Study of optical properties and molecular structure of plasma polymerized diethylene glycol dimethyl ether

This paper deals with plasma polymerization processes of diethylene glycol dimethyl ether. Plasmas were produced at 150 mtorr in the range of 10 W to 40 W of RF power. Films were grown on silicon and quartz substrates. Molecular structure of plasma polymerized films and their optical properties were analyzed by Fourier transform infrared spectroscopy (FTIR) and ultraviolet-visible spectroscopy. The IR spectra show C–H stretching at 3000–2900 cm^-1, C=O stretching at 1730–1650 cm^-1, C–H bending at 1440–1380 cm^-1, C–O and C–O–C stretching at 1200–1000 cm^-1. The concentrations of C–H, C–O and C–O–C were investigated for different values of RF power. It can be seen that the C–H concentration increases from 0.55 to 1.0 au (arbitrary unit) with the increase of RF power from 10 to 40 W. The concentration of C–O and C–O–C decreases from 1.0 to 0.5 au in the same range of RF power. The refraction index increased from 1.47 to 1.61 with the increase of RF power. The optical gap calculated from absorption coefficient decreased from 5.15 to 3.35 eV with the increase of power. Due to its optical and hydrophilic characteristics these films can be applied, for instance, as glass lens coatings for ophthalmic applications.     

Fabrication of completely filled carbon nanotubes with copper nanowires in a confined space

Carbon nanotubes (CNTs) filled completely with polycrystalline Cu nanowires were synthesized by laser vaporization of Cu and graphite under high-pressure Ar gas atmosphere. Depending on the Ar gas pressure (0.1–0.9 MPa) and the Cu content (1–40 at.%) in graphite targets for laser vaporization, various products with different morphologies were observed by scanning and transmission electron microscopy. The ratios of the Cu-filled CNTs and carbon nanocapsules particularly increased as Ar gas pressure was increased. The maximum ∼60% fraction of Cu-filled CNTs with outer diameter of 10–50 nm and length of 0.3–3 μm was achieved at 0.9 MPa from graphite containing 20 at.% Cu. Most of the encapsulated Cu-nanowires were surrounded by single, double, or triple graphitic layers. Although the yield of the Cu-filled CNTs was also dependent on the Cu content in the graphite targets, no unfilled CNTs were produced even for low Cu content. The growth of Cu-filled CNTs is explained by the formation of molten Cu–C composite particles with an unusually C-rich composition in a space confined by high-pressure Ar gas, followed by precipitating Cu and C from the particles and subjecting them to phase separation.     

EPR Equilibration Measurement of the C–H Bond Enthalpy in the Methylene Groups of 1,3,5-Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (Irganox)

On the basis of previous and current studies, it has been possible to evaluate and compare the bond dissociation energies of the phenol (O–H) bond and of the methylene and methyl (C–H) bonds in Irganox (trade name) by means of electron paramagnetic resonance records of galvinoxyl–irganoxyl hydrogen transfer reaction equilibria. The bond dissociation enthalpy of the C–H methylene and methyl bonds in Irganox was found to be 339.0 ± 3.0 kJ/mol, very close to the previously found value of 340.7 ± 3.0 kJ/mol for the O–H bond of some benzyl–phenolic antioxidant.     

Production and characterization of carbon nano colloid via one-step electrochemical method

We present a one-step electrochemical method to produce water-based stable carbon nano colloid (CNC) without adding any surfactants at the room temperature. The physical, chemical, and thermal properties of CNC prepared were characterized by using various techniques, such as particle size analyzer, zeta potential meter, TEM, XRD, FT-IR, turbidity meter, viscometer, and transient hot-wire method. The average primary size of the suspended spherical-shaped nanoparticles in the CNC was found to be ∼15 nm in diameter. The thermal conductivity of CNC compared with that of water was observed to increase up to ∼14% with the CNC concentration of ∼4.2 wt%. The CNC prepared in this study was considerably stable over the period of 600 h. With the assistance of FT-IR spectroscopy analysis, we confirmed the presence of carboxyl group (i.e., O–H stretching (3,458 cm⁻¹) and C=O stretching (1,712 cm⁻¹)) formed in the outer atomic layer of carbon nanoparticles, which (i) made the carbon particles hydrophilic and (ii) prevented the aggregation among primary nanoparticles by increasing the magnitude of zeta potential over the long period.     

