On the thermal expansion of CNT/Cu composites for electronic packaging applications

Carbon nanotubes (CNTs) exhibit both excellent high thermal conductivity and low coefficient of thermal expansion (CTE), which are an ideal reinforcement in composite materials for high performance electronic packaging applications. In the present study, CNT/Cu composites containing CNTs varying from 0 vol.% to 15 vol.% are prepared, and their CTE behavior is studied in detail. The results indicate that the CTE of 0–10 vol.% CNT/Cu composites is significantly decreased with increasing CNT content. However, as the CNT content increases to 15 vol.%, the decrease in CTE of the composites is pronouncedly reduced. Possible mechanisms are discussed in combination with CTE model predictions.     

Electrical, dielectric and surface wetting properties of multi-walled carbon nanotubes/nylon-6 nanocomposites

This paper reports that the multi-walled carbon nanotubes(MWCNT)/nylon-6 (PA6) nanocomposites with different MWCNT loadingshave been prepared by a simple melt-compounding method. Theelectrical, dielectric, and surface wetting properties of theCNT/PA6 composites have been studied. The temperature dependence ofthe conductivity of the CNT/PA6 composite with 10.0 wt{\%} CNTloading ($\sigma _{\rm RT} \sim 10^{-4}$ S/cm) are measured, andafterwards a charge-energy-limited tunnelling model (ln $\sigma (T)\sim T^{-1/2})$ is found. With increasing CNT weight percentage from0.0 to 10.0 wt%, the dielectric constant of the CNT/PA6composites enhances and the dielectric loss tangent increases twoorders of magnitude. In addition, water contact angles of theCNT/PA6 composites increase and the composites with CNT loadinglarger than 2.0 wt%even become hydrophobic. The obtainedresults indicate that the electrical and surface properties of thecomposites have been significantly enhanced by the embedded carbonnanotubes.     

Enhanced interface interaction between modified carbon nanotubes and magnesium matrix

Carbon nanotube (CNT)/metal interface interaction is critical to the mechanical properties of CNT-reinforced metal matrix composites (MMCs). In this paper, in order to realize the chemical modification of the interface interaction between CNTs and Mg matrix, different types of defects (monovacancy, carbon and oxygen adatoms, as well as p-type boron and n-type nitrogen substitution) are introduced in CNTs to investigate the effect of the defects on the interface interaction (E_ib) between CNT and Mg (0 0 0 1) surface. Moreover, two models (adsorption model and interface model) are compared and validated to investigate the interface interaction. It is revealed that the CNT with the carbon adatom has the highest E_ib with the Mg (0 0 0 1), and the effect of boron doping on E_ib is superior to the intermediate oxygen which has already been proved experimentally in the enhancement of the interface interaction in MMCs. In terms of the electronic structure analysis, we reveal the micro-mechanism of the increase of E_ib under the action of different types of defects, and propose that the presence of holes (boron dopant) and the unsaturated electrons in CNTs can generate the chemical interaction between CNT and Mg matrix effectively. Our results are of great scientific importance to the realization of robust interfacial bonding between CNTs and Mg matrix via the reinforcement modification, so as to enhance the mechanical properties of CNTs reinforced Mg matrix composites.     

Advanced LiTi<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C anode by incorporation of carbon nanotubes for aqueous lithium-ion batteries

Inferior rate capability is a big challenge for LiTi₂(PO₄)₃ anode for aqueous lithium-ion batteries. Herein, to address such issue, we synthesized a high-performance LiTi₂(PO₄)₃/carbon/carbon nanotube (LTP/C/CNT) composite by virtue of high-quality carbon coating and incorporation of good conductive network. The as-prepared LTP/C/CNT composite exhibits excellent rate performance with discharge capacity of 80.1 and 59.1 mAh g^?1 at 10 C and 20 C (based on the mass of anode, 1 C = 150 mA g^?1), much larger than that of the LTP/C composite (53.4 mAh g^?1 at 10 C, and 31.7 mAh g^?1 at 20 C). LTP/C/CNT also demonstrates outstanding cycling stability with capacity retention of 83.3 % after 1000 cycles at 5 C, superior to LTP/C without incorporation of CNTs (60.1 %). As verified, the excellent electrochemical performance of the LTP/C/CNT composite is attributed to the enhanced electrical conductivity, rapid charge transfer, and Li-ion diffusion because of the incorporation of CNTs.     

