ATAS® as a tool for analyzing, stabilizing and optimizing the graphite precipitation

in grey cast iron.

P. E. Persson1, A. Udroiu1, P. Vomacka1, Wang Xiaojing1 and T. Sjögren2

1
Novacast Foundry Solutions AB, Soft Center, SE-372 25 Ronneby, Sweden
2
SP Technical Research Institute of Sweden, SE-501 15 Borås, Sweden

Abstract

The world today is facing one of the greatest challenges of all times, that of climate
change. All aspects of our daily life need to be assessed in order to find solutions for
minimizing the environmental impact caused by different human processes. The industrial
impact is of course one of the major contributors. When discussing for example the
transportation sector and the automotive industry it is important to realize that there is no
filter or catalyst you can put on an engine to lower CO2 emissions. These emissions must
be lowered by using clean technologies in combination with high performance materials
produced by energy saving, environmentally friendly production processes. More deman-
ding emission laws are needed and they are coming into effect every few years. The
United Nations, through its Intergovernmental Panel on Climate Change has recently set a
goal of 50-80% decrease of carbon dioxide (CO2) emissions until 2050.

Adaptive thermal analysis system (ATAS®) is a well established tool for analyzing,
stabilizing and optimizing the production process for grey and ductile iron. ATAS® enables
foundries to measure the quality of the melt when producing grey and ductile iron.
Therefore ATAS® creates incentives to improve the production process in terms of, among
other benefits, saving energy, decreasing scrap rate, decreasing the amount of alloying
materials and consequently decreasing the overall environmental impact of a foundry.

In industrial applications today such as brake discs, brake drums, injection molds
using grey cast iron and working at high temperatures the distribution of various forms of
lamellar graphite (A, B, C, E and D) has become very important. In this study, the
formation and distribution of flake graphite during solidification was studied in a grey cast
iron alloyed with Cr and Ni.

As is well known, the formation and distribution of grey cast iron can be controlled
by adjustments in the chemical composition of the melt and by influencing the thermal
parameters of cooling curves. When monitoring the cooling curves the eutectic reaction
can be controlled by different treatments in the liquid phase such as preconditioning,
inoculation, deoxidizing and sulphides/silicates/nitrides introduction.

The presented article discusses a mathematical model for prediction of chemical

composition and optimization of thermal analysis parameters for obtaining optimal graphite
precipitation from the melt. Examples of different corrections to the melt evolution in order
to reach the optimal graphite formation and distribution during the production process are
given and verified by means of the introduced mathematical model.

1
Introduction

The use of cast iron in industrial applications is widespread and of the total
produced world tonnage of cast products 75% is made from cast iron [1]. Concerning the
use of grey cast iron it is strongly competitive due to its good castability, low cost and with
properties suitable for components demanding good wear resistance, thermo mechanical
resistance, fair mechanical strength and good machinability and weldability. Examples of
applications for grey cast irons are; engine components, brake discs, brake drums, molds
for injection or casting at high temperature. Typical for these applications are the relatively
high temperatures that the component is subjected to. The benefit of using grey cast iron
is the high thermal conductivity that is typically observed due to the existence of the
graphite phase. A critical parameter for achieving high thermal conductivity in grey cast
iron is the appearance of the graphite phase, where the growth mode and thereby the
distribution of the graphite phase is central [2]. The graphite phase is also controlling the
resulting strength of the material [3] and for components working at cyclic temperatures it
is of great importance to have good control of the resulting graphite distribution since it is
observed that the thermal fatigue resistance is improved by having an A distribution
compared to e.g. D or E distribution [4]. The distribution of lamellar graphite (A, B, C, E
and D) is normally described using ISO945 [5].

In this paper the formation of various distributions of flake graphite during

solidification, was studied. The studied grey cast iron was alloyed with Cr and Ni as given
in Table 1 and the samples were cast continuously in an industrial casting process.

Table 1. Chemical composition (wt%).

C Mn Si P S Cr Ni
Min. 3,35 0,5 1,8 - - 0,1 0,7
Max. 3,65 0,7 2,2 0,1 0,05 0,2 0,85

D;E type
A type

a.

Casting

Chill

b. c.
Figure 1. Schematic sketch of the component.

One of the components produced at this company had the need for D and E
distributed graphite for improved weldability in certain areas. To achieve this, a chill was
placed in this area as shown in Fig. 1. To study the influence of different cooling conditions
on graphite formation, a chill was used to increase the cooling rate in parts of the analysed
sample.

