Effect of (Mn + Cr) addition on the microstructure and thermal stability of spray-formed hypereutectic Al–Si alloys

This study aims to investigate the tensile mechanical behavior and fracture toughness of vinyl-ester/polyester hybrid nanocomposites containing various types of nanofillers, including multi- and double-walled carbon nanotubes with and without amine functional groups (MWCNTs, DWCNTs, MWCNT-NH₂ and DWCNT-NH₂). To prepare the resin suspensions, very low contents (0.05, 0.1 and 0.3 wt.%) of carbon nanotubes (CNTs) were dispersed within a specially synthesized styrene-free polyester resin, conducting 3-roll milling technique. The collected resin stuff was subsequently blended with vinyl-ester via mechanical stirring to achieve final suspensions prior to polymerization. Nanocomposites containing MWCNTs and MWCNT-NH₂ were found to exhibit higher tensile strength and modulus as well as larger fracture toughness and fracture energy compared to neat hybrid polymer. However, incorporation of similar contents of DWCNTs and DWCNT-NH₂ into the hybrid resin did not reflect the same improvement in the corresponding mechanical properties. Furthermore, experimentally measured elastic moduli of the nanocomposites containing DWCNTs, DWCNT-NH₂, MWCNTs and MWCNT-NH₂ were fitted to Halphin–Tsai model. Regardless of amine functional groups or content of carbon nanotubes, MWCNT modified nanocomposites exhibited better agreement between the predicted and the measured elastic moduli values compared to nanocomposites with DWCNTs. Furthermore, Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM) were used to reveal dispersion state of the carbon nanotubes within the hybrid polymer and to examine the CNT induced failure modes that occurred under mechanical loading, respectively. Based on the experimental findings obtained, it was emphasized that the types of CNTs and presence of amine functional groups on the surface of CNTs affects substantially the chemical interactions at the interface, thus tuning the ultimate mechanical performance of the resulting nanocomposites.     

Effects of amino group on the properties of carbon nanotubes

The surfaces of multi-walled carbon nanotubes were grafted with amino functional groups by reacting acyl-chloride-functionalized carbon nanotubes (CNTs) with hexamethylene diamine, which improves the surfactivity of CNTs. The dispersity, surface morphology, and thermogravimetry of acid-treated and amino-functionalized CNTs were investigated. Amino-functionalized CNTs were added into epoxy resin to analyze the effects of amino functional groups on the properties of resin composites. It was found that the properties of CNTs, such as morphology and scale, were not affected by amino functional groups, but the dispersity in water was highly improved. Amino-functionalized CNTs are better dispersed in resin matrix, and the mechanical properties of composites are improved significantly, whereas the conductivity of composites is not enhanced as expected.     

Electric field effects on CNTs/vinyl ester suspensions and the resulting electrical and thermal composite properties

In this study, electrical conductivity of a vinyl ester based composite containing low content (0.05, 0.1 and 0.3 wt.%) of double and multi-walled carbon nanotubes with and without amine functional groups (DWCNTs, MWCNTs, DWCNT-NH₂ and MWCNT-NH₂) was investigated. The composite with pristine MWCNTs was found to exhibit the highest electrical conductivity. Experiments aimed to induce an aligned conductive network with application of an alternating current (AC) electric field during cure were carried out on the resin suspensions with MWCNTs. Formation of electric anisotropy within the composite was verified. Light microscopy (LM), scanning electron (SEM) and transmission electron microscopy (TEM) were conducted to visualize dispersion state and the extent of alignment of MWCNTs within the polymer cured with and without application of the electric field. To gain a better understanding of electric field induced effects, glass transition temperature (T_g) of the composites was measured via Differential Scanning Calorimetry (DSC). It was determined that at 0.05 wt.% loading rate of MWCNTs, the composites, cured with application of the AC electric field, possessed a higher T_g than the composites cured without application of the AC electric field.     

