimethylene terephthalate) (PTT), poly(lactic acid) (PLA), and an ethylene methyl acrylate glycidyl methacrylate (EMAGMA) terpolymer blend matrix. Biocarbon was separated into different particle size ranges through sieving. Composites with biocarbon particles between 20-75 microns showed better dispersion and morphology compared to other size ranges. The addition of an epoxy-based chain extender resulted in finer dispersed polymer particles, significantly increasing impact strength. Maximum impact strength of 85
Abrasive jet micro-machining (AJM), in which abrasive parti-cles are accelerated by air and directed toward a target, has beenused to make components for micro-electromechanical (MEMS) and micro-fluidic capillary electrophoresis devices . One ofthe disadvantages of AJM is that the compressed air jet used topropel the erodent particles diverges significantly after the noz-zle exit, increasing the size of the blast zone and the width of thesmallest channel or hole that can be machined without the use of a patterned erosion-resistant mask that defines the micro-featureedges . Abrasive slurry jet micro-machining (ASJM) is similar to AJM except that pressurized water, instead of air, is used to accel-erate the suspended abrasive particles such as garnet or alumina(Al2O3). In both AJM and ASJM, the material removal occurs by ero-sion. However, for the same jet dimension and flow speed, slurryjets have a much lower divergence angle than air jets , allow-ing for the micro-machining of small features without the use ofpatterned masks.
Highly thermal conductive Boron Nitride/Polyrotaxane encapsulated PEG-based ...Javier García Molleja
Authors: Guang-Zhong Yin, Xiao-Mei Yang, Alba Marta López, Javier García Molleja, Antonio Vázquez-López and De-Yi Wang
Published in: European Polymer Journal 199 (2023) 112431
Because of copyright transfer to Elsevier only the first page is provided. Available at:
https://doi.org/10.1016/j.eurpolymj.2023.112431
IRJET - A Review on Effect of Waste Carpet Fibres and Palm Oil Fuel Ash on Se...IRJET Journal
This document reviews the effect of waste carpet fibers and palm oil fuel ash on self-compacting fiber reinforced concrete. It first provides background on palm oil fuel ash and waste carpet fibers, which are agricultural and industrial byproducts, respectively. It then summarizes several studies that have investigated using these materials in concrete. The studies found that palm oil fuel ash can replace cement in self-compacting concrete and improve strength and durability over time. Waste carpet fibers were shown to increase flexural and tensile strength when added to concrete. Combining waste carpet fibers and palm oil fuel ash in self-compacting concrete resulted in improved strength and durability characteristics while providing an environmentally-friendly use for these wastes.
This document reviews manufacturing technologies and properties of carbon/glass fiber-reinforced polymer composites. It begins by classifying common glass and carbon fibers, describing their properties. It then provides a detailed overview of manufacturing techniques for glass fiber-reinforced polymer (GFRP) and carbon fiber-reinforced polymer (CFRP) composites, from oldest to newest. The main properties of GFRP and CFRP composites are summarized based on literature, including mechanical, vibration, environmental, tribological and thermal properties. Applications and future research directions are also discussed.
This report provides an overview of the current status of torrefaction technologies and their market perspectives. It summarizes the basic principles of torrefaction, where biomass is heated to 250-350°C in a low oxygen environment, resulting in the partial removal of volatile matter. This makes the biomass brittle and hydrophobic. The report also outlines the technical and economic advantages of torrefied biomass compared to raw biomass and assesses several torrefaction technology types and their commercial initiatives. It identifies the key challenges for market implementation as technical performance, economics, and regulatory acceptance.
This document discusses converting plastic waste into fuel. It aims to solve the twin problems of plastic pollution and the need for alternative fuel sources. Plastic waste would be converted into valuable fuel through processes like pyrolysis and gasification. These processes involve heating plastic in the absence of oxygen to produce liquid and gas fuels. Converting plastic waste to fuel is proposed as an environmentally friendly solution that generates profit while reducing plastic in landfills and the problems they cause.
Sustainability of the product is becoming a crucial factor for success in the market. Sustainability theory and methods are quite general. This research constitutes a serious attempt to assess the sustainability of plastic sheet piling, and calculate the product carbon footprint. In the case of plastic sheet piling no significant previous research has been done to address sustainability. The product lifecycle including stages such as raw material production, manufacturing, transportation, installation, and disposal/recycling, and its related supply chain have been analysed in detail to identify those factors that have impact on the product carbon footprint and the three main dimensions of sustainability: environmental, social and economic. The installation stage, which is not normally addressed in this kind of studies, has been assessed by the development of a case study.
Thermal degradation kinetic study of polypropylene co-polymer (PPCP) nanocomp...IRJET Journal
This document summarizes a study on the thermal degradation kinetics of polypropylene co-polymer (PPCP) nanocomposites. Nanocomposites were prepared with PPCP, maleic anhydride grafted polypropylene (MAgPP), and multiwall carbon nanotubes (MWCNTs). Thermogravimetric analysis showed the thermal stability of the nanocomposites increased with higher MWCNT loading. The Coats-Redfern method was used to evaluate kinetic parameters like reaction order, activation energy, and frequency factor from the thermogravimetric data. The degradation mostly followed 0.5 order kinetics, with activation energies ranging from 120-355 kJ
POLYMER NANOCOMPOSITE ARE THE FUTURE for packaging industriesPrajwal Ghadekar
Flexible packaging consumption’s rapid growth represents a $38 billion market in the global Community. As the demand in the industry continues to rise at an average of 3.5% each year, flexible materials need to meet and exceed the high expectations of consumers And the stressors of the supply chain. Increased competition between suppliers Along with government regulations translates into innovations in films that enhance product and Package performance as well as address worldwide concerns with packaging waste.
One such innovation is polymer nanocomposite technology which holds the key to future Advances in flexible packaging. According to Aaron Brody in a December, 2003 Food Technology article, “…Nano composites appear capable of approaching the elusive goal of converting plastic into a superbarrier—the equivalent of glass or metal—without upsetting regulators” (Brody, 2003). This paper will discuss how nanocomposites are made and the growth of nanocomposite materials as a function of their numerous advantages in the packaging industry today and in the future.
This document summarizes research from Scion, a New Zealand research organization, on biopolymers and chemicals from 2014-2015. It discusses how Scion is supporting manufacturers through research on sustainable and biobased resources. Key points include Scion developing an eco-friendly bioplastic alternative to polystyrene foam called ZealaFoam, research finding that a biocomposite reinforced with wood fibers can be highly recyclable, and industrial extrusion trials being assisted by computer simulation to optimize natural fiber compounding processes.
What are the underlying biases and preconceived notions that we have about the products labelled "bio" or "green"? Are there other “bio”s that we need to be wary of?
Dr Jem's talk will cover bioplastics from a holistic perspective, with a focus on: types of bioplastics, pro's and con's of PLA, how is PLA 'industrially' recycled or composted, innovations in the bioplastics world, other plant-based packaging alternatives, etc.
Dr. Jem received his Ph.D. and 2 Masters degrees in biochemical engineering, and numerous awards in the USA, and worked 15 years in engineering, biotech, and pharmaceutical companies such as Ratheon, Serono, Diversa, with excellent track record with multiple awards. In 2000, he moved back to China to work for biotech and bioplastic companies such as Cargill and NatureWorks PLA. He has served as the China General Manager for Total Corbion PLA JV and previously for Corbion Purac since 2007, and serves as a Visiting Professor for several local Universities.
This document discusses various methods for depolymerizing polypropylene to reduce its molecular weight. It begins by providing background on how polypropylene is traditionally produced and some limitations of high molecular weight polypropylene for certain applications. It then reviews four main types of depolymerization methods - oxidative, thermal, radiation-based, and chemical - and discusses how each works and its effects. Specifically, it explores using heat, oxygen, ozone, radiation like x-rays, or free radicals to initiate depolymerization reactions that break polymer chains through scission or other reactions to reduce molecular weight and improve processability. The document aims to provide an overview of depolymerization techniques and their impact on polypropylene
IRJET- Use of Recycled Poly Lactic Acid (PLA) Polymer in 3D Printing: A ReviewIRJET Journal
This document summarizes research on using recycled poly lactic acid (PLA) polymer in 3D printing. It discusses how PLA can be recycled through a closed-loop process to produce 3D printing filament. Studies show that the mechanical and thermal properties of recycled PLA are similar to virgin PLA after one recycling cycle, but deteriorate with additional cycles. The document also examines combining recycled PLA with virgin PLA to improve properties. Adding 25% virgin PLA to recycled PLA maintained tensile strength after double recycling. Coating recycled PLA pellets with polydopamine also increased tensile strength of printed components, providing a potential method to enhance recycled plastics.
Innobioplast 2013 presentation dwa coffee cup developmentAtkinderek
This document summarizes a project to develop a compostable PLA coffee cup that can withstand hot coffee. A working group was formed between universities and companies to evaluate more sustainable cup options. Through various formulations and testing, it was found that a combination of PLLA and PDLA homopolymers with fillers provided sufficient stiffness at hot temperatures. However, the cups did not fully meet compostability standards after testing. Further development is still needed to optimize degradation.
This document summarizes a student's seminar report on polymer nanocomposites for packaging industries. The student discusses how polymer nanocomposites are made by dispersing nanoparticles into a polymer matrix. This creates a tortuous path that improves gas and moisture barrier properties. The student then outlines several key applications of polymer nanocomposites in packaging, such as reducing military food packaging waste and improving the barrier properties of multilayer PET bottles. Overall, the document introduces polymer nanocomposites and their advantages for packaging applications.
PLA aerogel as a universal support for the typical organic phase change ener...Javier García Molleja
Authors: Guang-Zhong Yin, Xiao-Mei Yang, Alba Marta López, Xiang Ao, Mei-Ting Wang, Javier García Molleja and De-Yi Wang
Published in: Journal of Energy Storage 73 (2023) 108869
Because of copyright transfer to Elsevier only the first page is provided. Available at:
https://doi.org/10.1016/j.est.2023.108869
This document discusses characterizing postconsumer resin (PCR) plastic through materials analysis to support increased recycling and reuse of plastics. It describes challenges with plastic waste and recycling efforts. Thermal and mechanical analysis techniques like DSC and DMA can provide detailed information on PCR properties to help manage variability and ensure suitability for applications. These analyses examine thermal behavior and properties under strain. Characterizing PCR can help increase recycled content in new plastics and support the development of a circular plastics economy.
2. while retaining its compostability. Industries are therefore
seeing a major shift in the marketplace from “compostability” to
“renewability”. However, being compostable and being renew-
able are not dependent or in conflict with each other, each has
its own advantages. Preference for “renewable carbon” instead
of “fossil carbon” stems from the very realization of our need to
reduce nonrenewable resource consumption, and greenhouse
gas (GHG) emissions. The Kyoto Protocol was the first critical
step taken toward a truly sustainable future; it mandates
emission cuts for industrialized nations. Ratified by 145 nations
around the world, the protocol entered into force in February
2005.4
At the 10 year mark, United Nation Framework
Convention on Climate Change (UNFCCC) announced those
countries who took on the targets of the protocol have
collectively reduced the emissions over 20% as opposed to the
aimed target of 5%.5
A successor climate change agreement
approved in Paris COP21 Conference, December 2015, has set
a goal to keep the world under 1.5 °C temperature rise.6
A
Japanese government directive says by 2020, 20 wt % of all
plastics used in Japan must be derived from renewable
resource.7
Leadership in Energy and Environmental Design
(LEED) certifications, carbon tax and other local regulations
are also driving the demand for durable biopolymers.
Current research around the world on PLA modification and
application is focused on producing high performance partially
renewable materials that can compete with conventional
plastics. However, much like other synthetic plastics, PLA has
its own inherent weakness that prevents it from being widely
adopted for durable applications, in particular its low toughness
and heat resistance. PLA has a very slow crystallization rate,
whereas a high level of crystallinity is desirable in finished
products as it dictates most of the mechanical and thermal
properties. The toughness and ductility of PLA have been
improved with multiple strategies including plasticization,
copolymerization, and melt blending with different tough
polymers, rubbers and thermoplastic elastomers. Research
progress in toughening PLA based on these strategies can be
found in several recent review articles.8−14
However, none of
these articles have articulated the efforts taken toward achieving
a PLA based material with improved short-term heat resistance.
