Graphene Nanoplatelets as Novel Reinforcement Filler in Poly(lactic acid)/Epoxidized Palm Oil Green Nanocomposites: Mechanical Properties

Graphene nanoplatelet (xGnP) was investigated as a novel reinforcement filler in mechanical properties for poly(lactic acid) (PLA)/epoxidized palm oil (EPO) blend. PLA/EPO/xGnP green nanocomposites were successfully prepared by melt blending method. PLA/EPO reinforced with xGnP resulted in an increase of up to 26.5% and 60.6% in the tensile strength and elongation at break of the nanocomposites respectively, compared to PLA/EPO blend. XRD pattern showed the presence of peak around 26.5° in PLA/EPO nanocomposites which corresponds to characteristic peak of graphene nanoplatelets. However, incorporation of xGnP has no effect on the flexural strength and modulus. Impact strength of PLA/5 wt% EPO improved by 73.6% with the presence of 0.5 wt% xGnP loading. Mechanical properties of PLA were greatly improved by the addition of a small amount of graphene nanoplatelets (<1 wt%).     

Mechanical,thermal, and morphology properties of poly(lactic acid) plasticized with poly(ethylene glycol) and epoxidized palm oil hybrid plasticizer

Poly(lactic acid) (PLA) has received great attention recently due to its good physical and mechanical properties such as high tensile strength and modulus, good processability and biodegradability. In this study, low molecular weight poly(ethylene glycol) (PEG) and epoxidized palm oil (EPO) were used as hybrid plasticizers to improve toughness and ductility of PLA. Using the solubility parameter, a tentative evaluation of the hybrid plasticizer that could act as the most effective plasticizer for PLA has been performed and the obtained results have been corroborated with the materials physical properties. Excellent plasticizing effect was obtained by hybrid plasticizer PEG:EPO with ratio 2:1. Addition of PEG:EPO (2:1) hybrid plasticizer to PLA shows a significant improvement of 12,402%, compared to neat PLA. The improvement in flexibility and decrease in rigidity for the plasticized PLA is well evidenced by lower glass transition temperature (T_g) and tensile modulus values. In relation to the thermal stability, a decrease in thermal properties of the hybrid plasticized PLA was observed due to the volatility of the plasticizers. Scanning electron microscopy (SEM) shows that the hybrid plasticizer was turned PLA's smooth surface to fibrous structure and rough fracture surface. POLYM. ENG. SCI., 56:1169–1174, 2016. © 2016 Society of Plastics Engineers     

Thermomechanical properties of alumina-filled plasticized polylactic acid: Effect of alumina loading percentage

Polylactic acid (PLA) is one of the most widely studied renewable and biodegradable polyesters and is expected to replace petrochemical-based synthetic polymers. In this study, we investigated the effect of the alumina volume fraction on the thermal and mechanical properties of polyethylene glycol (PEG)-plasticized PLA. The alumina particles were treated with maleic acid to improve their interaction with the PLA matrix. The field-emission scanning electron microscopy results revealed that the addition of alumina eliminated voids, leading to improved interfacial interactions between the PLA and alumina particles. The thermal conductivity of the neat PLA increased from 0.278 to 0.66?wm^?1 k^?1 with the addition of 30% alumina, which accounts for 137% increase. The tensile strength and Young's modulus of the neat PLA dropped by 52% and 56%, respectively, on the addition of 15% PEG plasticizer. However, the elongation at break increased from 5.4% to 207%, which was associated with a drop on the glass transition temperature values. The dynamic mechanical analysis results showed a drop in the storage modulus and height of the tan δ peak, revealing the increased flexibility of the composite after the inclusion of the plasticizer. The addition of 30% alumina exhibited a 41.6% increase on the stiffness of the PEG-blended PLA.     

