High performance PEEK/carbon nanotube composites compatibilized with polysulfones-I. Structure and thermal properties

Poly(ether ether ketone) (PEEK)/single-walled carbon nanotube (SWCNT) composites incorporating polysulfones as compatibilizers were fabricated by melt-blending, after pre-processing based on ball milling and mechanical treatments in an organic solvent. Their structure, morphology and thermal properties have been investigated. Microscopic observations showed a uniform distribution of the CNTs and good miscibility between the compatibilizer and matrix phases. The incorporation of wrapped SWCNTs leads to a remarkable increase in the degradation temperatures of the matrix in comparison with non-compatibilized samples, attributed to the high thermal stability of the polysulfones and the compatibilizing effect. The addition of very small CNT loadings raises the crystallization temperature and the degree of crystallinity of PEEK. At higher concentrations, the inactive nucleating activity of the nanofillers, the confinement of the polymer chains within the CNT network and the presence of an amorphous compatibilizer moderately hinder PEEK crystallization. Synchrotron X-ray diffraction experiments indicate the existence of reorganization phenomena of the matrix crystals during the heating of the composites. Improved thermal properties are found for composites incorporating arc-purified SWCNTs, attributed to the higher degree of debundling and lower metal content of these CNTs. These compatibilized composites are new materials for potential high-temperature structural applications.     

Mechanical and electrical properties of aligned carbon nanotube/carbon matrix composites

To synthesize carbon nanotube/carbon matrix (CNT/C) composites rivaling or exceeding the mechanical and electrical properties of current carbon fiber/carbon matrix composites, it is essential to align carbon nanotubes in the composite. In this work, we fabricated CNT/polyacrylonitrile (PAN) precursor composites with high degree of CNT alignment, and carbonized and graphitized them at high temperatures. Carbonizing the precursor composites significantly improved their elastic modulus, strength, and electrical conductivity. The matrix was uniformly carbonized and highly graphitized. The excellent mechanical and electrical properties make the CNT/C composites promising for many high temperature aerospace applications.     

Mechanical and electrical properties of multi walled carbon nanotube/ABC block terpolymer composites

Composites of multi-walled carbon nanotubes (MWCNTs) in ABC block terpolymer matrices of different compositions are studied. The composites were obtained by dispersion of MWCNTs in poly(styrene-block-butadiene-block-methyl methacrylate) (SBM) in a selective solvent for the M block, followed by solvent evaporation and compression molding. The structures of the MWCNT/SBM composites are investigated by transmission electron microscopy. The processing conditions, i.e. solvent cast or compression molding, induce different non-equilibrium microstructures and the MWCNTs modify the SBM organization only locally. We show that by fixing the processing procedure we are able to obtain samples with reproducible microstructure and properties. The electrical conductivity thresholds of these composites are lower than 1 wt.%. The reinforcing effect of the MWCNTs measured by dynamical mechanical analysis is mainly related to the SBM microstructures of the matrix and to the MWCNT dispersion quality.     

Development and characterization of PEEK/carbon nanotube composites

New poly(ether ether ketone) (PEEK) based composites have been fabricated by the incorporation of single-walled carbon nanotubes (SWCNTs) using melt processing. Their structure, morphology, thermal and mechanical properties have been investigated. Scanning electron microscopy observations demonstrated a more uniform distribution of the CNTs for samples prepared following a processing route based on polymer ball milling and CNT dispersion in ethanol media. Thermogravimetric analysis indicated a remarkable improvement in the thermal stability of the matrix by the incorporation of SWCNTs. Differential scanning calorimetry showed a decrease in the crystallization temperature with increasing SWCNT content, whilst no significant changes were observed in the melting of the composites. The crystallite size determined by X-ray diffraction decreased at high SWCNT loading, which is attributed to the spatial limitations on crystal growth by confinement within the CNT network. Dynamic mechanical analysis revealed an increase in the storage moduli, hence in the rigidity of the systems, with increasing SWCNT content. Their addition shifts the glass transition peak to higher temperatures due to the restriction in chain mobility imposed by the CNTs. Higher thermal stability and mechanical strength were found for composites with improved dispersion of the SWCNTs.     

