Thermosetting polyurethane multiwalled carbon nanotube composites

Thermosetting polyurethane (PU) multi‐walled carbon nanotube (MWCNT) nanocomposites at loadings up to 1 wt % were prepared via an addition polymerization reaction. The morphology of the nanocomposites and degree of dispersion of the MWCNTs was studied using a combination of scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM) and wide angle X‐ray diffraction (WAXD), and revealed the nanotubes to be highly dispersed in the PU matrix. Addition of just 0.1 wt % MWCNTs resulted in significant enhancements in stiffness, strength and toughness. Increases in Young's modulus, % elongation at break and ultimate tensile strength of 561, 302 and 397% were measured for the nanocomposites compared to the unfilled PU. The effect of the MWCNTs on the modulus of the PU was evaluated using the Rule of Mixtures, Krenchel and Halpin‐Tsai models. Only the Halpin‐Tsai model applied to high aspect ratio nanotubes was in good agreement with the modulus values determined experimentally. Strong interfacial shear stress was found between PU chains and nanotubes, up to 439 MPa, calculated using a modified Kelly‐Tyson model. Evidence for strong interfacial interactions was obtained from the Raman spectra of both the precursor materials and nanocomposites. When the MWCNTs were added to the isophorone diisocyanate an up‐shift of 14 cm^?1 and on average 40 cm^?1 was obtained for the position of the carbon‐hydrogen (C? H) out‐of plane bending (766 cm^?1) and isocyanate symmetric stretch (1420 cm^?1) modes respectively. Moreover, an up‐shift of 24 cm^?1 was recorded for the nanotube tangential mode (G‐band) for the 1.0 wt % nanocomposite because of the compressive forces of the PU matrix acting on the MWCNTs. The dynamic mechanical (DMA) properties of the PU thermoset and the nanocomposites were measured as a function of temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Influence of adding multiwalled carbon nanotubes on the adhesive strength of composite epoxy/sol–gel materials

The tensile shear strength of a composite epoxy/sol–gel system modified with different ratios of multiwall carbon nanotubes (MWCNTs) was evaluated using a mechanical testing machine. The experimental results showed that the shear strength increased when lower than ~0.07 wt% of MWCNTs were added in the composite solution. The increase of the shear strength was attributed to both the mechanical load transfer from the matrix to the MWCNTs and the high specific surface area of this material that increased the degree of crosslinking with other inorganic fillers in the formulation. However, a decrease in the adhesive shear strength was observed after more than ~0.07 wt% MWCNTs were added to the composite. The reason for this may be related to the high concentration of MWCNTs within the matrix leading to excessively high viscosity, dewetting of the substrate surfaces, and reduced bonding of MWCNTs with the matrix, thereby limiting the strength. SEM observation of the fracture surfaces for composite epoxy/sol–gel adhesive materials with 0.01 wt% MWCNTs showed a mixed interfacial/cohesive fracture mode. This fracture mode indicated strong links at the adhesive/substrate interface, and interaction between CNTs and the matrix was achieved; therefore, adhesion performance of the composite epoxy/sol–gel material to the substrate was improved. An increase of a strong peak related to the C–O bond at ~1733 cm^?1 in the FTIR spectra was observed. This peak represented crosslinking between the CNT surface and the organosilica nanoparticles in the MWCNTs-doped composite adhesive. Raman spectroscopy was also used to identify MWCNTs within the adhesive material. The Raman spectra exhibit peaks at ~1275 cm^?1 and in the range of ~1549–1590 cm^?1. The former is the graphite G-band, while the latter is the diamond D-band. The D-band and G-band represent the C–C single bond and C=C double bond in carbon nanotubes, respectively.     

