Kinetic Studies on Surface Segregation of

Manganese During Annealing of Low-Carbon

Steel
R. M, HUDSON, H. E. BIBER, E. J. OLES, Jr., AND C. J, WARNING

Surface s e g r e g a t i o n of manganese, an example of a s e l e c t i v e oxidation p r o c e s s , o c c u r s at

annealing t e m p e r a t u r e s when l o w - c a r b o n s t e e l is in contact with typical c o m m e r c i a l p r o -
tective a t m o s p h e r e s . L a b o r a t o r y kinetic studies show that the e n r i c h m e n t p r o c e s s fol-
lows a p a r a b o l i c r a t e law, that the r a t e constant in the low range of oxygen potential for
the annealing a t m o s p h e r e i n c r e a s e s l i n e a r l y with oxygen potential, and that although higher
r a t e s apply for r e l a t i v e l y high-manganese s t e e l s than for r e l a t i v e l y low-manganese
s t e e l s , the s a m e s u r f a c e - r e a c t i o n m e c h a n i s m applies. A r a t e e x p r e s s i o n was developed
that i m p l i c i t l y includes oxygen potential and f r e e manganese (uncombined, in solid solu-
tion) content in the s t e e l .

P R E V I O U S L Y r e p o r t e d work 1,2 d e m o n s t r a t e d that tentials (base ten l o g a r i t h m of oxygen p a r t i a l p r e s -

