聚乙二醇对聚乳酸/淀粉纳米晶复合材料性能的影响

以聚乳酸（PLA）和淀粉纳米晶（SNC）为主要原料,聚乙二醇（PEG）为增塑剂,采用溶剂蒸发法制备PLA/SNC和PLA/SNC/PEG复合材料,通过差示扫描量热仪（DSC）、热台偏光显微镜（PLM）、X射线衍射仪（XRD）、扫描电子显微镜（SEM）等研究了PEG对复合材料结晶行为、力学性能及界面相容性的影响。结果表明,PEG能够与SNC协同促进PLA结晶,使PLA/SNC/PEG复合材料的结晶速率明显提高;PEG的添加未改变PLA/SNC复合材料的结晶结构;随着PEG含量的增加,PLA/4 %（质量分数,下同）SNC复合材料的拉伸强度先升高后下降,断裂伸长率不断提高;当PEG含量为2 %时,PLA/4 %SNC/2 %PEG复合材料的力学性能最佳,拉伸强度为47.86 MPa,断裂伸长率为10.20 %,PLA与SNC间界面相容性得到改善。     

Interface compatibility and mechanisms of improved mechanical performance of starch/poly(lactic acid) blend reinforced by bamboo shoot shell fibers

Bamboo shoot shell fibers (BSSFs)/starch/poly(lactic acid) (PLA) ternary composites were prepared by blending BSSFs to starch/PLA matrices for the purpose of expanding BSSFs applications to enhance starch/PLA composites and creating a new low-cost biodegradable composite. The effects of BSSFs content (0–40 wt %) on the physical–mechanical properties were tested and interface compatibility and its mechanism to mechanical performance of BSSFs/starch/PLA composites were characterized by SEM-EDS, TG. The results showed that the mechanical strength, surface wettability, and water absorption of the composites continued improving when the BSSFs content increased from 0% to 20 wt %. However, mechanical modulus increased with increase in BSSFs content. The results of fracture microstructure and thermal property exhibited a good interfacial compatibility at low content of BSSFs and an interface debonding at high content of BSSFs. These investigations indicated that the BSSFs reinforcement to the composite is not consistent with interface compatibility of the ternary composites. The composites should be considered as a kind of green and low-cost biodegradable materials to replace traditional single-phase or multiphase materials. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47899.     

聚乳酸/淀粉复合发泡材料的研究(Ⅱ):改性淀粉对复合材料相容性、流变性能和发泡性能影响

制备了聚乳酸/改性淀粉复合材料及发泡材料,研究了聚乳酸/淀粉复合体系的相容性及流变性能,结果表明,糊化改性淀粉与聚乳酸具有较好的相容性,改性淀粉与聚乳酸复合材料具有较好的熔体粘弹行为,淀粉糊化改性后,复合材料的发泡性能得到优化,吸水性大大降低.     

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.     

TPU/PLA nanocomposites with improved mechanical and shape memory properties fabricated via phase morphology control and incorporation of multi-walled carbon nanotubes nanofillers

Shape memory polymer nanocomposites based on thermoplastic polyurethane (TPU)/polylactic acid (PLA) blends filled with pristine multi-walled carbon nanotubes (MWCNTs) and modified MWCNTs─COOH were fabricated by direct melt blending technique and investigated for its morphology, mechanical, thermal, electrical, and shape memory properties. Morphological characterizations by using transmission electron microscope (TEM) and field emission scanning electron microscope (FESEM) revealed better dispersion of MWCNTs─COOH in the polymer blend, which is attributed to the improved interfacial interactions between the polymer blends and MWCNTs-COOH. Loading of the MWCNTs-COOH in the TPU/PLA blends resulted in the significant improvements in the mechanical properties such as tensile strength and elastic modulus and these effects are more pronounced on increasing the MWCNTs─COOH loading amount, when compared to the pristine MWCNTs filled system. Thermal analysis showed that the glass transition temperature of the blends increases slightly with increasing loading of both pristine and modified MWCNTs in the system. The resistance of nanocomposites decreased from 2 × 10¹² Ω to 3.2 × 10¹⁰ Ω after adding 3% MWCNTs─COOH. The shape memory performance tests showed that the enhancement of shape recovery by 252% could be achieved at 3% MWCNTs loading, when compared to that of TPU/PLA blends.     