Synthesis and characterization of LiMn1-x Fe x PO4/carbon nanotubes composites as cathodes for Li-ion batteries

Carbon nanotubes (CNT) coated with LiMn_1-x Fe _x PO₄ (0.2?≤?x?≤?0.8), as possible cathode materials, was synthesized by using a sol–gel process (Polyol method), after annealing under flowing nitrogen. X-ray diffraction (XRD) patterns of the composites confirmed the formation of the olivine structured LiMn_1-x Fe _x PO₄ phase and no secondary phases were detected. The morphological investigation revealed the formation of agglomerates with particles size ranging between 300 and 700 nm. XRD investigation of composites shows difference of the morphology by doping CNT and carbon black in the composites. Transmission electron microscopy shows the growth of nano-sized particles on CNT (20–70 nm) and the agglomeration of primary particles to form secondary particles. The X-ray photoelectron spectroscopy showed that the Fe and Mn ions are in divalent states in the LiMn_1-x Fe _x PO₄ composites. The cyclic voltamograms showed the oxidation peaks of iron and manganese ions at 3.53–3.63 and 4.05–4.33 V, respectively, while the reduction peaks were found at 3.21–3.42 V (iron reduction) and 3.85–3.93 V (manganese reduction) depending on the iron content in the composition. The LiMn_0.6Fe_0.4PO₄/CNT composite (x?=?0.4) (with 20 %?wt CNT) delivered a specific capacity of 120 mAhg^?1 (at a discharge rate of C/20 and RT).     

Effect of carbon nanotube addition on the thermite reaction in the Al/CuO energetic nanocomposite

Abstract

In this work, the Al/CNT/CuO nano-thermite samples are prepared by ultrasonic mixing with variable CNT content. The morphology of nano-thermites analysed by electron microscopy revealed that the CNTs are dispersed and there are intimate contacts between fuels (Al and CNT) and oxidiser (CuO) constituents of the nano-thermite. Raman spectroscopy technique is used to analyse the structural integrity of the CNTs in the nano-thermite. The thermite reaction characteristics are evaluated by simultaneous thermogravimetric analysis/differential scanning calorimetry technique. The exothermic enthalpy of the Al/CNT/CuO nano-thermite samples increased with increasing CNT content. The effect of Al particle size and Al/Cu molar ratio variation on the thermite reaction enthalpy is also analysed. The ignition temperature of the thermite reaction is also lowered by 71 °C than that of Al/CuO nano-thermite. The activation energy for thermite reaction of Al/CNT/CuO nano-thermite is also lowered by 23% to that of pure Al/CuO. The residues of the nano-thermites after the thermite reaction at 1010 °C are collected and analysed by the X-ray diffraction.     

Fabrication of Fe/Fe<Subscript>3</Subscript>C-functionalized carbon nanotubes and their electromagnetic and microwave absorbing properties

Fe/Fe₃C-functionalized carbon nanotubes (CNTs) have been prepared by the floating catalyst chemical vapor-deposition method. It is demonstrated that the Fe and Fe₃C nanostructures are both encapsulated in the CNTs or decorated on the surface of CNTs. The Fe/Fe₃C content in the composites can easily be adjusted by changing the ferrocene concentration in the preparation. The electromagnetic properties of the CNTs have been evaluated in the frequency range of 2–18 GHz, and the nanocomposites exhibit excellent microwave absorbing performance. The CNT composites with higher Fe/Fe₃C content show enhanced microwave reflection losses. The significant influence of the Fe/Fe₃C nanostructures on the microwave absorption is realized by tuning the characteristic impedance of the nanocomposites. With increasing thickness, the maximum reflection loss peak shifts to lower frequency. The microwave absorbing performance of the composites is mainly caused by dielectric loss, resulting from the continuous CNT networks with excellent electrical conductivity.     

