Mechanical properties of biodegradable composites from poly lactic acid (PLA) and microcrystalline cellulose (MCC)

Biodegradable composites were prepared using microcrystalline cellulose (MCC) as the reinforcement and polylactic acid (PLA) as a matrix. PLA is polyester of lactic acid and MCC is cellulose derived from high quality wood pulp by acid hydrolysis to remove the amorphous regions. The composites were prepared with different MCC contents, up to 25 wt %, and wood flour (WF) and wood pulp (WP) were used as reference materials. Generally, the MCC/PLA composites showed lower mechanical properties compared to the reference materials. The dynamic mechanical thermal analysis (DMTA) showed that the storage modulus was increased with the addition of MCC. The X‐ray diffraction (XRD) studies on the materials showed that the composites were less crystalline than the pure components. However, the scanning electron microscopy (SEM) study of materials showed that the MCC was remaining as aggregates of crystalline cellulose fibrils, which explains the poor mechanical properties. Furthermore, the fracture surfaces of MCC composites were indicative of poor adhesion between MCC and the PLA matrix. Biodegradation studies in compost soil at 58°C showed that WF composites have better biodegradability compared to WP and MCC composites. The composite performances are expected to improve by separation of the cellulose aggregates to microfibrils and with improved adhesion. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2014–2025, 2005     

Effects of compatibilizer on the mechanical,rheological, and shape memory behaviors of poly(lactic acid) and poly(MnBM) blends

The effects of compatibilizer on the morphological, mechanical, rheological, and shape memory properties of poly(lactic acid) (PLA) and poly(methyl methacrylate-block-n-butyl acrylate-block-methyl methacrylate) (Poly(MnBM)) (80/20) blend were investigated. From the morphological results, the addition of 1 wt% SAN-MAH as a compatibilizer showed minimum Poly(MnBM) domain size among the blends with the SAN-MAH in the amounts from 0 to 7 wt%. Tensile and flexural strengths, and complex viscosity of the blends showed maximum when the SAN-MAH content was 1 wt%, which suggested the increased compatibility between the PLA and Poly(MnBM) phases. From the above results, the optimum compatibilizer content of the PLA and Poly(MnBM) blend was 1 wt%. The recovery ratio of tensile energy was found to be 83 and 56% for the PLA/Poly(MnBM) blend with and without the SAN-MAH (1 wt%), respectively. Upon blending the PLA and Poly(MnBM) (80/20) with SAN-MAH (1 wt%), the increase of recovered tensile energy was observed, and that the brittleness of PLA was improved to be ductile which resulted an improved shape memory behavior of the blend. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48591.     

Mechanical and thermal properties of starch‐filled poly(D,L‐lactic acid)/poly(hydroxy ester ether) biodegradable blends

The mechanical, structural, and thermal properties of injection‐molded composites of granular cornstarch, poly(D ,L ‐lactic acid) (PDLLA), and poly(hydroxy ester ether) (PHEE) were investigated. These composites had high tensile strengths, ranging from 17 to 66 MPa, at starch loadings of 0–70 wt %. Scanning electron microscopy micrographs of fracture specimens revealed good adhesion between the starch granule and the polymer matrix, as evidenced by broken starch granules. The adhesion of the starch granules to the polymer matrix was the greatest when the matrix PDLLA/PHEE ratios ranged from zero to unity. At a PDLLA/PHEE ratio of less than unity, as the starch content increased in the composites, there was an increase in the tensile strength and modulus, with a concurrent decrease in elongation. The effects of starch on the mechanical properties of starch/PDLLA composites showed that as the starch content of the composite increased, the tensile strength and elongation to break decreased, whereas Young's modulus increased. In contrast, the tensile strength of starch/PHEE composites increased with increasing starch content. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1775–1786, 2003     

The effect of poly(ethylene glycol) as plasticizer in blends of poly(lactic acid) and poly(butylene succinate)

