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Design, development and applications of novel techniques for studying surface mechanical properties

Research is reviewed for the adhesion, friction, and micromechanical properties of materials and examples of the results presented. The ceramic and metallic materials studied include silicon carbide, aluminum oxide, and iron-base amorphous alloys. The design and operation of a torsion balance adapted for study of adhesion from the Cavendish balance are discussed first. The pull-off force (adhesion) and shear force (friction) required to break the interfacial junctions between contacting surfaces of the materials were examined at various temperatures in a vacuum. The surface chemistry of the materials was analyzed by X-ray photoelectron spectroscopy. Properties and environmental conditions of the surface regions which affect adhesion and friction-such as surface segregation, composition, crystal structure, surface chemistry, and temperature were also studied.

Miyoshi, Kazuhisa↗

Friction and wear of some ferrous-base metallic glasses

Sliding friction experiments, X-ray photoelectron spectroscopy (XPS) analysis, and electron microscopy and diffraction studies were conducted with ferrous base metallic glasses (amorphous alloys) in contact with aluminum oxide at temperatures to 750 C in a vacuum. Sliding friction experiments were also conducted in argon and air atmospheres. The results of the investigation indicate that the coefficient of friction increases with increasing temperature to 350 C in vacuum. The increase in friction is due to an increase in adhesion resulting from surface segregation of boric oxide and/or silicon oxide to the surface of the foil. Above 500 C the coefficient of friction decreased rapidly. The decrease correlates with the segregation of boron nitride to the surface. Contaminants can come from the bulk of the material to the surface upon heating and impart boric oxide and/or silicon oxide at 350 C and boron nitride above 500 C. The segregation of contaminants is responsible for the friction behavior. The amorphous alloys have superior wear resistance to crystalline 304 stainless steel. The relative concentrations of the various constituents at the surfaces of the amorphous alloys are very different from the nominal bulk compositions.

Miyoshi, K.↗

Friction and wear of some ferrous-base metallic glasses

Sliding friction experiments, X-ray photoelectron spectroscopy (XPS) analysis, and electron microscopy and diffraction studies were conducted with ferrous base metallic glasses (amorphous alloys) in contact with aluminium oxide at temperatures to 750 C in a vacuum. Sliding friction experiments were also conducted in argon and air atmospheres. The results of the investigation indicate that the coefficient of friction increases with increasing temperature to 350 C in vacuum. The increase in friction is due to an increase in adhesion resulting from surface segregation of boric oxide and/or silicon oxide to the surface of the foil. Above 500 C the coefficient of friction decreased rapidly. The decrease correlates with the segregation of boron nitride to the surface. Contaminants can come from the bulk of the material to the surface upon heating and impart boric oxide and/or silicon oxide at 350 C and boron nitride above 500 C. The segregation of contaminants is responsible for the friction behavior. The amorphous alloys have superior wear resistance to crystalline 304 stainless steel. The relative concentrations of the various constituents at the surfaces of the amorphous alloys are very different from the nominal bulk compositions.

Miyoshi, K.↗

Heats of Segregation and Segregation Profiles of BCC Metals

The composition of metal alloy surfaces is often different from that of the bulk. Some alloys exhibit surface segregation, where one or more species reside preferentially at or near the surface. A detailed understanding of this behavior is necessary to correctly model such phenomena as adhesion or catalysis. Several phenomenological approaches to the problem have been put forward, falling into two broad categories: Thermodynamic approaches, where the equilibrium distribution of chemical species is computed. Atomistic approaches, where the tendency of a species to segregate is determined by computation of the energies of single atoms of that species in bulk and surface environments.

Good, Brian S.↗

Surface Composition of NiPd Alloys

Surface segregation in Ni-Pd alloys has been studied using the BFS method for alloys. Not only does the method predict an oscillatory segregation profile but it also indicates that the number of Pd-enriched surface planes can vary as a function of orientation. The segregation profiles were computed as a function of temperature, crystal face, and composition. Pd enrichment of the first layer is observed in (111) and (100) surfaces, and enrichment of the top two layers occurs for (110) surfaces. In all cases, the segregation profile shows oscillations that are actually related to weak ordering tendencies in the bulk. An atom-by-atom analysis was performed to identify the competing mechanisms leading to the observed surface behaviors. Large-scale atomistic simulations were also performed to investigate the temperature dependence of the segregation profiles as well as for analysis of the bulk structures. Finally, the observed surface behaviors are discussed in relation to the bulk phase structure of Ni-Pd alloys, which exhibit a tendency to weakly order.

