TEM investigation of TiNx-PACVD-coatings

The wear resistance of cermet cutting tools can be remarkably increased by TiN_x coatings. These layers are deposited at substrate temperatures of 723 K, 773 K and 973 K using a plasma-assisted chemical vapour deposition (PACVD) process. TEM investigations combined with EDXS analysis and electron diffraction gave information on structure and composition of the TiN_x layers and the interface range. X-ray structure investigations were performed additionally.The structure and the chlorine content of layers and interfaces change in dependence on the deposition temperature. All coatings show a columnar structure, but the fibre diameter increases with temperature. The fine-grained TiN_x layer deposited at 723 K has the highest chlorine content, a low-developed columnar structure and a 111 texture. The coatings deposited at 773 K and 973 K contain less chlorine impurities and have a 100 preferred orientation. The fibre structures at 723 K and 773 K can be resolved into single crystallites. By TEM investigations the fibres formed at 773 K are proved to be an accumulation of neighbouring and similarly oriented crystallites. Grain size determined by X-ray analysis and fibre diameter agree with each other. Grain sizes determined more exactly from TEM images are 6 nm at 723 K, 10 nm at 773 K and 30 nm at 973 K. In the interface region the thickness and the chlorine content of this zone decreases with increasing deposition temperature and simultaneously the layer adhesion increases.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

Surface characterisation of TiCxN1 − x coatings processed by cathodic arc physical vapour deposition: XPS and XRD analysis

The properties of titanium carbonitride (TiCN) can be controlled by maintaining the C―N ratio within the coating to a certain level. An experimental study was carried out to vary the composition and properties of TiCN using cathodic arc physical vapour deposition (CAPVD). The substrate used was tungsten carbide (WC-6Co), which was prepared in-house through a powder metallurgy process. In order to form the TiC_xN_1 − x coatings, titanium (Ti) was used as the cathode, while methane (CH₄) and nitrogen (N₂) gases were used as sources for C and N, respectively. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) were used to investigate the composition, chemical state, and bonding structure of the deposited coatings. The results show that the composition, intensity of elements, lattice parameter, and d-value of TiC_xN_1 − x coatings were successfully varied by controlling the CH₄ fraction (CH₄/N₂ ratio). With the increase in CH₄ fraction, the intensity of C and N within the TiC_xN_1 − x coatings increased and decreased, respectively. Consequently, the C―Ti and C―N bonds were increased and N―Ti bonds were decreased.     

Films of supersaturated Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Pb<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>S solid solutions: Composition prognostication,chemical synthesis,microstructure

Working conditions and the concentration regions of the joint precipitation of PbS and CdS at which substitution solid solutions Cd _x Pb_1–x can be formed were determined by calculation of ionic equilibria in the citrate-ammonia reaction mixture at 298 and 353 K with consideration for the conversion fractions of lead and cadmium sulfides into the corresponding sulfides. The hydrochemical precipitation onto glass-ceramic substrates was used to obtain Cd _x Pb_1–x S (0 < x ≤ 0.149) solid solution films with thicknesses of 0.5 to 1.7 μm and high supersaturation with the substituting component. All the films crystallize to form the B1 structure. The phase and elemental compositions and morphological specific features of the films were studied. It was shown that the thickness of the deposited layers is most strongly affected by the process temperature, ammonium hydroxide concentration, and relative amounts of the metal salts in the reaction mixture. It was found that there are oxygen and chlorine in the Cd _x Pb_1–x S solid solutions, and the distribution of these elements across the layer thickness was determined, with the layer-by-layer distribution of chlorine having a pronounced oscillatory nature. It was shown that, as the chemical precipitation temperature is raised, the content of CdS in the substitution solid solutions grows exponentially. The activation energies Ea.ic of the lead and cadmium interchange in the PbS crystal lattice were found to be, depending on the initial concentration of the lead salt, 75.3, 42.8, and 22.2 kJ mol^–1.     

