Diffusion of nickel in single- and polycrystalline Cr2O3

Chromia protective layers are formed on many industrial alloys to prevent corrosion by oxidation. Their role is to limit the inward diffusion of oxygen and the outward diffusion of cations. A number of chromia-forming alloys contain nickel as a component, such as steels, FeNiCr and NiCr alloys. To ascertain if chromia is a barrier to outward diffusion, nickel diffusion in chromia was studied in both single crystals and polycrystals in the temperature range 900–1100°C at an oxygen pressure of 10^?4 atm (argon + 100 ppm O₂). A nickel film of ～35 nm thick was deposited on the chromia surface and, after diffusing treatment, nickel penetration profiles were established by secondary ion mass spectrometry (SIMS). Two diffusion domains appear in polycrystals, the first domain is assigned to bulk diffusion and the second is due to diffusion along grain boundaries. For the bulk diffusion domain and diffusion in single crystals, using a solution of Fick's second law for diffusion from a thick film, bulk diffusion coefficients were determined at 900 and 1000°C. At the higher temperature, a solution of Fick's second law for diffusion from a thin film could be used. For the second domain in polycrystals, Le Claire's model allowed the grain boundary diffusion parameter (αD _gb δ) to be established. Nickel bulk diffusion does not vary significantly according to the microstructure of chromia. The activation energy of grain boundary diffusion is slightly greater than the activation energy of bulk diffusion, probably on account of segregation phenomena. Nickel diffusion was compared with cationic self-diffusion and with literature data on Fe and Mn heterodiffusion in the bulk and along grain boundaries. All results were analyzed in relation to the oxidation process of stainless steel.     

The microstructure of the base oxide on 304L steel

304L stainless steel specimens were subjected to 168 h of oxidation in dry oxygen at 600°C. The composition and microstructure of the oxide as well as the steel near the steel–oxide interface were investigated using SEM and TEM in conjunction with EDS analysis. It was found that the first oxide layers, referred to as the base oxide, consisted of 50–100 nm-sized corundum-type grains. Each grain contained oxides of chromium, iron plus a small amount of manganese in a solid solution with the chemical formula (Cr,Fe,Mn)₂O₃. In the oxide regions closest to the steel–oxide interface, the grain center compositions varied laterally from grain to grain, with the cation balance ranging between very chromium-rich (Cr:Fe=4:1) and very iron-rich (Cr:Fe=1:8). Within each oxide grain, the chromium level was generally higher in the center than near the boundary. This was due to the much quicker diffusion of iron (compared to chromium) at and through the oxide grain boundaries than in the bulk of the oxide grains, creating iron enrichment near the oxide grain boundaries. Compositional variation with respect to the distance from the steel–oxide interface was also noted. Chromium was richer in the oxide regions closer to the steel–oxide interface than farther out in the oxide and depleted from the steel regions bordering the steel–oxide interface. Manganese was also depleted in those steel regions although hardly enriched in the oxide just outside the steel–oxide interface. Nickel was less reactive than chromium, iron or manganese and hence was virtually absent from the oxide.     

Impacts of oxygen sensitization methods on the deposition and microstructure of ternary lead chalcogenide alloys

Oxygen sensitization and incorporation of ternary lead chalcogenide PbSe_1-xTe_x thin films was investigated with two methods: adding oxygen via PbO to the bulk source alloy and post-deposition oxygen annealing. Characterization of the composition, structure, and morphology of these films confirmed that they follow Vegard's law for lattice parameter, and adding PbO to the source alloy did not impact the lattice parameter. However, adding PbO changed the electrical carrier properties observed in Hall effect measurements without forming any new oxide phase. Conversely, post-deposition annealing increased the lattice parameter due to oxygen incorporation into the lattice via interstitials in samples with appropriate grain boundary orientations. Morphological analysis revealed that PbSe_0.8Te_0.2 films demonstrated (100) texture, while PbSe_0.6Te_0.4 films demonstrated (111) texture with resulting grain boundary orientations more favorable to oxygen diffusion and incorporation. This varying oxygen incorporation from PbO source and oxygen annealing methods reveals trends that can lead to improved photodetector performance.     