Noebe, Ronald D.↗

Ultra-Low-Temperature Homoepitaxial Growth of Sb-Doped Silicon

An ultra-low-temperature process for homoepitaxial growth of high-quality, surface-confined, Sb-doped silicon layers is presented. Non-equilibrium growth by molecular beam epitaxy (MBE) is used to achieve dopant incorporation in excess of 2x10(exp 14) per sq cm in a thin, surface-confined layer. Sb surface segregation larger than expected from theoretical models was observed, in agreement with other experimental works. Furthermore, this work details an entirely low-temperature process (less than 450 degree C) that can be applied to fully processed and aluminum-metallized silicon devices. One application of this process is the formation of a back-surface electrode for back-illuminated high-purity silicon imaging arrays.

Molecular beam epitaxy↗

Effects of Hydrogen Annealing, Sulfur Segregation and Diffusion on the Cyclic Oxidation Resistance of Superalloys: a Review

This review is based on the phenomenon of improved oxide scale adhesion for desulfurized superalloys. The proposed adhesion mechanism involves sulfur interfacial segregation and scale-metal bond weakening. Sulfur surface segregation on superalloys is examined as a function of temperature and sulfur content and related to classical behavior predicted by the McLean isotherm. Effective desulfurization to less than 1 ppmw can be accomplished by hydrogen annealing and is governed by sulfur diffusion kinetics in nickel. Hydrogen annealing results in excellent cyclic oxidation resistance for a number of advanced superalloys. The concept of a critical sulfur content is discussed in terms of practical annealing conditions and section thicknesses.

Smialek, J. L.↗

Effects of hydrogen annealing, sulfur segregation and diffusion on the cyclic oxidation resistance of superalloys: A review

This review is based on the phenomenon of improved oxide scale adhesion for desulfurized superalloys. The proposed adhesion mechanism involves sulfur interfacial segregation and scale-metal bond weakening. Sulfur surface segregation on superalloys is examined as a function of temperature and sulfur content, and is related to the classical behavior predicted by the McLean isotherm. Effective desulfurization to less than 1 ppmw can be accomplished by hydrogen annealing and is described by sulfur diffusion kinetics in nickel. Hydrogen annealing results in excellent cyclic oxidation resistance for a number of advanced superalloys. The concept of a critical sulfur content is discussed in terms of practical annealing conditions and section thicknesses.

Smialek, J. L.↗

Effect of Various Material Properties on the Adhesive Stage of Fretting

Various properties of metals and alloys were studied with respect to their effect on the initial stage of the fretting process, namely adhesion. Crystallographic orientation, crystal structure, interfacial binding energies of dissimiliar metal, segregation of alloy constituents and the nature and structure of surface films were found to influence adhesion. High atomic density, low surface energy grain orientations exhibited lower adhesion than other orientations. Knowledge of interfacial surface binding energies assists in predicting adhesive transfer and wear. Selective surface segregation of alloy constituents accomplishes both a reduction in adhesion and improved surface oxidation characteristics. Equivalent surface coverages of various adsorbed species indicate that some are markedly more effective in inhibiting adhesion than others.

Buckley, D. H.↗

Effect of various material properties on the adhesive stage of fretting

Various properties of metals and alloys have been studied with respect to their effect on the initial stage of the fretting process, namely adhesion. Crystallographic orientation, crystal structure, interfacial binding energies of dissimiliar metal, segregation of alloy constituents and the nature and structure of surface films have all been found to influence adhesion. High atomic density, low surface energy grain orientations exhibit lower adhesion than other orientations. Hexagonal metals in general manifest less adhesive wear than cubic metal. Knowledge of interfacial surface binding energies can assist in predicting adhesive transfer and wear. Selective surface segregation of alloy constituents can accomplish both a reduction in adhesion and improved surface oxidation characteristics. Equivalent surface coverages of various adsorbed species indicate that some are markedly more effective in inhibiting adhesion than others.

Buckley, D. H.↗

Effect of various material properties on the adhesive stage of fretting

Various properties of metals and alloys have been studied with respect to their effect on the initial stage of the fretting process, namely adhesion. Crystallographic orientation, crystal structure, interfacial binding energies of dissimiliar metal, segregation of alloy constituents and the nature and structure of surface films have all been found to influence adhesion. High atomic density, low surface energy grain orientations exhibit lower adhesion than other orientations. Hexagonal metals in general manifest less adhesive wear than cubic metal. Knowledge of interfacial surface binding energies can assist in predicting adhesive transfer and wear. Selective surface segregation of alloy constituents can accomplish both a reduction in adhesion and improved surface oxidation characteristics. Equivalent surface coverages of various adsorbed species indicate that some are markedly more effective in inhibiting adhesion than others.

