Preparation and properties of self-reinforced poly(lactic acid) composites based on oriented tapes

The inherent brittleness and poor thermal resistance of poly(lactic acid) (PLA) are two main challenges toward a wider industrial application of this bioplastic. In the present work, through the development of self-reinforced PLA (SR-PLA) or “all-PLA” composites, the high brittleness and low heat deflection temperature (HDT) of PLA have been overcome, while simultaneously improving the tensile strength and modulus of SR-PLA. The obtained composites are fully biobased, recyclable and under the right conditions compostable. For the creation of SR-PLA composites, first a tape extrusion process was optimized to ensure superior mechanical properties. The results show that SR-PLA composites exhibited enhanced moduli (2.5 times) and tensile strengths (2 times) and showed 14 times increase in impact energy compared to neat PLA. Finally, the HDT of SR-PLA was also increased by about 26 °C compared to neat PLA, mainly as a result of an increase in modulus and crystallinity.     

超细硫酸钡和轻质碳酸钙协同增韧聚乳酸混杂材料的制备及性能

采用熔融共混和模压成型工艺制备超细硫酸钡(BaSO_4)和轻质碳酸钙(CaCO_2)协同增韧聚乳酸(PLA)混杂材料。在保持CaCO_2质量分数恒定的情况下,着重考察了BaSO_4的含量对混杂体系的微观结构、力学性能、熔体流动速率和热稳定性的影响。结果表明:适量BaSO_4的引入在基体中分散均匀且界面结合良好,显著提高了材料的韧性。当BaSO_4的质量分数为15%时,PLA混杂材料的冲击韧度和断裂伸长率较PLA/CaCO_2体系分别提高了60.38%和151.90%。随着BaSO_4含量的增加,拉伸强度逐渐下降,而弹性模量却持续上升。总体上,BaSO_4的引入降低了PLA混杂材料的熔体流动速率,但对PLA的热分解行为影响甚微。     

Stretchable Light‐Emitting Diodes with Organometal‐Halide‐Perovskite–Polymer Composite Emitters

Intrinsically stretchable light‐emitting diodes (LEDs) are demonstrated using organometal‐halide‐perovskite/polymer composite emitters. The polymer matrix serves as a microscale elastic connector for the rigid and brittle perovskite and induces stretchability to the composite emissive layers. The stretchable LEDs consist of poly(ethylene oxide)‐modified poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate as a transparent and stretchable anode, a perovskite/polymer composite emissive layer, and eutectic indium–gallium as the cathode. The devices exhibit a turn‐on voltage of 2.4 V, and a maximum luminance intensity of 15 960 cd m^?2 at 8.5 V. Such performance far exceeds all reported intrinsically stretchable LEDs based on electroluminescent polymers. The stretchable perovskite LEDs are mechanically robust and can be reversibly stretched up to 40% strain for 100 cycles without failure.     

“Green” composites from recycled cellulose and poly(lactic acid): Physico-mechanical and morphological properties evaluation

“Green”/biobased composites were prepared from poly(lactic acid) (PLA) and recycled cellulose fibers (from newsprint) by extrusion followed by injection molding processing. The physico-mechanical and morphological properties of the composites were investigated as a function of varying amounts of cellulose fibers. Compared to the neat resin, the tensile and flexural moduli of the composites were significantly higher. This is due to higher modulus of the reinforcement added to the PLA matrix. Dynamic mechanical analysis (DMA) results also confirmed that the storage modulus of PLA increased on reinforcements with cellulose fibers indicating the stress transfers from the matrix resin to cellulose fiber. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) showed that the presence of cellulose fibers did not significantly affect the crystallinity, or the thermal decomposition of PLA matrix up to 30 wt% cellulose fiber content. Overall it was concluded that recycled cellulose fibers from newsprint could be a potential reinforcement for the high performance biodegradable polymer composites.     

