Influence of recycling of poly(lactic acid) on packaging relevant properties

The most promising representative of biodegradable plastics in packaging applications is polylactide (PLA). Despite this, there is only a small market of PLA in Europe. Reasons for that are the high price of PLA raw material and the lack of knowledge of the behavior in packaging applications. It has a number of peculiarities so producers of plastics packaging hesitate to use it. Like other polyesters, it can degrade at increased temperatures in the presence of moisture by hydrolysis whereby it loses its physical and chemical properties. In all production processes, production waste is generated (i.e., stamping grids or edge trim). In most cases, this waste is used. It is not known in detail, how an internal recycling process will influence the final product properties. One problem is hydrolysis by which the production waste is partially degraded. Target of this study is to analyze the recycling process of PLA within the context of necessary process adaptions and the effects upon ecological efficiency. Films for packaging containing multiple types and amounts of production waste will be produced by extrusion and tested concerning their mechanical properties. The analysis of the recycling behavior showed that internal PLA production waste is well suitable for recycling. The influence of the recycling on the molecular weight is negligible. The effect on the viscosity and thus on the extrusion process is higher. Packaging relevant properties like mechanical or optical properties are hardly influenced. Especially recycling with a recycling quota of up to 50% has an insignificant effect on the film properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41532.     

Multilayer coextrusion of graphene polymer nanocomposites with enhanced structural organization and properties

A potential advantage of platelet‐like nanofillers as nanocomposite reinforcements is the possibility of achieving two‐dimensional (2D) stiffening through planar orientation of the platelets. Forced assembly by multilayer coextrusion, which enables the in‐plane orientation of platelet‐like fillers in alternating layers, was used in this work to produce poly(lactic acid) (PLA)/graphene multilayer films. These films exhibited a multilayer structure made of alternating layers of neat PLA and PLA containing graphite nanoplatelets (GNPs). Electron microscopy revealed information on the orientation of the individual GNPs. X‐ray diffraction results indicated that the thickness of the individual GNPs was reduced during the multilayer coextrusion process. A significant reinforcement of 120% at an overall GNP loading of 1 wt % in PLA was achieved. This high effective reinforcement was attributed to the high degree of planar alignment, improved dispersion and exfoliation and increased aspect ratio of the GNPs in the composite layers after multilayer coextrusion. Improved water vapor barrier properties were also achieved as a result of the highly organized 2D nanofillers in the multilayer films. These industrial scalable multilayer nanocomposite films open up possibilities for lightweight and strong packaging materials for food and industrial applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46041.     

Effect of different biopolymers and polymers on the mechanical and permeation properties of extruded PHBV cast films

The biopolymer poly‐3‐hydroxybutyrate‐co‐3‐hydroxyvalerate (PHBV) is a promising material for packaging applications but its high brittleness is challenging. To address this issue, PHBV was blended with nine different biopolymers and polymers in order to improve the processing and mechanical properties of the films. Those biopolymers were TPS, PBAT, a blend of PBAT + PLA, a blend of PBAT + PLA + filler, PCL and PBS, and the polymers TPU, PVAc, and EVA. The extruded cast films were analyzed in detail (melting temperature, crystallinity, mechanical properties, permeation properties, and surface topography). A decrease in crystallinity and Young's modulus and an increase in elongation at break and permeability were observed with increasing biopolymer/polymer concentration. In PHBV‐rich blends (≥70 wt % PHBV), the biopolymers/polymers PCL, PBAT, and TPU increased the elongation at break while only slightly increasing the permeability. Larger increases in the permeability were found for the films with PBS, PVAc, and EVA. The films of biopolymer/polymer‐rich blends (with PBAT, TPU, and EVA) had significantly different properties than pure PHBV. A strong effect on the properties was measured assuming that at certain biopolymer/polymer concentrations the coherent PHBV network is disrupted. The interpretation of the permeation values by the Maxwell–Garnett theory confirms the assumption of a phase separation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46153.     

