Properties of well aligned SWNT modified poly (methyl methacrylate) nanocomposites

The PMMA/SWNT composites with good uniformity, dispersion and alignment of SWNT were fabricated in a stretching process. The semidried mixture was stretched along one direction at a draw ratio of 50 before it was dried, and then folded along the same direction stretching repeatedly for 100 times. The TEM and SEM observation demonstrated that SWNT in the PMMA/SWNT composite tend to align in the stretching direction. The electrical conductivity and the mechanical properties of composite rise with the increase of SWNT concentration, composite films showed higher conductivity and higher mechanical draw ratios along the stretched direction than perpendicular to it. The TGA revealed that embedding the SWNTs into the PMMA matrix also improves the thermal stability of the composite.     

Anisotropic properties of aligned SWNT modified poly (methyl methacrylate) nanocomposites

The poly (methyl methacrylate) (PMMA)/single-walled carbon nanotube (SWNT) composites with good uniformity, dispersion and alignment of SWNT were fabricated in an improved figuration process. The semidried mixture was stretched along one direction at a drawing ratio of 50 before it was dried, and then folded along the same direction stretching repeatedly for 100 times. The transmission electron microscopic (TEM) observation demonstrated that SWNT in the PMMA/SWNT composite tends to align in the stretching direction owing to a torque exerting on it in the stretching process. The electrical and mechanical properties of PMMA/SWNT composite were studied as a function of SWNT orientation and concentration. The aligned SWNT modified PMMA/SWNT composite presented highly anisotropic properties. The experimental results showed that the electrical conductivity and mechanical properties of composite rise with the increase of SWNT concentration, and that composite films showed higher conductivity and higher mechanical draw ratios along the stretched direction than perpendicular to it. The thermogravimetric analysis (TGA) revealed that embedding the SWNTs into the PMMA matrix also improves the thermal stability of the composite.     

单壁纳米碳管/聚酰亚胺复合材料的制备及导电特性

采用熔融聚合法和反复机械拉伸法,制备出定向排列单壁纳米碳管(SWNTs)/聚酰亚胺(PI)复合材料。研究了纳米碳管在复合体中的排列和分散情况。讨论了填充纳米碳管的质量分数对复合材料导电性能的影响,发现SWNTs填充质量分数很少时,复合体系呈现渗流行为,表现出良好的导电性和各向异性,其电导率随着填充纳米碳管的质量分数增加,电导率增大,而且在其拉伸方向比其垂直方向显示出较高的电导率,沿着其拉伸方向的渗流阈值比其垂直方向要低,说明单壁碳纳米管在复合物材料中呈现出良好的排列和均匀分散。     

Mechanical properties of epoxy nanocomposites reinforced with very low content of amino-functionalized single-walled carbon nanotubes

Functionalized single-walled carbon nanotubes (SWNTs) with amino groups were prepared by oxidation, acylation, and amidation of SWNT surfaces. Epoxy/SWNT composite membranes were fabricated using a very low content of amino-grafted SWNTs (< or = 0.08 wt%) as fillers. SWNTs with amino groups acted as a curing agent, covalently bonding to the epoxy matrix. The influence of SWNT content on the mechanical properties of epoxy/amino-functionalized SWNT composite membrane was investigated. It is found that the tensile strength of composites is enhanced with the increase of SWNTs. Only 0.01 wt% of SWNT-R-NH, leads to improvement of the epoxy tensile strength by 9.5%, and 0.08 wt% of SWNT-R-NH2 increased tensile strength by 13.6%. For comparison purposes, epoxy/pristine-SWNT films were also prepared. The improvement of the tensile strength of the amino-functionalized SWNTs system is more remarkable than that of pristine SWNT system at very low weight-percentage loading. The amino groups on the surface of SWNTs can be covalently attached to the epoxy matrix, which effectively improves the dispersion and adhesion of SWNTs in epoxy. This leads to the enhancement in mechanical properties of the epoxy composite. Mechanical results between functionalized and pristine nanotubes are discussed in detail.     