The effect of polyethylene glycol (PEG) on the mechanical and thermal properties of poly(lactic acid) (PLA)/poly(butylene succinate) (PBS) blends was examined. Overall, it was found that PEG acted as an effective plasticizer for the PLA phase in these microphase‐separated blends, increasing the elongation at break in all blends and decreasing the T_g of the PLA phase. Significant effects on other properties were also observed. The tensile strength and Young's modulus both decreased with increasing PEG content in the blends. In contrast, the elongation at break increased with the addition of PEG, suggesting that PEG acted as a plasticizer in the polymer blends. Scanning electron microscope images showed that the fracture mode of PLA changed from brittle to ductile with the addition of PEG in the polymer blends. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43044.     

Dynamic mechanical and thermal properties of plasticized poly(lactic acid)

The blends of low molecular weight triacetin (TAC) and oligomeric poly(1,3‐butylene glycol adipate) (PBGA) were used as multiple plasticizers to lubricate poly(lactic acid) (PLA) in this study. The thermal and mechanical properties of plasticized polymers were investigated by means of dynamic mechanical analysis and differential scanning calorimetry. Atomic force microscopy (AFM) was used to analyze the morphologies of the blends. Multiple plasticizers were effective in lowering the glass transition temperature (T_g) and the melting temperature (T_m) of PLA. Moreover, crystallinity of PLA increased with increasing the content of multiple plasticizers. Tensile strength of the blends decreased following the increasing of the plasticizers, but increased in elongation at break. AFM topographic images showed that the multiple plasticizers dispersed between interfibrillar regions. Moreover, the fibrillar crystallite formed the quasicrosslinkings, which is another cause for the increase in elongation at break. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1583–1590, 2006     

Effects of the chain‐extender content on the structure and performance of poly(lactic acid)–poly(butylene succinate)–microcrystalline cellulose composites

Composites of poly(lactic acid) (PLA) with poly(butylene succinate) (PBS) and microcrystalline cellulose (MCC) as reinforcements of the polymer matrix were prepared by melt blending to improve the brittleness of PLA. As a reactive compatibilizer, a chain extender was used in an attempt to solve the composites’ interfacial problems and to improve their mechanical properties; Fourier transform infrared spectroscopy indicated that the chain extender functionally reacted with PLA, PBS, and MCC mainly through end carboxyls or end hydroxyls. Scanning electron microscopy indicated that the chain extender significantly improved the cohesive interfacial forces. Differential scanning calorimetry and X‐ray diffraction showed that the chain extender inhibited crystallization, and these effects were greater when its percentage was increased. The addition of chain extender improved the tensile and impact strength of the composites, and this improvement was proportional to the chain‐extender percentage. However, the elongation at break decreased when the chain‐extender percentage was over 0.5% because of mild crosslinking within the resin matrix. Rheology indicated that the complex viscosity and storage and loss moduli of the composites increased with increasing amount of chain extender; this indicated that the addition of chain extender improved the melt strength and processability of the composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44895.     

Effect of rubber interparticle distance distribution on toughening behavior of thermoplastic polyolefin elastomer toughened polypropylene

In this study, a blend of polypropylene (PP) and two types of thermoplastic polyolefin elastomers (TPO) were prepared by melt mixing. The TPOs were either ethylene‐ or propylene‐based copolymer. The mechanical response and morphology of the blends were investigated using tensile and impact tests and scanning electron microscopy technique. There was significant increase in the impact strength of the TPO‐modified PP, which was an outcome of fine dispersion of TPO inclusions. In particular, the blends containing PP‐based TPO exhibited dramatic enhancement in toughness energy as featured by a plastic deformation in tensile test. The brittle‐tough transition had several deviations from theoretical models, in which generally the interparticle distance criterion was realized as a single parameter, only controlled the transition of brittle to tough behavior. Moreover, the brittle‐tough transition in tensile and impact mode tests was not coincident in the blend with a broad distribution of interparticle distance. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44068.     