Improvement of melt stability and degradation efficiency of poly (lactic acid) by using phosphite

Concurrent improvement of melt processing stability and degradation efficiency of poly(lactic acid) (PLA) is still a challenge for the industry. This article presents the use of phosphites: tris(nonylphenyl) phosphite (TNPP) and tris (2,4-di-tert-butylphenyl) phosphite (TDBP), to control the thermal stabilization, mechanical performance, and hydrolytic degradation ability of the compressed PLA films. The hydrolysis process is followed as a function of time at 45, 60, and 75°C. During melt extrusion, both phosphites function as a processing aid, besides acting as a chain extender stabilizing the PLA molecular weight. The phosphite structure plays a crucial role over crystallinity and water absorption, in controlling the hydrolytic degradation of PLA. The application of TNPP significantly catalyzes the hydrolysis of PLA, which is the initial step of the biodegradation process. The optimum amount of TNPP for best hydrolytic degradation efficiency and thermal stabilization of PLA is 0.5 wt%. The excessive TNPP loadings cause a drastic drop in PLA molecular weight and, as a consequence, a reduction of flexural strength. The reactions between PLA and phosphite molecules are discussed.     

Mixture design applied for the development of films based on starch,polyvinyl alcohol,and glycerol

Starch and polyvinyl alcohol (PVA) are biodegradable materials with potentiality to replace the conventional polymers in some applications. The aim of this work was to produce biodegradable films of PVA, cassava starch, and glycerol by thermoplastic extrusion using a mixture design to evaluate the effects of each component in the blend properties. Six formulations were prepared using a twin‐screw extruder coupled with a calender. All the materials were visually homogeneous and presented good processability. Mechanical properties were dependent on both the relative humidity conditioning and the formulation; higher relative humidities detracted the mechanical properties, which was associated to plasticizer effect of the water. Furthermore, the mechanical properties were better when higher concentrations of PVA were used, resulting in films with lower opacity, lower water vapor permeability, and higher thermal stability, according to TGA. Biodegradable materials based on starch, PVA, and glycerol have adequate mechanical and processing properties for commercial production. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42697.     

New biocomposite obtained using poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) and microfibrillated cellulose

This research evaluates the effects of filler content and silanization on thermal, morphological and mechanical properties of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH)-based composites. Microfibrillated cellulose (MFC) was obtained by a mechanical treatment of high-pressure homogenization, starting from oat hull fiber, a byproduct of the agri-food sector. MFC reinforced PHBH composites were prepared by melt compounding. SEM and FT-IR analysis showed a good dispersion of the filler in the polymeric matrix, denoting the effectiveness of the surface silanization process. The thermal stability of PHBH composites remains substantially unchanged, and the glass transition temperature marginally increases with the increase of the filler content. Furthermore, silanized MFC shows slightly reinforcing mechanical effects on PHBH composites, such as the increase of 10% of the Young modulus with an increase of the maximum tensile stress as well. This finding has an economical interest since the results showed that MFC, deriving from a byproduct, can be successfully used as filler, decreasing the cost of the bio-based compound leaving substantially unaltered its mechanical and thermal properties. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48953.     

Development and characterization of flax fiber reinforced biocomposite using flaxseed oil‐based bio‐resin

In this study, acrylated epoxidized flaxseed oil (AEFO) resin is synthesized from flaxseed oil, and flax fiber reinforced AEFO biocomposites is produced via a vacuum‐assisted resin transfer molding technique. Different amounts of flax fiber and styrene are added to the resin to improve its mechanical and physical properties. Both flax fiber and styrene improve the mechanical properties of these biocomposites, but the flexural strength decreases with an increase in styrene content. The mass increase during water absorption testing is less than 1.5% (w/w) for all of the AEFO‐based biocomposites. The density of the AEFO resin is 1.166 g/cm³, which increases to 1.191 g/cm³ when reinforced with 10% (w/w) flax fiber. The flax fiber reinforced AEFO‐based biocomposites have a maximum tensile strength of 31.4 ± 1.2 MPa and Young's modulus of 520 ± 31 MPa. These biocomposites also have a maximum flexural strength of 64.5 ± 2.3 MPa and a flexural modulus of 2.98 ± 0.12 GPa. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41807.     

Investigation of eco-friendly chemical treatments of apple pomace for producing high quality molded pulp biocomposite

Eco-friendly chemical treatments using citric acid (CA) and sodium bicarbonate were employed to remove pectin, hemicellulose, and extractives from apple pomace (AP) for improving AP fiber quality and maximizing its utilization in producing biocomposite boards with newspaper (NP) fibers (AP:NP ratio of 2:1) using molded pulp technique. CA treatment was further optimized at different pH and temperature and cellulose nanofiber (CNF, 0.15, 0.3% w/w pulp solids) was used as reinforcement agent to enhance mechanical property and water resistance of biocomposite boards. CA treatment improved AP fiber strength and cellulose content. AP treated by CA at pH 2.5 and 75°C with 0.15% CNF reinforcement produced AP/NP biocomposite board with high flexural strength, and dimension stability, and low density. Thermal analysis verified increased cellulose content, crystallinity, and thermal stability of CA treated AP fibers. This study provided new insight to improve fiber functionality and utilize AP for developing sustainable packaging.     

