Benard–Marangoni Instability as Possible Modifier of Surface Alloy Composition

Thermophysical properties of amorphous alloys represent the features of a given material specimen, and, as such, they are dependent, in general, on their elemental composition. Some properties are measured at surfaces, and others are measured for the bulk as a whole. Complications arise when the elemental composition varies as a function of position within the material specimen, as demonstrated by simultaneous measurements of thermal diffusivity and elemental composition by time-resolved spectroscopy of laser-produced plasma (LPP) plume emissions. To further understand the source of a rather common near-surface elemental composition anomaly, the evolution of the surface composition of Wood’s alloy under the influence of thermal cycling with, and without, a temperature gradient over the specimen has been investigated. Surface composition modifications have been found to take place by accumulation of irregularly spaced gray patches of an inhomogeneous composition on the surface in the presence of a temperature gradient. Determination of elemental composition by LPP spectroscopy shows the three-dimensional structure of the patches.     

Routes To Development Of Near-Surface Alloy Composition Anomaly

Thermophysical data in the literature for metallic alloys, including single-element specimens, exhibit a high degree of variability. Of interest is if the reasons are intrinsic. That there exists as a rule a surface layer whose elemental composition differs from that of the bulk has been demonstrated. Such a near-surface composition anomaly can, in principle, account for the significant part of the variability. The method of time-resolved spectroscopy of emissions from laser-produced plasma (LPP) plumes has been the key in this new development because both the elemental composition and thermal diffusivity can be measured simultaneously. Multiple application of LPP analysis leads to depth-resolved measurements. A variety of alloy specimens have been subjected to different scenarios of thermal cycling to find that thermal cycling modifies the near-surface composition profile of a given specimen. A new study has been carried out with Wood’s alloy as a model system by forcing the specimen into melting at increasing temperature. This investigation has revealed that the near-surface composition undergoes sharp irreversible changes when the highest elemental melting point has been exceeded before the specimen is cooled to resolidification. A possible mechanism is suggested. Paper presented at the Seventh International Workshop on Subsecond Thermophysics, October 6–8, 2004, Orléans, France.     

Development of Near-Surface Composition Anomaly

Many multi-element alloy specimens have been shown to possess a wide variety of near-surface elemental composition profiles, which are significantly different from the bulk composition. Such composition nonuniformity adversely affects the measurement of basic thermophysical properties in alloys. In this paper is presented a new investigation into the mechanisms by which such depth-dependent near-surface elemental composition develops. Specifically, specimens of a low melting-point metallic alloy, Wood's alloy, as a model system are examined under varying thermal cycling conditions within a chamber of controlled gaseous atmosphere. The near-surface composition and thermal diffusivity are measured as a function of depth. The method of time-resolved spectroscopy of laser-produced plasma plumes emanating from the specimen surface is used. Different surface composition profiles emerge depending on the dynamic range of the thermal cycling forced on a specimen.     

Evolution of Near-Surface Elemental Composition Profile and Its Effect on Thermal Diffusivity

In a series of recent experiments, utilizing the method of time resolved spectroscopy of laser-produced plasma (LPP) plumes from specimen surfaces, the near-surface elemental composition profiles were observed to be nonuniform and significantly different from the respective bulk composition. A new study of three alloy systems is reported, with a view toward establishing the causal relationship between the near-surface elemental composition profile of a specimen and its thermophysical properties in general and thermal diffusivity in particular. The systems in question are as follows: two-element Nichrome ribbon; four-element magnetic Mumetal foil; and four-element Wood's alloy. The method of LPP plume spectroscopy has been used throughout to successively expose new surface layers and measure the composition and thermal diffusivity. With two of the systems, modification of the near-surface elemental composition profiles has been forced. Sustained electrical heating of a Nichrome ribbon specimenrevealed preferential diffusion of chromium to the surface, affecting the spectral emissivity and thermal diffusivity as well as depth-dependent local heating rates. In the case of Wood's alloy a sample is melted and re-solidified under a protocol that highlights gravitational forcing. The noncontact spectroscopic method has been used to discover that the top and bottom surfaces acquire two different composition profiles and exhibit commensurate disparity in the measured thermal diffusivity profiles.     

