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Meurer et al.: Simulation of solidification and heat treatment of superalloy SC16

Zeitschrift für Metallkunde downloaded from www.hanser-elibrary.com by Kungliga Tekniska on September 14, 2015 For personal use only.

B. Meurer a,b , Ph. J. Spencer a,c , D. Neuschütz a

a RWTH Aachen, Lehrstuhl für Theoretische Hüttenkunde (now: Lehrstuhl für Werkstoffchemie), Aachen, Germany b Now with Michelin Roues France, La Chapelle Saint Luc, France c Now with The Spencer Group, Trumansburg, NY, USA

Simulation of solidification and heat treatment of nickel-base superalloy SC16

Thermodynamic equilibrium and Gulliver – Scheil as well as diffusion calculations using the DICTRA program have been made to simulate solidification and heat treatment of the nickel-base superalloy SC16. These simulations were validated by comparing them with own and literature ex- periments concerning directional solidification, heat treat- ment and differential thermal analysis (DTA) cycles. Equi- librium calculations predicted very well the element distribution in homogenized samples. Gulliver– Scheil based on the CALPHAD method and modified to serve multi-component systems proved to deliver sufficiently cor- rect data for the directional solidification of SC16. The ele- ment distribution obtained after cooling below the solvus temperature and by DTA heating and cooling cycles was, however, only described with acceptable precision by ap- plying the diffusion model. All these models require a sound multicomponent thermodynamic data set. Since DICTRA needs much more computing time than the other models it should only be applied wherever its higher preci- sion is actually asked for.

Keywords: Simulation of solidification; Simulation of heat treatment; Nickel-base superalloy; Equilibrium calcula- tions; Gulliver– Scheil model; Diffusion calculations

Simulation der Erstarrung und der Wärmebehandlung der Nickelbasis-Superlegierung SC16

Thermodynamische Gleichgewichts- und Gulliver– Scheil- Rechnungen sowie Diffusionsrechnungen mit dem Pro- gramm DICTRA wurden zur Simulation unterschiedlicher Prozesse der Erstarrung und Wärmebehandlung der Nickel- basis-Superlegierung SC16 durchgeführt. Diese Simulatio- nen wurden durch Vergleich mit eigenen und der Literatur entnommenen Experimenten zur gerichteten Erstarrung, zur Wärmebehandlung und zur zyklischen Erwärmung und Abkühlung mittels Differentialthermoanalyse (DTA) vali- diert. Mit Gleichgewichtsrechnungen konnte die Element- verteilung in homogenisierten Proben sehr gut vorhergesagt werden. Das für mehrkomponentige Systeme modifizierte Gulliver– Scheil-Modell lieferte recht genaue Ergebnisse zur gerichteten Erstarrung von SC16. Die Elementvertei- lung nach Abkühlung unter Solidus bzw. nach Durchlaufen der DTA-Zyklen wurde allerdings nur mit hinreichender Genauigkeit mit Hilfe des Diffusionsmodells wiederge- geben. Alle genannten Modelle erfordern einen zuverlässi-

Z. Metallkd. 94 (2003) 2

Carl Hanser Verlag, München

gen thermodynamischen Datensatz für multikomponentige Systeme. Da die DICTRA-Rechnungen im Vergleich zu den anderen Modellen ein Vielfaches an Rechenzeit erfor- dern, sollten sie auf die relevanten Fälle beschränkt werden.

1. Introduction

Simulations have become an important tool to understand

and to optimise the structural developments during solidifi- cation and heat treatment of multicomponent alloys. Up to now simulations on a microscopic and a macroscopic level are still distinguished. For calculations on a microscopic scale the CALPHAD method [1] is well suited to describe the phase equilibria in multicomponent alloys by means of thermodynamic data. This method in combination with the description of diffusion processes has been applied for dif-

[2].