The present study consists of three phases based on thermal, chemical and
metallographic analysis of 600 samples. Phase I (samples 1-320) focuses on data
collection and analysis of correlation. In Phase II (samples 321-440) the optimum in

2
chemical composition determined in Phase I is used and the resulting microstructure is
verified. An analysis of five different inoculants is also included in this phase. In Phase III
(samples 441-600) a fixed chemical composition and inoculation process was used to
verify the conclusions drawn in the two first phases.

Experimental methods

The formation of various graphite distributions (A, B, C, D, E) was studied and material
related parameters were determined by using;

• Thermal analysis system (ATAS®)

• Metallographic analysis
• Chemical analysis (spectrometer)

These data were used as the basis for mathematic correlation analysis.

Thermal analysis

Graphite precipitation is a phenomenon that is very difficult to control with standard

tools used in foundries, like chemical or metallographic analysis. In the last years, thermal
analysis tools have been further developed and it has become possible to control the
phenomenon of graphite precipitation. So far, thermal analysis tools have been used
mainly for the measurement of trends in the formation of defects during solidification of the
metal, but not to highlight the different distributions of graphite that are developed during
solidification of different cast iron alloys.

By using chemical analysis, information on the total amount of carbon can be

determined without specifying in what form it exists (free (graphite) or combined
(cementite)). Thus no information about shape and distribution of the graphite is attained.

Figure 2. Examples of structures formed during solidification of cast irons (left). Example of a
cooling curve extracted from the solidification of cast iron (right).

The thermal analysis of a material is a record of temperature versus time from the
liquid state until complete solidification. In practice the curve shows the characteristics of
solidification of the metal and the process that is applied to it. The thermal analysis reveals
the phase transformations during solidification and the solid state transformation. In the
case of cast iron the eutectic transformation, where the graphite-austenite eutectic is
formed, and the eutectoid transformation in which the austenite is transformed into ferrite
and/or cementite (Fig. 2) are revealed.
3
 Figure 3. Description of the analyzed parameters at cooling curve analysis.

In the present study the parameters measured and analyzed by thermal analysis during
the eutectic transformation are as follows (as given in Fig. 3):

− TE Gray – Stable eutectic temperature (grey solidification with formation of free

graphite)
− TE White - Metastable eutectic temperature (white solidified with the formation of
primary carbides)
− TLiq - Liquidus temperature.
− TElow - Low eutectic temperature. If TElow is too low the nucleation rate/inoculation is
too low. Risk for chill in corners and thin sections. Risk for undercooled graphite
shapes (type D and E).
− TEhigh - High eutectic temperature. The high eutectic temperature is dependent on the
alloy composition, as well as on the nucleation of eutectic and therefore on the
precipitation of graphite.
− S1 - Austenite precipitation. From the liquidus temperature down to the low eutectic
temperature, there is a precipitation of mainly primary austenite. S1 is calculated and
this is a relative value of the amount of primary austenite in hypoeutectic iron and
primary graphite in hypereutectic iron.
− R - Recalescence=TEhigh-TElow.
− GRF 2 - Graphite Factor 2. If too high, it indicates too little eutectic graphite at the end
of freezing especially if dT/dt_TS is high (closer to zero). Otherwise it can indicate
undercooled graphite shapes (type D and E). High GRF 2 indicates increased risk for
micro-shrinkages.
− TSol – Solidus temperature. Several elements segregate to the rest melt and lower the
solidus temperature. The risk for inverse chill is then high. A low solidus also increases
the risk for inverse chill i.e. formation of primary carbides at the last phases to solidify.
In general TS is a good quality assurance marker.
− ACEL - The active carbon equivalent, shows how the iron solidifies under the influence
of all basic elements, gases, oxides and other compounds present in the melt that
affect the solidification.

4
 As shown in Fig. 4 the germination/nucleation and growth of the nuclei of
graphite takes place in the intervals of the temperatures measured by thermal analysis:

Figure 4. Solidification in cast iron. The indicated temperatures are according to those described in
Fig. 3.

Depending on the position of the thermal parameters and their correlation to the
measured temperatures for gray and white solidification, different sizes and distributions
of graphite will be the result as shown in Fig. 5.

Figure 5. Formation of different types of graphite and the dependence on thermal parameters.

By changing the chemical composition of the cast iron it is possible to change the
temperature TE grey- TE white interval as shown in Fig. 6. Adding various chemical
elements can increase or decrease the difference between the two temperatures, thus
altering the solidification of the metal and the graphite distribution.

