Stability of a dry patch in a viscous flowing film

We investigate the dewetting of liquid films flowing down an incline. At low flow rate we observe the formation of stationary dry patches edged with a liquid rim. Their shape can be predicted by a simple model in which the rim weight is balanced by surface tension. Above a critical flow rate per unit length Γ_c of typical scale U_cl_c (U_c capillary velocity, l_c capillary length), these dry patches cannot remain stationary and are swept away. An improved model taking into account capillary effects linked to contact line curvature, hydrostatic pressure in the film and inertial effects predicts this loss of stability in good agreement with experiments for sufficiently high viscosity values.     

TEM study of locally coated nanopore fabricated by ion-beam-induced deposition in a thin membrane

We studied the formation of locally coated sub-10-nm nanopores fabricated by ion-beam milling and ion-beam-induced deposition (IBID) in a thin silicon nitride membrane. Two typical precursor gases representing conductive ((CH₃)₃Pt(CpCH₃), CPC for short) and insulating (tetra ethyl oxysilane, TEOS for short) material deposition are used. Three-dimensional electron tomography, EDX and EELS analysis are used to measure the changes in chemical composition and shape of the pores after their formation and at various stages of pore shrinkage. The formation and shrinkage are shown to be due to a shifting competition between IBID and material sputtering during ion-beam exposure. The chemical distribution at the rim of the nanopore is dependent on the precursor gases used: CPC forms a thin carbon layer with small embedded Pt particles at the top and inner surfaces of the nanopore, whereas TEOS forms SiO_xC_y with Ga particles dispersed at the rim of the nanopore.     

An infrared study of the surface chemistry of lithium titanate spinel (Li4Ti5O12)

While there are numerous studies examining the performance of lithium titanate spinel (LTS) as a lithium-ion battery, little is known about the surface chemistry of this material. In this paper, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy spectroscopy was used to study the type of surface groups present on LTS as a function of temperature. The surface was found to contain isolated and hydrogen-bonded TiOH groups and the dehydroxylation behavior with thermal treatment was similar to that of TiO₂. In addition, hexamethyldisilazane (HMDZ) and pyridine were used to probe the reactivity of surface hydroxyl groups and the presence of Lewis acid sites, respectively. The reaction of HMDZ occurred with both LiOH and TiOH groups to form Li-O-Si and Ti-O-Si. In addition, the reaction of gaseous CO₂ with the Li⁺ ions resulted in the formation of surface carbonate ions. The carbonate ions are removed by heating at 400 °C in air.     

From nitride to carbide: control of zirconium-based hard materials film growth and their characterization

High-quality thin films of ZrC_yN_1-y and the novel tribological material Zr_0.8Al_0.2C_yN_1-y have been grown by pulsed reactive crossed-beam laser ablation using Zr and Zr–Al ablation targets, respectively, and a pulsed gas. The gas mixture provided the carbon and nitrogen for the solid-solution films. Control of the stoichiometry (i.e. y) was determined by the relative partial pressures of the nitrogen- and carbon-containing gases. It was found that optimal control of the film chemistry was achieved by using the least thermally reactive gases. In this manner, it was possible to activate the gas species exclusively by collisions in the gas phase with the ablation-plume particles, thereby decoupling the chemistry from surface processes. The films were characterized for their chemical, crystallographic, optical, and tribological properties. All the films had very low impurity levels and a cubic rock salt crystal structure over the entire investigated temperature range between 100 and 600 °C. Exceedingly high quality epitaxial films could be grown on MgO (001) at 600 °C. Films grown on stainless steel were polycrystalline. The hardness of the films showed a maximum for both sets for stoichiometries predicted by a recent theoretical model for hardness based on band-structure calculations. In addition, all the films had an exceptionally low coefficient of friction versus steel. Received: 22 August 2001 / Accepted: 3 March 2002 / Published online: 19 July 2002     

Surface morphology changes of poly(ethyleneterephthalate) fabrics induced by cold plasma treatments

Some selective cold plasma processing modify specific surface properties of textile polymeric materials such as their dyeability, wettability and hydrorepellence. To correlate the sample surface changes with the acquired surface properties allows one to obtain information on the chemical and physical processing involved in plasma treatment. In this work, atomic force microscopy (AFM) has been applied to investigate the morphological and topographical surface modifications induced by RF cold plasma processing of poly(ethyleneterephthalate) (PET) fabrics. Rms surface roughness and surface area of the samples are measured before and after the treatments. The morphology changes have been analysed as a function of the treatment time and air gas pressure. Measurements have been performed also using plasmas produced by different gases such as He, Ar, SF₆ and CF₄. The PET shows different behaviour with different gas plasmas. In the case of air, He and Ar gases the sample surface modifications seem to be mainly due to etching effects, while the fluorine atoms grafting probably is responsible for surface rearrangement process using SF₆ and CF₄ gases. As a consequence different surface properties are produced in the plasma treated samples. Article presented at the International Conference on the Frontiers of Plasma Physics and Technology, 9–14 December 2002, Bangalore, India.     

