Journal of Magnetism and Magnetic Materials 26 (1982) 15-2 1 15

North-Holland Publishing Company

DECARBURIZATION RATE RELATED TO SURFACE OXIDATION OF GRAIN ORIENTED

SILICON STEEL

P. MARINI and G. ABBRUZZESE

Centro Sperimentule Metdurgico, Pomezia, Rome, Ita!v

The decarburization temperature of electrical steel (Si=3%) is a conditioning parameter for the residual minimal carbon
content left in the steel. It is well known that, when the decarburization temperature rises above 860°C the deepness of
decarburization starts to decrease. This fact has been related to the formation of an oxidized layer of silicon which, in certain
conditions of temperature and pHIO/pH2 ratio, brings the decarburization rate towards zero. The aim of present work consists
in determining the role of the various parameters in order to formulate a mathematical model which, starting from the
theoretical diffusion laws, will allow to control the decarburization process of the 3% silicon steel.

1. Experimental sample is introduced into the furnace.

The decarburization rate, as a function of tem-
perature, pHZO/pH2 ratio, silicon content and
thickness of the steel sheet, has to be determined
with the greatest accuracy.
The experimental apparatus is shown in fig. 1.
A quartz tube, 100 cm long (inner diameter 10
mm) is partially introduced in a furnace; the sam-
ple (8 X 30 mm*) is introduced in the cold section
of the tube and then pushed in the hot zone by
means of a magnet, in order to prevent any air
pollution of the decarburizing athmosphere. Gas
flow rate was strictly controlled by a volumetric
pump at 1000 cm3/min; water vapor content of
the gas (pure H2) was controlled by an automati-
cally thermostated bubbler. The gas stream was
introduced into an empty columns chromato-
graphic apparatus; the thermo-conductivity cell
therefore could countinuously measure the amount
of CO and CH, in the gas stream, as soon as the
The calibration curves were obtained introduc-
ing into the fumance a standard carbon steel
sample. A typical decarburization rate is shown in
fig. 2.
According to others. experimental works [2,4],
carbon is released in two well defined steps, the
first noticeable smaller than the second. It is im-
mediately evident that the total carbon extracted
from the sample at 930°C is smaller than that at
790°C.
The experimental work has been carried out on
two different, cold rolled commercial steels (A and
W.
g&Q
dt

*
1 2 3 4 5
l%srmo
- conductivity cell t(min)

Fig. 1. Experimental apparatus for decarburization study. Fig. 2. Decarburization rate of steel A.

0304-8853/82/0000-0000/$02.75 0 1982 North-Holland

16 P. Marini, G. Abbruzrese / Decarburization rate of grain oriented silicon steel

Si - 2.R71$
Si C Mn S Al N R - 0.028c.n
A 2.87 0.054 0.09 1 0.022 0.032 0.0072
B 3.19 0.026 0.071 0.023 0.002 0.0041

The decarburization rate of sample A, at four

different temperatures and at pHz0/pH2 = 0.245 is
shown in fig. 3. Even increasing the decarburiza-
tion time, a complete carbon release does not
occur if the temperature is higher than 830°C. The
_
effect of P~,~/P~? appears from fig. 4. The per- 7oL
centage of decarburization increases, by increasing 0 0.1 0.2 0.3 0.4 P H2O/P 82
the oxygen potential of the atmosphere.
Fig. 4. Percentage of decarburization as a function of the
Fig. 5 shows the effect of silicon content in the
PH~O/PH~ ratio.
steel, the higher the silicon content, the lower the
percentage of decarburization. Fig.6 shows the
effect of the thickness of the steel. 3 - 0 245
Experimental results strongly suggest that sili- PA2 '

100 8 = o.o2%l
con oxidation, at the sample surface, is the most t P
t 240.~~
important controlling parameter of the decarburi- De0
(I) 6 -_______ "--w---_-_-Q 790°c
zation process. A further experimental work on the --____
go .. ---.._ ---___ Q 830~
oxidation rate of silicon has been therefore carried o-s_
---___
out. --__
- “-0 06O~C
Many attempts have been done regarding the 80 .. m-N_
best analytical method for silica determination, ---_
--__
including oxygen solid cell. Observed poor accu- -w_
--a 9oooc
racy of instrumental analytical methods forced us 70
to use the wet chemical analysis. Samples of steel 2.1 2.8 2.9 3.0 3.1 3.2 Sic%)

A were introduced into the furnace at various Fig. 5. Percentage of decarburization for steel A and B.
temperatures and pH20/pH2 ratios for 30, 60, 120,
180 and 300s. After the heat treatment the sam-
t . 24Ome.z
ples were attacked in 30% sulfuric acid at 95” for Si I 2.8%