Thermophysical property measurement at high temperatures by laser-produced plasmas

Excitation by a high-power laser pulse of a material surface generates a sequence of plasma, fluid flow, and acoustic events. These are well separated in time, and their detection and analysis can lead to determination of material properties of the condensed phase target. We have developed a new methodology for real-time determination of molten metal composition by time-resolved spectroscopy of laser-produced plasmas (LPP). If the laser pulse is shaped in such a way that the movement of the bulk surface due to evaporation is kept in pace with the thermal diffusion front advancing into the interior of the target, the LPP plume becomes representative of the bulk in elemental composition. In addition, the mass loss due to LPP ablation is very well correlated with the thermal diffusivity of the target matter. For several elemental solid specimens, we show that the product of the ablation thickness and heat of formation is proportional to the thermal diffusivity per unit molecular weight. Such measurements can be extended to molten metal specimens if the mass loss by ablation, density, heat of formation, and molecular weight can be determined simultaneously. The results from the solid specimen study and the progress with a levitation-assisted molten metal experiment are presented.Paper presented at the Third Workshop on Subsecond Thermophysics, September 17–18, 1992, Graz, Austria.     

Effects of Surface Morphology and Composition Modification on Spectral Emissivity and Thermal Diffusivity Profile at High Temperatures

A new all-spectroscopic method for depth-resolved thermal diffusivity measurement of metallic specimens has been demonstrated. The method entails measurement of the mass entrained into a laser-produced plasma (LPP) plume in such a manner that the plume is representative of the specimen in elemental composition. Both the abundance of matter and its elemental composition are measured by time-resolved spectroscopy for each LPP plume. In order to delineate the morphology versus composition basis of the depth dependence, a new study on a Nichrome ribbon specimen heated by ohmic heating in a vacuum is presented. A set of depth-resolved thermal diffusivity measurements is carried out, while noting the attendant changes in the spectral emissivity and elemental composition at succeeding ablation layers. Additional measurements are carried out after the specimen has been treated under varying heating conditions. Preferential diffusion of chromium at high temperatures has been found to contribute to the dynamics of surface thermophysical properties at high temperatures. Representative LPP ablation is well suited for removal of surface impurities prior to thermophysical property measurements by the pulse heating technique.     

The structurally changed layer of superabrasive wheel and workpiece contact surfaces as a factor of improving their wear resistance (a Change of Elemental Composition)

The paper addresses the formation of a structurally changed contact surface layer in a superabrasive wheel and workpiece under thermal and plasma actions, which occurs through redistribution of elemental composition in the material subjected to such actions. The change of the elemental composition is shown to have an effect on mechanical characteristics of the contact surfaces and thus makes it possible to find conditions for improving their wear resistance.     

Thermal Diffusivity Measurement for Titanium Thin Films on Copper Substrate by Laser Produced Plasmas

The transport properties of condensed phase materials are, in principle, dependent on the local structure and composition of the specimen. This is particularly evident near the free surface of a solid alloy specimen where the morphology, composition, and thermal diffusivity exhibit significant depth dependence, as demonstrated in an earlier study of the depth-resolved thermal diffusivity of a galvanized steel specimen. A new non-contact method was used, based on time-resolved, spectroscopic measurement of the total mass removed from the specimen surface representatively in elemental composition by a high-power laser pulse. A new study of a titanium thin film of varying thickness deposited on a copper substrate is presented. The titanium thin film is first fabricated in a vacuum and then immediately analyzed for composition and thermophysical properties in situ, both by the method of representative laser-produced plasmas (LPP). Successive ablation layers of the thin film, as exposed by LPP ablation, have revealed the dependence of the thermophysical properties on film thickness as well as on depth. The existence of a characteristic length over which the substrate influences the dynamics of thermal transport in the titanium thin film has also been observed.     