Preparation of a new dialdehyde starch derivative and investigation of its thermoplastic properties

In order to obtain thermoplastic starch plastics with improved properties, a novel method of starch modification was developed in this study. Starch derivatives were prepared using the following procedures: pea starch was first oxidized to make dialdehyde starch (DAS) by sodium periodate under mild conditions, and this was then acetalized with glycol to give Gly-ADS. The modified starch was characterized by FT-IR, ¹H-NMR, TG, DSC, and XRD. The TG curves indicated that the thermal stability of Gly-ADS was better than that of DAS. The glass transition temperature of Gly-ADS with 95% carbonyl content (Gly-ADS95) was 97 °C by DSC. Although the intrinsic viscosity of DAS was less than that of pea starch, thermoplastic Gly-ADS (TPGly-ADS) exhibited good mechanical properties. The influence of moisture absorption on the mechanical properties of TPGly-ADS was also investigated. The results showed that TPGly-ADS possesses improved water resistance: the highest moisture absorption of TPGly-ADS95 was about 11%, and the tensile strength and the elongation at break were 18.1–14.6 MPa and 5.3–18%, respectively.     

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.     

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。     

Structure and properties of a compatible starch‐PCL composite using p‐phthaloyl chloride‐based prepolymer

Biodegradable composites from starch and hydrophobic polymer usually show poor compatibility. A novel p‐phthaloyl chloride‐based prepolymer (PCP) compatibilizer based on p‐phthaloyl chloride and polycaprolactone (PCL) diol (2000) was synthesized successfully and the chemical structure was characterized by Fourier transform infrared spectra and ¹H nuclear magnetic resonance (NMR). The PCP compatiblizer was mixed with starch granules to form a coating layer, and then the coated starch granules were melt‐compounded with PCL plastic to prepare compatible starch‐PCL composites with enhanced properties. The structural, mechanical, thermal properties, and water absorption of the composites were then investigated. It was found that the composites containing the PCP compatibilizer showed better interfacial interaction and compatibility between starch and PCL domains compared to the pure starch‐PCL composite, which led to the improved mechanical properties of the composites. The results were attributed to the ester linkage between the PCP compatibilizer and starch as well as the strong physical crosslinking between the PCP compatibilizer and PCL plastic through PCL‐PCL crystallinity. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45400.     

改性处理对聚乳酸/废旧报纸回收纤维复合材料性能的影响

采用注射成型的方法制备了聚乳酸/废旧报纸回收纤维复合材料,探讨了马来酸酐接枝聚丙烯改性处理和1 %的NaOH改性处理对复合材料性能的影响。结果表明,在复合材料中加入2 %的马来酸酐接枝聚丙烯后,聚乳酸与废旧报纸回收纤维的相容性得到改善,复合材料的力学性能得到提高。废旧报纸回收纤维经1 %的NaOH处理后,与聚乳酸的界面被优化,纤维的相对结晶度增大,二者的黏结性能得到改善,复合材料的力学性能也会得到提高。     

聚乳酸/聚丙烯/淀粉复合材料的制备及性能研究

采用模压成型制备了聚乳酸(PLA)/聚丙烯(PP)和PLA/PP/淀粉两种复合材料。主要研究了复合材料的热性能、力学性能和降解性能。结果表明:对于PLA/PP复合材料而言,复合材料的熔融温度先增加后降低,结晶度随PLA的含量增加而变大,而且出现了结晶双峰。力学性能相较与纯PLA,断裂伸长率明显提高,拉伸强度有所下降,最大下降28.02 MPa。降解性能随PLA增加而增强。而对于PLA/PP/淀粉复合材料,熔融温度变为先降低后增加的趋势,复合材料的玻璃化温度也减小,材料的可塑性得到提高;在PLA/PP比例相同条件下,PLA的结晶度有明显提高,PLA的结晶峰强度增加。对于力学性能,淀粉的加入,明显降低了其拉伸强度和断裂伸长率,PLA与PP质量比为3/7时,表现出硬而韧的特性,材料具有单向拉伸,不会立即脆断。对于材料降解性能,淀粉的存在对复合材料的降解能力得到明显的提高,当PLA与PP质量比为3/7时,材料的降解率最高为14.78%,是PLA/PP复合材料最大降解率的4.3倍,并且材料上出现了黄褐色斑点。     

