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Areas of Scientific Work

1. Phase Transformation Kinetics 1.1 Analysis and modelling of solid state phase transformation kinetics 1.2 Abnormal and normal kinetics; the austenite-ferrite phase transformation 1.3 Computer simulation of phase transformation kinetics and microstructure 2. Phase transformations in Laves phases 3. Reactions and phase transformations at surfaces and interfaces 3.1 Initial oxide-film growth on bare metals and alloys 3.2 Nitriding and nitrocarburizing 3.2.1 Nitride precipitation and coarsening; coherent and incoherent diffraction effects 3.2.2 Microstructure and residual stress 3.2.3 Unexpected formation of iron nitride by gas nitriding of nanocrystalline iron films 3.2.4 Unusual and extreme elastic anisotropy of '-Fe4N and of cementite, Fe3C 3.3 Diffusion-induced phase transformation in thin films systems

3.3.1 Metal-induced crystallization; tailoring the crystallization temperature 3.3.2 Driving force for Sn-whisker growth in the system Cu-Sn 4. Central Scientific Facilit 'X-ra diffraction' (CSFX)

Introduction
The approach to understanding phase transformations has to be of both micro- and macroscopical character. Apart from understanding transformation mechanisms on an atomic scale, the challenge is to use the detailed microstructural knowledge in building 'mesoscopical' transformation models. Computer simulations of diffusion and phase transformations will be indispensable. The department is "experiment driven". Research of the type as described here requires powerful experimental methods to characterise the (changing) microstructure of materials. The department excels in the application of X-ray diffraction methods, surface analytical and calorimetric and dilatometric methods. Methodological research will also always be an im-portant part of our research activity.

1. Phase Transformation Kinetics

Scientists: Prof. Dr F. Sommer, Dr C. Bos, Prof. Dr F. Liu, Prof. Dr Y.C. Liu. Doctoral Students: R. Bauer, E.Jgle 1.1. Analysis and modelling of solid state phase transformation kinetics On the basis of a general modular model for the quantitative description of solid-state phase
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transformation kinetics it has been shown that, even if the kinetic parameters (e.g. growth exponent, activation energy) distinctly vary during the course of transformation, the transformation mechanism can be the same [Intern. Mater. Reviews 52 (2007) 573; J. Mater. Sci. 42 (2007) 573]. The applicability of the models proposed has been tested for isothermally and isoch-ronally conducted phase transformations both by numerical simulations and by application to the crystallization kinetics of amorphous alloys and the kinetics of precipitation in supersatu-rated solid solutions. 1.2. Abnormal and normal kinetics; the austenite-ferrite phase transformation Abnormal transformation kinetics, characterized by the presence of two maxima in the trans-formation rate curve (Fig. 1), was recognized upon isochronal austenite( ) -ferrite() trans-formation of an ultra-low-nitrogen (0.005 at.%N) Fe-N alloy. The main (later), normal trans-formation stage of this transformation can be well described by a model based on site satura-tion, interface-controlled growth and an appropriate impingement correction.

Fig. 1: The ferrite-formation rate, df /dt, as a function of ferrite fraction, f , for Fe- 0.005at.%N at various cooling rates. The abnormal part of the transformation is due to autocatalytic nucleation of ferritic grains in advance of the migrating /&alpha: interface, which is caused by the accommodation of misfit stain energy [Metall. Mater. Trans. A39 (2008) 2306]. The kinetics of the transformation is greatly influenced by the development of misfit stress, in flagrant contrast with usual concepts based on only chemical driving forces. An uncommon transition of diffusion-controlled to interface-controlled transformation was found and explained for the transformation in ultra-low-carbon Fe-C alloys upon isochronal cooling [Int. J. Mater. Res. 99 (2008) 925]; upon isothermal transformation subsequent interface-controlled (extremely fast) and diffusion-controlled (sluggish) growth modes could be identified and modelled successfully adopting site-saturation for both stages [Acta Mater. 56 (2008) 3833].
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1.3. Computer simulation of phase transformation kinetics and microstructure The movement of interphase boundaries during the interface-controlled phase transformation from austenite to ferrite in iron was studied by atomistic simulations. It could be concluded that (i) a single atomic jump at the interface is not the rate determining step, but, instead, the transformation rate is controlled by a series of unfavourable jumps by groups of atoms at the interface, and that (ii) the amount of excess volume associated with an interface as well as its distribution has a significant influence on interface mobility and boundary self diffusion and that the effect is stronger for the latter. [Phil. Mag. 87 (2007) 2245]. If a valid description of phase transformation kinetics is available, the challenge is to describe the evolving microstructure upon phase transformation. The aim of ongoing work is to predict the grain-size distribution and by comparison with corresponding experimentally determined data, to identify the underlying mechanisms of the phase transformation. Nearfuture work will investigate the effect of residual stresses (e.g. caused by microstructural changes) on interface movement. This work is carried out as part of the Cluster of E cellence "Simulation Technolog " at the University of Stuttgart.