PPS/recycled PEEK/ carbon nanotube composites: Structure,properties and compatibility

Blends of poly(phenylene sulfide) (PPS) and recycled poly(ether ether ketone) (r‐PEEK) were prepared using a twin‐screw extruder. The carbon nanotube (CNT) added to the blends not only improved the compatibility of the two polymers, but also affected the morphology of the immiscible PPS/r‐PEEK blends. R‐PEEK always forms the dispersed phase and PPS the continuous phase in such blends. In the composite, CNT particles were observed in the PPS phase, mostly distributes in the interface between PPS and PEEK. The results show that r‐PEEK improves the impact and tensile strength of PPS, but does not provide nucleation effect on PPS. However, CNT improved the flexural modulus of PPS/r‐PEEK blends and promoted the crystallization of r‐PEEK rather than that of PPS. The prepared PPS/r‐PEEK blends provided larger electrical conductivity than neat polymers. Adding 20 wt % CNT to blend resulted in composite with the minimum volume resistivity, a reduction of four orders of magnitude, compared with that of the neat blend. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42497.     

Rheological and electrical properties of polycarbonate/multi-walled carbon nanotube composites

Rheological and electrical properties of the polycarbonate (PC)/multi-walled carbon nanotube (MWNT) were studied. The MWNT was funtoinalized by treating with the hydrogen peroxide (H₂O₂). The H₂O₂ treated MWNT was dried by thermal and freeze drying methods. From the morphological studies, the degree of entanglement of the MWNT was decreased after treating with the H₂O₂. For the H₂O₂ treated MWNT (thermal drying), the length of the MWNT was shortened compared that of the H₂O₂ treated MWNT (freeze drying). The rheological and electrical properties of the PC/MWNT (H₂O₂ treated) composites increased compared that of the PC/MWNT (untreated) composites. Also, the electrical conductivity showed higher value for the PC/MWNT (H₂O₂ treated, freeze drying) composites compared that of the PC/MWNT (H₂O₂ treated, thermal drying) composites. From the results of the morphological, rheological, and electrical properties of the PC/MWNT composites, it is suggested that the electrical and rheological properties of the PC/MWNT composites are affected by the MWNT-MWNT network structure, which is related with the MWNT morphologies such as the degree of aggregation and aspect ratio of the MWNT.     

Mechanical and thermo-mechanical properties of carbon nanotube reinforced composites

A study on the mechanical and thermo-mechanical properties of carbon nanotube (CNT) reinforced nanocomposites is presented in this article. Mori–Tanaka method is used for modeling the effective stiffness and coefficient of thermal expansion. Regression formulas were developed to describe the effects of CNT orientation, aspect ratio, and CNT volume fraction. Given the statistical distributions of CNT orientations and aspect ratios, the effective properties can be conveniently derived by numerical integration using these formulas.     

Mechanical and thermal properties of polyphenylene sulfide/multiwalled carbon nanotube composites

Polyphenylene sulfide (PPS)/multiwalled carbon nanotube (MWCNT) composites were prepared using a melt‐blending procedure combining twin‐screw extrusion with centrifugal premixing. A homogeneous dispersion of MWCNTs throughout the matrix was revealed by scanning electron microscopy for the nanocomposites with MWCNT contents ranging from 0.5 to 8.0 wt %. The mechanical properties of PPS were markedly enhanced by the incorporation of MWCNTs. Halpin‐Tsai equations, modified with an efficiency factor, were used to model the elastic properties of the nanocomposites. The calculated modulus showed good agreement with the experimental data. The presence of the MWCNTs exhibited both promotion and retardation effects on the crystallization of PPS. The competition between these two effects results in an unusual change of the degree of crystallinity with increasing MWCNT content. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Modulation of electrical properties in single-walled carbon nanotube/conducting polymer composites

