Corrosion Science, 1974, Vol. 14, pp. 391 to 399. PergamonPress.

Printed in Great Britain

THE INFLUENCE OF SILICON ON THE OXIDATION

PROPERTIES OF IRON*

I. SVEDUNG and N.-G. VANNERBERG

Department of Inorganic Chemistry, Chalmers University of Technology,
and the University of G6teborg, P.O. Box, S-402 20 G6teborg 5, Sweden

Abstract--Five Fe-Si alloys containing between 0.06 and 5.3 w/o have been oxidized in a gaseous
mixture of 20 v/o oxygen in argon. The oxidation temperatures were 500 °, 625 °, 800 °, 900 ° and 1000°C.
The reaction kinetics have been studied gravimetrically and the oxidized samples examined micro-
scopically, with an electron microprobe and with X-ray methods. The detrimental effect of silicon
on the oxidation rate of iron is most pronounced at high temperatures and silicon contents. For
comparative purposes, the oxidation of two chromium-nickel alloyed steels has been studied at
800 ° and 1000°C.

R~sumg---Cinq alliages Fe-Si, tenant de 0,06 b. 5,3 % pds, ont 6t6 oxyd6s dans un m61ange gazeux
argon-oxyg/me 20% Vol., b. 500 °, 625 °, 880 °, 909 ° et 1000°C. On a 6tudi6 gravim6triquement la cin&
tique des r~actions et on a examin6 les 6chantillons oxyd6s au microscope,/i la microsonde 61ectronique
et aux R X . L'effet pr6judiciable de Si sur la vitesse d'oxydation de Fe est maximale aux hautes
temp6ratures et teneurs en Si. A fin de comparaison, on a 6tudi6 l'oxydation tt 800 ° e t ~ 1000°C de
deux aciers au Cr-Ni.
Zusammenfassung--Fiinf Fe-Si-Legierungen mit einem Si-Gehalt zwischen 0,06 und 5,3 Gew. ~o
wurden in einem Gasgemisch von 20 Vol. % Sauerstoff in Argon oxydiert. Die Oxydationstemperaturen
waren 500, 625, 800, 900 und 1000°C. Die Reaktionskinetik wurde gravimetrisch untersucht und die
oxydierten Proben wurden mikroskopisch mit einer Elektronenmikrosonde und mit ROntgen-
methoden einer Untersuchung unterzogen. Der nachteilige Einfluss yon Silicium auf die Oxydations-
geschwindigkeit yon Eisen ist am deutlichsten bei hohen Temperaturen und hohem Siliciumgehalt. Zu
Vergleichszwecken wurde die Oxydation von zwei Chromnickelsttihlen bei 800 und 1000°C untersucht.

INTRODUCTION
ALTHOUGH the oxidation of silicon-containing steels in varying atmospheres and
temperatures has been investigated previously, 1-n the silicon content in a relatively
pure iron matrix has never been varied systematically. The present investigation
illustrates the influence of both low and relatively high contents of silicon on the
oxidation properties of iron in a temperature range of interest for different technical
operations, such as annealing and hot rolling.
High silicon contents are common in so-called dynamo steels and in ferritic cast
iron. Carbon has been found by other investigators n to have a destructive effect on
oxidation-protecting silicon-rich oxide phases formed on silicon alloyed steel.
Atmospheres containing reducing components, like hydrogen or carbon monoxide,
have also been shown to have a destructive influence on the protecting silica film
formed in gases with high oxygen pressures.2.Tm

EXPERIMENTAL
Preparation of samples
The different preparation techniques have been described in detail in a previous
*Manuscript received 8 August 1973, in revised form 17 October 1973.
391
392 I. SV~DU~G and N.-G. VANNERBERG

I=
r~

I- 0
Z

I-

0
N
Z

.<

f~
6666666

I-

Z
.<

[-
oE

6 6 6 ~ 6 6

r~

E
 The influence of silicon on the oxidation properties of iron 393

paper, xa The steels were made as round castings 12.9 m m dia, 100 m m high, and were
prepared and analysed by Surahammars Bruk Ltd., Sweden. Two commercial stain-
less steels were used as reference. The result of the analyses are given in T.able 1.

Oxidation procedure
The oxidation measurements were carried out with a micro thermobalance
(Mettler), the samples, round disks, 12 m m dia, 1 m m thick, being mounted on three
tips of boron nitride. A gaseous mixture of 20 v/o oxygen in argon at atmospheric
pressure was allowed to flow over the samples at 5 dm a h -1 (room temperature). The
furnace temperature was raised at a rate of 10° per min to the pre-selected value, which
was 500 °, 625 °, 800 °, 900 ° or 1000°C, and kept constant during the measurement,
which lasted for about 20 h. The weight gain due to oxygen uptake by the samples
was registered continuously.

Analysis of the corrosion products

The oxide films were investigated whilst they were still attached to the metal with
an X-ray diffractometer and the crystalline phases present were detected by the appear-
ance of their characteristic peaks. The oxide films were also studied with a scanning
electron microscope (SEM) and with an electron probe.

