Characterization of lignocellulosic–poly(lactic acid) reinforced composites

The effects of adding poly(lactic acid) (PLA) to the physical strength of paper test sheets prepared from three unbleached loblolly pine kraft pulps with different amounts of lignin and an aspen bleached chemothermomechanical pulp were studied. The physical strength studies demonstrated that relatively low levels of PLA addition (0.5–4.0%) could dramatically improve the tensile and burst strength properties as a function of the amount of PLA added. Hot pressing the test sheets was shown to be an important treatment for enhancing the strength properties. An analysis of untreated and PLA‐treated hot‐pressed test sheets by atomic force microscopy indicated that the addition of PLA markedly altered the surface properties of the sheets. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1346–1349, 2006     

Water bamboo husk‐reinforced poly(butylene succinate) biodegradable composites

The water bamboo husk is one of major agricultural wastes in Taiwan. In this study, the fiber and powder obtained from the water bamboo husk were chemically modified by coupling agents. Furthermore, the modified fiber and powder were added to the biodegradable polymer poly(butylene succinate) (PBS) separately, to form novel fiber‐reinforced composites. Morphologies, mechanical properties, and heat resistance of these water bamboo husk‐reinforced composites were investigated. The results indicate that the fibers modified by coupling agents exhibited better compatibility with the polymer matrixes than did the untreated fibers. Moreover, it is found that the thermal properties were improved as plant fiber was incorporated to those polymers. Furthermore, the mechanical properties were also increased with the addition of coupling agent‐treated fiber. On the other hand, it is found that the homogeneity of untreated powder‐containing samples is better than that of untreated fiber‐containing samples. Moreover, the results reveal that the powders modified with coupling agents were not effective in improving the mechanical properties of the reinforced PBS. This is due to the bulky structure of lignin leading to a smaller reaction ratio with the coupling agents. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 188–199, 2006     

Halloysite nanotubes immobilized by chitosan/tannic acid complex as a green flame retardant for bamboo fiber/poly(lactic acid) composites

In order to develop an environmentally benign flame retardant for bamboo/PLA composites (BPC), chitosan (CS) and tannic acid (TA) were used as cationic and anionic polyelectrolyte respectively to stabilize halloysite nanotubes (HNT) on the surface of bamboo fiber (BF) and poly(lactic acid) (PLA). Mechanical performance tests showed that the flexural properties of BPC were moderately enhanced with the addition of HNT, while the incorporation of CS/TA complex (FR) exhibited a slight increase. The results of thermogravimetric analysis demonstrated that CS/TA complex and HNT improved the thermal stability of the BPC synergistically, which increased the char residue. Limiting oxygen index and cone calorimetry tests were used to study the flammability of BPC and the results showed that the addition of CS/TA complex and HNT had a synergistic effect on the flame retardant performance of BPC materials. The macroscopic and microscopic morphological studies confirmed the formation of HNT layer in the matrix of BPC/5FR@5HNT samples, which facilitated more stabile char residue with the best flame retardant performance.     

Preparation of single poly(lactic acid) composites

An approach for making poly(lactic acid) (PLA) single‐polymer composites (SPCs) on the basis of PLA's slowly crystallizing characteristics was investigated. As a slowly crystallizing polymer, PLA can be processed with standard polymer processing techniques into end‐use products with varied crystallinities, from amorphous films to highly crystalline fibers. In this study, amorphous PLA sheets and crystalline PLA fibers/fabrics were laminated and compression‐molded to form an SPC at a processing temperature substantially lower than PLA's melting temperature. The effects of the major process conditions on the performance of the SPC were studied. The processing temperature played a profound role in affecting the fiber–matrix bonding properties. As the processing temperature increased, a drastic improvement in the interfacial bonding occurred at a temperature of around 135°C, which indicated the lower boundary of the process window. The compression‐molded SPC exhibited enhanced mechanical properties; particularly, the tearing strength of the fabric‐reinforced SPC was almost an order higher than that of the nonreinforced PLA. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Core‐shell structure of carbon nanotube nanocapsules reinforced poly(lactic acid) composites