Improvement of the oxidation behavior of Ti1-xAlxN hard coatings by optimization of the Ti/Al ratio

The oxidation behavior of cubic Ti_1-xAl_xN films was improved by decreasing the Ti/Al ratio from 50/50 in the direction of the phase transition between cubic and hexagonal structure. Metastable, polycrystalline, single-phase Ti_1-xAl_xN films were deposited on high speed steel (HSS) substrates by reactive magnetron sputtering ion plating (MSIP). The composition of the bulk was determined by electron probe microanalysis (EPMA), the crystallographic structure by thin film X-ray diffraction (XRD). A Ti_1-xAl_xN film with a Ti/Al atomic ratio of 38/62 was deposited in cubic NaCl structure, whereas a further decrease of the Ti/Al ratio down to 27/73 led to a two-phase film with both cubic and hexagonal constituents. The Ti_0.38Al_0.62N film was oxidized in synthetic air for 1 h at 800?°C. The oxidic overlayer was analyzed by X-ray photoelectron spectroscopy (XPS) sputter depth profiling, EPMA crater edge linescan analysis, and secondary neutrals mass spectroscopy (SNMS). Scanning electron microscopy (SEM) micrographs of the cross sectional fracture were taken for morphological examination. With higher Ti content, the Ti_1-xAl_xN formed a TiO_2-x rich sublayer beneath an Al₂O₃ rich toplayer, whereas the oxide layer on the Ti_0.38Al_0.62N film consisted of pure Al₂O₃. The thickness of the oxide layer was determined to 60–80 nm, about a quarter of the oxide layer thickness detected on Ti_0.5Al_0.5N films. The absence of a TiO_2-x sublayer was also confirmed by XRD. The results show a distinct improvement of the oxidation resistance of cubic Ti_1-xAl_xN films by increasing the Al content from x = 0.5 to 0.62, whereas a further increase leads to the hexagonal structure, which is less suitable for tribological applications due to its tendency to form cracks during oxidation.     

Investigations on microstructure,composition and properties of PECVD TiNx-coatings

Nearly stoichiometric TiN_x-coatings have been deposited on different substrates using a gaseous reaction mixture of TiCl₄, N₂, H₂ and Ar in a pulsed d.c. plasma discharge. The influence of substrate temperature, plasma power density, argon partial pressure and type of substrate on chlorine content, texture and microstructure of the coatings has been investigated keeping constant the other parameters of the plasma enhanced chemical vapor deposition (PECVD) process. Microstructure has been characterized by scanning electron microscopy (SEM) fractographs of the coatings and by determination of texture. The chlorine content quantitatively determined from energy-dispersive X-ray spectra (EDX) using a chlorine containing mineral as standard decreases on an increase of substrate temperature or plasma power density. Texture changes from 〈200〉 to 〈111〉 and random and microstructure changes from columnar growth to granular for decreasing substrate temperature as well as decreasing plasma power density. Argon partial pressure does not affect the microstructure but the texture. The properties of the coatings are independent of type of substrate for higher plasma power densities. Oxygen present at the surface of the substrate stimulates the development of a texture at low plasma power densities.     

High-pressure synthesis of solid solutions between trigonal LiNiO2 and monoclinic Li[Li1/3Ni2/3]O2

High-pressure synthesis in an oxygen-rich atmosphere yields solid solutions between LiNiO₂ and Li₂NiO₃ over the whole concentration range. Structural characterization of the high-pressure oxides was performed using powder XRD, SEM analysis, IR spectroscopy, EPR spectroscopy at 9.23 and 115 GHz and magnetic susceptibility measurements. The crystal structure of Li[Li_xNi_1−x]O₂ ,, changes from trigonal R-3m to monoclinic C2/m at Li-to-Ni ratio of 2 (or ). The incorporation of Li into NiO₂-layers causes a decrease in the mean Li-O and Ni_1-xLi_x-O bond distance. Li and Ni ions in the mixed Ni_1-xLi_xO₂-layers display a tendency to order at a short length scale in such a way that mimics the Li_1/3Ni_2/3-arrangment of the end Li[Li_1/3Ni_2/3]O₂ composition. The charge distribution in these oxides proceeds via Ni³⁺ and Ni⁴⁺ ions.     

Depth profile analysis of plasma assisted CVD hard materials coatings

The wear resistance of homogeneous and multilayer TiN_x., TiC_xN_y- and TiC_x-coatings is considerably determined by the layer composition and by the conditions at the interface. This work deals with the possibilities of different depth profile analysis methods for the study of TiN_x and TiC_x layers on hard metal and steel substrates prepared by plasma assisted CVD technique, and furthermore it demonstrates the performance of factor analysis for detailed investigation of a multilayer system consisting of amorphous C and TiC_x single layers.The hard materials coatings were investigated by different methods of depth profile analysis, which may be an important tool in the research of thin layer deposition for wear applications. The following techniques were used: GDOES, analytical TEM, electron microdiffraction and AUGER electron spectroscopy. By means of the combined application of energy dispersive X-ray spectrometry and microdiffraction a correlation of the depth profiles of both elemental concentrations and lattice parameters in TiC_x coatings could be revealed.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

