ARCHIVES

ISSN (1897-3310)
Volume 10
of Issue Special1/2010
203-206
FOUNDRY ENGINEERING
38/1
Published quarterly as the organ of the Foundry Commission of the Polish Academy of Sciences

Investigation of selected thermo-physical

properties in the Co-based superalloy:
Experiment and application study
J. Kasala a,*, H. Mäsiar a, I. Pernis a
a
Department of Technology and Materials, Alexander Dubček University of Trenčín,
Študentská 1, SK-911 50, Trenčín, Slovak Republic
*Corresponding author. E-mail address: kasala@tnuni.sk

Received 05.03.2010; accepted in revised form 23.03.2010

Abstract
Thermo-physical properties are the critical input parameters in computational models of solidification and casting simulations. In
thermodynamics, the enthalpy is quotient of thermodynamic potential of a system, which can be used to calculate the useful work
obtainable from a closed thermodynamic system under constant pressure. Differential thermal analysis has been used to study melting and
solidification paths in the cobalt based superalloy FSX-414. The temperature enthalpy curve was determined from differential thermal
analysis curves obtained from solidification curves. A solidification simulation of a cobalt base multi-component alloy casting was carried
out to predict cooling and shrinkage porosity in the casting of a turbine engine vane segment. The effect of latent heat on the heat transfer
calculation was considered by enthalpy method.
Keywords: cobalt alloy, differential thermal analysis, enthalpy curve, solidification path, DTA

Some of material properties are possible to find in literature and

1. Introduction
Superalloys are a class of materials specifically developed
for high-temperature application. Thermo-physical data of
materials usually exists for selected pure elements and a few
simple alloys. The techniques available for their measurement
are often subjected to considerable uncertainty. For highly
complex materials a complete thermodynamic description of the
system involves a huge amount of work, and the predicted
values differ from those measured. In order to withstand the
demanding conditions in a gas turbines, cobalt based
superalloys generally have complex compositions and small
changes in composition can radically affect the properties. The
various properties that make these alloys suitable for such
conditions, i.e. the high melting temperature, mean that studies
of the thermo-physical properties have to take place at elevated
temperatures [1-3], reducing the number of experimental
techniques available.
material databases, but usually not all data are available. A lot of
properties were investigated for low-temperature area and for
high-temperature area the data are missing. Furthermore the
properties are usually given as function of temperature and
composition, and effect of cooling rate on solidification path is
not solved.
Various methods can be used to determine the solidification
curves of alloys [4-6]. One of approach is to use differential
thermal analysis (DTA) that has become one of today’s routine
techniques for the characterization of materials [7]. In this
paper, the differential thermal analysis was carried out for cobalt
alloy FSX-414 to investigate melting and solidification paths in
the alloy. The primary aims of this investigation are:
1. To determine the enthalpy change during the solidification.
2. To determine solidus and liquidus temperatures.
The outcome of this investigation is to use the obtained data
for the simulation of a turbine vane segment casting.

ARCHIVES OF FOUNDRY ENGINEERING Volume 10, Special Issue 1/2010, 203-206 203
Table 1. Alloy composition in weight percent (wt%) of alloying elements in Co-base superalloy FSX-414
Chemistry C Cr Ni W Mn Si Fe B Co
FSX 414 0.213 30.35 11.08 6.75 0.96 0.99 1.92 0.01 Bal.

manipulated to calculate the enthalpy change from the DTA

2. Experimental measurement.
Differential thermal analysis is a technique based on the temperature
difference between reference cell and another that contains the sample,
for a constant heating or cooling rate. The solidus and liquidus 3. Results and discussion
temperatures are determined from the DTA curves from the values
associated with the endothermic and exothermic peaks. A schematic Differential thermal analysis was carried out for sample of
diagram of the DTA cell is shown in Fig. 1. The DTA instrument can alloy. Two endothermic peaks were found in the heating part of
be described in terms of double non-stationary calorimeter in which the the obtained curve while the cooling part of the curve displayed
thermal behaviour of the sample is compared with that of an inert two exothermic peaks, as illustrated in Fig. 2 and Fig. 3.
reference material A sample holder assembly consists of a
thermocouple each for the sample and reference, surrounded by a block
to ensure an even heat distribution. The resulting effects produced by
the change of the sample enthalpy content can be analysed at four
different levels [8], namely:
1. Identity (fingerprinting of sequences of individual thermal effects)
2. Quality (determination of point characteristics of individual effects
such as beginning, onsets, outsets, inflections and apexes)
3. Quantity (areas, etc.)
4. Kinetics (dynamic of heat sink, etc.)