Oxygen generation in anodized Ta–Cu alloys

Comparison is made of the influences of copper in the development of amorphous anodic films on Ta-Cu alloys, containing up to 57 at.%Cu, in ammonium pentaborate electrolyte at 293 K. The various films are based on tantala, with low concentrations of copper, relative to those of the alloys, since copper species migrate through the films more rapidly than Ta⁵⁺ ions and are lost to the electrolyte on reaching the film surface. Of particular interest, film growth on Ta-1.5at.% Cu alloy at 1, 0.1 and 0.01 mA cm^?2 proceeds with generation of oxygen, which is contained in nanoscale bubbles within the oxide. Bubbles are more numerous as the current density decreases. In the case of Ta-12at.% Cu and Ta-57at.%Cu alloys, the films are flawed extensively by more numerous oxygen bubbles, which are present mainly in the outer parts of the anodic films; oxygen production and film damage due to the bursting of bubbles limit the anodizing voltage to relatively low values. It is suggested that copper species modify the electron levels, and possibly structure, of the tantala-based films, thereby facilitating oxygen generation within the bulk film by oxidation of O^2- ions of the oxide.     

Oxygen diffusion in SrZrO3

Oxygen diffusion coefficients in SrZrO₃ polycrystals were determined using the isotopic exchange method with ¹⁸O as oxygen tracer. Diffusion treatments were performed at different temperatures between 1173 K and 1473 K. Oxygen diffusion profiles were established by secondary ion mass spectroscopy (SIMS). Classical diffusion equations were used to fit experimental results and to determine bulk diffusion (D_vol) and surface exchange (k) coefficients of oxygen in SrZrO₃ polycrystalline materials. From these values, bulk diffusion and grain boundary diffusion coefficients as well as oxygen surface exchange coefficients were determined. The activation energy of oxygen diffusion in the bulk is 2.1 eV, while for the diffusion in the grain boundary, 1.8 eV was found. The surface exchange reaction has an activation enthalpy of 1.2 eV.     

Surface exchange reactions and fast grain boundary diffusion in polycrystalline materials: Application of a spherical grain model

Laplace transforms of the solution functions to the diffusion equations for surface exchange reactions and fast grain boundary diffusion in polycrystalline materials of finite thickness have been derived by applying a spherical grain model. Diffusion profiles have been calculated for semi-infinite diffusion systems as well as thin films by application of numerical Laplace inversion. The surface exchange reaction at the surface of the sample (e.g. oxide ceramics) in contact with the constant diffusion source (e.g. gas phase) is assumed to be fairly slow such that the diffusion source is not in equilibrium with the surface during the diffusion anneal. Two limiting cases for the surface conditions are taken into account, viz. fast surface diffusion and a uniform ratio of the surface exchange coefficient/diffusion coefficient. The calculated profiles refer to Harrison's type-A diffusion kinetics. Apart from expressions for the effective diffusion coefficient, analogous relations for the effective surface exchange coefficient are proposed. Relaxation curves for the total amount of diffusant exchanged with the diffusion source are discussed in terms of the diameter of the spherical grains (average grain size), surface exchange coefficient, bulk and grain boundary diffusion coefficient, respectively.     

Short-Circuit Diffusion in Ceramics

This article discusses grain boundary diffusion in ceramics. It gives a brief review of the experimental data available for ionic oxides and the problems of interpretation associated with it. The fundamental differences between grain boundary diffusion in metals and ceramics are noted. Calculations of the segregation of defects and impurities to grain boundaries are discussed together with methods of calculating diffusion coefficients in these boundaries. New results for alumina and chromia are presented. The problem of defining a grain boundary width is discussed with respect to new calculations on nickel oxide.     

Study of interdiffusion of Ni/Fe layers by Auger Sputter profiling

Bulk and grain boundary diffusion of Fe into Ni films has been studied under UHV in the temperature range of ?150 to 500°C using AES and sputter profiling methods. The concentration profiles at the interface are corrected for the various broadening and damage effects inherent in ion bombardment. Grain boundary diffusion coefficients are derived on the basis of the Whipple model. The measured activation energies are 46 $\text{kcal}\text{mole}$ for bulk diffusion and 34 $\text{kcal}\text{mole}$ for grain boundary diffusion. An additional migration phenomenon not previously resolved is observed for very thin films annealed at relatively low temperatures (150–250°C). A possible mechanism involved in this initial “interface healing” is discussed.     

Characterization of surfaces by soft X-ray spectroscopy

Soft X-ray spectroscopy has important capabilities for investigating the surface region of metals and alloys. By calibrating the changes in the soft X-ray emission bands from both the metal and the oxygen, it is possible to determine the oxide thickness, the degree of oxidation, the element in the alloy with which the oxygen has combined, the relative amounts of alloying elements in the surface oxide, and the oxide state of a substrate metal that has a protective coating. For Ti-6Al-4V alloys there was an increase in surface oxygen after prebond treatment which was due to a change in the degree of oxidation rather than in oxide thickness, and the oxygen was combined with the titanium in the surface oxide. The oxygen K intensity distribution, from aluminum that was given a surface chromate treatment, showed that the oxygen is combined with the chromium. In Fe-Cr alloys there is an increase in the amount of chromium combined with oxygen relative to bulk chromium with decreasing chromium content. The oxide surface of steel with a 50 Å metal protective coating was reduced when the oxide of the protective metal coating had a heat formation greater than that of the iron oxide.     