Synthesis and characterization of bio-based polyesters derived from 1,10-decanediol

Two kinds of bio-based polyesters were synthesized from 1,10-decanediol (DD), dimethyl terephthalate (DMT) or 2,6-naphthalene dicarboxylic acid (NDCA). Chemical structure, thermal properties and crystal structures, tensile properties and rheological properties were investigated. The glass transition temperature and melting temperature of poly(decamethylene 2,6-naphthalate) (PDN) are higher than that of poly(decamethylene terephthalate) (PDT). Differential scanning calorimetry and wide-angle X-ray diffraction results suggested that PDT and PDN were semi-crystalline polymers. Equilibrium melting points of PDT and PDN were 129.5°C and 167.1°C, respectively. Compared with PDT, PDN exhibited the higher tensile strength (36.8 MPa) and lower elongation at break (224%) and the complex viscosity of PDN is more sensitive to temperature and oscillation frequency. Compared with the current available bio-based plastic poly(butylene succinate) (PBS), PDT and PDN exhibit higher melting temperature, faster crystallization rate and comparable tensile properties.     

Effects of the shapes and addition amounts of crosslinking reagents on the properties of poly-3-hydroxybutyrate/poly(caprolactone) blends

The effects of the shapes and addition amount of crosslinking reagents on the expression mechanisms of polymer properties of poly(3-hydroxybutyrate) (PHB) and poly(caprolactone) (PCL) blends are investigated. A static tensile test is carried out on 60%PHB/40%PCL blends by adding liquid and solid crosslinking reagents, showing that the Young's modulus of the blends decrease with increasing effective peroxide value of the crosslinking reagent. In addition, the elasticity of the blends increases only when the liquid crosslinker is added, even though T₁H analysis and scanning electron microscopy observation reveal that both crosslinking reagents improve the miscibility of the blend. Furthermore, the ¹H and ¹³C PST-MAS NMR spectra related to the molecular motions of polymer main chains in the blends increase with increasing effective peroxide value of the crosslinking reagents. However, the local molecular motions of substituents in the blends matched with the T₁C values reveal an opposite trend between the rigid PHB and flexible PCL with the addition of the solid crosslinker. The solid-state NMR spectral and relaxation time analyses suggest the possibility of the polymer chain scission as a side reaction, as well as the occurrence of intra-domain crosslinking, both of which reduce the toughness of the blends containing the solid crosslinker.     

Overmolded polylactide/jute-mat eco-composites: A new method to enhance the properties of natural fiber biodegradable composites

Environmentally friendly, biodegradable composites were prepared via overmolding of poly(lactic acid) (PLA) onto PLA/jute-mat, named as “ecosheets,” reinforced continuous fiber composite sheets. Film stacking procedure was used to prepare ecosheets via using a hot-press. The fiber orientation was changed as −45°/+45° and 0°/0°. −45°/+45° orientation exhibited higher properties as compared to 0°/0° for ecosheets; therefore, this construction was used to produce overmolded composites (OMCs). The mechanical tests showed that flexural modulus and strength of OMCs were improved in comparison to neat PLA. The dynamic mechanical analysis exhibited that the thermomechanical resistance of PLA was enhanced for OMCs. Scanning electron microscopy investigation showed that the jute/PLA interphase needs to be improved to further increase the properties. It was concluded that one of the biggest advantages of this novel technique was the increase of mechanical properties of PLA without altering the density. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48692.     

Potential of producing carbon fiber from biorefinery corn stover lignin with high ash content

The possibility of producing carbon fiber from an industrial corn stover lignin was investigated in the present study. As‐received, high‐ash containing lignin was subjected to methanol fractionation, acetylation, and thermal treatment prior to melt spinning and the changes in physiochemical and thermal properties were evaluated. Methanol fractionation removed most of the impurities in the raw lignin and also selectively removed the molecules with high melting points. However, neither methanol fractionation nor thermal treatment rendered melt‐spinnable precursors. The precursors were highly viscous and decomposed easily at low temperatures, attributed to the presence of H, G phenolic units, and abundant hydroxycinnamate groups in herbaceous lignin. A two‐step acetylation of methanol fractionated lignin greatly improved the mobility of lignin, while enhancing the thermal stability of the precursor during melt‐spinning. Fourier Transform Infrared and 2D‐NMR analysis showed that the contents of phenolic and aliphatic hydroxyls, as well as the hydroxycinnamates, decreased in the acetylated precursors. The optimum precursor was a partially acetylated lignin with a glass transition temperature of 85 °C. Upon oxidative stabilization and carbonization, the carbon fibers with an average tensile strength of 454 MPa and modulus of 62 GPa were obtained. The Raman spectroscopy showed the I_D/I_G ratio of the carbon fiber was 2.53. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45736.     