Biopolymer foams from Novatein thermoplastic protein and poly(lactic acid)

A batch processing method is used to fabricate foams comprising of a blend of poly(lactic acid) (PLA) and Novatein, a protein‐based thermoplastic. Various compositions of Novatein/PLA are prepared with and without a compatibilizer, PLA grafted with itaconic anhydride (PLA‐g‐IA). Pure Novatein cannot form a cellular structure at a foaming temperature of 80 °C, however, in a blend with 50 wt % of PLA, microcells form with smaller cell sizes (3.36 µm) and higher cell density (8.44 × 10²¹ cells cm^?3) compared to pure PLA and blends with higher amounts of PLA. The incorporation of 50 wt % of semicrystalline Novatein stiffens the amorphous PLA phase, which restrains cell coalescence and cell collapse in the blends. At a foaming temperature of 140 °C, NTP₃₀–PLA₇₀ shows a unique interconnected porous morphology which can be attributed to the CO₂‐induced plasticization effect. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45561.     

Morphology,mechanical, and rheological properties of poly(lactic acid)/ethylene acrylic acid copolymer blends processing via vane extruder

This work aimed to study, for the first time, the melt blending of poly(lactic acid) (PLA) and ethylene acrylic acid (EAA) copolymer by a novel vane extruder to toughen PLA. The phase morphologies, mechanical, and rheological properties of the PLA/EAA blends of three weight ratios (90/10, 80/20, and 70/30) were investigated. The results showed that the addition of EAA improves the toughness of PLA at the expense of the tensile strength to a certain degree and leads the transition from brittle fracture of PLA into ductile fracture. The 80/20 (w/w) PLA/EAA blend presents the maximum elongation at break (13.93%) and impact strength (3.18 kJ/m²), which is 2.2 and 1.2 times as large as those of PLA, respectively. The 90/10 and 80/20 PLA/EAA blends exhibit droplet‐matrix morphologies with number average radii of 0.30–0.73 μm, whereas the 70/30 PLA/EAA blend presents an elongated co‐continuous structure with large radius (2.61 μm) of EAA phase and there exists PLA droplets in EAA phase. These three blends with different phase morphologies display different characteristic linear viscoelastic properties in the low frequency region, which were investigated in terms of their complex viscosity, storage modulus, loss tangent, and Cole‐Cole plots. Specially, the 80/20 PLA/EAA blend presents two circular arcs on its Cole‐Cole plot. So, the longest relaxation time of the 80/20 blend was obtained from its complex viscosity imaginary part plot, and the interfacial tension between PLA and EAA, which is 4.4 mN/m, was calculated using the Palierne model. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40146.     

Mechanical properties of poly(ε‐caprolactone) and poly(lactic acid) blends

The aim of this work was to better understand the performance of binary blends of biodegradable aliphatic polyesters to overcome some limitations of the pure polymers (e.g., brittleness, low stiffness, and low toughness). Binary blends of poly(ε‐caprolactone) (PCL) and poly(lactic acid) (PLA) were prepared by melt blending (in a twin‐screw extruder) followed by injection molding. The compositions ranged from pure biodegradable polymers to 25 wt % increments. Morphological characterization was performed with scanning electron microscopy and differential scanning calorimetry. The initial modulus, stress and strain at yield, strain at break, and impact toughness of the biodegradable polymer blends were investigated. The properties were described by models assuming different interfacial behaviors (e.g., good adhesion and no adhesion between the dissimilar materials). The results indicated that PCL behaved as a polymeric plasticizer to PLA and improved the flexibility and ductility of the blends, giving the blends higher impact toughness. The strain at break was effectively improved by the addition of PCL to PLA, and this was followed by a decrease in the stress at break. The two biodegradable polymers were proved to be immiscible but nevertheless showed some degree of adhesion between the two phases. This was also quantified by the mechanical property prediction models, which, in conjunction with material property characterization, allowed unambiguous detection of the interfacial behavior of the polymer blends. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Mechanical properties of acrylonitrile–butadiene–styrene copolymer/poly(l‐lactic acid) blends and their composites