The preparation and electrical characterization of a new class of composite layers formed by dispersing single-walled carbon nanotubes (SWNT) in 1,8-diaminonaphthalene polymer, the poly(1,8-DAN), are described.The material was grown on the surface of Pt plates by electropolymerization of 1,8-diaminonaphthalene (1,8-DAN) monomer in the presence of nanotubes. This synthesis method allows the simultaneous deposition of both the host polymer matrix and the filler nanotubes. A series of composite films were prepared using untreated nanotubes as well as nanotubes treated with KOH, HNO₃ and HNO₃/H₂SO₄ solutions. The structural features of the nanotubes and of the films produced have been investigated using Raman spectroscopy. Insight into the nature of nanotube dispersion and nanotube-polymer association was gained by AFM and STM analysis and by FE-SEM inspection after removing the outermost portion of composite films.The charge transport in composite films is found to be strongly enhanced by the nanotube insertion. Depending on the SWNTs processing, currents up to 30 mA, higher by a factor of about 140 than those of the pure poly(1,8-DAN) films, were measured with an applied voltage of 250 mV.     

High electrical conductivity of nylon 6 composites obtained with hybrid multiwalled carbon nanotube/carbon fiber fillers

The synergetic effect of multiwalled carbon nanotubes (MWNTs) and carbon fibers (CFs) in enhancing the electrical conductivity of nylon 6 (PA6) composites was investigated. To improve the compatibility between the fillers and the PA6 resin, we grafted γ‐aminopropyltriethoxy silane (KH‐550) onto the MWNTs and CFs after carboxyl groups were generated on their surface by chemical oxidation with nitric acid. Fourier transform infrared spectroscopy and thermogravimetric analysis proved that the KH‐550 molecules were successfully grafted onto the surface of the MWNTs and CFs. Scanning electron microscopy and optical microscopy showed that the obtained modified fillers reduced the aggregation of fillers and resulted in better dispersion and interfacial compatibility. We found that the electrical percolation threshold of the MWNT/PA6 and CF/PA6 composites occurred when the volume fraction of the fillers were 4 and 5%, respectively. The MWNT/CF hybrid‐filler system exhibited a remarkable synergetic effect on the electrically conductive networks. The MWNT/7% CF hybrid‐filler system appeared to show a second percolation when the MWNT volume fraction was above 4% and a volume resistivity reduction of two orders of magnitude compared with the MWNT/PA6 system. The mechanical properties of different types of PA6 composites with variation in the filler volume content were also studied. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40923.     

Mechanical, electrical, piezoelectric and electro-active behavior of aligned multi-walled carbon nanotube/cellulose composites

Multi-walled carbon nanotubes (MWCNTs) were covalently grafted to cellulose to make an MWCNT/cellulose (M/C) composite. Aligned M/C composite was obtained by mechanical stretching process. The stretching effect was demonstrated by observing morphology as well as measuring mechanical, electrical and piezoelectric properties of the M/C composite. The influence of aligned MWCNTs on the actuator performance of the M/C composite was evaluated in terms of bending displacement and resonance frequency depending on the stretching ratio and environmental humidity level. The aligned MWCNTs contributed to remarkably enhancing the mechanical and piezoelectric properties, but also improving actuator performance of the M/C composite.     