5
 Figure 6. The effect of different alloying elements on eutectic temperatures.

Another possible way of changing the critical temperature (thermal parameters, as

shown in Fig. 7) is by treatment of the liquid (e.g. holding time, inoculations,
preconditioning, deoxidation). From a chemical composition point of view these treatments
have a minor effect, thus the spectroscopic control tools are not able to detect these small
changes. But the influence on the solidification is very important and can be analyzed only
with the aid of thermal analysis tools.

Figure 7. The effect of preconditioning, inoculation etc. on thermal parameters.

In the present study the ATAS ® system was used to, simultaneously, record the cooling
curves of the grey cast iron solidification for 4 channels (Fig. 8).

Figure 8. Four Quick-cups connected to the ATAS® system for thermal analysis.

6
 A chill was used to achieve formation of D and E graphite in the Quick-cups. It was
placed on top of the casting subsequent to pouring. The volume of the chill was designed
to have an effect similar to chills used in production.

Metallographic analysis

Samples prepared for metallographic analysis were taken from the center of the
cups used to record the cooling curves as shown in Fig. 9.

Figure 9. Sketch of the cutting of samples used for metallographic analysis.

For the analysis of the influence of the different cooling conditions on the formation
of various graphite distributions, the analyzed surface was divided into three areas:

Area 1: microstructure formation in contact with the chill (approx. 15 mm thickness).

Area 2: a transition zone.
Area 3: the area with minimum influence from the chill.

Figure 10. Examples of different analyzed graphite distributions.

7
 Three fields of view for each area were analyzed. The analysis consisted of
determining the percentage of the four groups of graphite distributions; A, B, C, D/E. Each
of these distributions was determined as a percentage in the interval 0 and 100%. The
numbers above each image in Fig. 10 refer to the percentage of the four different graphite
distributions.

Correlation analysis of thermal, metallographic and chemical data

The study of the formation of graphite during solidification is based on the

correlations between thermal, metallographic and chemical data, resulting from the 320
samples (Phase I) in a span of 20 days (with the process variations in terms of nucleation
of graphite, chemical composition and holding time). Some of these data are given in
Tables 2 and 3. The data in Tables 2 and 3 contain only the chemical elements and
thermal parameters that influence the formation of graphite.
The data for the graphite distribution are given in Table 4. Since Area 1 (Fig. 9)
consisted of 100% graphite type D/E, this data is not presented in the table. It is concluded
that the graphite that forms in the vicinity of the chill depends only on the cooling rate
imposed by the chill and not the other variables that were studied.

Table 2. Thermal parameters measured with the thermal analysis system ATAS®.
Nr. Thermal parameters
Test ATAS File name ACEL C TL TElow R TL-TElow GRF2
1 0903061439.ku5 4,10 3,62 1163,3 1148,0 1,8 15,3 35,7
2 0902191041.ku1 4,14 3,53 1164,0 1147,4 2,6 16,6 24,0
3 0902191046.ku3 4,14 3,53 1167,1 1148,0 1,6 19,1 36,3
4 0902191126.ku3 4,14 3,53 1162,5 1148,1 2,2 14,5 32,5
5 0902191144.ku1 4,13 3,53 1164,3 1147,6 1,7 16,8 36,8
6 0902191157.ku3 4,12 3,52 1162,6 1147,7 1,7 14,9 32,4
7 0902191227.ku1 4,14 3,51 1159,6 1147,7 2,1 12,0 34,1
8 0902191228.ku3 4,14 3,52 1168,1 1145,4 2,5 22,7 31,3
9 0902191410.ku1 4,14 3,54 1162,2 1145,5 2,4 16,7 32,3
10 0902191415.ku3 4,16 3,53 1156,2 1146,0 1,8 10,2 35,9
11 0902191452.ku1 4,14 3,55 1159,3 1147,1 2,2 12,2 28,1
12 0902191513.ku3 4,13 3,54 1159,4 1146,7 2,9 12,6 31,5
13 0902191605.ku3 4,14 3,51 1162,1 1147,0 2,5 15,1 28,8
. . . . . . . . .
. . . . . . . . .
. . . . . . . . .
315 0903101624.ku1 4,16 3,55 1162,5 1147,6 2,2 14,9 30,7
316 0903101627.ku3 4,14 3,57 1162,7 1146,6 1,8 16,0 31,7
317 0903110915.ku1 4,13 3,54 1162,4 1145,9 2,6 16,4 29,4
318 0903110910.ku3 4,10 3,60 1154,4 1145,7 3,0 8,6 30,3
319 0903110921.ku3 4,11 3,52 1155,1 1145,3 2,1 9,8 29,4
320 0903111133.ku1 4,14 3,51 1154,9 1146,4 2,7 8,5 29,9

