Structure and thermal properties of poly(lactic acid)/cellulose whiskers nanocomposite materials

The goal of this work was to produce nanocomposites based on poly(lactic acid) (PLA) and cellulose nanowhiskers (CNW). The CNW were treated with either tert-butanol or a surfactant in order to find a system that would show flow birefringence in chloroform. The nanocomposites were prepared by incorporating 5 wt% of the different CNW into a PLA matrix using solution casting. Field emission scanning electron microscopy showed that untreated whiskers formed flakes, while tert-butanol treated whiskers formed loose networks during freeze drying. The surfactant treated whiskers showed flow birefringence in chloroform and transmission electron microscopy showed that these whiskers produced a well dispersed nanocomposite. Thermogravimetric analysis indicated that both whiskers and composite materials were thermally stable in the region between 25 °C and 220 °C. The dynamic mechanical thermal analysis showed that both the untreated and the tert-butanol treated whiskers were able to improve the storage modulus of PLA at higher temperatures and a 20 °C shift in the tan δ peak was recorded for the tert-butanol treated whiskers.     

Isothermal crystallization behavior and mechanical properties of polylactide/carbon nanotube nanocomposites

Carbon nanotube (CNT)–reinforced polylactide (PLA) nanocomposites were prepared using a melt compounding process employing a twin-screw extruder. The isothermal crystallization kinetics of PLA/CNT nanocomposites according to Avrami’s theory were analyzed using differential scanning calorimetry in the temperature range 90–120 °C. There was a significant dependence of CNT on the crystallization behavior of the PLA matrix. The incorporation of CNT improved effectively the crystallization rate of PLA/CNT nanocomposites through heterogeneous nucleation. The nucleating effect of CNTs which increased the number of nucleation sites and decreased the average spherulite size was confirmed using polarized optical microscopy. The rheological properties of the PLA/CNT nanocomposites were also investigated. Changes in the microstructure of the PLA/CNT nanocomposites occurred by incorporating CNT. Furthermore, the tensile strength/modulus and thermal stability of PLA/CNT nanocomposites were enhanced when a very small quantity of CNT was added. This research accounts for the effect of CNTs, which significantly influenced the isothermal behavior, thermal stability, mechanical, and rheological properties of the PLA/CNT nanocomposites, providing a design guide for PLA/CNT nanocomposites in industrial fields.     

Nanodiamond/poly (lactic acid) nanocomposites: Effect of nanodiamond on structure and properties of poly (lactic acid)

Nanodiamond (ND)/poly (lactic acid) (PLA) nanocomposites with potential for biological and biomedical applications were prepared by using melting compound methods. By means of transmission electron microscopy (TEM), Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), Thermogravimetric analyses (TGA), Dynamic mechanical analyses (DMA), Differential scanning calorimetry (DSC) and Tensile test, the ND/PLA nanocomposites were investigated, and thus the effect of ND on the structural, thermal and mechanical properties of polymer matrix was demonstrated for the first time. Experimental results showed that the mechanical properties and thermal stability of PLA matrix were significantly improved, as ND was incorporated into the PLA matrix. For example, the storage modulus (E′) of 3 wt% ND/PLA nanocomposites was 0.7 GPa at 130 °C which was 75% higher than that of neat PLA, and the initial thermal decomposition was delayed 10.1 °C for 1 wt% ND/PLA nanocomposites compared with the neat PLA. These improvements could be ascribed to the outstanding physical properties of ND, homogeneous dispersion of ND nanoclusters, unique ND bridge morphology and good adhesion between PLA matrix and ND in the ND/PLA nanocomposites.     

石墨烯微片/天然橡胶纳米复合材料的研究

目的 研究石墨烯微片的添量对石墨烯微片/天然橡胶纳米复合材料性能的影响,并对机械共混法和胶乳共混法进行比较。方法 探索复合材料的制备工艺,利用扫描电镜(SEM)、透射电镜(TEM)、拉曼光谱(RDS)、万能力学试验机等对石墨烯微片和石墨烯微片/天然橡胶纳米复合材料的形貌、结构以及性能进行分析和研究。结果 测试结果表明,石墨烯微片作为填料添加到复合材料中,使复合材料的性能得到了增强。相比纯橡胶而言,石墨烯微片(10 phr)/天然橡胶复合材料的拉伸强度增加了41.5%,热导率增加了153.3%。结论 石墨烯微片可以大幅度提高复合材料的性能,并且胶乳共混法制备的复合材料的性能要优于机械共混法制备的复合材料的性能。     