Effects of thermoplastic poly(ether-ester) elastomer and bentonite nanoclay on properties of poly(lactic acid)

This work presented the influence of thermoplastic poly(ether-ester) elastomer (TPEE) and bentonite (BTN) on improving the mechanical and thermal properties of poly(lactic acid) (PLA). PLA was initially melt mixed with TPEE at six different loadings (5–30 wt%) on a twin screw extruder and then injection molded. The mechanical tests revealed an increasing impact strength and elongation at break with increasing TPEE loading, but a diminishing Young's modulus and tensile strength with respect to pure PLA. The blend at 30 wt% TPEE provided the optimum improvement in toughness, exhibiting an increase in the impact strength and elongation at break by 3.21- and 10.62-fold over those of the pure PLA, respectively. Scanning electron microscopy analysis illustrated a ductile fractured surface of the blends with the small dispersed TPEE domains in PLA matrix, indicating their immiscibility. The 70/30 (wt/wt) PLA/TPEE blend was subsequently filled with three loadings of BTN (1, 3, and 5 parts by weight per hundred of blend resin [phr]), where the impact strength, Young's modulus, tensile strength and thermal stability of all the blends were improved, while the elongation at break was deteriorated. Among the three nanocomposites, that with 1 phr BTN formed exfoliated structure and so exhibited the highest impact strength, elongation at break, and tensile strength compared to the other intercalated nanocomposites. Moreover, the addition of BTN was found to increase the thermal stability of the neat PLA/TPEE blend due to the barrier properties and high thermal stability of BTN.     

The effect of MBS on the heat resistant,mechanical properties,thermal behavior and rheological properties of PLA/EVOH blend

This work focuses on improve the mechanical properties of poly(lactic acid)/poly(ethylene-co-vinyl alcohol) (PLA/EVOH) blend and simultaneously remained a high Vicat softening temperature (VST) using appropriate contents of methyl methacrylate–butadiene–styrene copolymer (MBS) via simple melt blending. The effects of MBS on the heat resistant, mechanical properties, thermal properties and rheological behavior were examined in detail with various techniques. The VST of neat PLA significantly increased to 159 °C from 66.8 °C after blending with 50 wt% EVOH. However, the VST was gradually decreased with increasing MBS content but were still much higher than that of neat PLA. On the basis of the tensile and impact tests results, PLA/EVOH/MBS blends showed a considerably higher elongation at break and impact strength. For all PLA/EVOH/MBS blends, the thermal stability was increased compared than that of PLA/EVOH blend without MBS. With increasing MBS content, the complex viscosity and storage modulus of PLA/EVOH blend increased, especially at low frequencies, indicating that MBS enhanced the chain entanglement in the PLA/EVOH matrix. In addition, the results Han curves and Cole–Cole plots indicated that the relaxation time was increased when MBS was added.     

PLA/PPA共混材料的相容性和热力学性能

采用熔融共混的方法制备了聚己二酸丙二醇酯(PPA)增塑改性聚乳酸(PLA)材料,采用动态力学热分析(DMA)测试仪、差示扫描量热仪(DSC)、扫描电子显微镜(SEM)等手段研究了聚乳酸/聚己二酸丙二醇酯(PLA/PPA)共混材料的相容性、热性能和力学性能。结果表明,在PPA组分质量分数低(5%)的时候,共混物是完全相容体系;随着PPA组分含量的增加,共混物的玻璃化转变温度及冷结晶温度降低,断裂伸长率大幅度增加,当PPA质量分数为20%时,共混材料的断裂伸长率达到248%,获得了良好的增塑聚乳酸的效果。     

Mechanical and Thermal Properties of 3D-Printed Biocomposites of Polylactic Acid and Thermally Modified Wood Flour with Silver Nanoparticles

This study investigates the effects of thermal treatment and silver nanoparticles on the mechanical and thermal properties of additively manufactured wood/polylactic acid (PLA) specimens. The 5 and 10 wt% additions of the wood flour into the PLA matrix are done in the twin screw extruder. The test specimens are produced from the filaments with a diameter of 1.75 mm using 3D printer. The mechanical properties of the 3D-printed wood/PLA specimens are affected by the wood flour content, thermal treatment of wood, and silver nanoparticles. The 3D-printed neat PLA specimens have better mechanical properties than the wood flour-filled PLA specimens. The bending strength of the specimens enhances with increasing wood flour content while the tensile strength decreases. The increases in the mechanical properties reveal that the thermal treatment of the wood improves the compatibility between wood and PLA matrix, which hereby improves the interfacial adhesion. The addition of the silver nanoparticles positively affects the mechanical properties and it is more compatible with thermally modified wood particles as compared to the untreated wood particles.     