Fig. 2. Endothermic and exothermic peaks during heating and

cooling of the sample

Transition temperatures are obtained from the curve

corresponding to the cooling cycle i.e. the temperature at which
the heat flow curve deviates from baseline, see Fig. 3.

Fig. 1. Schematic diagram of the DTA cell [9]

The composition of investigated cobalt alloy FSX-414 is given in

Table 1. DTA specimen was taken from the alloy ingot. A Perkin-
Elmer Differential Thermal Analyses instrument was used for the
experiments incorporating a sample of the weight 151 mg. Experiments
were conducted using a dynamic high purity argon atmosphere. The
unit was calibrated using pure metals. The sample was subjected to
heating/cooling cycles as follows:
1. Heating from room temperature to 1550 oC at heating rate 10
K min-1 Fig. 3. Detail of peaks
2. Holding for 5 min at 1550 oC
3. Cooling from 1550 oC to room temperature at cooling rate 10 Fig. 2 and Fig. 3 show the measured DTA curves (heat flow
K min-1 versus temperature) during heating and cooling. The endothermic
The cooling rate chosen is usual of conditions encountered during peak during heating and exothermic peak during cooling
industrial equiaxed solidification. Heating and cooling curves were corresponds to melting and solidification, respectively. Solidus
recorded over DTA runs. The measured DTA cooling curve was

204 ARCHIVES OF FOUNDRY ENGINEERING Volume 10, Special Issue 1/2010, 203-206
Table 2. Enthalpy change corresponding to solidification path as a function of temperature
Temperature [oC] 1343.0 1352.4 1355.7 1362.4 1364.1 1364.5 1364.1 1363.2 1357.9
Enthalpy [Jg-1] 0 1.6 3.2 8.1 16.2 24.3 32.5 40.6 73.1
Temperature [oC] 1352.6 1348.3 1343.3 1340.4 1336.8 1331.5 1327.5 1315.7 1280.8
Enthalpy [Jg-1] 97.5 113.6 129.9 138.1 146.2 154.3 157.5 160.8 162.4

temperature is always difficult determine from the measurements
since the change in heat capacity during cooling at the solidus
temperature is gradual. In this study, solidus temperature was
determined by inspecting the intersection of the baseline and the
extrapolated tangent approximation of the heat flow curve in an
enlarged view. It was found that Tsolidus = 1281 oC. As shown in
Fig. 2 solidification commences with a small nucleation in DTA
curve, and the liquidus temperature was deduced from the point of
deviation during cooling as follows: Tliquidus = 1343 oC.
vane segment. In the numerical simulation the enthalpy appears in
the time derivative of the energy equation and the latent heat
released during solidification can be expressed by applying the
enthalpy method. The relationship between the enthalpy H,
temperature T and latent heat L is defined [14] by
H = ∫ c.dT + L(1 − f s )
where fs is fraction of solid. The heat transfer coefficients at air-
mould interfaces were determined on natural convections regimes
and critical length scales for the surface.
For the investment casting process simulation one of important
input parameter is the overall heat transfer coefficient H between
the ambient and shell mould which was given as a sum of the
convection heat transfer coefficient Hc and shell emissivity as
follows [15]:

H = H c + σ .ε (T 2 + TA2 ).(T + TA )

where T is the temperature of surface, TA is ambient temperature

and ε is the mould surface emissivity. There are different
correlations for the convention heat transfer coefficient in
Fig. 4. Enthalpy curve corresponding to solidification literature depending on the surface orientation, characteristic
length of the surface and relative position of surfaces. The air
Fig. 4 shows the calculated curve of enthalpy change (percent flow between adjacent casting surfaces is partially restricted.
area versus temperature) corresponding to solidification. From the Therefore the corellation on natural convection developed for the
calculated enthalpy curve, a nucleation undercooling for primary two parallel plate configuration expressed in term of Nusselt
dendrites is about 21 oC as seen in Fig. 4. The enthalpy change number is given by [15]
corresponding to solidification as a function of temperature is
given in Table 2. 3
1 ⎛ S ⎞⎛ ⎡ − 35L ⎤ ⎞ 4
Nu = Ra⎜ ⎟⎜⎜1 − exp ⎢ ⎟⎟
24 ⎝ L ⎠⎝ ⎣ Ra.S ⎥⎦ ⎠
4. Application study
Computer simulation has proven to be an effective tool in the where S is the distance between two blades of the vane segment,
foundry industry [10]. The goal of computer simulation is to L is characteristic length scale given as a ratio between the
accurately model all of the underlying physics of the process so surface area A and perimeter p, and Rayeigh number for air at
that important process variables may be identified and effectively
controlled [11 - 13]. In order for computer aided modelling to by
7
(
ambient temperature Ra = 9,07.10 . T − TA .L . ) 3