Fabrication of two types of one-dimensional Si–C nanostructures by laser ablation

Two types of one-dimensional (1D) nanostructures—amorphous silicon carbide (SiC) nanowires, 5–30 nm thick and 0.5–2 μm long, and carbon nanotubes (CNTs) filled completely with crystalline SiC nanowires, 10–60 nm thick and 2–20 μm long—were synthesized by the laser ablation of carbon-silicon targets in the presence of high-pressure Ar gas up to 0.9 MPa. All the CNTs checked by transmission electron microscopy contained SiC, and no unfilled CNTs were produced. We discuss the growth of the two nanostructures based on the formation of molten Si–C composite particles and their instabilities leading to the precipitation of Si and C.     

Electrodeposition of polyaniline–carbon nanotubes composite films and investigation on their role in corrosion protection of austenitic stainless steel by SNIFTIR analysis

Composite films of polyaniline (PANI) and carbon nanotubes (CNTs) were prepared by electrochemical co-deposition from solutions of the corresponding monomer containing two different kinds of CNTs. The first type was commercial (diameter = 110–170 nm, length = 5–9 μm) and the second one was home-made (diameter = 30 nm, length = 5–20 μm). The electrochemical behaviour of PANI–CNTs composite films was investigated with Cyclic Voltammetry and the surface morphology was analysed by Scanning Electron Microscopy (SEM). Subtractively Normalised Interfacial FT-IR procedure was used to investigate the presence of corrosion products when the films were deposited on stainless steel substrates and exposed to acid environment. The spectral investigations were utilised to understand the role of composite films in the corrosion protection and to discriminate the best performance CNTs.     

Infrared spectra of brassinolide and castasterone steroid phytohormones and their 24-epi derivatives

Absorption bands in IR spectra of brassinolide, castasterone, and their 24-epi derivatives in the frequency range 3800–1000 cm^–1 have been interpreted. A number of spectral features distinguishing brassinolide from castasterone have been found. The conducted analysis shows that the structural differences manifest themselves in IR spectra of the investigated brassinosteroids in the region of stretching vibrations of CO–H, C=O, C–OH, C–O–C, CH₃, CH₂, and CH groups. The main distinctions in IR spectra of brassinolides and castasterones are due to the B ring structure.     

Investigation of the interaction of evaporated aluminum with vapor deposited Teflon AF films via X-ray photoelectron spectroscopy

The interfacial bonding and mixing between evaporated aluminum and a vapor deposited Teflon AF (abbreviated to AF) film have been investigated with X-ray photoelectron spectroscopy. Graphite carbon (C–C), and aluminum carbide (Al–C), oxide (Al–O–C) and fluoride (Al–F) are formed when aluminum atoms are deposited on to the AF film. With increasing deposition of aluminum, the concentrations of these newly formed components increase gradually. Moreover, in situ annealing results in remarkable increases in the C–C, Al–C, Al–O–C and Al–F configurations and a decrease in metallic aluminum. No significant diffusion of aluminum into the AF film was observed during the annealing. The Al compounds form a layer at the Al/AF interface that acts as an adhesion promoter and diffusion barrier. Received: 21 October 2002 / Accepted: 22 October 2002 / Published online: 15 January 2003 RID="*" ID="*"Corresponding author. Fax: +49-431/880-6229, E-mail: sjding@yahoo.com     

XPS study of the chemical bonding in hydrogenated amorphous germanium–carbon alloys

A systematic study of the chemical bonding in hydrogenated amorphous germanium–carbon (a-Ge_1-xC_x:H)alloys using X-ray photoelectron spectroscopy (XPS) is presented. The films, with carbon content ranging from 0 at. % to 100 at. %, were prepared by the rf co-sputtering technique. Raman spectroscopy was used to investigate the carbon hybridization. Rutherford backscattering spectroscopy (RBS) and XPS were used to determine the film stoichiometry. The Ge 3d and C 1s core levels were used for investigating the bonding properties of germanium and carbon atoms, respectively. The relative concentrations of C–Ge, C–C, and C–H bonds were calculated using the intensities of the chemically shifted C 1s components. It was observed that the carbon atoms enter the germanium network with different hybridization, which depends on the carbon concentration. For concentrations lower than 20 at. %, the carbon atoms are preferentially sp³ hybridized, and approximately randomly distributed. As the carbon content increases the concentration of sp² sites also increases and the films are more graphitic-like. Received: 4 May 1999 / Accepted: 24 November 1999 / Published online: 24 March 2000     

