Electrical conductive CNT-PVA/PC nanocomposites with high tensile elongation

Electrically conductive CNT reinforced polycarbonate matrix nanocomposites with high strain-to-failure were fabricated by inserting polyvinylalcohol as a surface modifier through a melt blending process. The addition of PVA by coating the CNT through a simple ball milling process before melt blending with a polycarbonate matrix resulted in an increased percolation limit as compared to that prepared using uncoated CNTs, while the electrical conductivity was maintained at a similar level of 2 x 10(-2) S/cm. However, tensile elongation was considerably improved by the addition of PVA and remained at 81% even though 5 wt% of the CNTs were added for electrical conductivity, while elongation dropped to 25% when the CNTs were not coated with PVA. The addition of PVA induces homogeneous dispersion of CNTs during the melt blending process and can enhance both electrical conductivity and mechanical durability.     

Nanostructure and morphology of poly(vinylidene fluoride)/polymethyl (methacrylate)/clay nanocomposites: correlation to micromechanical properties

Nanocomposites based on poly(vinylidene fluoride) (PVDF)/poly(methyl methacrylate) (PMMA) with untreated clay were prepared in one step by reactive melt extrusion. Chemical reactions took place between the polymer matrices, the inorganic clay particles, and three reactive agents, leading to the PVDF/PMMA/clay nanocomposites. The microstructure characterizations were carried out by differential scanning calorimetry and wide-angle X-ray scattering (WAXS). The mechanical behavior was investigated by tensile experiments, impact tests, and microhardness measurements. The morphological characterization was carried out by optical and atomic force microscopy (AFM). The decrease of the melting and crystallization temperatures of the PVDF with the increasing PMMA content is attributed to the interactions between the oxygen of the PMMA carbonyl group and the PVDF’s hydrogen atom. WAXS analysis shows that there is neither an intercalation step nor total exfoliation in any composition. As the PMMA content increases, WAXS diagrams show either the PVDF α-crystallographic form, both, α- and β-forms, or only the β-form. For PMMA contents higher than 40 wt%, the materials became amorphous. The microhardness of the samples decrease for a PMMA content up to 20 wt%. The study by optical microscopy and AFM illustrates the significant effect in the presence of clay on the film’s surface morphology.     

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.     

Preparation, characterization and properties of acid functionalized multi-walled carbon nanotube reinforced thermoplastic polyurethane nanocomposites

The multi-walled carbon nanotube (MWNT) reinforced thermoplastic polyurethane (TPU) nanocomposites were prepared through melt compounding method followed by compression molding. The spectroscopic study indicated that a strong interfacial interaction was developed between carbon nanotube (CNT) and the TPU matrix in the nanocomposites. The microscopic observation showed that the CNTs were homogeneously dispersed throughout the TPU matrix well apart from a few clusters. The results from thermal analysis indicated that the glass transition temperature (T_g) and storage modulus (E′) of the nanocomposites were increased with increase in CNTs content and their thermal stability were also improved in comparison with pure TPU matrix. The rheological analysis showed the low frequency plateau of shear modulus and the shear thinning behavior of the nanocomposites. The electrical behaviors of the nanocomposites are increased with increase in weight percent (wt%) of CNT loading. The mechanical properties of nanocomposites were substantially improved by the incorporation of CNTs into the TPU matrix.     

Microstructures and tensile behavior of carbon nanotube reinforced Cu matrix nanocomposites

Carbon nanotubes (CNTs) have been considered as an ideal reinforcement to improve the mechanical performance of monolithic materials. However, the CNT/metal nanocomposites have shown lower strength than expected. In this study, the CNT reinforced Cu matrix nanocomposites were fabricated by spark plasma sintering (SPS) of high energy ball-milled nano-sized Cu powders with multi-wall CNTs, and followed by cold rolling process. The microstructure of CNT/Cu nanocomposites consists of two regions including CNT/Cu composite region, where most CNTs are distributed, and CNT free Cu matrix region. The stress–strain curves of CNT/Cu nanocomposites show a two-step yielding behavior, which is caused from the microstructural characteristics consisting of two regions and the load transfer between these regions. The CNT/Cu nanocomposites show a tensile strength of 281 MPa, which is approximately 1.6 times higher than that of monolithic Cu. It is confirmed that the key issue to enhance the strength of CNT/metal nanocomposite is homogeneous distribution of CNTs.     

