Focused Development of Magnesium Alloys Using the Calphad Approach**

By Rainer Schmid-Fetzer,* and Joachim Grbner

Models

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Calphad Approach
Data

Software

In traditional alloy development, experimental investigations with many different alloy compositions are performed. The selection criteria for multicomponent alloying elements and their compositions become diffuse in a traditional approach. Computational thermochemistry as used in the Calphad approach can provide a clear guideline for such selections and helps to avoid large scale experiments with less promising alloys. Thus, it is a powerful tool to cut down on cost and time during development of Mg-alloys. An overview of the Calphad method is given. As an example of applications, recent developments of new creep resistant magnesium alloys that show about 100 times less creep than the best commercial alloys are reported. Also outlined are the methods used in our long-term project of construction of the necessary thermodynamic magnesium alloy database for several alloying elements, such as Al, Li, Si, Mn, Ca, Sc, Y, and Zr, and rare earth elements (Ce, Gd, Nd), using the Calphad method combined with key experiments.
Process Simulation Direct Application

Stable & Metastable Phase Equilibria

Key Experiments

1. Introduction
The current revival of magnesium as a structural material is carried by a relatively small number of traditional Mgalloys. Compared to that, a large number of highly specialized and sophisticated aluminum alloys, not to speak of steel, was developed in an ongoing effort over the past decades. It is evident that there is an urgent need for the development of new or improved magnesium alloys if we want to fully exploit the potential of this fascinating lightweight material that also offers excellent castability, machinability, and bio-compatibility. Experiments on a technological scale for preparation and testing of new alloys are very expensive and time consuming. In view of the huge number of possible alloy components, compositions, and processing parameters, one would like to have at least an educated guess in which direction to go. In this report we want to show that thermodynamic calculations can provide much more than that. Computational thermochemistry based on the Calphad method is a modern tool that supplies quantitative data to guide the development of alloys or the optimization of materials processing.[1]

It enables the calculation of multicomponent phase diagrams and the tracking of individual alloys during heat treatment or solidification by calculation of phase distributions and phase compositions. It also allows the simulation of phase transformations during solidification of Mg-alloys, which are responsible for the development of as-cast microstructures. This can be done either by using the two simple extreme models of equilibrium solidification or Scheil solidification, or by more sophisticated models that require additional kinetic material parameters.[2] Other quantities of multicomponent Mg-alloys, important for materials processing,

[*] Prof. R. Schmid-Fetzer, Dr. J. Grbner Technical University of Clausthal Institute of Metallurgy Robert-Koch-Str. 42 D-38678 Clausthal-Zellerfeld (Germany) E-mail: schmid-fetzer@tu-clausthal.de

[**] Part of this work is supported in the Thrust Research Project SFB 390: Magnesium Technology by the German Research Council (DFG).

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WILEY-VCH Verlag GmbH, D-69469 Weinheim, 2001

1438-1656/01/1212-0947 $ 17.50+.50/0

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Schmid-Fetzer, Grbner/Focused Development of Magnesium Alloys Using the Calphad Approach are also provided by computational thermochemistry, for example the heat content, which is important for die casting, or the chemical potentials of individual alloy components, which are important for selective vaporization or oxidation. These are the basic data to understand and control the behavior of any novel or modified Mg-alloy. Large-scale experiments for new multicomponent alloys can then be focused on the most promising alloys identified in that approach. Long-term experiments with less promising alloys can be avoided. Thus, it is a powerful tool to cut down on cost and time during the development of magnesium alloys. Quantitative access to all these basic data in a consistent, numerical, and easily readable form isat least for multicomponent alloysvirtually impossible without the use of computational thermochemistry. The fundamental idea goes back to the introduction of the Calphad method by Larry Kaufman in 1970.[3] In a nutshell it is a method to calculate a myriad of data, ranging from stable and metastable phase equilibria down to the chemical potentials, from a unique set of thermodynamic model parameters of the alloy system. In the following, the foundations, applications, and recent advancements of the Calphad approach are briefly reviewed, emphasizing the predictive capability to multicomponent alloys. The ongoing long-term effort in developing a thermodynamic magnesium alloy database by modeling and key experiments is outlined. And, as an example of its application, the focused development of new creep resistant Mg-alloys is illustrated. Two generations of these new alloys, the first with

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high and the second with low scandium content, have been developed using computational thermochemistry as a powerful tool. Their creep properties are superior compared to the best commercial alloys.

2. The Calphad Approach

2.1. Foundations and Current State Phase diagrams provide the graphical presentation of the equilibrium state of a material as a function of temperature, pressure, and composition of the components. This is why they are frequently used as roadmaps for alloy design or a better understanding of the processing of materials. The thermodynamic properties of materials, such as the heat of solidification or the chemical activity of components, are also frequently used to understand, for example, metallurgical reactions of materials. These two aspects, phase diagrams and thermodynamic properties, have been treated separately for a very long time despite the fact that their fundamental interrelations had been established more than a century ago by J. W. Gibbs, whose work has been summarized by Hertz.[4] Eventually, the mathematical calculation of phase diagrams arose; some early examples between 1908 and 1970 are summarized by Kattner.[5] In 1970, Kaufman et al.[3] initiated the Calphad method (calculation of phase diagrams) with a detailed description of procedures together with a listing of computer software. The subsequent meetings of the ever

Rainer Schmid-Fetzer is Professor at the Institute of Metallurgy, Technical University of Clausthal. He graduated with a diploma in physics, earned his Dr.-Ing. degree and finished his Habilitation in the Institute of Ferrous Metallurgy and Foundry Technology at the TU Clausthal. Between 1982 and 1984 he was first Visiting Scientist and then Visiting Associate Professor at the University of Wisconsin-Madison, USA, where he became interested in functional materials. After returning to the TU Clausthal he started his research on electronic materials. In 1994 he was Visiting Scientist at the Microelectronics and Microsystems section of the Daimler-Benz Corporate Research Institute, Frankfurt. In 1997 he was Visiting Professor at the Dept. of Materials Science and Engineering, University of Wisconsin-Madison, contributing to an ongoing joint effort to develop a second generation of software for thermodynamic calculations in multicomponent systems. His research interests comprise the constitution and thermodynamics of materials, alloy development, interface reactions in bulk and thin film electronic materials, metals and composites and contacts to semiconductors. Professor Schmid-Fetzer has published over 160 papers, holds one patent, and received the Werner-Kster award of DGM in 1996. He is the current chairman of the DGM Applied Constitution Committee and vice chairman of the Alloy Phase Diagram International Commission.

Joachim Grbner studied mineralogy at the TU Stuttgart. In the Pulvermetallurgisches Laboratorium he started working in the field of thermodynamics of ceramic materials and obtained his Ph.D. at the Max Planck Institute for Metal Research in Stuttgart in 1994. He then participated in several international projects on metal themochemistry at the universities of Vienna and Barcelona. Since 1998 he works on the development of new magnesium alloys in the frame of the SFB 390 Magnesium Technology at the Institute of Metallurgy in Clausthal. During this time he contributed to the development of a multicomponent thermodynamic database for magnesium alloys.