Nano-structuring of PTFE surface by plasma treatment,etching, and sputtering with gold

Properties of pristine, plasma modified, and etched (by water and methanol) polytetrafluoroethylene (PTFE) were studied. Gold nanolayers sputtered on this modified PTFE have been also investigated. Contact angle, measured by goniometry, was studied as a function of plasma exposure and post-exposure aging times. Degradation of polymer chains was examined by etching of plasma modified PTFE in water or methanol. The amount of ablated and etched layer was measured by gravimetry. In the next step the pristine, plasma modified, and etched PTFE was sputtered with gold. Changes in surface morphology were observed using atomic force microscopy. Chemical structure of modified polymers was characterized by X-ray photoelectron spectroscopy (XPS). Surface chemistry of the samples was investigated by electrokinetic analysis. Sheet resistance of the gold layers was measured by two-point technique. The contact angle of the plasma modified PTFE decreases with increasing exposure time. The PTFE amount, ablated by the plasma treatment, increases with the plasma exposure time. XPS measurements proved that during the plasma treatment the PTFE macromolecular chains are degraded and oxidized and new –C–O–C–, –C=O, and –O–C=O groups are created in modified surface layer. Surface of the plasma modified PTFE is weakly soluble in methanol and intensively soluble in water. Zeta potential and XPS shown dramatic changes in PTFE surface chemistry after the plasma exposure, water etching, and gold deposition. When continuous gold layer is formed a rapid decrease of the sheet resistance of the gold layer is observed.     

Carbon nanotube grease with enhanced thermal and electrical conductivities

A stable and homogeneous grease based on carbon nanotubes (CNTs, single-wall and multi-wall) in polyalphaolefin oil has been produced without using a chemical surfactant. For example, for a 11 wt% (7 vol%) single-wall CNT (diameter 1–2 nm, length 0.5–40 μm) loading, the thermal conductivity (TC) of the grease shows a 60–70% increase compared to that for no nanotube loading. In addition, the grease is electrically conductive, has a high dropping point, good temperature resistance, and does not react with copper at temperatures up to 177 °C. The performance of carbon nanotube grease could be much better with the improvement of nanotube quality and purity. A possible explanation for these results is that of a high loading of CNTs (>10 wt%), they become associated with each other by van der Waals forces in the grease to form three-dimensional percolation networks. Time-dependent magnetic results demonstrate that, even under the influence of a strong outside magnetic field, the TC value remains constant. This phenomenon can be attributed to the existence of networks that makes magnetic alignment of nanotubes impossible.     

A first principles study of the adsorption and dissociation of CO<Subscript>2</Subscript> on the δ-Pu (111) surface

A complete understanding of the nature of the 5f electrons has been and continues to be a major scientific problem in condensed matter physics. Bulk and surface electronic structure studies of the actinides as also atomic and molecular adsorptions on the actinide surfaces provide a path towards this understanding. In this work, ab initio calculations within the framework of density functional theory have been used to study the adsorption of molecular CO₂ and the corresponding partially dissociated (CO + O) and completely dissociated (C + O + O) products on the δ-Pu (111) surface. The completely dissociated C + O + O configurations exhibit the strongest binding with the surface (7.92 eV), followed by partially dissociated products CO + O (5.08 eV), with molecular CO₂ adsorption having the lowest binding energies (2.35 eV). For all initial vertically upright orientations, the CO₂ molecule physisorbs or do not bind to the surface and the geometry and orientation do not change. For all initial flat lying orientations chemisorption occurs, with the final state corresponding to a bent CO₂ molecule with bond angles of 117°–130° and the elongation of the CO bond. For CO + O co-adsorption, the stable configurations corresponded to CO dipole moment orientations of 100°–172° with respect to the surface normal and the elongation of the CO bond. The most stable chemisorption cases correspond to anomalously large rumpling of the top Pu layer. The interactions of the CO₂ and CO with the Pu surface have been analyzed using the energy density of states and difference charge density distributions. The nature and the behavior of the 5f electrons have also been discussed in detail in the context of this study.     