Comparison of carbon-doped MgB2 bulks fabricated from pre-synthesized Mg/CNT and Mg/amorphous carbon composites

MgB₂ samples containing 2.5 wt% multi-walled carbon nanotubes (CNTs) and amorphous carbon (nano-C) were sintered at 800 °C. The doped samples were prepared from Mg/CNT and Mg/nano-C composites, which were previously synthesized from coarse Mg and fine Mg by chemical vapor deposition, respectively. We made comparisons between the two samples on the C-doping level, the MgO contents, and the effects of the carbon source on critical current density (J _c) by investigating the phase composition, microstructure, and magnetic properties. Compared with pure MgB₂ (coarse Mg), the J _c performance at high field was improved in the CNT-doped sample (coarse Mg) due to the high C substitution level induced lattice defects as pinning centers. However, J _c values of the amorphous C-doped sample with sufficient C doping decreased over the entire field in contrast with the pure sample (fine Mg), which exhibited the highest J _c performance among the samples. This is attributed to the much more MgO impurities, mostly generated during the preparation of Mg/C composites, than the CNT-doped sample.     

Effect of carbon nanotubes implantation on electrical properties of sisal fibre–epoxy composites

In this paper, the effects of carbon nanotubes (CNT) implantation and sisal fibre size on the electrical properties of sisal fibre-reinforced epoxy composites are reported. For this purpose, the epoxy composites reinforced with CNT-implanted sisal fibre of 5 mm and 10 mm lengths were prepared by hand moulding and samples characterized for their electrical properties, such as dielectric constant (ε′), dielectric dissipation factor (tan δ) and AC conductivity (σ_ac) at different temperatures and frequencies. It was observed that the dielectric constant increases with increase in temperature and decreases with increase in frequency from 500 Hz to 5 KHz. Interestingly, the sample having CNT-implanted sisal fibre of 5 mm length exhibited the highest value of dielectric constant than the one with length 10 mm. This is attributed to the increased surface area of sisal fibre and enhancement of the interfacial polarization. At a constant volume and a length of 5 mm of the fibres, the number of interfaces per unit volume element is high and results in a higher interfacial polarization. The interfaces decrease as the fibre length increases, and therefore, the value of ε′ decreases at 10 mm fibre length. The peak value of the dielectric constant decreases with increasing frequency. A continuous decrease in dissipation factor (tan δ) with increasing frequency for all samples was observed, while at lower temperatures, the values of tan δ remains approximately same. The AC conductivity for 5 mm length sisal epoxy composite and 10 mm length sisal fibre–epoxy composites is higher than that of pure epoxy at all the frequencies.     

Synthesis of modified multi-walled carbon nanotube poly(benzimidazole-imide) composites: assessment of morphological and thermo-mechanical properties

A fully aromatic poly(benzimidazole-imide) (PBI) containing triazole side units and amine-modified multi-wall carbon nanotube (MWCNT)/PBI composites were fabricated via a polymerization process of monomer reactants and solution mixing with ultrasonication excitation. The polymer and composites were characterized by field emission scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction. According to the microscopic characterizations, the MWCNTs homogeneously dispersed in the composites. The mechanical properties of the composite films were also measured by tensile test. The test results evidently indicated that the Young’s modulus increased by about 60.0% at 1 wt% CNT loading, and further modulus growth was observed at higher filler loading. The composite films hold preferable thermal stability the same as the pure PBI. The improvement of the mechanical and thermal properties was attributed to the incorporation of the surface modified CNTs. For CNT-reinforced polymer composites, strong interfacial adhesion and uniform dispersion of CNTs are more crucial factors for improving such properties.     

Ethylene glycol reflux synthesis of carbon nanotube/ceria core-shell nanowires

Carbon nanotube (CNT)/ceria core-shell nanowires were prepared facilely on a large scale under the boiling reflux of ethylene glycol. The composites are characterized by transmission electron microscopy, X-ray diffraction as well as Fourier transformed infrared spectra. It is found that the entire outer surface of CNTs is fully sheathed with a dense layer of uniform nanosized CeO₂, and that the thickness of the coating sheath can be readily manipulated by tuning the molar ratio of ceria to CNTs. Finally, a possible formation mechanism has been suggested as follows: with the high reaction temperature, ethylene glycol is partially converted to oxalic acid, and the surface hydroxyl groups of CeO₂ tiny particles react with oxalic acid to form the polymer-like inorganic-organic compounds. Subsequently, in view of the low-energy point, the polymer-like inorganic-organic compounds are coated on the surface of CNTs, and thus CNTs/ceria core-shell composites are obtained.     

