Mechanical behaviour and essential work of fracture of halloysite nanotubes filled polyamide 6 nanocomposites

Polyamide 6 (PA 6)/halloysite nanotubes (HNT) nanocomposites were prepared by melt-extrusion compounding via masterbatch dilution process. A homogeneous dispersion of HNTs in PA 6 matrix was achieved. Differential scanning calorimetric measurements showed that addition of HNTs into PA 6 matrix enhanced the crystallization temperature and degree of crystallinity, thus indicating an effective nucleation induced by the addition of HNTs. Upon halloysite addition, glass transition temperature, storage modulus, Young modulus, tensile strength and notched Charpy impact strength increased without loss of ductility. For the first time, the essential work of fracture (EWF) concept was used to analyse the toughening and fracture behaviour of PA 6/HNT systems. Significant increase (+38%) of the essential work of fracture of PA 6/HNT nanocomposites was noticed at HNTs contents as low as 4 wt.%.     

功能化石墨烯/埃洛石纳米管对聚丙烯的协同强韧化改性研究

以功能化氧化石墨烯(GO)-埃洛石纳米管(HNTs)杂化材料(GO@HNTs)为纳米填料,以聚丙烯(PP)为基体,通过熔融共混法制备了不同GO@HNTs 含量的GO@HNTs/PP纳米复合材材料,并对所得杂化填料和PP纳米复合材料的结构与性能进行系统研究。研究结果表明,功能化GO与HNTs之间存在化学相互作用,二者之间形成的“屏障效应”抑制了彼此在PP基体中的团聚。仅添加0.5%GO@HNTs杂化纳米填料后,PP复合材料的拉伸强度和冲击强度分别较纯PP提高了17.5%和80.4%,与单独添加相同含量的GO或HNTs所得复合材料的力学性能相比,GO@HNTs杂化纳米填料对PP基体具有明显的协同增强增韧改性作用。与纯PP相比,GO@HNTs/PP试样表现出更高的储能模量、损耗模量和玻璃化转变峰值。由于GO@HNTs的“异相成核效应”和“物理热阻效应”,有效提高了PP纳米复合材料的结晶温度、熔融温度、结晶度和耐热分解温度。     

Unsaturated polyester nanocomposites filled with nano alumina

Alumina nanoparticles (60–70 nm) were prepared by the sol–gel technique using citric acid and aluminum nitrate. Casting technique was used to make nanocomposites of unsaturated polyester (UPR) and nano alumina. Transmission Electron Microscopy (TEM) study demonstrated that nano alumina particles were dispersed uniformly in the UPR matrix and agglomeration of particles was found at higher filler loading (>5 wt%). The nanocomposites show higher tensile, flexural and impact strength than pristine UPR. Scanning Electron Microscopy (SEM) of the fractured surface of tensile test samples show that the ductile fracture of UPR was converted to brittle fracture with the addition of nano alumina. Dynamic Mechanical Analysis (DMA) studies showed the storage modulus increased up to 5 wt% loading of nano alumina. The impact strength and storage modulus results agree well. The thermogravimetric studies revealed that the nanocomposites were having higher thermal stability than the pure UPR. As the concentration of the nano alumina in the UP resin increased, the char yield was also increased.     

Electrical, thermal, and mechanical properties of polyarylene ether nitriles/graphite nanosheets nanocomposites prepared by masterbatch route

Graphite nanosheets (GN) reinforced polyarylene ether nitriles (PEN) nanocomposites were successfully fabricated through masterbatch route and investigated for morphological, thermal electrical, mechanical, and rheological properties. The SEM images showed that GN were well coated by phthalonitrile prepolymer (PNP) and dispersed in the PEN matrix. Thermal degradation and heat distortion temperature of PEN/GN nanocomposites increased substantially with the increment of GN content up to 10 wt%. Electrical conductivity of the polymer was dramatically enhanced at low loading level of GN; the electrical percolation of was around 5 wt% of GN. The mechanical properties of the nanocomposites were also investigated and showed significant increase with GN loading. For 10 wt% of GN-reinforced PEN composite, the tensile strength increased by about 18%, the tensile modulus increased by about 30%, the flexural strength increased by about 25%, and the flexural modulus increased by 90%. Rheological properties of the PEN/GN nanocomposites also showed a sudden change with the GN loading content; the percolation threshold was in the range of 3–4 wt% of GN.     

