Effect of carbon nanotubes dispersed in binder on properties of epoxy nanocomposite

Effect of quality parameters of starting raw materials, native carbon nanotubes (degree of defectiveness, thermal stability, morphology) on the properties of carboxylated and amidated nanotubes produced from these raw materials and on the homogeneity of a dispersion of amidated nanotubes in an epoxy oligomer was studied. The physicomechanical properties of epoxy nanocomposites produced from these dispersions were examined. It was found experimentally that an increase in the defectiveness of native nanotubes leads to a rise in the size of numerous aggregates in dispersions composed of an epoxy resin and amidated carbon nanotubes and, as a result, to deterioration of the physicomechanical characteristics of epoxy nanocomposites based on these dispersions.     

Formation of dispersed nanostructures from poly(ferrocenyldimethylsilane-b-dimethylsiloxane) nanotubes upon exposure to supercritical carbon dioxide

While incompatible block copolymers commonly assemble into several established classical or complex morphologies, highly asymmetric poly(ferrocenyldimethylsilane-b-dimethylsiloxane) (PFS-b-PDMS) diblock copolymers can also self-organize into high-aspect-ratio nanotubes with PDMS corona in the presence of PDMS-selective organic solvents. Exposure of these nanotubes on a carbon substrate to supercritical carbon dioxide (scCO2), also a PDMS-selective solvent, appears to promote partial dissolution of the copolymer molecules. At sufficiently high copolymer concentrations, the dissolved molecules subsequently re-organize within the scCO2 environment to form new copolymer nanostructures that redeposit on the substrate upon scCO2 depressurization. Transmission electron microscopy reveals that micelles form under all the conditions examined here, whereas nanotubes coalesce and vesicles develop only at relatively high temperatures. The extent to which the copolymer nanotubes dissolve and the size distribution of the replacement micelles are sensitive to exposure conditions. These results suggest that the phase behavior of PFS-b-PDMS diblock copolymers in scCO2 may be remarkably rich and easily tunable.     

Highly dispersed Pt catalysts on single-walled carbon nanotubes and their role in methanol oxidation

Well-dispersed Pt catalysts with very high utilization efficiencies for fuel cell reactions have been prepared by ethylene glycol reduction on polymer-wrapped single-walled carbon nanotubes (SWCNTs). By wrapping the SWCNTs in a polymer such as polystyrene sulfonate, we are able to break up the nanotube bundles to achieve better dispersion. These polymer-wrapped SWCNTs with platinum nanoparticles deposited on them show very high electrochemically active surface areas. The increase in utilization efficiencies for platinum catalysts on these SWCNT supports can be attributed to the increased surface areas and the well-dispersed nature of the carbon support and catalyst. The catalyst dispersion facilitates diffusion of reactant species which in turn results in higher methanol oxidation currents and more positive potentials for oxygen reduction.     

Adsorption of a polymeric siloxane surfactant on carbon black particles dispersed in mixtures of water with polar organic solvents

The adsorption of a rake-type polymeric siloxane surfactant (polydimethylsiloxane-graft-polyether copolymer) on carbon black (CB) particles dispersed in mixtures of water with polar organic solvents (ethanol, formamide, or glycerol) has been investigated. The adsorption obeys the Langmuir isotherm at low surfactant concentrations (below the critical micelle concentration, CMC). At these conditions, the average surface area occupied by one siloxane surfactant follows the sequence water+glycerol mixture >plain water >water+ethanol mixture. At higher surfactant concentrations in the solution in contact with the particles, a sharp increase in the adsorbed amount is observed. The adsorbed layer thickness has been determined by dynamic light scattering. Below the CMC the adsorbed layer thickness is less than 10 nm. Above the CMC, the adsorbed layer thickness increases to 20-30 nm, a length scale comparable to the diameter of the siloxane surfactant micelles in aqueous solution. This fact, together with SANS data that we have obtained in the absence of added polar organic solvent, indicates that the structure of the adsorbed layer is similar to that of micelles. The findings presented here are relevant to waterborne coatings and ink formulations, where polymeric surfactants are used in conjunction with polar organic solvents.     