RESULTS
The weight gains of the different sample materials as a function of the time are
illustrated in Figs. l(a)-(e). The curves shown are those for representative individuals
from three identical measurements. The oxidation-preventing effect of silicon is very
pronounced and the weight gain of the sample material containing 5.34 w/o silicon
(Si 5), after 20 h oxidation at 500°C (W < 0.01 mg/cm~), is so slight that it cannot be
accurately measured with the thermobalance. When oxidized at 500 ° and 625°C, the
samples labelled Si 3 and Si 4 show a very low scaling rate during the initial stages of
oxidation. The oxide then fails to protect the alloys, and higher oxidation rates are

0.7 . 500eC
--Sil
0.6

O-S

0.4

~ 0.3

~ O.Z
Si2
0.1 ~ Si4
o si 5
I I I I I I I I I
0 i 2 3 4 5 I0 15 ZO
t, h
FIG. l(a).
394 I. S V E D U N G a n d N.-G. VANNERBERG

1,5
~ Sit

oJ

! I / I I I t t I
0 I Z 3 4 5 IO 15 20
f, h
FIo. l(b).

800"0
Sl !

N I0

$i2

i I i i t 1 t I I I SiS
0 I 2 3 4 5 I0 15 ZO

t, h

FIG. 1(c).
FIGS. l(a)-(e). The weight increase as a function of time for samples with varying
silicon contents during isothermal oxidation at the temperatures indicated.

registered. The weight gain after 10 h oxidation has been chosen as a measure of the
oxidation rate of the different samples. These values have been related to the cor-
responding values for the sample with the lowest silicon content (Si 1, 0.06 w/o Si)
and the resulting relative values of the oxidation rates have been correlated with the
silicon content in Fig. 2.
The variation in weight gain after 10 h oxidation as a function of the reciprocal
temperature is indicated in Fig. 3. The deviations in the results from identical runs are
indicated. The weight gain (10 h) of the chromium-nickel alloyed steels, also indicated
in Fig. 3, falls between those for Si 4 and Si 5. Cr-Ni alloyed steel with a molybdenum
content of 2.5 w/o shows the lowest weight gain.
 T h e influence o f s i l i c o n o n the o x i d a t i o n p r o p e r t i e s o f i r o n 395

~o Sil

3: $i Z
IC

Si 3
~Si 4
I I I I I I I I I~'Si 5
0 I 2 3 4 5 I0 15 ZO
t, h

FIG. l(d).

70 IO00"U
--si2

50 Si I
N

~" zo

0
f I 2 3 4 ,5 I0
%'
15 20
t, h

FZG. l(e).

The oxide phases appearing on the different sample materials, according to the
X-ray analysis, are listed in Table 2. The preferred orientations, if any, of the hematite
crystals relative to the oxide surface are also indicated. The oxide scales have been
examined while still attached to the metal substrate, and, if these scales were sufficiently
thin, peaks from the iron phases were also registered. Such peaks have also been listed
in Table 2 since their presence indicates that no other crystalline phase is present in
the oxide scale in sufficient abundance to provide a measurable diffraction of the
X-rays.
According to the microprobe analysis, there is a marked enrichment of silicon
in the oxide close to the oxide-metal phase-boundary (Fig. 4). The thickness of the
scale varies with the orientation of the metal grains relative to the exposed surface, as
396 I. SVEDUNG and N.-G. VANNERBERG

0'5

0"2

0'1

~ 0'05

0-02

0"01

0OO5

O'OOZ

0"001 I I I I I I
0 I ?. 3, 4 5
Si w, %
FIG. 2. The relative variation of the weight increase, after 10 h oxidation, with the
silicon content.

TABLE 2. PHASES AND ORIENTATIONS OF Fe2Os SURFACE CRYSTALS ON SAMPLES wITH DIFFERENT SILICON
CONTENTS OXIDIZED FOR 20 h AT DIFFERENT TEMPERATURES, DETECTED BY MEANS OF X-RAY DIFFRAC'IION*

Temperature
Sample 500°C 625°C 800°C 900°C 1000°C

((301)
Si I h m Fe h m Fe h (110) m Fe h (001) h (001)
Si 2 h m Fe h m Fe h Fe h (001) h (001)
Si 3 h m Fe h m Fe h (110) Fe h Fe h ((301)
Si 4 h m Fe h m Fe h (110) Fe h Fe h Fe
Si 5 h Fe h Fe h Fe h Fe h Fe

shown in Fig. 5. Oxide nodules are f o u n d on the oxidized samples (Fig. 6) pre-
d o m i n a n t l y in the discontinuities o f the scale in c o n n e c t i o n with exposed grain
b o u n d a r i e s o f the s a m p l e material. T h e grain size o f the Si 4 a n d Si 5 exceeds t h e
grain size o f the Si 1, Si 2 and Si 3 by a b o u t one o r d e r o f m a g n i t u d e .
The weight gain o f the samples registered during o x i d a t i o n is the s u m o f the weight
gains due to scale f o r m a t i o n a n d so-called internal oxidation. Internal o x i d a t i o n
becomes m o r e p r o n o u n c e d for higher o x i d a t i o n temperatures, A case o f p r o n o u n c e d
internal o x i d a t i o n is shown in Fig. 7,
 Fe Oxide Cu Mount

~)-

-~'~'~"~'-"-~-'"~ t.~. ~-.. ) ~ . i .-- \~ ~- .