As the material properties of acrylonitrile–butadiene–styrene copolymer (ABS) have an excessively wide margin for applications in automobile console boxes, ABS partly replaced with poly(l ‐lactic acid) (PLA) may be used for the same purpose with improved ecofriendliness if the corresponding deterioration of the material properties is acceptable through the choice of appropriate additives. ABS composites with 30 wt % renewable components (PLA and cellulose pulp) were prepared by melt compounding, and the material properties were examined as a function of the additive content. The changes in the mechanical properties of the ABS/PLA blends were examined after the addition of cellulose pulp and two clays [Cloisite 25A (C25A) and sodium montmorillonite] as well as these two clays treated with bis(3‐triethoxysilylpropyl)tetrasulfide (TESPT). The heat distortion temperatures of the composites were measured as a function of the content of the TESPT‐treated C25A. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40329.     

Thermal and mechanical properties of plasticized poly(L‐lactic acid)

Acetyl tri‐n‐butyl citrate (ATBC) and poly(ethyleneglycol)s (PEGs) with different molecular weights (from 400 to 10000) were used in this study to plasticize poly(L‐lactic acid) (PLA). The thermal and mechanical properties of the plasticized polymer are reported. Both ATBC and PEG are effective in lowering the glass transition (T_g) of PLA up to a given concentration, where the plasticizer reaches its solubility limit in the polymer (50 wt % in the case of ATBC; 15–30 wt %, depending on molecular weight, in the case of PEG). The range of applicability of PEGs as PLA plasticizers is given in terms of PEG molecular weight and concentration. The mechanical properties of plasticized PLA change with increasing plasticizer concentration. In all PLA/plasticizer systems investigated, when the blend T_g approaches room temperature, a stepwise change in the mechanical properties of the system is observed. The elongation at break drastically increases, whereas tensile strength and modulus decrease. This behavior occurs at a plasticizer concentration that depends on the T_g‐depressing efficiency of the plasticizer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1731–1738, 2003     

3D printing of copper particles and poly(methyl methacrylate) beads containing poly(lactic acid) composites for enhancing thermomechanical properties

Poly(lactic acid) (PLA) composite filaments with different copper (Cu) contents as high as 40 and 20 wt% of poly(methyl methacrylate) (PMMA) beads have been fabricated by twin-screw extruder for 3D printing. A fused-deposition modeling (FDM) 3D printing technology has been used to print the PLA composites containing hybrid fillers of Cu particles and PMMA beads. The morphology, mechanical, and thermal properties of the printed PLA composites were investigated. The tensile strength was slightly decreased, but storage modulus and thermal conductivity of PLA composites were significantly improved by adding Cu particles in the presence of PMMA beads. The PLA composites with hybrid fillers of 40 wt% of Cu particles and 20 wt% of PMMA beads resulted in thermal conductivity of 0.49 W m⁻¹ K⁻¹ which was three times higher than that of the bare PLA resin. The facilitation of the segregated network of high-thermally conductive Cu particles with the PMMA beads in PLA matrix provided thermally conductive pathways and resulted in a remarkable enhancement in thermal conductivity.     

Reactive compatibilization of poly(l‐lactic acid)/poly(propylene carbonate) blends: Thermal,thermomechanical, and morphological properties