Hydroxylated α-Al2O3 (0 0 0 1) surfaces and metal/α-Al2O3 (0 0 0 1) interfaces

X-ray photoelectron spectroscopy was applied to study the hydroxylation of α-Al₂O₃ (0 0 0 1) surfaces and the stability of surface OH groups. The evolution of interfacial chemistry of the α-Al₂O₃ (0 0 0 1) surfaces and metal/α-Al₂O₃ (0 0 0 1) interfaces are well illustrated via modifications of the surface O1s spectra. Clean hydroxylated surfaces are obtained through water- and oxygen plasma treatment at room temperature. The surface OH groups of the hydroxylated surface are very sensitive to electron beam illumination, Ar⁺ sputtering, UHV heating, and adsorption of reactive metals. The transformation of a hydroxylated surface to an Al-terminated surface occurs by high temperature annealing or Al deposition.     

Spectroscopic Studies of Chemical Reactions in Strong Shock Waves

Shock tube provides a promising tool of studying high temperature chemical reaction in gases. The heating by shock wave is uniform, extremely fast and intense. So that the temperature may rise thousands of degrees in a fraction of a second. Observations of the effects of this heating on C₆H₆ has shown extensive decomposition into C₂ and CN.     

Magnetically controlled thermoelastic martensite transformations and properties of a fine-grained Ni<Subscript>54</Subscript>Mn<Subscript>21</Subscript>Ga<Subscript>25</Subscript> alloy

Comparative studies of physical characteristics (the electrical resistivity, the magnetic susceptibility, the magnetization, the bending deformation, and the degree of shape recovery during subsequent heating) of the Ni₅₄Mn₂₁Ga₂₅ ferromagnetic alloy as-cast and rapidly quenched from melt have been performed in the temperature range 2–400 K. The results are compared to the results of studying the structural–phase transformations by transmission and scanning electron microscopy and X-ray diffraction. It is found that the rapid quenching influences the microstructure, the magnetic state, the critical temperatures, and the specific features of thermoelastic martensite transformations in the alloy. It is found that the resource of the alloy plasticity and thermomechanical bending cyclic stability demonstrates a record-breaking increase in the intercritical temperature range and during subsequent heating.     

The effect of thermal treatment on the organization of copper and nickel nanoclusters synthesized from the gas phase

The condensation of 85000 Cu or Ni atoms from the high-temperature gas phase has been simulated by molecular dynamics with the tight binding potential. The efect of the subsequent thermal treatment on the shape and structure of synthesized particles was studied by simulating their gradual heating in a range of 100–1200 K. Some tendencies are revealed that are characteristic of the influence of heat treatment on the nanoparticles synthesized from the gas phase. It is concluded that short-term heating leads to significant ordering of the internal structure in 70% of agglomerated nanoparticles with the predominant formation of spherical shapes. In order to explain this result, the main mechanisms of cluster formation from the gas phase have been analyzed and it is found that the agglomeration temperature plays the main role in the formation of clusters with unified shape and structure. This opens the fundamental possibility of obtaining Cu and Ni nanoclusters with preset size, shape, and structure and, hence, predictable physical properties.     

Mechanism of small variations in energy of ultracold neutrons interacting with a surface

The cause of the small heating of ultracold neutrons (UCNs) by ～10^?7 eV with a probability of 10^?8–10^?5 per collision with a surface was investigated. Neutrons heated in this way will be called vaporized UCNs (VUCNs). It was established that a preliminary heating of a sample in vacuum up to a temperature of 500–600 K can increase small-heating probability P _VUCN by a factor of at least ～100 and 10 on a stainless steel and a copper surface, respectively. For the first time, an extremely vigorous small heating of UCNs was observed on a powder of diamond nanoparticles. In this case, both the VUCN spectrum and the temperature dependence of probability P _VUCN were similar to those previously obtained for stainless steel, beryllium, and copper samples. On the surface of single crystal sapphire, neither the small heating of UCNs nor nanoparticles were found. All these facts indicate that VUCNs are likely produced by inelastic scattering of UCNs on weakly bound surface nanoparticles being in permanent thermal motion.     