Processing and properties of poly(methyl methacrylate)/carbon nanofiber composites

Single wall carbon nanotubes, multiwall carbon nanotubes, as well as carbon nanofibers (CNF) are being used for reinforcing polymer matrices. In this study, poly(methyl methacrylate) (PMMA) nanocomposites have been processed by melt blending, containing two different grades (PR-21-PS and PR-24-PS) of CNF manufactured by Applied Sciences Inc. The amount of nanofibers used was 5 and 10% by weight, respectively. The PMMA/CNF composites were processed into 4 mm diameter rods and 60 μm diameter fibers using the small-scale melt processing fiber spinning equipment. At 5 wt% CNF, composite rods as well as fibers show over 50% improvement in axial tensile modulus as compared to the control PMMA rod and fibers, respectively. The reinforcement efficiency decreased at 10 wt% CNFs. The PMMA/CNF nanocomposite fibers also show enhanced thermal stability, significantly reduced shrinkage and enhanced modulus retention with temperature, as well as improved compressive strength. CNF reinforcement efficiency has been analyzed using the modified Cox model.     

Processing and properties of poly(methyl methacrylate)/carbon nano fiber composites

Single wall carbon nanotubes, multi-wall carbon nanotubes, as well as carbon nano fibers (CNF) are being used for reinforcing polymer matrices. In this study, poly(methyl methacrylate) (PMMA) nanocomposites have been processed by melt blending, containing two different grades (PR-21-PS and PR-24-PS) of CNF manufactured by Applied Sciences Inc. The amount of nano fibers used was 5 and 10 wt%, respectively. The PMMA/CNF composites were processed into 4 mm diameter rods and 60 μm diameter fibers using small-scale melt spinning equipment. At 5 wt% CNF, composite rods as well as fibers show over 50% improvement in axial tensile modulus as compared to the control PMMA rod and fibers, respectively. The reinforcement efficiency decreased at 10 wt% CNF. The PMMA/CNF nanocomposite fibers also show enhanced thermal stability, significantly reduced shrinkage and enhanced modulus retention with temperature, as well as improved compressive strength. The CNF reinforcement efficiency has been analyzed using the modified Cox model.     

Hybrid network structure and thermal conductive properties in poly(vinylidene fluoride) composites based on carbon nanotubes and graphene nanoplatelets

A small quantity of carbon nanotubes (CNTs) and graphene nanoplatelets (GNPs) were introduced into the poly(vinylidene fluoride) (PVDF)/GNP and PVDF/CNT composites, respectively, to prepare the corresponding ternary PVDF/CNT/GNP and PVDF/GNP/CNT composites. The results demonstrated that adding CNTs into the PVDF/GNP composites greatly promoted the formation of the hybrid network structure of fillers. This was much different from the scenario that adding GNPs into the PVDF/CNT composites. GNPs and CNTs exhibited excellent nucleation effects for the crystallization of PVDF matrix; however, the variation of the PVDF crystallinity was small. Adding CNTs into the PVDF/GNP composites greatly enhanced the electrical conductivity of the PVDF/CNT/GNP composites. This was also different from the scenario of the PVDF/GNP/CNT composites. Furthermore, the PVDF/CNT/GNP composites exhibit higher thermal conductivity and higher synergistic efficiency compared with the PVDF/GNP/CNT composites. The conductive mechanisms and the synergistic effects of the ternary composites were then analyzed.     

Application of cryomilling to enhance material properties of carbon nanotube reinforced chitosan nanocomposites

Cryomilled multiwall carbon nanotube (MWCNT) reinforced chitosan nanocomposites having improved conductivity have been prepared by solution casting method. The MWCNTs were crushed to smaller particles via cryomilling, which was effective in cleaving the nanotubes regularly as well as in reducing the entanglements and agglomeration. The cryomilled CNTs were chemically oxidized by acid and base methods, where basic oxidation generated high graphitic structure. The cryomilled and oxidized CNTs were characterized by XRD, Raman spectroscopy, FTIR and SEM. The conductivity of the nanocomposites was improved by cryomilling and it was further improved by chemical oxidation. Base oxidized cryomilled CNT/chitosan nanocomposites showed large improvement in conductivity compared to all other nanocomposites having 1 wt.% CNT content. Thermal stability and tensile properties of the CNT/chitosan nanocomposites also have been improved significantly by the incorporation of acid and base oxidized cryomilled CNTs. SEM picture of the fractured surface and FTIR showed nano-level dispersion of the functionalized CNTs and good chemical interaction between chitosan and CNTs respectively.     