2. Phase transformations in Laves phases

Scientists: Dr A. Leineweber Doctoral Students: J. Aufrecht, W. Baumann Within the Max Planck Society the inter-institutional research initiative "The nature of Laves phases" was founded in 2005 (with groups from MPI-CPfS, Dresden, MPIE, Dsseldorf, MPI-FKF, Stuttgart and MPI-MF, Stuttgart) to create a platform for experimental and theoretical investigations of intermetallic phases with strong interdisciplinary character. Within this initiative we study the mechanism and kinetics of polytypic phase transitions in Laves phases of the binary systems Ti-Cr, Hf-Cr and Nb-Cr. It was found that Lavesphase material having previously experienced a polytypic phase transformation contain specific types of stacking faults, which can be characterised using X-ray powder diffraction and high-resolution transmission electron microscopy (Fig. 2).

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Fig. 2: Stacking fault in C36-TiCr after phase transition from C14-TiCr2. The type of stacking faults in C36-TiCr2 and C36-NbCr2 is indicative of a partial-dislocation pair mechanism driving the phase transition starting hfrom a parent C14 phase.

3. Reactions interfaces

and

phase

transformations

at

surfaces

and

Scientists: Dr L.P.H. Jeurgens, Dr A. Leineweber, Dr R. Schacherl, Dr J.Y. Wang, Dr Z. Wang, Dr U. Welzel. Doctoral Students: : G. Bakradze, T. Gressmann, M. Nikolussi, E. Panda, F. Reichel, J.F. Sheng, M. Sobiech, M.S. Vinodh, M. Wohlschlgel, T. Whrle 3.1 Initial oxide-film growth on bare metals and alloys We have shown that ultrathin (< 5 nm) amorphous oxide films (Fig. 3), as well as ultrathin (< 5 nm) crystalline oxide films with an exceptionally high lattice mismatch with respect to that of the substrate [Acta Mater. 55 (2007) 6027], can be stabilized by relatively low surface and interface energies. Only above some critical oxide-film thickness, a transformation into an, according to bulk thermodynamics, more stable oxide structure is realized [Acta Mater. 56 (2008) 659]. Employing a model developed in our group [Phys. Rev. B 74 (2006) 144103], the thermodynami-cally preferred microstructures of thin oxide overgrowths on their metal substrates were pre-dicted, in very good agreement with experimental data, as function of growth temperature and orientation of the substrate (Fig. 4) [Acta Mater. 56 (2008) 659; J. Appl. Phys. 103 (2008) 093515; Surf. Interf. Anal. 40 (2008) 259; Acta Mater. 56 (2008) 4621].

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Fig. 3:HR-TEM micrograph of an amorphous Al2O3 oxide film grown on a bare Al{111} substrate by thermal oxidation for 6000 s at 373 K and pO2 = 110-4 Pa.

Fig. 4:Critical thickness up to which an amorphous oxide overgrowth is thermodynamically preferred as function of the growth temperature.

3.2 Nitriding and nitrocarburizing Nitriding and nitrocarburizing are widely used thermochemical surface treatments to greatly improve mechanical and chemical properties of iron-based materials. These treatments involve the uptake of the initially interstitially dissolved elements nitrogen and/or carbon and lead to the development of interstitial compounds as layers at the surface and/or precipitates in the matrix. This project focuses on unusual, hitherto not understood, fundamental aspects of the phase transformations involved, with an emphasis on the roles of misfit stress/distortion and the interplay of thermodynamics and kinetics. 3.2.1 Nitride precipitation and coarsening; coherent and incoherent diffraction effects The formation of alloying element nitrides leads to a long range strain field in the ferrite matrix surrounding the precipitate. Diffraction analysis of nitrided samples has revealed that separate reflections of inner nitrides are not observed and that the ferrite reflexions are extremely broadened and distorted. HRTEM investigations (see Fig. 5) show that the VN platelets are continuous, but that the atomic planes are slightly bent, and defects as dislocations can be discerned in the platelets. Because of the strong tetragonally anisotropic misfit be-tween precipitates and matrix, the coherently diffracting domain, comprising the precipitate and the surrounding matrix, can be considered as a b.c.t. "phase" (see Fig. 6). Thus the X-ray diffraction patterns obtained from such specimens originate from diffraction by a b.c.t. "phase" (VN platelets plus the surrounding tetragonally distorted ferrite) and by a b.c.c. "phase" (cubic ferrite), see Fig 6 [Acta Mater. 56 (2008) 4137].