s u r f a c e s e g r e g a t i o n of manganese, an example of a
s e l e c t i v e oxidation p r o c e s s , o c c u r s at annealing t e m -
p e r a t u r e s when l o w - c a r b o n s t e e l is in contact with
typical c o m m e r c i a l p r o t e c t i v e a t m o s p h e r e s . D i f f e r -
ences between the s u r f a c e and bulk c h e m i c a l composi-
tion for s t e e l s and other alloys have been r e c o g n i z e d
as important in affecting c o r r o s i o n r e s i s t a n c e , a p p e a r -
ance, and other p r o p e r t i e s . The effect of these changes
on the p r o p e r t i e s of sheet, s t r i p , and coated s t e e l p r o -
duct is being investigated and will be r e p o r t e d at
another time.
Elimination of manganese s u r f a c e s e g r e g a t i o n by
annealing at 1350~ (732~ in a vacuum (10 -5 T o r r or
1.33 • 10 -3 Pa) or in a d r y (dew point <-70~ or - 57~
< 0.0017 pct water vapor) hydrogen a t m o s p h e r e was
a c c o m p l i s h e d in l a b o r a t o r y experiments.2 It was i l l u s -
t r a t e d 2 that a lowering of f r e e manganese (uncombined
as sulfides, oxides, a n d / o r s i l i c a t e s ; in solid solution)
in s t e e l ( m e a s u r e d before annealing) lowers the level of
total (free and combined) manganese found in the s t e e l
s u r f a c e a f t e r annealing. Published f r e e e n e r g i e s of f o r -
mation for these inclusions 3-5 suggest that, once
formed, they a r e stable at annealing t e m p e r a t u r e s and
a r e not e a s i l y reduced by hydrogen. F u r t h e r , it was
shown 2 that s u r f a c e r e a c t i o n s involving s e l e c t i v e oxi-
dation of manganese during annealing that deplete the
s u r f a c e in f r e e manganese provide the driving f o r c e
for the s e g r e g a t i o n p r o c e s s . In our previous a r t i c l e , 2
p e r t i n e n t l i t e r a t u r e r e f e r e n c e s were reviewed.
The p r e s e n t a r t i c l e d e s c r i b e s an extension of our
p r e v i o u s work e in which the kinetics of manganese
s e g r e g a t i o n in the o u t e r m o s t 2000.~ (200 nm) of the
s t e e l surface was studied over a range of t e m p e r a -
t u r e s and in which the extent of s u r f a c e e n r i c h m e n t in
manganese during annealing was studied by using gas
m i x t u r e s that c o m p r i s e d a wider range of oxygen po-
R. M. HUDSONis Associate Research Consultant, H. E. BIBER is
Senior ResearchEngineer, E. J. OLES, JR., is Senior Research Engi-
neer, and C. J. WARNINGis Senior Research Engineer, all with the
Umted States Steel Corporahon Research Laboratory, Monroeville,
PA 15146.
Manuscript submitted October 20, 1976.
METALLURGICALTRANSACTIONSA
s u r e , in a t m o s p h e r e s ) than was covered h e r e t o f o r e .
MATERIALS AND EXPERIMENTAL WORK
The c h e m i c a l composition of the m a t e r i a l s used is
given in Table I. Two c o m m e r c i a l s t e e l s (C5 and D6)
and two z o n e - r e f i n e d i r o n - m a n g a n e s e b i n a r y alloys 6
low in r e s i d u a l e l e m e n t s (B1 and B2) were used. The
f r e e - m a n g a n e s e contents (uncombined as sulfide, oxide,
a n d / o r silicate; in solid solution) for these m a t e r i a l s
(derived from inclusion a n a l y s e s ) were, r e s p e c t i v e l y ,
0.21, 0.39, 0.31 and 0.60 pct. The c o m m e r c i a l s t e e l s
w e r e 0.0088 in. (0.22 mm) in thickness, and the iron-
manganese b i n a r y alloys were 0.012 in. (0.30 mm) in
thickness. All s p e c i m e n s , usually coupons 3/4 by 3 in.
(19 by 76 mm), were cleaned in acetone b e f o r e anneal-
ing.
The gas m i x t u r e s used w e r e obtained f r o m the
Matheson Company with a n a l y s e s furnished. F o r most
e x p e r i m e n t s a 6 pct hydrogen-94 pct nitrogen mixture
was used. F o r s o m e e x p e r i m e n t s hydrogen and a 25
pet hydrogen-75 pet nitrogen mixture were used. Ex-
p e r i m e n t a l p r o c e d u r e s for control of w a t e r - v a p o r
content in the gases and a d e s c r i p t i o n of the furnace
used for b e n c h - s c a l e e x p e r i m e n t s have been r e p o r t e d
in detail. 2
Two types of e x p e r i m e n t s w e r e conducted. In one
group, the two c o m m e r c i a l s t e e l s were exposed to a 6
pct hydrogen-94 pet nitrogen gas mixture that con-
tained 0.013 pet water vapor (dew p o i n t - 4 0 ~ or -40~
at t e m p e r a t u r e s of 1070, 1150, 1230, and 1350~ (577,
621, 666, and 732~ for v a r i o u s t i m e s . In another
group of e x p e r i m e n t s , the hold time and t e m p e r a t u r e
w e r e constant (7 h at 1350~ and gas m i x t u r e s con-
taining 6, 25, and 100 pct hydrogen were used at v a r i -
ous controlled l e v e l s of w a t e r - v a p o r content; the oxy-
gen potential was calculated for these gas m i x t u r e s
f r o m the following equation, 2 d e r i v e d f r o m f r e e - e n e r g y
information for the r e a c t i o n H~ + 1/2 O2 = H20:
25,743 PH20
log PO2 = - T + 5.726 + 2 l o g - p H z [1]
where T is the t e m p e r a t u r e in d e g r e e s Kelvin, and
VOLUME 8A, NOVEMBER 1977-1713
 Table 1. Chemie~ C,omposit/on of ~ r i a i s Os~ in L,bomtory Exp~in~nts

Sample Batk Compo~tion, Pct Combined Mn m Steel, Pet Free Mn (m Solid

N~mbe~ C Mn P S SI Cu Ni Cr Mo At N O As MnS As MnO or MnO.SiO~. Solution), Pet
C5 0 . 0 6 3 0 . 3 1 0 . 0 0 5 0~036 0.006 0.049 0.016 0.027 0.006 0~00t 0 . 0 0 3 0.040 O.(M3 0.0.57 0.2I
136 0.052 0.43 0.004 0.015 0.058 0.012 0.008 0 . 0 1 3 0,007 0.00t 0006 0 . 0 1 5 0,026 0.015 0.39
BI 0.00t (}.31 <0.00t <0.00t 0.00t <0.001 0.00t <0.001 <0.001 0.002 <0.001 0.001 0.000 0.000 0.31
B2 0201 O.60 <0.001 <0.001 0.00t <0.00I 0,001 <0.00t <0.001 0.002 <0.00t <0.001 0.000 Ck~30 0.60
: ..... : ' " : : . - : : : , ' ..... ,,u ,,, ., ...... , . ......................................................................................................................................