Direct Measurements of the Mechanical Strength of Carbon Nanotube–Poly(methyl methacrylate) Interfaces

Understanding the interfacial stress transfer between carbon nanotubes (CNTs) and polymer matrices is of great importance to the development of CNT‐reinforced polymer nanocomposites. In this paper, an experimental study is presented of the interfacial strength between individual double‐walled CNTs and poly(methyl methacrylate) (PMMA) using an in situ nanomechanical single‐tube pull‐out testing scheme inside a high‐resolution electron microscope. By pulling out individual tubes with different embedded lengths, this work reveals the shear lag effect on the nanotube–polymer interface and demonstrates that the effective interfacial load transfer occurs only within a certain embedded length. These results show that the CNT–PMMA interface possesses an interfacial fracture energy within 0.054–0.80 J/m² and a maximum interfacial strength within 85–372 MPa. This work is useful to better understand the local stress transfer on nanotube–polymer interfaces.     

Structure and properties of melt-processed PVDF/PMMA/polyaniline blends

Ternary blends composed of the matrix polymer poly(vinylidene fluoride) (PVDF) and poly(methyl methacrylate) (PMMA) with different proportions of thermally doped polyaniline (PAni) using an alkylated dopant (dodecylbenzenesulfonic acid) (DBSA) were prepared by melt mixing. The effectiveness of these blends was compared with the corresponding binary blends of PVDF or PMMA with PAni–DBSA complex. Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) measurements, thermal analysis by differential scanning calorimetry (DSC) and morphological studies by optical microscopy and scanning electron microscopy (SEM) were carried out to characterize the blends in light of the interactions between their components and on the resulting electrical conductivity. Though a notable dispersion of PAni–DBSA in the PMMA matrix was incurred along with better conductivity with respect to PVDF/PAni–DBSA and PVDF/PMMA/PAni–DBSA blends, the thin films based on PMMA/PAni–DBSA were found to be fragile in nature. However, the presence of PMMA in the ternary blends of PVDF/PMMA/PAni–DBSA provided improved dispersion of PAni–DBSA in the PVDF/PMMA host matrix as compared to PVDF/PAni–DBSA binary blends. An enhancement in the conductivity by about two orders of magnitude at >5 wt% PAni–DBSA was witnessed in the ternary blends than that of PVDF/PAni–DBSA binary blends. Thin films made of ternary blends of PVDF/PMMA/PAni–DBSA also offered superior mechanical properties and flexibility than that of PMMA/PAni–DBSA binary blends due to the contribution of PVDF in the blend.     

Al/CNT nanocomposite fabrication on the different property of raw material using a planetary ball mill

In recent years, significant research has been focused on the development of carbon nanotube (CNT) reinforced aluminum nanocomposites, which are quickly emerging because of their lightweight, high strength and other mechanical properties. The potential applications of these composites include the automotive and aerospace industries. In this study, powder metallurgy techniques are employed to fabricate aluminum (Al)/CNT nanocomposites with different raw material properties with optimized conditions. We successfully fabricated three different samples, including un-milled Al, un-milled Al with CNT and milled Al with CNT nanocomposites, in the presence of additional CNTs with various experimental conditions using a planetary ball mill. Scanning electron microscopy and field emission scanning electron microscopy are used to evaluate the particle morphology and CNT dispersion. The CNTs are well dispersed on the surface of the fabricated milled Al with CNT nanocomposites than un-milled Al with CNT nanocomposites for milling. The fabricated Al/CNT nanocomposites are processed by a compacting, sintering and rolling process. Vickers hardness measurements are used to characterize the mechanical properties. The hardness of the Al/CNT nanocomposites are improved milled Al with CNT nanocomposite compared other fabricated composites.     

Role of powder treatment and carbon nanotube dispersion in the fracture toughening of plasma-sprayed aluminum oxide-carbon nanotube nanocomposite

Al2O3 ceramic reinforced with 4-wt% multiwalled carbon nanotube (CNT) is plasma sprayed for improving the fracture toughness of the nanocomposite coating. Two different methodologies of CNT addition have been adopted in the powder feedstock to assist CNT dispersion in the nano-Al2O3 matrix. First, spray-dried nano-Al2O3 agglomerates are blended with 4 wt% CNT as powder-feedstock, which is subsequently plasma sprayed resulting in the fracture toughness improvement of 19.9%. Secondly, spray dried composite nano-Al2O3 and 4 wt% CNT powder was used as feedstock for attaining improved dispersion of CNTs. Plasma sprayed coating of composite spray dried powder resulted in increase of 42.9% in the fracture toughness. Coating synthesized from the blended powder displayed impact alignment of CNTs along splat interface, and CNTs chain loop structure anchoring the fused Al2O3 melt whereas coating synthesized from composite spray dried powder evinced anchoring of CNTs in the solid state sintered region and CNT mesh formation. Enhanced fracture toughness is attributed to significance of CNT dispersion.     