马来酸酐接枝共聚物增容聚乳酸/改性淀粉复合材料的制备与性能研究

采用熔融共混方法制备聚乳酸/改性淀粉复合材料。研究了不同含量的马来酸酐接枝共聚物对聚乳酸/改性淀粉复合材料力学性能的影响,并且采用差示扫描量热(DSC)仪和扫描电子显微镜(SEM)对复合材料的微观结构进行分析。结果表明,马来酸酐接枝共聚物的加入改善了聚乳酸与淀粉的相容性,提高了复合材料的力学性能,添加量为0.5份时复合材料的拉伸强度提高了61.6%,断裂伸长率提高了53.1%,弯曲强度提高了104.7%,同时还能提高复合材料的热变形温度和耐水性;改性淀粉与聚乳酸两相紧密连接。     

A new biodegradable blends prepared from polylactide and hyaluronic acid

In this article, the biodegradable polylactide/hyaluronic acid (PLA/HA) composites were prepared by a melt blending method. In addition, the acrylic acid grafted polylactide (PLA-g-AA) was studied as an alternative to PLA. The samples were characterized by a fourier transform infrared (FTIR) spectroscopy, a nuclear magnetic resonance (NMR), a differential scanning calorimetry (DSC), an Instron mechanical tester, and a scanning electron microscopy (SEM). As the result, due to the poor compatibility between PLA and HA, the mechanical properties of PLA/HA composites were worse than PLA. Much better dispersion and homogeneity of HA in the polymer matrix could be obtained when PLA-g-AA was used in place of PLA in the composite. The PLA-g-AA/HA composites could obviously improve the mechanical properties of PLA/HA ones, and the former provided a plateau tensile strength at break when the HA content was up to 20 wt%. Furthermore, the PLA-g-AA/HA was more easily processed than the PLA/HA because the former had lower viscosity than the latter, as they were molten. Biodegradation tests of blends were also studied under the enzymatic environment, and the result showed that the mass of blends reduced by about the HA content within 4 weeks.     

Influence of ammonium polyphosphate on the flame retardancy and mechanical properties of ramie fiber‐reinforced poly(lactic acid) biocomposites

Fully degradable natural fiber/degradable polymer composites have received much research attention and have various applications such as in automotive components. But flammability limits their application; it is important to improve the flame retardancy of fully degradable composites with environmentally friendly flame retardants. Flame‐retarded ramie fiber‐reinforced poly(lactic acid) (PLA) composites were prepared using three processes: (1) PLA was blended with ammonium polyphosphate (APP), and then the resulting flame‐retarded PLA was combined with ramie fibers; (2) ramie fibers underwent flame‐retardant treatment with APP, which were then compounded with PLA; and (3) PLA and ramie, both of which had been flame‐retarded using APP, were blended together. The APP in the composites is shown to be very effective in improving flame retardancy according UL94 test and limiting oxygen index measurements. Thermogravimetric analysis shows that the improved flame retardancy is due to increased char residue at high temperature. The loading of APP disturbs the compatibility between PLA and fibers, which can be directly observed using scanning electron microscopy. Furthermore it has an influence on the dynamic mechanical properties and mechanical properties according dynamic mechanical analysis and mechanical measurements. The results show that composites produced using the third process not only have the best flame retardancy but also comparatively better mechanical properties. Copyright © 2009 Society of Chemical Industry     

聚乳酸/纤维素共混复合材料的研究进展

叙述了天然纤维、改性纤维、纤维素衍生物与聚乳酸(PLA)复合材料的最新研究现状,围绕共混复合材料的相容性、分散性、力学性能以及应用等方面存在的优缺点,详细介绍了乙基纤维素(EC)、纤维素酯、羧甲基纤维素这3种纤维素衍生物与PLA共混制成复合材料,为纤维素/PLA共混复合材料的研发与应用提供参考。     

Modification of wood flour/PLA composites by reactive extrusion with maleic anhydride

MA modified wood flour/PLA composites were prepared by one‐step reactive extrusion, in which wood flour and poly(lactic acid) (PLA) were used as raw material, maleic anhydride (MA) was used as modifier, and dicumyl peroxide (DCP) was used as initiator. The influences of MA concentration on the morphology, thermal stability, rheological, and mechanical properties of the composites were studied. The addition of MA improved the compatibility of the composites significantly. The thermal and rheological results showed that with the increase of the concentration of MA, the thermal stability of the composites decreased, the storage modulus and complex viscosity of the composites also decreased. The MA modified composites had an enhanced mechanical strength compared to the unmodified one. As the concentration of the MA increased, the tensile and flexural strength of the composites first increased and then decreased, and reached a maximum when the concentration of MA was 1 wt %. The MA modified composites showed a better water resistance than the unmodified ones. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43295.     