For c/c 0 nickel-base superalloys Saunders [3] and Dupin [4] have developed thermodynamic databases. Saunders has also presented calculations comparing Scheil, equilib- rium and diffusion calculations [3, 5]. However, combined simulations of the solidification process on a microscopic and macroscopic scale using the CALPHAD method are rare [6]. Different experimental techniques are used to describe the properties of nickel-base superalloys. Phase equilibria are usually described with distribution coefficients. They are experimentally determined by directionally solidified samples with a planar interface. Differential thermal analy- sis is used to determine transformation temperatures and heat effects [7]. These values are used as boundary condi- tions for modelling directional solidification although the process and even the morphology upon solidification may vary. After solidification the c 0 precipitates exist in an unfa- vourable shape and morphology with respect to mechanical behaviour. The aim of a homogenisation is the dissolution of finely dispersed c 0 precipitates within the c matrix phase, the dissolution of the remaining interdendritic c/c 0 eutectic and the minimising of dendritic segregation [8]. Engström [9] modelled heat treatment and interdiffusion for nickel- base superalloys. The aim of the present investigation was to test the ap- plicability of numerical simulations based on primarily thermodynamic models to processes like solidification and heat treatment of complex multicomponent nickel-base al- loys. Since relevant experimental results have recently been

fusion calculations for c 0 -free nickel-base superalloys

139

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Meurer et al.: Simulation of solidification and heat treatment of superalloy SC16

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published on the nickel-base superalloy SC16 [10,11], this

alloy was chosen as a suitable example for the present work. The alloy SC16 has been suggested as a c 0 -strengthened single-crystal superalloy for application as blade material of land-based industrial gas turbines [10, 12]. Its chemical composition was based on the polycrystalline superalloy IN 738LC already in industrial use [10]. The main advan- tage of SC16 is seen in the absence of grain boundaries and hence in possibly higher operating temperatures. In the present paper, the solidification and the subsequent heat treatment of the nickel-base superalloy SC16 have been modelled on a microscopic scale using equilibrium, Scheil and diffusion calculations [1, 13 – 15]. For valida- tion, experimental investigations carried out by Malow et

al. [10] and Henkel [11] have been used. In addition, differ-

ential thermal analysis (DTA) measurements have been per-

formed by the present authors.

2. Experimental

DTA measurements have been performed at the Institut für Eisenhüttenkunde, RWTH Aachen. The samples (typically 200 mg) were placed into a crucible with 5 mm inner diam- eter. The measurements were carried out at heating and cooling rates of 10 K/min. The maximum temperature was 1450 °C. After the cooling cycle the samples were homoge- nised for 10 min at 1140 °C before another heating cycle started. Three cycles were carried out to ensure the reliabil- ity of the measurements. The maximum deviation in the measured transformation temperatures was ± 3 K. The chemical composition of the alloy investigated is given in Table 1.

Table 1. Chemical composition of nickel-base superalloy SC16 (mass%).

Ni

Al

Cr

Mo

Ta

Ti

70.42

3.49

16.03

3.04

3.50

3.50

3. Numerical calculations

Thermodynamic equilibrium calculations according to the CALPHAD method [1] have been made using appro- priate software [16]. The thermodynamic properties of the components are stored as polynomials describing the Gibbs energy as a function of phase, temperature and composition [17, 18]. Equilibrium is calculated by mini- mising the Gibbs free energy of the system. In the present work the thermodynamic database for multicomponent nickel-base alloys developed by Thermotech Ltd., UK and Rolls-Royce plc, UK [3, 5] was used. It is well suited to describe the alloy SC16 treated here except that it does not contain the element Ta. In the calculations, Ta was re- placed by Ni. Gulliver – Scheil calculations [14, 15] were made using these thermodynamic data. The model is based on the as- sumption that local equilibrium exists at the interfaces and that no diffusion occurs in the solid phases, while rapid mass transfer takes place in the liquid phase. There exist significant differences between the classical Gulli- ver-Scheil calculation which was developed for binary

systems using constant partition coefficients (linear phase boundaries) and the method used in this work. The meth- od described here is applicable for multicomponent sys- tems and provides information on solidification paths, heat effects and transformation temperatures [2, 3, 19,

20].

Simulations of diffusion-controlled phase transforma- tions have been made using the DICTRA software [13, 24] which describes one-dimensional diffusion processes in the solid and the liquid states. As a basis for the calcu- lations the program requires proper thermodynamic and kinetic databases for multicomponent systems. The ther- modynamic database used was again the one mentioned above. The thermodynamic properties were implemented using the ThermoCalc program [16] as a subroutine. The kinetic database used for all calculations was included into the DICTRA program [21]. Only volume diffusion was taken into account and treated on the basis of mobili- ties. The diffusion equation is solved in one dimension for multicomponent systems with Onsager’s extension of Fick’s law. The concentration dependence of the activity coefficient was taken into account. A composition-depend- ent diffusion coefficient matrix was used in the simula- tions [22]. The calculations were based on the assumption of local thermodynamic equilibrium at a moving interface and were made for a planar geometry. With regard to the microstructure, diffusion was treated in volume elements the size of which was half the secondary dendrite arm spacing for dendritic solidification processes. The solid phase transformation c ! c 0 has been calculated for a volume element with half the size of the c 0 precipitates within the c primary dendrites. No fitting parameters have been used. The calculations have been made for constant cooling rates, for the DTA cycles and for constant heating rates. Supercooling as well as coarsening or other kinetic effects have been neglected. The simulation of the solid phase transformation c ! c 0 was made with respect to one single precipitate for the overall composition of the alloy assum- ing no interaction between precipitates. The cooling rate for this process was assumed to be 1 K/s. A more detailed information about the cooling rate used in Malow et al. ex- periments [10] was not available. All the diffusion calcula- tions have been performed for a planar geometry.

