Effect of carbon nanoparticles of different shapes on mechanical properties of aromatic polyimide-based composite films

Nanocomposite films based on thermally stable polypyromellitimide are prepared via the introduction of cylindrical and laminar carbon nanoparticles—nanofibers and nanocones/disks—into the prepolymer solution. An increase in the filler concentration increases the elastic modulus and yield stress of the material. Moreover, in composites filled with nanofibers, both characteristics increase much less intensely than those of films containing nanocones/disks. Rigidity increases in composites filled with nanofibers when their concentration is below ～7 vol %. A further increase in concentration is accompanied by the aggregation of nanofibers. The introduction of the nanoparticles of both types into the polymer matrix stabilizes the behavior of the material under prolonged mechanical loading: both the creep strain and the relaxation intensity decline with an increase in the filler concentration. The introduction of nanocones/disks into the polyimide matrix results in a more pronounced stabilization of creep characteristics of films than that in the case of nanofibers.     

Analytical pyrolysis as a characterization technique for monitoring the production of carbon nanofilaments

The main step in the production of carbon nanofilaments is the catalytic nucleation and lengthening of the filament. An undesired parallel step in the production of carbon nanofilaments is their thickening by pyrolitic carbon vapor deposition consisting in an ordered polycondensation of carbon over an existing catalytic carbon nanofilament. The regular characterization of the structure of carbon nanofilaments (coated or not) is by transmission electron microscopy. However, this technique is not affordable in many cases because is expensive and complex. In the present work, the analytical pyrolysis is proposed to obtain clues of the structure of carbon nanofilaments. Several commercial carbon nanofilaments have been analyzed. The samples with a thicker soot layer evolve a higher amount of heavy PAHs in the pyrolysis runs than the ones free of soot. It has been observed that pyrene is a key compound in the pyrolytic carbon vapor deposition process and the resulting formation of soot over the carbon nanofilaments. The aim of this work is to get useful information about the quality of the carbon filaments by a cheap technique, the analytical pyrolysis.     

Silica/Silicone Nanofilament Hybrid Coatings with Almost Perfect Superhydrophobicity

A facile method for the preparation of silica/silicone nanofilament hybrid coatings with almost perfect superhydrophobicity (contact angle=179.8° and sliding angle=1.3°) is presented. The coatings are obtained by dip‐coating of silica nanoparticles, followed by chemical vapor deposition of silicone nanofilaments. Predominant growth of silicone nanofilaments onto aggregated silica nanoparticles generates a two‐tier structure. The effect of silica nanoparticle size on the growth of silicone nanofilaments, along with their anti‐wetting properties and transparency are investigated in detail. Surface roughness and anti‐wetting properties can be simply regulated by controlling the size of silica nanoparticles.     

Effect of nanoparticles of various types as fillers on mechanical properties of block samples of a heat-resistant polyimide material: A comparative analysis

A comparative study of the effects of various nanoparticles introduced into polyetherimide Ultem-1000 (Sabic)—such as carbon nanofibers, nanocones/discs, halloysite hydrosilicate nanotubes, and quasispherical zirconia particles doped with yttria―on the mechanical behavior of nanocomposites is performed. The introduction of nanoparticles into the polymer increases the Young’s moduli and yield stress of block materials relative to those of the unfilled polymeric material. These effects make themselves more pronounced with an increase in temperature, especially when сarbon nanocones/discs are used as a filler. The collected data are commensurable with the electron-microscopic study of the morphology of the material and its densitometry measurements, which make it possible to estimate the values of excess free volume in the studied composite materials, as well as with the previous data on the incorporation of analogous nanoparticles into polypyromellitimide films.     