Influence of carbon nanotube-polymeric compatibilizer masterbatches on morphological, thermal, mechanical, and tribological properties of polyethylene

Study was made of the effect of multiwall carbon nanotubes (MWCNTs) and polymeric compatibilizer on thermal, mechanical, and tribological properties of high density polyethylene (HDPE). The composites were prepared by melt mixing in two steps. Carbon nanotubes (CNTs) were melt mixed with maleic anhydride grafted polyethylene (PEgMA) as polymeric compatibilizer to produce a PEgMA-CNT masterbatch containing 20 wt% of CNTs. The masterbatch was then added to HDPE to prepare HDPE nanocomposites with CNT content of 2 or 6 wt%. The unmodified and modified (hydroxyl or amine groups) CNTs had similar effects on the properties of HDPE-PEgMA indicating that only non-covalent interactions were achieved between CNTs and matrix. According to SEM studies, single nanotubes and CNT agglomerates (size up to 1 μm) were present in all nanocomposites regardless of content or modification of CNTs. Addition of CNTs to HDPE-PEgMA increased decomposition temperature, but only slight changes were observed in crystallization temperature, crystallinity, melting temperature, and coefficient of linear thermal expansion (CLTE). Young’s modulus and tensile strength of matrix clearly increased, while elongation at break decreased. Measured values of Young’s moduli of HDPE-PEgMA-CNT composites were between the values of Young’s moduli for longitudinal (E₁₁) and transverse (E₂₂) direction predicted by Mori-Tanaka and Halpin-Tsai composite theories. Addition of CNTs to HDPE-PEgMA did not change the tribological properties of the matrix. Because of its higher crystallinity, PEgMA possessed significantly different properties from HDPE matrix: better mechanical properties, lower friction and wear, and lower CLTE in normal direction. Interestingly, the mechanical and tribological properties and CLTEs of HDPE-PEgMA-CNT composites lie between those of PEgMA and HDPE.     

碳纳米管在聚合物基体中的分散与有序排列研究--(Ⅰ)碳纳米管在聚合物基体中的分散

聚合物/碳纳米管（CNT）纳米复合材料，可将聚合物良好的加工性能和碳纳米管（CNTs）优异的功能化性质结合起来.目前，面临的主要挑战之一是如何提高CNTs在聚合物基体中的分散性.文中综述了优化物理共混、原位聚合和化学修饰等方法在改善CNTs在聚合物基体中分散性方面的最新研究动态。     

Self-sensing and mechanical performance of CNT/GNP/UHMWPE biocompatible nanocomposites

Ultra-high molecular weight polyethylene (UHMWPE)-based conductive nanocomposites with reduced percolation and tunable piezoresistive behavior were prepared via solution mixing followed by compression molding using carbon nanotubes (CNT) and graphene nanoplatelets (GNP). The effect of varying wt% of GNP with fixed CNT content (0.1 wt%) on the mechanical, electrical, thermal and piezoresistive properties of UHMWPE nanocomposites was evaluated. The combination of CNT and GNP enhanced the dispersion in UHMWPE matrix and lowered the probability of CNT aggregation as GNP acted as a spacer to separate the entanglement of CNT with each other. This has allowed the formation of an effective conductive path between GNP and CNT in UHMWPE matrix. The thermal conductivity, degree of crystallinity and degradation temperature of the nanocomposites increased with increasing GNP content. The elastic modulus and yield strength of the nanocomposites were improved by 37% and 33%, respectively, for 0.1/0.3 wt% of CNT/GNP compared to neat UHMWPE. The electrical conductivity was measured using four-probe method, and the lowest electrical percolation threshold was achieved at 0.1/0.1 wt% of CNT/GNP forming a nearly two-dimensional conductive network (critical value, t = 1.20). Such improvements in mechanical and electrical properties are attributed to the synergistic effect of the two-dimensional GNP and one-dimensional CNT which limits aggregation of CNTs enabling a more efficient conductive network at low wt% of fillers. These hybrid nanocomposites exhibited strong piezoresistive response with sensitivity factor of 6.2, 15.93 and 557.44 in the linear elastic, inelastic I and inelastic II regimes, respectively, for 0.1/0.5 wt% of CNT/GNP. This study demonstrates the fabrication method and the self-sensing performance of CNT/GNP/UHMWPE nanocomposites with improved properties useful for orthopedic implants.     