相容剂对长玻纤增强热塑性聚氨酯弹性体/聚乳酸复合材料性能的影响

采用熔体浸渍工艺制备长玻纤增强热塑性聚氨酯弹性体(TPU)/聚乳酸(PLA)复合材料;以苯乙烯-丙烯腈接枝甲基丙烯酸缩水甘油酯(SAG)作为相容剂,热塑性弹性体聚氨酯作为增韧剂,聚乳酸为基体树脂,考察苯乙烯-丙烯腈接枝甲基丙烯酸缩水甘油酯用量对长玻璃纤维增强聚TPU/PLA复合材料性能的影响。结果表明,加入苯乙烯-丙烯腈接枝甲基丙烯酸缩水甘油酯能改善长玻璃纤维增强聚TPU/PLA复合材料的相容性;长玻璃纤维增强聚TPU/PLA复合材料的拉伸强度、缺口冲击强度、弯曲强度和模量等力学性能及储能模量随着苯乙烯-丙烯腈接枝甲基丙烯酸缩水甘油酯用量的增加呈先增加后降低的趋势,而长玻璃纤维增强聚TPU/PLA复合材料的损耗因子则随苯乙烯-丙烯腈接枝甲基丙烯酸缩水甘油酯含量的增加呈现降低后增加的趋势;通过复合材料的形态分析表明,加入相容剂的复合材料中玻璃纤维与基体树脂界面强度增加,且玻璃纤维表面有一层包覆的树脂基体;通过分析得出,当相容剂添加量为6%时,长玻璃纤维增强聚TPU/PLA复合材料的拉伸强度、弯曲强度和模量、缺口冲击强度等力学性能最优。     

改性椰纤维增强聚乳酸复合材料力学性能

目的添加适量椰纤维(CF)改善聚乳酸(PLA)的力学性能,以适应产品的包装。方法采用熔融共混法制备不同CF含量的CF/PLA复合材料。通过力学性能测试、扫描电子显微镜观察和动态热力学性能测试,探讨添加不同含量的碱洗CF对复合材料力学性能的影响。结果与纯PLA相比,复合材料的拉伸强度降低,冲击强度增大,储能模量增大,玻璃化转变温度降低。当碱洗CF质量分数为3%时,复合材料的冲击强度比纯PLA增加了24%。结论添加CF有利于提高复合材料的力学性能,碱液浸泡更有利于改善CF和PLA基体的界面相容性。     

New biocomposites based on thermoplastic starch and bacterial cellulose

Bacterial cellulose, produced by Acetobacter Xylinum, was used as reinforcement in composite materials with a starch thermoplastic matrix. The composites were prepared in a single step with cornstarch by adding glycerol/water as the plasticizer and bacterial cellulose (1% and 5% w/w) as the reinforcing agent. Vegetable cellulose was also tested as reinforcement for comparison purposes. These materials were characterized by different techniques, namely TGA, XRD, DMA, tensile tests, SEM and water sorption assays. All composites showed good dispersion of the fibers and a strong adhesion between the fibers and the matrix. The composites prepared with bacterial cellulose displayed better mechanical properties than those with vegetable cellulose fibers. The Young modulus increased by 30 and 17 fold (with 5% fibers), while the elongation at break was reduced from 144% to 24% and 48% with increasing fiber content, respectively for composites with bacterial and vegetable cellulose.     

Flexible and Tough Poly(lactic acid) Films for Packaging Applications: Property and Processability Improvement by Effective Reactive Blending

This study demonstrates a practical means to overcome inherent brittleness problem of poly(lactic acid) (PLA) and make PLA feasible as packaging material. PLA with suitable processability is utterly required for package manufacturers, where flexible, tough PLA film is essential for packers and end users. Highly flexible PLA films with 60‐fold increase in elongation at break (Eb) over that of the neat PLA were successfully produced by integrating effective reactive blending and economical film blowing process. The ‘two‐step’ blending was used to prepare PLA compound; poly(butylene adipate‐co‐terephthalate) (PBAT – another biodegradable polymer) was first blended with 0.5–1% chain extender (epoxy‐functionalized styrene acrylic copolymer) (ESA), followed by subsequent blending with PLA in twin‐screw extruder. Blown films of reactive blend of PLA/PBAT/ESA (80/20/1) showed impressively high Eb of 250% versus a very low Eb of 4% for the neat PLA. Resulting blown films still possessed high modulus of 2 GPa, yield stress of 50–60 MPa and good toughness of ~100 MPa. Significant enhancement in the film's ductility was attributed to homogeneous blend with developed fine strand‐like structure as a result of effective in situ compatibilization and good interfacial adhesion between the PLA and PBAT. PLA/PBAT/ESA blend also offered improved processability. Resulting films had acceptable haze of ~10% for common packaging, and clearer film close to PLA (≤2%) could be obtained by designing PLA skin layers in multilayer structure. Films of PLA/PBAT/1%ESA exhibit potential as packaging material; their mechanical and optical properties are comparable with or even exceed some existing films used in the market. Copyright © 2015 John Wiley & Sons, Ltd.     