Si = 2 Al?
* = 0.02Rcn

0 1 2 3 4 5 0.02-I 0.028 0.029 0.030 dd

t(dlll
Fig. 6. Percentage of decarburization as a function of thickness
Fig. 3. Decarburization rate of steel A at various temperatures. obtained by the mathematical model.
 P. Marini, G. Abbrtuzese / Decarburization rate of grain oriented silicon steel 17

asymptotic value of the amount of silica produced

seems to be correlated to thepH20/pH2 ratio only.
The decarburization temperature on the contrary
acts prevailently on the oxidation rate of silicon.

2. Decarburization related to oxidation

It is well known from classical theory of selec-

tive internal oxidation that the precipitation front
of the insoluble oxide particles increases according
0 I 2 3 4 5 tfnin\
to a parabolic law. The fundamental parameters
are determined by a stoichiometric balance of
. a00 lc outward diffusion of the alloying element and of
. 330 'c
inward diffusion of oxygen [lo]. The theory fore-
. 730 lc
8iO3
sees [6] in the zone of internal oxidation a solute
enrichment that increases with increasing tempera-
ture and decreases with increasing oxygen poten-
tial. It has been shown that particular conditions
of temperature, alloy composition and oxygen
potential of the annealing atmosphere can cause a
transition from internal to external oxidation [ 131.
Wagner [ 13,141 has proposed that the transition
from internal to exclusive external oxidation should
0 1 2 3 4 t(ni”) occur when the solute content is sufficient to form
a critical volume fraction of internal oxides pre-
m BOO’C
. a50*c cipitated at the reaction front. Hence the transi-
tion is due to a reduced cross-section or a mecha-
nical blocking of the diffusion processes caused by
the precipitate oxide particles in the matrix. The
critical volume fraction of oxides necessary for the
/ transition should be an approximately constant

(9)

0 1 2 3 4 5 t(xinj

Fig. 7. Kinetics of silicon oxidation in steel A for different

PH~o/~, ratios.

about 10 min (the required time to detach the

silica layer). The residue after filtration is then
disgregated and analysed for silicon determina-
tion. The results are presented in fig. 7. The oxida-
tion rate of silicon is surprisingly analogous to the Fig. 8. Qualitatively silicon concentration in the oxidized layer
decarburization rate, as shown in fig. 3. The in blocking conditions.
18 P. Murini. G. A hhruzzese / Decurburizution rate of gruin oriented silicon steel

value for a given alloy system under any oxidizing 3. Mathematical model of Fe-38 Si decarburiza-
condition. When the solute concentration is a little tion
lower than the critical value for the exclusive ex-
ternal oxidation, the reaction front proceeds for a Decarburization of 3% silicon steel is char-
few micrometers and then stops because of the acterized by two different steps (fig. 2). A first
mechanical blocking of the inner oxides particles. partial decarburization occurs during the sample
For 3% silicon steel, in the examined experimental heating in good agreement with the thin sheet
conditions [l], such mechanical blocking due to diffusion law. As soon as silicon reacts with the
inner oxidation occurs. wet atmosphere (= 7OO’C) (fig. lo), an external
Not considering the very thin silica layer silicon oxidation occurs [3] and the impervious
(= 100 A) formed during the rise in temperature of thin layer of silica inhibits further decarburization.
the sample [8], the solute concentration in the Increasing the temperature, the oxygen poten-
inner oxidized layer should present a shape as tial becomes suitable for internal oxidation of
shown in fig. 8 [3,5]. As the internal oxidation silicon and the decarburization can start again. As
proceeds the decarburization rate progressively de- the oxidized particles are formed the decarburiza-
creases; depending on the working conditions, both tion rate decreases and finally stops when the
processes stop after a well defined time. As shown critical volume fraction of silica has been formed.
in fig. 7 the asymptotic values of silica in the The first decarburization, in the mathematical
830-900°C range seems to be, in first approxima- model has been therefore considered as a classical
tion, practically independant from temperature. At carbon diffusion during the rise in temperature of
lower temperature (79O’C) the oxidation of silicon the sample up to 7OO’C. Of course the higher the
seems to continue indefinitely according to a decarburization temperature the lower is the time
parabolic law; probably in the considered of the first decarburization (fig. 11).
pH20/pH, range a non-blocking internal oxidation The formation of the oxidized layer can be
occurs. mathematically treated according to silicon diffu-
In the examined experimental conditions silica sion from a thin sheet of material; the oxidation
is the most abundant component of the oxidized front has in fact a concentration -0 (fig. 12). On
layer. Only small amounts of iron oxides or faya- the other hand the thickness of the layer (a 2 pm)
lite were detected because of the shortness of the is a very small fraction of the whole thickness of
decarburization process and the relatively low tem- the steel sheet. The mathematical formulation has
perature [2]. The thickness of the oxidized layer been modified taking into account the mechanical
increases at constant temperature with the blocking of silica particles by introducing a limit-
pHZO/pH, ratio; at higher temperature the thick-
ness of the layer tends to decrease (fig. 9).

