Comparison of the thermal properties between composites reinforced by raw and amino-functionalized carbon materials

Carbon materials, such as graphite oxides, carbon nanotubes and graphenes, have exceptional thermal conductivity, which render them excellent candidates as fillers in advanced thermal interface materials for high density electronics. In this paper, these carbon materials were functionalized with 4,4′-diaminodiphenyl sulphone (DDS), to enhance the bonding between the carbon materials and the resin matrix. Their visibly different properties were investigated. It seems that DDS-functionalization can obviously improve the interfacial heat transfer between the carbon materials and the epoxy matrix. The thermal conductivity enhancement of D-Graphene composites (0.493 W/m K) was about 30% higher than that of D-MWNTs composites (0.387 W/m K) at 0.5 vol.% loading. The different effects among EGO, D-EGO, MWNTs, D-MWNTs and D-Graphene in polymer composites were also discussed. It was demonstrated that DDS-functionalized carbon materials had an obvious effect on the thermal performances of composite materials and were more effective in thermal conductivity enhancement.     

Preparation and properties of poly (p-phenylene sulfide)/multiwall carbon nanotube composites obtained by melt compounding

In this paper, electrical and mechanical properties of Poly (p-phenylene sulfide) (PPS)/multi-wall carbon nanotubes (MWNTs) nanocomposites were reported. The composites were obtained just by simply melt mixing PPS with raw MWNTs without any pre-treatment. The dispersion of MWNTs and interfacial interaction were investigated through SEM &TEM and Raman spectra. The rheological test and crystallization behavior were also investigated to study the effects of MWNTs concentration on the structure and chain mobility of the prepared composites. Though raw MWNTs without any pre-treatment were used, a good dispersion and interaction between PPS and MWNTs have been evidenced, resulting in a great improvement of electrical properties and mechanical properties of the composites. Raman spectra showed a remarkable decrease of G band intensity and a shift of D bond, demonstrating a strong filler–matrix interaction, which was considered as due to π–π stacking between PPS and MWNTs. The storage modulus (G′) versus frequency curve presented a plateau above the percolation threshold of about 2–3 wt% with the formation of an interconnected nanotube structure, indicative of ‘pseudo-solid-like’ behavior. Meanwhile, a conductive percolation threshold of 5 wt% was achieved and the conductivity of nanocomposites increased sharply by several orders of magnitude. The difference between electrical and rheological percolation threshold, and the effect of critical percolation on the chain mobility, especially on crystallization behavior of PPS, were discussed. In summary, our work provides a simple and fast way to prepare PPS/MWNTs nanocomposites with good dispersion and improved properties.     

Fabrication of polypropylene/carbon nanotubes composites via a sequential process of (rotating solid-state mixing)-plus-(melt extrusion)

In this study, a simple but effective method to realize excellent comprehensive performances in polypropylene (PP)/multi-walled carbon nanotubes (MWNTs) was developed. Before melt extrusion, solid-state iPP powders and MWNTs were pre-mixed upon high-speed rotating. By this way, the dispersion extent of nanotubes was significantly improved as comparing to the common one-step melt extrusion strategy. As validated by scanning electron microscopy, most of MWNTs exist as a form of filament bundles with size of hundreds nanometers; no obvious agglomerate was found even at high MWNTs content, 5%. The improvements of the major mechanical properties and electric conductivity were much efficient for the composites obtained via the two-step process of rotating solid-state mixing (RSSM)-plus-melt extrusion. The tensile strength, Young’s modulus and impact strength at 5% MWNTs content were enhanced for 35%, 42% and 45%, respectively, indicating an excellent strength-rigidity-toughness balance, which was hardly achieved in polyolefin/carbon nanotubes composite. It is believed that the method developed in this study is so far the most effective and convenient for efficiently dispersing nanotubes into the nonpolar, intractable thermoplastics and resulting in good properties, among a variety of fabrication method suggested in the previous researches. Importantly, the used RSSM equipment is a kind of frequently used dispersion machine, thus it has tremendous potential to be applied in industrial producing immediately.     