The influence of hydrogen-containing molybdenum and tungsten bronzes on the catalytic activity of palladium composite catalysts for the oxidation of H<Subscript>2</Subscript>, CO,and CH<Subscript>4</Subscript>

The influence of hydrogen-containing molybdenum and tungsten bronzes on the catalytic activity of palladium composite catalysts for the oxidation of H₂, CO, and CH₄ was studied. It was found that the composite catalysts containing H _x MO₃ phases (M = W or Mo), which were formed by the reduction of MoO₃ and WO₃ oxides with hydrogen in the presence of deposited Pd, showed higher catalytic activity in the oxidation of small molecules (H₂, CO, and CH₄) with excess oxygen than the traditional Pd/Al₂O₃ deposited catalyst with the same content of the deposited metal. It was shown that the thermal stability of the H _x MO₃ phases was the limiting factor influencing the activity of these composite catalysts.     

Der Einfluß von Wasserstoff auf Titancarbid

Zusammenfassung Beim Hydrieren von TiC_1-x -Proben wird erstens Wasserstoff in den Defektmischkristall des Monocarbids eingebaut. Zweitens entsteht eine ternäre Phase der ungefähren Zusammensetzung Ti₂CH, die eine hexagonal dicht gepackte Wirtzelle besitzt. Die Gitterparameter dieser ternären Phase werden ermittelt. Dehydrieren liefert wieder die wasserstoff-freien Phasen TiC_1-x oder TiC_1-x +-Ti. Die analoge ternäre Phase wird auch im System: Hf–C–H gefunden. Die Phasen Ti₂CH und Hf₂CH schließen sich in den Gitterparametern und vor allem imc/a-Verhältnis weitgehend an V₂C, (Cr_0,8 W_0,2)₂C bzw. Ta₂C und W₂C an.

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Hydrogen dissolves in titanium carbide having a carbon defect. A ternary compound of the approximative formula Ti₂CH has been detected, a hexagonal close packed parent lattice being determinated. Dehydrogenation leads to the starting carbides again. The formation of the analogous phase Hf₂CH has also been observed. The lattice of the both compounds can be related to those of the respective carbides such as V₂C, (Cr_0,8W_0,2)₂C, Ta₂C and W₂C.

     

Deposition of Diamond-Like Carbon Film in a Closed-Space CH4 RF Plasma

Deposition of diamond-like carbon (DLC) film and mass spectrometry measurements were carried out in a closed-space CH₄ rf (13.56 MHz) plasma (without both gas injection and vacuum pumping during the process). At pressures less than 0.6 Torr, the thickness of the DLC film deposited increased with increasing elapsed deposition time, and reached a maximum value, but after this the film thickness started to decrease, which was considered to be caused predominantly by ion-induced sputter etching. The maximum film thickness appeared at larger elapsed time for higher deposition pressure. The mass concentrations of hydrocarbon ions indicated anomalous behavior at early deposition times, but those of higher hydrocarbon ions are clearly increased at the point where the film thickness started to decrease. These results suggested that the ratio of precursor CH₃al density to the total hydrocarbon ion density (_CH3/_ion in the CH₄a was an important factor for the carbon film formation, and when this ratio reduced to a certain critical value with increasing elapsed deposition time, the deposited film was then re-etched predominately by the secondary higher hydrocarbon ions. At 1.0 Torr where a polymer-like soft carbon film was deposited, such re-etching of the deposited film was not observed.     

Titanium Anodes with Active Coatings Based on Iridium Oxides: The Corrosion Resistance and Electrochemical Behavior of Anodes Coated by Mixed Iridium,Ruthenium, and Titanium Oxides

A study of the corrosion resistance and electrochemical behavior of titanium anodes with active coatings prepared from mixed oxides iridium, ruthenium, and titanium (OIRTA) is continued. The dependence of the catalytic activity, selectivity, and corrosion resistance of these anodes with x mol % RuO₂ + (30 ? x ) mol % IrO₂ + 70 mol % TiO₂ is studied in conditions of chlorine electrolysis on the ratio of concentrations of IrO₂ and RuO₂ in them at a constant loading of iridium in the coatings. It is established that the maximum corrosion resistance and selectivity is inherent in OIRTA with the RuO₂ concentration close to 4 mol %. Partial curves, which describe the dependence of the rates of dissolution of iridium out of OIRTA and the evolution of chlorine and oxygen in them on the electrode potential, are obtained. The dependence of the rates of these processes on the solution pH, the concentration of NaCl in it, and the thickness of the active layer is studied. It is shown that the rate of dissolution of iridium out of OIRTA and the concentration of oxygen in chlorine at a constant potential increase approximately proportionally to the coating thickness, from whence it follows that the said processes proceed over the entire depth of the coating. An assumption is put forth that the chlorine evolution on OIRTA of the optimum composition, with a loading of iridium equal to 2.5 g m^?2, at high anodic currents occurs in an outer-kinetics regime in the presence of diffusion limitations on the removal of chlorine out of the coating's depth.     