Interfacial chemistry control in thin film solar cells based on electrodeposited CuIn(S,Se)2

In this work, we present a study on CuIn(S,Se)₂ absorbers prepared by electrodeposition followed by rapid thermal annealing promising to lower manufacturing cost. However the annealed material contains copper sulpho-selenide of Cu(S_y,Se_1 − y) type which is harmful for the electrical properties of photovoltaic devices. These phases are removed by a cyanide etching. Because of an intrinsic variability of absorber fabrication process, the presented survey is based on statistic approach. We highlighted the influence of a cyanide treatment on surface and bulk compositions. The surface composition follows a distribution according to a Cu(S,Se)-CuIn(S,Se)₂ system and the bulk composition agrees with Cu(S,Se)₂-CuIn₃(S,Se)₅ system. Moreover, surface composition can be modified by adjusting the cyanide concentrations of etching solution without any changes in the bulk one. It ensues that Cu(S,Se) is not only present on the surface but also in the bulk of samples.     

Phase Diagram of Antiferromagnet Film Sandwiches Between Ferromagnetic Surfaces

The Monte Carlo (MC) simulation is used to study the magnetic properties of a spin-1/2 Ising antiferromagnetic film sandwiches between two ferromagnetic surfaces. The influence of different exchange surface interactions on the phase diagram of such a film is studied. In the ordered phase, it is found that the antiferromagnetic layer of the film can change in ferromagnetic or ferrimagnetic phases, depending on the values of the surface, the perpendicular and the bulk magnetic couplings. Moreover, the sublattice magnetizations are computed as a function of temperature for a film of thickness n=10 and fixed values of magnetic couplings.     

Template-grown metal nanowires as resonators: performance and characterization of dissipative and elastic properties

Metal resonators can significantly extend the scope of nanoelectromechanical systems (NEMS) through access to a broader range of electrical, thermal, and surface properties. The material behavior of template-electrodeposited gold (Au) and rhodium (Rh) nanowires (NWs) and their performance as resonators was investigated. Nanowire integration by a bottom-up assembly scheme enabled creation of fixed-free metal beams without distortion or tension. Surprisingly, even a soft metal such as Au yielded viable nanocantilever resonators, with Q-factors of 600-950 in high vacuum, while stiffer RhNW had Q-factors of 1100-1300. NWs with diameter approximately 300 nm yield Young's modulus values of 44 +/- 12 GPa for Au and 222 +/- 70 GPa for Rh, both lower than bulk values. This observation is in agreement with two other measurement techniques.     

Laser-produced plasma measurement of thermal diffusivity of molten metals

We have shown that a laser-produced plasma plume which is representative in elemental composition of the condensed phase target can be reproducibly generated if the movement of the surface due to evaporation is kept in pace with the thermal diffusion front propagating into the bulk. The resulting mass loss is then strongly controlled by the thermal diffusivity of the target matter, and this relationship has been exploited to measure the thermal diffusivity of metallic alloys. We have developed a novel RF Ievitator-heater as a contamination-free molten metal source to be used as a target for LPP plume generation. In order to determine the mass loss due to LPP excitation, a new high-sensitivity transducer has been constructed for measurement of the resulting impulse imparted on the specimen. The impulse transducer is built onto the specimen holder within the levitation-assisted molten metal source. The LPP method has been fully exercised for measurement of the thermal diffusivity of a molten specimen relative to the value for its room temperature solid. The results for SS304 and SS316 are presented, together with a critique of the results. A numerical modeling of the specimen heating in the molten metal source and the physical basis of the new method are also presented.Paper presented at the Fourth International Workshop on Subsecond Thermophysics, June 27–29, 1995, Köln, Germany.     

