4. Discussion
Large pores exist in the center of the billet and the pores are up to 10 mm in width. These are similar porosity values of the same range as found in continuously cast billets of high carbon steels with columnar structure in the center [
18]. These carbon steels have a large solidification interval of 40–60 °C [
19]. The main reason for the large porosity in the case of A286 alloys is the large solidification interval, which was calculated to be as high as 117 °C, i.e., twice that of high carbon steel grades. Porosity in this range could be troublesome during forging and rolling processes and cause internal cracking and residual porosity.
Precipitates are mainly located in the interdendritic areas. The size of precipitates increases as the structure coarsens and then decreases closer to the center, which is consistent with the measured SDAS values. The equilibrium calculations using Thermo-Calc showed an amount of MC precipitates between 0.5% and 0.7%, which is similar to the amount of precipitates found in the image analysis, 0.5% to 0.7%. The TiC phase was found in the segregated interdendritic areas and in the grain boundaries in the form of flake-like precipitates. The elemental spot analyses showed that these consisted mainly of Ti, C, and around 2 atom% Mo. The morphology indicates a solid phase precipitation.
The Thermo-Calc calculation of components of the MC-phase above the liquidus temperature shows a TiN-phase which corresponds to the cubic orange inclusions in
Figure 14. During cooling to room temperature these inclusions should change their composition by replacing N with C according to
Figure 19. However, this did not happen, probably due to a fast cooling rate which limits the time for element exchange by diffusion.
The non-metallic spinel phase Al
2O
3-MgO were found in many TiN precipitates. It has been reported that spinel can act as inoculant for Ti(CN) [
20,
21].
The nickel-rich bright grey phase found in segregated areas, see
Figure 10, is presumed to be η-Ni
3Ti based on the analyzed Ni/Ti ratio and the acicular platelet morphology, which was formed in solid phase. Thermodynamic calculations show that η-Ni
3Ti is formed after solidification below 750 °C.
Phosphides were found in the last solidified melt. The composition of these phosphides varies, but the concentrations of P and S stands out. The phosphide precipitates could be a low melting point eutectic of a M
3P phase, which has been found both in high manganese austenitic steels and electrolytic iron alloyed with P [
13,
22]. The presence of regular phosphides in the structure also indicates the possibility of P rich segregate layers forming in grain boundaries, which cause grain boundary decohesion [
22]. Since these layers are only a few atomic layers in thickness they would be difficult to detect by using EDX analysis.
Continuous casting of stainless steel blooms that solidify primarily as austenite displays a columnar structure from the surface to the center [
23]. The alloy A286 also solidify as primary austenite and it was expected that the structure would be a 100% columnar structure. However, the results in
Figure 6 shows that an equiaxed zone exists in the center. During the investigation of the structure it was found that TiN precipitates existed in the whole cross section. However, these particles are not effective inoculants of austenite [
20,
24]. Particles of spinel were also found and if these particles are not covered by Ti(CN), they act as inoculants for austenite and promote the formation of an equiaxed structure [
24].
There are some anomalies at the billet surface region.
Figure 5a,b shows that there is a coarse dendrite structure and what looks like an oscillation mark. The most probable reason is the formation of a folding oscillation mark, giving a lower heat transfer and thus a coarser structure.
The secondary dendrite arm spacing, SDAS, is known to affect properties such as the strength and hardness of a material. Moreover, it affects the soaking time needed to reduce microsegregations, as well as the time to dissolve possibly detrimental phases precipitated in the interdendritic regions. The relation between SDAS and cooling rate,
, is usually expressed [
25,
26,
27] as follows:
where, the value of
K is in
K/s, and n is dimensionless. Usually n has values between −0.33 to −0.5 [
25,
26]. An investigation of the solidification structures of several Fe-Ni-Cr alloys, ranging from 5 to 20 wt % Cr and 5 to 30 wt % Ni, showed that K varied between 40 to 55 μm and n varied between −0.4 to −0.5 [
27]. The constants in Equation (3) are determined empirically in solidification experiments using controlled cooling rates. However, they can be estimated based on measured values of SDAS and a calculated cooling rate. To assess the cooling rate, a simulation of the solidification of the shell was done by assuming one-dimensional heat flow. Thereafter, Fourier’s second law was solved numerically using the software Comsol Multiphysics 5.4. The assumption is valid at small shell thicknesses.