Effect of oxidative treatment on the electrochemical properties of aligned multi-walled carbon nanotubes

Vertically aligned multi-walled carbon nanotubes (MWNTs) were grown on the surface of electroconductive silicon substrate by catalytic chemical vapor deposition (CCVD) of a mixture of toluene and ferrocene vapors at 800°С. The anisotropic structure of the array that is due to the mutual orientation of MWNTs makes such materials attractive for use as supercapacitor electrodes. The effect of iron nanoparticles encapsulated in MWNTs as a result of synthesis on the electrochemical capacity of the sample in a 1 М H₂SO₄ solution was studied. Iron was removed during the thermal treatment of the MWNT array in a 20% H₂SO₄ solution under the normal or hydrothermal conditions. The contribution of redox processes involving iron was shown to be comparable to the contribution of the double-layer capacity of MWNTs. The hydrothermal treatment allows easy separation of the array from the silicon substrate without any loss of electric coupling of MWNTs.     

Effect of substituents on electron energy redistribution in uracil derivatives and their ionization in polar solvents

It is assumed that the chemical reactivity may be described in terms of the appropriate energy density calculated for each atom. Indices of energy density for deprotonization of uracil, 5-nitro- and 5-aminouracil are presented. The results of a quantum chemical calculation of the deprotonization energy are in qualitative agreement with experimental pK and ΔH values.     

To dope or not to dope: the effect of sonicating single-wall carbon nanotubes in common laboratory solvents on their electronic structure

Single-wall carbon nanotubes (SWCNTs) are commonly dispersed via sonication in a solvent prior to functionalization. We show that solvents such as dichloromethane, chloroform, 1,2-dichloroethane, and o-dichlorobenzene lead to an upward shift in the Raman response of the SWCNTs. We have used o-dichlorobenzene as a model molecule to explain this effect, and an upward shift of 9 cm(-1) is observed in the D* band. This blue shift is associated with p-type doping and is triggered only when the nanotubes are sonicated in the solvent. Sonication decomposes the chlorinated solvents, and new species (Cl2 and HCl(g)) are formed. The catalytic Fe nanoparticles inherently present in the nanotubes are etched by chlorine and hydrogen chloride to form iron chlorides during sonication in the solvent. The dopant was identified by X-ray photoelectron spectroscopy. With such knowledge of doping, the choice of solvent becomes crucial for any chemical reaction and can be intentionally tuned to produce SWCNTs films for electronics applications.     

Contribution enthalpic in the interaction of activated carbon with polar and apolar solvents

A method is presented for calculating the contribution that enthalpies make for every component of mixtures of activated carbon–water and activated carbon–hexane to the immersion enthalpy using the concepts that are used in the solution enthalpies. The immersion enthalpies of microporous activated carbon in water and in hexane have values from ?18.97 to ?27.21 and ?25.23 to ?47.89 J g^?1, respectively. From the immersion enthalpies and mass relation of the activated carbon in each of the solvents, the differential enthalpies are calculated for the activated carbon in water, Hw_DIFac, with values between ?15.95 and ?26.81 J g^?1, as are the differential enthalpies for the activated carbon in hexane, ΔHh_DIFac, with values between ?6.86 and ?46.97 J g^?1. For a low mass relation of the mixture components the contributions to the immersion enthalpy of the activated carbon and water differ by 3.20 J g^?1, while the difference between the contributions of the activated carbon and hexane is 19.41 J g^?1.     

Effect of carbon nanotubes and their dispersion on thermal curing of polyimide precursors

The process of thermal imidization reaction is significant for temperature and time control in the polyimide industry. Here, we report the effect of carbon nanotubes and their states of dispersion on the thermal imidization of the precursor films of polyimide (poly(amic acid)) for the first time. The curing process was followed by measuring Fourier transform-infrared (FT-IR) spectra, fluorescence spectra, thermogravimetric-differential scanning calorimeter (TG-DSC) properties and the refractive indices of films. It was found that by evenly dispersing 1 wt% of carbon nanotubes assisted by a dispersant in the poly(amic acid),the full imidization temperature of the polyimide can be reduced from 300 °C to 250 °C. Different states of distribution of CNTs were observed by light microscopy and scanning electron microscopy, and proved that a better dispersion of carbon nanotubes dramatically enhanced the speed of imidization. Moreover, the DSC results showed that lower decomposition temperature of poly(amic acid) could be obtained with more uniform distribution of carbon nanotubes, which means the process of cyclodehydration of the poly(amic acid) was accelerated.     