Pg2o and PIh a r e the partial p r e s s u r e s of water va-

por and hydrogen, respectively, in atmospheres. F o r Tab~ IL Effect of Nne~li,~ Time and Tempe~tu~ on Surf.s Enrichment of
total gas p r e s s u r e at or close to 1 atmosphere (101.3 M~nganese-Bene,h - ~ Exl:x~.rimentsWith SteelsC5 anO D6 U~ng 6 Pet H~ ~nN2
kPa), the volume percentage amounts of water vapor (0,013 Pet Water Va~0or,-4O'~F Dew Point}
and hydrogen may be used instead of partial p r e s - Surface Manganesein 2000A Layer, Pct
sures (PH20/PH2 is approximately equal to pct H20/
Annealing C5 D6
pct Its), Temperaeare, ~F Time,h (O.21 Pet Free. Mn) (0.39 Pet F~ee Mn)
Surface-manganese analyses were made by using a
method combining chemical polishing and atomic-ab- t070 1 Not run 0.96
4 Not run 1.3
sorption spectrometry. Two strippings were used and 7 0,76 1.5
the extrapolation method described previously ~ was t4 Not run Z0
employed to estimate manganese contents in the
1150 I Not ran LI
outermost 2000~ (200 rim) layer of the s t e e l surface~ 4 Not ran 1.7
tn our previous work it was found that the manganese 7 L2 1.9
concentration gradient was most pronounced in this I4 Not mn 2.6
layer. Thus the kinetics developed in this article ap-
t230 1 Not Pan i ,6
ply to average manganese concentration in that portion 2 0~96 N~t ran
of the steel surface. 4 Not ma 3.3
Selected annealed specimens were examined 7 1.8 43
scanning electron microscopy (SEAl) and e n e r g y - d i s - t4. 2.8 5.5
persive X - r a y spectrometry. Other annealed speci- 1350 88 Not run t.0
mens were examined metallographicalty and by SIMS 1 NOt run 2.3
(Secondary Ion Mass Spectrometry) to develop more 2 1,2 4.3
detailed information regarding the manganese concen- 4 2,4 7.7
7 3.2 9,6
tration profile n e a r the surface. 14 No~-ma t3,6

RESULTS ,~N*DDISCUSSION
Type of Rate Law Associated With Starface
Segregation of Manganese • 10"4, respectively. Arrhenius plots of the base ten
logarithms of the parabolic rate constants vs the r e -
The data in Table It and Figs. 1 and 2 illustrate t.qat ciprocal of the t e m p e r a t u r e (in degrees Kelvin) r e -
f o r both the 0.31 pct manganese steel (C5) and the 0.43 sulted in a linear relationship for both steels.
pct manganese steel (D6), the level of surface enrich- It should be noted that although all the above-de-
ment in manganese increases with annealing time and scribed experiments were performed under nominally
with annealing temperature when a typical protective the same atmosphere conditions (6 pet H2 in Ne, 0.013
atmosphere is used (6 pct He in N~, 0.013 pet water pct water vapor), the oxygen potential calculated by
vapor). The g r e a t e r response of the higher-mangmuese Eq. [1] increases with temperature, as shown in Fig.
steel to surface enrichment in mang~uese under s i m i - 4, reflecting the g r e a t e r dissociation of water vapor
lar annealing conditions is apparent. at higher temperatures. Incorporation of oxygen-po-
The rate data conform reasonably well to the para- tential values in the r a t e expression will be considered
bolic expression later.

Effect, of Oxygen PotentiaI on Extent of Surface

where C is the surface manganese concentration in a
2000A surface layer, k is a parabolic rate constant, Segregation of Manganese
and t is the time in seconds. Swisher v has presented The influence of the oxygen potential of the atmos-
evidence that internal oxidation in iron-manganese al- phere on surface segregation of manganese was
loys follows a parabolic law. P a r a b o l i c - r a t e - l a w plots studied in experiments with Steels D6 and C5 and with
for Steel D6 a r e shown in Fig. 3; the parabolic rate iron-manganese binary alloys B1 and B2. In these
constants (in [pct Mn]~ s "~ units) a r e 1.0 x 10-4, 1.6 experiments specimens were heated f o r 7 h at 1350~
x 10-4, 7.0 x t0 -4, and 3.5 x !0 -s for 1070, 1150, 1230, in hydrogen and in various hydrogen-nitrogen mix-
and 1350~ respectively. F o r Steel C5 the parabolic tures, with water-vapor contents controlled to furnish
rate constants (same units) obtained f r o m similar a range of oxygen-potential values. The results of
plots are 2.3 • 10-s, 5.7 x 10 "~, 1.4 x 10-4, and 4.0 these experiments a r e summarized in Table Ill and in

t 7 t 4 - V O L U M E gA~ NOVEMBER ~977 METALLURGICAL TRANSACTIONS A

 Table III. Effect of Annealing-Atmosphere Compoution on Surface Enrichment of Manganese-Bench-Scale Experiments at 1350~F With
Steels and Iron-Manganese Binary Alloys, 7 h Hold Period