Evaluation of carbon nanocones/disks as sorbent material for solid-phase extraction

The potential of carbon nanocones/disks as sorbent material in solid-phase extraction (SPE) procedures has been evaluated. For this aim, a model analytical problem, the determination of chlorophenols in water samples, was selected. An accurately weighed amount of 20 mg of purified carbon nanocones/disks was packed in 3 mL commercial SPE cartridges. Once conditioned, up to 8 mL of water samples can be preconcentrated without analyte losses. The chlorophenols were eluted by using 200 μL of hexane. Aliquots of 2 μL of the organic extract were injected in the gas chromatograph–mass spectrometer for separation and quantification. The purification of the commercial nanocones/disks to reduce the presence of amorphous carbon has been successfully achieved by heating the carbon nanocones/disks at 450 °C for 20 min. Detection limits of chlorophenols were in the range 0.3–8 ng mL⁻¹ by using 2 mL of sample. Moreover, excellent average recovery values (98.8–100.9%) have been obtained after the analysis of water samples from different nature. Finally, the performance of the carbon nanocones/disks as sorbent material has been compared with that of multiwalled carbon nanotubes, providing the former better results under the experimental conditions assayed.     

Effect of zinc added to the Co/Al2O3 catalyst on the formation of carbon nanofilaments from methane and butadiene-1,3

The dynamics of carbon nanofilament growth from methane and butadiene-1,3 on Co-Zn/Al₂O₃ catalysts have been studied in the temperature range 500–750°C. The rate-limiting step in the growth of nanofilaments from butadiene is carbon atom diffusion through the bulk of the metal particle. In the case of methane, the process is controlled by one of the stages of hydrocarbon decomposition on the metal particle. The structure and morphology of the nanofilaments (composites) forming by the carbide cycle mechanism on fine zinc-promoted cobalt particles have been studied by electron microscopy and X-ray diffraction. The morphology and crystallographic properties of the nanofilaments depend on the ratio of the hydrocarbon decomposition rate (which is determined by the nature of the hydrocarbon) to the rate at which carbon atoms diffuse from their formation sites to the nanofilament formation sites (which is determined by the nature of the metal particle and by the carbon diffusion coefficient in the particle bulk). The properties of the resulting carbon nanofilaments can be controlled by varying the nature of the hydrocarbon to be decomposed and the reaction temperature and by introducing another metal into the cobalt particles.     

Effect of nanosized carbon fillers on the hydrolytic stability of films of a heat-resistant aromatic polyimide

The effect of carbon nanoparticles (nanofibers, nanocones/nanodiscs) introduced into a polypyromellitimide matrix on the stability of the mechanical and thermal characteristics of the resulting nanocomposite film materials in the course of hydrolysis in aqueous alkali was studied. The nanocomposite films are less resistant to hydrolysis than the unfilled films of the matrix polyimide. The decreased packing density in the nanocomposite material is considered to be the major factor responsible for the observed effects. A certain excess void volume in the nanocomposite appears owing to insufficient compatibility of the matrix polyimide with the nanoparticles, manifested in the course of the material preparation.     

Evaluation of single-walled carbon nanohorns as sorbent in dispersive micro solid-phase extraction

A new dispersive micro solid-phase extraction method which uses single-walled carbon nanohorns (SWNHs) as sorbent is proposed. The procedure combines the excellent sorbent properties of the nanoparticles with the efficiency of the dispersion of the material in the sample matrix. Under these conditions, the interaction with the analytes is maximized. The determination of polycyclic aromatic hydrocarbons was selected as model analytical problem. Two dispersion strategies were evaluated, being the functionalization via microwave irradiation better than the use of a surfactant. The extraction was accomplished by adding 1 mL of oxidized SWHNs (o-SWNHs) dispersion to 10 mL of water sample. After extraction, the mixture was passed through a disposable Nylon filter were the nanoparticles enriched with the PAHs were retained. The elution was carried out with 100 μL of hexane. The limits of detection achieved were between 30 and 60 ng L⁻¹ with a precision (as repeatability) better than 12.5%. The recoveries obtained for the analytes in three different water samples were acceptable in all instances. The performance of o-SWNHs was favourably compared with that provided by carboxylated single-walled carbon nanotubes and thermally treated carbon nanocones.     