Preparation and characterization of in situ polymerized cyclic butylene terephthalate/graphene nanocomposites

Graphene-reinforced cyclic butylene terephthalate (CBT) matrix nanocomposites were prepared and characterized by mechanical and thermal methods. These nanocomposites containing different amounts of graphene (up to 5 wt%) were prepared by melt mixing with CBT that was polymerized in situ during a subsequent hot pressing. The nanocomposites and the neat polymerized CBT (pCBT) as reference material were subjected to differential scanning calorimetry, dynamical mechanical analysis, thermogravimetrical analysis, and heat conductivity measurements. The dispersion of the grapheme nanoplatelets was characterized by transmission electron microscopy. It was established that the partly exfoliated graphene worked as nucleating agent for crystallization, acted as very efficient reinforcing agent (the storage modulus at room temperature was increased by 39 and 89 % by incorporating 1- and 5-wt% graphene, respectively). Graphene incorporation markedly enhanced the heat conductivity but did not influence the TGA behavior, except the ash content, due to the not proper exfoliation except the ash content.     

石墨烯/氧化石墨烯-聚乳酸的制备与表征

通过优化Hummers法制备了氧化石墨烯,并用水合肼还原法制备了石墨烯,且对自制的石墨烯和氧化石墨烯进行了测试及分析;然后通过溶液插层法制得纳米级聚乳酸/石墨烯和聚乳酸/氧化石墨烯复合材料,并对其分散性、热学性能以及力学性能进行了分析。对石墨烯和氧化石墨烯的表征结果说明,水合肼可以还原氧化石墨,所制备的石墨烯纯度较高。对聚乳酸/石墨烯和聚乳酸/氧化石墨烯复合材料的性能分析结果表明,在聚乳酸的结晶度、结晶速率和对聚乳酸的结晶成核上,石墨烯比氧化石墨烯具有更优异的表现,但在热稳定性能方面,氧化石墨烯比石墨烯优异;在力学性能方面,有增强和降低两种影响,添加少量氧化石墨烯时聚乳酸的力学性能降低,而含质量分数为0.5%的石墨烯复合材料在拉伸实验和冲击实验中的增强效果较为明显。     

Preparation and properties of polystyrene nanocomposites with graphite oxide and graphene as flame retardants

In this study, graphite oxides (GOs) with different oxidation degrees and graphene nanosheets were prepared by a modified Hummers method and thermal exfoliation of the prepared GO, respectively. Polystyrene (PS)/GO and PS/graphene nanocomposites were prepared via melt blending. X-ray diffraction results showed that GOs and graphene were exfoliated in the PS composites. It could be observed from the scanning electron microscope images that GOs and graphene were well dispersed throughout the matrix without obvious aggregates. Dynamic mechanical thermal analysis suggested that the storage modulus for the PS/GO1 and PS/graphene nanocomposites was efficiently improved due to the low oxygen content of GO1 and the elimination of the oxygen groups from GO. The flammability of nanocomposites was evaluated by thermal gravimetric analysis and cone calorimetry. The results suggested that both the thermal stability and the reduction in peak heat release rate (PHRR) decreased with the increasing of the oxygen groups in GOs or graphene. The optimal flammability was obtained with the graphene (5 wt%), in which case the reduction in the PHRR is almost 50 % as compared to PS.     

Novel toughened polylactic acid nanocomposite: Mechanical,thermal and morphological properties

The objective of the study is to develop a novel toughened polylactic acid (PLA) nanocomposite. The effects of linear low density polyethylene (LLDPE) and organophilic modified montmorillonite (MMT) on mechanical, thermal and morphological properties of PLA were investigated. LLDPE toughened PLA nanocomposites consisting of PLA/LLDPE blends, of composition 100/0 and 90/10 with MMT content of 2 phr and 4 phr were prepared. The Young’s and flexural modulus improved with increasing content of MMT indicating that MMT is effective in increasing stiffness of LLDPE toughened PLA nanocomposite even at low content. LLDPE improved the impact strength of PLA nanocomposites with a sacrifice of tensile and flexural strength. The tensile and flexural strength also decreased with increasing content of MMT in PLA/LLDPE nanocomposites. The impact strength and elongation at break of LLDPE toughened PLA nanocomposites also declined steadily with increasing loadings of MMT. The crystallization temperature and glass transition temperature dropped gradually while the thermal stability of PLA improved with addition of MMT in PLA/LLDPE nanocomposites. The storage modulus of PLA/LLDPE nanocomposites below glass transition temperature increased with increasing content of MMT. X-ray diffraction and transmission electron microscope studies revealed that an intercalated LLDPE toughened PLA nanocomposite was successfully prepared at 2 phr MMT content.     