Processing-structure–property relationships of SWNT–epoxy composites prepared using ionic liquids

Experimentally achieved mechanical properties of nanotube–epoxy composites fail to match theoretical expectations; shortcomings are mainly attributed to poor dispersion. The elastic modulus of a well-dispersed single walled carbon nanotube (SWNT)-ionic liquid-epoxy composite was evaluated in tension and compared to predictions by a micromechanics homogenization model. The model takes into account the mechanical properties of the constituent phases in addition to SWNT aspect ratio, spatial distribution, dispersion, and agglomeration. These parameters were evaluated using information obtained via scanning and transmission electron microscopy. The Young’s modulus of the composite shows excellent agreement with the model at low concentrations, while discrepancies at high SWNT concentrations are possibly due to composite processing limitations. At high concentrations the uncured composite mixture is above the rheological percolation threshold. As the polymer network reaches its maximum capacity for well-dispersed SWNTs, increasing volume fraction does not result in further significant reinforcing effects.     

SWNT composite coatings as a strain sensor on glass fibres in model epoxy composites

The preparation of a model glass-fibre/epoxy composite with single-walled carbon nanotubes (SWNTs) incorporated as a strain sensor on the fibre surface is described. A micromechanical study of stress transfer at the fibre–matrix interface followed using Raman spectroscopy properties is reported. The SWNTs were distributed along the fibre surface either by dispersing them in an amino-silane coupling agent or coating with an epoxy resin solution containing the SWNTs. The point-by-point mapping of the fibre strain in single fibre fragmentation tests has been undertaken for the first time using SWNTs on the fibres and the interfacial shear stress distribution along the fibre length was determined using the embedded SWNTs. The behaviour was found to be consistent with the classical shear-lag model. The effects of SWNT type and preparation procedure on the sensitivity of the technique were evaluated and optimized from single fibre deformation tests.     

Rheological behaviour and mechanical characterization of injectable poly(propylene fumarate)/single-walled carbon nanotube composites for bone tissue engineering

This work investigated the effects of the use of a surfactant or the functionalization of single-walled carbon nanotubes (SWNTs) on their dispersion in uncrosslinked poly(propylene fumarate) (PPF) and the mechanical reinforcement of crosslinked composites as a function of the SWNT concentration. Rheological measurements showed good dispersion of SWNTs in uncrosslinked PPF at low concentrations of 0.05?wt% and SWNT aggregation for higher concentrations for all formulations examined. Mechanical testing demonstrated significant reinforcement in the compressive and flexural mechanical properties of crosslinked nanocomposites which peaked for low SWNT concentrations of the order of 0.05?wt%. For example, a 74% increase was recorded for the compressive modulus and a 69% increase for the flexural modulus of nanocomposites with functionalized SWNTs at a 0.05?wt% loading. Nevertheless, this reinforcement was not related to the use of a surfactant or the functionalization of the SWNTs tested. Scanning electron microscopy examinations of fractured nanocomposite surfaces revealed the formation of SWNT aggregates at higher concentrations corroborating the rheological and mechanical data. These results suggest that the dispersion of individual SWNTs in a uncrosslinked formulation is pivotal to the development of injectable nanocomposites for bone tissue engineering applications.     

The effect of two neighboring defects on the mechanical properties of carbon nanotubes

The tensile behavior of single-walled nanotubes (SWNTs) having two defects (vacancy or Stone-Wales) positioned next to each other was simulated in this study to investigate the influence of the spatial arrangement of defects on the mechanical properties. The simulations were performed using classical molecular dynamics (MD) at the atomic scale. Two neighboring vacancy defects reduced the failure strength as much as 46% and the failure strain as much as 80% in comparison with those of pristine SWNTs, while two neighboring Stone-Wales defects reduced them as much as 34% and 70% respectively. SWNTs having two defects in the loading (axial) direction showed higher failure strength than SWNTs with defects perpendicular to the loading direction. For both types of defect, the closer the defects, the weaker the SWNTs. As result, the defect arrangement in the SWNT structure must be one of the key factors in determining its mechanical properties, as well as the population of defects.     