Wrapping of polyrhodanine onto tubular clay and its prominent effects on the reinforcement of the clay for rubber

Polyrhodanine (PRd) was wrapped onto the surface of halloysite nanotubes (HNTs) through the oxidative polymerization of rhodanine on Fe³⁺-impregnated-HNTs. The wrapping mechanisms were disclosed. The PRd-HNTs exhibited a prominent reinforcing effect for rubber. With the incorporation of 30 phr of PRd-HNTs, the tensile strength was increased by almost 8-fold, and the modulus (at 300% strain) was increased by 257% compared to neat SBR. More strikingly, with only 2.9 wt.% of PRd (relative to HNTs), the tensile strength and modulus of the composite were enhanced by 117% and 87%, respectively, suggesting the high efficiency of the modification. Such profound changes in the reinforcement were attributed to the formation of covalent linkages between PRd-HNTs and rubber through the participation of PRd-HNTs in curing process. In view of the versatility of PRd-wrapping procedure, this method offers significant insight into the interfacial design of rubber nanocomposites consisting of nonpolar matrices and inorganic reinforcements.     

Effect of Multi-Wall Carbon Nanotubes on the Mechanical Properties of Natural Rubber

Multi-walled carbon nanotubes (MWNTs) were used to prepare natural rubber (NR) nanocomposites. Our first efforts to achieve nanostructures in MWNTs/NR nanocomposites were formed by incorporating carbon nanotubes in a polymer solution and subsequently evaporating the solvent. Using this technique, nanotubes can be dispersed homogeneously in the NR matrix in an attempt to increase the mechanical properties of these nanocomposites. The properties of the nanocomposites such as tensile strength, tensile modulus, elongation at break and hardness were studied. Mechanical test results show an increase in the initial modulus for up to 12 times in relation to pure NR. In addition to mechanical testing, the dispersion state of the MWNTs into NR studied by Transmission Electron Microscopy (TEM) in order to understand the morphology of the resulting system     

Static and dynamic mechanical properties of polydimethylsiloxane/carbon nanotube nanocomposites

The purpose of this study is to investigate the static and dynamic mechanical properties of polydimethylsiloxane (PDMS) and the mixture of PDMS and carbon nanotubes. The PDMS/CNT nanocomposites were stirred by an ultrasonic instrument to prevent agglomerations. The tested specimens of nanocomposites were manufactured by using the thermoforming method at 150 °C for 15 min. A micro tensile tester was adopted in this testing system with a maximum load of 500 mN and a crosshead extension of 150 mm. The static elastic modulus can be calculated by means of a tensile test and the average elastic modulus of pure PDMS is 1.65 MPa. In addition, the Nano Bionix tensile tester was also used to perform the dynamic mechanical analysis. Its dynamic frequency range is from 0.1 Hz to 2.5 KHz. The dynamic properties of PDMS/CNT nanocomposites such as storage and loss modulus can be obtained by this system. The storage modulus increased with the CNT content and also with the higher frequencies. Finally, the nanoindentation measurement system was employed to characterize the mechanical properties of PDMS and PDMS/CNTs. The measurement results of elastic modulus by a nanoindentation test have the similar trend with the results obtained by the tensile test method.     

Ethylene vinyl acetate/expanded graphite nanocomposites by solution intercalation: preparation,characterization and properties

Nanodimensional reinforcing agents are introduced to polymer matrices to improve properties at very low loading. Natural graphite (NG) as such is not reinforcing in nature. But when modified to expanded graphite (EG) by high temperature heat treatment, this may be used as reinforcing nanofiller. In the present study, ethylene vinyl acetate (EVA) was reinforced with EG by solution intercalation, and the composite properties were compared with those of the virgin polymer and NG filled composite. The tensile strength exhibited an improvement of 35% with 4 wt% EG addition, while the modulus at 100% elongation was increased by 150% with respect to the control EVA. Another interesting feature was that unlike the conventional fillers, addition of EG did not reduce the elongation at break, due to the lubricating action of graphite. However, at a high loading of 8 wt%, the tensile strength showed a lower value, due to the agglomeration of graphite platelets. The storage modulus also showed increment with the addition of graphite without much change in the glass transition temperature. In addition to these, the EVA-EG nanocomposites exhibited high thermal conductivity and thermal degradation stability as compared to the virgin polymer. About 4 wt% of EG shifted the temperature of maximum rate of degradation by 14 °C towards higher temperature. These results were well supported by the swelling and morphological studies. The NG filled composite exhibited inferior properties to EVA-EG nanocomposites.     

