Diffusion Modeling of the Carburization

Process
J . I. GOLDSTEIN AND A . E. MOREN

M a t h e m a t i c a l m o d e l s have b e e n d e v e l o p e d f o r s i m u l a t i n g the c a r b u r i z a t i o n p r o c e s s .
One m o d e l s i m u l a t e s c a r b u r i z a t i o n in low a l l o y s t e e l s w h e r e t e m p e r a t u r e , t i m e , s u r f a c e
c a r b o n content, and diffusion coefficient v a r y d u r i n g the p r o c e s s . Two s t e p and v a c u u m
c a r b u r i z a t i o n a r e a m o n g the t r e a t m e n t s c o n s i d e r e d . The o t h e r m o d e l s i m u l a t e s the ef-
fect of m a j o r t e r n a r y a l l o y i n g a d d i t i o n s such a s Mn, Cr, Ni and Si d u r i n g c a r b u r i z a t i o n .
T h e i m p o r t a n c e of the off d i a g o n a l o r c r o s s diffusion coefficient D~2 on c a r b o n diffusion
i s c a l c u l a t e d . The C r a n k - N i c o l s o n finite d i f f e r e n c e equations a r e u s e d to p r o v i d e n u m e r i -
c a l s t a b i l i t y and f l e x a b i l i t y . C a l c u l a t e d c a r b o n p r o f i l e s f o r low a l l o y s t e e l s w e r e c o m -
p a r e d with e x p e r i m e n t a l d a t a a v a i l a b l e in the l i t e r a t u r e . A g r e e m e n t b e t w e e n c a l c u l a t e d
and m e a s u r e d d a t a was v e r y good. C h r o m i u m and s i l i c o n have l a r g e c r o s s coefficient ef-
f e c t s and i t is p r e d i c t e d t h a t t h e y have a l a r g e i n f l u e n c e on the a m o u n t of c a r b u r i z a t i o n
which w i l l o c c u r . E x p e r i m e n t a l d a t a f o r c a r b u r i z a t i o n t r e a t m e n t s of F e - C - C r a l l o y s a r e
in e x c e l l e n t a g r e e m e n t with m o d e l p r e d i c t i o n s of m a j o r i n c r e a s e s in e f f e c t i v e s u r f a c e
c a r b o n content and the f o r m a t i o n of c a r b i d e s in a u s t e n i t e at the c a r b u r i z a t i o n t e m p e r a -
t u r e . T h e s e c o m p u t e r m o d e l s a r e r e l a t i v e l y e a s y to a p p l y and can be u s e d to d e s i g n c a r -
burization treatments for specific alloy steels.

C A R B U R I Z A T I O N is one of the o l d e s t i n d u s t r i a l C s = s u r f a c e c o n c e n t r a t i o n of carbon,

p r o c e s s e s in which m a s s t r a n s p o r t - d i f f u s i o n p l a y s a C O = i n i t i a l c a r b o n l e v e l in F e ,
m a j o r r o l e . A s o u r c e of c a r b o n is p r o v i d e d at the D = diffusion coefficient for C in the y p h a s e , D~,
s u r f a c e of a low c a r b o n s t e e l . The c a r b o n d i f f u s e s which is a s s u m e d to be independent of concen-
into the s t e e l at high t e m p e r a t u r e s u s u a l l y 1600 to t r a t i o n , and
1800~ (871 to 982~ for t i m e p e r i o d s g e n e r a l l y C C = c a r b o n c o n c e n t r a t i o n a s a function of d i s t a n c e
f r o m a few h o u r s to a d a y . A c a r b o n g r a d i e n t is p r o - X and t i m e t f r o m the s u r f a c e at X = 0.
d u c e d in which the c a r b o n content d e c r e a s e s f r o m the
It is a s s u m e d that no v o l u m e changes o c c u r in the l a t -
s u r f a c e into the s t e e l .
t i c e d u r i n g diffusion. T h i s is a v a l i d a s s u m p t i o n for
In the p a c k o r gas c a r b u r i z i n g p r o c e s s the c a r b o n
i n t e r s t i t i a l diffusion p r o c e s s e s . F i g u r e 1 shows c a r -
c o n c e n t r a t i o n at the s u r f a c e of the s t e e l is c o n t r o l l e d
bon p r o f i l e s f o r v a r y i n g t i m e s at 1700~ and F i g . 2
by the CO/CO2 r a t i o in the gas a t m o s p h e r e , the t e m -
shows c a r b o n p r o f i l e s at 1600, 1700 and 1800~ f o r 8
p e r a t u r e and the s o l u b i l i t y of c a r b o n in the s t e e l .
h c a r b u r i z a t i o n t r e a t m e n t s a l l c a l c u l a t e d u s i n g Eq.
G u r r y 1 has c o n s i d e r e d the t h e r m o d y n a m i c a s p e c t s of
the h e a t t r e a t m e n t of p l a i n c a r b o n s t e e l s in CO/CO2 DISTANCE { . O O t " )
g a s m i x t u r e s p r o d u c e d in e n d o t h e r m i c o r e x o t h e r m i c 0 40 80 120 160
I I i L
g e n e r a t o r s . U s i n g the a n a l y s i s of G u r r y the c o m p o s i -
tion of the gas m i x t u r e in e q u i l i b r i u m with a s p e c i f i e d 1700~
D = CONST
s u r f a c e c a r b o n content can be c a l c u l a t e d . R e c e n t l y
H a r v e y 2 has d e s c r i b e d a s i m i l a r c a l c u l a t i o n s c h e m e
z 1.6
f o r the h e a t t r e a t m e n t of a l l o y e d s t e e l s . uJ
~9
The s i m p l e s t c a r b u r i z a t i o n p r o c e s s , w h e r e b y c a r - fig