4. Results and discussion

4.1. Solidification path

The solidification path of the alloy starts with the develop- ment of primary c-dendrites. After reaching the binary eu- tectic temperature # eut , the remaining liquid solidifies with the eutectic binary reaction liquid ! c + c 0 . Only in binary alloys the solidification is complete at this temperature. In a multicomponent alloy the eutectic reaction takes place over a temperature range until solidification is complete or other phases precipitate. As the solidus temperature of the alloy is very high and thus diffusion processes are still fast, the solid phase transformation c ! c 0 cannot be neglected upon further cooling. The transformation will cause the pre- cipitation of finely dispersed c 0 particles in the primary den- drite. The schematic microstructure of the as-cast state is shown in Fig. 1.

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Meurer et al.: Simulation of solidification and heat treatment of superalloy SC16

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Tekniska on September 14, 2015 For personal use only. Fig. 1. Schematic microstructure of the nickel-base

Fig. 1. Schematic microstructure of the nickel-base superalloy SC16 in the as-cast state after dendritic directional solidification.

4.2. Simulation of directionally solidified samples

Gulliver– Scheil calculations have been performed and compared with directionally solidified samples of the superalloy SC16, Fig. 2. The amount of eutectic obtained by means of the Gulliver– Scheil model is slightly higher than the measured one. Calculations with the diffusion model [20] delivered a curve almost identical to Scheil. Only after more than 90 % solidification, the diffusion curve deviated from Scheil leading to a fraction eutectic of 0.0015 and a eutectic temperature of 1205 °C instead of 0.02 and 1210 °C, respectively (Fig. 2). We therefore sup- port the view taken by other authors [2, 23] that the CAL- PHAD-based Gulliver– Scheil model is a good approach to simulate directional solidification of nickel-base superal-

loys.

For the simulation of cooling below the solidus tempera- ture the solid phase transformation c ! c 0 could not be ne- glected. Diffusion model simulations of DTA heating and cooling cycles, Fig. 3, showed that the c/c 0 reaction was nearly reversible, the reason being relatively small differ- ences of the diffusion coefficients in the c and the c 0 phases. The volume fractions of c 0 precipitates as simulated with the diffusion model are plotted in Fig. 3 together with the equilibrium calculations and with experimental results (grey bar) [10]. At temperatures below 800 °C, the equilib- rium fractions of c 0 were noticeably higher than the mea- sured values, while the simulated fractions based on the dif- fusion model agreed very well with the experiments. The

dif- fusion model agreed very well with the experiments. The Fig. 2. Calculated fraction solid versus

Fig. 2. Calculated fraction solid versus temperature curve for SC16 ac- cording to equilibrium and Gulliver–Scheil calculations.

cording to equilibrium and Gulliver–Scheil calculations. Fig. 3. Calculated and measured (Malow et al. [10]) amount

Fig. 3. Calculated and measured (Malow et al. [10]) amount for cafter solid phase transformation c ! c 0 (1 K/s; k = 0.45 lm). Heating and cooling curves calculated with the diffusion model.

diffusion calculations showed that the c/c 0 reaction slowed down and nearly stopped below 700 to 800 °C.