Optical and IR study of Li2O–CuO–P2O5 glasses

Infrared (IR) and UV spectra of ternary Li₂O–CuO–P₂O₅ glasses in two series Li₂O(65−X)%–CuO(X%)–P₂O₅(35%), X = 20, 30, 40 and Li₂O(55−X)%–CuO(X%)–P₂O₅(45%), X = (10, 20, 30) were studied. Infrared (IR) investigations showed the metaphosphate and pyrophosphate structures and with increase of CuO content in metaphosphate glass, the skeleton of metaphosphate chains is gradually broken into short phosphate groups such as pyrophosphate. IR spectra showed one band at about 1,220 and 1,260 cm⁻¹ for P₂O₅(35%) and P₂O₅(45%) series, respectively, assigned to P=O bonds. For CuO additions ≤20 mol%, the glasses exhibit two bands in the frequency range 780–720 cm⁻¹ which are attributed to the presence of two P–O–P bridges in metaphosphate chain. But for CuO addition ≥30 mol%, the glasses exhibit only a single band at 760 cm⁻¹ which is assigned to the P–O–P linkage in pyrophosphate group. In optical investigations, absorption coefficient versus photon energy showed three regions: low energy side, Urbach absorption, and high energy side. In Urbach’s region, absorption coefficient depends exponentially on the photon energy. At high energy region, optical gap was calculated and investigations showed indirect transition in compounds and decreases in optical gap with increases of copper oxides contents that is because of electronic transitions and increasing of nonbridging oxygen content.     

Characterization of low pressure chemical vapor deposited polymeric fluorinated carbon m (C:FX)n thin films with low dielectric constant

Thermal chemical vapor deposition of fluorinated carbon thin films in the polymeric form is described by hot filament decomposition of the gaseous C₃F₆O precursor. Decomposition at filament temperatures, ≤450 °C produces films in the ordered (CF₂)_2n polymeric chain structure as in a tetrafluoroethylene polymer. A composite of (CF₂)_2n chains structure and crosslinked m(C:F_x)_n phases are formed in films deposited at filament temperature ≥600 °C. Polymerization of :CF₂ radicals results in (CF₂)_2n chain structure and the crosslinked phase emerges from a separate process involving reaction among the CF₃, CFO and CF₃CO radicals and including CF₂. Substrate temperature affects both the C-to-F bonding configuration and the relative ratio of the composite phases. Dominant C–CF bonding structure in the low (<-5 °C) substrate temperature films is thermally less stable compared to the C–F structure, which dominates the crosslinked structure in films deposited at high (∼70 °C) substrate temperatures. Dielectric properties of the composite films are studied using the electrical equivalent model and a correlation with the C-to-F bond structure is established. High polymeric (CF₂)_2n phase determines the electrical impedance and the dielectric constant of the film, and the crosslinked phase imparts structural stability. PACS 81.15.Gh; 73.61.Ph; 77.84.Jd; 79.60.Fr     

The effects of ceramic fillers on the PMMA-based polymer electrolyte systems

The effects of ceramics fillers on the polymethylmethacrylate (PMMA)-based solid polymer electrolytes have been studied using ac impedance spectroscopy and infrared spectroscopy. The polymer film samples were prepared using solution cast technique, tetrahydrofuran (THF) used as a solvent, and ethylene carbonate (EC) has been used as plasticizer. Lithium triflate salt (LiCF₃SO₃) has been incorporated into the polymer electrolyte systems. Two types of ceramic fillers, i.e., SiO₂ and Al₂O₃, were then implemented into the polymer electrolyte systems. The solutions were stirred for several hours before it is poured into petri dishes for drying under ambient air. After the film has formed, it was transferred into desiccator for further drying before the test. From the observation done by impedance spectroscopy, the room temperature conductivity for the highest conducting film from the (PMMA–EC–LiCF₃SO₃) system is 1.36 × 10⁻⁵ S cm⁻¹. On addition of the SiO₂ filler and Al₂O₃ filler, the conductivity are expected to increase in the order of ∼10⁻⁴ S cm⁻¹. Infrared spectroscopy indicates complexation between the polymer and the plasticizer, the polymer and the salts, the plasticizer and the salts, and the polymer and the fillers. The interactions have been observed in the C=O band, C–O–C band, and the O–CH₃ band. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7-9, 2006.     