Thermal quenching of thermoluminescence in TLD-200, TLD-300 and TLD-400 after β-irradiation

The dosimetric characteristics of many TL materials are influenced by changes in location, size and shape of the glow curves due to changes in the heating rate. In this study, the effect of heating rate on the integrated peak areas of CaF₂:Dy (TLD-200), CaF₂:Tm (TLD-300) and CaF₂:Mn (TLD-400) crystals have been investigated after β-irradiation. It was observed that the peak temperatures of all peaks shifted to the high temperature sides and the integrated peak areas decrease as the heating rate increases due to thermal quenching, whose efficiency increases as temperature increases.     

Spectral emissivity modeling of steel 201 during the growth of oxidation film over the temperature range from 800 to 1100 K in air

This study explores the spectral emissivity modeling of steel 201 during the growth of oxidation film over the temperature range from 800 to 1100 K at 1.5 μm. The radiance coming from the specimen is received by an InGaAs photodiode detector. The specimen temperature is obtained by averaging the two platinum–rhodium thermocouples, which are tightly welded in the front surface of specimen near the measuring area viewed by the detector. The variation of spectral emissivity with the temperature is studied at a given heating time. The variation of spectral emissivity with the heating time is evaluated at a definite temperature. The strong oscillations of spectral emissivity are observed and discussed in detail, which originate from the interference effect between the radiation stemming from the oxidization film on the specimen surface and the radiation coming from the specimen surface. The measurement uncertainties of spectral emissivity contributed only by the surface oxidization are about 3.2–14.1%. At a given heating time, the variation of spectral emissivity with the temperature abides well by a simple analytic functional form. And at a definite temperature, the variation of spectral emissivity with the heating time can also be well reproduced by fitting except for the periodical oscillations.     

Finite element analysis of laser irradiated metal heating and melting processes

Laser technology has shown fast growth due to its demands in material processing and manufacturing. Laser material processing includes various applications like cutting, welding, drilling, cladding and surface treatment. In laser surface treatment, the material properties at the surface are altered through surface alloying and transformation hardening. In this study, an enthalpy-based computational model is developed for analyzing laser heating and melting of metals. The solution to the problem is obtained by using a finite element method and validated by comparing the results with that given by an analytical solution to a limiting case problem. A solution algorithm and a computational code are developed to estimate the temperature distribution, solid-liquid interface location and shape and size of the molten pool. The computational model is validated by comparing results with a limiting case analytical model. The study is conducted to analyze the heating rate, the heat affected zone, and the shape and size of the molten pool using a Gaussian laser beam.     

A gas flow proportional counter for the Mössbauer study of surfaces between 100 K and 400 K

A gas flow proportional counter has been constructed for operation between 100K and 400K without the need for an evacuated cryostat. The detector is temperature controlled and may be used for detecting conversion electrons or X-rays. Six different gases, pure He, He/1%CH₄, He/5%CH₄, He/10%CH₄, He/5%Co, and Ar/5%CH₄ have been investigated in order to obtain maximum efficiency and reliability of operation. At room temperature and above, all gases are suitable. At low temperatures, He/5%Co is the most suitable for electron detection, For X-ray detection, Ar/5%CH₄ is suitable over the entire temperature range.     

Analytical investigation into laser pulse heating and thermal stresses

Laser pulse heating of metallic surfaces results in rapid rise of temperature in the region irradiated by the laser beam. This in turn results in high temperature gradient in this region. The irradiated substrate material expands as a response to the temperature gradient. Consequently, high thermal stress levels are developed in the region of the high temperature gradient. In the present study, closed form solutions for temperature and stress fields due to a laser pulse decaying exponentially in time are presented. A Laplace transformation method is employed in the analysis. The resulting equations are non-dimensionalized with the appropriate parameters. It is found that temperature rises rapidly during the early heating period in the surface region. In this case, internal energy gain dominates the conduction losses from the surface vicinity. The thermal stress levels attain high values in the surface region. The stress wave developed is compressive and it propagates with a wave speed c₁ inside the substrate.     