Understanding the high temperature oxidation and ignition behaviour of two-phase Mg–Nd alloys and a comparison to single phase Mg–Nd

The oxidation kinetics and the mechanism of two-phase Mg–Nd alloys were investigated via isothermal heating experiments conducted in dry air at 500 °C for 12 h. The oxidation kinetic curves reveal improved oxidation resistance on neodymium (Nd)-containing alloys compared to pure Mg. A lower mass gain was detected at 2.5-%Nd than at 6-Nd%, which was related to the lower amount of intermetallic phase on the alloy surface. The intermetallic phase has a significant effect on the oxide growth stage. Nd₂O₃ formation on the intermetallic phases creates diffusion paths for oxygen to the metal/oxide interface, affecting both the oxidation kinetics and the oxidation resistance of the alloys. The formation of a Nd-depleted region at the subsurface due to extensive Nd oxidation at the oxide/intermetallic interface lowers the protective ability of the oxide scale. As increasing the Nd content of binary Mg–Nd alloys above 0.5 wt% shifts the alloys from single-phase region to two-phase region, it adversely affects the ignition resistance.     

Stabilization of high-pressure phases in nanocrystalline metals and alloys

It is shown experimentally that the formation of submicrocrystalline and nanocrystalline states significantly affects the stability of the high pressure hcp phase in iron-based alloys. It is established that the manganese segregation from the bulk of ɛ-phase grain to the grain boundary under high hydrostatic pressure can influence the stability of this phase in nanocrystalline alloys.     

Grain boundary ridge formation during initial high temperature oxidation of Mn/Al TRIP steel

Confocal scanning laser microscopy (CSLM) was used in real-time observation of alloy element oxidation of a Mn/Al TRIP steel in an Ar–O₂ atmosphere. CSLM images reveal a marked role of grain boundaries in the overall initial oxidation kinetics of the alloy, and consequently in the morphology of the initial surface oxide. The oxidation on the alloy surface is dominated by the formation of Mn-rich oxide ridges along grain boundary traces on the surface. Oxide ridge formation kinetics was quantified by measurements on images extracted from real-time recordings of surface oxide evolution. Oxide ridge growth was found to take place at a constant rate. Scanning electron microscopy (SEM) images of the oxidized surfaces showed homogenous oxide ridges along straight grain boundary traces and heterogeneous oxide ridges along non-straight grain boundary traces. A transport mechanism of Mn to the surface is proposed, which relies on grain boundary segregation of Mn and on a relationship between grain boundary diffusivity and grain boundary character. It is suggested that when regarding alloys with significant grain boundary segregation of a solute, separate Wagner balances for internal vs. external oxidation is required for the grain lattices and the grain boundaries, respectively.     

Kinetics characterization of the oxidation of Cu thin films at low temperature by using sheet resistance measurement

Film sheet resistance measurement was developed to obtain the oxidation kinetics of Cu thin films in the nanometer range. Cu thin films with smooth and homogenous surfaces were prepared by vacuum evaporation. Oxidation behaviour of Cu thin films at low temperatures from 180 °C to 260 °C in dry air has been studied. The results show that oxidation of Cu thin film follows a parabolic rate law with a considerable low activation energy of 0.57 eV, which is much lower than that reported for bulk Cu and the thick film. The observed rapid oxidation phenomenon may be attributed to the fast diffusion mechanism dominated by the defect-related grain boundary diffusion in thin films. PACS 07.50.-e; 73.61.-r; 82.65.+r     

Oxygen diffusion through thin Pt films on Si(100)

We have investigated the diffusion of oxygen through evaporated platinum films on Si(100) upon exposure to air using substrates covered with Pt films of spatially and continuously varying thickness (0–500 Å). Film compositions and morphologies before and after silicidation were characterized by modified crater edge profiling using scanning Auger microscopy, energy-dispersive X-ray microanalysis, scanning tunneling microscopy, and transmission electron microscopy. We find that oxygen diffuses through a Pt layer of up to 170 Å forming an oxide at the interface. In this thickness range, silicide formation during annealing is inhibited and is eventually stopped by the development of a continuous oxide layer. Since the platinum film consists of a continuous layer of nanometer-size crystallites, grain boundary diffusion of oxygen is the most probable way for oxygen incorporation. The diffusion constant is of the order of 10^–19 cm²/s with the precise value depending on the film morphology.     

