三乙酸甘油酯对PLA/PBAT共混体系性能影响

利用转矩流变仪将聚乳酸(PLA)、聚己二酸对苯二甲酸丁二酯(PBAT)和三乙酸甘油酯(GTA)熔融共混,利用差示扫描量热仪(DSC)、动态热机械分析仪(DMA)、万能材料试验机、冲击试验机、扫描电子显微镜(SEM)对共混物的热力学性能、力学性能以及微观形态结构进行测试和表征。实验发现,加入GTA后共混物的两相玻璃化转变温度呈相互靠近趋势,冷结晶温度和熔融温度都降低。当GTA加入量为3份时,共混物中分散相粒径减小,PLA/PBAT/GTA(80/20/3)组分的断裂伸长率得到明显提升,增加了2.6倍,由未加入GTA时的17.7%增长到64.1%。     

Polylactic acid composites incorporating casein functionalized cellulose nanowhiskers

Background

Polylactic acid (PLA) is considered to be a sustainable alternative to petroleum-based polymers for many applications. Using cellulose fiber to reinforce PLA is of great interest recently due to its complete biodegradability and potential improvement of the mechanical performance. However, the dispersion of hydrophilic cellulose fibers in the hydrophobic polymer matrix is usually poor without using hazardous surfactants. The goal of this study was to develop homogenously dispersed cellulose nanowhisker (CNW) reinforced PLA composites using whole milk casein protein, which is an environmentally compatible dispersant.

Results

In this study, whole milk casein was chosen as a dispersant in the PLA-CNW system because of its potential to interact with the PLA matrix and cellulose. The affinity of casein to PLA was studied by surface plasmon resonance (SPR) imaging. CNWs were functionalized with casein and used as reinforcements to make PLA composites. Fluorescent staining of CNWs in the PLA matrix was implemented as a novel and simple way to analyze the dispersion of the reinforcements. The dispersion of CNWs in PLA was improved when casein was present. The mechanical properties of the composites were studied experimentally. Compared to pure PLA, the PLA composites had higher Young’s modulus. Casein (CS) functionalized CNW reinforced PLA (PLA-CS-CNW) at 2 wt% filler content maintained higher strain at break compared to normal CNW reinforced PLA (PLA-CNW). The Young’s modulus of PLA-CS-CNW composites was also higher than that of PLA-CNW composites at higher filler content. However, all composites exhibited lower strain at break and tensile strength at high filler content.

Conclusions

The presence of whole milk casein improved the dispersion of CNWs in the PLA matrix. The improved dispersion of CNWs provided higher modulus of the PLA composites at higher reinforcement loading and maintained the strain and stress at break of the composites at relatively low reinforcement loading. The affinity of the dispersant to PLA is important for the ultimate strength and stiffness of the composites.

     

Biomimetic polysaccharide nanocomposites of high cellulose content and high toughness

Plant cell walls combine mechanical stiffness, strength and toughness despite a highly hydrated state. Inspired by this, a nanostructured cellulose network is combined with an almost viscous polysaccharide matrix in the form of a 50/50 amylopectin-glycerol blend. Homogeneous films with a microfibrillated cellulose (MFC) nanofiber content in the range of 10-70 wt % are successfully cast. Characterization is carried out by dynamic mechanical analysis, field-emission scanning electron microscopy, X-ray diffraction, and mercury density measurements. The MFC is well dispersed and predominantly oriented random-in-the-plane. High tensile strength is combined with high modulus and very high work of fracture in the nanocomposite with 70 wt % MFC. The reasons for this interesting combination of properties include nanofiber and matrix properties, favorable nanofiber-matrix interaction, good dispersion, and the ability of the MFC network to maintain its integrity to a strain of at least 8%.     