Preparation and characterization of a novel hydrophilic PVDF/PVA UF membrane modified by carboxylated multiwalled carbon nanotubes

Polyvinylidene fluoride (PVDF)/polyvinyl alcohol (PVA) ultrafiltration (UF) membranes were prepared via a phase inversion method employing the modification of carboxylated multiwalled carbon nanotubes (MWCNTs‐COOH). Various contents of MWCNTs‐COOHs (0.00–0.15 wt%, weight of casting solution) were added into PVDF/PVA/dimethyl sulfoxide systems for the fabrication of the plate UF membrane. Fourier transform infrared spectroscopy spectra identified the successful introduction of carboxyl through the C?O peak at 1730 cm^?1. Scanning electron microscopy images exhibited the external surface and the asymmetric morphology with the appearance of a sponge‐like inner structure. Atomic force microscopy analysis determined the roughness values and rougher topography. The hydrophilicity of the composite membrane containing 0.09 wt% of MWCNTs‐COOHs improved the most. This sample has the highest pure water flux, approximately doubled (126.6 L·m^?2·h^?1) compared to the PVDF/PVA membrane (68.6 L·m^?2·h^?1), an enhanced bovine serum albumin flux recovery rate, showing an increase of 17%, and the best fouling resistance ability. Meanwhile, the porosity and dynamic contactangle also indicate the enhancement of membrane hydrophilicity. Dextran (DEX) 600k rejection reached 91.0%. Break strength, elongation at break, and Young's modulus also had improvements of 60%, 215.5%, and 56.7%, respectively, when the MWCNTs‐COOH content was 0.12 wt%. POLYM. ENG. SCI., 56:955–967, 2016. © 2016 Society of Plastics Engineers     

Butterfly nanostructures via regioregularly grafted multi‐walled carbon nanotubes and poly(3‐hexylthiophene) to improve photovoltaic characteristics

Butterfly nanostructures were designed using multi‐walled carbon nanotubes (CNTs) grafted with regioregular poly(3‐hexylthiophene) (RR‐P3HT) chains (CNT‐graft‐P3HT). The secondary crystallization of RR‐P3HT free chains onto CNT‐graft‐P3HT reflected the donor–acceptor supramolecules with a butterfly configuration, in which the CNT acted as the body of the butterfly and seeded crystallization of P3HT free chains resulted in the wings having a width of 37–38 nm. Butterfly supramolecules demonstrated high melting point (241.2 °C), fusion enthalpy (31.5 J g^?1) and crystallinity (85.13%). High photoluminescence quenching and thus donating–accepting property were also detected for the butterfly nanohybrids with a bandgap energy of 1.94 eV. Incorporation of butterfly nanostructures in the active layer of photovoltaic devices (P3HT:butterfly) conspicuously affected the system characteristics including short circuit current density (J_sc; 10.84 mA cm^?2), fill factor (FF; 56%) and power conversion efficiency (PCE; 3.94%). The inclusion of phenyl‐C71‐butyric acid methyl ester molecules as second acceptor in thin‐film active layers further increased the efficacy of systems, i.e. J_sc of 12.23 mA cm^?2, FF of 63%, open circuit voltage of 0.66 V and PCE of 5.08%, without considering external treatments and additives. © 2018 Society of Chemical Industry     

Growth of carbon nanotubes with different morphologies by pyrolising acetylene

Abstract

Multiwalled carbon nanotubes (MWCNTs) with different morphologies have been prepared by pyrolysis of a mixture of acetylene-ferrocene over predeposited Co and Ni catalysts at 700°C. A high yield of carbon nanotubes with further purification have been obtained in the optimal conditions. The optimum synthesis parameters included synthesis temperature of 700°C, growth time of 30?min, flowrate of acetylene and hydrogen of 40 and 300?sccm respectively. Multiwall straight, curved, helically, coiled, planar-spiral and V-shaped nanotubes were found with diameters in the range of 10-70?nm and with lengths up to 5?μm. The morphology and structure features of the MWCNTs are characterised using scanning electron microscopy, transmission electron microscopy, energy dispersive spectra, Raman spectroscopy and thermogravimetry analyses.     