Degradation of nitrobenzene-containing wastewater by carbon nanotubes immobilized nanoscale zerovalent iron

Nanoscaled zerovalent iron (NZVI)–multiwalled carbon nanotubes (CNTs) composite materials were prepared by in situ reduction of Fe²⁺ onto CNTs for nitrobenzene (NB) degradation. The morphologies and the composites of the prepared materials were characterized by SEM, TEM, and XRD. The results showed that the agglomeration of NZVI decreased with NZVI dispersed well onto the surfaces of CNTs, the particle size of NZVI on CNTs was about 20–50 nm. The BET surface areas of NZVI–CNTs was about 95.8 m²/g, which was 39 % higher than that of bare NZVI. For storage, the prepared NZVI–CNTs were concentrated into slurry and stored in situ as fresh slurry without drying. Contrast experiment results showed that the removal efficiency of NB by NZVI–CNTs fresh slurry was 30 % higher than that of vacuum-dried NZVI–CNTs, which indicates that storing in situ as fresh slurry can be an alternative strategy for nanoparticle storage. Batch experiment results showed that NB could be degraded to aniline by NZVI–CNTs rapidly, and the appropriate pH can be conducted at a relatively wide range from 2.0 to 9.0. The optimum mass ratio of iron–carbon was 1:1, and removal efficiency of NB by NZVI–CNTs with this mass ratio can achieve 100 % within 1 min. The degradation process of NB to intermediates was accelerated significantly by NZVI–CNTs, however, there was still a long term for the intermediates to transfer completely into the final product of aniline. The existence of CNTs can improve the formation of aniline through accelerating the electron transfer by forming microscopic galvanic cells with NZVI.     

Synthesis of carbon nanotubes/alumina composites in supercritical media

Nanosized composites based on multiwall carbon nanotubes (CNTs) and Al₂O₃ have been obtained for the first time in supercritical (SC) media (water, hexane, and their mixture). For comparison, materials of the same net composition have been prepared by hydrothermal synthesis and sol–gel processing. The composites have been characterized by electron microscopy, X-ray diffraction, and thermal analysis. The structure of the materials synthesized in the SC media depends on the fluid composition. The most uniform composite containing alumina particles that are comparable in size to the CNT diameter and are stabilized on the carbon surface can be obtained in the SC mixture of hexane and water. When water and hexane are used separately, the formation of large alumina crystals on the CNT surface and contamination of the composite by the products of hexane pyrolysis and carbonization are, respectively, observed.     

Rapid microwave-assisted synthesis and electrochemical characterization of gold/carbon nanotube composites

Hybrid nanostructures composed of gold nanoparticles (NPs) and carbon nanotubes (CNTs) have been prepared by a microwave-assisted method in the mixed solvents of oleylamine and oleic. The morphology, structure and composition of as-obtained Au/CNT composites are characterized by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD). The composites show characteristic plasmon absorption of Au NPs in the Ultraviolet–visual spectrum. Fourier transform infrared spectrum shows the successful introduction of functional groups on the surface of CNTs, which are crucial factors to assist the nucleation in situ of Au NPs on the surface of CNTs. Electrochemical measurements show the enhancement electrochemical response for the gold electrode modified with Au/CNT composites.     

Control of morphology for energy dissipation in carbon nanotube forests

This study focuses on the effect of carbon precursor on the carbon nanotube (CNT) morphology and energy dissipation. Benzene, toluene, and m-xylene were used as carbon precursors for the synthesis of CNT forests following a chemical vapor deposition process. The results indicate that substituents on the benzene ring increase entanglement in the CNT forests. The absorbed energy was slightly greater for CNT forests synthesized using m-xylene than for toluene, but was much smaller for benzene. When compressed to a strain of 0.67, the toluene CNTs absorbed more energy than the m-xylene CNTs. The restitution was much higher for the forests synthesized with m-xylene than toluene while it further decreased for the forests made with benzene. A strong correlation is also observed between the average diameter of the CNTs and the number of methyl substituents on the benzene ring. The control of the entanglement of the CNT forests can potentially be used to design high energy absorbing composites for blast energy dissipation.     