形状记忆合金的力学及界面参数和体积分数对大块金属玻璃基复合材料增韧的影响

采用考虑塑性的超弹性材料模型和基于损伤塑性的准脆性材料模型,建立了三维单胞有限元模型,模拟了形状记忆合金颗粒增韧大块金属玻璃基复合材料的单调拉伸行为。讨论了形状记忆合金的力学参数、体积分数、界面厚度和界面材料参数对金属玻璃增韧效果的影响。结果表明:提高形状记忆合金的相变应变和马氏体塑性屈服应力将显著提高形状记忆合金颗粒增韧大块金属玻璃基复合材料的拉伸失效应变;形状记忆合金弹性模量超过50.0GPa、马氏体塑性屈服应力超过1.8GPa后,复合材料的拉伸失效应变变化不大。能同时兼顾失效应变和失效应力的形状记忆合金体积分数为15%左右。复合材料界面弹性模量和界面屈服应力的增加将提高复合材料的失效应力,但对失效应变影响不大;复合材料界面厚度的增加在提高失效应变的同时,也降低了复合材料的失效应力。     

Fabrication and characterization of fully biodegradable natural fiber-reinforced poly(lactic acid) composites

Polymer composites were fabricated with poly(lactic acid) (PLA) and cellulosic natural fibers combining the wet-laid fiber sheet forming method with the film stacking composite-making process. The natural fibers studied included hardwood high yield pulp, softwood high yield pulp, and bleached kraft softwood pulp fibers. Composite mechanical and thermal properties were characterized. The incorporation of pulp fibers significantly increased the composite storage moduli and elasticity, promoted the cold crystallization and recrystallization of PLA, and dramatically improved composite tensile moduli and strengths. The highest composite tensile strength achieved was 121 MPa, nearly one fold higher than that of the neat PLA. The overall fiber efficiency factors for composite tensile strengths derived from the micromechanics models were found to be much higher than that of conventional random short fiber-reinforced composites, suggesting the fiber–fiber bond also positively contributed to the composites’ strengths.     

Out‐of‐Plane 3D‐Printed Microfibers Improve the Shear Properties of Hydrogel Composites

One challenge in biofabrication is to fabricate a matrix that is soft enough to elicit optimal cell behavior while possessing the strength required to withstand the mechanical load that the matrix is subjected to once implanted in the body. Here, melt electrowriting (MEW) is used to direct‐write poly(ε‐caprolactone) fibers “out‐of‐plane” by design. These out‐of‐plane fibers are specifically intended to stabilize an existing structure and subsequently improve the shear modulus of hydrogel–fiber composites. The stabilizing fibers (diameter = 13.3 ± 0.3 µm) are sinusoidally direct‐written over an existing MEW wall‐like structure (330 µm height). The printed constructs are embedded in different hydrogels (5, 10, and 15 wt% polyacrylamide; 65% poly(2‐hydroxyethyl methacrylate) (pHEMA)) and a frequency sweep test (0.05–500 rad s^?1, 0.01% strain, n = 5) is performed to measure the complex shear modulus. For the rheological measurements, stabilizing fibers are deposited with a radial‐architecture prior to embedding to correspond to the direction of the stabilizing fibers with the loading of the rheometer. Stabilizing fibers increase the complex shear modulus irrespective of the percentage of gel or crosslinking density. The capacity of MEW to produce well‐defined out‐of‐plane fibers and the ability to increase the shear properties of fiber‐reinforced hydrogel composites are highlighted.     

Effect of matrix ductility on fatigue strength of unidirectional jute spun yarns impregnated with biodegradable plastics

Natural fiber-reinforced composites are carbon-neutral materials that are anticipated for use as an alternative to glass fiber-reinforced plastics. This study investigated the effects of matrix ductility on the fatigue strength of unidirectional jute spun yarns impregnated with biodegradable plastics. Polylactic acid (PLA) and polybutylene succinate (PBS) were used for the matrix. PLA is brittle, but it is widely used as a matrix of green composites. Because PBS has much higher ductility than that of PLA, it can be expected to have higher fatigue strength when subjected to the same strain amplitude as PLA. Fatigue tests were conducted with maximum stress set to 40–90% of the tensile strength. The stress ratio was set as 0.1. Results show that the matrix ductility strongly affects the fatigue strength and the fatigue mechanism of the composite. A matrix with better ductility was effective to improve fatigue strength.     