• •

-~ • M ,

FIG. 4. The distribution of silicon in the oxide scale of a sample containing 0.90 w/o Si
(Si 3) oxidized for 20 h at 625°C. The line along which the profile has been measured is
indicated, x 3000.
FIG. 5. The influence of the metal grain orientation relative to the oxidized sample
surface on the scaling rate. Same sample as in Fig. 4. x 1000.
FIG. 6. Oxide nodule on the sample shown in Fig. 4. z 200.
FIG. 7. Pronounced internal oxidation in a sample containing 0.90 w/o Si (Si 3)
oxidized for 20 h at IO00°C. x 300.
 The influence of silicon on the oxidation properties of iron 397

Temp, "C
KXX)900 800 625 500
I I I I .I

50

zo

-- o,.'

oz

0"1

0'05

0.0:~

0'01 I I I
0.75 1.00 1.25

I000/T
FIG. 3. The variation of the weight increase for the different samples, after I0 h
oxidation, with the reciprocal absolute temperature. The corresponding values for the
two chromium nickel alloys oxidized at 800° and 1000°C are indicated. Fe-Cr-Ni/x,
Fe-Cr-Ni-Mo A.

DISCUSSION
When exposed to a hot oxygen-containing gas mixture iron is covered with an
oxide film. I f the partial pressure of oxygen is sufficiently high, and the contact between
the metal and the oxide phases is maintained during the oxidation the reaction is
governed by the rate of diffusion of the iron ions through the scale.
By alloying iron with an element like silicon with a higher affinity for oxygen than
iron, new oxide phases may form fayalite (Fe2SiO4) or silica (SiO2).1. 7 It is the con-
centration of silicon in the metal phase that determines which silicon-containing phase
will form.
Due to the very low iron diffusibility through a silica film the oxidation rate of
an iron-silicon alloy is very markedly reduced relative to pure iron.
During the oxidation, tensions are built up in the oxide and metal phases and, due
to the very limited ability of the oxides to compensate for these tensions by plastic
deformations, ruptures appear in the covering oxide scale. These ruptures cause the
scaling rate to increase. The metal phase close to the oxide-metal boundary is depleted
in silicon during the oxidation. This is due to the preferred oxidation of silicon and its
limited diffusibility in the metal phase. Although the bulk concentration of silicon in
the alloy is so high that a film of silica is formed during the first stages of oxidation,
398 I. SVEDtmOand N.-G. VANNERBERG

the surface of the alloy exposed after the formation of a rupture in the silica film may
have a silicon concentration that is too low to prevent the formation of the wiistite
and fayalite phases. The scaling rate then fails to drop to the low value that cor-
responds to the protective silica film. Instead nodules appear (Fig. 6) in which the
previously formed silica is converted into fayalite. 10
In order to protect iron from rapid scaling by alloying with silicon it is necessary
to add so much to the iron that the concentration of silicon on the surface of the metal
phase during oxidation never drops under the critical value where a protective film
fails to form. For silicon the critical bulk concentration has been estimated to be about
3 per cent by w e i g h t : : Since the diffusibility of silicon in the iron phase is dependent
on the temperature, it is probable that the value of the critical bulk concentration of
silicon also alters with the oxidation temperature. The weight gain vs time curves
show that, for 500 ° and 625°C, the silicon content of the sample material with
3.10 w/o Si (Si 4) is too low to prevent scaling. At higher temperatures the same
material is more effectively protected during the oxidation period (20 h).
The appearance of a magnetite phase in the scale formed on samples with low
silicon contents indicates that the silicon probably occurs as fayalite, which explains
the relatively high scaling rates of these materials. The absence of the magnetite phase
in the scale indicates, on the other hand, that silicon is present as silica x2 thus resulting
in the very slow scaling rate of these alloys. That the silicon-containing oxide phases
could not be detected by X-ray diffraction is probably due either to their lack of
crystallinity or to their appearance in very thin layers.
Oxygen dissolves in the alloy to such a degree that it exceeds the equilibrium
value between silica and silicon. Oxygen also diffuses more rapidly through the alloy
than does silicon) 4 These circumstances lead to so-called internal oxidation or sub-
scale formation. The sub-scale (Fig. 7) consists of silica particles embedded in metallic
iron.
In cases where the mechanic properties are of less importance, iron-silicon alloys
may provide a good alternative to stainless steels as scaling-resistant materials.

Acknowledgements--We wish to thank Professor Georg Lundgren for valuable discussions, Professor
Helmut Fischmeister, Dr Dag Svedung, Surahammar, and Tekn. lic. Roger Carlsson for facilities
placed at our disposal, and Dr. Susan Jagner for revising the English text.
A grant from the Swedish Board for Technical Development has made this investigation possible
(Project No. 70-200/U136 and 71-230/U150).

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