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Schmid-Fetzer, Grbner/Focused Development of Magnesium Alloys Using the Calphad Approach growing Calphad group, organized by Larry Kaufman, soon attained the level of annual international conferences. These meetings together with the establishment of the international Calphad journal helped in the rapid development of sophisticated thermodynamic modeling procedures and their coupling to phase equilibrium calculations. One important development concerns the establishment of an acknowledged standard for the Gibbs energies of the pure elements in all their stable and metastable states,[6] based on the concept of lattice stabilities.[3,7,8] This standard is essential to enable the combination of separate assessments of binary systems to higher order systems. More advanced methods to model these unary data for elements and stoichiometric end-members of solutions have also been developed, addressing the heat capacity of crystalline phases,[9] liquid and amorphous phases,[10] enthalpy estimations for stable and metastable states,[11] enthalpies and entropies of transition,[12] k-transitions,[13] and periodic system effects.[14] Highlights of the developments of models for phases with a range of composition will be detailed in Section 2.3. This progress in thermodynamic modeling together with the capabilities of modern computational technology led to the current state of the Calphad approach, which is characterized by the following highlights. l A predictive capability allows the extrapolation of thermodynamic descriptions and phase equilibrium calculations from assessed binary systems to ternary, quaternary and higher order systems. This feature is indispensable for an application to real life alloys or processes, it will be described further in section 2.3. l Identification of key experiments drastically reduces the necessary experimental effort in multicomponent systems. Key experiments can be selected to give the maximum amount of information, either by verification of extrapolated descriptions or in assessing higher order interactions. The simultaneous evaluation of all experimental data irrespective of their type (phase equilibrium, thermodynamic data) and location in the multicomponent system is only possible with this approach and results in an internally consistent database of the entire system. l Stable and metastable phase equilibria can be calculated. By suspending individual phases, which may not form under specific conditions due to kinetic reasons, the complete metastable phase relations can be given quantitatively. l The driving forces for all phase transformations are available. l Local phase equilibria can be calculated, providing a numerical input to materials processing software, for example in solidification simulation or reactor modeling. l The reading of multicomponent phase diagrams is drastically simplified by the fact that all the interesting twodimensional sections in temperature, composition or even chemical potential can be readily calculated, plotted and read directly, instead of trying to envisage or construct them from an only graphically available set of phase diagrams and their complex projections. Moreover, for any selected individual alloy, the amounts of the phases present and their compositions can be calculated as function of temperature. It may be rather cumbersome to extract that information if only a printed set of ternary phase diagrams is given, and it is virtually impossible for quaternary or higher order systems. This powerful tool in materials research goes beyond a mere calculation of phase diagrams. This is why the term computational thermochemistry is frequently used to describe the current state of the Calphad approach. It is depicted in Figure 1 and will be detailed below.

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Calphad Approach
Models Data

Software

Stable & Metastable Phase Equilibria

Key Experiments

Process Simulation

Direct Application

Fig. 1. Sketch of the Calphad approach, combining thermodynamic modeling with key experiments and applications in an iterative database development.

2.2. Applications and Software Applications of the Calphad approach can be classified in four categories: direct applications, coupling with steady state reactor modeling, coupling with micro-kinetics, and coupling with macro-kinetics. Only the latter two require the knowledge of kinetic data of the materials system. The direct applications of information read from phase diagrams or thermodynamic equilibrium calculations started about a century ago with the first understanding of alloying behavior, microstructure development, and metallurgical reactions. These applications are far from being old-fashioned, though. Today we are able to apply quantitative phase equilibrium calculations in multicomponent multiphase materials to the development of technical alloys and also to the optimization of near-equilibrium processing conditions.[1] This goes as far as setting the electronic carrier concentration in CdTe semiconductors by annealing at appropriate partial pressures of Cd.[15] Many successful applications rely on the fact that the actual process conditions are close to equilibrium and a large number of examples covering metals, alloys, intermetallics, ceramics, semiconductors, geological materials, nuclear core materials, or even waste, and a variety of processes were given.[1] The calculations of solidification paths under equilibrium conditions or even with the popular Scheil model are also considered as very useful direct appli-

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Schmid-Fetzer, Grbner/Focused Development of Magnesium Alloys Using the Calphad Approach cations, since no kinetic data are needed when completely blocking the solid state diffusion in the Scheil model.[2] An application to the magnesium alloys AZ91 and AZ62 was given together with different experimental methods.[16] However, even materials processing far from equilibrium (such as splat cooling, mechanical alloying, and annealing of reactive thin film multilayers) requires a sound knowledge of thermodynamic data of equilibrium and metastable phases.[1719] Using the Calphad approach the driving forces for metastable phase formation or even complete metastable phase diagrams can be calculated to provide road maps for the engineering of these advanced materials. A coupling with steady state reactor modeling is done as follows. A reactor, e.g., an electric arc furnace can be modeled by splitting it up into a certain number of reactor stages. Within each stage a (local) equilibrium calculation can be performed using the thermodynamic data set of the materials system. In addition to the number of stages one has to specify the feed phases (amounts, compositions, temperatures, input stages), the enthalpy supplied/evolved or the temperature imposed on each stage, pressure of each stage, and optionally distribution coefficients of phases, which may simulate kinetic inhibitions. Steady-state equilibrium is attained by equilibrium calculations where the output of one stage is used as input of the next stage in co- and counter-current flow reactors. Convergence is usually achieved with reasonably estimated initial values for each stage obtained by separate equilibrium calculations. A nice example is the production of metallurgical grade silicon in an electric arc furnace, where the ChemSage software was used.[20] It should be noted that actual kinetic data (diffusion, fluid flow, ...) of the materials system are not necessary in this approach. The optionally imposed phase distribution coefficients are not considered as detailed kinetic data, for example, the imposed fraction of NH3 in MOCVD growth of nitride semiconductors in a simple one-stage reactor.[21] A coupling of the Calphad approach with micro-kinetics concerns mostly solid state transformations, growth or dissolution of precipitates, reactions at solid/solid interfaces, and so on. Fluid flow and heat transfer problems do not occur or are irrelevant. Thermal equilibrium is often assumed since thermal diffusion is much faster compared to species diffusion in solids. The framework of multicomponent (multiphase) diffusion is used, which requires the full data set of diffusion coefficients of all species in all phases. Possibly even the nucleation may be included with an appropriate model. The phase growth is usually assumed to be diffusion controlled. Appropriate software is designed with analytical and/or numerical methods.[1,2] Thermodynamic software and data sets are called as a subroutine to provide local equilibrium calculations and the driving forces for diffusion. These calculations yield quantitative data at locally prevailing temperature, pressure, composition, or chemical potentials. It is advisable to use the subroutine approach and not to fully integrate the thermodynamic and diffusion software. The thermochemical and phase equilibrium calculations in real systems may become rather complex and should be thoroughly tested separately for internal consistency and accuracy. A prominent example of this approach is the DICTRA software;[22] just a few applications are mentioned here for the multicomponent diffusion in steel.[22,23] Coupling computational thermochemistry with macrokinetics is at the front end of integration in materials processing software. Comprehensive simulation of dynamic, macroscale processes involving fluid flow constitute the highest level of complexity and requirement of additional system data. An example is the simulation of technical alloy casting, where three-dimensional simulations of the moving mushy solidification front, void formation at hot spots, and macrosegregation may be covered. Other aspects such as microsegregation, dendrite shape formation, and ultimately the development of microstructure is still mostly treated separately. Both aspects require thermodynamic equilibrium calculations at the core of appropriate process simulation software that tries to solve the simultaneous mass-, heat-, and momentum-transfer with moving phase boundaries.[2] Such process simulation software is working in the framework of computational fluid dynamics (CFD) or flow-sheeting. Depending on the complexity, a full set of data for the macro-kinetic description of the system may be needed, possibly including the micro-kinetic data. The current challenge is to incorporate exact thermodynamic phase equilibrium calculations into commercial software packages such as Phoenics, Fluent, Aspen, Process, and so on. To this aim a general software interface TQ (ChemApp) has been developed that allows to call the most widely used Gibbs energy minimizers as a subroutine.[1,24] An example for the casting process, where the link to thermodynamic software was programmed with another software interface, is given in the literature.[25] If the simulation of mushy zone is also included in an attempt to couple macro- and micro-kinetics, the computation time becomes a major issue.[26] Another problem is that the thermodynamic software subroutine has to be 100 % reliable and convergent for each individual complex equilibrium calculation even if starting from unrealistic initial values set by the process software. Envisaging about 105 calls of the thermodynamic subroutine, a single failure return would obstruct the process simulation. The early versions of software to calculate multicomponent phase equilibria, Solgasmix by Eriksson,[27] and to calculate (mainly binary) phase diagrams, the Lukas-programs,[28] were given away free as source code, which substantially fostered the development of the field. More general mathematical relations to calculate phase diagrams were laid out by Hillert,[29] and were eventually programmed in Thermocalc.[30] Currently a number of software packages, sometimes combined with databases, are commercially available. Frequently used are ChemSage and Fact, recently merged to become FactSage, MTDATA, Thermocalc, and a second genera-

