Physico-chemical and mechanical properties of nanocomposites prepared using cellulose nanowhiskers and poly(lactic acid)

A range of nanocomposites were prepared using cellulose nanowhiskers (CNWs) and poly(lactic acid) (PLA) via a solvent casting process. Acid hydrolysis process was used to produce CNWs from bleached cotton. Structural morphology and surface topography of the CNWs and nanocomposites were examined using transmission (TEM) and scanning electron microscopy. TEM images revealed rod-like whiskers in the nano-scale region which were dispersed within the PLA matrix. The presence of the functional groups of CNWs and PLA were confirmed via FTIR analysis. Tensile tests were conducted on thin films and the nanocomposites containing 1 wt% CNWs showed a 34 and 31% increase in tensile strength and modulus, respectively, compared to pure PLA. The dynamic mechanical analysis showed that the tensile storage modulus also increased in the visco-elastic temperature region with increasing CNWs content in the nanocomposites. Thermogravimetric analysis showed that all the materials investigated were thermally stable from room temperature to 210 °C. A positive effect of CNWs on the crystal nucleation of PLA polymer in the nanocomposites was observed using differential scanning calorimetry and X-ray diffraction analysis. The degradation profiles of the nanocomposites in deionised water over 1 week revealed a mass loss of 1.5–5.6% at alternate temperatures (25, 37 and 50 °C) and at the same conditions the swelling ratio and water uptake were seen to increase with CNWs content in the nanocomposites, which was strongly influenced by the presence of crystalline CNWs.     

Processing of cellulose nanowhiskers/cellulose acetate butyrate nanocomposites using sol-gel process to facilitate dispersion

Biobased nanocomposites based on cellulose nanowhiskers (CNWs) and cellulose acetate butyrate (CAB) were prepared using solvent exchange of CNWs to ethanol by sol-gel method followed by casting. The strong flow birefringence of the solutions indicated evenly dispersed cellulose nanowhiskers in the dissolved polymer CAB. Scanning electron microscopy of the nanocomposites confirmed well dispersed CNWs in the CAB matrix, which was further supported by the high transparency exhibited by the nanocomposites. The results of tensile tests indicated significant improvements in the mechanical properties of nanocomposites by increasing the CNWs contents. The Young’s modulus and strength increased 83% and 70%, respectively, for nanocomposites with 12 wt% of CNW, and the strain was not suppressed compared to the neat CAB. The dynamic mechanical thermal analysis demonstrated significant improvement in storage modulus with increasing CNW contents, and the tan δ peak position was moved towards higher temperature when CNW was added. It is expected that solvent exchange by the sol-gel route followed by casting of nanocomposites from the same solvent will provide a promising route for obtaining cellulose nanocomposites with well dispersed CNW, leading to improved mechanical properties, even with low nanowhisker contents.     

Controlled synthesis of train-structured montmorillonite/layered double hydroxide nanocomposites by regulating the hydrolysis of polylactic acid

Two-dimensional nanosheets obtained by exfoliation can assemble into new functional nanomaterial. One of the critical challenges is developing an efficient method to make the layered composite complete exfoliation, and another is regulating and controlling nanosheets assembly to obtain the nanocomposite with specific structure. In this article, the platelets of layered double hydroxides (LDH) and montmorillonite (MMT) are exfoliated completely and efficiently in polylactic acid (PLA) by melting blend for 10 min, and the monolayers of MMT or LDH can store stably in PLA for a long time. A new well-organized layered nanocomposite containing the nanosheets of LDH and MMT was gained by being exfoliated and assembling. The structure of MMT/LDH nanocomposite not only holds a periodically alternating structure, but also possesses a train structure, and the formation mechanism of train structure is proposed at the first time; furthermore, the structure of MMT/LDH could be regulated and controlled. Fortunately, even being exfoliated and assembled, MMT nanosheet or LDH nanosheet was not destroyed. The MMT/LDH nanocomposite with expectant structure can be obtained by this efficient and environmentally friendly method, and this method may easily be extended to other layered materials.     