Studies on a novel anion‐exchange membrane based on chitosan and ionized organic compounds with multiwalled carbon nanotubes for alkaline fuel cells

In this work, a novel hydroxyl‐anion‐conducting membrane composed of chitosan (CTS), an ionized organic compound ([QAIM]OH), and hydroxylated multiwalled carbon nanotubes (MWCNTs‐OH) has been fabricated through a blending‐casting method assisted by a glutaraldehyde (GA) crosslinking process that can improve the mechanical properties of the membrane effectively. Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy revealed that [QAIM]OH and MWCNTs‐OH were successfully introduced into the CTS matrix. A chemical crosslinking reaction between CTS and GA could be confirmed by FTIR, X‐ray photoelectron spectroscopy, and contact angle tests. By tuning the mass fraction of [QAIM]OH and MWCNTs‐OH in the membrane, the maximum OH^? conductivity (5.66 × 10^?3 S cm^?1 at room temperature) could be achieved for the composition CTS:[QAIM]OH (1:0.75 in mass) blend doped with 3% MWCNTs‐OH. At a current density of 59.9 mA cm^?2, a membrane electrode assembly fabricated with the CTS/[QAIM]OH/ MWCNTs‐OH membrane (1:0.5/3%) achieved a power density of 31.6 mW cm^?2 in a H₂/O₂ system at room temperature. Under the condition of intermediate temperature (100–140 °C) without water, the conductivities of the membranes increased with increasing temperature and the amount of [QAIM]OH, which acted as an ionic liquid in the membrane, indicating that the ionic transport behaviors could still be occurring. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46323.     

Functionalized multi‐wall carbon nanotubes/silicone rubber composite as capacitive humidity sensor

Functionalized multi‐wall carbon nanotubes (MWCNTs) treated by mixed acids have been used to develop a capacitive humidity sensor based on MWCNTs/silicone rubber (SR) composite film. The MWCNTs/SR composites were prepared through conventional solution processed method. The micrographs of MWCNTs/SR composites were observed by transmission electron microscopy (TEM) and scanning electron microscope. The FT‐IR spectra demonstrated the successfully grafting of ? OH groups on the treated MWCNTs. The sensing properties of the composite at different relative humidity (RH) and frequency were characterized and linear sensing responses of the MWCNTs/SR composites to RH were observed. The treated MWCNTs/SR composite film (Tr‐film) had higher sensitivity than that of the untreated MWCNTs/SR composite film (Un‐film). Experimental data indicate that the Tr‐film exhibits an excellent long‐term stability, small hysteresis, and fine reproducibility. The response and recovery time of the Tr‐film were 30 and 27 s, respectively. Thereby, such Tr‐film had potential applications as humidity sensors. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40342.     

Infrared study of combined effect of γ-radiation and elevated temperature on poly(vinyl chloride)

Infrared absorption spectroscopy has been used to investigate the combined effect of γ-radiation and heat on poly(vinyl chloride) (PVC). The recorded spectra showed that exposure of PVC samples to gamma doses from 0.5 to 15 Mrad results in remarkable changes in the absorbances of their absorption bands. Also, the exposure to doses from 3 to 15 Mrad results in an appearance of a C?O band at 1720 cm^?1 and O? H band at 3450 cm^?1. The nature of the formation of these bands was discussed in terms of peroxide-mediated oxidative degradation mechanism. Moreover, it was found that heat treatment of PVC samples over the temperature range 25–180°C causes no noticeable changes in their spectra apart from slight changes in the absorbances of the bands. On other hand, it was found that heat treatment of the irradiated samples causes considerable increase in the intensity of the C?O band. In addition to the well-defined and sharp band appearing at 1720 cm^?1, the spectra of the samples irradiated with 10 and 15 Mrad exhibited two bands at 1070 and 1120 cm^?1. The obtained data led also to the conclusion that the C? Cl bands cannot be used as a measure of crystallinity of PVC.     