纳米膨胀阻燃季戊四醇二磷酸酯双磷酰蜜胺有机改性蒙脱土/聚乳酸复合材料的制备及阻燃性能

将一种高效膨胀型无卤阻燃剂季戊四醇二磷酸酯双磷酰蜜胺(SPBDM)和有机改性蒙脱土(OMMT)添加到高分子量聚乳酸(PLA)中,熔融共混制备纳米膨胀型阻燃聚乳酸复合材料(SPBDM-OMMT/PLA)。采用XRD、TEM研究了纳米粒子的形态分布,并用热重分析法(TGA)、氧指数测试(LOI)、垂直燃烧测试(UL-94)探讨了该纳米阻燃SPBDM-OMMT/PLA复合材料的热性能和阻燃性能。研究表明,OMMT在PLA基体中有较好的分散性,高分子链插入层状硅酸盐片层间,形成了剥离型或插层型复合材料;相比纯PLA,加入SPBDM后改善了OMMT/PLA的高温热稳定性,最大热分解温度均向高温移动,且高温残炭质量分数大幅度提高;当SPBDM和OMMT质量分数分别为10.0%和1.0%时,纳米阻燃SPBDM-OMMT/PLA复合材料能达到较好的阻燃效果,LOI数值高达32%,相应垂直燃烧等级达UL-94V-0级。     

Plasticized polylactic acid nanocomposite films with cellulose and chitin nanocrystals prepared using extrusion and compression molding with two cooling rates: Effects on mechanical,thermal and optical properties

Triacetate citrate plasticized poly lactic acid and its nanocomposites based on cellulose nanocrystals (CNC) and chitin nanocrystals (ChNC) were prepared using a twin-screw extruder. The materials were compression molded to films using two different cooling rates. The cooling rates and the addition of nanocrystals (1 wt%) had an impact on the crystallinity as well as the optical, thermal and mechanical properties of the films. The fast cooling resulted in more amorphous materials, increased transparency and elongation to break, (approx. 300%) when compared with slow cooling. Chitin nanocomposites were more transparent than cellulose nanocomposites; however, microscopy study showed presence of agglomerations in both materials. The mechanical properties of the plasticized PLA were improved with the addition of a small amount of nanocrystals resulting in PLA nanocomposites, which will be further evaluated for film blowing and thus packaging applications.     

微波辅助原位聚合法制备聚乳酸/蛭石纳米复合材料

对蛭石(VMT)有机改性后,以丙交酯为单体,在催化剂存在的条件下采用微波辅助原位聚合法制备聚乳酸/蛭石(PLA/VMT)纳米复合材料。利用广角X射线粉末衍射法(WAXD)、傅立叶红外光谱法(FT-IR)以及差示扫描量热法(DSC)对材料进行了表征。对蛭石的添加量对材料的插层效果以及材料性能的影响进行了讨论。结果表明,在反应时间很短的情况下,蛭石即可以纳米尺寸分布在PLA中。随蛭石含量的不同,分别得到了剥离型和插层性PLA/VMT纳米复合材料。     

Ductile PLA nanocomposites with improved thermal stability

Polylactide (PLA) is used as a biomedical material because it is biodegradable, but the vast majority of biodegradable polymers in clinical use are composed of rather stiff materials that are unsuitable for use in numerous applications because they exhibit limited extendibility, weak mechanical strength, and poor thermal stability. We modified PLA with 2-methacryloyloxyethyl isocyanate (MOI) to prepare ductile PLA materials. By utilizing a novel sol–gel process, PLA nanocomposites were further prepared with improved mechanical properties and thermal stability. The 10% thermal decomposition temperature for PLA modified with 5% MOI and 5–10% silica was 21–32 °C higher than that of original pristine PLA. Elongation at break increased by 4–13 times when compared to neat PLA while the tensile strength was maintained at 30–40 MPa. These synthesized PLA nanocomposites can be applied as biomaterials with improved mechanical and thermal properties.     