Enhanced Mechanical Properties of Epoxy Nanocomposites by Mixing Noncovalently Functionalized Boron Nitride Nanoflakes

The influence of surface modifications on the mechanical properties of epoxy‐hexagonal boron nitride nanoflake (BNNF) nanocomposites is investigated. Homogeneous distributions of boron nitride nanoflakes in a polymer matrix, preserving intrinsic material properties of boron nitride nanoflakes, is the key to successful composite applications. Here, a method is suggested to obtain noncovalently functionalized BNNFs with 1‐pyrenebutyric acid (PBA) molecules and to synthesize epoxy–BNNF nanocomposites with enhanced mechanical properties. The incorporation of noncovalently functionalized BNNFs into epoxy resin yields an elastic modulus of 3.34 GPa, and 71.9 MPa ultimate tensile strength at 0.3 wt%. The toughening enhancement is as high as 107% compared to the value of neat epoxy. The creep strain and the creep compliance of the noncovalently functionalized BNNF nanocomposite is significantly less than the neat epoxy and the nonfunctionalized BNNF nanocomposite. Noncovalent functionalization of BNNFs is effective to increase mechanical properties by strong affinity between the fillers and the matrix.     

Water‐Rich Biomimetic Composites with Abiotic Self‐Organizing Nanofiber Network

Load‐bearing soft tissues, e.g., cartilage, ligaments, and blood vessels, are made predominantly from water (65–90%) which is essential for nutrient transport to cells. Yet, they display amazing stiffness, toughness, strength, and deformability attributed to the reconfigurable 3D network from stiff collagen nanofibers and flexible proteoglycans. Existing hydrogels and composites partially achieve some of the mechanical properties of natural soft tissues, but at the expense of water content. Concurrently, water‐rich biomedical polymers are elastic but weak. Here, biomimetic composites from aramid nanofibers interlaced with poly(vinyl alcohol), with water contents of as high as 70–92%, are reported. With tensile moduli of ≈9.1 MPa, ultimate tensile strains of ≈325%, compressive strengths of ≈26 MPa, and fracture toughness of as high as ≈9200 J m^?2, their mechanical properties match or exceed those of prototype tissues, e.g., cartilage. Furthermore, with reconfigurable, noncovalent interactions at nanomaterial interfaces, the composite nanofiber network can adapt itself under stress, enabling abiotic soft tissue with multiscale self‐organization for effective load bearing and energy dissipation.     

Natural and man-made cellulose fibre-reinforced poly(lactic acid) (PLA) composites: An overview about mechanical characteristics and application areas

The paper describes the production and the mechanical characteristics of composites made completely of renewable raw materials. Composites of different kinds of natural fibres like cotton, hemp, kenaf and man-made cellulose fibres (Lyocell) with various characteristics were processed with a fibre mass proportion of 40% and poly(lactic acid) (PLA) by compression moulding. Additionally, composites were made of fibre mixtures (hemp/kenaf, hemp/Lyocell). The composites were tested for tensile strength, elongation at break, Young’s modulus and Charpy impact strength. Their characteristics varied markedly depending on the characteristics of the raw fibres and fibre bundles and fibre mixtures used. While kenaf and hemp/PLA composites showed very high tensile strength and Young’s modulus values, cotton/PLA showed good impact characteristics. Lyocell/PLA composites combined both, high tensile strength and Young’s modulus with high impact strength. Thus, the composites could be applied in various fields, each meeting different requirements.     