Diameter dependence of interwall separation and strain in multiwalled carbon nanotubes probed by X-ray diffraction and Raman scattering studies

We have made a systematic study on the diameter dependent spectral features in X-ray diffraction (XRD) and Raman scattering studies of multiwalled carbon nanotubes (MWCNTs) of various diameters in the range 5?100 nm. High resolution transmission electron microscopy (HRTEM) imaging reveals a systematic decrease in the interwall separation from 3.8 Å down to 3.2 Å as the diameter of nanotubes increases from 5.8 nm to 63.2 nm. Analysis of the XRD patterns shows an exponential decrease in d₀₀₂ interlayer spacing with increasing tube diameter, in close agreement with the HRTEM results. Further, XRD profile line width shows inverse diameter dependence and exponential increase in intensity as the diameter of the MWCNTs increases. Raman spectra of different diameter nanotubes show different evolutions of metallic and semiconducting components in the G-band, as found from spectral deconvolution. The frequency and full width at half maximum (FWHM) of the semiconducting component of the G^? band gradually decreases as the tube diameter increases. Ratio of intensities of G^? band to D-band first shows a sharp fall as the tube diameter increases from 7 nm to 15 nm and then slowly increases with increasing diameter. On the other hand, G′ mode frequency shows large up shift when average diameter is increased from 7 nm to 15 nm and then saturates for higher diameter tubes. Analysis of Raman and XRD data reveals that the lowest diameter (7 nm) MWCNTs have features similar to those of the single walled nanotubes, while the spectral features are distinctly different for higher diameter MWCNTs due to the interaction among tube walls that is very significant for large diameter MWCNTs. Observed diameter dependence of the spectral features is explained in terms of nanotube curvature and atomic vibrations involving interaction among the walls in MWCNTs. The present study demonstrates the power of XRD for nondestructive evaluation of diameter distribution and interwall separation in MWCNTs with wide range of diameters.     

Isothermal crystallization kinetics of polypropylene in melt‐mixed composites of polypropylene and multi‐walled carbon nanotubes

The isothermal crystallization behaviour of the polypropylene (PP) phase in PP/multi‐walled carbon nanotubes (MWCNTs) composites has been investigated via differential scanning calorimetric analysis, which showed the influence of the varying dispersion level of MWCNTs in the respective PP matrix. PP/MWCNTs composites were prepared via melt‐blending technique, wherein two different grades of MWCNTs of varying average “agglomerate” size and varying entanglements (N‐MWCNTs and D‐MWCNTs) were utilized. Furthermore, the influence of melt‐viscosity of the PP phase was investigated on the crystallization kinetics of the PP/MWCNTs composites. Heterogeneous nucleation ability of MWCNTs has resulted in a decrease in half time of crystallization (t _1/2) from ～14 min for pure PP to ～6 min for PP/N‐MWCNTs and ～11 min for PP/D‐MWCNTs composites at 1 wt% of MWCNTs at 132 °C. Overall rate of crystallization (k) has significantly increased to 4.9 × 10^?2 min^?1 for PP/N‐MWCNTs composite as compared with 6.2 × 10^?3 min^?1 for PP/D‐MWCNTs composite at 0.5 wt% of MWCNTs at 132 °C. Moreover, the effect of a novel organic modifier, Li‐salt of 6‐amino hexanoic acid along with a compatibilizer (PP‐g‐MA) has also been investigated on the crystallization kinetics of the PP phase in PP/MWCNTs composites. POLYM. ENG. SCI., 57:1136–1146, 2017. © 2017 Society of Plastics Engineers     

Novel nanocomposite of poly(acrylonitrile‐co‐glycidyl methacrylate) crosslinked with Jeffamine‐functionalized multiwalled carbon nanotubes as gel polymer electrolytes