Influence of montmorillonite layered silicate on plasticized poly(l-lactide) blown films

Plasticized poly(l-lactide) (PLA) montmorillonite layered silicate (MLS) nanocomposites were compounded and blown-film processed using a co-rotating twin screw extruder. PLA was mixed with 10 wt% acetyltriethyl citrate ester plasticizer and 5 wt% of an organically modified montmorillonite at various screw speeds. Wide-angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM) determined that the compounded pellets and the blown film PLA/MLS nanocomposites were intercalated. The effect of processing screw speeds on the barrier, thermal, mechanical, and biodegradation properties of the nanocomposites were analyzed and compared to the neat polymer. Nanocomposite films show a 48% improvement in oxygen barrier and a 50% improvement in water vapor barrier in comparison to the neat PLA. The thermogravimetric analysis (TGA) showed an overall 9 °C increase in the decomposition temperature for all of the nanocomposites. Differential scanning calorimetry (DSC) has determined that the glass transition, cold crystallization and melting point temperatures were not significantly influenced by the presence of MLS. Mechanical properties of the nanocomposites showed that the Young's modulus increased by 20% and the ultimate elongation of the nanocomposites were not sacrificed in comparison to the neat samples. Biodegradation rates in soil were slightly greater for the PLA/MLS nanocomposite than the pure PLA. However, none of the PLA pure and nanocomposites achieved significant biodegradation levels after 180 days.     

Poly(lactic acid) blends with desired end-use properties by addition of thermoplastic polyester elastomer and MDI

The disadvantages of the poor mechanical properties of polylactic acid (PLA) limit its ability to be used in a wide number of applications. Melt blending of PLA and thermoplastic polyester elastomer (TPEE) has been performed in an effort to toughen the PLA without significant losses in modulus and ultimate tensile strength. In order to enhance the compatibility of PLA and TPEE, a diisocyanate compound was used as a reactive modifier. The thermal and mechanical properties, miscibility and phase morphologies of the blends were investigated. A blend of PLA and TPEE with a modifier does not lead to an important drop in tensile strength and modulus whereas the elongation at break is characterized by a significant increase (above 300%), compared with that of neat PLA and PLA/TPEE. The blends of PLA/TPEE/Modifier were found by thermal and fractured surface analysis to be an immiscible system with the addition of a modifier. However, the relative ductility of PLA/TPEE/Modifier is 34 times higher than that of neat PLA. The brittle fracture of neat PLA was transformed into a ductile fracture by the addition of a modifier.     

聚乳酸/DMSO增塑淀粉复合材料的制备与表征

采用聚乳酸分别和纯淀粉及二甲基亚砜(DMSO)塑化淀粉进行共混制备了淀粉/聚乳酸复合材料,通过力学性能测试,DSC测试,TG分析及SEM观察发现淀粉含量增加,材料力学性能降低,而经DMSO塑化淀粉共混物虽然其拉伸强度等力学性能降低,但冲击强度和弯曲应变均提高,且复合材料结晶度有较大提高,DMSO质量分数为3%时,复合材料的冷结晶温度降低9.4℃,熔融温度降低2.2℃。纯淀粉和聚乳酸共混复合材料呈现明显的两相结构,加入DMSO之后,界面黏结加强,呈现均相特征。     

Enhancing the mechanical properties of 3D printed polylactic acid using nanocellulose

We report here a systematic investigation of the mechanical properties of polylactic acid (PLA) processed by fused filament fabrication (FFF) 3D printing vs PLA processed by compression molding. Our results show that the tensile strength and modulus of FFF-PLA is 49% and 41% lower, respectively, than compression molded samples of PLA. We also demonstrate here an approach to augment the mechanical properties of 3D printed PLA using nanocellulose. Incorporation of a small quantity (1 wt%) of cellulose nanofibers (CNF) was found to enhance the tensile strength and modulus of 3D printed PLA by 84% and 63%, respectively. X-ray microtomography was used to probe the morphology of 3D printed PLA and PLA/CNF composites. 3D printed PLA/CNF composites had significantly lesser voids as compared to neat 3D printed PLA. Differential scanning calorimetry study revealed that CNF can accelerate the nucleation and crystallization of 3D printed PLA leading to enhanced crystallinity. The thermal stability of 3D printed PLA/CNF composites was not compromised by the addition of CNF. The enhanced mechanical properties of 3D printed PLA/CNF composites can be ascribed to higher crystallinity and lesser defects.     