8
 Table 3. Chemical composition (wt%) determined by optical emission spectroscopy.
Nr. Chemical composition
Test C Mn Si P S Cr Ni
1 3,61 0,55 2,00 0,069 0,017 0,165 0,803
2 3,56 0,52 1,96 0,065 0,016 0,163 0,811
3 3,54 0,53 1,98 0,064 0,016 0,157 0,772
4 3,55 0,55 2,04 0,067 0,016 0,164 0,736
5 3,54 0,54 2,05 0,067 0,017 0,160 0,715
6 3,55 0,53 2,04 0,066 0,016 0,158 0,734
7 3,49 0,52 2,07 0,064 0,017 0,157 0,747
8 3,49 0,54 2,01 0,064 0,017 0,151 0,713
9 3,56 0,54 2,10 0,068 0,020 0,161 0,696
10 3,59 0,55 2,03 0,066 0,019 0,152 0,688
11 3,56 0,53 2,05 0,067 0,020 0,180 0,705
12 3,54 0,52 2,00 0,065 0,018 0,187 0,744
13 3,55 0,52 1,96 0,061 0,017 0,171 0,699
. . . . . . . .
. . . . . . . .
. . . . . . . .
315 3,56 0,51 1,97 0,062 0,019 0,164 0,673
316 3,57 0,53 2,04 0,068 0,018 0,152 0,630
317 3,57 0,54 2,00 0,064 0,017 0,157 0,690
318 3,60 0,56 2,20 0,079 0,045 0,141 0,773
319 3,55 0,55 2,08 0,070 0,037 0,134 0,668
320 3,56 0,56 2,14 0,076 0,050 0,136 0,757

Table 4. Analysis of the graphite distribution. Percentages of the graphite distribution in areas 2
and 3.
Nr. Graphite distribution
Test A2 B2 C2 D2 A3 B3 C3 D3
1 50% 30% 5% 15% 60% 10% 25% 5%
2 55% 25% 10% 10% 60% 10% 30%
3 50% 25% 15% 10% 70% 5% 25%
4 40% 25% 25% 10% 65% 5% 25% 5%
5 30% 25% 30% 15% 70% 5% 20% 5%
6 30% 20% 30% 20% 35% 5% 35% 25%
7 10% 15% 45% 30% 80% 5% 15%
8 20% 20% 35% 25% 75% 10% 10% 5%
9 10% 25% 35% 30% 80% 10% 10%
10 15% 35% 35% 15% 85% 10% 5%
11 40% 25% 15% 20% 60% 10% 10% 20%
12 50% 20% 5% 25% 35% 10% 25% 30%
13 50% 20% 15% 15% 65% 5% 25% 5%
. . . . . . . . .
. . . . . . . . .
. . . . . . . . .
315 30% 25% 25% 20% 70% 10% 15% 5%
316 20% 30% 35% 15% 80% 10% 10%
317 40% 25% 25% 10% 75% 5% 20%
318 30% 45% 25% 95% 5%
319 35% 55% 10% 85% 5% 10%
320 30% 45% 25% 100%

An analysis of correlations in the experimental data was performed. The correlation

dependence between two variables, Y and X, was performed where, Y, (the form of
graphite in this work) is defined as the dependent or effect variable and X, (thermal and
chemical parameters) is identified as the independent or cause variable. The correlation
coefficient, r, indicates how strongly the specific X and Y correlate. An r-value of unity
indicates a perfect correlation between the parameters studied. The correlations are
discussed in the next section.

9
Results and discussion
Phase I - Data collection and analysis of correlations

Based on the sub-division shown in Table 5 these are referred to as Tables 5.1-5.6.
The correlation coefficients exceeding a value of 0.4 are discussed since lower values
indicate a too low correlation between the variables. Emphasis in the discussion is set on
maximizing type A graphite and minimizing type D and E graphite.

Table 5. Correlation coefficients of experimental data.