Multiwalled carbon nanotubes (MWCNTs) were functionalized with α,ω‐diamino poly(propylene oxide) (Jeffamine) of different molecular weights and crosslinked with poly(acrylonitrile‐co‐glycidyl methacrylate) [P(AN‐GMA)] to prepare a novel nanocomposite for applications in gel polymer electrolytes (GPEs). The synthesized copolymer was characterized by ¹H‐NMR, Fourier transform infrared, and thermal analysis. Scanning electron microscope observation revealed that the Jeffamine‐functionalized MWCNTs distributed uniformly in the nanocomposite membrane. The mechanical behaviors of the nanocomposite membranes were investigated. It was found that the crosslinked nanocomposite membranes of P(AN‐GMA) and Jeffamine‐functionalized MWCNTs exhibited much higher mechanical strength than the counterpart nanocomposite obtained by physical blending. Moreover, the weight content and molecular weights of Jeffamine had an effect on the mechanical properties of the nanocomposites. Differential scanning calorimeter measurements showed that the crosslinked nanocomposite membranes were amorphous. GPEs based on the nanocomposite were prepared and characterized by complex impedance measurements. The GPE based on the nanocomposite of P(AN‐GMA) crosslinked with 6 wt % of MWCNTs functionalized by Jeffamine D400 showed an ionic conductivity of about 3.39 × 10^?4 S cm^?1 at 25°C, which is much higher than the counterpart nanocomposite of physically blended P(AN‐GMA) and MWCNTs. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Epoxy composite foams with excellent electromagnetic interference shielding and heat‐resistance performance

Epoxy composite foams with improved heat‐resistant property and efficient electromagnetic interference shielding effectiveness (EMI SE) were fabricated through a two‐step foaming technique. A sort of novel and untraditional expandable microspheres was adopted to reduce the density of prepared materials. A multiscale conductive network system composed of multiwalled carbon nanotubes (MWCNTs) and nickel‐plated carbon fibers (NiCFs) was introduced in these foams. Benefitting from the synergistic effect between NiCFs and MWCNTs, the multiscale epoxy foam with best comprehensive performance achieved a greatly enhanced T_g at 178.3 °C and an exceptional specific EMI SE ranging from 52.8 to 72.6 dB cm³ g^?1 in X band (8.2–12.4 GHz) at low filler loading. These properties are greatly better than original epoxy foam with a T_g of 157.8 °C and specific EMI SE of 1.0–6.4 dB cm³ g^?1. Their shielding mechanisms were discussed and the results showed that reflection is dominating. The effects of microspheres content, foaming temperature, NiCFs content, and length were investigated. In general, we provided a feasible, convenient and cost‐effective method to fabricate light‐weight, heat‐resistant thermosetting epoxy foams with sufficient EMI shielding performance which has a potential to be applied in aerospace or electronic devices. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46013.     

In-situ growth of novel CNTs-graphene hybrid structure on Ni-silica nanocomposites by CVD method for oxygen evolution reaction

Carbon nanostructures are ideal materials for electrochemical reactions like oxygen evolution reaction (OER) due to excellent electrical conductivity, resistance to strong acidic as well as basic conditions and conductive support material for transition metals. In this work we have synthesized multiwalled carbon nanotubes MWCNTs along with graphene growth in-situ by CVD method at 650 °C on nickel-silica nanocomposites for OER in alkaline medium. After removal of silica, our material exhibited comparable OER performance with that of commercial Iridium supported carbon i.e. Ir/C (20 wt % Ir) electrocatalyst. The OER performance is attributed to the defective nature of MWCNTs in the form of surface discontinuities found on rolled graphene layers of carbon nanotubes along with MWCNTs-graphene interfaces which presumably contain dangling bonds as active sites for OER. The overpotential at current density of 10 mA/cm² exhibited by MWCNTs-graphene hybrid carbon nanostructured material was 310 mV in 1 M KOH solution at scan rate of 5 mV/s while commercial Ir/C material revealed overpotential of 305 mV under similar conditions.     

Laser raman studies on carbons

Laser Raman spectra were studied of natural graphite (SP-1) and carbonaceous materials including pyrolytic graphite, carbon black, glassy carbon, coal, “white” carbon and sputtered carbon. All of these carbons have two Raman bands at 1580 cm^?1 and 1360 cm^?1, except for natural graphite which has a single sharp Raman band at 1580 cm^?1. The relative intensity of the 1360 cm^?1 band to the 1580 cm^?1 band and the half band width increase going from graphite through glassy carbon to carbon black. The 1360 cm^?1 band in glassy carbon becomes sharper and stronger with the increase of heat-treatment temperature (HTT), while the addition of iron to the glassy carbon matrices results in a decrease in intensity and half band width of this band with increasing HTT and iron content. Sputtered carbon and “white” carbon, prepared from graphite irradiated by a high power laser, showed an additional broad band around 2140cm^?1. This band is believed to originate from conjugated acetylenic bands (—CC—)_n.     