Modification of brittle polylactide by novel hyperbranched polymer-based nanostructures

The inherent brittleness of polylactide (PLA) poses considerable scientific challenges and limits its large-scale applications. Here, we propose and demonstrate a new industrially relevant methodology to develop a polylactide (PLA)-based nanoblend having outstanding stiffness-toughness balance. In this approach, a hydroxyl functional hyperbranched polymer (HBP) was in-situ cross-linked with a polyanhydride (PA) in the PLA matrix during melt processing. There was formation of new hyperbranched polymer-based cross-linked particles in the PLA matrix. Transmission electron microscopy (TEM) and atomic force microscopy (AFM) revealed the sea-island morphology of PLA-cross-linked HBP blend. The domain size of cross-linked HBP particles in the PLA matrix was less than 100 nm as obtained from TEM. The presence of cross-linked hyperbranched polymer in the PLA matrix exhibited approximately 570% and approximately 847% improvement in the toughness and elongation at break, respectively, as compared to unmodified PLA. The increase in the ductility of modified PLA was related to stress whitening and multiple crazing initiated in the presence of cross-linked HBP particles. Formation of a networked interface as revealed by rheological data was associated with enhanced compatibility of the PLA-cross-linked HBP blend as compared to the PLA/HBP blend. The cross-linking reaction of HBP with PA was confirmed with the help of Fourier transform infrared spectroscopy (FTIR) and low-temperature dynamical mechanical thermal analysis (DMTA).     

Mechanical and Morphological Properties of Wood Plastic Biocomposites Prepared from Toughened Poly（lactic acid） and Rubber Wood Sawdust （Hevea brasiliensis）

The present research aims to utilize the acrylic Core-Shell Rubber （CSR） particles to reduce the brittleness in Wood Plastic Composites （WPC） prepared from poly（lactic acid） （PLA） and rubber wood sawdust （Hevea brasiliensis）. Experimental works consisted of two major parts. The first part concentrated on toughening PLA by using CSR particles. Mechanical tests revealed that PLA had become tougher with a more than five times increment in the impact strength when the CSR was added at only 5 wt%. The modified PLA was less stiff with the significant reductions of both elastic and flexural moduli and strengths. The second part focused on producing WPC from the toughened PLA and rubber wood sawdust. The tensile moduli and the strengths of the PLA composites increased with rubber wood content. The composites turned out to be more brittle with reductions of both the impact strength and the tensile elongation at break at all the sawdust contents. Toughening PLA/wood flour with 5 wt% CSR improved both the impact strength and the tensile elongation at break. The toughness enhancement was also depicted by the plastic deformation observed on the surfaces of fractured PLA/CSR/wood sawdust composites.     

Synthesis and mechanical properties of quaternary salts of chitosan-based films for food application

A novel method is described to synthesize quaternary salts of chitosan with dimethylsulfate and subsequently cast films. In an attempt to improve both mechanical and hydrophobic characteristics, the chitosan was previously modified by N-alkylation, introducing 4, 8 and 12 carbons moieties into the polymeric chain. Analysis by FTIR and solid-state CP-MAS (13)C NMR spectroscopy confirmed the success of both alkylation and quaternization processes. The average degree of quaternization of these N-methylated derivatives was calculated to be 35%. DMA measurements indicated that chitosan and its derivative films are typically brittle materials, exhibiting similar non-linear viscoelastic behaviors. The films of unmodified chitosan have a very small strain (approximately 2.8%), though they were the most resistant films (Young's modulus=2283 MPa; tensile strength >44.0 MPa). In general, the alkyl-chitosan derivatives appear to be more plastic than chitosan films but less resistant, e.g., for butyl chitosan: maximum strain=13.1%; tensile strength=13.4 MPa and Young's modulus=171 MPa. Conversely the quaternization reaction increased the hardness of the parent sample, viz. for quaternary salt of dodecyl chitosan: maximum strain=2.6%; tensile strength=38.3 MPa and Young's modulus=1792 MPa.     