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Schmid-Fetzer, Grbner/Focused Development of Magnesium Alloys Using the Calphad Approach tion of software, Pandat,[64] aiming at an automatic calculation of multicomponent phase diagrams without the need of user knowledge of the system. 2.3. Thermodynamic Modeling of Multicomponent Multiphase Equilibria The basic principle to find the equilibrium state of a multicomponent alloy (or system) is to minimize its total Gibbs energy, G, at constant temperature T, pressure P, and overall composition: G
0

0Y0 G0 x1 G1 x2 G0Y0 RT x1 ln x1 x2 ln x2 2  x1 x2 L0Y0 L1Y0 x1 x2 L2Y0 12 12 12

2

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x1 x2 XXX

(4)

n0 G0 = min
u

(1)

Hillert[31] pointed out the advantages of this specific formulation[32] of the power series for the excess term to the ideal solution when this equation is used for extrapolation to ternary systems. For a multicomponent solution phase with c components the following equation is used: G0 c
i1

where G is the molar Gibbs energy of any possible phase u in the system and nu is its amount. Minimization is done by distributing the given amount of alloy components onto the various available phases, subject to the overall material balance. The stable equilibrium is described by a phase assembly of all phases with nu > 0, whereas the metastable phases (nu = 0) do not materialize. Each phase has its own composition, which is generally different from the fixed overall alloy composition. We have thus to supply the functions Gu for all the phases. For the pure element i in the u phase the Gibbs energy G0Yu (T) i = Gu (T) i HiSER (2a)

xi G0Y0 RT i

c
i1

xi ln xi E GbinY0 (5)

E GternY0 E G

quatY0

XXX

The excess contributions originating from all the binary interactions (EGbin), ternary interactions (EGtern), or quaternary interactions (EGquat) are:
E

GbinY0

c1

i1 jbi

xi xj

v0

L#Y0 xi xj ij

(6)

GternY0

c2 c1 c

i1 jbi kbj

xi xj xk fL1Y0 xi ijk ijk (7)

is described by the equation G0Y0 T a b T c T ln T d T 2 e T 3 f T i

1 quatY0

L2Y0 xj ijk L3Y0 xk ijk g ijk ijk

c3 c2 c1 c i1

jbi kbj lbk

xi xj xk xl fL1Y0 xi ijkl ijkl

g T 7 h T 9

(2b) where

L2Y0 xj ijkl L3Y0 xk ijkl L4Y0 xl ijkl g (8) ijkl ijkl ijkl

where HHSER is the molar enthalpy of the stable element refi erence (SER) at 298.15 K and 1 bar. The values of the parameters a, b, c,... are usually taken from the SGTE compilation by Dinsdale.[6] Stoichiometric phases like the binary compound AmBn can be described by the relation
A Bn

ijk = (1xixjxk)/3

(9)

ijkl = (1xixjxkxl)/4

(10)

m G1X2

m n G0Y0 G0Y0 mn 1 mn 2 (3)

amn bmn T XXX

where the last two terms stand for the Gibbs energy of formation of AmBn from the pure components 1(=A) and 2(=B) in the specified reference state u. The molar Gibbs energy, Gu, of a binary disordered solution phase u, applicable for most liquids or substitutional solid solutions, is generally described as:

It is noted that in a ternary system (c = 3) dijk = 0 whereas in a quaternary system with xl 0 the same term dijk 0. Instead of Equations 7,8 one might have used seemingly simpler equations where the dijk and dijkl terms would have been omitted. The main advantage of the given formulation is that Equation 7 always reduces to the regular solution contribution if all the three L-parameters are identical: if L1Y0 L2Y0 L3Y0 L0 ijk ijk ijk ijk (11)