This perspective summarizes the most recent developments in
achieving super toughened and heat resistant PLA blends and
composites. Exhaustive literature available on these topics are
organized based on the strategies and approaches taken to
resolve the material problems. Various factors governing the
toughness and heat resistance of the blends and composites are
also discussed.
■ SUPER TOUGHENED BLENDS: CURRENT TREND
SEEKING TOUGHER PLA
Toughness: Definitions and Mechanisms. Toughness is
a complicated property; it is defined in terms of “impact
strength/toughness”, the ability to absorb sudden impact
energy without breaking and “tensile toughness”, the ability
to absorb energy while being pulled apart or stretched.
Emphasis is on the ability to absorb energy before fracture. A
good combination of strength and ductility is the key to
toughness. PLA is a brittle polymer with low crack initiation
energy (measured by unnotched impact test) and low crack
propagation energy (measured by notched impact test); it fails
by crazing. Although it may be relatively easy to improve the
ductility (elongation at break), it is much more challenging to
increase the impact toughness of PLA. Impact toughness
depends on many extrinsic (notch, temperature, loading mode,
specimen geometry, fracture behavior) and intrinsic (phase
morphology, chain structure and entanglements) variables. The
responsiveness of a particular polymer to be rubber toughened
is also said to depend on entanglement density (νe) and
characteristic chain ratio (C∞); these two will decide the
fracture behavior of crazing and yielding.15
See Wu’s work15
for
detailed understanding of these concepts.
Toughening mechanisms including shear yielding, multiple
crazing and a combination of both have been reported for
toughened PLA blends.9
According to toughening theo-
ries,15−19
stress concentration due to the presence of spherical
rubbery particles is the first step to complex toughening
process. Multiple crazing occurs when the stress required for
craze initiation is less than the yield stress. In this situation,
maximum triaxial stress concentrations at the dispersed
particles initiate crazes. Craze termination is the next natural
step in this mechanism through the formation of small multiple
crazes leading to crack propagation. New surfaces generated
during the creation of multiple crazes consume more energy
than a small number of large crazes. Shear yielding occurs when
the stress required for craze initiation is greater than yield
stress. Toughening by this mechanism is usually achieved by
hydrostatic tension in the dispersed particles acting as shear
band initiators. When the yield stress and craze initiation stress
are comparable or when there are interactions between the
shear bands and crazes formed in the matrix, the combination
of shear yielding and multiple crazing becomes the predom-
inant mechanism. Cavitation is another important precursor
phenomenon to any toughening mechanism. Two types of
cavitation have been observed in PLA toughened with a
rubbery phase: (i) internal cavitation, which occurs when the
interfacial bonding is strong between the rubber domains and
matrix; (ii) debonding cavitation, which occurs when there is
poor interfacial bonding strength. To prevent the localization of
strain, cavities formed either in the rubber particle (internal) or
the matrix (debonding) alters the triaxial stress state and favors
the formation of shear bands ultimately leading to shear
yielding of the matrix. Combination of internal and debonding
cavitation is also a possible mechanism.
The particle size, shape and distribution of toughening agent
can be tailored to reduce substantially the amount of impact
modifiers or elastomers required for a desired toughness.
Multicomponent blends containing reactive copolymers are
therefore being developed to tune the phase morphology in
interesting ways and obtain blends with moderate stiffness and
sufficient toughness by employing techniques like in situ
reactive compatibilization and dynamic vulcanization. These
processes increase interfacial strength by promoting chemical
reactions between blending components establishing strong
bridge for transmission of stresses. Resulting PLA blends with
drastic improvement in impact toughness are being referred to
as “super toughened” PLA. This term was first known to be
used by Wu15
for convenience to denote arbitrarily blends
having notched impact strength higher than 10 ft/lb or ∼530 J/
m (energy lost per unit width, North American standard),
which is approximately equal to 53 kJ/m2
(energy lost per unit
cross-sectional area, European standard) depending on the
dimension of the sample. Research work specifically focused on
achieving super toughened PLA blends (impact strength
beyond 35 kJ/m2
) is reviewed in this section. They are
categorized according to the type of reactive toughening
polymers and techniques used. This is followed by recom-
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3. mendations for future work. Range of impact properties thus far
obtained in super toughened PLA blends are summarized in
Table 1. Most of the articles in this section were focused on
achieving super toughness and have not investigated the effect
on crystallinity or heat resistance.
Reactive Compatibilization with Functional Mono-
mers. Successful application of a reactive compatibilization
technique has provided enormous opportunities to compatibi-
lize otherwise immiscible and incompatible blends. Reactive
compatibilization is therefore seen as a powerful technique to
enhance effectively the compatibility of PLA with other tough
polymers. Melt blending PLA with other suitable polymers in
the presence of a reactive monomer forms a graft copolymer at
the interphase, decreases the interfacial tension of the
immiscible polymer components and promotes interfacial
adhesion. A finer phase morphology developed in the blends
facilitates stress transfer between the two phases, thereby
improving the properties of the blends. Maleic anhydride,
glycidyl methacrylate, isocyanate and epoxy are some of the
widely investigated reactive monomers proving to be successful
in compatibilizing the blends of PLA with other bio- and
petroleum based polymers. In the work of Harada et al.,20
0.5%
lysine triisocyanate (LTI) was found to increase the impact
strength of PLA/PBS (90/10) blend from 18 kJ/m2
to 50−70
kJ/m2
. These improvements were attributed to effective
interfacial reactions accomplished between the isocyante
functionalities of LTI and carboxyl, hydroxyl end groups of
the blending polymers.
Glycidyl methacrylate (GMA) is one of the versatile
functional monomers tailored to meet a variety of applications.
A great number of PLA super toughening studies report use of
GMA in one or other forms to facilitate compatibility by
reacting with functional end groups of PLA. Effectiveness of
GMA in improving the toughness of PLA is explored mainly
through these three routes: (i) addition of GMA monomers or
copolymers such as ethylene glycidyl methacrylate (EGMA),
ethylene methyl acrylate glycidyl methacrylate (EMAGMA)
and ethylene butyl acrylate glycidyl methacrylate (EBAGMA),
(ii) addition of tough polymers grafted with GMA to facilitate
compatibility between the blending components (two-step
process of grafting followed by reactive compatibilization) and
(iii) addition of tough thermoplastic elastomers in combination
with GMA copolymers in one-step reactive extrusion. Factors
drastically affecting the toughening behavior of PLA blends
containing GMA are the reactive extrusion screw rpm and
residence time, which in turn affects important morphological
aspects such as dispersed phase size and interparticle distance.
Increasing the screw rpm from 30 to 200 in low molecular
weight PLA containing 20% EGMA was found to have a drastic
effect on elongation,21
as the value went up from 26% to
>200%. However, a super toughened PLA blend with 72 kJ/m2
of impact strength was achieved only after annealing the
processed samples at 90 °C for 2.5 h. Another parameter
appearing to have a significant effect on the resulting
toughening is GMA grafting content. Polyethylene octene
(POE), a metallocene catalyzed thermoplastic polyolefin
elastomer grafted with different percentages of GMA (1.8 and
0.8%), was used to toughen PLA.22,23
To achieve an impact
strength of 55 kJ/m2
, 45 wt % of POE-g-GMA (1.8%) had to be
blended with PLA,22
whereas in another study,23
20 wt % of
POE-g-GMA (0.8%) was sufficient to attain super toughness of
over 80 kJ/m2
. These super toughened blend systems were
proved to be efficient in absorbing external energy through a
combination of crazing and shear yielding mechanisms.
Poly(ether-block-amide), PEBA, a commercial class of thermo-
plastic copolyester elastomer from Arkema, is seen as an
efficient impact modifier for brittle polymers as it is highly
resistant to sudden impact even at very low temperatures (−40
°C). In spite of such favorable properties,24
30 wt % PEBA was
required to improve the impact strength of PLA to 60 kJ/m2
.
Zhang et al.25
used EMAGMA as a reactive interfacial
compatibilizer for blends of PLA/PEBA and achieved impact
strength up to 500 J/m, while maintaining tensile strength at 50
MPa (Figure 1). Performance improvements in these ternary
Table 1. Impact Strength Results for Super Toughened PLA Blends
technique/additives range of impact strength achieved reference
GMA based copolymers, thermoplastic elastomers and GMA grafted copolymers: notched Charpy: 46.1−72 kJ/m2
21−27
EGMA, POE, POE-g-GMA, PEBA, PEE EMAGMA, PEBA-g-GMA notched Izod: 40−80 kJ/m2
, 450−650 J/m
compatibilizers and chain extenders for PLA blends with PBS, PBSA, PBAT:
LTI, Joncryl, TPP
notched Izod: nonbreak 20, 28, 29
notched Charpy: 16−40 kJ/m2
acrylic impact modifiers and acrylic copolymer with GMA: 31−41
MBS, ABS-g-GMA, AcrylPEG, ACR with different BA and MMA content, KM-
365 and Paralloid BPM 500 from Rohm and Haas, Biomax strong from DuPont
notched Izod: 35−120 kJ/m2
540 J/m
dynamic vulcanization: 42−56
EBAGMA, EMAA based ionomers, PUEP, NR, ENR, UPE notched Izod: 480−800 J/m (nonbreak) 38−60 kJ/m2
random aliphatic copolyesters, polyurethanes, and other flexible polymers: 57−66
P(CL-co-LA), P(CL-co-VL), TPU, CPU, EVA notched Izod: 40−83 kJ/m2
450−550 J/m
Figure 1. Components, morphology and impact strength of
supertoughened PLA blends. [Reprinted with permission from ACS
Applied Materials and Interfaces, Vol. 6, K. Zhang, V. Nagarajan, M.
Misra, A. K. Mohanty. Supertoughened renewable PLA multiphase
blends system: Phase morphology and performance, 12436−12448,
Copyright 2014, American Chemical Society.]
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4. blends were attributed to their unique morphology of partial
encapsulation of PEBA by EMAGMA in PLA matrix. Interfacial
cavitation and good adhesion between phases resulted in
massive shear yielding of PLA matrix.
Vachon et al.26
used EMAGMA and poly(maleic anhydride-
alt-octadecene) (PMAOD) to compatibilize PLA and thermo-
plastic poly(ether ester) elastomer, PEE. A sharp transition in
impact strength values to 650 J/m was noticed in PLA ternary
blends containing 12% of PEE and 12% of EMAGMA, with
EMAGMA being more efficient compared to PMAOD.
Recently, Zhou et al.27
investigated the effect of adding GMA
grafted PEBA (PEBA-g-GMA) as an impact modifier for PLA
and thermoplastic starch acetate (TPSA). This work showed a
notched Izod impact strength of ∼60 kJ/m2
could be achieved
for PLA/TPSA/PEBA-g-GMA (70/15/15) blend. A TPSA
esterification degree of 0.04% was needed to improve the
compatibility between TPSA and PLA/PEBA-g-GMA. Proper-
ties of polymers are influenced to a greater extent by the length
of the macromolecule. When the macromolecular chain is
longer, the molar mass and entanglement degree is higher,
which increases the melt temperature and viscosity. Adding a
chain extender (CE) to PLA increases the molar mass of PLA
by connecting the short and long polymer chains via a reactive
functional end groups present in the CE. When a multifunc-
tional epoxy based chain extender, Joncryl was used for in situ
reactive compatibilization of PLA and poly(butylene succinate-
co-adipate), PBSA, the alteration of blend structure from linear
to long branched chains enhanced the impact strength of PLA/
PBSA (60/40) blend28,29
as shown in Figure 2.
The particle size of the PBSA dispersed phase was reduced
by 74% with the addition of 0.6% Joncryl, and further reduction
was noticed with increase in Joncryl content owing to effective
compatibilization. Dong et al.30
have also reported Joncryl is
effective in increasing the ductility and percentage elongation of
PLA/PBAT blends, to a maximum of 500%. As previous
studies29
have established the presence of induction time for
reactivity of Joncryl, the effect of increasing the temperature to
increase the reactivity of Joncryl could be an interesting aspect
of future investigations.
Acrylic Copolymers and Core−Shell Impact Modifiers.