Removal of N‐methylpyrrolidone hydrogen‐bonded to polyaniline free‐standing films by protonation–deprotonation cycles or thermal heating

Free‐standing films of polyaniline (PANI), in an emeraldine base state, prepared by evaporation of polymer solutions in N‐methylpyrrolidone (NMP) retain solvent even under dynamic vacuum drying as indicated by transmission Fourier transform infrared (FTIR) spectroscopy, where a band at 1670 cm^?1 is clearly observed. Upon protonation–deprotonation cycles in aqueous media the weight of the dry base film decreases indicating gradual loss of NMP. Transmission FTIR spectra shows also the washing out of NMP with a clear decrease in intensity of the hydrogen‐bonded >C?O stretching band (1670 cm^?1) of NMP. During this process the bands between 3500 and 3200 cm^?1, assigned to >N? H stretching in the PANI backbone, change intensity suggesting that intermolecular hydrogen‐bonded >N? H, with carbonyl oxygen of NMP, is replaced by free >N? H. This is clear evidence of specific interaction of NMP with the emeraldine base. A similar loss of NMP is observed during heating but evidence of polymer degradation is also present. A mechanism is proposed to account for the loss of hydrogen‐bonding ability upon protonation which requires delocalization of the radical cations in the protonated films. © 2001 Society of Chemical Industry     

Conductivity and mechanical properties of composites based on MWCNTs and styrene‐butadiene‐styrene block™ copolymers

Composites based on multiwall carbon nanotubes (MWCNTs) and the block copolymer styrene‐butadiene‐styrene with two different contents of styrene have been investigated and their electrical conductivity and mechanical properties have been evaluated. The composites were prepared by a solution casting procedure, using a dispersant agent for the MWCNTs. Conductivity values of 10^?4 and 1.6 S cm^?1 have been obtained for samples containing 1 and 12 wt % of MWCNTs, respectively. The percolation threshold achieved for these systems was ～0.25 wt %. According to dynamic mechanical analysis, the MWCNTs interact with both phases of the copolymers, acting as a reinforcement filler, whereas the dispersant agent acts as a plasticizer. However, it was shown that the reinforcing effect of the MWCNTs overcomes the latter, resulting in an overall improvement of mechanical properties of the composites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Characterization of chemically modified wood fibers using FTIR spectroscopy for biocomposites

Chemical modifications of wood fibers (Lignocel® C120) were performed for biocomposite applications, and chemically modified wood fibers were analyzed by FTIR spectroscopy. NaOH treatment showed band shifts from Cell‐I to Cell‐II in FTIR spectra from 2902 cm^?1, 1425 cm^?1, 1163 cm^?1, 983 cm^?1, and 897 cm^?1 to 2894 cm^?1, 1420 cm^?1, 1161 cm^?1, 993 cm^?1, and 895 cm^?1 and the change in peak height at 1111 cm^?1 and 1059 cm^?1 assigned for Cell‐I structure. Silane treatment showed peak changes at 1200 cm^?1 assigned as Si? O? C band, at 765 cm^?1 assigned as Si? C symmetric stretching bond, at 700 cm^?1 assigned as Si? O? Si symmetric stretching, and at 465 cm^?1 assigned as Si? O? C asymmetric bending. Benzoyl treatment resulted in an increase in the carbonyl stretching absorption at 1723 cm^?1 and in band characteristics of aromatic rings (1604 cm^?1 and 710 cm^?1) and a strong absorption at 1272 cm^?1 for C? O band in aromatic ring. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and thermal properties of multiwalled carbon nanotube/polybenzoxazine nanocomposites