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then
E

GternY0

c2 c1 c

i1 jbi kbj

xi xj xk L0 ijk

(12)

even in a quaternary or higher order system. Without using the dijk term in Equation 7 a residual quantity xixjxkLijk(1 xl) would be left in quaternary. This occurrence of xl would be incompatible with the regular interaction of the three species i-j-k, correctly given in Equation 12. Such a regular interaction can be derived from thermodynamic principles assuming different pairwise ij bond energies and an ideal entropy term.[33] The same reasoning is valid for the quaternary interaction.[65] This was clearly pointed out by Hillert[31,33] and in fact the Equations 510 are just extensions of his equations. The formulation is slightly different, the present dijk (and dijkl) variables are invariant to a permutation of indices whereas Hillert's original variables (mijk) are not. It should be also noted that the ternary and quaternary interaction terms in Equations 7 and 8 provide a subregular behavior with a linear composition dependence inside the {}-bracket. No higher terms have yet been used in practice. In a predictive approach from the known binary systems to a c-component system one would not use any ternary or quaternary interaction terms. If those are used at all it certainly does not make sense to envisage a higher than the subregular order given in Equations 7 and 8. Reviewing Equations 510 it becomes evident what is really meant by the predictive capability of this approach. Let us, for simplicity, assume that we deal with a c = 4 component magnesium alloy system, which comprises, in addition to stoichiometric compounds, just two solution phases, the liquid phase L and the (Mg) solid solution. Once EGbin of the six binary edge system have been assessed, GL and G(Mg) can be calculated from Equation 5, setting EGtern = EGquat = 0. This enables equilibrium calculations in the entire quaternary alloy system. It is a general experience that the binary interactions are most prominent, that is, the higher order interactions like EGtern are usually small. In the next level of refinement these calculations can be used to identify key experiments at decisive conditions in the four ternary edge systems, either to verify that EGtern ^ 0 or to determine quantitative values. In addition, solid solutions of binary compounds into the ternary systems and true ternary compounds have to be modeled. Using both EGbin and EGtern in Equation 5 results not only in experimentally supported calculations in the ternary edge systems, it also improves the reliability of calculations in the quaternary alloy system. In the next level key experiments in the quaternary system can be identified. Experience shows that generally EGquat ^ 0 if EGbin and EGtern are described properly. This interactive approach extrapolative calculations key experimentssupported modeling is also useful during assessment of the EGbin of individual binaries. In ternary

or higher order systems, however, it is indispensable considering the huge number of possible experimental conditions that cannot be handled by a plain trial and error approach, due to limited resources. More complex solution phases require models that take the specific physical nature of the interactions between the components and/or the crystalline structure of the phase into account. This reduces the number of adjustable parameters and can provide realistic functional behaviors, which are out of the scope of Equation 4, such as a sharp bend in the Gux curve. A classical example is the WagnerSchottky model[34] for ordered intermetallic phases, which derives the composition dependence of the Gibbs energy from the generation and interaction of point defects in the perfect crystal. Substantial progress had been made on the thermodynamic modeling of solutions,[35] specifically for liquids,[36] selected intermetallic compounds,[37] orderdisorder phase transitions,[38] oxides,[39] electronic materials,[40] and more advanced models for the composition dependence of intermediate phases.[41]

3. Magnesium Database Development

3.1. Thermodynamic Modeling In order to use the Calphad approach as a tool in magnesium alloy design, a high quality thermodynamic database for Mg-alloys is needed. Development of a reliable thermodynamic database for multicomponent alloys requires a combination of experiments and computational thermochemistry with a feedback of data from alloy application. Since numerous binary and ternary subsystems have to be treated and validated with key experiments before multicomponent alloys can be calculated reliably, this development becomes a longterm project. In our group a thermodynamic database for several alloying elements, e.g., Al, Li, Si, Mn, Ca, Sc, Y, Zr and rare earth elements has been under construction for more than six years and is still ongoing. The base of this 13-component system are the binary systems. Figure 2 gives an overview of the necessary systems and the current state of assessment. Highlighted in the first column are the included elements. Also shown are the current quaternary aim systems Al-Mg-Li-Si and Mg-Mn-Sc-RE (with RE = Ce, Gd, Sc, and
Al-Ca Al-Ce Al-Gd Al-Li Al-Mg Al-Mn Al-Nd Al-Sc Al-Si Al-Y Al-Zn Al-Zr Ca-Ce Ca-Gd Ca-Li Ca-Mg Ca-Mn Ca-Nd Ca-Sc Ca-Si Ca-Y Ca-Zn Ca-Zr Ce-Gd Ce-Li Ce-Mg Ce-Mn Ce-Nd Ce-Sc Ce-Si Ce-Y Ce-Zn Ce-Zr Gd-Li Gd-Mg Gd-Mn Gd-Nd Gd-Sc Gd-Si Gd-Y Gd-Zn Gd-Zr Li-Mg Li-Mn Li-Nd Li-Sc Li-Si Li-Y Li-Zn Li-Zr Mg-Mn Mg-Nd Mg-Sc Mg-Si Mg-Y Mg-Zn Mg-Zr Mn-Nd Mn-Sc Mn-Si Mn-Y Mn-Zn Mn-Zr Al-Li-Si Nd-Sc Nd-Si Nd-Y Nd-Zn Nd-Zr Al-Mg-Li Sc-Si Sc-Y Sc-Zn Sc-Zr Al-Mg-Si Si-Y Si-Zn Si-Zr Mg-Li-Si Y-Zn Y-Zr Mg-Mn-Sc Zn-Zr Al-Mg-Li-Si Mg-Mn-RE Mg-Sc-RE Mg-RE-Mn-Sc Mn-Sc-RE Gray: done RE = Ce, Gd, Y light: missing
Fig. 2. The binary systems of the currently developed 13-component Mg-alloy database and some selected multicomponent systems.

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Schmid-Fetzer, Grbner/Focused Development of Magnesium Alloys Using the Calphad Approach Y).78 independent binary systems are necessary as basis for a 13-component system. 26 of them could be taken from literature and included in our database after checking the consistency. For 23 binary systems the thermodynamic descriptions were created by our group. These systems with existing consistent thermodynamic data sets are marked with a gray background in Figure 2. Two main paths for the current Mgalloy development are indicated by arrows. The first group of alloys are Li-containing, aiming at a further density reduction and improved ductility. The second group with Sc and REadditions aims at increased creep resistance. In this paper the second group is discussed as an example of focused alloy development. To create the thermodynamic phase descriptions the Calphad method is used as given above and depicted in Figure 1. After critically reviewing the experimental data and selecting the appropriate models for all phases, the actual determination of the thermodynamic parameters (e.g., the amn, bmn, or Lm,u) is done by multidimensional least square opij timization. This optimization is, depending on the complexity of the system, stepwise until finally all parameters of that system are optimized simultaneously taking all the experimental information (phase equilibria and thermodynamic quantities) into account. 3.2. Key Experiments Coupled with Modeling and Applications In Mg-systems the experimental literature data were very sparse in both phase diagram data and thermodynamic properties. Only a few ternary system were investigated in more detail and calculated thermodynamically.[42,43,44] An attempt to apply these calculations for alloy development was published.[45] Several experimental methods are being applied in our group to produce a sufficient experimental basis for a multicomponent Mg-database. For preparation of highly reactive and evaporating alloys containing Mg, Li, and Ca the levitation melting technique was adapted. The main advantages are crucible free melting, suppressing of evaporation with protective gas overpressure, and visual control of energy supply to avoid overheating. Other preparation methods include arc and electron beam melting for extremely high melting intermetallic phases, see Table 1.
Table 1. Methods for key experiments in Mg-database development

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Fig. 3. Cross section of a sealed tantalum crucible used for experiments with liquid Mg alloys.