Surface Manganese in 20OOALayer, Pet

Steels Iron-Manganese Binary Alloys
Oxygen Potential Gas Composltmn C5 D6 B1 B2
(Log Po=) H2 in N2, Pet Dew Point, ~ Water Vapor, Pet (0.21 Pet Free Mn) (0.39 Pct Free Mn) (0.31 Pct Free Mn) (0.60 Pet Free Mn)

-27.7 100 -40 0.013 1.9 2.3 1.3 3,2

-26.5 100 -17 0.050 3,6 6,3 Not run Not run
-25.3 6 -40 0.013 3.5 96 2.8 11 2
-24.2 6 -17 0.050 3,9 1t 0 30 10.9
--23.1 25 +32 0,60 2,6 10.0 2.1 7,2
-21.9 6 +32 0.60 I3 7.6 Not run Not run
-21.1 6 +56 1.50 0 85 2.0 0 99 0.87
-20.8 6 465 2.08 0.77 1.1 Not run Not run
--20.5 6 +75 2.90 0.48* 2.7" Not run Not run

*Specimens as produced were gray in color and not reacnve with stripping soluUon. Values shown were determined after specLmenswere heated for 5 min in H : ( ~ 0 ~
dew point) at 1350~ to reduce oxides, and then stnpped,

i i ~ ......., , , i t l t l i ] l i l I

14

12

i 1350OF
1350~F

1C ~ ANNEALED IN 6% H2--94% N 2
.a
CONTAINING 0013% WATER
r VAPOR (DEW POINT, -40*F)

~ 8

i0
,w 1230~F

3~
"~360"~' C5 1230 ~

1070~F

0i ] [ I I l I I I 1 I I I I I
2 4 6 I~ 10 12 14 2 4 6 8 10 12 14
TIME, bouts
TIME, hours
Fig. l--Rate of surface enrichment in manganese for steel D6 Fig. 2 - - C o m p a r i s o n of steels D6 and C5 in s u r f a c e - e n r i c h -
a n n e a l e d in 6 p c t H 2 - 9 4 p e t N 2 c o n t a i n i n g 0.013 p c t w a t e r v a - ment r a t e s d u r i n g a n n e a l i n g a t 1230 and 1 3 5 0 ~
p o r (dew p o i n t - 4 0 ~

F i g s . 5 and 6. T h e h i g h e s t l e v e l s of s u r f a c e m a n g a n e s e p o t e n t i a l of - 24.2 and then d e c r e a s e d a s the o x y g e n p o -