Modelling of diffusion and conductivity relaxation of oxide ceramics

A two-dimensional square grain model has been applied to simulate simultaneously the diffusion process and relaxation of the dc conduction of polycrystalline oxide materials due to a sudden change of the oxygen partial pressure of the surrounding gas phase. The numerical calculations are performed by employing the finite element approach. The grains are squares of equal side length (average grain size) and the grain boundaries may consist of thin slabs of uniform thickness. An additional (space charge) layer adjacent to the grain boundary cores (thin slabs) either blocking (depletion layer) or highly conductive for electronic charge carriers may surround the grains. The electronic transport number of the mixed ionic-electronic conducting oxide ceramics may be close to unity (predominant electronic conduction). If the chemical diffusion coefficient of the neutral mobile component (oxygen) of the grain boundary core regions is assumed to be higher by many orders of magnitude than that in the bulk, the simulated relaxation curves for mass transport (diffusion) and dc conduction can deviate remarkably from each other. Deviations between the relaxation of mass transport and dc conduction are found in the case of considerably different electronic conductivities of grain boundary core regions, space charge layers, and bulk. On the contrary, the relaxation curves of mass transport and electronic conductivity are in perfect coincidence, when either effective medium diffusion occurs or the effective conductivity is unaffected by the individual conductivities of core regions and possible space charge layers, i.e. the grain boundary resistivity is negligible.     

Chemically abrupt interface between Ce oxide and Fe films

A chemically abrupt Fe/Ce oxide interface can be formed by initial oxidation of an Fe film followed by deposition of Ce metal. Once a Ce oxide layer is formed on top of Fe, it acts a passivation barrier for oxygen diffusion. Further deposition of Ce metal followed by its oxidation preserve the abrupt interface between Ce oxide and Fe films. The Fe and Ce oxidation states have been monitored at each stage using X-ray photoelectron spectroscopy.     

Interdiffusion in two-layer Pd/Ag films II. “Cold” homogenization mechanisms

Interdiffusion processes in thin epitaxial polycrystalline Pd/Ag films in the temperature range 20–500°C are studied by transmission electron microscopy, electron diffraction and electrical resistance methods. Homogenization is investigated both during condensation and under conditions of postcondensation annealing.The basic processes of homogenization associated with GB diffusion along migrating boundaries. It is found that in real polycrystal films with wide spectrum of grain sizes few mechanisms can occur simultaneously or subsequently: recrystallization induced diffusion, diffusion induced grain boundary migration, activation of bulk diffusion in fine grain clusters, bulk diffusion through interphase boundary. The conditions for prevailing one of them can be provided by changing condensation and postcondensation annealing temperatures or by choosing certain grain size.     

Application of auger ewlectron depth profile analysis to thin film interdiffusion studies

Because of its good depth resolution, the Auger electron depth profile analysis allows to investigate diffusion phenomena in thin films directly. Complicated calibration procedures, however, are needed to correct for the matrix effects inherent in the Auger method, particularly artefacts due to the sputtering process. In this paper, two types of thin-film systems are presented in order to determine diffusion coefficients from depth profiles: double-layer and periodic multi-layer film structures. Compared to the double-layer films, the multi-layer structure has the advantage of less stringent requirements on depth resolution and allows to detect smaller diffusion effects. Finally, it is shown how grain boundary and bulk diffusion data can be extracted separately from the composition profiles.     

On the surface chemical reactions of metal and oxide XPS samples at 300–400° at a high vacuum produced by oil diffusion pumps

Metal and oxide surface reactions formed by heating in the spectrometer at 300–400° at a vacuum of ca. 10^?9 Torr (oil diffusion pumps) were studied. As a result of spectral observations before and after heating, the metals studied were classified into five groups. In the first group, oxide films on the metal surface are easily evaporated because of the high vapour pressure of oxide; in the second, the oxide films are easily reduced in the spectrometer; in the third, the oxide film formed on the metal is reduced but the bulk oxide is not easily reduced; in the fourth, very stable oxide films are formed and the bulk oxide is also stable; and finally in the fifth, the oxide film formed on the metal is apparently reduced, yet the bulk oxide is very stable.     

Doping of ZrO2 by ion mixing

The morphology and structure of ZrO₂ films grown in steam-water medium on an ion-doped surface of zirconium and its E110 and E635 alloys have been studied. It has been found that the properties of oxide films are determined mostly by the conditions of ion-implantation doping at large oxidation times. It has been shown by the example of samples doped simultaneously with Al, Fe, Mo, and Y that the formation of a multiphase oxide film occurs due to the diffusion redistribution of implanted atoms during oxidation.