环氧树脂复合材料的制备及力学性能

通过配方设计,以硅烷偶联剂改性的空心玻璃微珠(HGB)为填料,端羧基液体丁腈橡胶(CTBN)为增稠剂和增韧剂,环氧树脂(EP)为基体,经变温分段固化技术制备环氧树脂/端羧基丁腈橡胶/空心玻璃微珠(EP/CTBN/HGB)三元泡沫复合材料并研究其力学和流变性能。结果表明,CTBN使得复合材料由脆性断裂变为韧性断裂;CTBN劣化了复合材料模量而HGB弥补了复合材料模量;当CTBN、HGB含量分别为12%(质量分数)和30%(体积分数)时,三元复合材料的冲击、弯曲、拉伸强度及弯曲模量均优于纯EP。另外,纯环氧树脂和EP/CTBN共混物的黏度呈现出牛顿流体的流变行为,而三元共混物的黏度表现出明显的剪切变稀现象。     

Effect of aluminum trihydroxide on flame retardancy and dynamic mechanical and tensile properties of kenaf/poly(lactic acid) green composites

In this work, the effect of aluminum trihydroxide (ATH) on the flame retardancy and dynamic mechanical and tensile properties of kenaf/poly(lactic acid) green composites was explored. Prior to composite fabrication, poly(lactic acid) (PLA) pellets filled with ATH powder at different loadings (0, 10, 20, 30, and 50?wt.%) were processed by using a twin-screw extrusion technique. The green composites were fabricated using the pellets and chopped kenaf fibers by a compression molding method. The kenaf fibers were used as primary reinforcement, and the contents were fixed to 40?wt.% of the total, and the average fiber length was 3?mm long. It was noticeable that the flame retardancy of kenaf/PLA green composite with ATH was improved by 66%, and the storage modulus and tensile modulus were enhanced by 136 and 59%, respectively, compared with the kenaf/PLA counterpart without ATH. It was concluded that the ATH incorporated into PLA by extrusion technique played a significant role not only as flame-retardant but also as secondary reinforcement of kenaf/PLA green composites.     

Stretchable Organometal‐Halide‐Perovskite Quantum‐Dot Light‐Emitting Diodes

Stretchable light‐emitting diodes (LEDs) and electroluminescent capacitors have been reported to potentially bring new opportunities to wearable electronics; however, these devices lack in efficiency and/or stretchability. Here, a stretchable organometal‐halide‐perovskite quantum‐dot LED with both high efficiency and mechanical compliancy is demonstrated. The hybrid device employs an ultrathin (<3 µm) LED structure conformed on a surface‐wrinkled elastomer substrate. Its luminescent efficiency is up to 9.2 cd A^?1, which is 70% higher than a control diode fabricated on the rigid indium tin oxide/glass substrate. Mechanical deformations up to 50% tensile strain do not induce significant loss of the electroluminescent property. The device can survive 1000 stretch–release cycles of 20% tensile strain with small fluctuations in electroluminescent performance.     

PLA/algae composites: Morphology and mechanical properties

Bio-composites with poly(lactic) acid as matrix and various algae (red, brown and green) as filler were prepared via melt mixing. Algae initial size (below 50 μm and between 200 and 400 μm) and concentration (from 2 to 40 wt%) were varied. First, algae morphology, composition and surface properties are analysed for each algae type. Second, an example of algae particle size decrease during processing is given. Finally, tensile properties of composites are analysed. The surface of algae flakes was covered with inorganic salts affecting filler–matrix interactions. The Young’s modulus of composites increased at 40 wt% load of algae as compared with neat PLA although the strain at break and tensile strength decreased. In most cases the influence of algae type was minor. Larger flakes led to better mechanical properties compared to the smaller ones.     

Thermo-mechanical characterization of Manicaria Saccifera natural fabric reinforced poly-lactic acid composite lamina

The development and thermo-mechanical characterization of a novel green composite lamina, made of PolyLactic Acid (PLA) reinforced with a natural fabric extracted from Manicaria Saccifera palm, are presented. The composite was characterized by thermal-analysis (TGA), tensile, flexural, and izod impact tests, and scanning electronic microscopy (SEM). TGA analysis showed that the degradation process of the composite started earlier than that of neat PLA due to the lower thermal stability of the fabric. The mechanical tests showed that PLA properties were improved. The tensile strength, elastic modulus and impact resistance were improved by 26%, 51% and 56% respectively. Good dispersion and mechanical interlocking of PLA into the fabric were seen by SEM explaining the improvements of the mechanical properties of the composite. In summary, the good tensile properties and the excellent energy absorption capabilities of the MF/PLA composite lamina show great potential of Manicaria fabric as reinforcement in green composites.