Effect of multi-wall carbon nanotubes on the mechanical properties of natural rubber

Multi-walled carbon nanotubes (MWNTs) were used to prepare natural rubber (NR) nanocomposites. Our first effort to achieve nanostructures in MWNTs/NR nanocomposites were formed by incorporating carbonnanotubes in a polymer solution and subsequently evaporating the solvent. Using this technique, nanotubess can be dispersed homogeneously in the NR matrix in an attempt to increase the mechanical properties of these nanocomposites. The properties of the nanocomposites such as tensile strength, tensile modulus, tear strength, elongation at break and hardness were studied. Mechanical test results show an increase in the initial modulus for up to 12 times in relation to pure NR. In addition to mechanical testing, the dispersion state of the MWNTs into NR was studied by transmission electron microscopy (TEM) in order to understand the morphology of the resulting system. According to the present study, application of the physical and mechanical properties of carbon nanotubes to NR can result in rubber products which have improved mechanical, physical and chemical properties, compared with existing rubber products reinforced with carbon black or silicone.     

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.     

两次挤出制备尼龙66/纳米SiO2复合材料及其结构与性能

通过双螺杆两次挤出技术制得了尼龙66/SiO2纳米微粒复合材料,发现二次挤出的复合材料的拉伸强度、断裂伸长率、杨氏模量、简支梁缺口冲击强度较纯尼龙66均有很大程度的提高,并通过动态力学热分析研究了复合材料的动态力学性能,复合材料的储能模量及玻璃化转变温度均有不同程度的提高。借助SEM分析了复合材料的拉伸断面形貌,并用DSC研究了复合材料的结晶行为。     

纳米OMMT/EVA-g-PU复合材料

采用熔融接枝与熔融插层相结合的方法,成功制备了纳米OMMT/EVA-g-PU复合材料。通过FTIR及13C NMR测试表明,端—NCO的聚氨酯(PU)预聚体与皂化乙烯-醋酸乙烯酯共聚物(EVA)间发生接枝反应。采用X射线衍射仪(XRD)与透射电镜(TEM)观察了蒙脱土(OMMT)在基体中的分散状态,用电子万能试验机、动态力学分析仪(DMA)和热重分析仪(TG)分析了复合材料的力学性能、储能模量和热性能。结果表明：OMMT主要以插层型分布在基体中;当OMMT的质量分数为3%时,复合材料的断裂强度、杨氏模量和撕裂强度分别为7.96 MPa、7.12 MPa和49.97 MPa;复合材料的储能模量随 OMMT含量的增加而升高,当OMMT的质量分数为7%时,复合材料的储能模量相对于纯EVA 提高了2 倍多;复合材料的热稳定性能也要优于纯EVA,并随OMMT含量的增加而升高。     

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.     

The effect of process parameters on physical and mechanical properties of commercial low density polyethylene/ORG-MMT nanocomposites

Polyethylene/organo-montmorillonite clay (org-MMT) nanocomposites were prepared utilizing PP-g-MA as a compatibilizer by melt intercalation method. In order to increase the miscibility of polyethylene (PE) with nanoparticle surface at firs, a primary masterbatch consist of compatibilizer and org-MMT was prepared then, this compound was melt intercalated with PE to synthesis the PE/org-MMT nanocomposites. In this study, the presence of commercial low density polyethylene in Nanocomposites structure and also the effect of process parameters such as: amount of nanoparticles, mixing rate and mixing time on nanocomposite structure and properties have been investigated. The X-ray diffraction (XRD) and transmission electron microscopy (TEM) results showed that the interlayer distance of nanoparticle layers increased and a partially intercalated structure was prepared by melt intercalation method. Interaction between polyethylene chains and nanoparticle layers could be improved if the control of above parameters causes to penetrate the chains into nanoclay layers; by an optimization, this effect could improve the physical and mechanical properties. The DSC data revealed that melting temperature has slowly increased and crystalinity has lightly decreased. Consequently we can claim the thermal properties of LDPE/clay nanocomposite did not considerably change with clay content. A rise in the mechanical properties such as yield stress and modulus was observed by tension test; by addition of 5% clay content the tensile strength increased about 7%, the tensile modulus enhanced about 60% and the yield stress increased about 16% in comparison with the pure LDPE.     

亚麻纤维增强聚乳酸可降解复合材料的制备与性能

将制浆造纸用亚麻短纤维与聚乳酸(PLA)熔融共混,用注塑方法成型亚麻纤维/聚乳酸复合材料试样。通过差示扫描量热实验(DSC)、动态力学性能测试(DMA)、热重分析(TGA)和力学性能测试等方法,研究了聚乳酸和亚麻纤维在不同质量配比下,复合材料热性能、动态力学性能和力学性能的变化规律。随着亚麻纤维的加入,复合材料的结晶度增大,热稳定性增强,储能模量得到提高,力学性能也有了明显变化:纤维含量为20%时,拉伸强度为45.88 MPa,比纯PLA的增加了21%;同时,弯曲模量的增幅达到30%。     