Ultrastrong and high gas-barrier nanocellulose/clay-layered composites

Nanocellulose/montmorillonite (MTM) composite films were prepared from 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized cellulose nanofibrils (TOCNs) with an aspect ratio of >200 dispersed in water with MTM nanoplatelets. The composite films were transparent and flexible and showed ultrahigh mechanical and oxygen barrier properties through the nanolayered structures, which were formed by compositing the anionic MTM nanoplatelet filler in anionic and highly crystalline TOCN matrix. A composite film with 5% MTM content had Young's modulus 18 GPa, tensile strength 509 MPa, work of fracture of 25.6 MJ m(-3), and oxygen permeability 0.006 mL μm m(-2) day(-1) kPa(-1) at 0% relative humidity, respectively, despite having a low density of 1.99 g cm(-3). As the MTM content in the TOCN/MTM composites was increased to 50%, light transmittance, tensile strength, and elongation at break decreased, while Young's modulus was almost unchanged and oxygen barrier property was further improved to 0.0008 mL μm m(-2) day(-1) kPa(-1).     

Improvement in ductility of chitosan through blending and copolymerization with PEG: FTIR investigation of molecular interactions

Chitosan is an important biomaterial used widely in medical applications. One of the key concerns about its use is the fragile nature of chitosan films. By comparing the component molecular interactions using FTIR, this study attempts to understand how the ductility of chitosan can be improved by blending and copolymerizing with poly(ethylene glycol) (PEG). An improvement in ductility was obtained for all compositions of blend as manifested by a decrease in modulus and an increase in strain at break. For comparable PEG composition (approximately 30%), the properties of the solution-cast blend were better than those of the grafted copolymer. Therefore, blending may be a more efficient way to improve ductility of chitosan. FTIR characterization of the materials revealed subtle decreases in molecular interactions upon annealing the partially miscible blend. These may not be apparent in DSC or X-ray diffraction, yet they play a key role in the mechanical behavior. It appears that in the case of the graft copolymer the improvement in the properties comes from suppression of the crystallinity of each component and not from component interactions. On the other hand, in the blend, the improvement appears to come predominantly from the "well-dispersed", "kinetically trapped" phase morphology and from the intermolecular interactions. Therefore, annealing the blend leads to decreased intermolecular interactions, phase coarsening, and deterioration in properties.     

Properties of polylactic acid composites reinforced with oil palm biomass microcrystalline cellulose

In this work, polylactic acid (PLA) composites filled with microcrystalline cellulose (MCC) from oil palm biomass were successfully prepared through solution casting. Fourier transform infrared (FT-IR) spectroscopy indicates that there are no significant changes in the peak positions, suggesting that incorporation of MCC in PLA did not result in any significant change in chemical structure of PLA. Thermogravimetric analysis was conducted on the samples. The T₅₀ decomposition temperature improved with addition of MCC, showing increase in thermal stability of the composites. The synthesized composites were characterized in terms of tensile properties. The Young's modulus increased by about 30%, while the tensile strength and elongation at break for composites decreased with addition of MCC. Scanning electron microscopy (SEM) of the composites fractured surface shows that the MCC remained as aggregates of crystalline cellulose. Atomic force microscopy (AFM) topographic image of the composite surfaces show clustering of MCC with uneven distribution.     

Properties of a plasticised starch blend. Part 1: Influence of moisture content on fracture properties

The effect of moisture content on tensile and fracture properties of a plasticised starch/high molecular weight polyol blend was investigated. A wide range of mechanical behaviour was achieved by varying slightly the water uptake of this material. At low moisture content, the Young’s modulus was 3800 MPa and the yield stress, 54 MPa. When the moisture content reached 15 wt%, their values dropped, respectively, to around 1500 MPa and 21 MPa. As the material behaviour varies greatly over the moisture content range, two fracture mechanics techniques were employed: the linear elastic fracture mechanics approach to characterise brittle behaviour and the essential work of fracture method to investigate a more ductile material. At low moisture content, the measured strain energy release rate at fracture, J_Q was very low and showed little dependency on the moisture content. As the moisture content increases, the material becomes increasingly ductile and displayed a brittle-to-ductile transition at 12% of moisture content, which corresponded to the glass transition temperature of the added polyol.     