Poly(l ‐lactic acid) (PLLA) was blended with poly(propylene carbonate) (PPC) with various compositions by a melt‐blending process to evaluate their general properties for a potential flexible packaging field. The mechanical properties, including the tensile strength and modulus, revealed a tendency to decrease with the addition of ductile PPC; this was induced by the poor interfacial adhesion between PLLA and PPC with the cavities and clear edges and was observed through morphological observation. Reactive compatibilization was applied to improve the interfacial adhesion between PLLA and PPC, and the elongation at break was profoundly enhanced because of the improved interfacial adhesion between the two phases. The compatibilized PLLA/PPC blends showed considerable improvements in the storage modulus in the transition region with stable thermal stability; this could be a benefit for thermal processing. The addition of PPC had a great effect on the solidlike behavior and increased the elasticity of the PLLA/PPC blends. Up to 2.0 phr maleic anhydride showed a great efficiency in enhancing the dynamic storage modulus and complex viscosity of the PLLA/PPC blends. We also confirmed that it was feasible to fabricate PLLA/PPC blends with controllable barrier properties with combination of PLLA and PPC under reactive compatibilization while retaining the biodegradability. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43388.     

An efficient plasticization method for poly(lactic acid) using combination of liquid‐state and solid‐state plasticizers

A combined use of solid plasticizer [poly(ethylene glycol), PEG] with a nominal M_w of 2000 g/mol and liquid plasticizer (epoxidized soybean oil, ESO) for plasticizing poly(lactic acid) (PLA) is proposed in this study. This plasticization method brought an obvious improvement in the melting flowability of the modified PLA, which has been verified by a lower balance torque during blending and a four times increase in the melt flow index compared to neat PLA. Meanwhile, the brittleness of this glassy polymer was also improved significantly; all composites with different contents of combined plasticizers displayed an obvious yield stage and toughness fracture surfaces. The mechanisms of the plasticizing effects were investigated by polarizing optical microscopy and scanning electron microscopy. The PLA/ESO/PEG blends formed a complex reinforcement structure. ESO existed as tiny droplets and uniformly dispersed in the PLA spherulites, and strip‐shaped PEG accumulated along the boundaries of interspherulites. The combined use of these two plasticizers, a liquid one and a solid one, had an excellent effect on plasticizing PLA, not only on melt flowability but also on mechanical properties. Thus, the application areas for PLA could be further expanded, such as melt blowing and melt extrusion. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46669.     

Effects of aging on the thermomechanical properties of poly(lactic acid)

In this study, we examined the role of environmental parameters and physical structure in the aging process of poly(lactic acid) (PLA). The role of heating history on the aging behavior of the material was also investigated. PLA samples with a D ‐content of 4.25% were exposed to a relative humidity of 80% at three different temperatures, 20, 40, and 50°C (below the glass‐transition temperature of the material), at various aging periods of 30, 60, 80, 100, and 130 days. Selected samples were subjected to two consecutive heating runs. The stability of PLA was monitored by a number of techniques, including size exclusion chromatography, differential scanning calorimetry, dynamic mechanical analysis, and tensile measurements. The initial thermal processing (150°C) of the material resulted in an overall molecular weight reduction. A substantial lowering of properties was observed for PLA samples aged at 20°C for 30 days. No further loss of properties was observed for samples aged up to 40°C for several time intervals. A major portion (80–90%) of the induced changes in the tensile properties could be reversed after drying. At 50°C and 100 days of aging, a sharp decrease in the overall properties was noticed. The results seem to confirm the earlier finding that PLA degradation driven by hydrolysis needs a higher temperature (>50°C) in combination with ample time to take place. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation,characterization, electrical and antibacterial properties of sericin/poly(vinyl alcohol)/poly(vinyl pyrrolidone) composites