A model for oxidation-driven surface segregation and transport on Pt-alloys studied by atom probe tomography

Using a purpose-built 3D atom probe, we have previously shown that exposure to oxidising gases (NO, N₂O, O₂) induces Rh surface segregation in Pt–Rh alloys, the extent of which is strongly dependent on treatment temperature, crystallographic plane and the presence of ternary alloy additions. In this paper, the segregation trends identified on three different crystallographic surfaces of Pt–Rh are analysed using thermodynamic and kinetic arguments. The segregation model we present is generic for diffusion on alloy surfaces in the presence of active gases. From it we obtain activation energies and diffusion coefficients for the processes of metal-oxide species diffusion both perpendicular to and laterally across the surface. Using these we propose a simple model for the interaction of chemically active gases with the surfaces of such alloys. Applying this understanding to sequential oxidation/reduction treatments would in principle allow improved control of the surface composition of alloy catalysts. Related applications of this model include optimisation of core–shell catalyst nanoparticles.     

Synthesis and properties of aligned ZnO microtube arrays

Two kinds of different aligned zinc oxide (ZnO) crystal microtube arrays were prepared on silicon (1 0 0) substrates by using of a simple thermal chemical reaction vapor transport deposition method. The synthesizing processes were done by using of heating the mixture of zinc oxide and graphite powders at 1150 °C in a quartz tube with one side opened to the air. The O₂ gas (99.9%) and air had been introduced as the assistant gases, respectively. Both the flow rates were 100 ml/min. And the temperature of the Si (1 0 0) substrate region was about 400 °C. There is no other metal catalyst on the Si wafers in the process. After growing for 30 min, one kind of synthesized sample is trumpet-shaped hexagonal microtube arrays assisted with O₂ gas and another produced sample is the uniform hexagonal microtubes only assisted with air. As the increasing of preparing time, their maximal lengths can range from several 10 μm to mm scale. The microstructure, room temperature photoluminescence properties and growth mechanism of both aligned microtube arrays were investigated and discussed.     

Determination of the Energy Flux of a Commercial Atmospheric‐Pressure Plasma Jet for Different Process Gases and Distances Between Nozzle Outlet and Substrate Surface

The energy flux of an atmospheric‐pressure plasma jet for surface treatment has been investigated by a calorimetric probe. Generally, the investigations exhibit that the main contributions of the total energy influx from the plasma to the substrate surface originate from the neutrals regarding high gas temperature coupled with a high gas flow. The use of nitrogen as process gas shows a higher energy flux compared to oxygen and air presumably caused by increased gas temperature as well as by higher molecule formation and recombination energy of N₂. Moreover, the lateral expansion of the plasma beam could be roughly determined by a spatially resolved analysis of the energy influx. A top part mounted on the nozzle, commonly used for the injection of additional precursor gases, showed a significant effect on the flow behavior and collision entailed relaxation of the excited plasma species leading to a restraining of the plasma jet. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Boron-doped diamond synthesized by chemical vapor deposition as a heating element in a multi-anvil apparatus

ABSTRACT

We tested boron-doped diamond (BDD) synthesized by chemical vapor deposition (CVD) as a heating element in a multi-anvil apparatus. We succeeded in manufacturing BDD into a tubular shape by laser cutting and electric discharging machining. The BDD tube shaped by the electric discharging machining was contaminated by discharging electrode materials (Mo and W), which affected the heating performance. The laser-cut BDD tube has a clean surface and, therefore, had a good heating performance. We succeeded in generating temperature as high as 2670?K at a pressure around 30?GPa with laser-cut heater. Heating reproducibility was confirmed through repeated heating and cooling cycles. The recovered sample shows that a higher temperature generation above 2670?K was prevented by eutectic melting of ZrO₂ thermal insulator and Al₂O₃ sample. Owing to the commercial availability with a reasonable price, CVD–BDD heaters are more practical than a high-pressure synthesized BDD heaters for wide applications.     

Nitrogen release during reaction of coal char with O2, CO2, and H2O

The chemistry of char-N release and conversion to nitrogen-containing products has been probed by studying its release and reactions with O₂, CO₂, and H₂O. The experiments were performed in a fixed bed flow reactor at pressures of up to 1.0 MPa. The results show that the major nitrogen-containing products observed depend on the reactant gas; with O₂, NO, and N₂ being the major species observed. Char-N reaction with CO₂ produces N₂ with very high selectivity over a broad range of pressures and CO₂ concentrations, and reaction with H₂O gives rise to HCN, NH₃, and N₂. Observed distributions of nitrogen-containing products are little affected by pressure when O₂ and CO₂ are the reactant gases, but increasing pressures in the reaction with H₂O results in the formation of increasing proportions of NH₃. Formation of NH₃ is also promoted by increasing concentrations of H₂O in the feed gas. The results suggest that NO and HCN are primary products when O₂ and H₂O, respectively, are used as the reactant gases, and that the other observed products arise from interactions of these primary products with the char surface.