Influence of polar solvents upon the complex formation of 18-crown-6 with cations in chloroform

The complex formation of crown ethers with cations in nonpolar medium with small amounts of polar solvents added has been studied. The goal has been to get deeper insight into the influence of solvation (hydration) of the salts for the formation of complexes with the macrocyclic ligand 18-crown-6 (18C6). A linear dependence of the reaction enthalpy for complex formation between 18C6 and alkali metal cations in chloroform in the presence of water or methanol has been observed. The presence of acetonitrile or acetone has had no influence upon the measured reaction enthalpies. The influence of methanol on the complex formation between 18C6 and alkali metal cations in chloroform is weaker than in the case of water. This underpins the selective solvation of alkali cations in chloroform after the addition of small amounts of water or methanol. The experiments have been performed using calorimetric titrations.     

Influence of acid treatments of carbon nanotube precursors on Ni/CNT in the synthesis of carbon nanotubes

The Ni/CNT catalyst was fabricated by directly dipping carbon nanotube precursors refluxed in 4 M of nitric acid into Ni electroless plating bath, and used to synthesize new carbon nanotubes. The experimental results indicate that the duration of acid-treatment of carbon nanotubes precursors exerts a great influence on the catalysis of Ni/CNT in the synthesis of carbon nanotubes and hence the structures of the new carbon nanotubes. When the carbon nanotubes precursors were refluxed for 0.5 h in 4 M of nitric acid, bamboo-shaped carbon nanotubes (BSCNT) or Y junction carbon nanotubes in the carbon products were obtained. As the duration of acid-treatment of carbon nanotubes precursors increased to 6 h, the as-prepared Ni/CNT displayed higher activity, and the carbon nanotube products were high pure without any Y junction structure or any separation layers in hollow.     

Effect of polar solvents on the optical properties of water-dispersible thiol-capped cobalt nanoparticles

We were able to stabilize cobalt nanoparticles dispersible in water by optimizing the synthetic procedure using small polar thiol containing compounds as the capping agents. The nanoparticles were found to be spherical. The optical properties of the cobalt nanoparticles were investigated by monitoring the changes in the surface plasmon resonance (SPR) spectrum in various polar solvents. The extent of solvent dependence of the SPR spectrum was found to be dependent on the nature of the capping agent, the size of the cobalt nanoparticles, as well as the nature of the solvent. The Drude model was applicable for the particles capped with mercaptopropionic acid, while the effect of variations in the free electron density in the particles at different solvents became predominant in the nanoparticles capped with mercaptoethanol. The absorption spectra of the Co nanoparticles were simulated with the help of the classical Mie theory, and the results supported the effect of free electron density due to different capping agents on the spectra of the particles.     

Study of the nonenzymatic glucose sensor based on highly dispersed Pt nanoparticles supported on carbon nanotubes

An amperometric biosensor for sensitive and selective detection of glucose has been constructed by using highly dispersed Pt nanoparticles supported on carbon nanotubes (Pt-MWCNTs) as sensing interface. The Pt-MWCNTs were synthesized by using the two-step pyrolysis method. This composite shows good electrocatalytic activity towards the oxidation of glucose in alkaline and thus can be used to selectively detect glucose. We found that detection potential and Nafion amount covered on the Pt-MWCNTs modified glassy carbon electrode had considerable influence on the selectivity for amperometric detection of glucose. Under optimal detection conditions (detection potential of 0.0 V versus SCE and 10 μL 1.5% Nafion), selective detection of glucose in the glucose concentration range of 1.0-26.5 mM (correlation coefficient, >0.999) can be performed. The results demonstrate that the Pt-MWCNTs composite is promising for the fabrication of nonenzymatic glucose sensors.     

Effect of the multistage chemical treatment of carbon nanotubes on their purity and quality of walls

The effect of chemical methods that include the gas-phase and liquid-phase selective oxidation methods, of hydrochloric acid when used in different sequences, and of concentrated nitric acid on the purification efficiency of carbon nanotubes after their synthesis is studied. Changes in the quality of walls of this material at different stages of purification are studied physicochemically.     