天然橡胶/蒙脱土原土纳米复合材料的制备与性能

用机械混炼反应插层法,通过引入第三组分RH,制备了天然橡胶／蒙脱土原土纳米复合材料,实现了对天然橡胶的补强,在这种复合材料中,蒙脱土原土的层间距显著增大,蒙脱土无机片层在橡胶基体中达到了纳米级分散．蒙脱土原土与天然胶纳米复合保持了较低的滚动阻力,显著地提高了天然胶的抗湿滑性．     

Synthesis and properties of melamine-formaldehyde/ montmorillonite nanocomposites

In this paper, intercalated and partially exfoliated melamine-formaldehyde (MF)/montmorillonite (MMT) nanocomposites have been synthesized successfully via in-situ polymerization based on pristine montmorillonite, acidified montmorillonite and organic modified montmorillonite respectively. The obtained nanocomposites were characterized by XRD, TEM, TGA, and Raman spectroscopy. Free formaldehyde content of those composites was also determined by acetyl acetone technique. It was found that acidified montmorillonite and organic modified montmorillonite could catalyze the polycondensation reaction of methylolmelamines. The thermal stability and chemical resistance of those two nanocomposites were also improved dramatically compared to pure melamine-formaldehyde resin.     

接枝细菌纤维素改性聚乳酸复合材料的制备与性能

聚乳酸(PLA)作为新型的绿色友好材料有非常广阔的应用前景。为有效解决PLA韧性差、结晶速率低等问题,本文提出了以纤维素改性PLA的方法。首先以细菌纤维素(BC)为底物,使L-丙交酯(LLA)在其表面进行原位开环聚合,得到了BC-g-PLA接枝产物;然后将该接枝产物作为增韧剂添加到PLA中,采用溶液浇筑的方法制备得到复合薄膜材料。结果表明：溶液接枝法的反应效率比熔融接枝法更高,接枝率可达到76.60%;通过FTIR、核磁共振波谱仪与XRD对接枝产物进行结构测试,证实了PLA成功接枝到BC表面;通过偏光显微镜观察复合薄膜材料晶体形貌发现BC-g-PLA作为异相成核剂,添加量为0.6%时,对球晶的均匀细化程度最高;通过力学性能测试发现,PLA薄膜增韧改性后断裂伸长率可提高175%,拉伸强度可提高22.7%;通过差示扫描量热仪测试复合薄膜材料的结晶性能,结晶度从未改性的2.53%提高到13.26%,结晶速率也有所增加。     

Thermal properties of PMMA/montmorillonite clay nanocomposites

Polymer/Clay offer tremendous improvement in wide range of physical and engineering properties for polymers with low filler loading. In nanotechnology polymer/clay nanocomposites use smectitetype clays that have layered structures. In this work, Poly (methyl methacrylate) (PMMA) was synthesized by free radical addition polymerization in the presence of high power ultrasound. The Poly (methyl methacrylate) (PMMA)-Montmorillonite (MMT) clay nanocomposites were synthesized by two different techniques viz., ultrasonic mixing and magnetic stirring. An analysis of the XRD data confirms that the composites are in the nanometer scale. The FTIR spectra show that there is strong interaction between the clay and the polymer that enhances the thermal stability. The thermal stability of the experimental nanocomposite prepared by the two processes is compared. Further analysis of XRD data shows that intercalation as well as exfoliation has taken place in both the types of nanocomposites preparation. An analysis of the TG, DTG curves reveal that the thermal stability is found to increase by nearly 30% for ultrasonic mixing than that of magnetic stirring.     

丁腈橡胶/有机蒙脱土纳米复合材料的结构及性能研究

通过机械共混法制备了丁腈橡胶/有机蒙脱土(NBR/OMMT)纳米复合材料.X射线衍射(XRD)和透射电镜(TEM)表征了复合材料的纳米结构.通过硫化仪研究了有机蒙脱土用量对复合材料硫化性能的影响,同时研究了复合材料的力学性能、热空气老化性、耐油性和热稳定性.结果表明:有机蒙脱土的加入在一定程度上提高了复合材料的力学性能,热空气老化性,耐油性及热稳定性,而且对复合材料的硫化性能有明显的影响.     