Comparative study on electrical properties of copper nanowire/polypropylene and carbon nanotube/polypropylene composites

Nanocomposites using copper nanowires (CuNWs) or carbon nanotubes (CNTs) as fillers with polypropylene (PP) as matrix were prepared by miscible solution mixing and precipitation method. Comparative studies on electrical conductivity and electromagnetic interference shielding properties were reported. On the conductivity curve, a plateau was found for both CuNW/PP composite and CNT/PP composite. The plateaus are located at a different concentration range for each composite type: for CuNW/PP composite, it is between 0.8 and 1.7 vol %, while for CNT/PP composite the plateau occurs in a narrower range between 0.4 and 0.6 vol %. The shielding effectiveness (SE) increases with increased concentration of fillers. CNT/PP composite has higher SE at concentrations less than 2 vol %; the two curves cross near 10 dB at this point and at concentrations higher than 2 vol %, CuNW/PP composite has higher SE. © 2014 American Institute of Chemical Engineers AIChE J, 61: 296–303, 2015     

Electromagnetic interference shielding properties of polymer-grafted carbon nanotube composites with high electrical resistance

Poly(methyl methacrylate) (PMMA)-grafted multiwalled CNTs were prepared, and then dispersed into additional PMMA matrix, yielding highly insulated PMMA–CNT composites. The volume resistivity of PMMA–CNT was as high as 1.3 × 10¹⁵ Ω cm even at 7.3 wt% of the CNT. The individual CNTs electrically-isolated by the grafted PMMA chains in PMMA–CNT transmitted electromagnetic (EM) waves in the frequency range of 0.001–1 GHz, whereas the percolated CNTs in a conventional composite prepared by blending PMMA with the pristine CNTs strongly shielded the EM waves. This result suggests that the intrinsic conductivity of the CNT itself in PMMA–CNT does not contribute to the EM interference (EMI) shielding in the frequency range of 0.001–1 GHz. On the other hand, PMMA–CNT exhibited EMI shielding at the higher frequency range than 1 GHz because the dielectric loss of the CNT itself was rapidly increased over 1 GHz. At 110 GHz, PMMA–CNT with 7.3 wt% of the CNT had EMI SE of as high as 29 dB (0.57 mm thickness), though is slightly lower than that of the percolated conventional composite (35 dB). Thus, it is demonstrated that the highly insulated PMMA–CNT has the good EMI shielding at extremely high frequency range (30–300 GHz).     

Preparation and properties of multi-walled carbon nanotube/carbon/polystyrene composites

Multi-walled carbon nanotube (MWCNT)/C/polystyrene (PS) composite materials were prepared by in situ polymerization of monomer in preformed MWCNT/C foams. MWCNT/C foams were preformed using polyurethane foam as template. The preformed MWCNT/C foams had a more continuous conductive structure than the carbon nanotube networks formed by free assembly in composites. The structure of the MWCNT/C foam network was characterized with scanning electron microscopy. The MWCNT/C/PS composites have an electric conductivity higher than 0.01 S/cm for a filler loading of 1 wt.%. Enhancement of thermal conductivity and mechanical properties by the preformed MWCNT/C foam were also observed.     

Mechanical and electrical properties of carbon nanotube buckypaper reinforced silicon carbide nanocomposites

The nanocomposite was produced via phenolic resin infiltrating into a carbon nanotube (CNT) buckypaper preform containing B₄C fillers and amorphous Si particles followed by an in-situ reaction between resin-derived carbon and Si to form SiC matrix. The buckypaper preform combined with the in-situ reaction avoided the phase segregation and increased significantly the volume fraction of CNTs. The nanocomposites prepared by this new process were dense with the open porosities less than 6%. A suitable CNT–SiC bonding was achieved by creating a B₄C modified interphase layer between CNTs and SiC. The hardness increased from 2.83 to 8.58 GPa, and the indentation fracture toughness was estimated to increase from 2.80 to 9.96 MPa m^1/2, respectively, by the reinforcing effect of B₄C. These nanocomposites became much more electrically conductive with high loading level of CNTs. The in-plane electrical resistivity decreased from 124 to 74.4 μΩ m by introducing B₄C fillers.     