In this study “core‐shell” structure of carbon nanotube (CNT) nanocapsules, which aimed at toughening poly(lactic acid) (PLA) were designed by a synthetic strategy consisting of two reaction steps. The first step was to produce reactive chemical bond to bridge CNTs and PLA. So coupling agent KH570 was used to modify CNTs (CNTs‐KH570). The second step involved ring open polymerization of lactide (LA). Lactide polymerized into PLA under catalysis and meanwhile grafted onto CNTs via KH570 (CNTs‐KH570‐PLA). Thus, the CNTs nanocapsules were constructed. Fourier transform infrared spectroscopy (FTIR) showed coupling agent KH570 succeeded in linking CNTs and PLA during LA polymerization. In addition, scanning electron microscopy (SEM) and transmission electron microscope (TEM) indicated CNTs dispersed homogeneous in PLA matrix and the compatibility between them was excellent. The mechanical test also suggested the designed nanocapsules had good effect on toughening PLA composites. This research found one economical and simple way to improve PLA mechanical properties and further broaden its application in many fields. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44919.     

Fabrication of reinforced and toughened poly(lactic acid)/poly(butylene adipate-co-terephthalate) composites through solid die drawing process

In this study, poly(butylene adipate-co-terephthalate) (PBAT) was introduced to poly(lactic acid) (PLA) matrix to improve its inherent poor toughness. Besides, the orientation structure was also introduced via die drawing process to compensate for strength loss. The results indicate that die drawing process contributes to improve the mechanical properties of PLA. The tensile strength, modulus, and elongation at break of die-drawn pure PLA increased by 76.6, 36.1, and 1,375.0%, respectively, compared with those of isotropic PLA. Moreover, the tensile strength can be further improved by the addition of PBAT. The die drawing process can remarkably improve crystallinity, and the orientation factor is high when the PBAT content is less than 30 wt%. By combining the PBAT with highly oriented structure imported by die drawing process, it is possible to prepare simultaneously reinforced and toughened materials, which provides a new insight into the modification of PLA.     

Development of ductile green flame retardant poly(lactic acid) composites using hydromagnesite&huntite and bio-based plasticizer

Turning brittle poly(lactic acid) (PLA) to ductile form via plasticizer inclusion is an effective option in the case of processing with high amounts of additives. Additionally, the integration of natural flame retardants to PLA involving bio-based plasticizer enables to use of environmentally friendly composites in conditions where fire resistance performance is required. In the current study, ductile green fire retardant PLA composites were manufactured using hydromagnesite&huntite (HH) as a natural fire retardant additive and acetyl tributyl citrate as a bio-based plasticizer. The influences of plasticizer and HH contents on the fire retardant, thermal and mechanical performances of the composites were explored. According to test results, the limiting oxygen index (LOI) value of PLA reduced from 29.2 to 28.0 and the UL-94 V rating changed from V2 to BC with the addition of 20 wt% plasticizer owing to the reduction in melt viscosity. The peak heat release rate (pHRR) and average heat release rate (avHRR) values increased steadily as the concentration of plasticizer increased due to the formation of a more porous residue structure stemming from the increased transportation rate of gases. In order to produce ductile flame retardant material, the plasticizer content was required to 20 wt% of HH. The highest LOI value (36.2) and UL-94 rating of V0 were achieved with the inclusion of 70 wt% HH in the presence of 20 wt% plasticizer. Improvement in impact resistance and reduction in tensile strength were observed as the added amount of plasticizer increased.     

Utilization of linseed cake as a postagricultural functional filler for poly(lactic acid) green composites

Linseed cake (LC), a byproduct of linseed oil extraction, is used as a functional filler for production of biodegradable composites. To determine the influence of residual linseed crude oil contained in lignocellulosic filler on the properties of the poly(lactic acid) (PLA)-based composites with 5–30% filler content, two types of LC were analyzed: a defatted and an unmodified one. Complex analysis of the composites' properties change was conducted in relation to their structure modification caused by the addition of a waste filler. It was found that the addition of LC resulted in simultaneous plasticization and improved crystallization of PLA. Lignocellulosic particles and crude linseed oil contained in the LC powder provided a modifying effect, influencing the level of crystallinity and mechanical and thermomechanical properties. Using LC may thus overcome one of the main drawbacks of PLA, which is brittleness and low crystallinity. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47152.     