聚乳酸/聚己二酸-对苯二甲酸丁二酯对土壤细菌群落结构的影响及其降解菌的筛选

【背景】近年来,聚乳酸/聚己二酸-对苯二甲酸丁二酯(polylactide/polybutyleneadipateco-terephthalate,PLA/PBAT)可降解地膜得到了广泛的使用,然而材料使用对土壤微生物的影响却鲜有报道。【目的】以新疆土壤为例,研究PLA/PBAT地膜的使用对土壤中微生物群落结构的影响;并从土壤中筛选可降解PLA/PBAT的菌株,为土壤环境的原位修复提供技术支持。【方法】采用高通量测序的方法对比使用PLA/PBAT地膜前后土壤中细菌群落的结构变化;采用筛选培养基从土壤中分离、鉴定PLA/PBAT的降解菌,通过改变不同培养条件研究菌株降解效果。【结果】使用PLA/PBAT地膜后,土壤中酸杆菌门、芽单胞菌门的相对丰度上升,变形菌门、放线菌门的相对丰度下降,这可能是地膜降解过程中其中间产物对土壤pH及微生物的抑制作用所致;并从土壤中分离出一株PLA/PBAT降解菌XJ11,初步鉴定为Delftiatsuruhatensis,在外加1.5%胰蛋白胨的PLA/PBAT (规格1×1×0.05 cm)筛选培养基中,接种菌液1 mL,在pH为7.2、37°C、130 r/min的条件下,7d内PLA/PBAT的降解率可达6.87%。【结论】PLA/PBAT地膜的使用可以改变土壤细菌群落结构,从环境中筛选出高效的PLA/PBAT降解菌成为解决地膜污染的有效措施。     

Solid state microcellular foamed poly(lactic acid): morphology and property characterization

Poly(lactic acid) or PLA is a plant-based biodegrable plastic which exhibits many properties that are equivalent to or better than many petroleum-based plastics. However, there have been few commercial applications due to its lower impact resistance and higher cost than synthetic plastics. In this paper, the concept of creating microcellular foamed structures in PLA as a means to improve its shortcomings is presented. The effect of the foaming conditions (temperature and time) on the void fraction, volume expansion ratio, impact strength and tensile properties of foamed PLA is discussed. Each step of microcellular processing is addressed including: the manufacture of PLA film; the saturation of the samples with gas; the microcellular foaming of PLA; the void fraction determination, volume expansion ratio calculation, impact and tensile property characterization of foamed samples. The microcellular morphologies developed in PLA samples were a strong function of the foaming conditions. Due to the presence of foamed microcells, a twofold expansion ratio and significant improvements in the impact resistance (twofold increase over unfoamed PLA), strain at break (up to twofold increase over unfoamed PLA) and toughness (up to fourfold increase over unfoamed PLA) were achieved in PLA.     

Effect of polysaccharide structure on mechanical and thermal properties of galactomannan-based films

Films were prepared from guar gum and locust bean gum galactomannans. In addition, enzymatic modification was applied to guar gum to obtain structurally different galactomannans. Cohesive and flexible films were formed from galactomannans plasticized with 20-60% (w/w of polymer) glycerol or sorbitol. Galactomannans with lower galactose content (locust bean gum, modified guar gum) produced films with higher elongation at break and tensile strength. The mechanical properties of films were improved statistically significantly by decreasing the degree of polymerization of guar gum with mannanase treatments (4 h) of 2 and 10 nkat/g, whereas 50 nkat/g produced films with low elongation at break and tensile strength. Galactomannans with approximately 6 galactose units per 10 mannose backbone units resulted in films with 2 peaks in loss modulus spectra, whereas films from galactomannans with approximately 2 galactose groups per 10 mannose units behaved as a single phase in dynamic mechanical analysis.     