Formation of carbon nanofilaments from C6-C16 alkanes over nickel-containing catalysts

The properties of 85%Ni/Al₂O₃ and NiO/Sibunit series catalysts have been studied in the formation of carbon nanofilaments from n-hexane, n-undecane, and n-hexadecane. In the temperature range 450–600°C, the reactivity of these hydrocarbons decreases in the following order: n-hexane > n-undecane > n-hexadecane. The deposition rate of carbon nanofilaments from n-hexane or n-undecane over the 85%Ni/Al₂O₃ catalyst in the range 450–600°C slightly depends on the reaction temperature. The activation energy of the formation of carbon nanofilaments from n-hexane is 10 kcal/mol and that from n-undecane, 13.5 kcal/mol. The rate-limiting reaction is the interaction of a paraffin molecule with the nickel metal surface. As the reaction temperature increases to 700°C, the formation rates of carbon nanofilaments from the C₆-C₁₆ paraffin hydrocarbons are equalized, which is associated with the increase in the intensity of thermal pyrolysis reactions of alkanes. The resulting olefins, first of all, ethylene and propylene, become major contributors to carbon formation.     

Equilibrium locations for nested carbon nanocones

Potentially, carbon nanostructures are very important as ideal components to create many novel nano-devices. Such devices including nano-oscillators, ultra-fast optical filters and nano-bearings, are based on the unique mechanical and electronic properties of carbon nano-structures. Common carbon nanostructures used are usually C₆₀-fullerenes, carbon nanotubes, carbon nano-bundles and carbon nanotori. In the synthesis and production of carbon nanostructures, carbon nanocones tend to occur less frequently, and it is known that five different size cones may occur, depending on the number of pentagons in the atomic network. However, the simple geometric structure of carbon nanocones certainly facilitates calculations for their potential energy. Here, the Lennard–Jones potential energy function and the usual continuum approximation are employed to determine the energy for two such nested carbon nanocones which are located co-axially. We show graphically the energy profiles for any two carbon nanocones arising from the five possible structures. For both two distinct cones and two identical cones, we find that the equilibrium location moves further away from the vertex as the number of pentagons is increased. However, we observe that the equilibrium position occurs such that one cone is always inside the other, and therefore, we might expect that nested double-cones are formed according to these results.      

Hydrolytic Stability of Films of Aromatic Polyimides and Composites on Their Basis,Filled with Carbon Nanocones

Variation of the mechanical and thermal characteristics of poly(4,4′-oxydiphenylenepyromellitimide) and poly{1,3-bis(3′,4-dicarboxyphenoxy)benzene [4,4′-bis)4′-N-phenoxydiphenylsulfone]imide} films and nanocomposites based on these polyimides and filled by carbon nanocones/disks in the course of hydrolysis in an alkaline solutions was studied. The goal of the study was to obtain systematic information about the influence exerted by carbon nanoparticles introduced into polyimide films with varied chemical structure on the stability of the resulting film materials against a prolonged action of active hydrolyzing media. It was shown that the hydrolytic stability of the materials under study is largely determined by the molecular packing density. Introduction of nanoparticles into the polymers under study may result in that the concentration in the material of the excess free volume localized at polymer–filler interfaces increases. This, in turn, causes a decrease in the hydrolytic stability of the nanocomposite film as compared with unfilled films of the matrix polyimide. The opportunity was considered of raising the hydrolytic stability of the polyimide and nanocomposite material by making higher the average packing density.     

Growth of unusual carbon nanofilaments in methane pyrolysis

Two types of carbon nanofilaments (nanotubes) differing markedly in morphology and growth rate grow on substrate plates containing a supported catalyst in a methane atmosphere at ～1050°C. According to provisional estimates, nanofilaments of one of these types grow at a rate of 5–10 μm/s, which is 50–100 times as high as the growth rate observed for ordinary catalytic filaments (tubes). These filaments are as long as several millimeters, being 50 to 100 nm in diameter. A preliminary examination of their structure has demonstrated that there is no catalyst particle at the filament end and that the filament is likely a carbon-rich polymer. A possible mechanism of the growth of these carbon filaments is discussed.     

