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Kinetic Studies On Surface Segregation of Manganese During Annealing of Low-Carbon Steel
Kinetic Studies On Surface Segregation of Manganese During Annealing of Low-Carbon Steel
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.
*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 ~
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
B2
Z -: -26 (Fe- O 60% Mn)
=< k CALCULATED I
-3 FROM DATA 1-27
IN TABLE []
L
De
==
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 ~
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
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
pct water vapor, the oxygen potentials calculated for 1350 t230 1150 1070
C5 O D6
o