TL-
TL TElow R GRF2 C Mn Si P S Cr Ni A2 B2 C2 D2 A3 B3 C3 D3
TElow
TL 1,00
TElow 0,08 1,00
R -0,28 0,49 1,00
TL-TElow 0,55 -0,79 -0,58 1,00
GRF2 0,18 -0,49 -0,72 0,52 1,00
C -0,43 0,14 0,27 -0,38 -0,35 1,00
Mn -0,40 -0,33 0,01 0,03 0,18 0,48 1,00
Si -0,65 -0,31 0,17 -0,14 -0,01 0,44 0,74 1,00
P -0,67 0,05 0,27 -0,45 -0,21 0,60 0,68 0,79 1,00
S -0,68 -0,31 0,32 -0,16 -0,17 0,49 0,68 0,84 0,70 1,00
Cr 0,41 0,26 0,00 0,04 -0,05 -0,27 -0,66 -0,66 -0,55 -0,73 1,00
Ni 0,06 0,33 0,29 -0,24 -0,13 0,11 0,06 -0,03 0,24 0,02 0,11 1,00
A2 0,64 0,42 -0,23 0,04 0,03 -0,27 -0,62 -0,85 -0,54 -0,91 0,68 0,21 1,00
B2 -0,52 0,06 0,75 -0,37 -0,29 0,83 0,58 0,48 0,62 0,54 -0,38 -0,07 -0,36 1,00
C2 0,07 -0,52 -0,20 0,48 0,34 -0,20 0,07 0,25 -0,18 0,12 -0,02 -0,38 -0,42 -0,30 1,00
D2 -0,67 -0,35 0,28 -0,11 -0,07 0,20 0,59 0,83 0,55 0,92 -0,71 -0,12 -0,98 0,31 0,27 1,00
A3 -0,68 -0,34 0,29 -0,13 -0,12 0,48 0,70 0,89 0,69 0,99 -0,73 -0,01 -0,93 0,54 0,16 0,93 1,00
B3 -0,45 -0,74 0,67 -0,23 -0,04 -0,06 0,24 0,43 0,11 0,94 -0,47 -0,42 -0,90 0,16 0,38 0,88 0,89 1,00
C3 0,63 0,39 -0,23 0,06 0,04 -0,32 -0,60 -0,82 -0,54 -0,85 0,57 0,30 0,96 -0,38 -0,48 -0,91 -0,87 -0,86 1,00
D3 0,60 0,14 -0,34 0,25 0,19 -0,44 -0,59 -0,68 -0,58 -0,90 0,76 -0,17 0,75 -0,53 0,16 -0,82 -0,89 -0,62 0,62 1,00

The strongest effect on thermal parameters arises from the treatment of the melt
and not to a large extent from the chemical composition. Thus, a more thorough analysis
of the specific values of the thermal parameters is discussed in Phase II in this paper. By
analysing the correlations between chemical and thermal parameters (Tables 5.1 and 5.2)
it is observed that C, Si, P and S lower the liquidus temperature while Cr raises it. The
dependence to the R-value in Table 5.1 indicates that the free growth of the graphite
phase increases with an increase in TElow while it decreases as TElow-TL increases
(indicating a low ACEL).

The data in Table 5.4 is useful for the optimization of additions to favor the
formation of graphite type A. Depending on the distance from the chill (Areas 2 and 3)
different influences from the alloying elements can be observed. For instance, in Area 2
the A-type graphite is promoted by an increase in Cr and a decrease in Mn, Si, P and S.
The opposite is true for the formation of A-type graphite in Area 3. Type A graphite in Area
3 is also favored by C. Regarding the formation of type D and E graphite the opposite is
true in chemical composition to favor formation of A-type graphite.

Table 5.5 contains the degree of dependence of the formation of various types of
graphite with respect to the thermal parameters recorded by thermal analysis tool ATAS®.
Having a constant chemical composition, the thermal parameters of solidification are
highly influenced by the condition of the liquid metal (melting cycle, holding time, the mix of
charge) and treatment of the metal in liquid state (preconditioning, inoculations). The
chemical analysis does not reveal these fundamental changes to graphite precipitation
(nucleation, development and distribution of graphite). Knowing the correlation between
the thermal parameters and graphite precipitation can give input on how the solidification
of cast iron can be changed with suitable interventions, beyond the change of chemical
composition. It is seen that an increase in type A graphite in Area 2 is facilitated by

10
increasing the liquidus temperature (TL). This also lowers the amount of type D and E
graphite. For the precipitation of graphite in Area 3 the reverse correlations are observed.

As was indicated in the previous discussion the precipitation of graphite and its
distribution depends on the distance from the chill and opposite correlations are observed
for A-type graphite and D/E-type formation for the two studied areas. This is confirmed by
the coefficients presented in Table 5.6 which show that high amounts of A graphite in Area
2 give rise to low amounts in Area 3 and vice versa for the D/E graphite.