Metallopyrrole-capped carbon nanocones

We design nickel-doped and nitrogen-doped carbon nanocones with various amounts of buckling that feature square-planar, (approximate) tetrahedral, and octahedral coordination. The optimized geometries and electronic structures of these novel metallocarbon complexes are calculated by using the B3LYP (Gaussian03) and GGA-BLYP (ADF) exchange-correlation functionals. We analyze buckling and stability of the nanocones, and discuss their potential for additional functionalization at the metallic site.     

Formation of BaSO4 fibres with morphological complexity in aqueous polymer solutions

BaSO4 fibres with morphological complexity were formed in aqueous solution with polyacrylate and partially monophosphonated poly(ethyleneoxide)-block-poly(methacrylic acid) additives by a simple precipitation reaction. For polyacrylate, formation of the fibrous deposits was strongly dependent on the level of supersaturation (S) and Ba2+:polymer molar ratio (R). At S = 60 to 80, and R = 3 to 14, highly anisotropic crystalline fibres consisting of bundles of BaSO4 nanofilaments were formed after several weeks, although the yield was low. The nanofilaments were also organized into cone-shaped aggregates at S = 80, and at lower R values these formed higher-order structures that consisted of multiple cone-on-cone assemblies with remarkable self-similarity. Increasing the supersaturation produced ovoid or cross-shaped dendritic particles for the range of molar ratios studied. In contrast, BaSO4 crystallisation in the presence of a partially phosphonated block copolymer gave a high yield of BaSO4 fibres up to 100 microm in length, and consisting of co-aligned bundles of 30 nm-diameter defect-free single-crystal nanofilaments with a uniform growth tip. A model for the defect-free growth of BaSO4 nanofilaments in aqueous polymer solutions based on amorphous precursor particles, vectorially directing forces and van der Waals attraction is proposed.     

Combination of π-π stacking and electrostatic repulsion between carboxylic carbon nanoparticles and fluorescent oligonucleotides for rapid and sensitive detection of thrombin

On the basis of simultaneous electrostatic repulsion and π-π stacking interactions of carboxylic carbon nanoparticles (cCNPs) with single-stranded DNA, a noncovalent assembly of cCNPs and fluorescent aptamers is reported for rapid, sensitive, and selective detection of thrombin.     

Cone-type multi-shell in the hollow core of multi-wall carbon nanotube

Cone-stacked nanotubes with thick layers of deposited carbon obtained by a catalytic chemical vapor deposition method are annealed at high temperature. Phase separation between cone-stacked nanotubes and amorphous carbon layers occurs during annealing due to different structural transformation behaviors, resulting in the formation of multi-wall carbon nanotubes containing a cone-type multi-shell arrangement. The apex angles of the nanocones are about 40°. This type of carbon nanotube shows different physical and electrical properties.     

High-density assembly of gold nanoparticles on multiwalled carbon nanotubes using 1-pyrenemethylamine as interlinker