r e a c h e d w e r e f o r the h i g h e r - m a n g a n e s e s t e e l (D6) and
the h i g h e r - m a n g a n e s e b i n a r y a l l o y (B2). Note that the
s u r f a c e m a n g a n e s e l e v e l s i n c r e a s e d with an i n c r e a s e
in oxygen p o t e n t i a l in the l o w e r r a n g e of o x y g e n p o t e n -
t i a l s , b u t t h a t the s u r f a c e m a n g a n e s e l e v e l s d e c r e a s e d
in the h i g h e r r a n g e of oxygen p o t e n t i a l s . SEM e x a m i n a -
tion of S t e e l D6 a n n e a l e d at oxygen p o t e n t i a l s of - 2 5 . 3
a n d - 21.1 ( T a b l e III) i n d i c a t e d that the s u r f a c e m o r -
phology in both c a s e s f e a t u r e d the p r e s e n c e of m a n g a n -
e s e - r i c h p a r t i c l e s which w e r e s i m i l a r in s i z e and f r e -
q u e n c y . Q u a n t i t a t i v e e s t i m a t e s of m a n g a n e s e c o n c e n -
t r a t i o n a t v a r i o u s d e p t h s f r o m the s u r f a c e r e q u i r e d
the u s e of o t h e r t e c h n i q u e s , a s d e s c r i b e d .
Note that a s the oxygen p o t e n t i a l was i n c r e a s e d f r o m
its l o w e s t v a l u e , the a m o u n t of m a n g a n e s e o b s e r v e d
in the 2000,~ l a y e r i n c r e a s e d to a m a x i m u m a r o u n d a
t e n t i a l was f u r t h e r r a i s e d . T h i s o b s e r v a t i o n was con-
f i r m e d by s e c o n d a r y ion m a s s s p e c t r o m e t r y (SIMS)
which showed that s t e e l s a n n e a l e d at an oxygen p o t e n -
t i a l of - 2 4 . 2 had c o n s i d e r a b l y m o r e m a n g a n e s e on
t h e i r s u r f a c e s than s t e e l s a n n e a l e d at an oxygen p o t e n -
t i a l o f - 2 1 . 1 . It was e x p e c t e d that t h e r e would be
g r e a t e r o x i d a t i o n of m a n g a n e s e with i n c r e a s e s in o x y -
gen p o t e n t i a l , and the SIMS a n a l y s i s showed that t h i s
w a s the c a s e but that it o c c u r r e d at depths even
g r e a t e r than 2000A b e n e a t h the s u r f a c e . T h e m a n g a n -
e s e c o n c e n t r a t i o n - d e p t h p r o f i l e s of the s a m p l e s a n -
n e a l e d at an oxygen p o t e n t i a l o f - 24.2 w e r e s t e e p e r
in the o u t e r s u r f a c e - l a y e r s than t h o s e f o r s a m p l e s an-
n e a l e d at a p o t e n t i a l of - 2 1 . 1 , and b e l o w a c e r t a i n
depth the l a t t e r d i s p l a y e d the g r e a t e r a m o u n t of m a n -
g a n e s e . If o u r k i n e t i c a n a l y s i s had b e e n b a s e d on

METALLURGICAL TRANSACTIONS A VOLUME 8A, NOVEMBER 1 9 7 7 - 1 7 1 5

thicker layers, the maxima in Figs. 5 and 6 would be
shifted toward the higher oxygen potential end of the
plot; however, for our purposes, the outermost 2000A
layer was selected as the region of interest and the
data used in this study were restricted to that region,
Theoretically, ~ oxygen potentials greater t h a n - 27.6
represent conditions oxidizing to manganese at 1350~
in a steel that contains 0A pet manganese; at the same
I I ....I"" I ~
temperature, oxygen potentials above - 20.5 represent
conditions oxidizing to both iron and manganese, The
runs made with Steels D6 and C5 at an oxygen potential
o f - 2 0 . 5 produced a visible surface oxide that could
not be removed by the usual chemical-polishing tech-
niques. These specimens were subsequently heated
for 5 min in hydrogen (-40~ dew point) to reduce the
iron oxides and were then analyzed by the stripping
technique. Surface manganese levels were higher for
Steel D6 than for C5 under the conditions just de-
"J ! " '~ ~ I I T......... I "'
scribed.

C~ ~ kt /
180
C ~ SURFACE Mn IN /
2o~ok LAYER. / -75 -63
DEW POINT IN 6% H2-"94% N 2 MIXTURE,*F
-443 ~t7 +4 § §
160 t =TIMEIN SECONDS ~f/
k = PARABOLICRATECONSTANT

~20

>-
10s
5

~ Be ~B
N

< 6(] 9

4~
<

1230~
20 9

1 tBO~ 2
,,,,'v,, ~ , , .... ~-
2 4 6 8 10 12 14
TIM;E, hours 0 I I I 1 1 t I 2/4, ,,,,, I I t l ~ t
-27 -26 -25 ~ 23 --22 ~21
F i g . 3--Parabolic-rate-law plots for steel D6 annealed in 6
LOG P02
pet H~--94 pct N~ containing 0.013 pet water vapor (dew point
-40~ Fig. 5--Surface enrichment in manganese for steels D6 a n d
C5 a s i n f l u e n c e d b y o x y g e n p o t e n t i a l of annealing atmosphere:
TEMPERATURE, ~F 7 h at 1 3 5 0 ~
1350 1230 1150 1070
I

DEW POINT IN 6% H2--'94% N 2 MIXTURE,~

- 75 '- 63 40 - 17 "~ +32 +56 +65 +75

B2
Z -: -26 (Fe- O 60% Mn)