Charged point defects in semiconductors

Native point defects control many aspects of semiconductor behavior. Such defects can be electrically charged, both in the bulk and on the surface. This charging can affect numerous defect properties such as structure, thermal diffusion rates, trapping and recombination rates for electrons and holes, and luminescence quenching rates. Charging also introduces new phenomena such as nonthermally photostimulated diffusion, thereby offering distinctive mechanisms for defect engineering. The present work incorporates the first comprehensive account of semiconductor defect charging, identifying correspondences and contrasts between surfaces and the bulk as well as among semiconductor classes (group IV, groups III–V, and metal oxides). For example, small lattice parameters, close-packed unit cells, and basis atoms with large atomic radii all inhibit the formation of ionized interstitials and antisites. The charged defects that exist in III–V and oxide semiconductors can be predicted with surprising accuracy from the chemical potential and oxygen partial pressure of the ambient. The symmetry-lowering relaxations, formation energies, and diffusion mechanisms of bulk and surface defect structures often depend strongly on charge state with similar qualitative behavior, although for a given material surface defects do not typically take on the same configurations or range of stable charge states as their counterparts in the bulk.     

Revealing nano-chemistry at lattice defects in thermoelectric materials using atom probe tomography

The population of all non-equilibrium lattice defects in materials is referred to as microstructure. Examples are point defects such as substitutional and interstitial atoms, and vacancies; line defects such as dislocations; planar defects such as interfaces and stacking faults; or mesoscopic defects such as second-phase precipitates. These types of lattice imperfections are usually described in terms of their structural features, breaking the periodicity of the otherwise regular crystalline structure. Recent analytical probing at the nanoscale has revealed that their chemical features are likewise important and characteristic. The structure of the defects as well as their individual chemical composition, that is their chemical decoration state, which results from elemental partitioning with the adjacent matrix, can significantly influence the electrical and thermal transport properties of thermoelectric materials. The emergence of atom probe tomography (APT) has now made routinely accessible the mapping of three-dimensional chemical composition with sub-nanometer spatial accuracy and elemental sensitivity in the range of tens of ppm. Here, we review APT-based investigations and results related to the local chemical decoration states of various types of lattice defects in thermoelectric materials. APT allows to better understand the interplay between thermoelectric properties and microstructural features, extending the concept of defect engineering to the field of segregation engineering so as to guide the rational design of high-performance thermoelectric materials.     

Magnetism in nanoclusters and cluster-assembled thin films

Increasing attention has been focused on the magnetic behavior of nanoparticles with diameters of 1-5 nm (approximately 50-5000 atoms). In this size range fundamental magnetic parameters such as the orbital and spin magnetic moments per atom deviate significantly from bulk values, and studying clusters addresses fundamental problems in mesoscopic magnetism, which is not as well understood as in either the atomic or the bulk regimes. There is also a growing realization of the enormous industrial potential of materials built by depositing preformed nanoclusters instead of atoms. If the clusters are size-selected and deposited in conjunction with an atomic vapor of a matrix material, it is possible to produce granular films in which there is independent control over the particle size and volume fraction. Using this technique, it also becomes possible to make granular mixtures of miscible materials. This unprecendented degree of control over the properties of the films holds the promise of new magnetic materials with "engineered properties." To fully realize this potential requires a greater understanding of not only the individual particles, but also how they interact in dense assemblies. There has been great progress in understanding some aspects of the magnetic behavior of nanoclusters and cluster-assembled materials. The mechanisms that generate spin and orbital moments that are enhanced by up to 36 and 200%, respectively, relative to the bulk in isolated clusters are well understood as is the dynamical behavior of the magnetic moment. Not so well understood is the observed magnetic anisotropy, which often has a different symmetry than the bulk. In dense assemblies, the nature of the interparticle coupling and the relative importance of dipolar and exchange interactions also require further research.     

Simultaneous Multitemperature Measurements of Thermal Diffusivity and Composition

It has been well established that thermal forcing of disordered multielement metallic alloys results in permanent modification of their thermal transport properties. The mechanism depends on the detail of heating and its duration, and entails rearrangement of the spatial distribution of constituent atoms within the material proper. It presents a serious complication in developing a body of properties data as a function of temperature because establishment of a thermal state for a specimen is often cast into question. A new general technique is presented for simultaneous multiple-temperature measurements of thermal diffusivity and local composition for a single specimen. The specimen is heated steeply into a state of temperature nonuniformity. The measurement is carried out by time-resolved spectroscopy of single-shot laser-produced plasma (LPP) plume emissions; analysis is made of the emissions as a function of position within the laser focal area. The procedure for analysis is presented together with the results for 80 mass% Ni-20 mass% Cr Nichrome specimens.     