Small-angle x-ray scattering of distorted lamellar structures

Small-angle x-ray scattering (SAXS) intensity for the lamellar structure of polymeric materials has been formulated with consideration of structural defects such as the finiteness of the lamellar stack, the lamellar bend, and the paracrystalline distortions. In particular, the effects of the lamellar bend on the SAXS profile have been elucidated on the basis of Vonk'xss formula γ₁(x) – γ(x)exp(?2x/d). Here, the scattering profile due to the lamellar bend is shown to be expressed by a Cauchy function. The integral breadth is equal to 2π/d, being independent of the order of scattering. As an example of the SAXS analysis based on the theory, the characterization of the lamellar structure in the “hard” elastic polypropylene films is reported. The long period and the lamellar thickness are evaluated from the correlation function, and the distortion length and Hosemann's g factor are estimated according to the procedure presented here. On the basis of these structural parameters, the relationship between the manufacturing process and the lamellar structure of the polypropylene films is discussed. © 1993 John Wiley & Sons, Inc.     

Macromolecular models for branched PVC. I. Copolymer of vinyl chloride with isopropenyl chloride

A new type of model for study of polymer anomalies by copolymerization is proposed. For branched PVC, the vinyl chloride–isopropenyl chloride copolymer was used as the macromolecular model. A regulatory and inhibitory action of isopropenyl chloride during the polymerization was demonstrated. To determine the composition of the copolymer, methods based on elemental analysis and NMR and infrared spectra were utilized. It was found that the copolymer composition is very close to that of the polymerization mixture. The structure of the copolymer was studied from infrared spectra. It was found that both forms T_CHH and T_HHH are present, the former being present in a larger quantity. The possibility of the utilization of spectral methods on macromolecular systems to determine the structure and content of a chlorine atom bound to a tertiary carbon atom (Cl_T) in the presence of an excess of chlorine bound to a secondary carbon was verified.     

Influence of substrate temperature and N2/Ar flow ratio on the stoichiometry,structure and hardness of TaNx coatings deposited by DC reactive sputtering

The effect of substrate temperature and N2/Ar flow ratio on the stoichiometry, structure and hardness of TaN_x coatings prepared on (111) Si substrates by DC reactive sputtering was investigated. For the structural, chemical and morphological analysis, X‐ray diffraction (XRD), Auger electron scanning and atomic force microscopy were respectively used. Hardness values of thin films were determined using the work of indentation model from nanoindentation measurements. TaN stoichiometric coatings were obtained for samples deposited at room temperature. The stoichiometric TaN phase was not obtained by increasing the temperature up to 773 K, even when increasing the N₂/Ar flow ratio. Even when a saturation in nitrogen content was achieved, nitrogen vacancies are still present in those samples. For coatings prepared at 773 K and low N₂/Ar flow ratio, a phase mixture between TaN_x and cubic α‐Ta was observed, while a cubic structure δ‐TaN was formed by increasing the N₂/Ar flow ratio. A maximum in hardness and (38 GPa) was obtained for the sample deposited at 773 K and a N₂/Ar flow ratio of 0.2, which presented a δ‐TaN cubic crystalline structure and a roughness value of 1.6 nm. Copyright © 2015 John Wiley & Sons, Ltd.     

Electrochemical hydrogen storage in TiC0.6, not in TiC0.9

We demonstrate that hydrogen can be electrochemically loaded, at room temperature, in the non-oxide ceramic TiC_0.6. A capacity of 2.9 wt.% is easily reached, corresponding to the formula TiC_0.6H_1.6. We also demonstrate that hydrogen absorption was not possible in TiC_0.9. This surprising result is interpreted in terms of absence of long-range ordered carbon vacancies, contrary to TiC_0.6. It seems that TiC_0.6 behaves like an intercalation compound for hydrogen.     