微型注塑制备碳纳米管硅橡胶导电复合医用材料

柔性导电材料是制备一些尖端医疗电子器件的重要材料。文中采用高速机械搅拌、超声波分散、球磨工艺制备了综合性能优异的碳纳米管液体橡胶纳米复合材料,碳管分散均匀,导电率最高可达25S/m,柔韧性保持不变。医疗电子器件具有微型化高精度的特点,需采用微加工成型技术,文中研究了液体橡胶柔性导电材料的微注射成型技术,考察了微加工条件对材料的导电性能的影响。结果显示,注射压力和模具温度越高,材料的导电率越低,其他加工条件则对材料导电性能影响不大。在拉伸的循环实验中导电率随应变呈指数变化。     

Preparation,solubility, and electrorheological properties of carbon nanotubes/poly(methyl methacrylate) nanocomposites by in situ functionalization

Poly(methyl methacrylate) (PMMA) nanobeads-decorated multi-walled carbon nanotubes (MWNTs) and single-walled carbon nanotubes (SWNTs) nanocomposites were prepared using two processing steps. Initially, spherical PMMA nanoparticles were synthesized using an emulsion polymerization method. Afterward, the PMMA nanobeads were decorated to MWNTs and SWNTs using benzoyl peroxide as an initiator in water during a high temperature refluxing process. The results confirmed the linkage of the nanotubes to the surrounding PMMA nanobeads via a covalent bond. The resultant nanocomposites showed high solubility in chloroform without flocculation after 24 h. In addition, the nanotubes/PMMA nanocomposites were characterized by electrical resistance measurements to analyze their electrical conductivity and examined as electrorheological (ER) materials when dispersed in silicone oil.     

Modeling electrical conductivities of nanocomposites with aligned carbon nanotubes

We have developed an improved three-dimensional (3D) percolation model to investigate the effect of the alignment of carbon nanotubes (CNTs) on the electrical conductivity of nanocomposites. In this model, both intrinsic and contact resistances are considered, and a new method of resistor network recognition that employs periodically connective paths is developed. This method leads to a reduction in the size effect of the representative cuboid in our Monte Carlo simulations. With this new technique, we were able to effectively analyze the effects of the CNT alignment upon the electrical conductivity of nanocomposites. Our model predicted that the peak value of the conductivity occurs for partially aligned rather than perfectly aligned CNTs. It has also identified the value of the peak and the corresponding alignment for different volume fractions of CNTs. Our model works well for both multi-wall CNTs (MWCNTs) and single-wall CNTs (SWCNTs), and the numerical results show a quantitative agreement with existing experimental observations.     

Self sensing carbon nanotube (CNT) and nanofiber (CNF) cementitious composites for real time damage assessment in smart structures

The self sensing properties of cementitious composites reinforced with well dispersed carbon nanotubes and carbon nanofibers were investigated. The electrical resistance of cementitious nanocomposites with w/c = 0.3 reinforced with well dispersed carbon nanotubes (CNTs) and nanofibers (CNFs) at an amount of 0.1 wt% and 0.3 wt% of cement was experimentally determined and compared with resistivity results of nanocomposites fabricated with “as received” nanoscale fibers at the same loading. Results indicate that conductivity measurements, besides being a valuable tool in evaluating the smart properties of the nanocomposites, may provide a good correlation between the resistivity values measured and the degree of dispersion of the material in the matrix. The addition of CNTs and CNFs at different loadings was proven to induce a decrease in electrical resistance, with the nanocomposites containing 0.1 wt% CNTs yielding better electrical properties. Furthermore, conductivity measurements under cyclic compressive loading provided an insight in the piezoresistive properties of selected nanocomposites. Results confirm that nanocomposites, reinforced with 0.1 wt% CNTs and CNFs, exhibited an increased change in resistivity, which is indicative of the amplified sensitivity of the material in strain sensing.     