=< k CALCULATED I
-3 FROM DATA 1-27
IN TABLE []
L
De

< -4 -20 ~' B

==
5 -2g d
6

J
O

=<

-7 -31

OJ
8 ..... [ } .................. -27 -26 -25 -24 -23 -22 -21
09 ]O 11 12
LOG PO2
tTEMPERATURE, Ketvm] I X ~03
F i g . 4--Arrhenius plots of parabolic rate constants calculated F i g . 6 - - S u r f a c e e n r i c h m e n t in m a n g a n e s e f o r F e - M n binary
f r o m data in Table II obtained by using 6 pct H2-94 pct N 2 alloys B1 a n d B2 as influenced by o x y g e n p o t e n t i a l of anneal-
(0.013 pet water v a p o r ) . ing atmosphere: 7 h at 1 3 5 0 ~

1716-VOLUME 8A, NOVEMBER 1977 METALLURGICAL TRANSACTIONS A

 D e p e n d e n c e of P a r a b o l i c R a t e C o n s t a n t s o n
Oxygen Potential
T h e r e l a t i o n s h i p of t h e p a r a b o l i c r a t e c o n s t a n t a t
1 3 5 0 ~ t o o x y g e n p o t e n t i a l s i n t h e r a n g e - 2 7 , 7 t o - 24.2
w a s e x a m i n e d f o r b o t h s t e e l s . F r o m t h e d a t a in T a b l e 6
IV p a r a b o l i c r a t e c o n s t a n t s w e r e c a l c u l a t e d ; t h e s e /e %
v a l u e s a r e p l o t t e d i n F i g , 7 a s a f u n c t i o n of o x y g e n p o -
tential. Note that over the range studied/e is linearly
dependent on oxygen potential and that an extrapolated
v a l u e of l o g PO~ f o r k = 0 i s o n t h e o r d e r of t h e l o g
PO 2 value (-27,6) that represents equilibrium for the
reaction
"_-2
1 o3
Mn + ~ 02 = MnO [3]

e s t i m a t e d f r o m t h e r m o d y n a m i c c o n s i d e r a t i o n s .2 T h e 2

functional dependence can be expressed as

k = h' [ l o g P o 2 - l o g PO2(E) ] [4] 1

w h e r e k ' i s t h e s p e c i f i c r a t e c o n s t a n t a n d l o g P O~cE)
(3 ..... I I ............... t
is the equilibrium oxygen potential for the temper- - 28 - 27 - 26 - 25 - 24 23

a t u r e i n v o l v e d . T h i s e q u a t i o n h o l d s f o r - 2 4 . 2 >- l o g OXYGEN POTENTIAL, fog P 0 2

PO2 >- log PO2(E).
Fig. 7--Relationship of parabolic r a t e constant (calculated
To estimate k', the k values calculated from the f r o m data in T a b l e IV) to oxygen potential for runs made at
data in Table If were divided by [logPO2 - log P 02(E)]. 1350~
Values of log POe(E) for 1070, 1150, 1230, and 1350~
a r e - 34.9,-32.6,- 30.4, and-27.6, respectively. For
an atmosphere containing 6 pct hydrogen and 0.013 TEMPERATURE,~

pct water vapor, the oxygen potentials calculated for 1350 t230 1150 1070

these same temperatures are - 29.9, - 28.4, - 27.0, and

-25.2, respectively. Values of k' so calculated were
used for the Arrhenius plots shown in Fig. 8, The
slopes of the plots shown in Fig. 8 do not significantly
differ (95 pct confidence intervals). It appears that
even though higher enrichment rates are associated
with steels of higher manganese content, the same sur-
SLOPE = ( - 1 0 7 : 042) x 104
face-reaction mechanism applies for low and high- -3
O
manganese steels.

C5 O D6
o

Table IV. Effect of Annealing-Atmosphere Composition on Surface Enrichment m

With Manganese-Bench.Scale Experiments at 1350~F With Steels C5 and D6
Using Controlled Oxygen Potentials
(Gas Compositions Shown in Table lid 95% C O N F I D E N C E I N T E R V A L
I N D I C A T E D FOR SLOPES

Surface Manganesem 2000A

Oxygen Potential Layer, Pct k' = k / [ l o g P o 2 - log PO21E)}

(Log PO2) Time, h Steel C5 Steel D6

t I I I ....
-27,7 7 1,9 23 e9 10 11 12
14 2.9 65 [TEMPERATURE. Ketvlnl I x 103

-26,5 2 Not run 33 Fig. 8 - A r r h e n i u s plots of specific r a t e c o n s t a n t s calculated