During thermal analysis (DTA) the alloys were protected in a sealed tantalum crucible, Figure 3. The development of techniques for producing these crucibles and sealing the lids free of micro-cracks were found to be essential for reproducible DTA measurements of these highly reactive and easily vaporizing alloys. For phase and crystal structure analysis Xray diffractometry at room and high temperature, electron microscopy, and metallography are also used in a combined approach. These techniques have been applied in our work on ternary and quaternary alloy systems for improvement of creep resistance,[46] thermal stability, spray forming (Mg-Mn-Sc-RE, Mg-Al-Ca-RE) and density reduction (Mg-Li-Al-Si, Mg-AlCa-Si).[47,48] Thermodynamic descriptions supported by experimental work of several subsystems were published for Mg-Sc,[49] Mn-Sc,[50] Al-Sc,[51] Al-Gd-Mg,[52] Gd-Li-Mg,[53] Ca-Li-Mg,[54] Al-Li-Si,[55,56] and Al-Ca.[57] The thermodynamic and technical application of the ternary Al-Mg-Sc system was also discussed.[58,59] In the following the new cerium containing quaternary system Mg-Mn-Sc-Ce together with Mg-Mn-Sc-Gd, Mg-MnSc-Y, and Mg-Mn-Sc-Zr are shown as example for the selection of new creep resistant alloys using computational thermochemistry. More details of alloy selection in the quaternary systems Mg-Mn-(Sc, Gd, Y, Zr) will be published soon.[60]

4. First Generation of Creep Resistant Ternary Mg-Mn-Sc-(Ce) Alloys

4.1. Ternary Mg-Mn-Sc Alloys Investigations started with binary Mg-Sc alloys. Scandium was chosen for precipitation hardening because of its large solubility in (Mg) and the retrograde solubility at lower temperatures. The binary phase diagram had to be re-investigated,[61] it is shown in Figure 4. However, binary MgSc precipitates form very slowly during aging and improve the mechanical properties only slightly because of their incoherent interface. Therefore, Mn was added as second alloying element. The precipitation of Mn2Sc was predicted by thermodynamic calculations. Mn2Sc precipitations form coher-

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1600 1400 1200

Temperature [C]

Temperature [C]

DTA on Heating DTA on Cooling Single Phase Two-Phase limits [97Vos] [69Bea]

800

L L + Mn2Sc

L + Mn2Sc + Sc L + (Mg) + Mn2Sc

1000 800 600 400 200 0

Liquid

600

(Sc)
(Mg)

400

(Mg) + Mn2Sc + CeMg12

(Sc)

200

MgSc
0 20 40 60 at. % Sc
[61]

(Mg) + Mn2Sc + CeMg12 + MgSc

Mg

80

100

Sc

Fig. 4. The binary Mg-Sc phase diagram.

4.2 Ce 1.5 Mn 94.3 Mg 0.0 Sc

10

wt.% Sc

4.2 Ce 1.5 Mn 79.3 Mg 15.0 Sc

ently and were found to be very efficient for improving creep resistance and hardness. New MgSc15Mn1 or MgSc6Mn1 alloys show about 100 times better creep resistance than the best commercial WE43 alloy at 350 C and 30 MPa.[46] In spite of the good properties of this first generation of Mg-Mn-Sc alloys, the high cost of Sc addition (6 wt.-% Sc or more) initiated a search for a second generation by investigating quaternary systems. Additional alloying elements Ce, Gd, Y, and Zr were considered for this purpose to achieve a sufficient quantity of suitable precipitates to improve mechanical properties using a minimum of expensive alloy element addition. These element combinations Mg-Mn-(Sc, Ce, Gd, Y, Zr) form a variety of quaternary systems and within those there is a huge amount of possibilities to select alloy compositions. Therefore phase diagram and other calculations were performed to identify promising candidates. 4.2. Alloy Selection in the Mg-Mn-Ce-Sc System For a first alloy selection several vertical sections of phase diagrams in various ranges of Mn and Ce were calculated. For practical reasons the Mn content was limited at 1.5 wt.-%. First, alloys were cast with 3 to 5 wt.-% Ce and up to 15 wt.-% Sc. The reason for the addition of these high alloying elements was the lack of knowledge about the amount and the mechanical effect of the precipitations that are possibly formed during heat treatment. The calculated quaternary phase equilibria are presented in two-dimensional sections with constant Mn and Ce content. Figure 5 shows a Tx section with constant Mn and Ce content (1.5 wt.-% Mn, 4.2 wt.-% Ce) for Sc contents varying from 015 wt.-%. Primary crystallization of Mn2Sc phase can be observed for a wide range of higher Sc contents. The L + Mn2Sc phase field and several different solid phases stable at lower temperatures can be seen.

Fig. 5. Phase diagram section with 4.2 wt.-% Ce, 1.5 wt.-% Mn, and Sc content from 015 wt.-%. Dotted line indicates the MgCe4.2Mn1.5Sc6.3 alloy.

A large variety of phase diagram sections can be calculated using the thermodynamic database. At this point the question of how to identify promising alloy candidates from all these calculated diagrams becomes important. Which phase diagram features are related to which alloy processing steps? What is needed is a list of beneficial phase diagram features, derived from the relevant alloy processing steps. The most important of these points are given in Table 2, they are applied in the following discussion. Figure 6 shows the phase amounts during equilibrium solidification for an alloy with 1.5 wt.-% Mn, 4.2 wt.-% Ce, and 6.3 wt.-% Sc, indicated by the dotted line in Figure 5. Small amounts of primary Mn2Sc and significantly larger amounts of CeMg12 are expected in this alloy. In fact, in the micrograph of this alloy after T5 heat treatment (aged after casting) finegrained Mn2Sc as well as larger crystals of CeMg12 can be seen in Figure 7.[62] It will be shown later that the finely distributed Mn2Sc particles have a very positive effect. One alloy with higher Sc content was studied to promote the favored Mn2Sc precipitations. The calculated phase amounts in Figure 8 for an alloy with 1.5 wt.-% Mn, 3.2 wt.-% Ce, and 9.0 wt.-% Sc show

Table 2. Beneficial phase equilibrium features and their relevance for (Mg)-alloy processeing

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900

900

Mn2Sc

Mn2Sc

(Mg)

liquid

(Mg)

liquid

Temperature [C]

Temperature [C]

600

600

CeMg12

CeMg12

300

(Mg)

300

(Mg) MgSc

MgSc
0 0 0.2 0.4 0.6 8 1.0

0 0 0.2 0.4 0.6 0.8 1.0

Phase amounts [mol]

Fig. 6. Calculated equilibrium phase amounts for the MgCe4.2Mn1.5Sc6.3 alloy.