Biodegradable composites of poly(butylene succinate‐co‐butylene adipate) reinforced by poly(lactic acid) fibers

Biodegradable composites of poly(butylene succinate‐co‐butylene adipate) (PBSA) reinforced by poly(lactic acid) (PLA) fibers were developed by hot compression and characterized by Scanning electron microscopy (SEM), differential scanning calorimetry (DSC), dynamic mechanical analyzer, and tensile testing. The results show that PBSA and PLA are immiscible, but their interface can be improved by processing conditions. In particular, their interface and the resulting mechanical properties strongly depend on processing temperature. When the temperature is below 120 °C, the bound between PBSA and PLA fiber is weak, which results in lower tensile modulus and strength. When the processing temperature is higher (greater than 160 °C), the relaxation of polymer chain destroyed the molecular orientation microstructure of the PLA fiber, which results in weakening mechanical properties of the fiber then weakening reinforcement function. Both tensile modulus and strength of the composites increased significantly, in particular for the materials reinforced by long fiber. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43530.     

茶粉/聚乳酸复合材料的增韧改性

为高值化利用茶产业剩余物资源,以茶粉（TD）为生物质填料,聚乳酸（PLA）为基体,以甘油（GL）、聚乙二醇400（PEG400）、环氧大豆油（ESO）和乙酰柠檬酸丁酯（ATBC）为增塑剂,制备了可降解TD/PLA增韧复合材料,并采用红外吸收光谱、热重分析、转矩流变仪、扫描电镜及力学性能测试等考察了增塑剂对TD/PLA复合材料结构与性能的影响。结果表明：4种增塑剂都可改善TD/PLA复合材料的加工流变性,GL的添加不利于复合材料韧性,PEG、ATBC及ESO的添加提高了复合材料韧性,其中ESO增韧效果最佳,其添加制备的复合材料断裂伸长率及缺口冲击强度分别提高了154.23%和65.53%,GL增韧效果最差,ATBC增韧后复合材料力学强度和模量最高。FTIR分析表明,ATBC和ESO可与PLA发生一定相互作用,使C-O键红外吸收峰位增大,其增韧后复合材料吸水率下降。ESO添加提高了TD/PLA复合材料的维卡软化点和热稳定性。SEM图片显示,TD/PLA/ESO复合材料断面粗糙,ESO分散较均匀,与PLA部分相容,而TD/PLA/GL复合材料断面出现严重相分离结构。该研究结果可为进一步探索聚乳酸基茶塑复合材料制备及应用提供试验数据和理论参考。     

Study on flax fiber toughened poly (lactic acid) composites

Poly (lactic acid) (PLA) is a renewable and biodegradable polymer with high modulus, high strength but low toughness. Blending PLA with plant fiber has been believed an available strategy to improve the toughness of PLA. PLA/Flax composites were fabricated by extrusion and injection molding processes. The flax fiber surfaces were modified before blending to improve the compatibility, and the chemical structures of both untreated and treated fiber were characterized by Fourier transform infrared spectroscopy. Results of mechanical test showed that the impact strength and elongation at break of PLA/Flax composites were remarkably higher than PLA. The impact fractures of PLA/Flax composites were also observed by scanning electron microscope. The results showed uniform dispersion of fibers in PLA matrix and good compatibility between treated fibers and PLA matrix. Moreover, it can be observed that crazing propagation was hindered by fibers and transcrystalline developed along fibers by polarized optical microscope. Differential scanning calorimetry analysis was carried out to study the crystallinity of PLA and it was found that incorporation of fiber improved the crystallinity of PLA. The toughening mechanism of PLA/Flax composites was discussed according to the results. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42573.     

Preparation of poly(lactic acid) and modified starch composites

In this article, the pretreatment before extrusion between the PLA and the modified starch was researched. The research on the composites of PLA and the modified starch focused on improving its compatibility and mechanical properties. The pretreatment samples were characterized by solid ¹³C-NMR and the chemical titration of the carboxyl end (–COOH) groups in PLA. The results illuminated that the pretreatment reaction was successful and the –COOH in PLA had reacted with the –OH in modified starch. The compatibility of the composites was determined by differential scanning calorimetry and scanning electron microscopy. The results showed that pretreatment could improve the compatibility of the composites. The mechanical properties of the composites were also enhanced. This approach is identified as a reasonable method to produce commercial PLA/modified starch composites with economical feasibility.     