Incorporation of wheat starch and coupling agents into poly(lactic acid) to develop biodegradable composite

Abstract

Composites of poly (lactic acid) (PLA)/wheat starch and PLA/wheat starch/methyldiphenyldiisocyanate, were prepared and characterised in this study. The effects of incorporating different coupling agents on the physical properties and morphology of the composites were studied. Extrusion technology and injection moulding techniques were used to prepare standard tensile and impact test pieces. Tensometry was used to investigate the tensile properties of the composites and impact testing using falling weight technique was used to investigate impact strength. To investigate the thermal behaviour of the composites, differential scanning calorimetry was employed. Water absorption properties of the composites were also investigated. Scanning electron microscopy was used to investigate the morphology of the composites. Starch can be incorporated in a PLA matrix at 10% level without difficulty in processing by extrusion followed by injection moulding to make shaped mouldings in the presence of MDI. With 10% wheat starch and 2% MDI, blends of wheat starch/PLA can reach the tensile strength, elongation, impact strength properties of raw PLA. In the presence of 2% MDI and 10% glycerol, blends of PLA and starch make an entirely flexible material.     

Thermal,morphological, and mechanical properties of biobased and biodegradable blends of poly(lactic acid) and chemically modified thermoplastic starch

In this study, poly(lactic acid) (PLA) was blended with chemically modified thermoplastic starch (CMPS) in a twin‐screw extruder. The characteristic properties of PLA/CMPS blends were investigated by observing the morphology, thermal, and mechanical properties, and biodegradability. Differential scanning calorimetry showed that the PLA/CMPS were thermodynamically immiscible. However, scanning electron microscopy and Fourier transform infrared studies revealed that the interfacial adhesion was improved by the PLA‐g‐starch copolymers that were formed at the interface through a transesterification reaction between PLA and CMPS. The crystallinity of the PLA component in the blend was increased by the addition of the CMPS and was highly affected by the morphology of the blend. The tensile strength and elongation were found to decrease in a linear trend with increasing CMPS content. The biodegradability of the blends increased with increasing CMPS content, while initial time lag decreased. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Mechanical,morphological, and thermal properties of chemically treated pine needles reinforced thermosetting composites

Natural fibers are widely used as reinforcement in composites. Pine needles are one of the major biowaste generated by Pinus roxburgii plant. This species is found abundantly in the forests of Himachal Pradesh. In this work, composites of urea–resorcinol–formaldehyde resin‐reinforced with Pine needles fibers were prepared. Fibers were chemically modified to improve their compatibility with matrix. These fibers were mercerized with NaOH solution and acetylated to increase their hydrophobic character. The chemically modified fibers were characterized with Fourier transform infrared spectra, ¹³C‐nuclear magnetic resonance (NMR) spectroscopy, and scanning electron microscopy. The composites were prepared with treated and untreated fibers containing 30% fibers by weight using compression molding technique. The morphology of the materials thus obtained was evaluated by scanning electron microscopy. The chemical modifications of fibers improve fiber–matrix adhesion and also have markedly effect on mechanical properties of composites. Moreover, the thermal resistance of these composites was improved on chemical modification. These results indicate that chemically modified fibers exhibit better compatibility with the polymer matrix than that of untreated fiber. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci, 2013     

PLA/蔗渣复合材料的制备及其性能的研究

以蒸汽爆破后的甘蔗渣纤维(BF)和聚乳酸(PLA)为原料,采用模压的方法制备了PLA/BF复合材料,研究了温度以及蒸汽爆破预处理对复合材料力学性能的影响,并通过红外光谱和电子扫描电镜分析了其作用机理。结果表明,随着温度的升高,纤维的分散性变好,BF与PLA得界面黏结性能变好,复合材料的力学性能提高,温度为230℃时复合材料的力学性能最佳;而蒸汽爆破预处理可提高纤维素的含量,增大纤维的比表面积,使复合材料的力学性能得到改善。