Highly Tough and Thermally Stable Polylactide Blends Compatibilized with Glycidyl Methacrylate-Grafted Polypropylene

To attain eco-friendly and sustainable polylactide (PLA) materials possessing highly enhanced toughness, thermal stability, and processability without significant loss in elastic modulus, for the first time, PLA-dominant blends with 1–30 wt% glycidyl methacrylate-grafted polypropylene (PPGMA) loadings are fabricated via an efficient masterbatch melt-compounding process. For the purpose, PPGMA is fabricated via in situ grafting reaction of PP with GMA and styrene. The scanning electron microscope images reveal that PLA/PPGMA blends do not show recognizable phase-separated domains, unlike immiscible PLA/PP blends. The Fourier-transform infrared spectroscopic and melt-rheological analyses support the presence of specific interactions between PLA and PPGMA as well as the compatibilizing effect of PPGMA-g-PLA formed during the melt-compounding. The thermal analyses demonstrate that PPGMA component accelerates the crystallization of PLA in the blends and that the thermal decomposition temperatures of PLA/PPGMA blends are higher than those of neat PLA and PPGMA components. The dynamic mechanical analysis shows that a maximum storage modulus is attained for PLA-dominant blend with 30 wt% PPGMA. Noticeably, the impact strength (≈305.6 J m⁻¹) of PLA-dominant blend with only 5 wt% PPGMA loading is almost three times higher than that (≈111.6 J m⁻¹) of neat PLA and it is very comparable to the value (≈316.9 J m⁻¹) of neat PP.     

Assessment of mechanical performance,thermal stability and water resistance of novel conductive poly(lactic acid)/modified natural rubber blends with low loading of polyaniline

Biodegradable conductive polymer blends made from poly(lactic acid) (PLA), liquid natural rubber (LNR) and polyaniline (PANI) were prepared via a melt‐blending technique assisted by ultrasonic treatment. The effects of PANI at low loading (0.03 to 0.11 wt%) on the electrical conductivity and mechanical, thermal and physical properties of PLA/LNR/PANI blends were investigated. It was found that the mechanical properties of samples improved when PANI was introduced into PLA/LNR. Tensile results showed that the optimum loading of PANI was achieved at 0.07 wt% with an improvement of 8% in tensile strength compared to neat PLA/LNR. Although it was at low loading, the incorporation of PANI promoted an outstanding electrical conductivity to PLA/LNR blends. Thermal analysis of the PLA/LNR/PANI blends was conducted using differential scanning calorimetry and thermogravimetry. The thermal stabilities of the blends were improved markedly with the presence of PANI. Comparing to PLA/LNR, the incorporation of PANI component improved the resistance towards water absorption. Variable‐pressure scanning electron microscopy micrographs of PLA/LNR/PANI confirmed the good mixing of PANI with PLA/LNR and strong interaction networks among the PANI, PLA and LNR components. © 2018 Society of Chemical Industry     

Improvement in toughness and crystallization of poly(L‐lactic acid) by melt blending with ethylene/methyl acrylate/glycidyl methacrylate terpolymer

Melt blending of poly(lactic acid) (PLA) and ethylene/methyl acrylate/glycidyl methacrylate terpolymer (EGA) containing relatively high‐concentration epoxide groups (8 wt%) was performed to improve the toughness and crystallization of PLA. The results of nonisothermal and isothermal crystallization investigation showed that the addition of EGA accelerated the crystallization rate and increased the final crystallinity of PLA in the blends. Significant enhancement in toughness and flexibility of PLA were achieved by the incorporation of the EGA elastomer. When 20 wt% EGA added, the impact strength increased from 3.0 kJ m^?2 of neat PLA to 59.8 kJ m^?2 and the elongation at break increased from 4.9 to 232.0%. The failure mode changed from brittle fracture of neat PLA to ductile fracture of the blend. POLYM. ENG. SCI., 53:2498–2508, 2013. © 2013 Society of Plastics Engineers     