Plasticization of poly(L-lactide) with poly(propylene glycol)

A new plasticizer for poly(L-lactide) (PLA)-poly(propylene glycol) (PPG) is proposed. The advantage of using PPG is that it does not crystallize, has low glass transition temperature, and is miscible with PLA. PLA was plasticized with PPGs with nominal Mw of 425 and 1000 g/mol. Poly(ethylene glycol) (PEG), long known as a plasticizer for PLA, with nominal Mw of 600 g/mol, was also used to plasticize PLA for comparison. The thermal and tensile properties of PLA and PLA with 5-12.5 wt % of the plasticizers were studied. In blends of PLA with PPGs the glass transition temperature was lower than that of neat PLA. Both PPGs enhanced the crystallizability of PLA albeit less than PEG. All of the plasticizers increased also the ability of PLA to plastic deformation which was reflected in a decrease of yield stress and in an increase of elongation at break. The effect was enhanced by the higher PPG content and also by lower molecular weight of PPG. A phase separation occurred only in the blend containing 12.5 wt % of PPG with higher molecular weight. The evidences of crazing were found in deformed samples of PLA with low plasticizer content, whereas the samples with higher content of plasticizers crystallized due to deformation.     

In Vitro Fracture Testing of Submicron Diameter Collagen Fibril Specimens

Mechanical testing of collagenous tissues at different length scales will provide improved understanding of the mechanical behavior of structures such as skin, tendon, and bone, and also guide the development of multiscale mechanical models. Using a microelectromechanical-systems (MEMS) platform, stress-strain response curves up to failure of type I collagen fibril specimens isolated from the dermis of sea cucumbers were obtained in vitro. A majority of the fibril specimens showed brittle fracture. Some displayed linear behavior up to failure, while others displayed some nonlinearity. The fibril specimens showed an elastic modulus of 470 ± 410 MPa, a fracture strength of 230 ± 160 MPa, and a fracture strain of 80% ± 44%. The fibril specimens displayed significantly lower elastic modulus in vitro than previously measured in air. Fracture strength/strain obtained in vitro and in air are both significantly larger than those obtained in vacuo, indicating that the difference arises from the lack of intrafibrillar water molecules produced by vacuum drying. Furthermore, fracture strength/strain of fibril specimens were different from those reported for collagenous tissues of higher hierarchical levels, indicating the importance of obtaining these properties at the fibrillar level for multiscale modeling.     

Mechanical properties of armchair silicene nanoribbons with edge cracks: a molecular dynamics study

Silicene has been proven to be a promising material with attractive electronic properties. During the synthesis of silicene, structural defects such as edge crack are likely to be generated and such defects in silicene have impacts on its properties. Herein, molecular dynamics simulations were performed to investigate the mechanical properties of the armchair silicene nanoribbons (ASiNRs) with edge cracks. Our results showed that the mechanical properties of the ASiNRs decrease because of the existence of edge crack. Both the pristine ASiNRs and the ASiNRs with edge cracks show brittle fracture behaviours. The crack length plays an important role in determining the critical strain and fracture strength of the ASiNRs. Moreover, we investigated the effects of strain rate and temperature on the mechanical properties of the ASiNRs with edge cracks. We observed that the increasing strain rate increases the critical strain and fracture strength while decreasing the Young’s modulus. Low-strain rates also changes the expanded directions of cracks in the ASiNRs. We also found that the increasing temperature could significantly decrease the mechanical properties of the ASiNRs with edge cracks.     