Acrylic polymers such as poly(methyl methacrylate), PMMA,
and poly(butyl acrylate), PBA, have been found to be partially
miscible with PLA; therefore, they have been used to toughen
PLA.31,32
Achieving significant increase in impact strength is
however a challenge in simple binary blends of PLA with such
polymers.31−33
Researchers have looked into core−shell acrylic
copolymers such as methyl methacrylate−butadiene styrene,
acrylonitrile−butadiene styrene and methyl methacrylate−butyl
acrylate copolymers to super toughen PLA.34−40
The rubbery
core provides impact resistance whereas the glassy shell imparts
rigidity. Outer shell can be designed specifically to be
compatible with the PLA matrix. Core−shell composition,
particle diameter and its distribution, grafting percentage and
cross-linking degree are all important factors to achieve the
necessary toughening and they have all been investigated in
detail in PLA matrix. Acrylic impact modifiers (ACRs)
containing different ratios of methyl methacrylate, MMA
(hard/shell monomer) and butyl acrylate, BA (soft/core
monomer) were used to super toughen PLA.36,37
Impact
strength and elongation at break gradually increased with
increase in the amount of soft monomer in the ACR. In PLA/
ACR (90/10) containing BA/MMA in the ratio of 90/10, the
unnotched impact strength was significantly increased to 68 kJ/
m2
compared to 17 kJ/m2
for neat PLA. Tensile and flexural
properties were not drastically reduced as the ACR content was
only 10%.36
As the concentration of MMA hard shell monomer
increased, the impact strength initially increased and then
decreased, signifying the presence of a critical concentration of
MMA. The highest notched Izod impact strength of 77.1 kJ/m2
was achieved when the ACR core−shell ratio was optimized at
79.2/20.8 for the 80/20 PLA/ACR blend.37
With increase in
BA content, the interactions between ACR and PLA were
postulated to get stronger and the interface between these
phases was indistinct. Internal and debonding cavities in the
ACR domains induced crazes and shear bands in the PLA
making the matrix around the ACR particles to deform easily to
achieve shear yielding as shown in the schematic,36
Figure 3.
Poly(ether glycol) methyl ether acrylate, abbreviated as
AcrylPEG, has been most effective in imparting super
toughness to PLA thus far. Two different approaches were
investigated by Kfoury et al.:38
(i) polymerization of AcrylPEG
to poly(AcrylPEG) using free radical initiator, Luperox and (ii)
direct one step reactive extrusion with PLA, where in situ
grafting of AcrylPEG onto PLA backbone was achieved.
Substantial improvement of notched Izod impact strength to
102 kJ/m2
was achieved for PLA with 20 wt % AcrylPEG, and
35 kJ/m2
for PLA with poly(AcrylPEG). Commercial non-
Figure 2. Notched impact strength as a function of PBSA content and
Joncryl weight fraction. The schematic depicts the modification of the
PLA/PBSA blend interface by Joncryl through the formation of
nonlinear copolymer. [Reprinted from Polymer, Vol. 80, V. Ojijo, S. S.
Ray. Supertoughned biodegradable polylactide blends with nonlinear
copolymer interfacial architecture obtained via facile in situ reactive
compatibilization, 1−17, Copyright 2015, with permission from
Elsevier, License number: 3794351260132.]
Figure 3. A simple schematic of a possible mechanism by which ACR
toughens PLA. [Adapted from BioResources, Vol. 9, X. Song, Y. Chen,
Y. Xu, C. Wang. Study of tough blends of polylactide and acrylic
impact modifier, 1939−1952, 2014.]
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5. biodegradable acrylic impact modifiers available under the
tradename Paraloid BPM-50039
and KM-36540
from Rohm and
Haas, and Biomax Strong41
from DuPont are also available to
toughen PLA. PLA blends with Paraloid BPM-50039
possessed
good flexibility compared to neat PLA, impact strength
however did not improve beyond 40 J/m. PLA has been
reported to show brittle to ductile transitions when KM-365
and Biomax Strong are added beyond 20 wt %. In some cases,
impact modifiers were observed to hinder the crystallization of
PLA and decrease the tensile properties of the blends.
Dynamic Vulcanization. Dynamic vulcanization is one of
the most versatile areas of polymer modification. It is a process
in which selective vulcanization of elastomer with non-
vulcanizing thermoplastic is achieved during shearing in melt
mixing, leading to the formation of a two-phase material where
particulate cross-linked elastomeric phases are dispersed in the
plastic matrix.42
Zhang et al.43
introduced a super toughened
PLA ternary blends with moderate tensile strength and
modulus by melt blending PLA with ethylene n-butyl acrylate
GMA (EBAGMA) and ethylene methacrylic acid based zinc
ionomer (EMAA-Zn). Unlike other blends, in addition to
reactive compatibilization between PLA and EBAGMA,
dynamic vulcanization of EBAGMA was also achieved. Ternary
blends containing EMAGMA/ionomer weight ratio ≥ 1, Zn
metal ion, higher percentage of MMA functionality and
increased degree of neutrality were found to have enhanced
interfacial compatibility and hence higher impact strength.44−46
Morphological analysis based on SEM images demonstrated
that with the increase in EMAA-Zn content, the occluded
subinclusion phase of EMAA-Zn turned to continuous phase
within the “salami”-like dispersed domains. This morphology
was not dependent on reactive blending temperature; however,
higher reactive extrusion temperatures resulted in an
unfavorably higher degree of cross-linking in EBAGMA that
was resisting internal cavitation.
Polyurethane elastomer prepolymer (PUEP) with isocyanate
(−NCO) terminal groups vulcanized to a rubber phase has
been shown to toughen PLA.47
The −NCO groups reacted
with hydroxyl, carboxyl end groups of PLA to form urethane
linkages in addition to vulcanization reaction of the PUEP.
These reaction products bridged the PLA phase with vulcanized
rubber phase of PUEP. Predominant internal cavitation in
dynamic vulcanized blends imparted major toughening effect to
PLA/PEUP (70/30) blends with impact strength of 55 kJ/m2
and elongation values reaching over 400%. In another recent
work, researchers have developed super tough PLA materials
through in situ reactive blending with polyethylene glycol based
diacrylate (PEGDA) monomers.48
The cross-linking of acrylate
groups resulted in phase separated morphology with PEGDA as
the dispersed phase. Sea-island morphology had been the
typical, predominant morphology of thermoplastic vulcanizates
(TPVs) but Chen49,50
and Yuan et al.51,52
discovered it is
possible to achieve continuous cross-linked rubber phase in
peroxide induced dynamic vulcanization of PLA with natural
rubber (NR) and epoxidized natural rubber (ENR). Impact
strength results and SEM morphology of dynamic vulcanized
PLA/NR (65/35)49
are shown in Figure 4. After cryofracture
and etching of PLA phase, formation of continuous honey-
comb-like network structure by the NR phase was clearly
visible. Extensive plastic deformation of the surrounding PLA
deformed the rubber domains due to heterogeneous stress
fields and enhanced the toughness. A brittle ductile transition
was observed at PLA/ENR (60/40) blend ratio with notched
Izod impact strength of 47 kJ/m2
, which was 15 times higher
compared to 3 kJ/m2
for neat PLA.50
At dicumyl peroxide
(DCP) content beyond 0.03 phr, interfacial adhesion between
phases were enhanced and a higher degree of cross-linking was
achieved in ENR. “Fully biobased and super tough PLA TPV”
displaying a quasi-co-continuous morphology with vulcanized
unsaturated polyester elastomer (UPE) is yet another
successful effort to super toughen PLA using dynamic
vulcanization.53
Tensile and impact strength of PLA/UPE
TPVs improved from 3.2 MJ/m3
and 16.6 J/m to 99.3 MJ/m3
and 586 J/m, respectively. Other researchers have also
experimented with the dynamic vulcanization technique on
PLA blends of biobased polyester elastomers (BPE),54
ethylene
covinyl acetate (EVA)55
and ultrafine fully vulcanized powder
rubber (UFPR).56
They have been successful in achieving
tremendous improvements in elongation at break (>400%);
however, the impact strength is either not reported or very low
in the case of UFPR.
Melt Blending with Random Aliphatic Copolyesters,
and Other Toughening Polymers. In a series of studies,
Joziasse57
and Odent et al.58−60
synthesized random biode-
gradable copolyester: CL with D,L-lactide, (P[CL-co-LA]) and
CL with δ-valarectone (VL), (P[CL-co-VL]) to be used as
impact modifiers for PLA. When silica nanoparticles (10%)
were added to PLA blends containing these copolyesters,
spherically dispersed domains converted to cocontinuous
morphology, increasing the impact strength to 39.7 kJ/m2 vs
2.7 kJ/m2
for neat PLA.60
Li et al.61
prepared sliding graft
copolymer (SGC) where PCL side chains are bound to
polyrotaxane (PR) cyclodextrin rings and used them to
toughen PLA. Methylene diphenyl diisocyanate (MDI) was
used as the reactive compatibilizer. Blends of PLA/SGC/MDI
displayed super toughening with impact strength values as high
as 48.6 kJ/m2
. Unfortunately, preparing such copolymers is not
currently economically viable to be adopted by the industry for
wide scale production. Unique combination of toughness,
durability and flexibility makes thermoplastic polyurethane
elastomers (TPU) a suitable material to blend with PLA.
Addition of 30% TPU to PLA resulted in blends with impact
strength of 315 J/m and elongation at break of 363%.62
Liu et
al.63
noticed that toughening PLA by in situ polymerization of
PEG and PMDI to form cross-linked polyurethance (CPU) was
successful, where the impact strength of PLA with 30% CPU
increased from 16 to 546 J/m. Liu et al.64
introduced PDLA
into PLLA/TPU blends to form stereocomplex crystals that can
dramatically improve the melt viscosity and change the sea-
Figure 4. (a) Notched Izod impact strength of neat and dynamically
vulcanized PLA/NR blends, (b) SEM Images of dynamically
vulcanized PLA/NR (65/35). [Reprinted with permission from ACS
Applied Materials and Interfaces, Vol. 6, Y. Chen, D. Yuan, C. Xu.
Dynamically vulcanized biobased polylactide/natural rubber blend
material with continuous cross-linked rubber phase, 3811−3816,
Copyright 2014, American Chemical Society.]
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6. island morphology of PLLA/TPU to a unique network-like
structure. High levels of crystallinity in these blends were
achieved by injecting the samples into a preheated mold at 130
°C and postannealing. This resulted in PLLA/TPU/PDLA
(70/15/15) blends with remarkable improvement in impact
strength up to 63.2 kJ/m2
. Ethylene-co-vinyl acetate (EVA)
with different vinyl contents and ethylene acrylic elastomer
(EAE) has also been found to impart super toughness to PLA
at 20 wt %.65,66
Formation of shear bands initiated by the
internal cavitation of EVA resulted in shear yielding type of
fracture behavior in the blend, no crazing or interfacial
debonding occurred. As a consequence of numerous internal
cavitations, stress whitening was noticed on a macroscopic scale
as shown in the Figure 5.
■ EVALUATION OF FACTORS AFFECTING
TOUGHNESS: INSIGHTS FOR FUTURE WORK
In any rubber toughened polymers, factors such as rubber
content, type, particle size, particle size distribution and
interparticle distance are closely interrelated and greatly affect
the resulting toughening effect. The majority of all inves-
tigations concerning super toughened PLA have reported the
existence of an optimum loading level of the toughening agent,
and beyond this level fracture toughness ceases to improve or
in some cases starts to decline. This might be due to several
intrinsic factors related to the microstructure and the efficiency
of rubber to support any kind of toughening mechanism at high
rubber contents when there is not much matrix material to
undergo plastic deformation. Toughness improvements can be
expected only in a certain rubber content range, in which the
rubber is dispersed in desired particle sizes and size distribution
to cavitate effectively or fibrillate for maintaining a substantial
degree of structural integrity in response to impact. The
experimental evidence reported for such a limit is 20−30 wt %
of rubber content; therefore, modeling and theoretical work can
be developed to predict and explain this limit in future. The
rubbery phase added as a toughening agent is generally
preferred to be compatible with PLA to such an extent that
there is satisfactory dispersion and wetting but not completely
miscible to result in a single homogeneous phase morphology.