Evaluation and visualization of the percolating networks in multi-wall carbon nanotube/epoxy composites

In this study, epoxy-based nanocomposites containing multi-wall carbon nanotubes (CNTs) were produced by a calendering approach. The electrical conductivities of these composites were investigated as a function of CNT content. The conductivity was found to obey a percolation-like power law with a percolation threshold below 0.05 vol.%. The electrical conductivity of the neat epoxy resin could be enhanced by nine orders of magnitude, with the addition of only 0.6 vol.% CNTs, suggesting the formation of a well-conducting network by the CNTs throughout the insulating polymer matrix. To characterize the dispersion and the morphology of CNTs in epoxy matrix, different microscopic techniques were applied to characterize the dispersion and the morphology of CNTs in epoxy matrix, such as atomic force microscopy, transmission electron microscopy, and scanning electron microscopy (SEM). In particular, the charge contrast imaging in SEM allows a visualization of the overall distribution of CNTs at a micro-scale, as well as the identification of CNT bundles at a nano-scale. On the basis of microscopic investigation, the electrical conduction mechanism of CNT/epoxy composites is discussed.     

Experimental study to assess the effect of carbon nanotube addition on the through-thickness electrical conductivity of CFRP laminates for aircraft applications

The present paper tests experimentally the through-thickness electrical conductivity of carbon fiber-reinforced polymer (CFRP) composites laminates for aircraft applications. Two types of samples were prepared: Type A samples with carbon nanotubes (CNTs) and Type B samples without CNTs. During the electrical experiments, electrical currents of several mA were injected through the specimens. Electrical resistance was monitored simultaneously in order to deduce the changes in the through-the-thickness electrical conductivity caused by the addition of CNTs. Improvement of electrical conduction by two orders of magnitude was achieved through the addition of 1 wt% carbon nanotubes as compared to classic CFRP without CNTs. For moisture saturated samples, the influence of moisture absorption on such measures was found to be negligible.     

Micromechanics modeling of the electrical conductivity of carbon nanotube (CNT)–polymer nanocomposites

A mixed micromechanics model was developed to predict the overall electrical conductivity of carbon nanotube (CNT)–polymer nanocomposites. Two electrical conductivity mechanisms, electron hopping and conductive networks, were incorporated into the model by introducing an interphase layer and considering the effective aspect ratio of CNTs. It was found that the modeling results agree well with the experimental data for both single-wall carbon nanotube and multi-wall carbon nanotube based nanocomposites. Simulation results suggest that both electron hopping and conductive networks contribute to the electrical conductivity of the nanocomposites, while conductive networks become dominant as CNT volume fraction increases. It was also indicated that the sizes of CNTs have significant effects on the percolation threshold and the overall electrical conductivity of the nanocomposites. This developed model is expected to provide a more accurate prediction on the electrical conductivity of CNT–polymer nanocomposites and useful guidelines for the design and optimization of conductive polymer nanocomposites.     

RTM processing and electrical performance of carbon nanotube modified epoxy/fibre composites

This investigation focuses on nanoparticle filtration in the processing of multiscale carbon and glass fibre composites via resin transfer moulding. Surface modified and unmodified carbon nanotubes (CNTs) were incorporated into a commercial epoxy resin. The dispersion quality was evaluated using electrical measurements of the liquid suspensions. The manufacturing process was adapted to the challenges posed by the modified rheological behaviour of the CNT loaded resin. Nanoparticle filtration was observed; with some of the unmodified systems following so called ‘cake filtration’ behaviour. This resulted in nonlinear flow behaviour that deviated from the ideal response observed in RTM filling in conventional composites. The electrical conductivity of relatively high fibre volume fraction multiscale carbon and glass laminates increased by less than an order of magnitude with the addition of the nanotubes.     