马来酸酐/二乙烯基苯接枝聚乳酸对微晶纤维素/聚乳酸复合材料性能的影响

研究了马来酸酐(MAH)/二乙烯基苯(DVB)接枝聚乳酸(PLA-g-DVB/MAH)对微晶纤维素(MCC)/聚乳酸(PLA)复合材料性能的影响。首先采用熔融接枝法,将DVB作为MAH的共聚单体接枝到PLA分子链上制备PLA-g-DVB/MAH接枝聚合物,然后以PLA-g-DVB/MAH为相容剂,采用注射成型法制备MCC/PLA复合材料。利用FTIR对PLA-g-DVB/MAH进行表征,探究了PLA-g-DVB/MAH对MCC/PLA复合材料流变及力学性能的影响。结果表明,MAH成功接枝到PLA上,并得到接枝聚合物PLA-g-DVB/MAH;添加PLA-g-DVB/MAH后,MCC/PLA复合材料的储能模量、复数黏度、平衡扭矩以及剪切热都有明显升高;PLA-g-DVB/MAH的添加有利于改善MCC和PLA的界面相容性,进而提高了MCC/PLA复合材料的力学性能。     

Mechanical and thermal properties of wood fibers reinforced poly(lactic acid)/thermoplasticized starch composites

Thermoplasticized starch (TPS) filled poly(lactic acid) (PLA) blends are usually found to have low mechanical properties due to poor properties of TPS and inadequate adhesion between the TPS and PLA. The purpose of this study was to investigate the reinforcing effect of wood fibers (WF) on the mechanical properties of TPS/PLA blends. In order to improve the compatibility of wood with TPS/PLA blends, maleic anhydride grafted PLA (MA‐g‐PLA) copolymer was synthesized and used. TPS, TPS/PLA blends, and WF reinforced TPS/PLA composites were prepared by twin‐screw extrusion and injection molded. Scanning electron microscope and crystallinity studies indicated thermoplasticity in starch. WF at two different weight proportions, that is, 20% and 40% with respect to TPS content were taken and MA‐g‐PLA at 10% to the total weight was chosen to study the effect on mechanical properties. At 20% WF and 10% MA‐g‐PLA, the tensile strength exhibited 86% improvement and flexural strength exhibited about 106% improvement over TPS/PLA blends. Increasing WF content to 40% further enhanced tensile strength by 128% and flexural strength by 180% with respect to TPS/PLA blends. Thermal behavior of blends and composites was analyzed using dynamic mechanical analysis and thermogravimetric analysis. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46118.     

New poly(lactic acid) composites produced from coffee beverage wastes

In this study, aiming to reduce the environmental impact of plastics, new composite materials containing recycled fibers from used paper coffee cups and oil extracted from spent coffee grounds (SCG) were produced. Accordingly, the cellulose fibers were chemically modified using lactic acid to be used as poly(lactic acid) filler reinforcement. The obtained results revealed that its addition improved the mechanical properties of the ensuing composites. The addition of 30% wt/wt of unmodified and modified fibers increased the Young modulus by 53% and 72%, respectively. In addition, enhanced biodegradability was obtained due to higher water absorption (up to 4% wt/wt). In parallel, coffee oil was used as a plasticizer and the affinity between the plasticizer and polymer matrix was confirmed by the lack of phase separation, by the improved flexibility of derived materials (the addition of 40% wt/wt of plasticizer increased the elongation at break by 86%) and by the better processability of the ensuing materials (the addition of 30% wt/wt of plasticizer increased the MFI by 205%). Overall, the results suggest that the use of modified cellulose fibers and the addition of SCG oil-based plasticizer can be promising routes to produce eco-friendly plastics.     