Preparation,structure and thermal properties of polylactide/sepiolite nanocomposites with and without organic modifiers

Polylactide-based nanocomposites containing unmodified and organic modified sepiolite were prepared through a solution casting method. The structure and properties of materials were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). From the results it can be concluded that the bundles of sepiolite have been dispersed into small aggregates containing several nanorods without destroying the crystal structure. Sepiolite nanofibers were well dispersed in the PLA matrix, exhibiting a randomly orientation with the contact among them in all cases. But the thermal stability of nanocomposites has been improved more by introducing unmodified sepiolite than that with organic modified sepiolite, which has also been confirmed by molecular dynamics simulation results that hydrophobic parts of organic modifiers could prevent the interaction between PLA molecules and sepiolite surface.     

Investigation on microwave absorption capacity of nanocomposites based on metal oxides and graphene

Graphene and its nanocomposites were prepared via solution mixing process. Graphene based polymer nanocomposites were prepared by two step process. Firstly, graphene/poly(3-methyl thiophene)(PMT)/BaTiO₃ nanocomposite was prepared by in situ chemical oxidation polymerization technique. In the second step these nanocomposites were dispersed in thermoplastic polyurethane (TPU) matrix by solution blending process. All the four nanocomposites in TPU [30 % modified graphene (P1), 30 % Poly(3-methyl thiophene) (P2), 30 % graphene/PMT/BaTiO₃ (P3) and 15 % graphene/PMT/BaTiO₃ + 15 % Fe₃O₄ (P4)] were analyzed by different analytical techniques like X-ray diffraction (XRD), scanning electron microscopy (SEM), Energy-dispersive X-ray spectroscopy (EDX) and transmission electron microscopy (TEM). Microwave absorbing property was measured by Agilent vector network analyzer (ENA E5071C) in the X-band region (8–12 GHz). Microwave absorption result was interpreted with the help of complex permittivity and permeability of the prepared materials. Matching of both dielectric loss and magnetic loss is essential for an effective radar absorbing material (RAM). P1, P2, P3 and P4 showed the maximum return loss of ?14.37, ?9.3, ?30.02 and ?47.59 dB respectively. Thermal stability of the RAMs was determined by the help of thermogravimetric analysis (TGA) instrument. Among the all, P4 showed better thermal property. All results support their use as RAM in different field.     

PLA/I.34TCN纳米复合材料的制备及其性能研究

将改性纳米黏土I.34TCN与聚乳酸(PLA)经过二次熔融混合制备了PLA/I.34TCN纳米复合材料。TEM表征结果显示,较高的黏土剥离程度提高了黏土在PLA中的分散性,使两相之间的界面作用力增强,同时可以使两相之间具有较大的界面增塑区;DSC表征结果显示,剥离型纳米黏土对纳米复合材料起到了结晶成核剂的作用,提高了纳米复合材料的结晶度。上述两方面的原因综合改善了纳米复合材料的力学性能,当黏土质量分数为2%时,PLA/I.34TCN纳米复合材料中黏土的剥离程度最高,使得该纳米复合材料的断裂伸长率显著提高,最多可提高101.00%,是纯PLA的18倍。TG表征结果发现,纳米复合材料的热稳定性能随I.34TCN含量的增加而逐渐增加。     

Non-covalently modified reduced graphene oxide/polyurethane nanocomposites with good mechanical and thermal properties

Non-covalently modified graphene nanosheets were prepared by reduction graphene oxide with hydrazine hydrate and simultaneous non-covalent functionalization via 1-allyl-methylimidazolium chloride (AmimCl) ionic liquid. Atomic force microscopy revealed that AmimCl ionic liquid modified graphene (IL-G) was well-dispersed in a single exfoliation with a thickness of around 0.96 nm in DMF. Subsequently, the prepared IL-G nanosheets were incorporated into polyurethane (PU) to fabricate IL-G/PU nanocomposites by solution blending. X-ray diffraction disclosed an exfoliated morphology of IL-G nanosheets dispersed in the PU matrix, while the fractured morphology of the IL-G/PU nanocomposites showed that IL-G nanosheets presented a wrinkled morphology when dispersed in the matrix. Both techniques revealed homogeneous dispersion and good compatibility of IL-G nanosheets with PU matrix, indicating the existence of interfacial interactions. At 0.608 wt% loadings of IL-G nanosheets, the tensile strength and storage modulus of the composites were increased by 68.5 and 81.1 %, respectively. High thermal properties were also achieved at a low loading of IL-G nanosheets. An approximately 40 °C improvement in temperature of 5 % weight loss and 34 % increase in thermal conductivity were obtained at just 0.608 wt% loading of IL-G nanosheets.     