Variation in chemical,colloidal and electrochemical properties of carbon nanotubes with the degree of carboxylation

Multiwalled carbon nanotubes (CNTs) were carboxylated via microwave irradiation where the treatment time was varied to alter the degree of functionalization, and as many as one in 15 carbons in the CNT could be oxidized. Chemical, physical, electrochemical, and colloidal behavior of the carboxylated CNTs was studied. All properties changed with the degree of functionalization to a point beyond which they appeared to remain constant. The surface area increased from 173.9 to 270.9 m²/g while the critical coagulation concentration (CCC) values increased from 142.14 to 168.69 mM in the presence of NaCl, and the corresponding increase was from 0.97 to 5.32 mM in the presence of MgCl₂. As seen from cyclic voltammetry curves, the functionalized CNTs showed mainly non-Faradic interactions with Na₂SO_4, but showed Faradic behaviors in alkaline KOH.     

Novel Cu–Cr alloy matrix CNT composites with enhanced thermal conductivity

Carbon nanotubes (CNTs) are incorporated into the Cu–Cr matrix to fabricate bulk CNT/Cu–Cr composites by means of a powder metallurgy method, and their thermal conductivity behavior is investigated. It is found that the formation of Cr₃C₂ interfacial layer improves the interfacial bonding between CNTs and Cu–Cr matrix, producing a reduction of interfacial thermal resistance, and subsequently enhancing the thermal conductivity of the composites. The thermal conductivity of the composites increases by 12 % and 17 % with addition of 5 vol.% and 10 vol.% CNTs, respectively. The experimental results are also theoretically analyzed using an effective medium approximation (EMA) model, and it is found that the EMA model combined with a Debye model can provide a satisfactory agreement to the experimental data.     

AC conductivity and dielectric behavior of polyaniline/sodium metavenadate (PANI/NaVO3) composites

The conducting polyaniline/sodium metavenadate (PANI/NaVO₃) composites were synthesized by single step in situ polymerization technique by placing finely grinded powder of NaVO₃ during the polymerization of aniline. The formation of mixed phases of the polymer together with the conducting emeraldine salt phase was confirmed by spectroscopic techniques like FTIR. SEM images indicated a systematic morphological variation of particles aggregated in the composite matrix as compared to the pristine PANI. AC conductivity and dielectric behavior of these composites were investigated in the frequency range 50 Hz to 5 MHz. It is found that AC conductivity obeyed the power law index and the variation of conductivity with wt% of NaVO₃ could be related to conductivity relaxation phenomenon. These composites have shown high dielectric constant, which is related to polarization. It is seen that both dielectric constant and dielectric loss decrease with increase in frequency. Variations in measured parameters of AC response with increasing frequency of these composites are found to follow systematic trends that are similar to those observed with temperature and doping.     

Superior capacitive characteristics of RuO2 nanorods grown on carbon nanotubes

Carbon nanotubes (CNTs) were used as the electric double layer capacitor (EDLC) material and were synthesized by using thermal chemical vapor deposition (TCVD). To enhance the EDLC capacity, the ruthenium dioxide (RuO₂) nanorods were grown on CNTs by using metal organic chemical vapor deposition (MOCVD). The synthesized CNTs were the principal part and template, and the RuO₂ nanorods were grown outwardly from CNTs. The increase of effective specific area between electrode and electrolyte played an important role in enhancing the capacitance. Different concentrations of KOH were used as electrolyte to measure the capacitance to find the variation of capacitance. Moreover, the RuO₂/CNT composites demonstrated a stable cycle life. The results showed that the RuO₂/CNT composites were a promising supercapacitor device material.     

Unique dielectric properties in polyaniline/poly(vinylidene fluoride) composites induced by temperature variation

To explore an effect of temperature on the dielectric properties in polyaniline/poly(vinylidene fluoride) (PANI/PVDF) composites, the dielectric properties of these composites with different volumetric fractions of PANI (?_PANI) were studied in a wide temperature range. An increase in the effective conductivity (σ_eff) and dielectric permittivity (?_eff) was observed with increasing temperature in all PANI/PVDF composites. Particularly, for the composite with ?_PANI = 0.01, less than the percolation threshold (?_C = 0.045), the increase in σ_eff and ?_eff was most significant. A tunneling effect could be responsible for the unique dielectric properties. The results provided us useful information related to the microstructure of composites, which was not reported previously. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)