SiO2/环氧树脂基纳米复合材料的室温和低温力学性能

利用溶胶-凝胶法制备了SiO₂/环氧树脂基复合材料,研究了材料的室温与低温(77 K)下的力学性能。结果表明,适量SiO₂的引入提高了室温与低温下材料的拉伸强度、断裂伸长率和冲击强度,即SiO₂含量在2%时可同时起到增强、增韧作用。采用扫描电镜(SEM)和透射电镜 (TEM)分别对复合材料的断口形貌和高温焚烧后残留物纳米颗粒进行了观察。还利用动态力学分析(DMA)研究了二氧化硅的引入对复合材料的影响。      

Effect of nanoparticles on tensile,impact and fatigue properties of fibre reinforced plastics

Advanced composite, fibre-reinforced polymer (FRP), has been favoured for certain aerospace, military, marine and automotive applications. Polymer nanocomposites containing layered silicates have attracted much attention. These exhibit increased modulus, decreased thermal expansion coefficient, increased solvent resistance and enhanced ionic conductivity when compared to the polymer alone. Here we have developed eight different combinations of composites FRP with nanoclay (montmorillonite) by layered manufacturing techniques (LM) and measured the mechanical properties. The measurement showed that the tensile strength, impact strength and fatigue life are greatly increased. A plausible explanation for high increase of properties has also been discussed.     

Preparation and characterization of poly(methyl methacrylate)-clay nanocomposites via melt intercalation: Effect of organoclay on thermal, mechanical and flammability properties

The PMMA nanocomposites were prepared by melt processing method. The influence of organoclay loading on extent of intercalation, thermal, mechanical and flammability properties of poly(methyl methacrylate) (PMMA)-clay nanocomposites were studied. Three different organoclay modifiers with varying hydrophobicity (single tallow vs. ditallow) were investigated. The nanocomposites were characterized by using wide angle X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, differential scanning calorimetry (DSC), and tensile tests. The intercalation of polymer chain within the silicate galleries was confirmed by WAXD and TEM. Mechanical properties such as tensile modulus (E), tensile strength, percentage elongation at break and impact strength were determined for nanocomposites at various clay loadings. Overall thermal stability of nanocomposites increased by 16-17 °C. The enhancement in T_g of nanocomposite is merely by 2-4 °C. The incorporation of maleic anhydride as compatibilizer further enhanced all the properties indicating improved interface between PMMA and clay. The flammability characteristics were studied by determining the rate of burning and LOI.     

Microstructure and properties of polyurethane nanocomposites reinforced with methylene-bis-ortho-chloroanilline-grafted multi-walled carbon nanotubes

Methylene-bis-ortho-chloroanilline (MOCA), an excellent cross-linker widely used to prepare cured polyurethane (PU) elastomers with high performance, was used to modify a multi-walled carbon nanotube. PU/carbon nanotube (CNT) nanocomposites were prepared by incorporation of the MOCA-grafted CNT into PU matrix. Fourier transform infrared spectra have shown that the modified CNTs have been linked with PU matrix. The microstructure of composites was investigated by Field-Emission Scanning Electron Microscopy. The results of Dynamic Mechanical Thermal Analysis and Differential Scanning Calorimetry have investigated the grafted CNTs as cross-linker in the cured composites. The studies on the thermal and mechanical properties of the composites have indicated that the storage modulus and tensile strength, as well as glass transition temperature and thermal stability are significantly increased with increasing CNT content.     

Effect of pretreatment of bagasse fibers on the properties of chitosan/microfibrillated cellulose nanocomposites

Bleached bagasse pulp was pretreated with dilute alkali and xylanase enzymes before isolation of microfibrillated cellulose using ultra-high friction grinding and high-pressure homogenization. The isolated nanofibers were used with chitosan polymer to prepare chitosan nanocomposites by solution casting at nanofiber loading from 2.5 to 20%. The effect of nanofibers loading on moisture sorption, dry and wet tensile strength, crystallinity, thermal stability, and dynamic mechanical thermal properties was studied using tensile testing, X-ray diffraction (XRD), thermogravimetric analysis (TGA), and dynamic mechanical thermal analysis (DMTA). Nanocomposites with good transparency were obtained at the different nanofibers loadings. Chitosan nanocomposites made using nanofibers isolated from bagasse fibers treated with xylanase or alkali showed higher dry and wet tensile strength than those made using nanofibers isolated from untreated bagasse pulp. DMTA results showed higher storage modulus and indicated higher glass transition temperature for the chitosan nanocomposites than that of neat chitosan. XRD patterns showed that, at low nanofibers loading, addition of bagasse nanofibers to chitosan matrix increased ordering of chitosan chains upon drying the nanocomposites films.