When the two phases are miscible as in PEG-plasticized PLA,
the elongation ratio (percentage) is improved tremendously but
the inability of the second phase to act as stress concentrator
does not favor multiple crazing or shear yielding resulting in
blends with only moderate toughness. Similarly, low toughness
was reported for PLA with in situ formed PU containing non-
cross-linked product that acted as a plasticizer.63
In the case of
PLA/EVA blends, toughness improvements were marginal
because of the formation of homogeneous morphology below
20 wt % EVA.65
Toughness improvement is also the highest at an optimum
rubber particle size. When the dispersed phase is incompatible
with the matrix, it would exist as spherical particles to reduce
surface tension. If the components in the blend have good
compatibility, uniform dispersion of the rubbery toughening
agent with relatively small particle size can be expected. With an
overlap in stress fields around the well dispersed particles,
plastic deformation can propagate through the entire matrix
giving rise to effective energy dissipation. Reactive compatibi-
lization has been found to reduce the particle size of the
thermoplastic elastomer or rubbery copolymer consider-
ably20,23,29,63
and in some cases their shape evolves from
spherical to distinct cocontinuous morphology.29,61
The shape
and size of the dispersed particles are dependent on the
dynamic viscosity, the shear rate of melt blending, and the
interfacial tension. The dispersed particles will have the smallest
average size when the viscosity ratio of the two phases is closer
to unity and when the interfacial tension is lower.17
Higher
shear rate generated by increasing the screw rotation speed in
an extruder can drastically reduce the particle size of the rubber.
For example, increasing the screw rpm from 30 to 200
significantly decreased the particle size of EGMA in high
molecular weight PLA (PLA-H) compared to low molecular
weight PLA (PLA-L).21
Proximity of viscosity ratio to unity in
the case of PLA-H reduced the particle size to 50−100 nm
whereas in PLA-L it was reduced to 100−300 nm.21
However,
very small particle size may not be beneficial for achieving super
toughness as small particles may not effectively absorb the
energy of the external force. Other researchers who quantified
the particle size of dispersed phase in super toughened PLA
also have established the fact that having optimum particle size
had resulted in superior toughening effect.20,23,63
On the basis
of the theories of Wu,15,16
the entanglement density, νe is
recognized to be one of the main factors governing the
Figure 5. Morphology of the PLA/EVA50 (80/20) blends after impact testing: (a) initial impact bars, (b) optical images, and TEM images of (c)
undeformed part, (d−d″) the stress whitening zone at different magnifications. [Reprinted from European Polymer Journal, Vol. 48, P. Ma, D. G.
Hristoca-Bogaerds, J. G. P. Goossens, A. B. Spoelstra, Y. Zhang, P. J. Lemstra. Toughening of poly(lactic acid) by ethylene-co-vinyl acetate copolymer
with different vinyl acetate contents, 146−154, Copyright 2012, with permission from Elsevier, License number: 3794310181202.]
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7. deformation mechanism. For brittle polymers in general super
toughening is predicted to occur at an optimum νe of 0.1
mmol/cc, as massive crazing and yielding of the matrix occurs
at this level of νe.16
Depending on composition, PLA is
predicted to have νe in the range of 0.12−0.14 mmol/cc.57,67
Using Wu’s relationship16
between optimum rubber particle
size, do and νe,
= −d vlog 1.19 14.1o e (1)
the do for PLA can be calculated to be in the range of 0.16−0.31
μm. On the basis of theoretical investigations, this range can be
expected to be the guiding value of particle size in future PLA
work aiming at achieving successful super toughening effect.
However, if the dispersed rubber phase contains rigid
subinclusions as in the case of core−shell or salami-like
morphology in ternary blends, the inclusion phase can anchor
the load bearing fibrils to the matrix, which can effectively
reduce premature cavitation. Therefore, in an alternative view,
particle size range required to achieve optimum toughness also
depends on other factors such as strain rate, morphology of the
dispersed particles, rubber content and the rubber shear
modulus.
Unfortunately, PLA super toughening studies have not
delved into the effect of particle size distribution. Bimodal
particle size distribution was observed when P[CL-co-VA] with
high molar mass was used to toughen PLA samples prepared by
compression molding.59
Although a super toughening effect
was not achieved, compression molded samples containing
P[CL-co-VA] in bimodal particle size distribution attained
higher impact strength compared to their injection molded
counterparts. Such improvements in compression molded
samples were thought to be because of the relatively larger
size of the microdomains in them compared to the morphology
of injection molded samples. The authors did not provide
further explanation behind this experimental observation.
Smaller particles can toughen the localized shear bands formed
in between the large particles.68
This makes the crack tip region
sustain higher fracture load by maintaining a higher critical
stress level. If this critical stress level generates greater triaxial
stress ahead of the crack tip, it causes higher degree of
cavitation in the larger particles; consequently, the adjacent
matrix undergoes shear yielding before fracture.68
Optimum
size and biomodal distribution would be necessary to achieve
synergistic super toughening. There is great scope for
interesting future work on examining the effects of such
biomodal particle size distribution. One way to achieve such
distribution in PLA matrix would be to use small fine rubber
particles in combination with large coarse particles. Synergistic
toughening with a combination of 1−2 and 70 μm rubber
particles from recycled tires has been observed in epoxy resin.69
Another factor to consider for efficient rubber toughening is
the average interparticle distance, L. According to toughening
theories,18
L should be below a value, Lc, in order for the
rubbery particles to effectively initiate plastic deformation in the
surrounding matrix, despite L being directly related to rubber
particle size and content. In PLA toughened with POE-g-
GMA,23
when the rubber content and particle size were
increased, interparticle distance was reduced. The critical value,
Lc for effective toughening of the blend was found to be 0.5
μm.23
However, there is no unique agreement between
researchers whether Lc is more important than content and
size. If so, the ultimate goal of manipulating the content and
size will be to drive the L below the Lc. On the other hand,
observations reporting very small particle size but no substantial
toughening effect do not follow this theory on L and Lc.
Further studies are needed to establish any possible relation-
ships.
■ HEAT RESISTANCE: CRITICAL ASPECT
CONFERRING DURABILITY
Heat resistance can be defined as the ability of a material to
maintain properties of interest at a desired level at the
maximum service temperature for a prolonged period of time.
Having a certain level of heat resistance is one of the principal
criteria for material selection. The heat resistance of PLA
depends on its level of crystallinity and crystallization behavior.
The crystallization model suggests the chain segments of
semicrystalline PLA coexist in three different forms: (i)
crystalline fraction, (ii) rigid amorphous fraction (RAF) and
(iii) mobile amorphous fraction (MAF).70
Crystalline fraction
is where the chain segments are all in ordered crystalline state.
Random long molecular chains of amorphous fraction coexist
with the crystalline chains.70,71
When a polymer approaches its
glass transition temperature, Tg, molecular chains of the
crystalline region are unlikely to move due to strong
intermolecular interactions, but chains of the amorphous
phase move freely. Within the amorphous region, there are
some chain segments that are rigid, consequently hindering free
movement of the entire long chain. This fraction is referred to
as rigid amorphous fraction (RAF). The remaining long
molecular chains in the amorphous region are known as
MAF.70−72
PLA with very low degree of crystallinity has a great
proportion of its chains in the MAF, which has high mobility
near its Tg and therefore exhibits very low heat resistance, with
distortion temperatures often occurring close to its Tg. When
the crystallization of PLA is facilitated with external aids such as
nucleating agents, the proportion of the crystalline and rigid
amorphous fraction is increased, which impedes chain mobility
and resists heat induced distortions, resulting in enhanced heat
resistance.71,72
A schematic of the CF, RAF and MAF is shown
in the graphical abstract.
Heat resistance is often quantified by the detection of a
softening point under a certain load. The two most commonly
adopted techniques measure: heat deflection or distortion
temperature (HDT) and Vicat softening temperature (VST).
HDT is defined as the temperature at which a specimen
deflects 250 μm, under a specified load and thickness at a
heating rate of 2 °C per min.72
The two common loads used
are 0.46 MPa (66 psi) and 1.8 MPa (264 psi). VST is defined as
the temperature at which the specimen is penetrated to a depth
of 1 mm by a flat-ended needle with a 1 mm2
cross-sectional
area.72
Common loads are 10 and 50N with heating rates of
either 50 or 120 °C per hour depending on the standards
followed.73,74
It is generally understood VST is the temperature
at which a material loses its form-stability and HDT is the
temperature at which material loses its load bearing capacity.
However, the difference in assessing the softening point by
HDT or VST is mainly a matter of defining the “end point”.74
VST values are usually higher than the HDT values, and the
difference is quite modest in the case of PLA, which shows
HDT of ca. 55 °C and VST of 65 °C. Various techniques and
methods have been explored to improve the crystallinity and
heat resistance of PLA. This section reviews the state-of-the art
technologies for improving the heat resistance of PLA by (i)
addition of nucleating agents and stereocomplex; (ii) adopting
different processing strategies; (iii) blending with heat resistant
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8. polymers; and (iv) fabrication of biocomposites with natural
fibers and nanoreinforcements. A summary of PLA blends with
improved HDT/VST is presented in Table 2.
Nucleating Agents and Processing Strategies. Nucleat-
ing agents can effectively promote crystallization by providing
nucleation sites around which the polymer chains can
crystallize. Shorter crystallization half time achieved with the
addition of nucleating agents can help to increase the
crystallinity and shorten the molding cycle time. Nucleating
agents for PLA include, but are not limited to, talc,75,76
N,N′-
ethylene bis-stearamide (EBS),77
carbon nanotubes,78
metal
salts of phenylphosphonic acid,79
multiamide and hydrazide
compounds,80−85
barium sulfate,86
titanium dioxide,86
calcium
carbonate (CaCO3),86
nano-CaCO3
87
and orotic acid.88
Numerous investigations have been conducted on improving
crystallization of PLA with the help of nucleating agents.
However, only a handful of them corelate the increase in
crystallinity due to nucleation to increase in heat resistance
measured through HDT/VST. Recently, TMC-328, a commer-
cial heterogeneous multiamide nucleating agent, has been
found to enhance greatly the heat resistance of PLA at a very
small concentration (0.2%).72
Benoylhydrazide (BH) com-
pounds, in particular octamethylenedicarboxylic dibenzoylhy-
drazide (OMBH) and decamethylenedicarboxylic dibenzoylhy-
drazide (DMBH), are known to impart enhancement in the
crystallization of PLA.84,89
The nucleation ability (Tc and ΔHc)
of OMBH was found to be higher than that of DMBH, and
ethylenebis (12-hydroxystearylamide), EBH/talc mixture at 1
wt % loading in PLA.84
In addition to using hydrazide
nucleating agent, a high molding temperature of 110 °C was
adopted to achieve substantial improvements (results are in
Table 2). In spite of the successful enhancement of the
crystallization rate of PLA through the addition of nucleating
agents, obtaining injection molded articles of PLA with high
crystallinity remains difficult with a fast mold cooling rate.
Nucleated PLA molded in room temperature molds with fast
cooling (>100 °C/min) does not show substantial improve-
ment in HDT. Therefore, the effect of performing annealing
postprocessing on the mechanical and thermal properties, and
the fracture behavior of PLA has been studied. The crystallinity
of PLA has been found to increase consistently through
annealing in most of the studies and the increase lead to an
improvement in its heat resistance and overall mechanical
performance. Park et al.90
and Nascimento et al.91
performed
annealing of PLA under various conditions to obtain micro-
structures with different spherulite sizes and densities. The heat
resistance of PLA was markedly improved when its crystallinity
was increased by annealing. PLA with 1% EBH molded at room
temperature and then annealed for 1, 2, 4, 10 and 20 min at 105
°C showed increasing HDT with increasing annealing time. A
sharp step change in HDT was noticed when the crystallinity
went 25%, indicating a threshold for crystallinity content.77
However, annealing adds a postprocessing step, which may not
be economical or industrially feasible.
