Papers by Author: Helmut Mehrer

Abstract: We remind the reader to some common features of metallic and oxide glasses. We then introduce the radiotracer method for diffusion studies, which can be applied for both types of glasses. We provide an overview on diffusion in metallic glasses in which we consider both types of metallic glasses – conventional and bulk metallic glasses. In the last part we discuss diffusion and ionic conduction in oxide glasses. For ionic glasses, conductivity measurements are an important complement to tracer diffusion studies. We remind the reader to the method of impedance spectroscopy. We discuss results for soda-lime silicate glasses, single alkali borate glasses and mixed alkali borate glasses and present evidence for collective jump processes in glasses.

Abstract: In this paper, a brief history of the contributions of many of the major researchers in the field of solid state diffusion is presented starting from 1829 up to the present day. People who are still making significant contributions to the field are mentioned. The authors are well aware that such an attempt is necessarily incomplete and inevitably based on personal knowledge and flavour.

Abstract: Elemental semiconductors play an important role in high-technology equipment used in industry and everyday life. The first transistors were made in the 1950ies of germanium. Later silicon took over because its electronic band-gap is larger. Nowadays, germanium is the base material mainly for γ-radiation detectors. Silicon is the most important semiconductor for the fabrication of solid-state electronic devices (memory chips, processors chips, ...) in computers, cellphones, smartphones. Silicon is also important for photovoltaic devices of energy production.Diffusion is a key process in the fabrication of semiconductor devices. This chapter deals with diffusion and point defects in silicon and germanium. It aims at making the reader familiar with the present understanding rather than painstakingly presenting all diffusion data available a good deal of which may be found in a data collection by Stolwijk and Bracht [1], in the author’s textbook [2], and in recent review papers by Bracht [3, 4]. We mainly review self-diffusion, diffusion of doping elements, oxygen diffusion, and diffusion modes of hybrid foreign elements in elemental semiconductors.Self-diffusion in elemental semiconductors is a very slow process compared to metals. One of the reasons is that the equilibrium concentrations of vacancies and self-interstitials are low. In contrast to metals, point defects in semiconductors exist in neutral and in charged states. The concentrations of charged point defects are therefore affected by doping [2 - 4].

Abstract: In this Chapter, we review knowledge about diffusion in quasi-crystalline alloys (quasicrystals). In Section 1 we first remind the reader of some major aspects of the quasi-crystalline state and in Section 2 we introduce phase diagrams with quasi-crystalline phases, for which detailed diffusion studies are available. We mention in Section 3 the more common experimental methods for diffusion studies. The diffusive motion of atoms in quasi-crystalline alloys can be studied by the same techniques used for crystalline metallic alloys and intermetallics – measurements of radiotracer diffusion and diffusion of stable isotopes and solute atoms by SIMS profiling. The best-studied quasi-crystalline alloys are icosahedral AlPdMn, icosahedral ZnMgRE (RE = rare earth metal), and decagonal AlNiCo. The major diffusion results for these quasicrystals are reviewed in Sections 4, 5, and 6. Section 7 is devoted to the pressure dependence of diffusion in quasicrystals and to a comparison of the activation volumes with those of crystalline metals. Positron annihilation studies are also mentioned, which together with activation volumes for diffusion strongly favour a vacancy mechanism in quasicrystals. The major results and conclusions are summarized in Section 8.