Phase amounts [mol]

Fig. 8. Calculated equilibrium phase amounts for the MgCe3.2Mn1.5Sc9.0 alloy.

no remarkable differences to the alloy with 6.3 wt.-% Sc in Figure 6. The low-temperature formation of MgSc should be disregarded because of the very slow kinetics and the incoherence of this precipitate. In other words the higher Sc-content does not substantially improve the calculated amount of mechanically efficient precipitates. In fact, the mechanical properties of this alloy with 9 wt.-% Sc show no remarkable difference to that with 6.3 wt.-% Sc.[62] The amount of the favored Mn2Sc particles is mainly controlled by the Mn-content. Therefore the Sc-content could be decreased to economically and technically suitable amounts and possibly be supported by precipitates stemming from cheaper rare earth element additions. In a second generation of creep resistant alloys, promising quaternary candidates were selected primarily by computational thermochemistry.

5. Second Generation of Creep Resistant, Low Scandium Alloys

5.1. Alloy Selection in the Mg-Mn-Sc-Gd System Several vertical sections in the quaternary Mg-Mn-Sc-Gd system were studied in the ranges of 01.5 wt.-% Mn, 010 wt.-% Sc, and 010 wt.-% Gd. The calculated quaternary phase equilibria are presented in two-dimensional sections with constant Mn and Gd content. Figure 9 shows a Tx section with constant Mn and Gd content (1 wt.-% Mn, 5 wt.-%

800

L (liquid) L + (Mg)
600

L+ Mn2Sc

Temperature [C]

(Mg)
(Mg) + Mn12Gd

(Mg) + Mn23Sc6

(Mg) + Mn2Sc

400

200

(Mg) + Mn12Gd (Mg) + Mn2Sc + + GdMg5 GdMg5 + Mn23Sc6 + Mn23Sc6

0.2 0.4

(Mg) + Mn2Sc + GdMg5

(Mg) + Mn2Sc + GdMg5 + MgSc
0.6 0.8
5.0 Gd 1.0 Mn 93.0 Mg 1.0 Sc

0
5.0 Gd 1.0 Mn 94.0 Mg 0.0 Sc

wt.% Sc

Fig. 7. Micrograph of MgCe4.2Mn1.5Sc6.3 alloy (T5 heat treated).[62]

Fig. 9. Phase diagram section with 5 wt.-% Gd, 1 wt.-% Mn, and Sc content from 01 wt.-%. Dotted lines indicate the MgGd5Mn1Sc0.3 and the MgGd5Mn1Sc0.8 alloy.

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Schmid-Fetzer, Grbner/Focused Development of Magnesium Alloys Using the Calphad Approach Gd) for Sc contents varying from 01 wt.-%. A preferable primary solidification of (Mg), a large one-phase field of (Mg) and several different solid phases stable at lower temperatures can be seen. For an alloy with 1 wt.-% Mn, 5 wt.-% Gd, and 0.8 wt.-% Sc (indicated by the right dotted line in Fig. 9) equilibrium phase amounts during solidification and heat treatment are given in Figure 10. At the liquefaction temperature of 650 C, primary (Mg) is formed and consumes the melt totally down to the solidification point at 619 C. At 590 C the first precipitate Mn2Sc starts forming, which can be seen in the inset of Figure 10. Large amounts of the second precipitate GdMg5 start forming at 425 C. Similar positive features are observed for an alloy with only 0.3 wt.-% Sc. The equilibrium phase amounts during solidification and heat treatment for the alloy with 1 wt.-% Mn, 5 wt.-% Gd, and 0.3 wt.-% Sc (indicated by the left dotted line in Fig. 9) are given in Figure 11. The Mn23Sc6 phase is formed as first precipitate in the solid state. Both alloys fulfill all features illustrated in Table 2 and were classified as very promising for further large scale creep experiments. In fact, first results of these alloys show a creep resistance similar to the previous ternary high-scandium Mg-Mn-Sc alloys, i.e., about 100 times better than commercial WE43 alloys at 350 C and 30 MPa, see further.
800

REVIEWS

800

(Mg)
Temperature [C]
600 800 600 400 400 200

liquid

(Mg)
Mn23Sc6 GdMg5 Mn2Sc
0 0.02 0.04 0.06 0.08 0.1

liquid

GdMg5

200

0 0 0.2 0.4 0.6 0.8 1.0

Phase amounts [mol]

Fig. 11. Calculated equilibrium phase amounts for the MgGd5Mn1Sc0.3 alloy.

800

L + (Mg)
600

L (liquid)

L+ Mn2Sc

Temperature [C]

(Mg) + Mn12Y
400

(Mg)

Mn2Sc + Mn12Y (Mg) + Mn2Sc + Mg24Y5

(Mg)
600 800 600 400 400 200

liquid

(Mg) + (Mg) + Mn12Y + Mg24Y5 (Mg) + Mn2Sc + Mn12Y + Mg24Y5

0.4 0.6

Temperature [C]

(Mg)
Mn2Sc
liquid

200

GdMg5 MgSc
0 0.02 0.04 0.06 0.08 0.1

(Mg) + Mn2Sc + Mg24Y5 +MgSc

0.8

GdMg5

200

5.0 Y 1.0 Mn 94.0 Mg 0.0 Sc

0.2

(Mg)

wt.% Sc

5.0 Y 1.0 Mn 93.0 Mg 1.0 Sc

Fig. 12. Phase diagram section with 5 wt.-% Y, 1 wt.-% Mn, and Sc content from 01 wt.-%. Dotted line indicates the MgY5Mn1Sc0.8 alloy.

0 0 0.2 0.4 0.6 0.8 1.0

Phase amount [mol]

Fig. 10. Calculated equilibrium phase amounts for the MgGd5Mn1Sc0.8 alloy.

5.2. Alloy Selection in the Mg-Mn-Sc-Y System In the Mg-Mn-Sc-Y system several vertical sections in the ranges of 01.5 wt.-% Mn, 010 wt.-% Sc, and 010 wt.-% Y were studied. Figure 12 shows a Tx section of a calculated quaternary phase diagram with constant Mn and Y content (1 wt.-% Mn, 5 wt.-% Y) for Sc contents varying from 01 wt.-%. A large one-phase field of (Mg) and several differ-

ent solid phases stable at lower temperatures can be seen, e.g., in the corresponding diagram for Gd. Differences compared to the Gd system can be observed concerning the stable solid phases and the formation temperatures. In the whole range of primary crystallization of (Mg) the secondary phase is Mn12Y. The desired Mn2Sc precipitate forms only at temperatures below 500 C or even lower with decreasing Sc content. For an alloy with 1 wt.-% Mn, 5 wt.-% Y, and 0.8 wt.-% Sc, indicated by the dotted line in Figure 12, phase amounts during equilibrium solidification are given in Figure 13. At the liquefaction temperature 644 C, primary (Mg) is formed and consumes the melt totally down to the solidification point at 613 C. The Mn12Y phase is only stable in the solid state in a