超顺排碳纳米管/硅橡胶复合材料各向异性的电学性能和力学性能

采用直接浸润法制备了具有不同层数的超顺排碳纳米管(SACNT)薄膜与硅橡胶的复合材料,使碳纳米管薄膜能够在硅橡胶基体表面均匀分散。测量了SACNT薄膜/硅橡胶复合材料在各个方向的导电性能和力学性能,研究了影响复合材料导电性和力学性能的因素。实验结果表明:SACNT薄膜/硅橡胶复合材料的导电性和杨氏模量都随着碳纳米管薄膜厚度的增加而增加,且具有显著的各向异性。垂直于碳纳米管排列方向的电阻率平均比平行方向的大一个数量级。当碳纳米管层数为240层时,平行于碳纳米管排列方向的杨氏模量为116.9 MPa(比纯硅橡胶基体增加了142倍),而垂直方向的杨氏模量仅为1.23 MPa(比纯硅橡胶基体增加50%),两者之间相差近100倍。结果表明,可以通过选择不同的参数,获得具有特定导电性和杨氏模量的SACNT薄膜/硅橡胶复合材料,并在实际中加以应用。     

Effects of stretching on mechanical properties of aligned multi-walled carbon nanotube/epoxy composites

Composites based on epoxy resin and differently aligned multi-walled carbon nanotube (MWCNT) sheets have been developed using hot-melt prepreg processing. Aligned MWCNT sheets were produced from MWCNT arrays using the drawing and winding technique. Wavy MWCNTs in the sheets have limited reinforcement efficiency in the composites. Therefore, mechanical stretching of the MWCNT sheets and their prepregs was conducted for this study. Mechanical stretching of the MWCNT sheets and hot stretching of the MWCNT/epoxy prepregs markedly improved the mechanical properties of the composites. The improved mechanical properties of stretched composites derived from the increased MWCNT volume fraction and the reduced MWCNT waviness caused by stretching. With a 3% stretch ratio, the MWCNT/epoxy composites achieved their best mechanical properties in this study. Although hot stretching of the prepregs increased the tensile strength and modulus of the composites considerably, its efficiency was lower than that of stretching the MWCNT sheets.     

Transparent conductive thin film synthesis based on single-walled carbon nanotubes dispersion containing polymethylmethacrylate binder

Transparent conductive hybrid thin films of single-walled carbon nanotubes (SWNTs) and polymethyl methacrylate (PMMA) are fabricated using dispersions containing SWNTs and water-borne PMMA binder. The polymer binder was used as adhesion promoter between the SWNTs and the substrate. The polymer binder content in the SWNTs dispersion is varied to obtain the optimum optical transmittance, electrical conductivity, and mechanical adhesion. The PMMA and SWNT network formed the composite over substrate. The fabricated SWNTs/PMMA hybrid films are immersed in nitric acid (HNO3) and thionyl chloride (SOCl2) to improve electrical conductivity. SWNTs films with 0.2-0.6 mg/ml polymer binder have sheet resistance of 80-140 ohms/sq at a transmittance of about 80% and a strong adhesion on glass substrate. Furthermore, the electrical stability of the films is improved via the PMMA addition. This results indicates that the SWNTs/PMMA hybrid films fabricated by this method can be used as an alternative of indium tin oxide (ITO) film on flexible substrate.     

Structure and properties of highly oriented polyoxymethylene/multi-walled carbon nanotube composites produced by hot stretching

Highly-oriented polyoxymethylene (POM)/multi-walled carbon nanotube (MWCNT) composites were fabricated through solid hot stretching technology. With the draw ratio as high as 900%, the oriented composites exhibited much improved thermal conductivity and mechanical properties along the stretching direction compared with that of the isotropic samples before drawing. The thermal conductivity of the composite with 11.6 vol.% MWCNTs can reach as high as 1.2 W/m K after drawing. Microstructure observation demonstrated that the POM matrix had an ordered fibrillar bundle structure and MWCNTs in the composite tended to align parallel to the stretching direction. Wide-angle X-ray diffraction results showed that the crystal axis of the POM matrix was preferentially oriented perpendicular to the draw direction, while MWCNTs were preferentially oriented parallel to the draw direction. The strong interaction between the POM matrix and the MWCNTs hindered the orientation movement of molecules of POM, but induced the orientation movement of MWCNTs.     