Effect of bismaleimide reactive extrusion on the crystallinity and mechanical performance of poly(lactic acid) green composites

Poly(D ‐,L ‐lactic acid) (PDLA) and PDLA‐wood pulp fiber injection molded composites were modified with very small amounts (< 1 wt %) of N′‐(o‐phenylene)dimalemide and 2,2′‐dithiobis(benzothiazole) by reactive extrusion and their resulting mechanical and thermal properties characterized. The modification produced an increase in the percent crystallinity (X_c), heat deflection temperature (HDT), impact energy, tensile strength, and modulus in PDLA. A significant reduction in the melting temperature (T_m) and an increase in the thermal resistance (T_max) were also found. Fourier‐Transform infrared spectroscopy (FTIR) suggests the creation of hydrogen bonds, a thiol ester and/or ester bond during the modification. Reactive extrusion of commercially available poly(lactic acid) (PLA) by means of N′‐(o‐phenylene)dimalemide and 2,2′‐dithiobis(benzothiazole) provides a low cost and simple processing method for the enhancement of the properties of this biopolymer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Additive manufacturing of green composites: Poly (lactic acid) reinforced with keratin materials obtained from Angora rabbit hair

In this research, additive manufacturing of polylactic acid (PLA) reinforced with keratin was studied. Keratin was obtained from Angora rabbit hair and modified with NaOH. Scanning electron microscopy (SEM) images showed that the modified surfaces were rougher than untreated surfaces. Furthermore, SEM images in the composites' fracture regions showed surface changes, associated with the nature of the reinforcement. Likewise, thermomechanical properties of the composites were attributed to the nature of the reinforcement and the type of keratin. Besides, the 3D printed composites showed higher thermal conductivity values than PLA with the addition of keratin. Cytotoxicity tests revealed an improvement in cell growth compared to the control and PLA. These results are meaningful toward the development of high thermal conductors and biocompatible composites with applications in different fields, where the use of only natural polymers is necessary.     

Enhanced biodegradation and processability of biodegradable package from poly(lactic acid)/poly(butylene succinate)/rice-husk green composites

This work aims to study the possibility to process PLA/PBS/RH green composites into hexagonal plant-pots employing a large-scale industrial operation using injection molding. Green composites based on poly(lactic acid) (PLA), poly(butylene succinate) (PBS), and rice husk (RH) with various RH contents (10–30%wt.) were produced successfully using a twin-screw extruder. The compatibility of RH-matrix was improved by chemical surface modifications using a coupling agent. RH was analyzed as an effective filler for PLA to develop green composites with low cost, high biodegradability, improved processability, and comparable mechanical properties as unfilled PLA. With increasing RH content, tensile modulus of the composites increased gradually. The addition of PBS, at PLA/PBS ratio of 60/40, improved the elongation at break and impact strength of PLARH30 by 55% and 7.1%, respectively. The suitable processing temperatures for PLA decreased from 220–230°C to 170–180°C when 30%wt. RH was composited into PLA matrix and were further reduced when PBS was applied. After biodegradation via either enzymatic degradation or hydrolysis, surface erosion with a large number of voids, mass loss, and the substantial decrease in tensile strength of all the composites were observed. In addition, the biodegradation of the composites has been improved by the addition of either RH or PBS.     

Enhancing the durability of poly(lactic acid) composites by nucleated modification

Biodegradable poly(lactic acid) (PLA) composites were prepared using an innovative combination of wood fiber (WF) and 1,3,2,4‐bis(3,4‐dimethylobenzylideno)sorbitol (DMDBS). DMDBS acted as an effective nucleating agent, which improved the mechanical properties and slowed down the degradation of the WF/PLA composites. The enzymatic degradation of the composites was examined by immersing in proteinase K or cellulase buffer. The presence of DMDBS resulted in a 26.7% increase of the crystallinity compared to the WF/PLA composites. The increase in crystallinity enhanced the thermal stability and tensile strength of the WF/DMDBS/PLA composites by 8.5%. The durability of the WF/DMDBS/PLA composites after nucleated modification was enhanced after enzymolysis. After nucleated modification, the surface of the WF/PLA composites showed clear cracks due to degradation, while these appeared about 2 weeks later in the case of the WF/DMDBS/PLA composites. The results revealed that the introduction of cellulase degraded WF in the composites, which increased hydrolysis or enzymolysis sites. The combination of nucleated modification and enzyme buffer gave an expanded downstream application of WF/PLA composites in packaging and agricultural materials. © 2019 Society of Chemical Industry