Synthesis and material properties of elastomeric high molecular weight polycycloacetals derived from diglycerol and meso-erythritol

Copolymerizing glutaraldehyde with tetraols such as diglycerol, meso-erythritol, and pentaerythritol is particularly effective for forming very high molecular weight polycycloacetals (M_n up to 65,000 g/mol) with elastomeric properties and up to 70% biorenewable content by weight. Altering the tetraol monomer feed ratio provides control over the polycycloacetal's tensile properties. The polymerizations are high-yielding, readily scalable, and employ commercially available starting materials that are used without further purification. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48780.     

Esterification of Kraft lignin as a method to improve structural and mechanical properties of lignin‐polyethylene blends

Lignin is a promising candidate for blends with thermoplastic polymers. Still, this endeavour is a challenge due to poor compatibility between both components. In this article, the effect of lignin esterification on the improvement of the compatibility between hardwood Kraft lignin and high‐density polyethylene (PE‐HD) is investigated. For this purpose, lignin was esterified with acetic, propionic, and butyric anhydride; its amount in the blends varied from 10 to 40%. Light microscopic images of blends show a reduction in particle size and a more homogeneous distribution with increasing length of the ester carbon chains (C2 to C4). Modification of lignin enhances the moduli and strength characteristics of the blends. Butyrated lignin performs best, as tensile strength of blends can be retained near that of pure PE‐HD with up to 40% lignin content. An additional investigation of unmodified lignin with reduced particle size confirms that modification is the decisive factor to enhance blend properties; a sole reduction of particle size is insufficient. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44582.     

Compatibility improvement of poly(lactic acid)/thermoplastic starch blown films using acetylated starch

The present research aims to improve the compatibility between relatively hydrophobic poly(lactic acid) (PLA) and hydrophilic thermoplastic starch (TPS) and the properties of the PLA/TPS blends by replacing TPS from native cassava starch (TPSN) with TPS from acetylated starch (TPSA). The effects of the degree of acetylation (DA) of acetylated starch, that is, 0.021, 0.031, and 0.074, on the morphological characteristics and properties of PLA/TPS blend are investigated. The melt blends of PLA and TPS with a weight proportion of PLA:TPS of 50:50 are fabricated and then blown into films. Scanning electron microscopy confirms the dispersion of TPS phase in the PLA matrix. Better dispersion and smaller size of the TPS phase are observed for the PLA/TPSA blend films with low DA of acetylated starch, resulting in improved tensile and barrier properties and increased storage modulus, thermal stability, and T_g, T_cc, and T_m of PLA. Elongation at break of the PLA/TPSA blend increases up to 57%, whereas its water vapor permeability and oxygen permeability decrease about 15%. The obtained PLA/TPSA blend films have the potential to be applied as biodegradable flexible packaging.     

A new approach for flexible PBAT/PLA/CaCO3 films into agriculture

The use of flexible films in agriculture has increased intensely in the last 15 years bringing benefits to producers. However, environmental impacts increased due to their incorrect post‐use disposal which leads the degradable films to emerge as an alternative. The production films of poly(butylene adipate‐co‐terephthalate) and poly(lactic acid) reinforced with calcium carbonate (CaCO₃) was studied focusing on producing lower cost materials and flexible films. Four different films (reinforcement compositions) were prepared by melt extrusion with 10 and 20 wt % of CaCO₃. Mechanical and thermal properties, crystallinity, water absorption, and soil degradation, were evaluated. The addition of reinforcement leads to improved compatibility between the polymers in the matrix, which usually presented phase segregation. The films showed better mechanical properties with the addition of CaCO₃. Highly orientated amorphous structures were obtained leading to low water absorption and low degradation in the simulated soil. This low degradation, suggests that the obtained films would be of interest in flexible mulch films manufacturing, particularly for Muridori plantation system, where long‐term plantations are needed. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46660.     