Poly(vinyl alcohol) reinforced with large-diameter carbon nanotubes via spray winding

For practical application of carbon nanotube (CNT)/polymer composites, it is critical to produce the composites at high speed and large scale. In this study, multi-walled carbon nanotubes (MWNTs) with large diameter (∼45 nm) and polyvinyl alcohol (PVA) were used to increase the processing speed of a recently developed spraying winding technique. The effect of the different winding speed and sprayed solution concentration to the performance of the composite films were investigated. The CNT/PVA composites exhibit tensile strength of up to 1 GPa, and modulus of up to 70 GPa, with a CNT weight fraction of 53%. In addition, an electrical conductivity of 747 S/cm was obtained for the CNT/PVA composites. The good mechanical and electrical properties are attributed to the uniform CNTs and PVA matrix integration and the high degree of tube alignment.     

Preparation polystyrene/multiwalled carbon nanotubes nanocomposites by copolymerization of styrene and styryl-functionalized multiwalled carbon nanotubes

Styryl-functionalized multiwalled carbon nanotubes (p-MWNTs) were prepared by esterification based on the carboxylate salt of carbon nanotubes and p-chloromethylstyrene in toluene. Then in situ radical copolymerization of p-MWNTs and styrene initiated by 2,2′-azobis(isobutyronitrile) (AIBN) was applied to synthesize composites of styryl-functionalized multiwalled carbon nanotubes and polystyrene (PS) (p-MWNTs/PS). Characterizations carried out by FT-IR, ¹H NMR, UV–vis show that styryl group covalently bond to the surface of MWNTs. The results of UV showed that the solutions of p-MWNTs/PS in chloroform have the hyperchromic effect. Transmission electron microscopy (TEM) images of p-MWNTs/PS composites and scanning electron microscopy (SEM) images of fracture surface of p-MWNTs/PS composites showed the functionalized nanotubes had a better dispersion than that of the unfunctionalized MWNTs in the matrix. The results of thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) suggested that the thermal stability of p-MWNTs/PS composites improved in the presence of MWNTs.     

Facile preparation and characterization of free-standing stiff carbon-based composite films with excellent performance

Novel free-standing stiff all carbon films based on multi-walled carbon nanotube (MWNT)/glassy carbon (GC) with excellent performance were fabricated. MWNTs, as excellent reinforcing materials, were successfully dispersed in polyimide (PI) matrix by in situ polymerization. The resultant MWNT/PI nanocomoposite films were used as precursors and underwent carbonization process. As a result, all carbon constituted MWNT/GC composite films were obtained. Mechanical results showed the maximum 3-point bending strength and modulus reached 575.5 MPa and 7.7 GPa respectively, improved by 54% and 78% compared to those of neat GC films. This method is simple, and the free-standing composite films can be prepared in large scales, which hold great potential in many applications.     

Investigation of the electrical conductivity of HDPE composites filled with bundle-like MWNTs

Bundle-like multi-walled carbon nanotubes (MWNTs) were melting-mixed with high-density polyethylene (HDPE). MWNTs are distributed in the matrix mostly isolated. Agglomerates are observed at higher concentrations. The electric conductivity of the composites follows the theory of a percolation system, and the charge transport shows different models. The temperature dependence of the electrical conductivity for the composites shows that both positive (PTC) and negative (NTC) temperature coefficients appear near the melting temperature of matrix. The NTC behaviors within the temperature range below the melting point depend on the MWNTs concentration and the NTC intensity increases with the increasing MWNTs concentration.     

Growth of carbon nanotubes on carbon fibre substrates to produce hybrid/phenolic composites with improved mechanical properties

Carbon nanotubes were grown by chemical vapor deposition (CVD) on different carbon fibre substrates namely, unidirectional (UD) carbon fibre tows, bi-directional (2D) carbon fibre cloth and three dimensional (3D) carbon fibre felt. These substrates were used as the reinforcement in phenolic resin matrix to develop hybrid CF–CNT composites. The growth morphology and other characteristics of the as grown tubes were analyzed by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and thermal gravimetry (TGA) which confirmed a copious growth of multiwalled carbon nanotubes (MWNTs) on these substrates. The mechanical properties of the hybrid composites was found to increase with the increasing amount of deposited carbon nanotubes. The flexural strength (FS) improved by 20% for UD, 75% for 2D and 66% for 3D hybrid composites as compared to that prepared by neat reinforcements (without CNT growth) under identical conditions. Flexural modulus (FM) of these composites also improved by 28%, 54% and 46%, respectively.     