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800

5.3. Alloy Selection in the Mg-Mn-Y-Zr System

REVIEWS

(Mg)
600 800

liquid

Temperature [C]

(Mg)
Mn12Y Mn2Sc Mg24Y5 MgSc
0 0.02 0.04 0.06 0.08 0.1

600 400 400 200

liquid

Mg 24Y5

0 0 0.2 0.4 0.6 0.8 1.0

Phase amount [mol]

Fig. 13. Calculated equilibrium phase amounts for the MgY5Mn1Sc0.8 alloy.

high temperature range from 605 to 322 C and may not form at all during fast cooling. The established Mn2Sc and the new Mg24Y5, even in very large amount, could form by aging in a favorable temperature range. This makes MgMn1Y5Sc0.8 also a promising alloy. In order to check if the amount of Mn2Sc could be raised by increasing the manganese content to 1.5 wt.-%, we can examine Figure 14 for the alloy MgMn1.5Y5Sc0.8. This alloy is disqualified since Mn2Sc forms as the primary phase from the liquid, clearly seen in the inset of Figure 14. (Mg) forms only secondary, and even Mn12Y forms as a tertiary phase during solidification. Such a microstructure cannot be repaired by heat treatment. It would be difficult to envisage such a drastic change caused by raising the Mn-content from 1.0 to 1.5 wt.-% without the thermodynamic calculations.
800

(Mg)

200

For complete substitution of expensive scandium, zirconium was checked as a possible alloying element. The impact of such a substitution can be seen in Figure 15 for scandiumfree alloys with 1 wt.-% Mn, 4.5 wt.-% Y, and 01 wt.-% Zr. This phase diagram section shows a very steeply rising liquefaction line, 1000 C are reached for less than 0.1 wt.-% Zr. Moreover, and actually the reason for the steep liquefaction line, a huge primary crystallization field, L + Mn2Zr, stretches over the entire composition range in Figure 14. Only for extremely small Zr-additions, not discernible in Figure 15, is a primary (Mg) solidification expected. The reason for this destructive phase diagram feature is the extremely high thermodynamic stability of Mn2Zr in comparison to the other phases. Since yttrium does not play a significant role in that part, the only way to diminish the L+Mn2Zr primary field would be a drastic reduction of the manganese content. But this would also drastically reduce the amount of beneficial Mn-containing precipitates. As a result, the entire quaternary Mg-Mn-Y-Zr alloy system is disqualified. 5.4. Defining the Commercial Creep Resistant Benchmark Alloy In order to assess the results on the creep resistance measurements of the selected new alloys a commercial alloy has to be chosen as a benchmark. The history of commercially developed creep resistant alloys is briefly summarized in Table 3. These alloys usually contain about 0.7 wt.-% Zr as a grain refiner. The influence of the rare earth elements (RE) on the creep resistance generally decreases in the series Nd (Pr) > Ce > La.[63]

1000

L (liquid)
800

600

Temperature [C]

(Mg)
800

L + Mn2Zr
L + (Mg) + Mn2Zr

liquid

600

Temperature [C]

Mn2Sc
400 600 400 200

(Mg)

Mn12Y Mn2Sc

liquid

400

(Mg) + Mn2Zr + Mn12Y

(Mg) + Mn2Zr

200

Mg 24Y5

0 0 0.2

MgSc
0.02 0.04 0.06 0.08 0.1 0.4 0.6 0.8

(Mg)

Mg24Y5

200

(Mg) + Mn2Zr + Mn12Y + Mg24Y5

0.2 0.4 0.6 0.8

(Mg) + Mn2Zr + (a Zr) + Mg24Y5

0 0

Phase amount [mol]

1.0

4.5 Y 1.0 Mn 94.5 Mg 0.0 Zr

wt.% Zr

4.5 Y 1.0 Mn 93.5 Mg 1.0 Zr

Fig. 14. Calculated equilibrium phase amounts for the MgY5Mn1.5Sc0.8 alloy. This alloy contains only 0.5 wt.-% Mn more than that in Figure 13 but shows unfeasible primary solidification of Mn2Sc.

Fig. 15. The phase diagram section with 5 wt.-% Y, 1 wt.-% Mn, and Zr content from 01 wt.-% shows detrimental primary solidification of Mn2Zr in the entire composition range These alloys cannot be completely molten under technical conditions.

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Table 3. Commercial creep resistand Mg-alloys

1.0

T=350C, =30 MPa

110 s WE43
-6 -1

0.8

strain [%]

0.6

0.4

MgCe4Mn1Sc6 MgMn1Sc15 MgCe3Mn1Sc9 MgMn1Sc6 1 10 s-1

-8

0.2

20

40

The current end point of commercial alloys is given by the WE series containing Y and rare earth elements. In fact, the maximum stress that can be tolerated at 200 C for 100 h and 0.2 % elongation is highest for the WE series as shown in Figure 16. The alloy WE43 with T6 heat treatment was chosen as the benchmark alloy. Die casting alloys such as AE42 or AS21, known to be more creep resistant than standard AZ or AM alloys, are not included in the comparison since they rank even below the ZE alloys in Figure 16.

time [103 s]

60

80

Fig. 17. Creep curves of first generation (high scandium) alloys at 350 C after T5 treatment[62] compared to the WE43 benchmark.

6. Alloy Preparation and Creep Resistance Measurements

6.1. First Generation of Mg-Mn-Sc-(Ce) Alloys The most promising alloy compositions identified by the thermochemical calculations were prepared by squeeze casting by our project partners within the Thrust Research Project SFB 390, Magnesium Technology, at the TU Clausthal. Yield strength and creep rates of these alloys were measured in the as-cast condition and also after heat treatment.[62] It is clearly seen from Figure 17 that the secondary creep rate at 350 C of our first generation (high-scandium) alloys is better by a factor of 100 compared to the WE43 benchmark alloy.

The first generation of alloys showed a strong annealing response due to the formation of the Mn2Sc precipitates. The existence of the Mn2Sc precipitates was confirmed by X-ray diffraction, SEM and TEM investigations and energy dispersive X-ray microanalysis. A micrograph showing finely dispersed Mn2Sc precipitates in a MgSc6Mn1 alloy after T5 treatment is shown in Figure 18.[62] At 400 C an increase of the secondary creep rate can be observed for the Ce-containing alloys, Figure 19. This disadvantage is partly compensated by higher creep ductility caused by significant grain boundary gliding in the Ce-containing alloys.[62] Comparing Ce-containing alloys with different Sc-content, no significant change in the creep rate can be observed, Figure 20. The result is in line with the calculations in section 4.2 and the minimized Sc-contents of the second generation alloys.