竹纤维增强聚乳酸复合材料热老化性能

采用氢氧化钠和异氰酸酯处理的界面调控方法对竹纤维(BF)增强聚乳酸(PLA)复合材料界面进行调控,通过注射成型工艺制备BF/PLA复合材料。利用FTIR、XRD、凝胶渗透色谱及SEM等分析手段研究了BF/PLA复合材料热老化性能。研究发现: 热老化过程中PLA分子链中的C O不断水解,分子链的C—O断裂生成聚合度更低的小分子量的PLA,PLA结晶度减小,PLA与BF的接合界面被破坏,拉伸强度和冲击强度随老化时间的增加逐渐降低。BF/PLA复合材料在80℃热老化16天后拉伸强度和冲击强度分别降低了75%和77.6%,在100℃热老化32 h后拉伸强度和冲击强度分别降低了80.3%和83.4%。温度对BF/PLA复合材料老化影响显著,温度越高,老化速度越快。     

玻璃纤维增强淀粉/聚乳酸复合材料——纤维用量对性能的影响

以玉米淀粉和聚乳酸(PLA)为原料,甘油为增塑剂,通过熔融挤出法制备玻璃纤维增强淀粉/PLA复合材料。研究了玻璃纤维用量对复合材料断面形貌、力学性能、耐水性能和熔融性能的影响。结果表明,随着玻璃纤维用量增多,纤维与基体间的机械咬合作用使复合材料断裂面变得粗糙;纤维用量超过4%后,纤维之间产生相互缠结,对复合材料基体的增强效果减弱,使得断裂面的粗糙度下降。受玻璃纤维对基体增强效果的影响,随着纤维用量增多,复合材料的拉伸强度、弯曲强度和断裂伸长率都逐渐增大,吸水率逐渐降低,玻璃纤维用量为4%达到临界值。复合材料的储能模量随着玻璃纤维用量增多而增大,而熔融指数和复数粘度却随着玻璃纤维用量增多而降低。     

Mechanical properties of cellulose nanofiber (CNF) reinforced polylactic acid (PLA) prepared by twin screw extrusion

The aim of this study was to develop cellulose nanofiber (CNF) reinforced polylactic acid (PLA) by twin screw extrusion. Nanocomposites were prepared by premixing a master batch with high concentration of CNFs in PLA and diluting to final concentrations (1, 3, 5 wt.%) during the extrusion. Morphology, mechanical and dynamic mechanical properties (DMA) were studied theoretically and experimentally to see how different CNF concentrations affected the composites’ properties. The tensile modulus and strength increased from 2.9 GPa to 3.6 GPa and from 58 MPa to 71 MPa, respectively, for nanocomposites with 5 wt.% CNF. The DMA results were also positive; the storage modulus increased for all nanocomposites compared to PLA; being more significant in the high temperature region (70 °C). The addition of nanofibers shifted the tan delta peak towards higher temperatures. The tan delta peak of the PLA shifted from 70 °C to 76 °C for composites with 5 wt.% CNF.     

Structure and properties of hybrid PLA nanocomposites with inorganic nanofillers and cellulose fibers

Polylactide reinforced with 3 wt% of organo-modified montmorillonite, 5 wt% of stearic acid-modified calcium carbonate nanoparticles, 15 wt% of cellulose fibers (PLA/MMT, PLA/NCC, PLA/CF) and hybrid composites containing 15 wt% of fibers in addition to montmorillonite (PLA/MMT/CF) or calcium carbonate (PLA/NCC/CF) were prepared and examined. The nanoparticles were dispersed in polylactide almost homogeneously; montmorillonite was exfoliated during processing. T_g of polylactide remained unaffected but its cold crystallization was enhanced; the cold-crystallization behavior of the hybrid composites was dominated by nanofillers nucleating ability. The fibers and calcium carbonate decreased whereas exfoliated montmorillonite improved the thermal stability of the materials. Polylactide, PLA/NCC and PLA/MMT exhibited ability to plastic deformation, although the latter the weakest. Tensile behavior of the hybrid composites was strongly influenced by the fibers and similar to that of PLA/CF. All the fillers increased the storage modulus below T_g; that of PLA/MMT/CF and PLA/NCC/CF was improved with respect to polylactide by 50% and 45%, respectively.     