4.3. Simulation of element distribution of quenched samples directionally solidified

Equilibrium calculations have been used to predict concen- tration profiles and distribution coefficients. The results are in good agreement with measurements for directionally so- lidified samples with a planar interface reported by Henkel [11] and Malow et al. [10], Table 2. In the semi-solid state the concentration profiles of the quenched alloy were mea- sured across the interphase c/liquid. The exact quenching temperature was not reported for these experiments. For the simulations the quenching temperature was estimated to be 1330 °C. Test calculations showed that a variation of ± 10 K did not result in significant changes in the concen- tration profiles. The maximum deviation between calcu- lated and measured concentrations was ± 1 mass% in each phase. The calculated distribution coefficients are a result of the thermodynamic equilibrium calculation and are de- pendent on temperature and element interactions. There- fore, the measurement of distribution coefficients at only one temperature is unsatisfactory for the description of the phase relationship in a multicomponent alloy. The depend- ence of temperature and interactions is obvious for ele- ments with a high tendency to segregate. The deviations be- tween calculations and experiments [10] for Mo and Ti were higher than for other elements. The simulations showed a better agreement with results reported by Henkel [11]. His experimental results seem to be more reliable, e. g. for Mo,

Table 2. Calculated and measured distribution coefficients

k i ¼ c c

i

=

c liquid

i

(mass%) for Ni-base superalloy SC16.

 

Element

 

Experiment

Simulation

[10]

[10]

[11]

Al

 

0.98

1.17

0.97

0.94

– 1.00

Cr

0.88

0.78

0.99

1.04

– 1.09

Mo

2.87

2.60

0.92

0.74

– 0.69

Ta

3.98

1.60

0.80

Ti

0.85

0.78

0.67

0.65

– 0.79

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since not only the distribution coefficients, but also the con- centration profiles have been reported in his paper.

4.4. DTA measurements and simulations

DTA measurements performed with the superalloy SC16 and cooling and heating rates of 10 K/min have been simu- lated by means of diffusion calculations. For the simula- tions the dendrite arm spacing of the alloy was estimated to be k 2 = 120 lm. The calculations predicted that the alloy solidified as c phase without precipitation of eutectic. This is in agreement with our experiments where no eutectic temperature peak could be detected by DTA. The size of the dendrites and the morphology proved to be different from samples solidified directionally. In DTA cycling, back diffusion could not be neglected, Fig. 4. The simulation of

the solidification was continued down to a temperature of 1140 °C. At this temperature above the solvus temperature the system was homogenised for 10 min before the simula- tion of the heating cycle started. Because of the homogeni- sation and overheating effects the solidus temperature was shifted 34 K higher as compared to the results of the cool- ing experiments. The displacement velocity of the interface c/liquid was much slower in this case than for the cooling experiments. Calculated and measured transformation tem- peratures as well as the latent heat evolution were in good agreement as can be seen in Table 3. The deviation of all measured transformation temperatures in this investigation was max. ± 3 K.

4.5. Simulation of homogenised samples

Equilibrium calculations have been carried out to predict element distributions measured by Malow et al. [10]. Calcu- lated and measured element distributions in the c matrix and the c 0 precipitates after two different heat treatments are presented, Table 4. As Ta was not implemented in the database the calculated results were shifted systematically to higher Ni contents. At high temperatures (1000 °C) the calculated equilibrium volume fraction of c 0 (29 %) was smaller than the measured one (44 %). It is assumed that quenching was too slow in the experiments [10] to freeze equilibrium conditions. The solid phase transformation c ! c 0 would have to be taken into account. During cooling to room temperature the amount of c 0 precipitates increased again causing a higher c fraction than predicted by equilib- rium calculations. The measured amount of c 0 phase (44 vol%) was very close to the measured value for the as- cast sample, Fig. 3.

5. Summary

Thermodynamic equilibrium, Gulli- ver– Scheil and diffusion calculations have been carried out for the nickel- base superalloy SC16 and compared with experiments performed by the authors or reported in the literature. Dif- ferent solidification and heat treatment processes could be simulated with one consistent thermodynamic and diffu-

be simulated with one consistent thermodynamic and diffu- Fig. 4. Calculated cooling and heating cycle for

Fig. 4. Calculated cooling and heating cycle for DTA measurement (10 K/min, k 2 = 120 lm).

Table 3. Calculated and measured phase transformations and latent heats during the cooling and heating cycles of DTA measurements.

 

Cooling: 10 K/min

Heating: 10 K/min

Experiments

Simulation

Experiments

Simulation

# Liq. / °C

1342, 1345, 1346

1358

1355, 1356, 1356 1318, 1319, 1318 +113, +118, +115

1358

# Sol. / ° C

1290, 1289, 1289 –168, –191, –176

1293

1327

DH/J/g

–188

+113

Table 4. Measured concentration profiles (Malow et al. [10]) in stable phases after different heat treatments in comparison with equli- brium calculations.