All the correlations discussed above are true but the amounts of different alloying
elements to be added or removed to maximize the desired graphite type and minimize the
undesirable must be clarified. To be able to isolate the individual effect of the different
parameters multiple linear regression analysis has been used. Linear regression is a
method for estimating the conditional expected value of a dependent variable, in our case
the percentage of the different types of graphite, and the values of other independent
variables. The coefficients determined by the regression analysis are presented in Table 6:

Table 6. Calculated regression coefficients.

Regression coefficients
A2 B2 C2 D2 A3 B3 C3 D3
Constant -22,244 -32,841 1,671 34,753 -17,409 5,121 30,721 -5,187
C 15,435 10,105 -2,858 -9,617 4,967 -1,417 -1,137 -2,186
Mn -7,570 13,067 5,022 -15,500 2,038 0,699 -17,626 16,997
Si -18,318 -5,643 13,507 -4,789 10,705 -0,895 -7,782 -2,120
P 111,079 61,637 -130,626 164,023 -86,645 8,082 51,309 -3,069
S -739,986 0,000 0,000 0,000 190,170 77,893 -531,265 220,415
Cr 95,548 -3,167 -58,786 33,214 -89,593 1,660 29,423 36,082
Ni 1,475 -0,346 -2,079 3,244 1,205 -0,190 1,417 -1,339

Different regression equations can be derived from the data in Tables 6 & 8,
correlating the influence of the different alloying elements to the resulting graphite
distribution. Eq. 1 gives an example of one of the regression equations derived for the
formation of type A graphite in area 2. Observe the inverse correlation for type A formation
in Area 2 and 3 for additions of Mn, Si, P, S and Cr.

% graphite A in area 2(A2) = -22.24 + 15.44(%C) - 7.57(%Mn) – 18.32(%Si) + 111.08(%P)

– 739.99(%S) + 95.55(%Cr) + 1.48(%Ni) (Equation 1)

In order to achieve a maximum of type A graphite in areas 2 and 3 and minimize the
formation of graphite B, C, D/E, the chemical composition was aimed to be designed
according to these criteria.

For this purpose an optimization algorithm, SIMPLEX, was used. The algorithm of
simplex was designed by George Dantzig in 1947 and is a numerical method for solving
linear programming problems. It is cited as one of the top ten algorithms of the 20th
century by the magazine Computing in Science and Engineering [6].

The linear programming problem of this work is to maximize the percentage of type
A graphite in areas 2 and 3 and minimizing type B, C, D and E graphite in these areas. In
the solutions to this problem a system of linear inequalities, called restrictions, must be
respected. The restrictions are set in Table 7.

11
 Table 7. Restrictions for the linear programming problem.
Solution C Mn Si P S Cr Ni A2 B2 C2 D2 A3 B3 C3 D3
1 unlimited unlimited unlimited unlimited unlimited unlimited unlimited 100% 0% 0% 0% 100% 0% 0% 0%
2 unlimited unlimited unlimited unlimited unlimited unlimited <=1,50 100% 0% 0% 0% max. 0% 0% 0%
3 unlimited unlimited <=2,20 unlimited unlimited unlimited <=1,00 100% 0% 0% 0% 100% 0% 0% 0%
4 <=3,80 unlimited unlimited unlimited unlimited unlimited <0,85 100% 0% 0% 0% max. 0% 0% 0%
5 <=3,80 unlimited unlimited unlimited unlimited unlimited <0,85 max. 0% 0% 0% 100% 0% 0% 0%
6 Table 1. Table 1. unlimited Table 1. Table 1. Table 1. Table 1. max. 0% 0% 0% 100% 0% 0% 0%
7 Table 1. Table 1. Table 1. Table 1. Table 1. Table 1. Table 1. max. min. min. min. max. min. min. min.

The response of the simplex algorithm is presented in Tables 8 and 9.The solutions
are given in terms of chemical composition (Table 8) and as a prediction of graphite type
related to the chemical composition (Table 9).

Table 8. Optimized chemical composition according to the simplex algorithm analysis.

Planned chemical analysis(SIMPLEX results)
Solution
C Mn Si P S Cr Ni

1 4,15 0,46 2,70 0,034 0,022 0,31 2,87

2 4,22 0,23 2,20 0,020 0,030 0,30 1,50
3 4,43 0,07 2,28 0,020 0,033 0,28 1,00
4 3,80 0,40 2,20 0,046 0,017 0,25 0,85
5 3,80 0,41 2,48 0,065 0,019 0,20 0,85
6 3,65 0,28 1,55 0,029 0,031 0,14 0,85
7 3,65 0,50 2,20 0,044 0,018 0,18 0,80

Table 9. Predicted graphite type according to the chemical compositions given in Table 8.
Preditions of graphite types(SIMPLEX results)
Solution
A2 B2 C2 D2 A3 B3 C3 D3
1 100% 100% -9%
2 100% -2% -18% -22% 76% 24%
3 100% -8% -42% 100% -2% -27%
4 100% 4% 42% 15% 38%
5 11% 35% 44% 10% 100% -16%
6 -16% 116% 100% 14% -13%
7 5% 33% 62% 94% 5% 1%
Note: The calculations of the graphite of the various types, in Table 9 may be negative
numbers for graphite B, C, D / E. In the discussion the negative values have been set to "0 %".
Values exceeding 100% in the calculations have been set to 100%.