4 1.8 4.7 f r o m data in Table II obtained by using 6 pct H2-94 pct N2
7 3.6 6.3 (0.013 pct w a t e r vapor).
14 3.2 Not run
-253 88 Not run 10
1 Not run 2.3
2 1.2 43 D e p e n d e n c e of P a r a b o l i c R a t e C o n s t a n t s o n F r e e
4 2.4 7.7 Manganese Content in Steel
7 32 9,6
14 Not run 13 6 F r o m p r e v i o u s w o r k 2 i t i s k n o w n t h a t t h e l e v e l of
s u r f a c e e n r i c h m e n t i n m a n g a n e s e , C, a t t a i n e d u n d e r
-24.2 2 1.8 6.0
4 2.5 10.0 s t a n d a r d a n n e a l i n g c o n d i t i o n s (7 h a t 1 3 5 0 ~ 6 pct H2-
7 3.9 11.0 94 p c t Nz, - 40~ d e w p o i n t ; l o g P 02 = - 25.3) i n c r e a s e s
w i t h a n i n c r e a s e i n t h e l e v e l of f r e e m a n g a n e s e C f r e e

METALLURGICAL TRANSACTIONS A VOLUME 8A, NOVEMBER 1977-1717


1350
-1
-2
5,
u...3
o
E- SLOF'E =-9741 • "~33
< --4
.J
95% CONFIDENCE
INTERVAL NOTED
-6
O C5
-7 II D6
-8 091 |01 ................
[TEMPERATURE. Kelwn] "I x l03
Fig. 9-Arrhenius plots of rate constants k" calculated from
data in Table II obtained by using 6 pet H2-94 pct Nz (0.013
pct water vapor).
(in solid solution). The functional relationship found
for a number of c o m m e r c i a l steels given the afore-
mentioned standard annealing treatment was of the
form
C = A (Cfree)n
where A = 24.0 and n = 1.29 • 0.14 (95 pct confidence
interval for n). Assuming that the functional relation-
ship expressed by Eq. [5] also holds for other anneal-
ing conditions (use of the limited data in Tables II, III,
and IV to test its validity indicates that it does), in
view of the general parabolic rate law found, the spe-
cific rate constant k' shown in Eq. [4] can be impli-
citly related to C free by the relationship
k ' = k " (Cfree)2n
where k", as defined, would be independent of oxygen
potential and manganese content in the steel. Taking
base ten logarithms for both sides of Eq. [6] and r e -
arranging terms,
log k" = log k ' - 2n log Cfree.
The last t e r m on the right is - 1.07 for Steel D6 and
- 1 . 7 7 for Steel C5.
Using the above method of analysis, the k " values
are roughly independent of manganese concentration,
consistent with the assumptions made. Values of k "
calculated at 1070, 1150, 1230, and 1350~ were, r e -
spectively, 2.3 • 10 -4, 4.5 • 10-4, 2.5 x 10 4, and 1.8
• 10-2 for Steel D6 and 2.7 • 10"a, 8.3 • 10-4, 2.4 • 10 -3,
and 1.0 x lif e for Steel C5.
GENERAL CONSIDERATIONS
Surface segregation of manganese in steel during
annealing depends on temperature, time, initial free
1718-VOLUME 8A, NOVEMBER 1977
TEMPERATURE, ~
manganese content in the steel, and oxygen potential
1230 1150 1070
of the atmosphere. At a given temperature for oxygen
potentials in the range - 2 7 . 7 t o - 24.2 (representing
commonly encountered c o m m e r c i a l conditions), the
following rate expression described the data obtained:
C 2 = k " (Cfree)2'6 [log Po2 - log PO2~E)]t [8]
where the symbols have the meaning designated in the
above discussion.
F r o m the slopes of the linear Arrhenius plots shown
in Figs. 4, 8, and 9, "activation e n e r g i e s " can be c a n
culated. F r o m Fig. 4 values of 41.2 and 32.0 kcal per
mole (172 and 134 k.J/mole) a r e calculated for steels
D6 and C5 respectively; although the atmosphere used
in all of these experiments was the same (6 pct H2-
94 pct N2, 0.013 pct H20), the oxygen potential at dif-
ferent temperatures was not. By taking the changing
oxygen potentials into account and redefining the rate
constants on this basis the plots in Fig. 8 lead to cal-
culated respective "activation e n e r g i e s " of 49 and 40
kcal (205 and 167 kJ/mole); because of the scatter in
111 ...................... ;~2 the data these slopes are not significantly different,
however, and the composite value of 44.5 kcal per