As an alternative to annealing, researchers84,92,93
have looked
at increasing the mold temperature during the injection
molding process. This technique can be called as an in-mold
annealing process, where the cooling time is increased to
facilitate effective demolding of the samples. Harris and Lee92
increased the injection mold temperature to 110 °C and were
successful in obtaining PLA molded articles with high
percentage of crystallinity and high HDT. However, the
problem with this step is molding cycle time of ∼2 min is
required due to higher cooling time; demolding of the
processed components would be difficult with short cooling
cycle. Li and Huneault93
also observed similar effect of mold
temperature on crystallinity as shown in Figure 6. At mold
Table 2. PLA Blends with Improved Heat Resistance:
Summary of Results
PLA blends with improved heat
resistance
softening point from HDT
and VST reference
nucleating agents, stereocomplex
TMC-328 (0.6%) 134.3 °C (VST, 10N) 72
OMBH (1%) 124 °C (HDT, 0.45 MPa) 84
EBH/talc mixture (1%) 110 °C (HDT, 0.45 MPa) 84
PLLA/PDLA (50/50) blend 150 °C (HDT, 0.45 MPa) 103
PLLA/hPLLA (95/5) no deformation at 70 °C,
50 g for 5 min
105
processing strategies
PLA/1% EBH, 10 min
annealing at 105 °C
93 °C (HDT, load not
mentioned)
77
PLA with NA annealing at 80
°C for 15 min
HDT, 0.45 MPa
PLA/2% EBS 70 °C 92
PLA/2% talc 77 °C
PLA/talc/PEG (80/10/10) VST, 10N
23 °C epoxy mold 123.6 °C 95
90 °C steel mold 117.9 °C
blending PLA with heat resistant
polymers and nanofillers
PLA/POM (60/40) and (50/
50)
∼72 and 135 °C (HDT,
0.45 MPa)
99
PLA/PHBV/PBS (30/60/
10) and (10/60/30)
72.2 and 87.5 °C (HDT,
0.45 MPa)
100
PLA/organically modified
MMT (93/7)
112 °C (HDT, 0.98 MPa) 108
PLA/ OMSFM (96/4) and
(90/10)
92 and 117 °C (HDT,
0.98 MPa)
109
PLA/5% DCPD capsules 78.05 °C (HDT, load not
mentioned)
110
Figure 6. Effect of molding temperatures on crystallinity (Xc)
developed for PLA with 5% acetyl triethyl citrate (ATC) and 1% talc.
[Reprinted from Polymer, Vol. 48, H. Li, M. A. Huneualt. Effect of
nucleation and plasticization on the crystallization of poly(lactic acid),
6855−6866, Copyright 2007, with permission from Elsevier, License
number: 3794330203855.]
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9. temperatures below 50 °C, low crystallinity level was observed,
and crystallinity reached maximum level at 80 °C mold
temperature with a combination of 5% plasticizer and 1% talc.
In most of the above reviewed works,72,77,84,89
addition of
nucleating agent in combination with annealing or high
temperature molding was helpful in increasing the mechanical
properties. Increase in crystallinity increased the tensile and
flexural modulus. In some cases, increased number of spherulite
structures with low spherulite size was believed to consume
more energy and thus increase the impact strength of PLA
samples containing nucleating agents.
On the contrary, Vadori et al.94
have showed increasing the
mold temperature of PLA decreases the impact toughness and
percentage elongation of high impact PLA. Unique approach of
using epoxy based PolyJet mold instead of steel mold for
conventional injection molding to produce PLA parts with high
crystallinity has been proposed to offer promising results
(Table 2).95
Because of low thermal conductivity of epoxy
based PolyJet mold, PLA parts containing nucleating agents
produced from this mold had a significantly higher level of
crystallinity, thermal and mechanical properties compared to
PLA samples molded from steel molds. When PLA is injected
into 23 °C steel mold, it is cooled below its Tg in 15 s due to
high thermal conductivity of the steel mold, whereas, in PolyJet
mold, PLA material stays above Tg for around 66 s, allowing the
material to crystallize. As a result, VST of PLA molded in 23 °C
PolyJet mold increased to 118−124 °C compared to VST of
60−65 °C for PLA samples obtained from 23 °C steel mold.
Use of such PolyJet molds show promise in achieving higher
levels of crystallinity for PLA at room temperature molding
conditions.
Blending with Heat Resistant Polymers, Stereo-
complexation, and Use of Nanofillers. Blending PLA
with heat resistant engineering polymers such as polycarbon-
ate,96
poly(acrylonitrile−butadiene−styrene),97
nylon,98
poly-
oxymethylene99
can improve the HDT of PLA when there is
good compatibility between the blending polymers. Biodegrad-
able ternary blends of PLA, PHBV and PBS with balanced
stiffness and toughness attained HDT of ∼72 °C with 30 wt %
PLA in the blend.100
Polyoxymethylene, POM, has a high HDT
of 160 °C and it crystallizes fast with 70−80% crystallinity
content.99
Nonetheless, having POM as a dispersed phase in
PLA did not help in improving the HDT; to achieve desired
improvements in HDT, POM should be the major phase in the
blend as significant improvements were observed with phase
inversion, beyond 40%.99
Two different monomers, D-lactide
and L-lactide, exist due to chirality of PLA. Homopolymers of D-
and L-lactide (PDLA and PLLA) have faster crystallization and
higher melting points compared to common PLA, which has a
small percentage of D-lactide with atactic stereoregularity in a
majority of L-lactide. A stereocomplex of two polymers with
same structure but different configuration has a melting
temperature between 190 and 230 °C. Stereocomplex (SC)
PLA can work as a nucleating agent promoting the formation of
ordered structures. Various mixtures of PLLA and PDLA have
been investigated101−104
and 50−50 blend with stereocomplex
crystalline structure improved the HDT to 150 °C. Never-
theless, the high cost of PDLA is a bottleneck to stereo-
complexation due to difficulty in production of D-lactide and
hence PDLA. In a recent publication, Yin et al.105
used high
melting point PLLA homocrystallites (hPLLA) as a nucleating
agent to improve the thermomechanical properties of PLA.
About a 20 °C difference in melting point between PLA
(4032D, Ingeo NatureWorks) and hPLLA helped to keep
hPLLA crystallites unmelted at the processing temperature of
170 °C. Presence of 5% hPLLA accelerated PLLA crystal-
lization at a remarkable rate compared to PLA containing the
same amount of talc and SC PDLA. PLLAs, with and without
talc and PDLA, were noticed to deform in less than 2 min when
placed in an oven at 70 °C for 5 min under a constant load of
50 g, whereas PLLA with hPLLA crystallites showed no visible
deformation for 5 min, HDT/VST needs to be measured for
any practical comparisons. This work, however, has contributed
to new ways of tailoring the crystallization of PLLA without
involving any post processing techniques and more importantly
without compromising the biodegradable nature of the
polymer.
Incorporation of nanoparticles into PLA is a relatively new
strategy that researchers are exploring to improve the heat
resistance of PLA. Although addition of 2 wt % talc to PLA
resulted in 3 °C HDT improvement,106
addition of 8 wt %
montmorillonite (MMT) to PLA increased its HDT by 28
°C.107
Layered silicate nanocomposites offer desired improve-
ment in HDT only when the silicate layers of the clay are
intercalated, stacked and well distributed in PLA matrix.108,109
Organomodified montmorillonite (OMMT) containing tri-
methyl octadecyl ammonium cation at 7 wt % increased the
HDT of PLA to ∼112 °C,109
10 wt % of organically modified
synthetic fluorine mica (OMSFM) increased the HDT of PLA
to ∼117 °C,108
under a deflection load of 0.98 MPa.
Dicyclopentadiene (DCPD) filled urea formaldehyde micro-
capsules added to arrest the crack propagation and promote
self-healing in PLA was observed to act as a nucleating agent.110
Formation of stable cocontinuous morphologies of heat
resistant polymer with the aid of well intercalated nanoparticle
is a recently explored promising strategy to increase the
crystallinity. PLA phase interpenetrated with a continuous
framework of nylon (30 wt %) and 3 phr OMMT showed
resistance to temperature up to ∼160 °C (Figure 7); however,
the HDT at 0.25 mm was the same as that of neat PLA.98
Figure 7. (a) Sample deflection recorded during creep tests for the
sample PLA (squares), PA11 (diamonds), PLA70 (circles) and
PLA70-C3 (triangles). The pictures show the samples PLA70 (b)
and PLA70-C3 (c) at the end of the test, which is after the
temperature had reached ≈160 °C. [Reprinted from Macromolecular
Materials and Engineering, Vol. 299, A. Nuzzo, S. Coiai, S. C.
Carroccio, N. Dintcheva, C. Gambarotti, G. Flippone. Heat resistant
fully biobased nanocomposite blends based on poly(lactic acid), 31−
40, Copyright 2013, with permission from Elsevier, License number:
3794371367676.]
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10. ■ PLA BLENDS WITH CONCURRENT
IMPROVEMENTS IN TOUGHNESS AND HEAT
RESISTANCE
Having higher crystallinity in a semicrystalline polymer
sometimes negatively affects the impact strength, hence the
inverse relationship between HDT and impact strength.
Crystallites in the polymer can act as stress concentrators,
thereby causing the stress acting on a small volume of the
material to grow much higher than the average stress applied to
the entire sample.11
As a result, material breaks at a stress value
typically less than the expected critical value.11
Shear yielding
and multiple crazing are also observed to decrease due to the
presence of crystallites. Unfortunately, little attention has been
paid to achieving PLA blends with balanced toughness and heat
resistance because it is still a challenge to control simulta-
neously phase structure and matrix crystallization of blends.
Perhaps the most useful work toward the search for such PLA
blends are confined to using nonbiodegradable engineering
polymers such as polycarbonate (PC) having high impact
strength and heat resistance. Several commercial PLA/PC
blends111−114
have been developed, which are seen as
environmentally benign materials containing over 50%
biodegradable and renewably sourced polymer, PLA. Addition
of over 40% PC to PLA has shown some promise in increasing
the impact strength of PLA; however, increasing the heat
resistance of this blend has remained a challenge without the
use of compatibilizers. Hashima et al.96
developed a four-
component super toughened blend containing PLA/PC/
EGMA/SEBS (40/40/15/5) where SEBS toughened PLA in
the presence of EGMA and a further improvement in
toughness and heat resistance was achieved through the
incorporation of PC in the blend. Wang et al.115
investigated
the effect of compatibilizers, epoxy (EP) resin and poly-
(butylene succinate-co-lactate), PBSL for PLA/PC binary
blends. Combination of PBSL (10%) and EP (10%) in the
presence of catalyst, tetrabutyl ammonium bromide (TBAB,
1%) in 50/50 blend of PLA/PC resulted in significant and
concurrent improvement in impact strength and heat
resistance, the values are listed in Table 3. Chain extenders
such as Joncryl and tetraglycidyl-4,4′-diaminodiphenylmethane
(TGDDM) in combination with small percentage of acrylic
impact modifiers (BPM-520) have been used to improve the
interfacial interactions in PLA/PC blends.116,117
Although
PLA/PC blends showed phase separated morphology and
there were no sign of PLA−PC chain entanglements, interfacial
connection was established between the chain extender and
blending polymers that increased the impact strength and heat
resistance upon annealing.
■ PLA BIOCOMPOSITES: THE QUEST CONTINUES
FOR HIGH PERFORMANCE
A biocomposite is a multiphase system, where plant-derived
fiber or mineral/synthetic filler is dispersed in the biopolymer
matrix; either the matrix or the reinforcement phase is
biobased.118,119
Toughened PLA biocomposites have a far
greater potential for minimizing the limitations of PLA, hence
major research efforts are being taken to develop and
commercialize them. Numerous research works have been
conducted in the field of PLA composites; however, most of the
works report only marginal improvements in impact strength
and HDT.120−125
The scope of this section has been limited to
reviewing the research progress in injection molded PLA
biocomposites that used tough PLA blends as the matrix for
incorporation of fibers and fillers. The increase in fracture
toughness observed for PLA biocomposite is not as high as in
the case of neat PLA. For instance, improving the toughness of
neat PLA by 20-fold might increase the fracture toughness of
the composite by 3−6-fold only. Such poor translation of
matrix toughness into the composite is due to the presence of
fiber, which is a constraint that suppresses elastic deformation
of the matrix at the crack front. However, having a toughened
PLA blend as a starting material to incorporate fibers can be a
good way to achieve a balanced performance. Furthermore, cost
of developing such blends can be offset to a certain extent by
adding less expensive lignocellulosic fibers.