[MPa]

180 160 140 120 100 80 60

165

161

Load 100 h, 200C

T4 solution heat treated T5 aged T6 solution h.tr. + aged

Yield strength, R

p0, 2 00, 00 , 1 2

88 52

40
20 0 WE54 T6 WE43 T6 QE22 T6 ZE41 T5

12

AZ81 T4

Alloy
Fig. 16. Creep properties of commercial magnesium alloys. Fig. 18. Micrograph of MgSc6Mn1 (T5) alloy.[62]

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T=400C, =30 MPa

10

T=350C, =30 MPa

15

9.710 s
-5
8

-1

WE43
-1

WE43 T6

strain [%]

-5

strain [%]

1.610 s MgCe3Mn1Sc9
6

MgY4Mn1Sc1 F
10

MgGd10Mn1Sc0.8 F

3.310 s
-6

-1

MgCe4Mn1Sc6 1.9 10 s-1

-7

110 s
-6

-1

MgGd5Mn1Sc0.3 F
-8 -1 3 to 610 s

MgMn1Sc15 -6 2.4 10 s-1

0 5 10

MgMn1Sc6
0

15

time [10 s]

20

10

time [10 s]

15

Fig. 19. Creep curves of first generation (high scandium) alloys at 400 C[62] compared to the WE43 benchmark.

Fig. 21. Creep curves[62] of second generation (low scandium) alloys, identified by the Calphad approach, compared to the WE43 benchmark. The alloy with only 0.3 wt.-% Sc shows best properties, see also Figure 11.

T=350C, =30 MPa

1.0

0.8

110 s WE43
-6 -1

7. Conclusions
Focused magnesium alloy development is possible using the powerful tool of thermodynamic calculations. Alloy compositions with promising possibilities of alloy microstructure design can be selected by means of thermodynamically calculated phase diagrams, phase amount charts, and solidification curves. Most importantly, element combinations and compositions with unwanted properties can be recognized before starting large-style experiments, thus reducing the experimental effort to a reasonable volume. The next step, the experimental study of mechanical properties of identified promising alloys, has shown excellent results both in the first generation (ternary and high scandium) and second generation (quaternary, low scandium) of new creep resistant alloys. Obviously, these experiments cannot be replaced by thermodynamic calculations. However, considering the huge number of less promising alloy combinations that could have been selected by trial and error from multicomponent systems, the focused alloy development following this approach avoids a waste of time and effort. Received: May 18, 2001

strain [%]

0.6

0.4

MgCe3Mn1Sc1
0.2

MgCe3Mn1S

c9

MgCe4Mn1Sc6 -8 1 10 s-1
0 20 40

time [103 s]

60

80

Fig. 20. Creep curves of Mg-Ce-Mn-Sc alloys at 350 C after T5 treatment.[62]

6.2. Second Generation of Creep Resistant, Low Scandium Alloys The second generation (low scandium) alloys were selected from the most promising candidates identified by the thermodynamic calculations given in Section 5 from the cerium-free alloys. The creep curves for these low scandium quaternary alloys are shown in Figure 21.[62] Again, an almost 100 times lower creep rate is achieved at 350 C and 30 MPa compared to the best commercial alloy WE43. The best alloy MgGd5Mn1Sc0.3 with the smallest elongation after 15104 s contains only 0.3 wt.-% of expensive Sc. It is exactly one of the few most promising alloys indicated by the thermodynamic calculations. The calculated equilibrium phase amounts during solidification and heat treatment for this alloy was shown in Figure 11. This is considered to be a substantial progress compared to the first generation of alloys with much higher scandium contents of 6 or 15 wt.-% Sc.

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Cacciamani, P. Riani, A. Saccone, R. Ferro, A. Pisch, R. Schmid-Fetzer, Intermetallic 1999, 7, 101. [52] J. Grbner, D. Kevorkov, R. Schmid-Fetzer, Z. Metallkd. 2001, 92, 22. [53] D. G. Kevorkov, J. Grbner, R. Schmid-Fetzer, V. V. Pavlyuk, G. S. Dmytriv, O. I. Bodak, J. Phase Equilibria 2001, 22(1), 34.

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[10] [11]

[12] [13] [14]

[15]

[16]

[17] [18]

[19] [20] [21] [22] [23] [24]

[25]

[26] [27] [28] [29] [30]

960

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Schmid-Fetzer, Grbner/Focused Development of Magnesium Alloys Using the Calphad Approach [54] J. Grbner, R. Schmid-Fetzer, A. Pisch, C. Colinet, V. V. Pavlyuk, G. S. Dmytriv, D. G. Kevorkov, O. I. Bodak, Thermochin. Acta, submitted. [55] D. G. Kevorkov, J. Grbner, R. Schmid-Fetzer, J. Solid State Chem. 2001, 156, 500. [56] J. Grbner, D. Kevorkov, R. Schmid-Fetzer, J. Solid State Chem. 2001, 156, 506. [57] D. G. Kevorkov, R. Schmid-Fetzer, Z. Metallkd. 2001, 92, 946. [58] J. Grbner, R. Schmid-Fetzer, A. Pisch, G. Cacciamani, P. Riani, N. Parodi, G. Borzone, A. Saccone, R. Ferro, Z. Metallk. 1999, 90(8), 72. [59] A. Pisch, J. Grbner, R. Schmid-Fetzer, Mater. Sci. Eng. 2000, A289, 123. [60] J. Grbner, R. Schmid-Fetzer, J. Alloys Comp. 2001, 320/2, 296. [61] A. Pisch, R. Schmid-Fetzer, G. Cacciamani, P. Riani, A. Saccone, R. Ferro, Z. Metallkd. 1998, 89(7), 474. [62] F. von Buch, Entwicklung hochkriechbestndiger Magnesiumlegierungen des Typs Mg-Sc(-X-Y), Mg-Gd und Mg-Tb, Ph.D. Thesis, TU Clausthal, Germany 1999. [63] M. M. Avedesian, H. Baker (Eds), ASM Specialty Handbook Magnesium and Magnesium Alloys, ASM International, Materials Park, Ohio 1999. [64] More and updated information can be found at the corresponding websites: ChemSage at http://gttserv.lth.rwth-aachen.de/gtt/, Fact at http://www.crct.polymtl.ca/fact/fact.htm, FactSage at http://www.factsage.com/, MTDATA at http://www.npl.co.uk/npl/cmmt/mtdata/, Pandat at http://www.computherm.com/, Thermocalc at http:// www.thermocalc.se/ [65] It should be noted that the binary interaction of Eq. 6 could equivalently be written in the same style as Eqs. 7 and 8:
E

REVIEWS

GbinY0

c1 c

i1 jbi

xi xj

n m0

Am1Y0 xi ij ij

nv

xj ij

(13)

where ij = (1xixj)/2

(14)

The subregular behavior is given for the order n = 1. The conversion between the parameters em1Y0 and ij Lm,u has been given by Hillert. [31] Since virtually all ij binary assessments are published in the form of Eq. 6 instead of Eq. 13 it is reasonable to keep this form in the general Gibbs energy equation for a c-component solution phase.

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