导电炭黑/氯化丁基橡胶力学和电性能的研究

通过共混法制备了导电炭黑/氯化丁基橡胶复合材料,研究了复合材料的拉伸性能与导电、介电性能。研究发现,随着导电炭黑和硫化剂含量的增加,拉伸强度先出现一个极大值随后下降,在炭黑用量为5%,硫化剂用量为3%时,拉伸强度最大,为9.1 MPa;而断裂伸长率一直下降。当导电炭黑超过5%以后,电导率迅速增加,出现渗流现象。介电常数实部ε′和介电损耗因子tanδ随导电炭黑用量的增加而增大,但当导电炭黑用量较高(20%)时,在高频时,ε′和tanδ都下降。     

High performance polymer composites on PEEK reinforced with aluminum oxide

A study on high performance poly(ether‐ether‐ketone) (PEEK) composites prepared by incorporating aluminum oxide (Al₂O₃), 0 to 50 wt % by hot compaction at 15 MPa and 350°C was described. Density, thermogravimetric analysis/differential scanning calorimetry, and scanning electron microscopy (SEM) were employed to evaluate their density, thermal stability, crystallinity, and morphology. Experimental density was found higher than theoretical density, which indicates that composite samples are sound. It was found that the addition of micron sized (< 15 μm) Al₂O₃ increased the peak crystallization temperature by 12°C when compared with neat PEEK with insignificant increase in melting temperature. Half‐time of crystallization is reduced from 2.05 min for the neat PEEK to 1.08 min for PEEK incorporated with 30 wt % Al₂O₃ because of the strong nucleation effect of Al₂O₃. The thermal stability of composites in air atmosphere was increased by 26°C. However, thermal stability in nitrogen atmosphere decreases at lower concentration of Al₂O₃ but increases above 20 wt % of Al₂O₃. Uniform dispersion of Al₂O₃ particles was observed in PEEK polymer matrix by SEM. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4623–4631, 2006     

A strategy for enhancement of mechanical and electrical properties of polycarbonate/multi-walled carbon nanotube composites

Two poly(3-hexylthiophene)-g-polycaprolactones (P3HT-g-PCLs) with different degrees of polymerization (DP) of P3HT backbone were synthesized and used as a compatibilizer for bisphenol A polycarbonate (PC)/multi-walled carbon nanotube (MWCNT) composites. Both field emission-scanning electron microscopy and melt-state rheology show that MWCNTs are homogeneously dispersed in PC matrix when P3HT-g-PCL is added to PC/MWCNT composites. As a consequence, the mechanical and electrical properties of PC/MWCNT composites are dramatically improved when a small amount of P3HT-g-PCL is added to PC/MWCNT composites. It is also found that P3HT-g-PCL with lower DP of P3HT backbone is more effective to homogeneously disperse MWCNTs in PC matrix than that with higher DP of P3HT. This is because the π-π interaction between MWCNTs and P3HT-g-PCL with lower DP of P3HT is stronger than the case of P3HT with higher DP of P3HT, as evidenced by fluorescence emission spectra.     

Mechanical and thermophysical properties of carbon/carbon composites with hafnium carbide

Carbon/carbon (C/C) composites with addition of hafnium carbide (HfC) were prepared by immersing the carbon felt in a hafnium oxychloride aqueous solution, followed by densification and graphitization. Mechanical properties, coefficients of thermal expansion (CTE), and thermal conductivity of the composites were investigated. Results show that mechanical properties of the composites decrease dramatically when the HfC content is greater than 6.5 wt%. CTE of the composites increases with the increase of HfC contents. The composites with addition of 6.5 wt% HfC show the highest thermal conductivity. The high thermal conductivity results from the thermal motion of CO in the gaps and pores, which can improve phonon–defect interaction of the C/C composites. Thermal conductivities of the composites decrease when the HfC content is greater than 6.5 wt%, which is due to formation of a large number of cracks in the composites. Cracks increase the phonon scattering and hence restrain heat transport, which results in the decrease of thermal conductivity of the composites.