PLA blended with tough biopolymers such as PBAT and
PCL have been explored as a matrix system to incorporate
natural fibers.126−128
In most cases, surface treatment has
proved to be effective in promoting interfacial interactions
between the relatively hydrophobic matrix and hydrophilic
filler. Having 30 wt % PBAT in PLA−PBAT/alkali treated saw
dust (70/30) composites improved the unnotched Izod impact
strength by 50%.126
The surface of Kenaf treated with 2% silane
coupling agent was observed to become hydrophobic with the
ability to bind active groups of the polymer.127
Chemical
interactions formed between hydroxyl, silanyl and alkoxy
groups increased the impact strength of the PLA−PBAT
biocomposites by 22%.127
By treating ramie fiber with silane
coupling agent (KH550) for in situ polymerized PLLA−PCL
matrix, tensile and impact strength increased from 12.14 MPa,
30.0 J/m to 23.45 MPa, and 88.9 J/m, respectively.128
Incorporation of Cordenka fiber at 25 wt % has been shown
to triple the impact strength of PLA without any tough
component being present; however, more research is needed
toward the effect of this fiber on HDT.129
Although addition of
5 wt % lignin resulted in toughness improvement in PLLA130
from 8.2 to 12.5 kJ/m2
, addition of 5 wt % of lignin-g-rubber-g-
PDLA to PLLA exhibited a 7-fold enhancement in toughness
(from stress−strain curves) compared with neat PLLA. This
Table 3. PLA Blends with Concurrent Improvement in
Impact Strength and Heat Resistance
PLA blend formulations
notched Izod
impact
strength
HDT at
specified load
and deflection reference
PLA/PC/EGMA/SEBS (40/
40/15/5)
0.45 MPa, 0.36
mm
96
40 °C mold temperature 65.9 kJ/m2
88.6 °C
80 °C mold temperature 63.3 kJ/m2
94.5 °C
PLA/PC/PBSL/EP/TBAB 0.45 MPa, 0.25
mm
115
(50/50/5/0/0) 36.6 kJ/m2
94.8 °C
(50/50/10/0/0) 65.1 kJ/m2
76.8 °C
(50/50/10/10/0) 25.4 kJ/m2
82.5 °C
(50/50/10/10/0.1) 34.0 kJ/m2
94.2 °C
PLA/PC with Joncryl or
TGDDM (70/30/0.3phr)
1.82 MPa, 0.32
mm
116
room temperature
molding followed by
annealing at 120 °C for
6h
∼30 kJ/m2
(Joncryl)
∼86 °C
(Joncryl)
∼13 kJ/m2
(TGDDM)
∼81 °C
(TGDDM)
PLA/PC/BPM/Joncryl (85/10/
5/0.3phr)
0.45 MPa, 0.32
mm
sample molded at room
temperature sample
annealed at 120 °C for
6h
∼10 kJ/m2
∼57 °C 117
∼40 kJ/m2
∼135 °C
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11. improvement is significant considering the copolymer contains
only 3.8 wt % of rubber.131
In the case of PLA/pine wood floor
composites, notched Charpy impact strength was found to
increase gradually with increase in addition of wood floor and
further increment in impact strength was achieved by
toughening the PLA matrix with styrene−butadiene−styrene
(SBS) block copolymer.132
Use of reactive impact modifiers can
form ductile interface between PLA and fiber, thus increasing
the resultant properties. With this hypothesis, ethylene acrylate
copolymer (Biomax) was used as an impact modifier (IM) for
PLA/kenaf fiber (KF) composites.133
Impact strength and
elongation at break increased, but only at a high loading level of
40 wt % coupled with substantial reduction in tensile strength
and modulus. Liu et al.134
compared the toughening effect of
three different reactive elastomers: polyoxyethylene grafted
with maleic anhydride (POE-g-MAH), ethylene−propylene−
diene rubber grafted with maleic anhydride (EPDM-g-MAH)
and ethylene−acrylate−glycidyl methacrylate copolymer
(EAGMA) on PLA/basalt fiber composites. EAGMA at 20
wt % imparted the most toughening effect by recording a value
of 33.7 KJ/m2
for unnotched charpy impact strength.134
Other
mineral fillers such as barium sulfate135
and calcium
sulfate136,137
have also been reported to increase the toughness
of the PLA composites. PLA based nanocomposites prepared
by incorporation of nanofillers such as cellulose nanofibers and
nanowhikers,138
nanocalcium carbonate,139−141
nano- and
mesoporous silica,142−145
halloysite nanotubes,146,147
nano-
clay147−150
and titanium oxide nanoparticles151
exhibited
good improvement in toughness, mechanical and barrier
properties. However, none of these studies have reported the
heat resistance of the developed materials. Although the
hybridization of PLA with impact modifier and nanoparticle
can offer a toughened composite material, challenges exist in
achieving good level of dispersion and distribution of the
nanoparticles, its compatibility with the matrix and ease of
processing.
On the flip side, a considerable number of research
investigations have shown the heat resistance of injection
molded PLA biocomposites to increase with fiber/filler
incorporation in spite of affecting impact strength negatively.
Crushed Kenaf fiber152
has been reported to significantly
increase the HDT of injection molded PLA composites when
added beyond 10 wt %, as shown in Figure 8.
Stiffness and HDT of the PLA were improved with the
addition of newspaper fibers/talc hybrid with drastic reduction
to impact strength.153,154
HDT of the PP−PLA composites
could be increased to 120 °C with 30% Oat hull but in a major
phase of PP, with a drastic reduction in impact strength.155
Incorporating 30 wt % agricultural residues like soy stalk, corn
stalk, wheat straw and their hybrids in PLA matrix did not
provide a desired increase in HDT. Only the modulus of the
composites increased while impact strength remained essen-
tially the same as virgin or neat PLA.156
In such cases, addition
of fibers alone would not be sufficient to increase the HDT, a
combinatorial approach of adding fibers, and use of high mold
temperature could be beneficial.
By taking super toughened PLA blend developed based on
PEBA and EMAGMA25
as the matrix material, such
combination of approaches have proved to be successful in
achieving concurrent improvement in impact strength and
HDT of PLA biocomposites.157
Although the impact strength
reduced as expected with addition of 10 wt % miscanthus, it
was still considerably higher than the neat PLA matrix,
exhibiting 120 J/m (Figure 9). A high mold temperature of
110 °C was required to improve the HDT to 85 °C. A high
level of crystallinity developed in the composites facilitated
easier demolding of the samples and the total cycle time was
limited to 1 min including cooling, making it an industrially
feasible technique.157
Promise of further significant improvement in properties and
possibilities of cost reduction with use of specialty additives and
processing strategies continues to excite areas of composite
material research.
■ CONCLUSIONS: QUO VADIS PLA RESEARCH?
Biobased content is an important driver in development of
durable biopolymer blends and composites. Many major
industries and business operations are moving toward
sustainable sourcing and use of renewable materials. Principles
Figure 8. Distortion temperature under load (DTUL) of PLA/crushed
Kenaf fiber. [Reprinted from Journal of Applied Polymer Science, Vol.
100, S. Serizawa, K. Inoue, M. Iji. Kenaf fiber reinforced poly(lactic
acid) used for electronic products, 618−624, Copyright 2006, with
permission from John Wiley and Sons, License number:
3794390263152.]
Figure 9. Impact strength and HDT of PLA biocomposites with and
without nucleating agent (NA) molded at different mold temperatures
and injection cycle times. PLA blend/MS (90/10) at (A) 30 °C, 30 s;
(B) 110 °C, 60 s. PLA blend/MS/NA (89/10/1) at (C) 30 °C, 30 s;
(D) 60 °C, 60 s; (E) 90 °C, 60 s; (F) 110 °C, 60 s; (G) 120 °C, 60 s.
[Reprinted with permission from ACS Applied Materials and
Interfaces, Vol. 7, V. Nagarajan, K. Zhang, M. Misra, A. K. Mohanty.
Overcoming the Fundamental Challenges in Improving the Impact
Strength and Crystallinity of PLA Biocomposites: Influence of
Nucleating Agent and Mold Temperature, 11203−11214, Copyright
2015, American Chemical Society.]
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12. of green chemistry, sustainability and engineering are being
integrated in the R&D to achieve a good balance of product
performance and environmental friendliness. Extensive research
effort has been devoted to developing PLA blends and
biocomposites with desirable morphology and crystallinity for
durable applications. However, achieving feasible and econom-
ical manufacturing processes for mass production of such
materials has been quite a challenge. Enhancing matrix
crystallization has been reported to be an effective strategy
toward creating heat resistant PLA blends. Both thermal
annealing and nucleating agent induced matrix crystallization
could significantly enhance heat resistance of the blends, while
maintaining or further increasing the toughening efficiency.
However, increasing matrix crystallinity alone cannot guarantee
toughness improvement in most cases because suitable
morphology must be obtained for PLA matrix to undergo
plastic deformation. Specifically, optimum elastomer content,
particle size and interparticle distance are identified to be the
most important deciding factors for toughening PLA. Reactive
compatibilization along with dynamic vulcanization techniques
have been shown to tailor successfully the morphology of the
blends. Recent explorations have revealed that a unique
network-like or cocontinuous morphology unevenly distributed
in the matrix to exhibits much better super toughening
compared to the common sea-island morphology containing
well dispersed spherical elastomer particles in a polymer matrix.
The network-like distribution of the elastomer particles can
facilitate the percolation of the stress field as the plastic
deformation of the matrix around them at lower content.
Adding inorganic nanoparticles with strong self-networking
capability in polymer melts has been shown to assist in the
transition of morphology from immiscible sea-island structure
to the network-like, cocontinuous structure.
Approach of adding nucleating agents and natural fiber in
combination with a high molding temperature to a super
toughened PLA blend has resulted in composites with
concurrent improvements in both the impact strength and
HDT. Epoxy based mold with low thermal conductivity has
demonstrated significant advantages over conventional steel
molds. Future work is needed to shed light on the effect of
applying an intense shear flow field through oscillation shear
injection molding (OSIM) to trigger dramatic enhancement of
Table 4. Commercial Toughened and/or Heat Resistant PLA Formulations for Durable End Use Applications
company grade impact strength
HDT at 0.45 MPa
(°C)
tensile
strength
(MPa) comment reference
RTP Co. RTP 2099 X Series 694−854 J/m
(notched Izod)
96−124 48−52 PLA−PC blends 111
43−187 J/m
(notched Izod)
91−160 38−114 PLA with glass fibers or talc
PolyOne
Corporation
reSound FR 620 J/m (notched
Izod)
112 PLA−engineering plastic blend 112, 158
Kingfa Sci & Tech
Co., Ltd.
Ecopond AFR-97 55 kJ/m2
(notched
Izod)
84 (1.82 MPa) 52 PLA−PC and PLA−ABS blends, >40%
biobased
113
UGM ABS Ltd. ECO PELLET LA Series 12−27 kJ/m2
(notched Charpy)
78−92 48−58 PLA−PC and PLA−ABS blends 114
Interfacial
Solutions
deTerra XP698 880 J/m (notched
Charpy)
38 PLA blend, compostable, >85%
biobased
159
Teknor Apex
Company Inc.
Terraloy 3D-40040 Series 267 J/m (unnotched
Izod)
75 PLA blend, extrusion filament for use in
3D printers
160
Corbion Carbion Purac
(development grades)
5−23 kJ/m2
(notched
Charpy)
85−120 30−45 PLLA/PDLA blends with and without
talc
161
Sukano Polymers Sukano Bioloy 003, 004
NC001
60−70 kJ/m2
(unnotched
Charpy)
50−90 35−50 PLA blend, compostable (EN13432),
35−97% biobased
162
Toray Industries
Inc.
ECODEAR V751X53,
V751X52
21−24 kJ/m2
(notched Charpy)
81 49−52 PLA blend 163
Unitika Ltd. Terramac TE 7000, 7307,
7300, 8210, 8300
2.0−4.0 kJ/m2
(notched Charpy)
110−140 50−70 compostable (ISO 14855) 164
NatureWorks
LLC
Ingeo 3100HP, 3260HP 16−32 J/m (notched
Izod)
149−151 63−65 PLA with nucleating agent, mold
temperature of 120 °C
165
Supla Co., Ltd. SUPLA 135 150 PLA blend (90% PLA) 166
SK Chemicals Ecoplan-Dura 40 J/m (notched
Izod)
100 42 compostable, 80−100% biobased 167
FKuR Plastics Bio-Flex F 6513 3 kJ/m2
(notched
Charpy)
68−130 32 PLA blend, HDT of up to 130 °C by
appropriate processing
168
NaturePlast PLI 013, PLE 013, high
temperature
89 kJ/m2
(unnotched
Charpy)
123−133 injection and extrusion grades 169
Barlog Plastics KEBACOMP FE 120204 5 kJ/m2
(notched
Izod)
100 compostable (ISO 13432) 170
EcolBiotech
Co.,Ltd.