Dynamic mechanical thermal analysis of biocomposites based on PLA and PHBV—A comparative study to PP counterparts

The primary objective of this study was the investigation of thermo‐mechanical behavior of cellulosic fiber reinforced polylactid (PLA) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) biopolymers. Both PLA and PHBV were processed with 30 wt % of cellulosic fibers; moreover, to improve the processability and mechanical performance, PHBV was previously blended with 30% by weight poly(butylene adipate‐co‐butylene terephthalate) (PBAT). Secondary target was the comparison of the obtained results to natural fiber reinforced polypropylene (PP) composites reinforced with exact the same fibers and processed by using identical techniques. For validation the thermo‐mechanical properties, a dynamic mechanical thermal analysis (DMTA) was applied. Storage modulus (E′), loss modulus (E″), and loss factor (tan δ) were determined. The DMTA results indicate decreased polymer chain motion with resulting improvement of stiffness expressed by the storage modulus. Finally, the effectiveness of fiber on the moduli was investigated. The C coefficient differs in dependence on fiber type, use of coupling agent, and the reference temperature in glassy state. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3175–3183, 2013     

Ecofriendly modification of acetosolv lignin from oil palm biomass for improvement of PMMA thermo‐oxidative properties

The environmentally friendly esterification of acetosolv lignin (AL), obtained from pressed oil palm mesocarp fibers, is described, for the improvement of thermo‐oxidative properties of poly(methyl methacrylate) (PMMA) films. Acetylation of AL was performed in ecofriendly conditions using acetic anhydride in the absence of catalysts. Acetylated acetosolv lignin (AAL) was successfully obtained in only 12 min with a solvent‐free and catalyst‐free microwave‐assisted procedure. Lignins were characterized by Fourier transform infrared spectroscopy, size exclusion chromatography, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC), confirming the efficacy of the methodology employed. AL and AAL as fillers in different concentrations (1% and 5%) were added to PMMA films. The thermal and mechanical properties of the lignin‐incorporated films were analyzed by TGA, DSC, and dynamic mechanical analysis (DMA). The films incorporated with lignin and acetylated lignin presented initial degradation temperature (T_onset) and onset oxidative temperature (OOT) values higher than pure PMMA films, contributing thus to an enhancement of thermo‐oxidative stability of PMMA. The DMA analyses showed that incorporation of AL or AAL increased the storage modulus (E′) of PMMA films, but did not affect their glass‐transition temperatures (T_g). The results indicate the potential use of oil palm mesocarp lignin to enhance the thermo‐oxidative properties of PMMA without compromising its mechanical response. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45498.     

Starch foams containing biomass from the second generation cellulosic ethanol production

Second generation bioethanol is produced from lignocellulose which comes from agricultural waste instead of agricultural feedstock. This study utilized the residuals from the extraction of C5 and C6 sugars in the second generation bioethanol while 20 and 40 wt % of the biomass was blended with starch into a starch/biomass foam. After adding the biomass into starch foam, the morphology of the starch foam changed significantly, showing rough surfaces, higher cell densities, as well as smaller cell areas than the starch only foam. Adding the biomass into the starch overall resulted in the reduction of the compressive strength, the stiffness, and the density of the starch foam. The water sensitivity of the starch foam/biomass was reduced by 60%, indicating a significant improvement of the hydrophilic nature of the starch foam. The foam/biomass demonstrated a lower thermal stability than neat starch foam due to the decomposition of the biomass. The study concluded that the biomass from the second generation cellulosic ethanol process possess similar physical, mechanical, and thermal properties as the other starch foam composite, and yet, no additive is required. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41940.     

Comparative study on the properties of cross-linked cellulose nanocrystals/chitosan film composites with conventional heating and microwave curing

Cross-linking of chitosan film composites was carried out by using conventional heating and microwave curing methods in this study. Non-cross-linked and glutaraldehyde (GA) cross-linked neat chitosan and cellulose nanocrystals (CNC)/chitosan film composites were cured by either conventional oven heating or microwave irradiation. Tensile strength and Young's modulus of chitosan composites were enhanced significantly by the addition of CNC and GA especially for the microwave-cured samples. The changes in chemical interaction of the chitosan film composites was determined by Fourier transform infrared (FTIR) spectroscopy. The microwave-cured GA-cross-linked chitosan film composites were more thermally stable than non-cross-linked and conventionally heated GA-cross-linked chitosan film composites due to the formation of a more stable structure between GA and chitosan. Nevertheless, the reduced antimicrobial efficacy of film composites against Escherichia coli, Bacillus subtilis, and Saccharomyces cerevisiae was observed in cross-linked film composites compared with non-cross-linked composites.