A comprehensive study on thermal conductivities of wavy carbon nanotube-reinforced cementitious nanocomposites

The thermal conductivities of cementitious nanocomposites reinforced by wavy carbon nanotubes (CNTs) are determined by the effective medium (EM) micromechanics-based method. The nanocomposite is composed of sinusoidally wavy CNTs as reinforcement and cement paste as matrix. The interfacial region between the CNTs and cementitious material is considered in the analysis. The effects of volume fraction and waviness parameters of CNTs, interfacial thermal resistance, type of CNTs placement within the matrix including aligned or randomly oriented CNTs, cement paste properties on the thermal conductivity coefficients of the nanocomposite are studied. The estimated values of the model are in very good agreement with available experimental data. Two parameters of CNT waviness and interfacial region contributions should be included in the modeling to predict realistic results for both aligned and randomly oriented CNT-reinforced nanocomposites. The results reveal that thermal conductivities K₂₂ (transverse in-plane thermal conductivity) and K₃₃ (longitudinal in-plane thermal conductivity) of the nanocomposites are remarkably dependent on the CNT waviness. Also, it is found that the CNT waviness moderately affects the thermal conductivity of a cementitious nanocomposite containing randomly oriented CNTs. However, the non-straight shape of CNTs does not influence the value of thermal conductivity K₁₁ (transverse out of plane thermal conductivity). The achieved results can be useful to guide the design of cementitious nanocomposites with optimal thermal conductivity properties.     

Functionalized Carbon‐Nanotube Sheet/Bismaleimide Nanocomposites: Mechanical and Electrical Performance Beyond Carbon‐Fiber Composites

Since their discovery in 1991, carbon nanotubes (CNTs) have been considered as the next‐generation reinforcement materials to potentially replace conventional carbon fibers for producing super‐high‐performance lightweight composites. Herein, it is reported that sheets of millimeter‐long multi‐walled CNTs with stretch alignment and epoxidation functionalization reinforce bismaleimide resin, which results in composites with an unprecedentedly high tensile strength of 3081 MPa and modulus of 350 GPa, well exceeding those of state‐of‐the‐art unidirectional carbon‐fiber‐reinforced composites. The results also provide important experimental evidence of the impact of functionalization and the effect of alignment reported previously on the mechanical performance and electrical conductivity of the nanocomposites.     

Glass-fibre-reinforced composites with enhanced mechanical and electrical properties - Benefits and limitations of a nanoparticle modified matrix

Nanoparticles and especially carbon nanotubes (CNTs) provide a high potential for the modification of polymers. They are very effective fillers regarding mechanical properties, especially toughness. Furthermore, they allow the implication of functional properties, which are connected to their electrical conductivity, into polymeric matrices. In the present paper, different nanoparticles, as fumed silica and carbon black, were used to optimise the epoxy matrix system of a glass-fibre-reinforced composite. Their nanometre-size enables their application as particle-reinforcement in FRPs produced by the resin-transfer-moulding method (RTM), without being filtered by the glass-fibre bundles. Additionally, an electrical field was applied during curing, in order to enhance orientation of the nanofillers in z-direction. The interlaminar shear strengths of the nanoparticle modified composites were significantly improved (+16%) by adding only 0.3 wt.% of CNTs. The interlaminar toughness G_Ic and G_IIc was not affected in a comparable manner. The laminates containing carbon nanotubes exhibited a relatively high electrical conductivity at very low filler contents, which allows the implication of functional properties, such as stress-strain monitoring and damage detection.     

Evaluation and modelling of electrically conductive polymer nanocomposites with carbon nanotube networks

Superior electrical, thermal, and mechanical properties of carbon nanotubes (CNTs) have made them effective filler for multifunctional polymer nanocomposites (PNCs). In particular, electrically conductive PNCs filled with CNTs have been researched extensively. These studies aimed to increase the PNCs' electrical conductivity (σ) and to minimize the percolation thresholds (ϕ_c). In this work, we have developed an improved model to describe the CNT networks and thereby evaluate the PNCs' ϕ_c and σ. The new model accounts for the electrical conductance contributed by the continued CNT network across the boundary of adjacent representative volume elements. It more realistically represents the interconnectivity among CNTs and enhances the evaluation of the structure-to-property relationship of PNCs' σ.     