In this article, we describe the formation of carbon nanotube (CNT)-gold nanoparticle composites in aqueous solution using 1-pyrenemethylamine (Py-CH2NH2) as the interlinker. The alkylamine substituent of 1-pyrenemethylamine binds to a gold nanoparticle, while the pyrene chromophore is noncovalently attached to the sidewall of a carbon nanotube via pi-pi stacking interaction. Using this strategy, gold nanoparticles with diameters of 2-4 nm can be densely assembled on the sidewalls of multiwalled carbon nanotubes. The formation of functionalized gold nanoparticles and CNT-Au nanoparticle composites was followed by UV-vis absorption and luminescence spectroscopy. After functionalization of gold nanoparticles with 1-pyrenemethylamine, the distinct absorption vibronic structure of the pyrene chromophore was greatly perturbed and its absorbance value was decreased. There was also a corresponding red shift of the surface plasmon resonance (SPR) absorption band of the gold nanoparticles after surface modification from 508 to 556 nm due to interparticle plasmon coupling. Further reduction of the pyrene chromophore absorbance was observed upon formation of the CNT-Au nanoparticle composites. The photoluminescence of 1-pyrenemethylamine was largely quenched after attaching to gold nanoparticles; formation of the CNT-Au nanoparticle composites further lowered its emission intensity. The pyrene fluoroprobe also sensed a relatively nonpolar environment after its attachment to the nanotube surface. The present approach to forming high-density deposition of gold nanoparticles on the surface of multiwalled carbon nanotubes can be extended to other molecules with similar structures such as N-(1-naphthyl)ethylenediamine and phenethylamine, demonstrating the generality of this strategy for making CNT-Au nanostructure composites.     

Using ordered carbon nanomaterials for shedding light on the mechanism of the cathodic oxygen reduction reaction

Insufficient understanding of the mechanism of the cathodic oxygen reduction reaction puts constraints on the improvement of the efficiency of polymer electrolyte fuel cells (PEMFCs). We apply ordered catalytic layers based on vertically aligned carbon nanofilaments and combine experimental rotating ring-disk studies with mathematical modeling for shedding light on the mechanism of the oxygen reduction reaction on Pt nanoparticles. Based on the experimental and simulation evidence we propose a dual path ORR mechanism which comprises a "direct 4e(-)" and a "series 2e(-) + 2e(-)" pathway and explains switching between the two. For the first time we show that below 0.8 V the "direct" path may be discarded and the ORR predominantly occurs via H(2)O(2) mediated pathway, while in the potential interval between ca. 0.8 V and the onset of the ORR the "direct" path is dominating.     

Dendritic Domains with Hexagonal Symmetry Formed by X‐Shaped Bolapolyphiles in Lipid Membranes

A novel class of bolapolyphile (BP) molecules are shown to integrate into phospholipid bilayers and self‐assemble into unique sixfold symmetric domains of snowflake‐like dendritic shapes. The BPs comprise three philicities: a lipophilic, rigid, π–π stacking core; two flexible lipophilic side chains; and two hydrophilic, hydrogen‐bonding head groups. Confocal microscopy, differential scanning calorimetry, XRD, and solid‐state NMR spectroscopy confirm BP‐rich domains with transmembrane‐oriented BPs and three to four lipid molecules per BP. Both species remain well organized even above the main 1,2‐dipalmitoyl‐sn‐glycero‐3‐phosphocholine transition. The BP molecules only dissolve in the fluid membrane above 70 °C. Structural variations of the BP demonstrate that head‐group hydrogen bonding is a prerequisite for domain formation. Independent of the head group, the BPs reduce membrane corrugation. In conclusion, the BPs form nanofilaments by π stacking of aromatic cores, which reduce membrane corrugation and possibly fuse into a hexagonal network in the dendritic domains.     

Control of the Induced Handedness of Helical Nanofilaments Employing Cholesteric Liquid Crystal Fields

In this paper, a simple and powerful method to control the induced handedness of helical nanofilaments (HNFs) is presented. The nanofilaments are formed by achiral bent-core liquid crystal molecules employing a cholesteric liquid crystal field obtained by doping a rod-like nematogen with a chiral dopant. Homochiral helical nanofilaments are formed in the nanophase-separated helical nanofilament/cholesteric phase from a mixture with a cholesteric phase. This cholesteric phase forms at a temperature higher than the temperature at which the helical nanofilament in a bent-core molecule appears. Under such conditions, the cholesteric liquid crystal field acts as a driving force in the nucleation of HNFs, realizing a perfectly homochiral domain consisting of identical helical nanofilament handedness.