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Fig. 5: HR-TEM for a nitrided specimen of Fe-2.23at.%V alloy. (a) VN platelet with an indication of defects (see arrows). (b) Detail of a single platelet (see arrow), revealing the bending of the lattice planes at the location of the platelet.

Fig. 6: (a) Schematic view of a VN platelet coherent with the surrounding ferrite matrix. (b) Schematic view of the contributions of the tetragonally distorted b.c.t. "phase" (VN platelet plus surrounding ferrite) and the cubic b.c.c. "phase" (cubic ferrite) to the total diffraction profile. 3.2.2 Microstructure and residual stress The precipitation of alloying-element nitrides as CrN in the matrix of iron-based substrates is usually thought to lead to compressive residual stress in the surface region, which is considered responsible for the pronounced increase of the fatigue resistance. Detailed XRD analysis of the residual stress depth profiles in nitrided Fe-Cr alloys has shown that this picture can be much too simple: highly complicated dependencies of stress on depth can occur with, unusually alternating, regions of tensile and compressive stress.

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Fig. 7: (a) Residual stress depth-profile measured for a specimen of nitrided Fe-4 wt.% Cr alloy. (b) Schematic representation of stress development upon nitriding. The residual stress depth profile development could successfully be modelled as the consequence of stress build up and relaxation processes in the microstructure: see Fig. 7 [Acta Ma-ter. 56 (2008) 1196]. 3.2.3 Unexpected formation of iron nitride by gas nitriding of nanocrystalline iron films It was surprisingly found that formation of -Fe3N1+x occurs upon nitriding of nanocrystalline iron at thermodynamic conditions at which pure '-Fe4N1-x should form according to bulk thermodynamics: see the double tangent constructions pertaining to the (/gas,) '/gas and /gas equilibria, on the basis of the Gibbs energies as function of nitrogen content, in Fig. 8.

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Fig. 8:Gibbs energies as functions of the atom fraction nitrogen, xN, for -Fe, ' and at T = 550C, p = 1 atm and r = 1 atm-1/2.

Now, due to the curvature of a (spherical) nanocrystalline particle an extra pressure p = 2 /r, with as the interfacial energy and r as the radius of the particle, acts on it giving rise to an increase in Gibbs energy (Gibbs-Thomson effect). It followed that a radius of 40nm and an interfacial energy of 1.6 J/m2 for the ' crystallites suffice to thermodynamically stabilize the phase. [Appl. Phys. Lett. 91 (2007) 141901]. 3.2.4 Unusual and extreme elastic anisotropy of '-Fe4N and of cementite, Fe3C

Many basic physical properties of the transition-metal nitrides are unknown, due to the difficulty to grow single crystals or to prepare these materials in massive solid form. By use of total-energy calculations and by comparing the results with X-ray-diffraction measurements, single-crystal elastic constants could be determined for ' iron nitride and for cementite. The results show that the interstitial atoms dissolved in the metal matrix can dramatically change the elastic properties of the phase. For '-Fe4N a reversal of the elastic anisotropy occurs with respect to fcc iron (austenite; Fig. 9a) [Acta Mater. 55 (2007) 5833] and cementite was shown to be extremely elastically anisotropic (Fig. 9b) [Scripta Mater. 59 (2008) 814].

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Fig. 9:(a)Elastic anisotropy of 'Fe4N. Reversal of the elastic anisotropy of '-Fe4N in comparison with austenite (fcc; dotted line).

Fig. 9:(b) cementite.

Elastic

anisotropy

of

3.3 Diffusion-induced phase transformation in thin films systems 3.3.1 Metal-induced crystallization; tailoring the crystallization temperature The transformation of solid silicon and germanium from its amorphous to its crystalline form is one of the most important processes in semiconductor technologies. This crystallization process is obstructed at low temperatures due to the strong, covalent bonding between the Si and Ge atoms in the amorphous solid: amorphous Si and Ge (a-Si, a-Ge) can only be crystal-lized at high temperatures around 700C. Yet, crystallization can be induced at low tempera-ture if the a-Si or a-Ge is in contact with crystalline Al. We have demonstrated, both theo-retically and experimentally, that the thickness of a thin-enough Al film (< 20 nm) on top of a-Si provides an extremely sensitive tool to tailor the crystallization temperature of a-Si, down to as low as 150C (Figs. 10 and 11).

Fig. 10:The low-temperature crystallization of a-Si in the presence of an ultrathin aluminum overlayer. Initially, grain boundaries in the Al over-layer get 'wetted' by a-Si. Beyond a critical thickness of the wetting a-Si film, crystallization can initiate at these wetted Al grain boundaries.