Fabrication of multi-walled carbon nanotube-reinforced carbon fiber/silicon carbide composites by polymer infiltration and pyrolysis process

Multi-walled carbon nanotube (MWNT)-reinforced carbon fiber/silicon carbide (C_f/SiC) composites were prepared using a polymer infiltration and pyrolysis (PIP) process. The MWNTs used in this study were modified using a chemical treatment. The MWNTs were found to be well dispersed in the matrix after ultrasonic dispersion, and the mechanical properties of the C_f/SiC composite were significantly improved by the addition of MWNTs. The addition of 1.5 wt.% of MWNTs to the C_f/SiC composite led to a 29.7% increase in the flexural strength, and a 27.9% increase in the fracture toughness.     

Evaluation of the chemical interaction between carbon nanotubes functionalized with TGDDM tetrafunctional resin and hardener DDS

In this work, the chemical interaction between carbon nanotubes (MWCNT) functionalized with acyl chloride (SOCl₂) and polymer chain tetrafuncional N,N,N′,N′-tetraglycidyl-4,4′-diaminodiphenylmethane (TGDDM) and hardener 4,4′diaminodiphenyl sulfone (DDS) has been monitored by Fourier transform infrared spectroscopy (FTIR) with a attenuated total reflectance (ATR) coupled. MWCNT were obtained from the pyrolysis of a mixture of camphor and ferrocene into a oven. The functionalization process was done by oxidative treatment in order to incorporate carboxylic group over the walls of MWCNT, before to be used SOCl₂. The functionalized carbon nanotubes were evaluated by X-ray photoelectron spectroscopy (XPS), Raman and transmission electron microscopy (TEM). Nanostructured composites were processed by using epoxy resin with MWCNT in varying percentages. In this work it was observed that different percentages of functionalized nanotubes modify the interaction between the composite matrix and curing agent, where can be observed that in specimens with content less than 1 wt% MWCNT the chemical bond occurs preferentially from the opening of the SO double bond of the hardener and when is used MWCNT content higher than 1 wt% there is little chemical interaction with the SO bond of the hardener and most MWCNT binds to amine.     

Electroactive shape memory polymer based on optimized multi-walled carbon nanotubes/polyvinyl alcohol nanocomposites

The development of shape memory polymers (SMPs) has gained remarkable attention due to their wide range of applications, from biomedical to electromechanical. In this work, we have developed and optimized an electroactive SMP based on polyvinyl alcohol/multi-walled carbon nanotubes (PVA/MWNTs) composites. When a constant voltage of 60 V was applied to the optimized sample, the polymer shape could be recovered to the original form within 35 s. Different weight fractions of MWNT/PVA composites were prepared by using a simple solution blending and transitional solution casting method, and their microstructures, electrical conductivities, thermal conductivities, and electroactive shape memory properties were investigated. According to our systematic analysis, the enhanced performance can be attributed to the reinforcement of MWNTs that led to the improved electrical and thermal conductivities of the PVA matrix.     

Thermo-physical properties and TEM analysis of silver based MMCs utilizing metallized multiwall-carbon nanotubes

Metal matrix composites with embedded multiwall-carbon nanotubes (MWNT) are attractive because MWNTs exhibit high intrinsic thermal conductivity. Thus to improve the thermal conductivity of a metal matrix, silver matrix composites with MWNT were prepared by “chemical” mixing, different active elements were introduced enhancing the bonding between inclusions and matrix. The evolution of the thermal conductivity and the coefficient of thermal expansion CTE as a function of the MWNT concentration and the presence of active elements cobalt, molybdenum or nickel in the silver matrix in Ag–X/MWNT composites are presented. A transition from weak to strong matrix/MWNT bonding is observed by adding active elements, the latter leading concomitantly to an increase in thermal conductivity and a decrease in CTE. The thermal conductivity was found to increase by up to 10% for a composition of 0.2 wt.% MWNT and cobalt as active element and a 6% decrease in CTE compared to a pure silver reference.     