Abstract: In this Chapter we review knowledge about diffusion and cation conduction in oxide glasses. We first remind the reader in Section 1 of major aspects of the glassy state and recall in Section 2 the more common glass families. The diffusive motion in ion-conducting oxide glasses can be studied by several techniques – measurements of radiotracer diffusion, studies of the ionic conductivity by impedance spectroscopy, viscosity studies and pressure dependent studies of tracer diffusion and ion conduction. These methods are briefly reviewed in Section 3. Radiotracer diffusion is element-specific, whereas ionic conduction is not. A comparison of both types of experiments can throw considerable light on the question which type of ions are carriers of ionic conduction. For ionic conductors Haven ratios can be obtained from the tracer diffusivity and the ionic conductivity for those ions which dominate the conductivity.In the following sections we review the diffusive motion of cations in soda-lime silicate glass and in several alkali-oxide glasses based mainly on results from our laboratory published in detail elsewhere, but we also take into account literature data.Section 4 is devoted to two soda-lime silicate glasses, materials which are commonly used for window glass and glass containers. A comparison between ionic conductivity and tracer diffusion of Na and Ca isotopes, using the Nernst-Einstein relation to deduce charge diffusivities, reveals that sodium ions are the carriers of ionic conduction in soda-lime glasses. A comparison with viscosity data on the basis of the Stokes-Einstein relation shows that the SiO₂ network is many orders of magnitude less mobile than the relatively fast diffusing modifier cations Na. The Ca ions are less mobile than the Na ions but nevertheless Ca is considerably more mobile than the network.Section 5 summarizes results of ion conduction and tracer diffusion for single Na and single Rb borate glasses. Tracer diffusion and ionic conduction have been studied in single alkali-borate glasses as functions of temperature and pressure. The smaller ion is the faster diffusing species in its own glass. This is a common feature of all alkali oxide glasses. The Haven ratio of Na in Na borate glass is temperature independent whereas the Haven ratio of Rb diffusion in Rb borate glass decreases with decreasing temperature.Section 6 reviews major facts of alkali-oxide glasses with two different alkali ions. Such glasses reveal the so-called mixed-alkali effect. Its major feature is a deep minimum of the conductivity near some middle composition for the ratio of the two alkali ions. Tracer diffusion shows a crossover of the two tracer diffusivities as functions of the relative alkali content near the conductivity minimum. The values of the tracer diffusivities also reveal in which composition range which ions dominate ionic conduction. Tracer diffusion is faster for those alkali ions which dominate the composition of the mixed glass.Section 7 considers the pressure dependence of tracer diffusion and ionic conduction. Activation volumes of tracer diffusion and of charge diffusion are reviewed. By comparison of tracer and charge diffusion the so-called Haven ratios are obtained as functions of temperature, pressure and composition. The Haven ratio of Rb in Rb borate glass decreases with temperature and pressure whereas that of Na in Na borate glass is almost constant.Section 8 summarizes additional common features of alkali-oxide glasses. Activation enthalpies of charge diffusion decrease with decreasing average ion-ion distance. The Haven ratio is unity for large ion-ion distances and decreases with increasing alkali content and hence with decreasing ion-ion distance.Conclusions about the mechanism of diffusion are discussed in Section 9. The Haven ratio near unity at low alkali concentrations can be attributed to interstitial-like diffusion similar to interstitial diffusion in crystals. At higher alkali contents collective, chain-like motions of several ions prevail and lead to a decrease of the Haven ratio. The tracer diffusivities have a pressure dependence which is stronger than that of ionic conductivity. This entails a pressure-dependent Haven ratio, which can be attributed to an increasing degree of collectivity of the ionic jump process with increasing pressure. Monte Carlo simulations showed that the number of ions which participate in collective jump events increases with increasing ion content – i.e. with decreasing average ion-ion distance. For the highest alkali contents up to four ions can be involved in collective motion. Common aspects of the motion process of ions in glasses and of atoms in glassy metals are pointed out. Diffusion in glassy metals also occurs by collective motion of several atoms.Section 10 summarizes the major features of ionic conduction and tracer diffusion and its temperature and pressure dependence of oxide glasses.

Abstract: 800x600 Intermetallics are compounds of two metals or of metal(s) and semimetal(s). Their structures are usually different from those of the constituents. Some intermetallics are interesting functional materials, others have attracted attention as high-temperature structural materials. We remind the reader of some fundamentals of solid-state diffusion and to the major techniques for tracer diffusion measurements, interdiffusion studies and the growth kinetics of layers in solid diffusion couples. Starting from self-diffusion, which is the most basic diffusion phenomenon in any solid, the paper covers the main features of diffusion in binary intermetallics from the systems Cu-Zn, Ni-Al, Fe-Al, Mg-Al, Ni-Ge, Ni-Ga, Fe-Si, Ti-Al, Ni-Mn, Mo-Si, Co-Nb and Ni-Nb.. We illustrate the influence of phase transitions on diffusion and point out some common features of diffusion in intermetallics. We discuss in detail diffusion in silicides of iron, molybdenum and of silicides of refractory metals. We also consider aluminides of iron, nickel, and titanium and in the aluminium-magnesium system. We consider diffusion in intermetallics of the cobalt-niobium and nickel-niobium system and in in the Nb-Sn and V-Ga systems. We finish with some remarks about grain boundary diffusion in intermetallics. Normal 0 21 false false false UK X-NONE X-NONE MicrosoftInternetExplorer4 /* Style Definitions */ table.MsoNormalTable {mso-style-name:"Table Normal"; mso-tstyle-rowband-size:0; mso-tstyle-colband-size:0; mso-style-noshow:yes; mso-style-priority:99; mso-style-parent:""; mso-padding-alt:0cm 5.4pt 0cm 5.4pt; mso-para-margin:0cm; mso-para-margin-bottom:.0001pt; mso-pagination:widow-orphan; font-size:10.0pt; font-family:"Calibri","sans-serif";}

Abstract: Firstly, this paper reminds the reader of some basic facts about the glassy state, then of the various ways to produce amorphous metals with particular emphasis on the route of vitrification from the melt. Vitrification of an undercooled melt is the most important route from the viewpoint of the application of metallic glasses. We compare diffusion in some metallic glasses with related crystalline metals. Glassy metals, also called metallic glasses, comprise conventional [1] and bulk metallic glasses [2,3]. We remind the reader of the major experimental techniques for diffusion studies in metallic glasses. The paper then reviews our current understanding of diffusion in glassy metals (see also [4,5,6]), including conventional as well as bulk metallic glasses and undercooled melts. We cover the temperature dependence of diffusion in metallic glasses and discuss the spectrum of activation parameters of glassy metals and its difference to the corresponding one of crystalline metals. We mention the pressure dependence and the isotope effect and we discuss tracer diffusion and viscosity diffusion for a bulk metallic glass and its undercooled melt. Finally we mention computer simulations of atomic jump processes. The diffusion mechanism in metallic glasses differs from that in crystalline metals and involves thermally activated, highly collective (chain-like or caterpillar-like) diffusion jumps. Finally, we mention diffusion along shearbands in a plastically deformed glassy metal.