In this study, we focused on the fabrication of poly(vinyl alcohol) (PVA)/poly(vinyl pyrrolidone) (PVP)/sericin composites via a simple solution‐blending method. The composites were characterized by Fourier transform infrared (FTIR) spectroscopy, UV spectroscopy, X‐ray diffraction (XRD), scanning electron microscopy (SEM), differential scanning calorimetry, thermogravimetric analysis (TGA), and measurements of the conductivity, tensile strength, and antibacterial activity against Staphylococcus aureus. The results of FTIR and UV spectroscopy implied the occurrence of hydrogen bonding between sericin and the PVA/PVP blend. The structure and morphology, studied by XRD and SEM, revealed that the sericin particles were well dispersed and arranged in an orderly fashion in the blend. The glass‐transition temperature (T_g) of the composite was higher than that of the pure blend, and the T_g value shifted toward higher temperatures when the volume fraction of sericin increased. TGA indicated that sericin retarded the thermal degradation; this depended on the filler concentration. The mechanical and electrical properties, such as the tensile strength, alternating‐current electrical conductivity, dielectric constant, and dielectric loss of the composites, were higher than those of the pure blend, and these properties were enhanced when the concentration of sericin was increased up to 10 wt % filler content, whereas the elongation at break of the composite decreased with the addition of sericin particles. The antibacterial properties of the composite showed that sericin had a significant inhibitory effect against S. aureus. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43535.     

Mechanical and thermal properties of poly(lactic acid)/starch blends with dioctyl maleate

Poly(lactic acid) (PLA)/starch blends were prepared blending with dioctyl maleate (DOM). DOM acted as a compatibilizer at low concentrations (below 5%), and markedly improved tensile strength of the blend. However, DOM functioned as a plasticizer at concentrations over 5%, significantly enhancing elongation. Compatibilization and plasticization took place simultaneously according to the analysis of, for example, mechanical properties and thermal behavior. With DOM as a polymeric plasticizer, thermal loss in the blends was not significant. Water absorption of PLA/starch blends increased with DOM concentration. DOM leaching in an aqueous environment was inhibited. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1697–1704, 2004     

Microstructural,mechanical, and thermal‐insulation properties of poly(methyl methacrylate)/silica aerogel bimodal cellular foams

Novel poly(methyl methacrylate) (PMMA)/silica aerogel bimodal cellular foams were prepared by melt mixing and a supercritical carbon dioxide foaming process. The effects of the silica aerogel content on the morphologies and thermal‐insulating and mechanical properties of the foams were investigated by scanning electron microscopy, mechanical tests, and heat‐transfer analysis. The experimental results show that compared to the pure PMMA foam, the PMMA/silica aerogel microcellular foams exhibited more uniform cell structures, decreased cell sizes, and increased cell densities (the densities of the foams were 0.38–0.45 g/cm³). In particular, a considerable number of original nanometric cells (ca. 50 nm) were evenly embedded in the cell walls and on the inner surfaces of the micrometric cells (<10 μm). A 62.7% decrease in the thermal conductivity (0.072 W m⁻¹ K⁻¹) in comparison to that of raw PMMA after 0.5 wt % silica aerogel was added was obtained. Mechanical analysis of the PMMA/silica aerogel foams with 5 and 2 wt % silica aerogel showed that the compressive and flexural strengths were distinctly improved by 92 and 52%, respectively, and the dynamic storage moduli increased. The enhanced performance showed that with the addition of silica aerogel into PMMA, one can obtain thermal‐insulation materials with a favorable mechanical strength. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44434.     

Ultrafine fly ash as a reinforcing filler in poly(lactic acid) matrix

Fly ash, inexpensive and not eco‐friendly material, is the residue from the coal burning in thermal power stations. If ways can be found to use it, it will facilitate applications for the ash materials and simultaneously reduce the pollution. In this study, silane‐grafted ultrafine fly ash (S‐UFA) was used as a reinforcing filler in poly(lactic acid) (PLA) to prepare a series of PLA/S‐UFA composites. The tensile strength of PLA/S‐UFA composites increases with the increase of S‐UFA content when less than 20 wt %; after a loading fraction greater than 30 wt %, the tensile strength of the composites decreases with the increasing S‐UFA weight fraction. The morphology of PLA/S‐UFA composites was observed by scanning electron microscope (SEM). X‐ray diffraction (XRD) analysis was applied to investigate the crystal structure of S‐UFA and the composites. The thermal properties of these composites were studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The TGA results showed that the thermal stability of PLA/S‐UFA composites slightly decreased with the increasing S‐UFA loading fraction. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43716.