Curing effects of single-wall carbon nanotube reinforcement on mechanical properties of filled epoxy adhesives

Enhancing epoxy adhesives using nanoscale fillers requires understanding processing-structure–property relationships as a function of nanoscale filler loading. In particular, the effects of adding nanoscale reinforcement to filled epoxies, such as those qualified for space applications, have yet to be characterized. In this effort, the addition of single-walled carbon nanotubes (SWNTs) to Hysol 9309.2 epoxy was investigated using a multi-scale mechanical characterization approach. Effects of SWNTs on the kinetics of epoxy curing were characterized and modeled using macromechanical dynamic mechanical analysis (DMA). Adhesion between SWNTs and microfiber reinforcement was identified with scanning electron microscope (SEM), and effects of SWNTs on mechanical properties of the filled epoxy were quantified using micromechanical tensile testing. Effects of SWNT reinforcement on mechanical behavior of the epoxy matrix were also characterized using nanomechanical characterization. This multi-scale mechanical characterization enabled the effects of SWNTs to be isolated from the epoxy and filler phases inherent in the adhesive.     

Solvent-free preparation of high-toughness epoxy--SWNT composite materials

Multicomponent nanocomposite materials based on a high-performance epoxy system and single-walled carbon nanotubes (SWNTs) have been prepared. The noncovalent wrapping of nitric acid-treated SWNTs with a PEO-based amphiphilic block copolymer leads to a highly disaggregated filler with a boosted miscibility in the epoxy matrix, allowing its dispersion without organic solvents. Although direct dispersion of acid-treated SWNTs results in modestly improved epoxy matrix mechanical properties, the incorporation of wrapped SWNTs produces a huge increase in toughness (276% improvement at 0.5 wt % loading) and impact strength (193% at 0.5 wt % loading) with no detrimental effect on the elastic properties. A synergistic effect between SWNTs and the block copolymer is revealed on the basis of tensile and impact strength results. Atomic force microscopy has been applied, obtaining stiffness mappings that identify nanostructure features responsible of the dynamic mechanical behavior. The electrical percolation threshold is greatly reduced, from 0.31 to 0.03 wt % SWNTs when block copolymer-wrapped SWNTs are used, and all the measured conductivity values increased up to a maximum of 7 orders of magnitude with respect to the baseline matrix (1 wt % wrapped-SWNTs loading). This approach provides an efficient way to disperse barely dispersible SWNTs without solvents into an epoxy matrix, and to generate substantial improvements with small amounts of SWNTs.     

Effects of carbon nanotube alignment on electrical and mechanical properties of epoxy nanocomposites

This paper reports the alignment of multi-walled carbon nanotubes (MWCNTs) in an epoxy matrix as a result of DC electric fields applied during composite curing. Optical microscopy and polarized Raman spectroscopy are used to confirm the CNT alignment. The alignment of CNTs gives rise to much improved electrical conductivity, elastic modulus and quasi-static fracture toughness compared to those with CNTs of random orientation. An extraordinarily low electrical percolation threshold of about 0.0031 vol% is achieved when measured along the alignment, which is more than one order of magnitude lower than 0.034 vol% with random orientation or that measured perpendicular to the aligned CNTs. The examination of the fracture surfaces identifies pertinent toughening mechanisms in aligned CNT composites, namely crack tip deflection and CNT pullout. The significance of this paper is that the technique employed here can tailor the physical, mechanical and fracture properties of bulk nanocomposites even at a very low CNT concentration.     

On the estimation of mechanical properties of single-walled carbon nanotubes by using a molecular-mechanics based FE approach

Carbon nanotubes (CNTs) have attracted considerable attention in scientific communities due to their remarkable mechanical, thermal and electrical properties (high stiffness, high strength, resilience, etc.). In particular, mechanical properties of single wall nanotubes (SWNTs) have a Young’s modulus of about 1 TPa if normalized to their diameter showing why they are widely considered as reinforcing elements in advanced low weight composite structures. The determinations of mechanical properties of SWNT are currently investigated both experimentally and theoretically. However, to determine CNTs mechanical properties in a direct experimental way is a challenging and not economical task because of the technical difficulties and the costs involved in the manipulation of nanoscale objects. Due to the handling difficulty, estimation of mechanical properties using computer simulations are being performed by several author with different approaches.     