Heat treatment

 

Phase

 

Chemical composition (at.%)

 

vol.%

 

Ni

Al

Ti

Ta

Cr

Mo

# = 1250 ° C/3 h +

c-matrix

Experiment

63.1

4.2

1.2

0.7

28.0

2.8

# = 850 ° C/1000 h

Simulation

65.3

3.7

0.7

28.0

2.8

c

0

Experiment

70.6

17.0

6.4

1.4

3.6

0.9

44

 

Simulation

74.5

12.8

8.9

3.4

0.4

42

# = 1250 ° C/3 h +

c-matrix

Experiment

64.3

5.9

1.3

0.6

25.5

2.3

# = 1000 ° C/300 h

Simulation

67.2

5.3

2.1

23.1

2.4

c

0

Experiment

71.4

15.7

6.7

1.7

3.6

0.7

44

 

Simulation

74.3

12.5

9.3

3.5

0.4

29

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sional data set in good agreement with experimental results. Remaining deviations between calculations and experi- ments may be attributed to the incomplete thermodynamic database where Ta was not included. Equilibrium calcula- tions have been successfully performed to predict the ele- ment distribution after different homogenisation treat- ments. The Gulliver – Scheil model has been used as a good approach to simulate directional solidification of the nickel-base superalloy SC16. For cooling below the solvus temperature diffusion controlled c ! c 0 phase transforma- tion has been taken into account. Cooling and heating cy- cles measured by DTA could only be simulated by means of diffusion calculations to obtain sufficient agreement with experimental data. Wherever appropriate, the less complex calculations (equilibrium and Gulliver – Scheil, respec- tively) appear preferable to the diffusion treatment because they require at least two orders of magnitude shorter com- puting times.

Financial support from the Deutsche Forschungsge- meinschaft (Collaborative Research Centre SFB 370 ,,Inte- grative Werkstoffmodellierung“) is gratefully acknowl- edged. The authors wish to thank Dr. Saunders for providing the thermodynamic database and Dr. Mukherji, Hahn-Meitner Institute, Berlin, Germany, for providing samples of the alloy SC16.

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[12] T. Khan, P. Caron, in: E. Bachelet et al. (Eds.), Proc. Conf. on High Temperature Materials for Power Engineering; Liège, Bel- gium, 24–27 Sept. 1990, Kluwer Acad. Publ., Dordrecht (1990)

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[13] J.-O. Andersson, L. Höglund, B. Jönsson, J. Ågren, in: G.R. Purdy (Ed.), Fundamentals and Applications of Ternary Diffusion, Per- gamon Press, New York (1990) 153. [14] E. Scheil: Z. Metallkd. 34 (1942) 70. [15] G.H. Gulliver: Metallic Alloys, Griffin, London (1922) 120. [16] B. Sundman, B. Jansson, J.-O. Andersson: Calphad 9 (1985) 153.

[17] T. Buhler, S.G. Fries, P.J. Spencer, H.L. Lukas: J. Phase Equilibria 19 (1998) 317. [18] I. Hurtado, T. Jantzen, P.J. Spencer: Ber. Bunsenges. Phys. Chem. 102 (1998) 1088. [19] B. Meurer, P.J. Spencer, D. Neuschütz: J. Chim. Phys. 94 (1997)

889.

[20] B. Meurer: Doctoral Thesis, RWTH Aachen, Fortschr.-Ber. VDI, Reihe 20, Nr. 281, Düsseldorf, VDI-Verlag (1988). [21] T. Helander (Ed.): MOB (Mobility) solution database of Jan. 1995. Division of Physical Metallurgy, Royal Institute of Technol- ogy, Stockholm, Schweden. [22] B. Jönsson: Z. Metallkd. 85 (1994) 502. [23] W.J. Boettinger, U.R. Kattner, S.R. Coriell, Y.A. Chang, B.A. Mueller: Processes VII, Proc. Seventh Conf. on Modeling Casting and Welding Processes, London Sept. 10–15, 1995 (1995) 649. [24] A. Borgenstam, A. Engström, L. Höglund, J. Ågren: J. Phase Equilibria 21 (2000) 269.

(Received January 21, 2002)

Correspondence address

Prof. Dr.-Ing. D. Neuschütz Lehrstuhl für Werkstoffchemie RWTH Aachen, D-52056 Aachen, Germany Tel.: +49 241 802 5970 Fax: +49 241 802 2295 E-mail: neuschuetz@lth.rwth-aachen.de