EcolGreen EGP Series 382−477 J/m
(unnotched Izod)
62−72 31.7−45.5 nanocomposite with 12 different
additives, compostable
171
GEHR Plastics ECOGEHR PLA-L 59.8 kJ/m2
(notched
Izod)
58.4 (VST) 49.5 PLA blend with lignin and fatty acid,
compostable, >80% biobased
172
WinGram
Industrial Co
Ltd.
Ecoplant HRS heat resistance up
to 120 °C
compostable (ISO 14855) 173
Teijin Ltd. Biofront grade J20, J201,
L201
highly heat
resistant
stereocomplex PLA melting point of 210
°C
174
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13. crystallization kinetics of PLA. Durable blends of PLA/PC have
shown promising properties with simultaneous improvements
in impact and heat resistance in the presence of compatibilizer
and chain extenders. Thermally stable fillers like biochar from
different fiber sources can be added to such highly toughened
engineering plastic based blends. Properties of these
composites can be tailored to have enhanced performance
with affordable cost to performance ratios for industrial
applications. Much research is needed in the direction of
developing such high performance PLA composites. Future
technological development may focus on the emergence and
exploitation of such renewable carbon based fillers for PLA
materials to serve the need of the era for lightweight, carbon
neutral durable materials.
Many PLA formulations with improved toughness and/or
HDT are available in the market for durable applications, as
summarized in Table 4. Most of the impact modifiers used are
high molecular weight polymeric materials with a flexible
component such as acrylic rubber, and hence the problem of
migration is not a concern. However, these impact modifiers
are typically nonbiodegradable. Minimal use of even 5% may
prevent the products from being certified compostable due to
the stringent requirements of the American and European
compostability standards. ASTM D6400-12 describes that
organic constituents present at concentrations of less than 1%
do not need to demonstrate biodegradability. However, the
sum of such unproven constituents should not exceed 5%.175
Finally, one might ask when and where durable PLA materials
may find application. Before answering, we should consider the
evolution of bioplastics industry, which has had multiple shifts
in direction. The first phase was focused on biodegradable and/
or compostable characteristics, primarily intended for single use
packaging applications. The second phase offered compostable
and renewable resource based alternative for nondegradable
petroleum based commodity plastics. The current trend is the
development of durable bioplastics. Commercialization argu-
ably marks the success of research and development efforts, but
the timeline should not be compared to that of mature
technologies. Although PLA based materials are aimed for high
volume applications in interior automotive parts and other
structural and semistructural applications, they will initially find
application in consumer goods such as cell phone casings,
personal and home care products.
■ AUTHOR INFORMATION
Corresponding Author
*A. K. Mohanty. E-mail address: mohanty@uoguelph.ca. Tel.:
+1-519-824-4120 ext. 56664. Fax: +1-519-763-8933
Notes
The authors declare no competing financial interest.
Biographies
Ms. Vidhya Nagarajan is currently a Ph.D. candidate in Biological
Engineering, Bioproducts Discovery & Development Centre (BDDC)
at the University of Guelph, ON, Canada. Vidhya graduated with a
Master’s degree from University of Guelph in 2012. She is a recipient
of highly qualified personnel (HQP) scholarship from Ontario
Ministry of Agriculture, Food and Rural Affairs (OMAFRA). She is
also a HQP of the AUTO21 Network of Centers of Excellence
program, a national research initiative supported by the Government
of Canada. She holds a Bachelor’s degree in Polymer Technology from
Crescent Engineering College, Anna University, India. The primary
focus of her research is processing and characterization of biopolymer
blends and composites for sustainable industrial applications. She has
published 6 peer reviewed journal articles, 1 patent application (filed)
and coauthored 2 book chapters.
Dr. Amar Mohanty, Professor and Premier's Research Chair in
Biomaterials and Transportation, is the Director of the Bioproducts
Discovery & Development Centre (BDDC) at the University of
Guelph, ON, Canada. Dr. Mohanty's research interests include natural
fiber composites, biobased and biodegradable polymers, biorefinery,
biocarbon reinforcement, reactive extrusion and utilization of biofuel
and biomass coproducts. He has more than 600 publications to his
credit, including 274 peer-reviewed journal articles (including accepted
manuscripts), four edited books, 20 book chapters, and 40 patents
awarded/applied. He has received distinguished awards for his work,
including the “Andrew Chase Forest Product Award” from the
American Institute of Chemical Engineers and most recently the
“Lifetime Achievement Award”, from the BioEnvironmental Polymer
Society (BEPS) in the year 2015. Dr. Mohanty holds the Alexander
von Humboldt Fellowship at the Technical University, Berlin. His
ResearchGate score is 44.43, higher than 97.5% of the 7 million
ResearchGate members. His research impact resulted in 16 962
citations with h-index of 62 (Google Scholar, as of April 2016).
ACS Sustainable Chemistry & Engineering Perspective
DOI: 10.1021/acssuschemeng.6b00321
ACS Sustainable Chem. Eng. 2016, 4, 2899−2916
2911
14. Dr. Manjusri Misra is a Professor in the School of Engineering and
holds a joint appointment in the Department of Plant Agriculture at
the University of Guelph, ON, Canada. Dr. Misra’s current research is
primarily focused on novel biobased polymers, and composite
materials from agricultural and forestry resources for the sustainable
bioeconomy; and application of nanotechnology in materials uses. She
has coauthored more than 450 publications, including 250+ peer-
reviewed journal papers, 24 book chapters, and 15 granted patents. She
was an editor of the CRC Press volume, “Natural Fibers, Biopolymers
and Biocomposites,” Taylor & Francis Group, Boca Raton, FL (2005);
American Scientific Publishers volume “Packaging Nanotechnology”,
Valencia, California (2009), and “Polymer Nanocomposites”, Springer
(2014). She was the chief editor of “Biocomposites: Design and
Mechanical Performance” Woodhead Publishing (2015). She was the
2009 President of the BioEnvironmental Polymer Society (BEPS). She
is one of the Associate Editors of the journal “Advanced Science
Letters”. Dr. Misra received the prestigious “Jim Hammer Memorial
Award” from the BioEnvironmental Polymer Society in 2012.
■ ACKNOWLEDGMENTS
We gratefully acknowledge the financial support from (1) the
Ontario Ministry of Agriculture, Food, and Rural Affairs
(OMAFRA)- University of Guelph Bioeconomy-Industrial
Uses Theme (Project # 200425); (2) the Ontario Ministry of
Economic Development and Innovation (MEDI), Ontario
Research Fund, Research Excellence Round 4 program (ORF-
RE04) (Project # 050231 and 050289); and (3) the Natural
Sciences and Engineering Research Council (NSERC) Canada
Discovery Grants (Project # 400322) and Networks of Centres
of Excellence (NCE) AUTO21 Program (Project # 460372).
■ REFERENCES
(1) Drumright, R. E.; Gruber, P. R.; Henton, D. E. Polylactic acid
technology. Adv. Mater. 2000, 12 (23), 1841−1846.
(2) Auras, R.; Harte, B.; Selke, S. An overview of polylactides as
packaging materials. Macromol. Biosci. 2004, 4 (9), 835−864.
(3) Bioplastics facts and figures. http://docs.european-bioplastics.
org/2016/publications/EUBP_facts_and_figures.pdf (accessed Janu-
ary 2016).
(4) Kyoto Protocol. http://unfccc.int/kyoto_protocol/items/2830.
php (accessed December 30, 2016).
(5) As Kyoto Protocol turns 10, UN says ‘first critical step’ must
trigger new 2015 emissions-curbing deal. http://www.un.org/apps/
news/story.asp?NewsID=50099#.Vw-FMtL2Y3E (accessed December
30, 2015).
(6) United Nations conference on climate change. http://www.
cop21.gouv.fr/en/ (accessed December 30, 2015).
(7) Kuzuhara, Y. Biomass Nippon StrategyWhy “Biomass Nippon”
now? Biomass Bioenergy 2005, 29 (5), 331−335.
(8) Krishnan, S.; Pandey, P.; Mohanty, S.; Nayak, S. K. Toughening
of Polylactic Acid: An Overview of Research Progress. Polym.-Plast.
Technol. Eng. 2015, DOI: 10.1080/03602559.2015.1098698.
(9) Odent, J.; Raquez, J.; Dubois, P. Highly Toughened Polylactide-
Based Materials through Melt-Blending Techniques. In Biodegradable
Polyesters; Fakirov, S., Ed.; Wiley-VCH Verlag GmbH & Co. KGaA:
Berlin, 2015.
(10) Zeng, J.; Li, K.; Du, A. Compatibilization strategies in poly(lactic
acid)-based blends. RSC Adv. 2015, 5 (41), 32546−32565.
(11) Kfoury, G.; Raquez, J.; Hassouna, F.; Odent, J.; Toniazzo, V.;
Ruch, D.; Dubois, P. Recent advances in high performance
poly(lactide): From “green” plasticization to super-tough materials
via (reactive) compounding. Front. Chem. 2013, 1 (32), 1−46.
(12) Liu, H.; Zhang, J. Research progress in toughening modification
of poly(lactic acid). J. Polym. Sci., Part B: Polym. Phys. 2011, 49 (15),
1051−1083.
(13) Anderson, K. S.; Schreck, K. M.; Hillmyer, M. A. Toughening
polylactide. Polym. Rev. 2008, 48 (1), 85−108.
(14) Rasal, R. M.; Janorkar, A. V.; Hirt, D. E. Poly(lactic acid)
modifications. Prog. Polym. Sci. 2010, 35 (3), 338−356.
(15) Wu, S. Chain structure, phase morphology, and toughness
relationships in polymers and blends. Polym. Eng. Sci. 1990, 30 (13),
753−761.
(16) Wu, S. Control of intrinsic brittleness and toughness of
polymers and blends by chemical structure: a review. Polym. Int. 1992,
29 (3), 229−247.
(17) Wu, S. Formation of dispersed phase in incompatible polymer
blends: Interfacial and rheological effects. Polym. Eng. Sci. 1987, 27 (5),
335−343.
(18) Wu, S. Phase structure and adhesion in polymer blends: a
criterion for rubber toughening. Polymer 1985, 26 (12), 1855−1863.
(19) Perkins, W. G. Polymer toughness and impact resistance. Polym.
Eng. Sci. 1999, 39 (12), 2445.
(20) Harada, M.; Ohya, T.; Iida, K.; Hayashi, H.; Hirano, K.; Fukuda,
H. Increased impact strength of biodegradable poly(lactic acid)/
poly(butylene succinate) blend composites by using isocyanate as a
reactive processing agent. J. Appl. Polym. Sci. 2007, 106 (3), 1813−
1820.
(21) Oyama, H. T. Super-tough poly(lactic acid) materials: Reactive
blending with ethylene copolymer. Polymer 2009, 50 (3), 747−751.
(22) Su, Z.; Li, Q.; Liu, Y.; Hu, G.; Wu, C. Compatibility and phase
structure of binary blends of poly(lactic acid) and glycidyl
methacrylate grafted poly(ethylene octane). Eur. Polym. J. 2009, 45
(8), 2428−2433.
(23) Feng, Y.; Hu, Y.; Yin, J.; Zhao, G.; Jiang, W. High impact
poly(lactic acid)/poly(ethylene octene) blends prepared by reactive
blending. Polym. Eng. Sci. 2013, 53 (2), 389−396.
(24) Han, L.; Han, C.; Dong, L. Morphology and properties of the
biosourced poly(lactic acid)/poly(ethylene oxide-b-amide-12) blends.
Polym. Compos. 2013, 34 (1), 122−130.
(25) Zhang, K.; Nagarajan, V.; Misra, M.; Mohanty, A. K.