Evaluation of the influence of nanoparticles' shapes on the formation of poly(lactic acid) nanocomposites obtained employing the solution method

PLA nanocomposites were prepared by adding organically modified montmorillonite clay (Viscogel B8) and a homoionic clay (NT25), as well as unmodified silica (A200) and modified organic silica (R972). All nanocomposites were obtained by the solution intercalation method using chloroform as a solvent. The materials obtained were essentially characterized by X-ray diffraction and low-field nuclear magnetic resonance relaxometry, through the measurement of proton spin-lattice relaxation time (LF-NMR). Both clays and silicas used to obtain the polymeric nanocomposites showed good dispersion in the polymeric matrix. The relaxation times were distinct for each type of nanoparticle used. The nanocomposite formed with homoionic clay, NT25, presented an increase in the relaxation data, indicating formation of intercalated nanocomposites, contrary to the action of the organoclay Viscogel B8, which preferentially formed an exfoliated nanocomposite. When unmodified and organo-modified silica were added to PLA, an increase in the relaxation time of the polymer matrix was observed. According to the relaxation data, the organosilica R972 dispersed better in the polymeric matrix and consequently interacted better than the A200.     

The synthesis of graphene nanoribbon and its reinforcing effect on poly (vinyl alcohol)

The graphene nanoribbon was prepared from the carbon nanotubes using the chemical approach, and was used for preparing the poly (vinyl alcohol) nanocomposites. It was discovered that the prepared graphene nanoribbon contained a lot of oxygen groups. Due to the presence of these oxygen groups, the nanoribbon could homogeneously disperse in both water and poly (vinly alcohol) matrix. It was also found that there were strong interactions between the graphene nanoribbon and the poly (vinyl alcohol) through hydrogen bonding. The interactions gave rise to the thermal stability of the host polymer. Furthermore, the presence of the nanofiller also resulted in a significant improvement of the mechanical performance of the prepared nanocomposites. The tensile strength and the Young’s modulus of the nanocomposite loaded with 2.0 wt% graphene nanoribbon increased by 85.7% and 65.2% respectively. The overall results indicate that the graphene nanoribbon is suitable for preparing high-performance polymer composites.     

Facile preparation,characterization and performance of noncovalently functionalized graphene/epoxy nanocomposites with poly(sodium 4-styrenesulfonate)

Graphene was noncovalently functionalized with poly(sodium 4-styrenesulfonate) (PSS) and then successfully incorporated into the epoxy resin via in situ polymerization to form functional and structural nanocomposites. The morphology and structure of PSS modified graphene (PSS-g) were characterized with transmission electron microscopy, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The effects of PSS-g additions on tensile, electrical and thermal properties of the epoxy/graphene nanocomposites were studied. Noncovalent functionalization improved interfacial bonding between the epoxy matrix and graphene, leading to enhanced tensile strength and modulus of resultant nanocomposites. The PSS-g additions also enhanced electrical properties of the epoxy/PSS-g nanocomposites, resulting in a lower percolation threshold of 1.2 wt%. Thermogravimetric and differential scanning calorimetric results showed the occurrence of a two-step decomposition process for the epoxy/PSS-g nanocomposites.     

氰酸酯树脂/氧化石墨烯纳米复合材料的制备及表征

通过溶液插层的方法制备氰酸酯树脂/氧化石墨烯纳米复合材料,采用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)和热重分析(TGA)研究纳米复合材料的结构和性能,采用电子万能试验机研究纳米复合材料的力学性能。研究表明,异氰酸苯酯改性氧化石墨在二甲基甲酰胺中经超声处理后剥离形成氧化石墨烯薄片;添加氧化石墨烯后纳米复合材料的力学性能和耐热性显著改善。当氧化石墨烯的含量为基体树脂的1%时,纳米复合材料的拉伸强度、弯曲强度和冲击强度分别为82.9 MPa、148.6 MPa和12.9 kJ/m2,1000℃时的残炭率达45.1%。