Poly(lactic acid)/ethylene vinyl acetate copolymer blend composites with wood flour and wollastonite: Physical properties,morphology, and biodegradability

In the present study, poly(lactic acid) (PLA), a biodegradable plastic, was melt‐blended with five weight percentages (10–50 wt%) of ethylene vinyl acetate (EVA) copolymer, a non‐biodegradable plastic, having a vinyl acetate content of 19 wt% and a melt flow index of 530 g/10 min, on a twin screw extruder, followed by an injection molding. The blends at 10 and 20 wt% EVA revealed a noticeably increased impact strength and strain at break over the pure PLA, and the blend at 10 wt% EVA exhibited the highest impact strength and strain at break. The 90/10 (wt%/wt%) PLA/EVA blend was then selected for preparing either single or hybrid composite with wood flour (WF) and wollastonite (WT). The filler loading was fixed at 30 parts by weight per hundred of resin throughout the experiment, and the WF/WT weight ratios were 30/0, 20/10, 15/15, 10/20, and 0/30. The prepared composites were examined for their mechanical and thermal properties, melt flow index, flammability, water uptake, and biodegradability as a function of composition. All the composites showed a filler‐dose‐dependent decrease in the impact strength and strain at break, but an increase in the tensile and flexural modulus (optimal at 0/30 WF/WT) and tensile and flexural strength (optimal at 30/0 WF/WT) as compared with the neat 90/10 (wt%/wt%) PLA/EVA blend. In addition, the melt flow index, char residue, anti‐dripping ability, water uptake, and biodegradability of the composites were also higher than those of the neat blend. J. VINYL ADDIT. TECHNOL., 25:313–327, 2019. © 2019 Society of Plastics Engineers     

Effects of thermoplastic polyurethane on the properties of poly(lactic acid)/organo‐montmorillonite nanocomposites based on novel vane extruder

Polylactic acid (PLA)/organo‐montmorillonite (OMMT) nanocomposites toughened with thermoplastic polyurethane (TPU) were prepared by melt‐compounding on a novel vane extruder (VE), which generates global dynamic elongational flow. In this work, the mechanical properties of the PLA/TPU/OMMT nanocomposites were evaluated by tensile, flexural, and tensile tests. The wide‐angle X‐ray diffraction and transmission electron microscopy results show that PLA/TPU/OMMT nanocomposites had clear intercalation and/or exfoliation structures. Moreover, the particles morphology of nanocomposites with the addition of TPU was investigated using high‐resolution scanning electronic microscopy. The results indicate that the spherical TPU particles dispersed in the PLA matrix, and the uniformity decreased with increasing TPU content (≤30%). Interestingly, there existed abundant filaments among amount of TPU droplets in composites with 30 and 40 wt% TPU. Furthermore, the thermal properties of the nanocomposites were examined with differential scanning calorimeter and dynamic mechanical analysis. The elongation at break and impact strength of the PLA/OMMT nanocomposites were increased significantly after addition of TPU. Specially, Elongation at break increased by 30 times, and notched impact strength improved 15 times when TPU loading was 40 wt%, compared with the neat PLA. Overall, the modified PLA nanocomposites can have greater application as a biodegradable material with enhanced mechanical properties. POLYM. ENG. SCI., 54:2292–2300, 2014. © 2013 Society of Plastics Engineers     

Physico-chemical,thermal, and mechanical properties of PLA-nHA nanocomposites: Effect of glass fiber reinforcement

In this study, tri-layered composites were prepared by reinforcing poly-lactic acid (PLA) nano-hydroxyapatite (n-HA) (1 and 5 wt%) and 20 mol% continuous phosphate glass fibers (PGF). Initially, the effect of addition of 1 and 5% n-HA on the structural, thermal, mechanical, and thermo-mechanical properties of 100% PLA was investigated. With 5 wt% n-HA addition the tensile modulus (TM), flexural modulus (FM), tensile strength (TS), and flexural strength (FS) of 100% PLA was improve by 14.9, 47.4, 6, and 32.9%, respectively. Whereas, the un-notched impact strength of the nanocomposites suffer 2% deterioration. However, T _g decreased by 0.3°C and T _c increased by 10°C as 5 wt% n-HA was added to 100% PLA. Afterwards, the 5% n-HA/PLA composite were reinforced with 20 mol% continuous PGF and the TM, FM, TS, and FS of the tri-layered composites were 162.6, 412.5, 28.4, and 157.4% higher as compared to 100%PLA. Furthermore, the storage modulus of the 1% n-HA-filled composites was 500 MPa lower than 100%PLA, while 5 wt% n-HA-filled composites showed similar storage modulus as 100% PLA. 5 wt% n-HA-filled composite showed the highest peak of loss modulus which may be attribute to the chain segment of PLA matrix after the incorporation of HA. Thus, n-HA and PGF reinforcement resulted in improved mechanical properties of the composites and have great potential as biodegradable bone fixation device with enhanced load-bearing ability.     