Supertoughened Renewable PLA Reactive Multiphase Blends System:
Phase Morphology and Performance. ACS Appl. Mater. Interfaces 2014,
6 (15), 12436−12448.
(26) Vachon, A.; Pépin, K.; Béland, O.; Monfette, W. G.; Rochette,
A.; Vuillaume, P. Y. Thermal, Mechanical and Morphological
Properties of Binary and Ternary PLA Blends Containing a Poly(ether
ester) Elastomer. J. Biobased Mater. Bioenergy 2015, 9 (2), 205−217.
(27) Zhou, L.; Zhao, G.; Feng, Y.; Yin, J.; Jiang, W. Toughening
polylactide with polyether-block-amide and thermoplastic starch
acetate: Influence of starch esterification degree. Carbohydr. Polym.
2015, 127 (2015), 79−85.
(28) Ojijo, V.; Ray, S. S.; Sadiku, R. Toughening of biodegradable
polylactide/poly(butylene succinate-co-adipate) blends via in situ
reactive compatibilization. ACS Appl. Mater. Interfaces 2013, 5 (10),
4266−4276.
(29) Ojijo, V.; Ray, S. S. Super toughened biodegradable polylactide
blends with non-linear copolymer interfacial architecture obtained via
facile in-situ reactive compatibilization. Polymer 2015, 80, 1−17.
ACS Sustainable Chemistry & Engineering Perspective
DOI: 10.1021/acssuschemeng.6b00321
ACS Sustainable Chem. Eng. 2016, 4, 2899−2916
2912
15. (30) Dong, W.; Zou, B.; Yan, Y.; Ma, P.; Chen, M. Effect of Chain-
Extenders on the Properties and Hydrolytic Degradation Behavior of
the Poly(lactide)/Poly(butylene adipate-co-terephthalate) Blends. Int.
J. Mol. Sci. 2013, 14 (10), 20189−20203.
(31) Meng, B.; Deng, J.; Liu, Q.; Wu, Z.; Yang, W. Transparent and
ductile poly(lactic acid)/poly(butyl acrylate) (PBA) blends: structure
and properties. Eur. Polym. J. 2012, 48 (1), 127−135.
(32) Zhang, G.; Zhang, J.; Wang, S.; Shen, D. Miscibility and phase
structure of binary blends of polylactide and poly(methyl meth-
acrylate). J. Polym. Sci., Part B: Polym. Phys. 2003, 41 (1), 23−30.
(33) Ye, S.; Ting Lin, T.; Weei Tjiu, W.; Kwan Wong, P.; He, C.
Rubber toughening of poly(lactic acid): Effect of stereocomplex
formation at the rubber-matrix interface. J. Appl. Polym. Sci. 2013, 128
(4), 2541−2547.
(34) Zhang, H.; Liu, N.; Ran, X.; Han, C.; Han, L.; Zhuang, Y.; Dong,
L. Toughening of polylactide by melt blending with methyl
methacrylate−butadiene−styrene copolymer. J. Appl. Polym. Sci.
2012, 125 (S2), E550−E561.
(35) Sun, S.; Zhang, M.; Zhang, H.; Zhang, X. Polylactide toughening
with epoxy-functionalized grafted acrylonitrile−butadiene−styrene
particles. J. Appl. Polym. Sci. 2011, 122 (5), 2992−2999.
(36) Song, X.; Chen, Y.; Xu, Y.; Wang, C. Study on Tough Blends of
Polylactide and Acrylic Impact Modifier. BioResources 2014, 9 (2),
1939−1952.
(37) Li, W.; Zhang, Y.; Wu, D.; Li, Z.; Zhang, H.; Dong, L.; Sun, S.;
Deng, Y.; Zhang, H. The Effect of Core−Shell Ratio of Acrylic Impact
Modifier on Toughening PLA. Adv. Polym. Technol. 2015, DOI:
10.1002/adv.21632.
(38) Kfoury, G.; Raquez, J.; Hassouna, F.; Leclère, P.; Toniazzo, V.;
Ruch, D.; Dubois, P. Toughening of poly(lactide) using polyethylene
glycol methyl ether acrylate: Reactive versus physical blending. Polym.
Eng. Sci. 2015, 55 (6), 1408−1419.
(39) Ge, X.; George, S.; Law, S.; Sain, M. Mechanical properties and
morphology of polylactide composites with acrylic impact modifier. J.
Macromol. Sci., Part B: Phys. 2011, 50 (11), 2070−2083.
(40) Liang, H.; Hao, Y.; Bian, J.; Zhang, H.; Dong, L.; Zhang, H.
Assessment of miscibility, crystallization behaviors, and toughening
mechanism of polylactide/acrylate copolymer blends. Polym. Eng. Sci.
2015, 55 (2), 386−396.
(41) Taib, R.; Ghaleb, Z.; Mohd Ishak, Z. Thermal, mechanical, and
morphological properties of polylactic acid toughened with an impact
modifier. J. Appl. Polym. Sci. 2012, 123 (5), 2715−2725.
(42) Liu, H.; Chen, F.; Liu, B.; Estep, G.; Zhang, J. Super toughened
poly(lactic acid) ternary blends by simultaneous dynamic vulcanization
and interfacial compatibilization. Macromolecules 2010, 43 (14), 6058−
6066.
(43) Liu, H.; Song, W.; Chen, F.; Guo, L.; Zhang, J. Interaction of
microstructure and interfacial adhesion on impact performance of
polylactide (PLA) ternary blends. Macromolecules 2011, 44 (6), 1513−
1522.
(44) Liu, H.; Guo, L.; Guo, X.; Zhang, J. Effects of reactive blending
temperature on impact toughness of poly(lactic acid) ternary blends.
Polymer 2012, 53 (2), 272−276.
(45) Liu, H.; Guo, X.; Song, W.; Zhang, J. Effects of metal ion type
on ionomer-assisted reactive toughening of poly(lactic acid). Ind. Eng.
Chem. Res. 2013, 52 (13), 4787−4793.
(46) Song, W.; Liu, H.; Chen, F.; Zhang, J. Effects of ionomer
characteristics on reactions and properties of poly(lactic acid) ternary
blends prepared by reactive blending. Polymer 2012, 53 (12), 2476−
2484.
(47) Lu, X.; Wei, X.; Huang, J.; Yang, L.; Zhang, G.; He, G.; Wang,
M.; Qu, J. Supertoughened Poly(lactic acid)/Polyurethane Blend
Material by in Situ Reactive Interfacial Compatibilization via Dynamic
Vulcanization. Ind. Eng. Chem. Res. 2014, 53 (44), 17386−17393.
(48) Fang, H.; Jiang, F.; Wu, Q.; Ding, Y.; Wang, Z. Supertough
Polylactide Materials Prepared through In Situ Reactive Blending with
PEG-Based Diacrylate Monomer. ACS Appl. Mater. Interfaces 2014, 6
(16), 13552−13563.
(49) Chen, Y.; Yuan, D.; Xu, C. Dynamically vulcanized biobased
polylactide/natural rubber blend material with continuous cross-linked
rubber phase. ACS Appl. Mater. Interfaces 2014, 6 (6), 3811−3816.
(50) Wang, Y.; Chen, K.; Xu, C.; Chen, Y. Supertoughened Biobased
Poly(lactic acid)−Epoxidized Natural Rubber Thermoplastic Vulcan-
izates: Fabrication, Co-continuous Phase Structure, Interfacial in Situ
Compatibilization, and Toughening Mechanism. J. Phys. Chem. B
2015, 119 (36), 12138−12146.
(51) Yuan, D.; Xu, C.; Chen, Z.; Chen, Y. Crosslinked bicontinuous
biobased polylactide/natural rubber materials: Super toughness,“net-
like”-structure of NR phase and excellent interfacial adhesion. Polym.
Test. 2014, 38, 73−80.
(52) Yuan, D.; Chen, Z.; Xu, C.; Chen, K.; Chen, Y. Fully Biobased
Shape Memory Material Based on Novel Cocontinuous Structure in
Poly(Lactic Acid)/Natural Rubber TPVs Fabricated via Peroxide-
Induced Dynamic Vulcanization and in Situ Interfacial Compatibiliza-
tion. ACS Sustainable Chem. Eng. 2015, 3 (11), 2856−2865.
(53) Liu, G.; He, Y.; Zeng, J.; Li, Q.; Wang, Y. Fully biobased and
supertough polylactide-based thermoplastic vulcanizates fabricated by
peroxide-induced dynamic vulcanization and interfacial compatibiliza-
tion. Biomacromolecules 2014, 15 (11), 4260−4271.
(54) Kang, H.; Hu, X.; Li, M.; Zhang, L.; Wu, Y.; Ning, N.; Tian, M.
Novel biobased thermoplastic elastomer consisting of synthetic
polyester elastomer and polylactide by in situ dynamical crosslinking
method. RSC Adv. 2015, 5 (30), 23498−23507.
(55) Ma, P.; Xu, P.; Liu, W.; Zhai, Y.; Dong, W.; Zhang, Y.; Chen, M.
Bio-based poly(lactide)/ethylene-co-vinyl acetate thermoplastic vul-
canizates by dynamic crosslinking: structure vs. property. RSC Adv.
2015, 5 (21), 15962−15968.
(56) Zhao, Q.; Ding, Y.; Yang, B.; Ning, N.; Fu, Q. Highly efficient
toughening effect of ultrafine full-vulcanized powdered rubber on
poly(lactic acid) (PLA). Polym. Test. 2013, 32 (2), 299−305.
(57) Joziasse, C.; Topp, M.; Veenstra, H.; Grijpma, D.; Pennings, A.
Supertough poly(lactide) s. Polym. Bull. 1994, 33 (5), 599−605.
(58) Odent, J.; Leclère, P.; Raquez, J.; Dubois, P. Toughening of
polylactide by tailoring phase-morphology with P [CL-co-LA] random
copolyesters as biodegradable impact modifiers. Eur. Polym. J. 2013, 49
(4), 914−922.
(59) Odent, J.; Raquez, J.; Duquesne, E.; Dubois, P. Random
aliphatic copolyesters as new biodegradable impact modifiers for
polylactide materials. Eur. Polym. J. 2012, 48 (2), 331−340.
(60) Odent, J.; Habibi, Y.; Raquez, J.; Dubois, P. Ultra-tough
polylactide-based materials synergistically designed in the presence of
rubbery ε-caprolactone-based copolyester and silica nanoparticles.
Compos. Sci. Technol. 2013, 84, 86−91.
(61) Li, X.; Kang, H.; Shen, J.; Zhang, L.; Nishi, T.; Ito, K.; Zhao, C.;
Coates, P. Highly toughened polylactide with novel sliding graft
copolymer by in situ reactive compatibilization, crosslinking and chain
extension. Polymer 2014, 55 (16), 4313−4323.
(62) Li, Y.; Shimizu, H. Toughening of polylactide by melt blending
with a biodegradable poly(ether) urethane elastomer. Macromol. Biosci.
2007, 7 (7), 921−928.
(63) Liu, G.; He, Y.; Zeng, J.; Xu, Y.; Wang, Y. In situ formed
crosslinked polyurethane toughened polylactide. Polym. Chem. 2014, 5
(7), 2530−2539.
(64) Liu, Z.; Luo, Y.; Bai, H.; Zhang, Q.; Fu, Q. Remarkably
enhanced impact toughness and heat resistance of poly(L-lactide)/
thermoplastic polyurethane blends by constructing stereocomplex
crystallites in the matrix. ACS Sustainable Chem. Eng. 2016, 4 (1),
111−120.
(65) Ma, P.; Hristova-Bogaerds, D.; Goossens, J.; Spoelstra, A.;
Zhang, Y.; Lemstra, P. Toughening of poly(lactic acid) by ethylene-co-
vinyl acetate copolymer with different vinyl acetate contents. Eur.
Polym. J. 2012, 48 (1), 146−154.
(66) Likittanaprasong, N.; Seadan, M.; Suttiruengwong, S. Impact
property enhancement of poly(lactic acid) with different flexible
copolymers. IOP Conf. Ser.: Mater. Sci. Eng. 2015, 87, 012069.
ACS Sustainable Chemistry & Engineering Perspective
DOI: 10.1021/acssuschemeng.6b00321
ACS Sustainable Chem. Eng. 2016, 4, 2899−2916
2913