Buckley, D. H.↗

Adhesion, friction and Auger spectroscopy analysis of a commercial cobalt base aircraft turbine shroud alloy

A commercially used cast cobalt base alloy was investigated as a turbine shroud material which revealed a surface enriched with tungsten and carbon suggesting a surface layer of tungsten carbide. Adhesion and friction of this segregated surface layer are higher than for the bulk cobalt base alloy composition. Auger spectroscopy analysis of the segregation of tungsten in the alloy indicates that it occurs between 850 and 1000 C.

Buckley, D. H.↗

Analysis of Surface and Bulk Behavior in Ni-Pd Alloys

The most salient features of the surface structure and bulk behavior of Ni-Pd alloys have been studied using the BFS method for alloys. Large-scale atomistic simulations were performed to investigate surface segregation profiles as a function of temperature, crystal face, and composition. Pd enrichment of the first layer was observed in (111) and (100) surfaces, and enrichment of the top two layers occurred for (110) surfaces. In all cases, the segregation profile shows alternate planes enriched and depleted in Pd. In addition, the phase structure of bulk Ni-Pd alloys as a function of temperature and composition was studied. A weak ordering tendency was observed at low temperatures, which helps explain the compositional oscillations in the segregation profiles. Finally, based on atom-by-atom static energy calculations, a comprehensive explanation for the observed surface and bulk features will be presented in terms of competing chemical and strain energy effects.

Bozzolo, Guillermo↗

The Effect of Hydrogen Annealing and Sulfur Content on the Oxidation Resistance of PWA 1480

For many decades the dramatic effect of trace amounts of reactive elements on alumina and chromia scale adhesion has been recognized and widely studied. Although various theories have been used to account for such behavior, the connection between scale adhesion and sulfur segregation was initially reported by Smeggil et al. This study found strong surface segregation of sulfur from very low levels in the bulk which could then be curtailed by the addition of reactive elements. It was assumed that the reactive elements, which are strong sulfide formers, acted by getting sulfur in the bulk thus precluding sulfur segregation and weakening of the oxide-metal bond. Subsequent studies confirmed that adhesion could be produced by reducing the sulfur impurity level, without reactive elements. The understanding of this phenomenon has been applied to modern single crystal superalloys, where the addition of Y, although very effective, is problematic. Also problematic is definition of the level of sulfur that is acceptable and below which no further adhesion benefit is reached. Published works have indicated a broad transition defined by various materials and oxidation tests. The present study describes the oxidation behavior of one superalloy (PWA 1480) as a function of various sulfur contents produced by hydrogen annealing for various temperatures, times, and sample thicknesses. The purpose is to define more precisely a criterion for adhesion based on total sulfur reservoir and segregation potential.

Smialek, James L.↗

Theoretical Studies of the Surface Tension of Liquid Metal System

A major goal of this project is to understand the surface tension and other thermophysical properties of liquid metals and alloys from a fundamental viewpoint. The approach is to calculate these quantities by a first principles technique which combines the statistical-mechanical theory of the liquid state with an electronic pseudopotential theory of electrons in metals. The inhomogeneity of the surface is treated using an ionic-density-functional formalism developed with the support of NASA. Of particular interest are the variation of surface tension with temperature and impurity concentration: such variations strongly influence the types of convection which make take place in a low-gravity environment. Some progress has already been achieved in computing the reduction of surface tension due to the presence of low-surface-tension impurities, and the corresponding surface segregation of such impurities. In the coming year, it is planned to concentrate on the surface properties of materials of particular interest to the MSA program: Si, Ga and GaSn alloys. An additional goal is to gain some theoretical understanding of the high temperature thermophysical properties of liquid metals, particularly high melting point materials which have not been studied extensively from a theoretical viewpoint.