The heat transfer was matched so as to keep the surface temperature, T
surface, at 1000 °C throughout the simulation. Thereby, the cooling rate could be assessed by using the following equation:
where,
tf is the local solidification time. The parameters used in the simulation are shown in
Table 5.
The solid and liquid temperature lines are plotted against the shell thickness in
Figure 20a. The width of t
f increases with increasing shell thickness. In
Figure 20b the calculated cooling rate is plotted against the measured SDAS values. A linear curve fitting, dotted line in the figure, was applied to evaluate the values for K and n. The obtained values were K = 31.7 μm and n = −0.38.
Porosities starts to appear in the interdendritic areas at 30 mm from the billet surface, as shown in
Figure 9. The fraction of porosity, f
porosity, in the columnar structure is about 0.001, which corresponds to a solid fraction, f
s, of 0.999. The liquid feeding in the mushy zone towards the billet surface is almost complete in order to compensate for the solidification shrinkage:
where,
is the solidification shrinkage, which usually has a value of 0.03 for steel,
is the solid density, and
is the liquid density. By having a
value it is possible to calculate the fraction of liquid,
fL, that is necessary to create the measured area fraction of porosity when liquid feeding has stopped as follows:
The pressure gradient,
, in the mushy zone is the driving force for the interdendritic liquid flow,
, which is estimated using Darcy’s law [
29]:
where,
K is permeability (m
2) and
μ is dynamic viscosity (kg/m·s).
Heinrich and Poirier [
30] have proposed the following expression for the permeability:
where,
is the primary dendrite arm spacing [m]. By combining Equations (7) and (8), the pressure gradient in the mushy zone can be expressed as:
The liquid flow can be estimated by the following relation [
31]:
where,
is the velocity of the solidification shell obtained from the solid line in
Figure 20.
It is well known that a large solidification interval, T
L-T
s, leads to an extended mushy zone entailing more resistance for liquid feeding.
Figure 21a shows a plot of f
s = 1 to f
s = 0.4 versus the distance from the billet surface at the times 35 s, 110 s, 220 s, and 350 s. The colored lines denote the times at which the shell is completely solidified, f
s = 1, at the distances 10 mm, 20 mm, 30 mm, and 40 mm. The feeding distance through the mushy zone, f
s < 1, indicated with arrows, increases further in from the billet surface. It is almost four times longer for the 40 mm distance as compared with the 10 mm distance. This increase in feeding distance could explain the start of a porosity formation at 30 mm. Equation (9) was solved numerically to study how the pressure varies in the mushy zone at the distance 30 mm. When the pressure drops below the equilibrium pressure for gas in the liquid, conditions for pore formation exist. The input values of parameters for the calculations are given in
Table 6.
The results of the calculations are presented in
Figure 21b as the pressure plotted verses the distance in the mushy zone and solid fraction. The pressure drops sharply when f
s > 0.97 i.e., very close to the position, within 1.5 mm, where the shell has solidified completely. This value correlates well to the calculated value of the fraction of liquid at the start of porosity formation at 30 mm distance from the surface. Thus, conditions exist for gas pore formation. For values of f
s < 0.97, there seems to be almost no resistance to a liquid flow, due to the very small pressure drop.
In the equiaxed zone the area% of porosity sharply increases to a value of 0.15%. This can be attributed to the lower permeability and longer liquid feeding distance in an equiaxed zone.
The results in
Figure 16 show that the segregation index for Ti increases from approximately 2 to 3.9 at a distance 45 mm from the billet surface. One reason for the increase is the start of the equiaxed zoned at approximately 50 mm from the billet surface. However, the same behavior cannot be seen for the Mo segregation index, which is nearly constant from the surface to the center. At this time it is not possible to determine the reason for the sharp increase of the segregation index of Ti. This high Ti segregation could adversely affect the hot ductility of the billets center area.
The homogenization time prior to hot rolling is one important process parameter to be determined to improve the hot ductility. The measured SDAS values in
Figure 6 are used to estimate the homogenization time from the surface to the center of the billet. We considered the relation between diffusion time,
, and SDAS,
, by using Einstein’s Brownian motion equation expressing the diffusion time as follows:
where
, is the diffusion constant and
is the homogenization time, which will give a rough estimate of the time it takes to homogenize the cast product. The difference in diffusion time in the cross section is written as the ratio between the SDAS value at an increasing distance,
x, from the surface,
, and the SDAS value at the surface,
, such as:
Figure 22 shows the results from calculations using Equation (12). The results show that it would take approximately 30 times longer to homogenize the structure at 60 mm than at the billet surface.