Analyzing solution no.1 (Table 9, first line) it predicts 100% of type A graphite in
area 2 and 100% type A graphite in area 3, but with a chemical composition not economic
and out of range for technical specifications (C = 4.15, Mn = 0.48, Si = 2.70, P = 0.034, S
= 0.022, Cr = 0.31; Ni = 2.87). Going back to Table 7, we find that there are no restrictions
for the chemical composition but with the restrictions of 100% graphite A2 and 100%
graphite A3. In practice, the chemical analysis of row 7 in Table 8 is the best result that
can be achieved within the restrictions in chemical composition given in Table 1. It is
obvious that the change of chemical analysis has limitations regarding the control of the
resulting graphite structure (A2=5%, A3=94%).

The chemical composition determined by the described simplex algorithm was

tested with positive results on castings in production (Phase II - samples 321-440).

12
Phase II - Analysis of graphite precipitation using the parameters recorded by the
thermal analysis tool, ATAS®, as input data

The purpose of this phase of the project is to consider the chemical composition
proposed from the analysis in Phase I. In combination with this chemical composition the
effect of using different inoculants was analyzed. The inoculants were added in the Quick-
cups and five inoculants in added quantities of 0.1% were studied. The studied parameters
were the types of graphite formed and the change in the values of thermal parameters.
The chemical compositions of the five inoculants are presented in Table 10 and the
graphite types in Table 11

Table 10. Chemical composition of the studied inoculants (wt%).

Inoculant Si Ca Ti Bi Al RE Ba
1 54,11 0,97 9,10
2 74,70 1,35 0,82 0,71 0,51
3 76,04 1,40
4 66,24 1,59 0,87 1,13
5 58,70 31,08 1,32

Table 11. The achieved graphite types using the inoculants described in Table 11.
Graphite distribution
Inoculant
A2 B2 C2 D2 A3 B3 C3 D3
Uninoculated 10% 30% 60% 85% 10% 5%
1 50% 50% 70% 30%
2 40% 30% 30% 40% 10% 30% 20%
3 40% 60% 40% 40% 20%
4 100% 70% 30%
5 100% 80% 20%

By the use of the different inoculants it is possible to determine how the mode of
solidification influences the thermal parameters as the chemical composition is constant. In
Table 12 the parameters from the thermal analysis are presented. The desired
appearance of the graphite phase is type A in both Areas 2 and 3. Comparing the data in
Tables 11 and 12 it is observed that a maximum formation of type A graphite is achieved
when TElow is high, R has an intermediate value and GRF2 is low. This means that
inoculants 4 and 5 give a structure close to the desired. Based on the data for inoculants 4
and 5, the desired range (Table 13) for the thermal parameters is derived.

Table 12. Thermal parameters for different inoculants.

Thermal parameters
Inoculant
TL TElow R S1 GRF2
Uninoculated 1171,5 1130,1 6,3 41 41
1 1172,3 1142,0 1,3 39 61
2 1171,6 1140,4 5,2 31 36
3 1171,6 1142,5 1,4 41 69
4 1171,2 1143,2 3,5 35 40
5 1171,4 1144,0 3,2 34 39

Table 13. Range for the thermal parameters to achieve a maximum of type A graphite.
Thermal parameters
TL TElow R S1 GRF2
min. 1170,0 1146,0 2,5 30 37
max. 1174,0 1142,0 4,0 40 43

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 Taking into account the findings described above, tests with a mixture of inoculants
4 and 5 in proportions of 50/50% were performed. This mixture of inoculants was added in
a total amount of: 0.05, 0.10, 0.15 and 0.20% to the melt and two castings at each level
were analyzed. The results are shown in Table 14.

Table 14. The effect of different amounts of inoculants 4 and 5.