Development and characterisation of novel electrospun polylactic acid/tubular clay nanocomposites

A novel material formulation method of polylactic acid /tubular clay nanocomposites via electrospinning was introduced and the important processing parameters such as solution concentration, clay loading, material feed rate were particularly investigated. The hybrid fibre diameter, the clay dispersability and the thermal properties of such nanocomposites were then characterised by using the scanning electron microscopy, wide-angle X-ray diffraction and differential scanning calorimetry, respectively, to establish a fundamental structure–property relationship for the future application.     

盐酸西替利嗪/蒙脱土纳米复合物的制备及其结构与性能

以钙基蒙脱土为原料,采用微波-力化学法制备钠基蒙脱土(MMT)。采用溶液离子交换法制备盐酸西替利嗪(CTH/MMT) 纳米复合物,研究了MMT 对CTH 的吸附规律。利用XRD、FTIR、TG等分析了CTH/MMT复合物的结构。通过体外人工模拟胃、肠液中的释放实验表征了CTH/MMT的缓释效果、缓释机制及其动力学。结果表明,CTH插层于MMT层间,层间距由1. 25 nm增至2. 13 nm。MMT对CTH 插层吸附等温线符合Freundlich吸附等温方程,其吸附动力学符合二级动力学方程。体外的缓释试验表明,CTH/MMT具有良好的缓释效果,MMT可作为盐酸西替利嗪的控释载体材料。      

苯乙烯-丙烯酸丁酯/蒙脱土复合乳液制备及涂层耐蚀性研究

通过半连续乳液聚合法以苯乙烯,丙烯酸丁酯和蒙脱土为主要原料合成了苯丙乳液/蒙脱土纳米复合材料。透射电镜表征了粒子的形貌,表明乳液胶粒呈球形,粒径分布范围约为110nm;XRD表征改性乳液的结构,表明苯丙乳液插层到蒙脱土层间形成插层与部分剥离型纳米复合材料;TG、DTG表征复合材料的热稳定性,表明与苯丙乳液相比,纳米复合材料的热稳定性提高了22℃,2%质量分数蒙脱土改性乳胶膜最大分解速率温度提高了16℃;Tafel极化曲线表征改性前后涂层在钢材基板上的耐腐蚀性,不同质量分数的复合乳液的腐蚀电位均有不同程度的正移,2%蒙脱土质量分数改性的乳液耐蚀性最好。     

Effect of compound organification of montmorillonite on the structure and properties of polypropylene/montmorillonite nanocomposites

In this paper, reactive organic montmorillonite (RMMT), prepared with compound alkylammoniums, were used in ternary-monomer solid phase graft copolymerization in order to enhance the melting intercalation of montmorillonite (MMT), stabilize the intercalated structure, and prepare the exfoliated polypropylene/montmorillonite (PP/MMT) nanocomposites (PPMN). The structure and properties of PPMN were studied by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscope (TEM), etc. Results show that the compound organification, solid phase graft copolymerization really favored the melting intercalation. The compound organification and exothermic process of the solid phase copolymerization promoted the melting intercalation. The mechanical properties, melt flow rate and Vicat softening point of PPMN significantly had a preferable reinforced state at 6–8 phr PP/MMT graft copolymers (PPGM). The increase of the mechanical properties and thermal properties was owed to the reinforcement of the exfoliated MMT and the compatibilization of the oligomers built by the polar monomers during the solid phase graft copolymerization. The improvement of the fluidity of PPMN derived from the plasticization of the exfoliated MMT and oligomers. Translated from Chinese Journal of Materials Research, 2006, 20(2): 197–202 [译自: 材料研究学报]     