New alignment procedure of magnetite–CNT hybrid nanofillers on epoxy bulk resin with permanent magnets

The main properties of epoxy composites reinforced with aligned carbon nanotubes (CNTs) have been studied. The alignment was carried out in a specific designed device applying a weak magnetic field (0.3 T) with permanent magnets. CNTs were modified with magnetite nanoparticles (Fe₃O₄) functionalized, in a one-stage-process which does not require use of strong acids or aggressive treatments which could affect the structural integrity of CNTs. The study by transmission electron microscopy confirmed that the Fe₃O₄ nanoparticles were closely bonded over CNT surfaces. The thermo-mechanical and tensile properties of composites measured were higher than neat epoxy resin and were similar for both composites: reinforced with neat CNTs and magnetite–CNT hybrid nanofillers. The electrical behaviour indicates a high anisotropy for aligned composites, showing an increase of one order of magnitude for the electrical conductivity in the direction of aligned nanotubes.     

Dispersion and reinforcing mechanism of carbon nanotubes in epoxy nanocomposites

Carbon nanotube based epoxy composites have been fabricated at room temperature and refrigeration process using sonication principle. Flexural moduli, electrical conductivity, glass transition temperature of epoxy resin as well as nanocomposite samples have been determined. Distribution behaviour of carbon nanotubes in the epoxy matrix was examined through scanning electron microscopy. Composite samples showed better properties than resin samples due to strengthening effect of the filled nanotubes. Refrigerated nanocomposites obtained increasing mechanical property because of better dispersion due to low temperature settlement of polymers. Improvement of electrical conductivity was due to the fact that aggregated phases form a conductive three-dimensional network throughout the whole sample. The increasing glass transition temperature was indicative of restricting movement of polymer chains that ascribe strong interaction presented between carbon nanotubes and epoxy chains that was again supplemented by Raman study and SEM.     

Carbon nanotubes based high temperature vulcanized silicone rubber nanocomposite with excellent elasticity and electrical properties

In the present study, we have fabricated a series of high temperature vulcanized silicone rubber (HTVSR)/carbon nanotubes (CNTs) nanocomposites with different CNT contents. The CNTs were pretreated by the chitosan salt before being incorporated into the HTVSR. The nanocomposites were then characterized in terms of morphological, thermal, mechanical and electrical properties. It was found that the chitosan salt pretreated CNTs dispersed uniformly within the HTVSR matrix, improving the thermal and mechanical properties of the HTVSR. The nanocomposites could remain conductive without losing inherent properties after 100 times of repeated stretching/release cycles by 100%, 200%, and even 300%. Moreover, the nanocomposites had good response to the compressed pressures. The results obtained from this study indicate that the fabricated nanocomposites are potential to be used in many electrical fields such as the conductive elastomer or the pressure sensor.     

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.     

STM investigation of carbon nanotubes connected by functional groups

Chemical functionalization of carbon nanotubes (CNTs) is essential for many applications. Attachment of functional groups to nanotubes can dramatically increase the solubility of the nanotube material. Sidewall functional groups should react with polymers and improve the mechanical properties of nanocomposites. Tubes interconnected by chemical bonds will have a reduced contact resistance and can be used for interconnection purposes in nanoscale circuits. Carbon nanotubes covered with functional groups attached to their exterior wall were analyzed using scanning tunneling microscopy (STM) and TEM. The functionalization was carried out in three steps: acid treatment in H₂SO₄/HNO₃ (3:1) mixture, reaction with SOCl₂ and reaction with diaminopropanol (DAP). The binding force between the nanotubes connected by functional groups and the mechanical stability of the connection was investigated.