Stroud, D. G.↗

A sulfur segregation study of PWA 1480, NiCrAl, and NiAl alloys

Some nickel based superalloys show reduced oxidation resistance from the lack of an adherent oxide layer during high temperature cyclic oxidation. The segregation of sulfur to the oxide-metal interface is believed to effect oxide adhesion, since low sulfur alloys exhibit enhanced adhesion. X ray Photoelectron Spectroscopy (XPS) was combined with an in situ sample heater to measure sulfur segregation in NiCrAl, PWA 1480, and NiAl alloys. The polished samples with a 1.5 to 2.5 nm (native) oxide were heated from 650 to 1100 C with hold times up to 6 hr. The sulfur concentration was plotted as a function of temperature versus time at temperature. One NiCrAl sulfur study was performed on the same casting used by Browning to establish a base line between previous Auger Electron Spectroscopy (AES) results and the XPS results of this study. Sulfur surface segregation was similar for PWA 1480 and NiCrAl and reached a maximum of 30 at% at 800 to 850 C. Above 900 C the sulfur surface concentration decreased to about 3 at% at 1100 C. These results are contrasted to the minimal segregation observed for low sulfur hydrogen annealed materials which exhibit improved scale adhesion.

Jayne, D. T.↗

N-Type delta Doping of High-Purity Silicon Imaging Arrays

A process for n-type (electron-donor) delta doping has shown promise as a means of modifying back-illuminated image detectors made from n-doped high-purity silicon to enable them to detect high-energy photons (ultraviolet and x-rays) and low-energy charged particles (electrons and ions). This process is applicable to imaging detectors of several types, including charge-coupled devices, hybrid devices, and complementary metal oxide/semiconductor detector arrays. Delta doping is so named because its density-vs.-depth characteristic is reminiscent of the Dirac delta function (impulse function): the dopant is highly concentrated in a very thin layer. Preferably, the dopant is concentrated in one or at most two atomic layers in a crystal plane and, therefore, delta doping is also known as atomic-plane doping. The use of doping to enable detection of high-energy photons and low-energy particles was reported in several prior NASA Tech Briefs articles. As described in more detail in those articles, the main benefit afforded by delta doping of a back-illuminated silicon detector is to eliminate a "dead" layer at the back surface of the silicon wherein high-energy photons and low-energy particles are absorbed without detection. An additional benefit is that the delta-doped layer can serve as a back-side electrical contact. Delta doping of p-type silicon detectors is well established. The development of the present process addresses concerns specific to the delta doping of high-purity silicon detectors, which are typically n-type. The present process involves relatively low temperatures, is fully compatible with other processes used to fabricate the detectors, and does not entail interruption of those processes. Indeed, this process can be the last stage in the fabrication of an imaging detector that has, in all other respects, already been fully processed, including metallized. This process includes molecular-beam epitaxy (MBE) for deposition of three layers, including metallization. The success of the process depends on accurate temperature control, surface treatment, growth of high-quality crystalline silicon, and precise control of thicknesses of layers. MBE affords the necessary nanometer- scale control of the placement of atoms for delta doping. More specifically, the process consists of MBE deposition of a thin silicon buffer layer, the n-type delta doping layer, and a thin silicon cap layer. The n dopant selected for initial experiments was antimony, but other n dopants as (phosphorus or arsenic) could be used. All n-type dopants in silicon tend to surface-segregate during growth, leading to a broadened dopant-concentration- versus-depth profile. In order to keep the profile as narrow as possible, the substrate temperature is held below 300 C during deposition of the silicon cap layer onto the antimony delta layer. The deposition of silicon includes a silicon- surface-preparation step, involving H-termination, that enables the growth of high-quality crystalline silicon at the relatively low temperature with close to full electrical activation of donors in the surface layer.

Blacksberg, Jordana↗

Use of LEED, Auger emission spectroscopy and field ion microscopy in microstructural studies

Surface research tools such as LEED, Auger emission spectroscopy analysis, and field ion microscopy are discussed. Examples of their use in studying adhesion, friction, wear, and lubrication presented. These tools have provided considerable insight into the basic nature of solid surface interactions. The transfer of metals from one surface to another at the atomic level has been observed and studied with each of these devices. The field ion microscope has been used to study polymer-metal interactions and Auger analysis to study the mechanism of polymer adhesion to metals. LEED and Auger analysis have identified surface segregation of alloying elements and indicated the influence of these elements in metallic adhesion. LEED and Auger analysis have assisted in adsorption studies in determining the structural arrangement and quantity of adsorbed species present in making an understanding of the influence of these species on adhesion possible. These devices are assisting in the furtherance of understanding of the fundamental mechanism involved in the adhesion, friction, wear, and lubrication processes.

Ferrante, J.↗