聚丙烯/蒙脱土纳米复合材料的结构与性能

采用复合季胺盐制备反应性有机蒙脱土并参与三单体固相接枝聚合,加强蒙脱土（MMT）的熔融插层和稳定MMT的插层结构,制备剥离型的聚丙烯／蒙脱土纳米复合材料（PPMN）．通过X射线衍射（XRD）、傅立叶变换红外光谱（FTIR）,透射电镜（TEM）等测试手段研究了PPMN的结构和性能．结果表明：复合有机化和固相接枝的确加强了MMT的熔融插层．MMT的复合有机化和固相接枝的放热过程有助于MMT层间涨大和MMT剥离结构的形成．当PPGM的添加量在6—8phr时,PPMN的力学性能、流动性能和热性能达到一个较好的增强状态．PPMN力学性能和热性能的提高归功于剥离的蒙脱土的增强作用和接枝低聚物原位形成的界面增容作用;PPMN流动性能的改善来源于剥离的蒙脱土和固相接枝形成的低聚物的增塑作用．     

The relationship between microstructure and mechanical properties of carbon nanotubes/polylactic acid nanocomposites prepared by twin-screw extrusion

Twin-screw extrusion was applied to prepare the carbon nanotubes/polylactic acid (CNT/PLA) nanocomposites. Five different extruded plates were produced under variation of CNT concentrations. The internal microstructures were also observed by optical microscope to examine the distribution and dispersion of CNT in the PLA. Besides, the crystallinity of the CNT/PLA nanocomposites was investigated by differential scanning calorimetry (DSC) and density method. The effects of the CNT concentrations on the mechanical and electrical properties of the nanocomposites were investigated. Scanning electron microscope (SEM) was performed to observe the CNT dispersion in the nano-scale. These results suggested that the crystallinity was increased with the increase of CNT concentrations, demonstrating that CNT played a role as a nucleating agent in PLA. Moreover, the mechanical and electrical properties of PLA have been improved by a proper incorporation of CNTs due to a good distribution and dispersion of the CNTs.     

Synthesis and properties of sandwiched films of epoxy resin and graphene/cellulose nanowhiskers paper

Graphene (GN)-based composite paper containing 10 wt.% cellulose nanowhiskers (CNWs) exhibiting a tensile strength of 31.3 MPa and electrical conductivity of 16 800 S/m was prepared by ultrasonicating commercial GN powders in aqueous CNWs suspension. GN/CNWs freestanding paper was applied to prepare the sandwiched films by dip coating method. The sandwiched films showed enhanced tensile strength by over two times higher than the neat resins. The moduli of the sandwiched films were around 300 times of the pure resins due to the high content of GN/CNWs paper. The glass transition temperature of the sandwiched films increased from 51.2 °C to 57.1 °C for pure epoxy (E888) and SF (E888), and 49.8 °C to 64.8 °C for pure epoxy (650) and SF (650), respectively. The bare conductive GN/CNWs paper was well protected by the epoxy resin coating, which is promising in the application as anti-static materials, electromagnetic interference (EMI) shielding materials.     

竹纤维质量分数对竹纤维增强聚乳酸复合材料性能影响

以1.5%异氰酸酯(MDI)界面改性剂改性处理后的竹纤维和聚乳酸为原料,通过注射成型工艺制备竹纤维增强聚乳酸复合材料,探讨竹纤维质量分数对复合材料界面、力学性能、吸水率、热性能的影响。结果表明,随着竹纤维质量分数的增加,复合材料拉伸强度、冲击强度、存储模量以及热稳定性均先增大后减小,24h吸水率逐渐增大,损耗因子逐渐降低。竹纤维质量分数为50%时,复合材料的拉伸强度和冲击强度分别达到最大值63.2MPa和11.6kJ/m2,复合材料存储模量最大,热稳定性最好。