Dispersion control and characterization in multiwalled carbon nanotube and phenylethynyl-terminated imide composites

The inherent multifunctional properties of carbon nanotubes provide an opportunity to create novel composites, but their dispersion into a polymer matrix is challenging due to nanotube dimensions, interparticle forces, and poor interaction with the polymer. In this study, we used melt mixing to disperse multiwalled carbon nanotubes (MWNTs) in a polyimide resin under various process conditions to understand the efficacy of the process and the energy required to achieve dispersion and distribution. Through controlled variation of process conditions, we achieved various degrees of nanotube dispersion and distribution. The different dispersion and distribution states were observed by microscopy and correlated with the magnitude of the changes seen in the glass transition temperature and viscosity when compared to the neat resin. The results of these studies will be used to assess the compatibility of nanocomposite resins with composite fabrication methods and predict appropriate processing conditions for producing multiscale composites.     

Morphology and electrical properties of polyamide 6/polypropylene/multi-walled carbon nanotubes composites

Morphology, electrical properties and conductive mechanisms of polyamide 6/polypropylene/muti-walled carbon nanotubes (PA6/PP/MWNTs) composites with varied compositions and different blending sequences were investigated. The MWNTs were found to be located preferentially in the PA6 phase in the composites, whatever the PA6 was continuous or dispersed phase. While the incorporation of MWNTs changed the dispersed PA6 phase from spherical to elongated or irregular shape. The PA6/PP/MWNTs (20/80/4) composite with a dispersed PA6 phase exhibited a higher electrical conductivity in comparison with the PA6/PP/MWNTs (50/50/4) composite which has a co-continuous phase and exhibits double percolation. This was due to the formation of a conductive MWNTs networks in the PA6/PP/MWNTs (20/80/4) composite as proved by means of field emission scanning electron microscopy and rheological measurements. The morphology and electrical properties of the PA6/PP/MWNTs (20/80/4) composites were significantly influenced by blending sequences. When blending 3.9 phr MWNTs with a pre-mixed PA6/PP/MWNTs (20/80/0.1) composite, the dispersed PA6 phase formed an elongated structure, which was beneficial to the electrical properties.     

Aligned carbon nanotube-polystyrene composites prepared by in situ polymerisation of stacked layers

In situ polymerisation provides a route to polystyrene (PS) matrix composites reinforced with aligned multi-walled carbon nanotubes (MWNTs). As shown, fully densified composites can be prepared; by varying the number of layers of aligned MWNT arrays, desired thickness of the composite can be manufactured. These aligned composites have characteristic anisotropic electrical and thermal properties.     

Grain size effect on the strengthening behavior of aluminum-based composites containing multi-walled carbon nanotubes

Strengthening efficiency of multi-walled carbon nanotubes (MWCNTs) is investigated for aluminum-based composites with grain sizes ranging from ∼250 to ∼65 nm. The strength of composites is significantly enhanced proportional to an increase of the MWCNT volume. However, the increment differs depending on deformation mode of the matrix. The strengthening efficiency of MWCNTs in ultrafine-grained composites is comparable with that predicted by the discontinuous fiber model, whereas the efficiency becomes half of the theoretical prediction as grain size is reduced below ∼70 nm. For nano-grained aluminum, activities of forest dislocations diminish and dislocations emitted from grain boundaries are dynamically annihilated during the recovery process, providing a weak plastic strain field around MWCNTs. The observation may provide a basic understanding of the strengthening behavior of nano-grained metal matrix composites.     