Effect of polar aprotic solvents on the trimerization of phenyl isocyanate by organometallic catalysts

Studies of the trimerization of phenyl isocyanate by organometallic catalysts in the presence of various solvents have shown that dipolar aprotic solvents, such as DMSO and DMF, even in small amounts enhance greatly the rate of reaction. In accordance with their mode of action and of the effect of DMSO or DMF, the catalysts could be divided into three groups. Group I comprises tributyltin oxide, Ti(OBu)₄ and Zr(OBu)₄, which give a fast addition to the isocyanate. Maximum increase in rate was observed at DMSO:PhNCO = 1:1 due to the formation of a 1:1 charge transfer complex between them. Group 2 comprises naphthenates of Pb.Zr and Co which form complexes with the isocyanate, the reaction being much faster with the C.T. complex of DMSO and PhNCO: maximum increase in rate was observed at low DMSO concentrations, about the same as that of the catalyst. Group 3 comprises nucleophiles such as the amine catalysts, where the enhancement in rate was not great, due to the same mode of nucleophilic interaction of the catalyst and DMSO or DMF with the isocyanate.     

Effect of polar aprotic solvents on the trimerization of aliphatic isocyanates by organometallic catalysts

The polymerization of aliphatic isocyanates by organometallic catalysts such as tributyltin oxide, Ti(OBu)₄ or Zr(OBu)₄ was slow and no enhancement in rate was found on addition of DMF or DMSO, contrary to what was found with PhNCO. However, similar to the latter, fast reactions were observed with catalysts such as Pb- or Co-naphthenate in the presence of DMSO. The results were explained, on the basis of spectral evidence, as due to the weak interaction of DMSO or DMF with the aliphatic isocyanate and formation of a charge transfer complex between them in very low concentration.     

Enhancement of lipase activity in non-aqueous media upon immobilization on multi-walled carbon nanotubes

Background  

Immobilization of biologically active proteins on nanosized surfaces is a key process in bionanofabrication. Carbon nanotubes with their high surface areas, as well as useful electronic, thermal and mechanical properties, constitute important building blocks in the fabrication of novel functional materials.     

Effect of fluorination on the stability of carbon nanofibres in organic solvents

Beneficial effects of fluorination on the stability of carbon nanofibre (CNF) dispersion in organic solvents as a function of time are evidenced. Because of their excellent friction properties, fluorinated CNFs (CF_0.85) can be used as nanoparticles of tribo-active phase in lubrication; however, they have to be added into a matrix. We have shown that mixtures of CF_0.85 are more stable than CNF solutions. Investigations by ultraviolet–visible spectroscopy have been carried out 2 h after sonication and after an ageing of 4 months. Hansen solubility theory was used, and after ageing, tribological and Raman spectroscopy experiments showed no significant modification of physicochemical properties of the CF_0.85.     

Effect of the excitation wavelength on the ultrafast charge recombination dynamics of donor-acceptor complexes in polar solvents

The effect of the excitation wavelength on the charge recombination (CR) dynamics of several donor-acceptor complexes (DACs) composed of benzene derivatives as donors and of tetracyanoethylene or pyromellitic dianhydride as acceptors has been investigated in polar solvents using ultrafast time-resolved spectroscopy. Three different wavelength effects have been observed. (1) With complexes exhibiting two well-separated charge-transfer bands, the CR dynamics was found to be slower by a factor of about 1.5 upon excitation in the high-energy band. This effect was measured in both fast and slow relaxing solvents and was discussed in terms of different DAC geometries. (2) When the CR is faster than diffusive solvation, a slowing down of the CR with increasing excitation wavelength accompanied by an increase of the nonexponential character of the dynamics was measured. This effect appears only when exciting on the red edge of the charge-transfer absorption band. (3) When the driving force for CR is small, both nonequilibrium (hot) and thermally activated CR pathways can be operative. The results obtained with such a complex indicate that the relative contribution of these two paths depends on the excitation wavelength.     

Effect of local strain on the reactivity of carbon nanotubes

The heats of addition of H atom and Me^· radical to carbon atoms of a capped (10,10)-nanotube were calculated by the molecular dynamics (MD) method with Brenner"s potential. According to calculations, the reaction heats linearly depend on the pyramidalization angle, which is a quantitative measure of the local curvature and strain in the planar carbon sheet in the vicinity of the reaction center. Depending on the pyramidalization angle (0—20°), the change in the reaction energy can reach 1 eV. Comparison of the results obtained for a model reaction CH₃ ^· + H^· CH₄ using the ab initio approach and MD simulations with Brenner"s potential shows that this potential can be used in studies of the effect of pyramidalization of the carbon center on its reactivity.