successfully implemented into the design stage, it should perform Then the convection heat transfer coefficient can be determined
a wide variety of tasks. Due to highly complex nature of the from the Nusselt number by
investment casting process, especially in the aerospace industry,
the accuracy strongly depends on the input thermo-physical 0,0262
properties of materials and ability to model the heat loss in the H c = Nu
ceramic mould involving self-radiation effects. The values of L
solidus and liquidus temperatures and enthalpy change obtained
from DTA experiment (Table 2) were used for the numerical Computer simulations were conducted for the filling and
simulation of the investment casting process of the turbine engine solidification of the vane segment. The input data and material

ARCHIVES OF FOUNDRY ENGINEERING Volume 10, Special Issue 1/2010, 203-206 205
properties were used based on the DTA experiment, equations
from this section and material database in Procast.
The simulation showed that due to filling and self-radiation
effects, there would be shrink defect in the middle blade of vane
segment as can be seen in Fig. 5.
Fig. 5 Solid fraction profile in cross section of vane segment
5. Conclusions
DTA measurement of the superalloy FSX-414 allowed:
- the evaluation of liquidus and solidus temperatures
- the evaluation of enthalpy change corresponding
solidification of the melt
- to have accurate input thermo-physical properties for
reliable simulations of the complex solidification
process
Acknowledgements
The authors thank the Slovak Academy of Sciences in
Bratislava for the DTA experiments.
References
[1] Chester T. Sims, Norman S. Stoloff, William C. Hagel:
Superalloys II, John Wiley & Sons, 1987
206 ARCHIVES OF FOUNDRY ENGINEERING Volume 10, Special Issue 1/2010, 203-206
[2] Orłowicz A.W., Trytek A.: Nadtapianie powierzchniowe
odlewów z superstopu na bazie kobaltu MAR-M509.
Archiwum Odlewnictwa, PAN, t.4, z.14, p.348-355, 2004.
[3] Orłowicz W., Trytek A.: Podatność odlewów ze stopu MAR-
M509 do nadtapiania powierzchniowego. 6th International
Scietific Conference TRANSFER, 15. - 17. September 2004,
A Dubcek University of Trencin, z.2, p.361-364, 2004
[4] Backerund L., Krol E., Tamminen J.: Solidification
Characteristics of Aluminium Alloys. Vol 1, SkanAluminium,
Oslo, Norway, 1986.
[5] Backerund L., Krol E., Tamminen J.: Solidification
Characteristics of Aluminium Alloys. Vol 2, SkanAluminium,
De Plaines, IL, 1990.
[6] Rappaz M.: Application of Inverse Methods to the Estimation
of Boundary Conditions and Properties, Modelling of
Casting, Welding and Advanced Solidification Processes,
London, 1985
[7] Čaplovič, Ľ.: Apply of Selected Experimental Technics in
Materials Engineering. Dresden, Forschungszentrum Dresden,
2009. Properties of Solids, Elsevier (Amsterdam) 1984.
[8] Šesták J.: Thermophysical Properties of Solids, Elsevier,
Amsterdam, 1984
[9] Gallagher P.K.: Handbook of Thermal Analysis and
Calorimetry: Principles and Practice. Volume 1. 2003.
[10] Orłowicz W., Mróz M.,Tupaj M.: Application of computer
simulation to projecting of the castings. Acta Metallurgica
Slovaca, 11, 2005, p.41-44
[11] Bähr R., Djurdjevic M., Pavlovic J.: 8. Magdeburger
Maschinenbau - Tage & 7. MAHREG, Innovationsforum,
Magdeburg, Germany, 10-11. October, 2007, p. 210-219
[12] Molnár D., Dúl J.: Simulation of casting processes: Filling,
solidification, residual stresses calculation. World Technical
Forum 2009 and 46th Foundry Days, 1-3 June, Brno, 2009
[13] Pavlovic J., Djurdjevic M., Bouska O., Bähr R.: 44th
Foundry Days and 4tbInternational PhD Foundry
Conference, Brno, 16-17. October, 2007, p.12-22
[14] Voller V., Cross M.: Accurate Solutions of Moving Boundary
Problems Using the Enthalpy Method. Int. J. Heat Mass Transfer,
Vol. 24, 1981, p. 545-556
[15] Sabau A.S.: Numerical simulation of the investment casting
process. AFS Transactions, 2005