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Fig. 11:(a) Dependence of the crystallization temperature of amorphous silicon on the aluminum overlayer thickness: (b) In-situ observation by HRTEM of the crystallization and growth of a Si grain within an original Al grain boundary during annealing of an a-Si/Al bilayer at 150C. The temperature at which the crystallization occurs is governed by a delicate balance of the crystallization energy and the crystallization-induced changes of the interface and surface energies. This energy balance can be adjusted through a variation of the Al overlayer thick-ness, leading to a striking dependence of the crystallization temperature of a-Si on the Al overlayer thickness (Fig. 11a). This work demonstrates in general how surface and interface energetics control diffusion, wetting and phase transformations in low-dimensional systems. [Phys. Rev. Lett. 100 (2008) 125503; Phys. Rev. B 77 (2008) 045424]. 3.3.2 Driving force for Sn-whisker growth in the system Cu-Sn Sn coatings on Cu substrates are prone to the formation of Sn whiskers on the Sn surface (Fig. 12). The Cu6Sn5 formation, occurring due to preferential Cu diffusion along the Sn grain boundaries intersecting the Cu/Sn interface, is accompanied by a volume expansion and as a consequence, residual compressive stresses can be generated in the Sn thin films (Fig. 13). Near-surface stress-depth profiles for specimens which do exhibit and which do not exhibit Sn-whisker growth as obtained upon ageing at ambient temperature for specimens after one day (before whisker formation for the specimen exhibiting whisker growth) and after about 8 months (during whisker growth for the specimen exhibiting whisker growth), investigated by laboratory and synchrotron X-ray diffraction stress measurements, revealed, for the first time, a vertical stress gradient as driving force for spontaneous Snwhisker formation (Fig. 14) [Appl. Phys. Lett. 93 (2008) 011906.].

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Fig. 12:Scanning electron mi-croscopy images of Snwhiskers growing on an electrodeposited Sn coating.

Fig. 13:Illustration of the processes taking place in Sn thin films (thicknesses of several microns) deposited on Cu substrates upon ageing at ambient temperatures.

Fig. 14:Near-surface stress-depth profiles for whisker-prone and whiskerresistant specimens for an ageing time of 8 months.

4. Central Scientific Facilit 'X-ra diffraction' (CSFX)

Head: Dr U. Welzel Doctoral Students: J. Chakraborty, A. Kumar, Y. Kuru, M. Sobiech, M. Wohlschlgel The central scientific facility X-ray diffraction (CSFX) is a laboratory for powder diffraction, i.e. the diffraction analysis of polycrystalline materials. Apart from qualitative and quantitative phase analysis, a broad variety of dedicated analyses can be performed: texture analysis, (macro)stress measurements, analysis of the crystalline imperfection (i.e. analysis of the diffraction line broadening), non-ambient X-ray diffraction measurements, structure deter-mination from powder patterns, and - for thin film investigations - high resolution diffracto-metry and reflectometry. The CSFX, in an integrated way with the department Mittemeijer, is a centre of excellence in the following areas: The CSFX is world-leading in the diffraction analysis of mechanical stresses [see review J. Appl. Cryst. 38 (2005) 1], the investigation of elastic grain interaction in polycrystalline materials [see review JOM 59 (2007) 66] and line broadening analysis for the investigation of the crystalline imperfection [see review Z. Kristallogr. in press]. Diffraction instrumentation: Use of new optical components; parallel beam diffraction em-ploying laboratory diffractometers and non-ambient diffraction measurements [J. Appl. Cryst. 41 (2008) 124]. Non-ambient, in-situ diffraction: In-situ investigation of stress evolution, interdiffusion and phase formation in thin film systems [J. Appl. Cryst. 41 (2008) 428; Thin Solid Film 516 (2008) 7615].

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Fig. 15:(a) Real-time stress evolutions in (a) the Al phase and (b) the crystallized Ge phase as function of temperature during thermal cycling of an a-Ge/c-Al bilayer specimen (in situ XRD analysis). An example of the impact of our methodological research is the following (cf. also Section 3.3.3.1): The real-time evolution of stress during metal-induced crystallization (MIC) and subsequent layer exchange in amorphous a-Ge/Al bilayers was explored by in situ X-ray diffraction (XRD) analysis in the temperature range of 25 C to 250 C [Acta Mater. 2008, doi:10.1016/j.actamat. 2008.06.026] (see Fig. 15). Lateral grain growth of c-Ge at the location of the original Al sublayer occurs at the expense of the smaller nanograins of c-Ge nucleated at the location of the original a-Ge sublayer. This Ostwald ripening process at anomaly low temperatures leads to a gradual
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exchange of the positions of the Al and crystallized Ge sublayers in association with the observed stress change.

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