混杂功能化碳纳米管/聚氨酯复合材料的制备及性能

以多壁碳纳米管（MWNTs）为原料,采用不同改性方法制得了羧化碳纳米管（MWNTs-COOH）、共价功能化碳纳米管（MWNTs-NH₂）、非共价功能化碳纳米管（MWNTs-PPA）和混杂功能化碳纳米管（MWNTs-COOH-PPA）,将这4种改性碳纳米管按不同质量分数分别加入聚氨酯（PU）中制备了复合材料。使用万能材料试验机和热失重分析仪测试了复合材料的力学和热学性能,研究了碳纳米管对复合材料性能的影响。结果表明:通过在碳纳米管表面接枝少量的共价官能团防止非共价包覆的剥离,混杂功能化方法既能够改善碳纳米管在基体中的分散性,又能够保持其与基体界面间结合力,复合材料增强效果最明显。耐热性良好的碳纳米管的添加提高了PU基体的热分解温度,提高程度由于其功能化方式的不同而稍有差别。MWNTs-COOH-PPA/PU复合材料的力学性能最优,当碳纳米管含量（质量分数,下同）为0.3%时,其拉伸强度与纯PU相比提高104%,其热分解温度与MWNTs-COOH/PU相当,优于纯PU,但低于MWNT8-NH₂/PU和MWNTs-PPA/PU。     

Poly(vinylidene fluoride)-assisted melt-blending of multi-walled carbon nanotube/poly(methyl methacrylate) composites

Multi-walled carbon nanotubes (MWNTs) were sonicated in the dimethylformamide solution of poly(vinylidene fluoride) (PVDF). The PVDF-covered MWNTs were then melt-blended with poly(methyl methacrylate) (PMMA). The dynamic mechanical behavior of various composites was studied. The presence of a small amount of PVDF leads to a significant improvement in the storage moduli of the MWNT/PMMA composites at low temperatures. The storage modulus of a PVDF/MWNT/PMMA composite containing 0.5 wt.% PVDF is almost twice as that of a MWNT/PMMA composite at 50°C. However, a further increase in the PVDF content leads to a reduction of the storage modulus. The beneficial effect of PVDF diminishes at higher temperatures.     

Electrical and mechanical characterization of stretchable multi-walled carbon nanotubes/polydimethylsiloxane elastomeric composite conductors

Stretchable, elastomeric composite conductor made of multi-walled carbon nanotubes (MWNTs) and polydimethylsiloxane (PDMS) has been fabricated by simple mixing. Electrical percolation threshold, amount of filler at which a sharp decrease of resistance occurs, has been determined to be ∼0.6 wt.% of MWNTs. The percolation threshold composition has also been confirmed from swelling experiments of the composite; the equilibrium swelling ratio slightly increases up to ∼0.6 wt.%, then decreases at higher amount of filler MWNTs. Upon cyclic stretching/release of the composite, a fully reversible electrical behavior has been observed for composites having filler content below the percolation threshold value. On the other hand, hysteretic behavior was observed for higher filler amount than the threshold value, due to rearrangement of percolative paths upon the first cycle of stretching/release. Finally, mechanical moduli of the composites have been measured and compared by buckling and microtensile test. The buckling-based measurement has led to systematically higher (∼20%) value of moduli than those from microtensile measurement, due to the internal microstructure of the composite. The elastic conductor may help the implementation of various stretchable electronic devices.     

Multi-walled carbon nanotube-reinforced silicon carbide fibers prepared by polymer-derived ceramic route

Multi-walled carbon nanotube (MWNT)-reinforced silicon carbide (SiC) ceramic fibers were successfully prepared by blending MWNTs (0-0.5 wt.%) with polycarbosilane, followed by melt spinning, curing, and pyrolysis. The MWNTs used in this study were modified with a chemical treatment. It was found that the MWNTs were well-dispersed in the matrix and aligned with the axis of the fibers after ultrasonic dispersion combined with melt spinning. Mechanical measurements revealed that significant improvement in Young’s modulus and tensile strength was achieved by incorporating MWNTs into the ceramic fibers. The addition of 0.5 wt.% MWNTs led to a 93.6% increase in the Young’s modulus and a 38.5% increase in the tensile strength.