I
0.50
p
- VJ - 0.078 1 4T - lOW/nin
At
2 I 1
p R2

1 ~~ /
,--
P A20
-
p A2
- 0.245

_________
=o*o24o
0.25 /
1
I t
1
I
i
1 o
L

01 : 8 I
mo 830 MO 'f(W) ga0 mo400600800 1000 T(V)

Fig. 9. Thickness of the oxidized layer in steel A. Fig. IO. Thermogravimetdcal analysis for steel B.
 P. Murini, G. Ahbruzzese / Decurburiration rate of grain oriented silicon steel 19

plied by the factor 1 -(f-Q/W-L), where

f= the actual volume fraction of silica, f, = the
starting volume fraction of silica, f, = the critical
volume fraction of silica.
The actual volume fraction of silica increases
through the thickness of the oxidized layer up to
the critical volume fraction. According to the pro-
posed model for the silica concentration in the
oxidized layer, fig. 8, the volume fraction of silica
does not increase linearly [3,5]. Good approxima-
tion can be obtained taking a quadratic depen-
dence of the volume fraction from the thickness of
the layer
0 13 20 ‘)o 40 t(mea!
-YJiis f=fo + aE2, (2)
- T,?lo1c .
where 5 is the thickness of the layer and (Y=
Fig. 11. Heating rate of the sample for two different working constant.
temperatures of the furnace. In order to render the experimental data con-
sistent with the starting eqs. (1) it is necessary to
establish a relationship between extracted Si and
ing factor to the outward diffusion of silicon: The silicon volume fraction. Being the silicon extracted
classical expressions for the outward flux of silicon related to the thickness of the oxidized layer in
and carbon can be generally formulated non-blocking conditions by Si(t) = Ji[, (2) can be
easily modified in to
(1)
f=f, + ySi’(t), (3)
where Si = extracted silicon, C = extracted carbon,
Dsi = diffusion coefficient of silicon in Fe-3% Si; the limiting factor therefore becomes (1 - Si*( t)/
Dsi = 1.8 exp( - 5OOOO/RT), DC = diffusion coef- Sif). The final expression for the silicon extracted
ficient of carbon in Fe-3% Si; DC = 0.85 from the steel is
exp( - 27200/RT) [IS].
Taking into account the critical volume fraction (4)
of silica the classical expressions have been multi-
the critical silicon is obtainable from the experi-
mental values of the silica formed at the surface of
I the samples fig. 7.
41 A simplified expression for Si(t), valid for very
-_- -___ ---_ x.
0 low percentage (C 0.2%) of extracted silicon and
Sl
therefore suitable for our purposes, is:

(5)

% where Si, = concentration of Si in the steel, t =

time in s, X = half-thickness. Hence

)I
0 X
dSi SiiD,, Si *
Fig. 12. Theoretical concentration of silicon and oxygen during
dt= 1.497 Sib’
1-x , (6)
the lntemal oxidation process. (
 20 P. Murini, G. Ahbruzrese / Decarburizution rate of grain oriented silicon steel

by integrating (3) 8 I 0.03cm

1_ Si’W
-=exp(-2kt),K=
SiiDsi
0.
Si:, 1.497 Si2X2
f *
An analogus expression is suitable to describe 0.15
the decarburization; the blocking for silicon oxida- I
4 t - 24080~
tion acting in the same way for carbon extraction. j 0.1
The expression for the decarburization of a thin
sheet of material is well described by the equation: 3
5 0.0

C(t) = CO[1 - 0.811 exp( -2.467Dcr/h2)]. (7) 1

*
For carbon extraction: -I60 800 a40 a80 T(W)

Wt)
I 1
Si2( t) Fig. 13. Fraction of residual carbon as a function of the
-=g(C,D,) l-- .
dt Sif temperature obtained by the mathematical model.