Interaction of –CClx (x=1–3) with Ru2 and RuSn dimers: a density functional study

Density functional calculation were performed on the Ru₂ and RuSn metal dimers and the species formed from their interaction with –CCl_x (x=1–3) fragments. The importance of these fragments in the hydrodechlorination of carbon tetrachloride has been motivated this study aiming to contribute to understand the effect of the tin in the performance of the noble metals based catalysts. We have observed that the carbon tetrachloride does not form a precursor with the metal dimers. The CCl₄ readily dissociates forming adsorbed chlorine and –CCl₃ complexes. The chlorine atoms prefer to adsorb on the bridge sites and the RuSn–Cl binding energy is about 5 kcal mol⁻¹ larger than the Ru₂–Cl binding energy. The Ru₂–CCl_x (x=1–3) binding energies are larger than the respective RuSn–CCl_x (x=1–3) binding energies. However, the reaction energy of the dechlorination of CCl₄ leading to adsorbed –CCl_x (x=1–3) and chlorine is thermodynamically more favorable for RuSn than the Ru₂. The differences between Ru₂ and RuSn systems have been discussed based on the different interaction mechanism due to the presence of the tin center and its affinity for the chlorine atoms.     

Glycolate Ti1 − x Fe x (OCH2CH2O)2 − x/2 as a precursor for the preparation of quasi-one-dimensional (1D) solid solutions Ti1 − x Fe x O2 − 2x/2 (0 ≤ x ≤ 0.1)

Quasi-one-dimensional (1D) solid solutions Ti_{1 ? x} Fe _x (OCH₂CH₂O)_{2 ? x/2} (0 < x ≤ 0.1) with the structure of anatase were prepared by heating the glycolate Ti_{1 ? x} Fe _x (OCH₂CH₂O)_{2 ? x/2} in an atmosphere of air at a temperature of >450°C. The conditions of formation and the properties of the new glycolate Ti₃Fe₂(OCH₂CH₂O)₉ were described. It was found that the synthesized Ti_{1 ? x} Fe _x O_{2 ? 2x/2} solid solutions exhibit photocatalytic activity in the reaction of hydroquinone oxidation in an aqueous solution on irradiation with UV light. A correlation between the rate of oxidation of hydroquinone and the concentration of iron in the catalyst was established. A procedure for the preparation of titanium dioxide with the structure of anatase doped with iron and carbon (Ti_{1 ? x} Fe _x O_{(2 ? x/2) ? yCy)} and also composites on its basis, which contain an excess amount of carbon, was proposed.     

Conductive polyethylene-carbon black composites by elongational-flow injection molding Part 3. Study of the structure and morphology

The morphology and structure of high molecular weight linear polyethylene (M _w 450000) filled with carbon black and processed using molds that introduce an elongational flow component during injection molding has been examined using electron microscopy and x-ray diffraction techniques. The study of fracture surfaces reveals the display of shish-kebabs oriented along the injection direction with segregated longitudinal channels of carbon black particles. Molecular and lamellar changes in orientation are, furthermore, studied across the thickness of the moldings. It is shown that addition of carbon black particles to injection-molded polyethylene induces significant changes in lamellar orientation. Thus, while lamellar overgrowth proceeds perpendicular to the fiber axes within carbon free channels, lamellae grow randomly within carbon-enriched regions where flow is less pronounced.     

Mixed Valence Tungsten(IV,V) Compounds with Layered Structures (Part II)): Synthesis and Crystal Structures of Cu1−x[W2O2Cl6] and Cu1−x[W4O4Cl10]

The reaction of CuCl with WOCl₃ at 400 °C leads to a mixture of Cu_1?x[W₂O₂Cl₆] ( 1 ) and Cu_1?x[W₄O₄Cl₁₀] ( 2 ) in form of black lustrous needles. Both compounds crystallize in space group C2/m with a = 12.7832(5) Å, b = 3.7656(2) Å, c = 10.7362(3) Å, β = 119.169(2)° for 1 and a = 12.8367(19) Å, b = 3.7715(7) Å, c = 15.955(3) Å, β = 102.736(5)° for 2 . The structures are made up of WO₂Cl₄ octahedra. In the case of 1 two octahedra are edge‐sharing via chlorine atoms to form pairs which are linked via the trans‐positioned oxygen atoms to form infinite double strands . In the structure of 2 two of these double strands are condensed via terminal chlorine atoms to form quadruple strands . Like for all members of the M_x[W₂O₂X₆] structure family (X = Cl, Br) nonstochiometry with respect to the cations M was observed. The copper content of 1 and 2 was derived from the site occupation factors of the respective structure refinements. For several crystals examined the copper content varied between x = 0.27 and 0.17 for 1 and x = 0.04 for 2 . In both structures the oxochlorotungstate strands are negatively charged and connected to layers by the monovalent copper ions, which are tetrahedrally coordinated by the non‐bridging chlorine atoms of the strands. The structure models imply disorder of the Cu⁺ ions over closely neighboured sites.