Preparation of functional nanostructured particles by spray drying

When particle dimensions are reduced to the order of several nanometers, their physical and chemical properties deviate significantly from the bulk properties of such materials. Because of this, there is abundant potential for their use in future technologies including electronic and optoelectronic, mechanical, chemical, cosmetic, medical, drug, and food technologies. However, due to their extremely small sizes, the particles suffer from many problems related to their surface and thermal stability, shape preservation, handling, assembly in devices, etc. It is therefore an important challenge to solve these problems by developing slightly larger particles (e. g. on the submicrometer scale) in which the properties generated by the nanoscale material are preserved. One approach to this is to trap nanoparticles in a micrometer-sized inert matrix. This approach allows the nanoscale properties to be retained, since nanoparticles are separated from each other in the inert matrix. The inert matrix also serves as a coating medium that inhibits any chemical changes to the surface of the nanoparticles. Their larger size allows easy handling or assembly in devices. A promising method for designing and fabricating these composite structures is a spray method, in which spherical particles can be produced. In this paper, we review the nanostructural processing (synthesis) of submicrometersized particles by a spray method, which provides a restricted reaction environment (such as pores or cages) in the matrix for their synthesis and handling. The characterization and potential applications of these composites are also discussed.     

Temperature oscillation techniques for simultaneous measurement of thermal diffusivity and conductivity

Simple temperature ocillation techniques are described for the last measurement of thermal dill'usivity and conductivity of liquids. The liquid specimen is a slab bounded above and below by a reference material. Two Peltier elements mounted on the outer Surfaces of the reference layers generate temperature ocillationS of these surfaces. Temperature waves propagate tluough the reference layers into the specimen. The thermal dilhusivity of the specimen is deduced by measuring all evaluating the amplitude attenuation and or the phase shift between the fundamental temperature oscillations at the surface of the liquid specimen and at a well-defined position inside the specimen. If the thermal diffusivity of the specimen is known. the thermal conductivity is determined by the measured amplitude attenuation and or the phase shill between the fundamental temperature oscillations at the surface of the reference layer and at the surface of the specimen. Slab and semi-infinite body geometries are considered. Measurement cells are designed and experiments are carried out with water, ethanol. heptane. monane. and glycerine. The results of the measurements of thermal dilhusivity asree very well, and those of thermal conductivity reasonably well, with the data obtained from the literature.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19-24, 1994, Boulder, Colorado, U.S.A.Author to whom correspondence should be addressed.     

Hydrogen distribution in titanium materials with low outgassing property

This paper addresses a hydrogen outgassing mechanism in titanium materials with extremely low outgassing property by investigating hydrogen atoms distribution in depth around the surface in a titanium material and stainless steel. The evacuation time dependence of depth profiles of positive hydrogen ions was measured by time-of-flight secondary ion mass spectrometry (TOF-SIMS). In the stainless steel, concentration of hydrogen atoms decreases slowly at the surface oxide layer, while it decreases rapidly in the bulk by vacuum evacuation. Thus, the surface oxide layer is considered to prevent hydrogen diffusions in the bulk. On the other hand, in the titanium material, hydrogen atoms show maximum concentration at the boundary between the surface oxide layer and the bulk titanium. Moreover, concentration of hydrogen atoms decreases rapidly at the surface oxide layer, while those decrease slowly in the deep region below the surface-bulk boundary by vacuum evacuation. It is suggested that the boundary between the surface oxide layer and bulk titanium plays a role of a barrier for bulk hydrogen diffusions. These facts give very low hydrogen concentration near the surface, which results in an extremely low outgassing rate in titanium materials.     

Structure features of modified thermally extended graphite

Experimental data on microrelief, elemental composition, and distribution of the modifier over the surface of thermally extended graphite are given. Morphological changes of thermally extended graphite particles induced by the temperature and variations of distribution of cluster formations of the modifier over the thermally extended graphite particle surface depending on the concentration of the initial modifying compound are shown.