Mechanical,morphological, thermal properties and hydrolytic degradation behavior of polylactic acid/polypropylene carbonate blends prepared by solvent casting

The preparation of polylactic acid (PLA) and polypropylene carbonate (PPC) blend films by using the solvent casting method is to improve the properties of pure PLA. The blends' mechanical and thermal properties, morphological as well as hydrolytic degradation behavior are evaluated. The tensile test proved that the increase of PPC from 0 wt% to 75 wt% could improve the elongation of pure PLA when the graph showed a significant increase of the elongation from 10% to 1000%. Scanning Electron Microscopy (SEM) supported the significant increase in elongation of the blends when it shows a definite phase separation in 75/25 PLA/PPC, where 25% of PPC has formed islands in the PLA matrix. Differential scanning calorimetry indicates the partial miscibility of the blends where two peaks of the glass transition temperature moved towards each other when the amount of PPC increases. Fourier transform infrared (FTIR) spectroscopy revealed a possible intermolecular interaction between two polymers, which affects the miscibility of the blends. Finally, the hydrolytic degradation test indicates that the degradation started from the PLA phase and the blends' degradation rate decrease as wt% of PPC increase.     

Ductile PLA modified with methacryloyloxyalkyl isocyanate improves mechanical properties

The majority of the biodegradable polymers in clinical use are composed of stiff materials that exhibit limited extendibility with unsuitably high Young’s modulus and low elongation at break values that make them non-optimal for various biomedical applications. Polylactide (PLA) is often used as a biomedical material because it is biodegradable, but the physical and mechanical properties of PLA need to be improved for biomedical applications. In order to improve the flexibility and strength of biodegradable PLA, various reaction conditions were studied. Urethane structure polymer materials were prepared; PLA was reacted with a small amount of methacryloyloxyethyl isocyanate (MOI) to obtain a ductile PLA with markedly improved mechanical properties. Elongation at break increased by 20 times when compared to neat PLA. Impact resistance (notched) improved 1.6 times. Thus, this modified PLA biodegradable polymer may have greater application as a biomedical material with increased mechanical properties.     

Plasticization of poly(lactic acid) with oligomeric malonate esteramides: Dynamic mechanical and thermal film properties

Two oligomeric malonate esteramides and an oligomeric malonate ester were synthesized with the intention to plasticize poly(lactic acid), PLA. The synthesis was performed by reacting diethyl bishydroxymethyl malonate (DBM) with adipoyl dichloride and one of two diamines, that is, triethylene glycol diamine (TA) and polyoxypropylene glycol diamine (PA), or triethylene glycol (TEG), giving three platicizing agents denoted as DBMATA, DBMAPA, and DBMAT, respectively. The synthesis products were characterized by size exclusion chromatography and Fourier transform infrared spectroscopy, and blended with PLA at a concentration of 15 wt %. Dynamic mechanical analysis, differential scanning calorimetry, and tensile testing were used to investigate the physical properties of films from the resulting blends. All three plasticizers decreased the glass transition temperature of PLA, and the largest decrement was observed for PLA/DBMATA. Films of DBMATA and DBMAT showed enhanced flexibility in strain at break as compared to neat PLA. Subsequently, it was found that thermal annealing of the plasticized materials (4 h at 100°C) encouraged cold crystallization, inducing phase separation in the blends, and caused them to regain the brittleness of neat PLA. On the other hand, by aging (6 weeks) the blends at ambient conditions, cold crystallization could be avoided and the flexibility in the films maintained. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 992–1002, 2005