Hence
step of decarburization [function, as shown before
d(l -C/Co) = -2.467$exp(-2kt). (9) (fig. 1l), of the furnace temperature]; if t = t,,
(1 -C/C,) dt
C = 0; if t + 00, C = C,(l - exp( -6/2k).
Integrating (9) The percentage of decarburization depends
therefore from: a) temperature, through the factor
C(t) = Co{ 1 - exp(S/2k[exp( -2k(t - tr>) - 11)) I S/2k, b) pH20/pH2, through the factor k which
containes the expenmental value of Si,.The carbon
(10)
extraction during the first decarburization step
where 6 = 2.467 Dc/A2, C, = carbon concentra- proceeds according to the classical diffusion laws;
tion at the beginning of the second step of de- approximately the total amount of carbon ex-
carburization, t, = starting time for the second tracted during the rise in temperature of the sam-

Table I
Theoretical and experimental values of decarburization tests

T PHIO/PH, C Si S C,,,(final) C,,(final) Dec. model

(“Cl :s, (W) (%) (cm) (ppm) (ppm) (S)

790 0.078 240 0.054 2.87 0.028 33 31 94. I

790 0.245 130 0.026 3.19 0.027 26 28 88.9
790 0.245 180 0.054 2.87 0.027 29 27 94.8
830 0.245 240 0.054 2.87 0.03 40 45 91.6
830 0.245 100 0.026 3.19 0.027 35 33 87.2
830 0.078 240 0.054 2.87 0.03 68 71 86.7
860 0.445 180 0.054 2.87 0.028 38 34 93
860 0.245 180 0.054 2.87 0.028 60 58 89
860 0.445 120 0.026 3.19 0.027 28 25 90
900 0.245 180 0.054 2.87 0.028 115 110 79.6
900 0.245 300 0.054 2.87 0.028 112 I10 79.6
900 0.445 180 0.054 2.87 0.028 67 73 86
 P. Murini, G. Abbrurrese / Decarburimtion rate of grain oriented silicon steel
ple in ranges between 10 and 14% of the total
carbon (10% for a decarburization temperature of
9OO”C, 14% for 79O’C).
Hence, the total carbon extracted can be calcu-
lated by
C(t) = C,(O.lO-0.14) + C,[l - (O.lO-0.14)]
X { 1 - exp(S/2k[exp(-2k(t- t,)) - 11)).
In table 1 the agreement between the theoretical
and experimental values of some decarburization
tests is shown.
Fig. 13 presents, as function of the temperature,
the theoretical values of residual carbon obtained
from the model. The mathematical model has been
developed without introducing any calibration
parameter; it is therefore conditioned by the accu-
racy of theoretical diffusion data.
4. Conclusions
The proposed mathematical model connects, in
the examined experimental conditions, all the
parameters involved in the decarburization of 3%
silicon steels:
a) time of decarburization,
b) thickness of the strip,
c) silicon content of the steel,
e) temperature of decarburization,
f) PH20/PH2 ratio.
21
The only experimental parameter is the critical
silica content in the oxidized layer. An improved
model can be obtained by a better knowledge of
the critical volume fraction of silica in the oxidized
‘layer.
Acknowledgement
We acknowledge with pleasure the support of
this work by the Temi S.p.A., Terni, Italy.
References
[I] A.L. Geiger, J. Appl. Phys. 49 (1978) 2040.
[2] T. Yamazaki, Trans. ISIJ 9 (1969) 66.
[3] A. Datta et al., Proc. 3rd Intern. Conf. on Soft Magn.
Mater., Bratislava (1977) p. 492.
[4] A. Mayer, Stahl F&n 83 (1963) 1169.
[5] K.H. Schmidt, Stalwerke Bochum Report (1980).
[6] K. Bohnenkamp and H.J. Engell, Arch. Eisenhiittenenwe-
sen 35 (1964) IO1I.
[7] N. Morito and T. Ichida, Corrosion Sci. I7 (1977) 961.
[8] N. Morito and T. I&da, Scripta Met. IO (1976) 619.
[9] K.H. Schmidt, J. Magn. Magn. Mat. I9 (1980) 72.
[IO] R.A. Rapp, Corrosion 21 (1965) 382.
[I I] J. Moreau and J. Bernard, Acta Met. IO (1962) 247.
[I21 K.H. Schmidt et al., J. Magn. Magn. Mat. I3 (1979) 22.
[I31 R.A. Rapp, Acta Met. 9 (1961) 730.
[ 141 G. Wagner, Z. Elektrochem. 63 (1959) 772.
[IS] M.A. KrishtaI, Diffusion Processes in Iron Alloys (Jerusa-
lem, 1970) (Moscow, 1963) p. 119.