Inoculant 4
+ A2 B2 C2 D2 A3 B3 C3 D3
Inoculant 5
0,05% 80% 20% 80% 20%
0,05% 80% 20% 90% 10%
0,10% 80% 20% 70% 30%
0,10% 90% 10% 80% 20%
0,15% 90% 10% 80% 20%
0,15% 90% 10% 80% 20%
0,20% 90% 10% 70% 20% 10%
0,20% 80% 20% 80% 20%

With the aim of maximizing the percentage of type A graphite, it is observed that an
addition of 0.15% gives a maximum for Area 2 and 0.05% a maximum for Area 3,
respectively. Taking into account the difficulties to inoculate with 0.05% in production it
was decided that the industrial application test, consisting of a month of production
(sample 441 to nr. 600), would be inoculated by an amount of 0.15% in a mixture
(50%+50%) of inoculants 4 and 5.

Phase III – Industrial application of optimized grey cast iron

With an optimized chemical composition (Phase I) and inoculation process (Phase

II) data for one month’s production were acquired. The data from these samples (441-600)
are presented together with the data from Phases I and II in Fig. 11.The evolution of
graphite precipitation during this study is depicted and the phases (I, II and III) are
indicated.

Fig. 11 shows that optimization of chemical composition has a low effect on the
precipitation of type A graphite in Area 2. The average in Phase I increases from 40% to
45% for Phase II, but also D/E type graphite in this area increases from 20% to 30%. The
optimization of chemical composition has a good effect on type A graphite evolution in
Area 3 where, in average, Phase I gives 60% compared to 75% in Phase II without an
increase in type D and E graphite.

The most potent means of maximizing the amount of type A graphite in both Areas
2 and 3 is achieved by the optimization of the inoculation process (as seen in Phase III).
The undesired graphite types are minimized by this optimization.

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 100%
A2 B2
90%
C2 D2
80%

70%

60%
I II III
50%

40%

30%

20%

10%

0%
10 60 110 160 210 260 310 360 410 460 510 560

100%
A3 B3
90%
C3 D3
80%

70%

60%

50%

40%
I II III
30%

20%

10%

0%
10 60 110 160 210 260 310 360 410 460 510 560

Figure 11. Evolution of graphite precipitation during the different phases.

(Phase I - Samples 1-320; data collection and analysis of correlation and regression.
Phase II - Samples 321-440; verification of the optimization of the chemical composition with
SIMPLEX. Phase III - Samples 441-600; optimization and verification of the thermal
parameters of solidification
The graph lines are 60 averages based on 10 data points of a total of 600 samples.)

Conclusions

• To minimize the amounts of undesired types of graphite (B, C, D and E) and maximize
the amount of type A graphite the most potent means is optimization of the inoculation
process. It is shown that the amounts and chemistry of different inoculants most
strongly affect the precipitation of graphite and the resulting graphite distribution.
• From the study an interval for some thermal parameters was determined for which an
optimum in graphite precipitation was observed.
• Depending on the distance from the chill, A or D/E type graphite formed in opposite
amounts. High amounts of type A and low amounts of D/E graphite formed close to the
chill and vice versa for the area further away from the chill.
• It was observed that the alloying elements had different effects on graphite formation
depending on the distance from the chill. Close to the chill, an increase in C, Mn, Si, P
and S decreased the amount of A-type graphite and the opposite correlation was
observed for the area further away from the chill.

15
• This study shows that it is possible to optimize graphite distribution in a casting by
using thermal analysis in combination with metallographic and chemical analysis. A
fundamental improvement is achieved by regression analysis of the data.

References

1. D.M. Stefanescu: “Modeling of cast iron solidification – The defining moments”,

Metallurgical and Materials Transactions A, 2007, Vol. 38A, No. 7, pp. 1433-1447.
2. D. Holmgren, A. Diószegi and I.L. Svensson: “Effects of inoculation and solidification
rate on the thermal conductivity of grey cast iron”, 2006, 67th World Foundry Congress,
June, Harrogate, United Kingdom.
3. T. Sjögren and I.L. Svensson: “The effect of graphite fraction and morphology on the
plastic deformation of cast irons”, Metallurgical and Materials Transactions A, 2007, Vol.
38A, No. 4, pp. 840-847.
4. P.A. Blackmore and K. Morton: “Structure-property relationships in graphitic cast irons”,
International Journal of Fatigue, 1982, July, pp. 149-155.
5. ISO 945-1:2008, “Microstructure of cast irons – Part 1: graphite classification by visual
analysis”, International Organization for Standardization, 2008.
6. J.C. Nash: “The (Dantzig) simplex method for linear programming”, Computing in
Science and Engineering, 2000, Vol. 2, No. 1, pp. 29-31.

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