Single wall nanotube and vapor grown carbon fiber reinforced polymers processed by extrusion freeform fabrication

Single wall carbon nanotubes (SWNTs) and vapor grown carbon fibers (VGCFs) were compounded with poly(acrylonitrile-co-butadiene-co-styrene) (ABS) to create composite materials for use with Extrusion Freeform Fabrication (EFF). The composite materials possessed homogeneously dispersed fibers that were oriented with EFF processing. The VGCF and SWNT reinforced materials processed by EFF displayed improved tensile modulus compared to similarly processed ABS and composite material with isotropic fiber orientation, and the SWNT reinforced material displayed the highest properties, strength and modulus, of the materials studied. The materials containing oriented VGCFs and SWNTs showed modulus improvements of 44 and 93%, respectively.     

High‐Performance Partially Aligned Semiconductive Single‐Walled Carbon Nanotube Transistors Achieved with a Parallel Technique

Single‐walled carbon nanotubes (SWNTs) are widely thought to be a strong contender for next‐generation printed electronic transistor materials. However, large‐scale solution‐based parallel assembly of SWNTs to obtain high‐performance transistor devices is challenging. SWNTs have anisotropic properties and, although partial alignment of the nanotubes has been theoretically predicted to achieve optimum transistor device performance, thus far no parallel solution‐based technique can achieve this. Herein a novel solution‐based technique, the immersion‐cum‐shake method, is reported to achieve partially aligned SWNT networks using semiconductive (99% enriched) SWNTs (s‐SWNTs). By immersing an aminosilane‐treated wafer into a solution of nanotubes placed on a rotary shaker, the repetitive flow of the nanotube solution over the wafer surface during the deposition process orients the nanotubes toward the fluid flow direction. By adjusting the nanotube concentration in the solution, the nanotube density of the partially aligned network can be controlled; linear densities ranging from 5 to 45 SWNTs/μm are observed. Through control of the linear SWNT density and channel length, the optimum SWNT‐based field‐effect transistor devices achieve outstanding performance metrics (with an on/off ratio of ~3.2 × 10⁴ and mobility 46.5 cm²/Vs). Atomic force microscopy shows that the partial alignment is uniform over an area of 20 × 20 mm² and confirms that the orientation of the nanotubes is mostly along the fluid flow direction, with a narrow orientation scatter characterized by a full width at half maximum (FWHM) of <15° for all but the densest film, which is 35°. This parallel process is large‐scale applicable and exploits the anisotropic properties of the SWNTs, presenting a viable path forward for industrial adoption of SWNTs in printed, flexible, and large‐area electronics.     

Key factors in electrical engineering with composite materials

The electrical properties of glass fabric epoxy laminates can be very dependant on the chemical composition of the ‘size’ applied to the glass fibres to protect them during weaving and to enhance their mechanical performance. The electrical losses in the warp and weft direction can be two orders of magnitude greater than in the plane perpendicular to the fabric plies. The mechanism is one of ionic conduction along the size coating the fibre and is aggravated by the moisture generated during the cure of an epoxy resin (0.2%) and the presence of voids acting as capillaries for the diffusion of moisture into or out of the laminate. A size giving good mechanical strength does not necessarily ensure good electrical performance. Examples of successful structures and components are included.     

Experimental and theoretical studies of transport through large scale, partially aligned arrays of single-walled carbon nanotubes in thin film type transistors

Gate-modulated transport through partially aligned films of single-walled carbon nanotubes (SWNTs) in thin film type transistor structures are studied experimentally and theoretically. Measurements are reported on SWNTs grown by chemical vapor deposition with systematically varying degrees of alignment and coverage in transistors with a range of channel lengths and orientations perpendicular and parallel to the direction of alignment. A first principles stick-percolation-based transport model provides a simple, yet quantitative framework to interpret the sometimes counterintuitive transport parameters measured in these devices. The results highlight, for example, the dramatic influence of small degrees of SWNT misalignment on transistor performance and imply that coverage and alignment are correlated phenomena and therefore should be simultaneously optimized. The transport characteristics reflect heterogeneity in the underlying anisotropic metal-semiconductor stick-percolating network and cannot be reproduced by classical transport models.