Dispersion and functionalization of carbon nanotubes for polymer-based nanocomposites: A review

Carbon nanotubes (CNTs) hold the promise of delivering exceptional mechanical properties and multi-functional characteristics. Ever-increasing interest in applying CNTs in many different fields has led to continued efforts to develop dispersion and functionalization techniques. To employ CNTs as effective reinforcement in polymer nanocomposites, proper dispersion and appropriate interfacial adhesion between the CNTs and polymer matrix have to be guaranteed. This paper reviews the current understanding of CNTs and CNT/polymer nanocomposites with two particular topics: (i) the principles and techniques for CNT dispersion and functionalization and (ii) the effects of CNT dispersion and functionalization on the properties of CNT/polymer nanocomposites. The fabrication techniques and potential applications of CNT/polymer nanocomposites are also highlighted.     

Improvement of toughness and electrical properties of epoxy composites with carbon nanotubes prepared by industrially relevant processes

The addition of carbon nanotubes (CNTs) to polymeric matrices or master batches has the potential to provide composites with novel properties. However, composites with a uniform dispersion of CNTs have proved to be difficult to manufacture, especially at an industrial scale. This paper reports on processing methods that overcome problems related to the control and reproducibility of dispersions. By using a high pressure homogenizer and a three-roll calendaring mill in combination, CNT reinforced epoxies were fabricated by mould casting with a well dispersed nanofiller content from 0.1 to 2 wt%. The influence of the nano-carbon reinforcements on toughness and electrical properties of the CNT/epoxies was studied. A substantial increase of all mechanical properties already appeared at the lowest CNT content of 0.1 wt%, but further raising the nanofiller concentration only led to moderate further changes. The most significant enhancement was obtained for fracture toughness, reaching up to 82%. The low percolation thresholds were confirmed by electrical conductivity measurements on the same composites yielding a threshold value of only about 0.01 wt%. As corroborated by a thorough microscopic analysis of the composites, mechanical and electrical enhancement points to the formation of an interconnected network of agglomerated CNTs.     

多巴胺改性聚苯硫脲与聚偏氟乙烯共混复合材料的制备与性能

聚苯硫脲（ArPTU）是一种新型高击穿、低损耗的材料,为提高其储能密度,在与聚偏氟乙烯（PVDF）共混的过程中,如何提高其溶解性,降低界面问题,成为研究热点之一。利用多巴胺（DA）对其进行改性可以有效地改善其与PVDF的界面问题。采用溶液流延热压的方法制备出不同共混比的多巴胺改性聚苯硫脲共混聚偏氟乙烯（DA/ArPTU-PVDF）复合薄膜。并采用X射线衍射仪、扫描电子显微镜、核磁共振、凝胶渗透色谱、阻抗分析仪等对其进行表征。结果表明:当DA/ArPTU-PVDF中DA/ArPTU质量分数为10wt%~15wt%时,PVDF的β晶型相对含量显著增加,这是其介电性能增加的主要原因之一;100 Hz时,介电常数最大可以达到10.3（10wt% DA/ArPTU）,同时介电损耗降低,最低达到了0.008（25wt% DA/ArPTU）。复合材料的储能密度也有明显提高,最大可以达3.0 J/cm3（10wt% DA/ArPTU）,相对于纯PVDF提高了63.3%。此外,复合材料的击穿特性相比于纯PVDF具有很大的提高,最大可达556.4MV/m（15wt% DA/ArPTU）。而且,改性后的复合材料力学性能也有了很大的提高。最大断裂伸长率可以达到196.7%（5wt% DA/ArPTU）,展现出了柔性高击穿储能材料的潜力。      

Properties of polycarbonate (PC)/multi-wall carbon nanotube (MWCNT) nanocomposites prepared by melt blending

This investigation deals with an easy method to develop electrical conductivity in polycarbonate (PC)/multi-wall carbon nanotube (MWCNT) nanocomposites with low loading of MWCNT. This was achieved by melt-blending of in-situ bulk polymerized low molecular weight poly(methyl methacrylate) (PMMA)/MWCNT nanocomposites and PC in various compositions at 280 degrees C in internal mixer. Differential scanning calorimetry (DSC) study showed single Tg in (85/15 w/w) PC/PMMA blend, indicating miscibility of PC and PMMA in the blend. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) studies of the melt-blended PC/PMMA/MWCNT nanocomposites revealed homogeneous dispersion and distribution of MWCNTs in PC matrix. Finally, through optimizing the blending composition of PC and PMMA/MWCNT nanocomposites, electrical conductivity of 3.74 x 10(-7) S x cm(-1) was achieved in the (85/15 w/w) PC/PMMA/MWCNT nanocomposites with the MWCNTs loading as low as approximately 0.37 wt%. Storage modulus of PC was found to increase significantly in presence of small amount (0.37 wt%) of MWCNTs in the nanocomposites.