mole (186 kJ/mole) may be assigned to both steels.
Taking the effect of initially present free manganese
into account and again redefining the rate constants
on this basis, the plot in Fig. 9 leads to a calculated
activation energy of 44.6 kcal per mole (187 kJ/mole).
Bradford s reported a value of 60.4 kcal per mole
(253 kJ/mole) for the internal oxidation of r i m m e d
steel in the temperature range f r o m 1250 to 1650~
(677 to 899~ He points out that "subtraction of the
heat of solution of oxygen leaves a diffusion activation
[5] energy of approximately 40 kcal per mole (167 k J /
mole); this value lies between the activation energy
for normal interstitial diffusion and that for substitu-
tional diffusion, and therefore suggests a process that
is more involved than either interstitial or substitu-
tional diffusion of oxygen." The activation energies
calculated from our Arrhenius plots are of the same
o r d e r of magnitude as B r a d f o r d ' s estimate for diffu-
sion activation energy in his internal oxidation study.
[6]
SUMMARY
To better understand the process of surface s e g r e -
gation of manganese, bench-scale studies were con-
ducted with steels and iron-manganese binary alloys
[7] under a variety of time, temperature, and annealing-
atmosphere compositions. It was found that at tem-
peratures ranging from 1070 to 1350~ (577 to 732~
the rate of enrichment could be described by the p a r a -
bolic law
C 2 = kt
where C is the concentration of manganese in the outer-
most 2000-angstrom-thick layer (200 nm) of steel, k is
a parabolic rate constant, and t is the time at tempera-
ture. The oxygen potential of the annealing atmos-
phere (defined as the base ten logarithm of oxygen
partial p r e s s u r e , in atmospheres) is taken into account
by the expression
k = k' [log PO 2 - log PO2~E)]
METALLURGICALTRANSACTIONSA
where k' is another constant, tog PO2~E) is the equili-
brium oxygen potential for formation of MnO by the
reaction Mn + 1/2 O2 = MnO, and for - 24.2 >- log Poz
>- log P 02r E~.
Inclusidn of a term in the rate expression related to
the free manganese (uncombined as suffides, oxides,
a n d / o r silicates) content in the steel was considered.
F o r k' = k" C~n free, where 2n is approximately 2.6,
values calculated for k" appear to be independent of
manganese concentration.
While the surface enrichment of manganese in-
c r e a s e s with an increase in oxygen potential f r o m the
equilibrium oxygen potential for formation of MnO up
to about - 2 4 . 2 , for higher oxygen potentials the sur-
face manganese level d e c r e a s e s .
ACKNOWLEDGMENTS
The assistance of G. W, Huggins in c a r r y i n g out
many of the bench-scale controlled-atmosphere ex-
METALLURGICAL T R A N S A C T I O N S A
periments described in this paper is acknowledged as
a r e the atomic-absorption spectroscopy analyses by
J. E. Friedline and C. C. Wareham and their co-
workers.
REFERENCES
1. J- P- Servais, H~Graas, and V. Leroy Centre de Recherches Metatlurgaques
(CtL~t) Metallurgical Reports, t 975, no. 44, pp. 2%42.
2 R.M. Hudson, H E, Biber, E. J Oles, Jr,, and C. L Warning:Met. Trans., 1976,
rot. 7A, pp 1857-65.
3 F D. Richardson and J H- E. Jeffes J. Iron Steellnst., 1948, vol. t60, pp.
261-70.
4 F.D. Richardson, J. H. E. Jeffes, and G. Withers d. Iron Steel Inst., 1950. vol.
166, pp. 213-34.
5 F. D Richardson and J. H. E. Jeffes" J. Iron Steel Inst., 1952, vok t 71, pp.
165-75
6. W. C. Leslie, J. T. Mlchalak, and F. W Aul" Iron and Its Dilute Solid Solutions,
C W. Spencer and F E. Wemer, eds., p. 174, Intersclence Publishers, New
York, N.Y,, 1962.
7. J. H. Swisher: Trans. TMS-Ah~E, 1968, voi. 242, pp. I035-38.
8. S. A. Bradford. Trans. TMS-AIME, I964, vol. 230, pp. t400-05.
VOLUME 8A, NOVEMBER 1977-1719