In this study, we prepared nanocomposites comprising multiwalled carbon nanotubes (MWCNTs) and polybenzoxazine (PBZ). The MWCNTs were purified through microwave digestion to remove most of the amorphous carbon and metal impurities. After purification, MWCNTs were treated with H₂SO₄/HNO₃ (3 : 1) to introduce hydroxyl and carboxyl groups onto their surfaces. Raman spectroscopy revealed the percentage of nanotube content improved after prolonged microwave treatment, as evidenced by the decrease in the ratio of the D (1328 cm^?1) and G (1583 cm^?1) bands. For the untreated MWCNTs, the I_D/I_G ratio was 0.56. After microwave treatment for 40 min, the value decreased to 0.29, indicating that the percentage of nanotube content improved. Dynamic mechanical analyses (DMAs) revealed that the storage moduli and the T_gs of the MWCNTs/PBZ nanocomposites were higher than that of the pristine PBZ. This is due to the nanometer‐scale MWCNTs restricting the motion of the macromolecular chains in the nanocomposites. Transmission electron microscopy (TEM) image revealed that the MWCNTs were well dispersed within the PBZ matrix on the nanoscale when the MWCNT content was less than 2.0 phr. The coefficient of thermal expansion (CTE) of the nanocomposites decreased on increasing the MWCNTs content. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Structural and optical properties of diamond and nano-diamond films grown by microwave plasma chemical vapor deposition

We compare structural and optical properties of microcrystalline and nanocrystalline diamond (MCD and NCD, respectively) films grown on mirror polished Si(100) substrates by microwave plasma chemical vapor deposition. The films were characterized by SEM, Raman spectroscopy, XRD, and AFM. Optical properties were obtained from transmittance and reflectance measurements of the samples in the wavelength range of 200–2000 nm. Raman spectrum of the MCD film exhibits a strong and sharp peak near 1335 cm⁻¹, an unambiguous signature of cubic crystalline diamond with weak non-diamond carbon bands. Along with broad non-diamond carbon bands, Raman spectra of NCD films show features near 1140 cm⁻¹, the intensity of which is significantly higher in the film grown at 600°C compared to the NCD film grown at higher temperature. The Raman feature near 1140 cm⁻¹ is related to the calculated phonon density of states of diamond and has been assigned to nanocrystalline or amorphous phase of diamond. XRD patterns of the MCD film show sharp peaks and NCD films show broad features, corresponding to cubic diamond. The rms surface roughness of the films was observed to be approximately 60 nm for MCD film that reduced substantially to 17 and 34 nm in the NCD films grown at 600 and 700°C, respectively. Tauc's optical gap for the diamond film is found to be approximately 5.5 eV. NCD grown at 700°C has a high optical absorption coefficient in the whole spectral region and the NCD film grown at 600°C shows very high transmittance (∼78%) in the near IR region, which is close to that of diamond. This indicates that the NCD film grown at 600°C has the potential for applications as optical windows since its surface roughness is significantly low as compared to the MCD film.     

SERS studies on single-walled carbon nanotubes submitted to chemical transformation with sulfuric acid

Surface-enhanced Raman scattering (SERS) at 676.44 nm and 1064 nm excitation wavelengths was used to investigate chemical transformation of single-walled carbon nanotubes (SWNTs) deposited on a gold support. Sulfuric acid was used as the chemical reagent. Special attention was paid to the changes in the Raman bands associated to radial and tangential vibration modes. Partial restoration of the Raman spectra by a subsequent alkaline treatment indicates a transformation with a certain degree of reversibility. The recovery reaction achieved with a 0.5 M KOH solution showed that the variations of tangential and radial band groups are not correlated. The intensity changes of the radial bands is a principal indicator for the chemical transformation of the SWNTs. Particular attention was paid to radial bands at 164 and 176 cm⁻¹, observed with 1064 nm and 676.44 nm excitation wavelength, respectively, and their 14 cm⁻¹ up-shifted replicas i.e. the bands at 178 and 190 cm⁻¹. A different behavior of these bands in the anti-Stokes side was observed.