Mechanical properties of collagen fascicles from the rabbit patellar tendon

Tensile and viscoelastic properties of collagen fascicles of approximately 300 microns in diameter, which were obtained from rabbit patellar tendons, were studied using a newly designed micro-tensile tester. Their cross-sectional areas were determined with a video dimension analyzer combined with a CCD camera and a low magnification microscope. There were no statistically significant differences in tensile properties among the fascicles obtained from six medial-to-lateral locations of the patellar tendon. Tangent modulus, tensile strength, and strain at failure of the fascicles determined at about 1.5 percent/s strain rate were 216 +/- 68 MPa, 17.2 +/- 4.1 MPa, and 10.9 +/- 1.6 percent (mean +/- S.D.), respectively. These properties were much different from those of bulk patellar tendons; for example, the tensile strength and strain at failure of these fascicles were 42 percent and 179 percent of those of bulk tendons, respectively. Tangent modulus and tensile strength of collagen fascicles determined at 1 percent/s strain rate were 35 percent larger than those at 0.01 percent/s. The strain at failure was independent of strain rate. Relaxation tests showed that the reduction of stress was approximately 25 percent at 300 seconds. These stress relaxation behavior and strain rate effects of collagen fascicles differed greatly from those of bulk tendons. The differences in tensile and viscoelastic properties between fascicles and bulk tendons may be attributable to ground substances, mechanical interaction between fascicles, and the difference of crimp structure of collagen fibrils.     

Preparation and characterization of polyaniline/chitosan blend film

Films consisting of a blend of a chitosan hydrogel and a conductive polymer, polyaniline (PANI), were prepared and characterized for their electrical and mechanical properties. Polyaniline in emeraldine base (EB) form was dispersed in chitosan solution and blend films were obtained by solution casting. The PANI particles in the blend films were then doped with HCl where we observed reductions in the film tensile strength and Young's modulus by about 30%, but the films electrical conductivity increased by 6 orders of magnitude. The highest electrical conductivity of the blend films was of the order 10⁻⁴ S/cm. The electrical and mechanical properties of the films varied with polyaniline content, acid dopant type, acid dopant concentration, and doping time.     

Structural characterization and properties of starch/konjac glucomannan blend films

In this work, a series of glycerol-plasticized pea starch/konjac glucomannan (ST/KGM) blend films was prepared by a casting and solvent evaporation method. The structure, thermal behavior, and mechanical properties of the films were investigated by means of Fourier Transform Infrared Spectroscopy, wide-angle X-ray diffraction, scanning electron microscopy, differential scanning calorimetry, and tensile testing. The results indicated that strong hydrogen bonding formed between macromolecules of starch (ST) and konjac glucomannan (KGM), resulting in a good miscibility between ST and KGM in the blends. Compared with the neat ST, the tensile strength of the blend films were enhanced significantly from 7.4 to 68.1 MPa with an increase of KGM content from 0 to 70 wt%. The value of elongation at break of the blend films was higher than that of ST and reached a maximum value of 59.0% when the KGM content was 70 wt% and 20% of glycerol as plasticizer. The incorporation of KGM into the ST matrix also led to an increase of moisture uptake for the ST-based materials. The structure and properties of pea starch-based films were modified and improved by blending with KGM.     

Fabrication and characterization of poly(lactic acid)/acetyl tributyl citrate/carbon black as conductive polymer composites

By using acetyl tributyl citrate (ATBC) as the plasticizer of poly(lactic acid) (PLA) and carbon black (CB) as conductive filler, electrically conductive polymer composites (CPC) with different CB and ATBC contents were prepared. FTIR revealed that the interaction existed between PLA/ATBC matrix and CB filler and ATBC could improve this interaction. The rheology showed that ATBC could obviously decrease the shear viscosity and improve the fluidity of the composites but just the reverse for CB. With the increasing of CB contents, the enforcement effect, storage modulus, and glass-transition temperature increased but the elongation at break decreased. PLA/ATBC/CB composites exhibited the low electrical percolation thresholds of 0.516, 1.20, 2.46, and 2.74 vol % CB at 30, 20, 10, and 0 wt % ATBC. The conductivity of the composite containing 3.98 vol % CB and 30 wt % ATBC reached 1.60 S/cm. Scanning electron microscopy revealed that the addition of ATBC facilitated the dispersion of the CB in the PLA matrix. Water vapor permeability (WVP) showed that, at the same CB contents, the more ATBC contents there were, the less the values of WVP were.