Abstract: Starting from fundamental aspects of thermal vacancies and solid-state self-and solute diffusion, this paper reviews procedures for tracer-and interdiffusion studies and of the major techniques for vacancy studies by dilatometry and positron annihilation in metals. Equilibrium vacancy and diffusion studies performed on pure iron and aluminium are mentioned at first. We also comment some peculiarities of solute diffusion in aluminium. Positron annihilation and differential dilatometry studies for Fe-Al alloys with various compositions are summarized and new experimental studies by the authors are reported for vacancy migration in Fe₆₁Al₃₉. All these studies indicate a relatively high fraction of thermal vacancies with relatively low mobility in this type of iron-aluminides as compared to pure metals. Tracer diffusion of iron and of several substitutional solutes such as Co, Ni, Cr, Mn, Zn, and In in Fe-Al from the Münster laboratory are summarized. The diffusion studies of Fe-Al cover various alloy composition between Fe₃Al and FeAl and several structures such as A2, B2 and D0₃. Interdiffusion coefficients obtained from diffusion couples between Fe-Al alloys are discussed together with Fe tracer diffusion data. The Darken-Manning equation is used to deduce Al diffusivities therefrom. The latter are hardly accessible to radiotracer experiments due to a lack of a suitable Al tracer. Diffusion of Al is slightly faster than diffusion of Fe indicating diffusion mechanisms with coupled jumps of Fe and Al atoms.

Abstract: Molybdenum disilicide (MoSi₂) is an interesting material for high-temperature applications. It has a high melting temperature, good thermal and electrical conductivity and an excellent oxidation resistance. For many years the primary use of MoSi₂ has been in heating elements, which can be used for temperatures up to 1800°C. Since the 1990s the potential of MoSi₂ as a high-temperature structural material has been recognized as well. Its brittleness at lower temperatures and a poor creep resistance above 1200°C have hindered its use as in load-bearing parts. These disadvantages may be offset at least partly by using it together with a second material in a composite or an alloy. Projected applications of MoSi₂-based materials include, e.g. stationary hot section components in gas turbine engines and glow plugs in diesel engines. For future research and development directions of MoSi₂-based composites diffusion is a crucial property because creep is closely connected with diffusion. This paper is devoted to the basic diffusion and defect properties of MoSi₂. Data of Si and Mo as well as Ge diffusion from the Münster laboratory for both principal directions are briefly summarized. For all three kinds of atoms diffusion perpendicular to the tetragonal axis is faster than parallel to it. The diffusivities of Mo in both directions are many orders of magnitude slower than those of Si and Ge. The huge asymmetry between Mo and Si (or Ge) diffusion suggests that atomic motion of each constituent is restricted to its own sublattice. Positron annihilation studies on MoSi₂ from the Stuttgart laboratory are reviewed as well. They show that formation of thermal vacancies occurs primarily on the Si sublattice but cannot exclude vacancy formation on the Mo sublattice at higher temperatures. Correlation factors for Si and Mo diffusion via sublattice vacancies in the respective sublattices of MoSi₂ have been calculated recently mainly by Monte Carlo simulation techniques and are also briefly described. Diffusion, in particular self-diffusion, is discussed in connection with literature data on high-temperature creep, which is diffusion-controlled. Grain-size effects of creep have been reported and can be attributed to Nabarro-Herring and Coble creep. Power-law creep is attributed to diffusion-controlled dislocation creep. Some details are, however, not completely understood, presumably due to a lack of theoretical concepts for creep in uniaxial, stochiometric compounds and due to missing information on grain-boundary diffusion.

Abstract: This paper reviews typical results of tracer diffusion and ionic conduction in soda-lime silicate glass and in single-alkali and mixed-alkali borate glass obtained in our laboratory and published in detail elsewhere. We have studied tracer diffusion of modifier cations and ionic conduction as functions of composition, temperature and, in the case of borate glass, also as function of pressure. We compare tracer diffusion with charge diffusion and in the case of soda-lime glass also with viscosity diffusion. The Haven ratios for soda-lime glass are temperature independent. For sodium borate glass the Haven ratio is almost temperature- and pressure-independent, whereas it decreases significantly with decreasing temperature and increasing pressure for rubidium borate glass. It also decreases with increasing alkali content. We attribute these facts to collective atomic jump events, in which several ions move simultaneously in a string-like or chain-like fashion. We also illustrate the mixed-alkali effect, which was studied by conductivity measurements and by tracer diffusion for mixed sodium-rubidium borate glasses.