Exposure to nanoscale particles and fibers during machining of hybrid advanced composites containing carbon nanotubes

This study investigated airborne exposures to nanoscale particles and fibers generated during dry and wet abrasive machining of two three-phase advanced composite systems containing carbon nanotubes (CNTs), micron-diameter continuous fibers (carbon or alumina), and thermoset polymer matrices. Exposures were evaluated with a suite of complementary instruments, including real-time particle number concentration and size distribution (0.005–20 μm), electron microscopy, and integrated sampling for fibers and respirable particulate at the source and breathing zone of the operator. Wet cutting, the usual procedure for such composites, did not produce exposures significantly different than background whereas dry cutting, without any emissions controls, provided a worst-case exposure and this article focuses here. Overall particle release levels, peaks in the size distribution of the particles, and surface area of released particles (including size distribution) were not significantly different for composites with and without CNTs. The majority of released particle surface area originated from the respirable (1–10 μm) fraction, whereas the nano fraction contributed ~10% of the surface area. CNTs, either individual or in bundles, were not observed in extensive electron microscopy of collected samples. The mean number concentration of peaks for dry cutting was composite dependent and varied over an order of magnitude with highest values for thicker laminates at the source being >1 × 10⁶ particles cm⁻³. Concentration of respirable fibers for dry cutting at the source ranged from 2 to 4 fibers cm⁻³ depending on the composite type. Further investigation is required and underway to determine the effects of various exposure determinants, such as specimen and tool geometry, on particle release and effectiveness of controls.

Formation of hydrogenated amorphous carbon films from polymer pyrolysis

Free-standing and supported hydrogenated amorphous carbon films (a:C–H) were prepared upon pyrolysis of the polymer formed by ethanolamine (EA) and citric acid (CA), under an ambient atmosphere at 300 °C. EA facilitates the formation of the macroscopic films, while CA is essential for obtaining the a:C–H microstructure, which comprises a mixture of sp² and sp³ carbon. Received: 29 May 2001 / Accepted: 17 August 2001 / Published online: 20 December 2001     

Atmospheric pressure chemical vapour synthesis of silicon–carbon nanoceramics from hexamethyldisilane in high temperature aerosol reactor

Silicon–carbon nanoceramics have been synthesised from hexamethyldisilane (HMDS) by the atmospheric pressure chemical vapour synthesis (APCVS). Direct aerosol phase synthesis enables continuous production of high purity materials in one-stage process. The particle formation is based on the decomposition of the precursor in a high temperature reactor. Reaction of the gas phase species leads to homogeneous nucleation and formation of the nanoparticles with a narrow size distribution (geometric mean diameter range of particle number size distribution 160–200 nm with 1.5–1.6 geometric standard deviation at reaction temperatures 800–1200 °C). A systematic investigation of the influence of the process temperature on the powder characteristics, including the particle size, crystallinity, chemical structure, surface and bulk composition and surface morphology, was carried out. At the reactor temperature of 800 °C, the synthesised nanoparticles were amorphous preceramics containing mostly SiC₄, Si–CH₂–Si and Si–H units. The composition of the powder turned towards nanocrystalline 3C–SiC (crystal size under 2 nm) when the reaction temperature was increased to 1200 °C. The reaction temperature appeared to be a key parameter controlling the structure and properties of the synthesised powders.     

Surface vibrations and the nature of the adsorption state: C2H2 on Pt(111)

Molecular vibrations of C₂H₂ and C₂D₂ adsorbed on Pt(111) at 140 K and ∼300K have been measured by high resolution electron energy loss spectroscopy. The comparison of C₂H₂ and C₂D₂ spectra allows an unambiguous assignment of the observed losses to the excitation of C−H bending, C−H stretching, and C−C stretching modes of nondissociatively adsorbed acetylene. From the relative intensities of losses the hybridisation state is determined to be nearsp ². The C−C stretching frequency indicates a C−C bond order of ∼1.8.     

Microwave dielectric properties of the 5.5Li<Subscript>2</Subscript>O–Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>–7TiO<Subscript>2</Subscript> ceramics

A new Li₂O–Nb₂O₅–TiO₂ (LNT) ceramic with the Li₂O:Nb₂O₅:TiO₂ mole ratio of 5.5:1:7 was prepared by solid state reaction route. The phase and structure of the ceramic were characterized by X-ray diffraction and scanning electron microscopy (SEM). The microwave dielectric properties of the ceramics were studied using a network analyzer. The microwave dielectric ceramic has low sintering temperature (∼1075°C) and good microwave dielectric properties of ε _r=42, Q×f=16900 GHz (5.75 GHz), and τ _f =63.7 ppm/°C. The addition of B₂O₃ can effectively lower the sintering temperature from 1075 to 875°C and does not induce degradation of the microwave dielectric properties. Obviously, the LNT ceramics can be applied to microwave low temperature-cofired ceramics (LTCC) devices.