bon d i f f u s e s into a p l a i n c a r b o n s t e e l at one t e m p e r a -

t u r e can be d e s c r i b e d b y the V a n - O s t r a n d D e w e y
1.2
s o l u t i o n to the diffusion equation: z
o
:t=2hrs
Cc - CS
z
CO - CS = e r r (X/2 vrDt) [1] 0.8
z
o
where C9
Z
0

t.) 0.4
J. I. GOLDSTEINis Professor of Metallurgy and Materials Engineering, Lehigh
University, Bethlehem, PA 18015, and A. E. MOREN, formerly Graduate Assist-
ant, Metallurgy and Materials EngineeringDepartment, Lehigh University, is now
Assistant Professor, Physics Department, WheelingCollege, Wheeling, WV 26003. OL- I
This paper is based on a presentation made at a symposium on "Carburizing o ,io 21o 40 5o
and Nitriding: Fundamentals, Processesand Properties" held at the Cincinnati DISTANCE ( r a m )
Meeting of the Metallurgical Society of AIME, November 11 and 12, 197 S under Fig. 1 - - C a r b o n c o n c e n t r a t i o n v s d i s t a n c e c u r v e s f o r v a r y i n g
the sponsorship of the Heat Treatment Committee. t i m e s at 1700~ D r Binary Fe-C.
ISSN 0360-2133178/I113-1515500.75/0
METALLURGICAL TRANSACTIONS A 9 1978 A M E R I C A N S O C I E T Y F O R M E T A L S A N D VOLUME 9A, N O V E M B E R 1978-1515
THE METALLURGICAL SOCIETY OF AIME
 DISTANCE (OOI") d i a g o n a l o r c r o s s diffusion coefficients. 8 The c a r b o n
0 40 80 120 160
i i flux can be e i t h e r i n c r e a s e d or d e c r e a s e d by this ef-
fe ct.
T h e s e 3 m a j o r c o m p l i c a t i o n s to the s t a n d a r d c a r -
b u r i z a t i o n p r o c e s s d i s c u s s e d above cannot be s i m u -
lated by Eq. [1] although H a r r i s s has developed a
(2: technique to account for the diffusion period when c a n
culating total case depth. The p u r p o s e of this paper
F-:
is to d e s c r i b e c o m p u t e r models which will allow the
c a l c u l a t i o n of c a r b o n g r a d i e n t s for conditions where
g T, t and C s v a r y and for t e r n a r y alloys as well. Cal-
<[
F- culated c a r b o n g r a d i e n t s will also be c o m p a r e d to
z a v a i l a b l e e x p e r i m e n t a l data.
w 08

3
g NUMERICAL ANALYSIS
m
rr
<
o
04 B i n a r y Diffusion
The diffusion of c a r b o n in i r o n can be d e s c r i b e d by
F i c k ' s second law:

(D ( 0 C ) ).
b b , -
0 1.0 2.0 50 40 50 OC 0 [2]
DISTANCE (ram) ot oX
Fig. 2--Carbon concentration v s distance curves, calculated F o r the case where D is not a function of c o n c e n t r a -
for 8 h carburization treatments at 1600, 1700 and 1800~
D r Binary Fe-C. tion Eq. [2] r e d u c e s to:

[1]. A n a v e r a g e diffusion coefficient a D~ = 0.12

OC _ D-- [3]
~t 8X~"
• exp ( - 3 2 , 0 0 0 / R T ) cm2/s, was used in the c a l c u l a -
The most useful methods for solving d i f f e r e n t i a l
t i o n s . The value of C s was set at the m a x i m u m s o l u -
equations such as the diffusion equation a r e the
b i l i t y of c a r b o n in the ~ phase at the t e m p e r a t u r e of
finite d i f f e r e n c e t e c h n i q u e s . One of these, the C r a n k -
i n t e r e s t . 4 T h e s e c a l c u l a t i o n s a r e r e s t r i c t e d however
N i c o l s o n finite d i f f e r e n c e analog, as d e s c r i b e d by yon
to s i m p l e c a r b u r i z a t i o n p r o c e s s e s and F e - C a l l o y s .
R o s e n b e r g , 9 is s e c o n d - o r d e r c o r r e c t with r e s p e c t
H a r r i s S has developed an e m p i r i c a l technique, u s i n g
to both independent v a r i a b l e s X and t and, in addition,
c a r b o n p r o f i l e data f r o m c a r b u r i z e d s t e e l s , for de-
s t a b l e o v e r a l a r g e range of i n c r e m e n t s of the v a r i a -
t e r m i n i n g the effect of t i m e and t e m p e r a t u r e on the
bles.
case depth, the m a x i m u m d i s t a n c e of c a r b o n diffusion
The finite d i f f e r e n c e technique e m p l o y s a one di-
f r o m the s u r f a c e , and on the c a r b o n g r a d i e n t . T h i s
m e n s i o n a l space grid. The c o m p o s i t i o n d i s t r i b u t i o n
technique has been applied with adequate r e s u l t s to
of c a r b o n in the ~ phase is shown s c h e m a t i c a l l y
c a r b u r i z a t i o n t r e a t m e n t s in p l a i n c a r b o n and in alloy
within such a space grid in F i g . 3(a). L is the total
s t e e l s as well.
length of the grid. C i r e p r e s e n t s the c a r b o n concen-
T h r e e m a j o r c o m p l i c a t i o n s to the p r e v i o u s d e s c r i p -
tion of the c a r b u r i z a t i o n p r o c e s s should however be t r a t i o n at any grid point i or node along the grid. The
diffusion p r o b l e m is bounded s p a t i a l l y by a constant
noted.
c a r b o n c o n c e n t r a t i o n at the s u r f a c e of the s t e e l at
A) D~ is a function of c o n c e n t r a t i o n . A c c o r d i n g to
grid point i = 2, and a z e r o m a s s t r a n s f e r b o u n d a r y
the m e a s u r e m e n t s of W e l l s and Mehl, a the diffusion
where the c a r b o n g r a d i e n t O C / O X = 0 at X = L, that
coefficient i n c r e a s e s with c a r b o n content. C a r b o n
is at grid point i = I D . The size of each grid s p a c i n g
p r o f i l e s will t h e r e f o r e differ in d e t a i l f r o m those cal-
AX7 is equal to L / ( I D - 2).
culated f r o m Eq. [1]. L i m i t e d c a l c u l a t i o n s a c c o u n t i n g
for this effect have b e e n made. s The finite d i f f e r e n c e equations used in the C r a n k
N i c o l s o n method to solve Eq. [3] a r e p r e s e n t e d below:
B) In many c a r b u r i z a t i o n t r e a t m e n t s t e m p e r a t u r e T
a n d / o r s u r f a c e c a r b o n c o n c e n t r a t i o n CS may v a r y with n§
t i m e . A f t e r a n i n i t i a l p e r i o d of c a r b u r i z a t i o n , C S , a n d OC ~ C i - Cn [41
p o s s i b l y T, is u s u a l l y lowered. The l a t t e r p a r t of the O t At
t r e a t m e n t is called the diffusion step. C S may also
n+l n+l
Vary with t i m e in this diffusion step. T h e s e o p e r a - i/2 2c i + ci_
t i o n a l v a r i a t i o n s a r e often made to i n s u r e that m a x i - OX2 (~u
m u m h a r d e n a b i l i t y will be obtained at the s t e e l s u r -
face a f t e r the quench.
n
+ Ci+ 1 - 2
n
C i +Ci_l
n} . [5]
C) M a j o r t e r n a r y solute i m p u r i t i e s (Mn, Cr, Si, (~)~
Ni, and so forth) m a y have a m a j o r effect on c a r b o n
diffusion d u r i n g the c a r b u r i z a t i o n p r o c e s s . If any of At any t i m e step, c n - 1 , cn., and c n § a r e known v a l u e s
the solute i m p u r i t i e s a r e i n h o m o g e n e o u s l y d i s t r i - a$1(1. ~ hn i+_l 1 , b~ ni + l a n d C ni ++i1 ~a r e u n k s own Values.
buted in the alloy, for e x a m p l e by g r a i n b o u n d a r y The s u b s c r i p t i and s u p e r s c r i p t n r e f e r to the space
s e g r e g a t i o n or by s u r f a c e o r i n t e r n a l oxidation, the p o s i t i o n of a p a r t i c u l a r grid point (Fig. 3) and the
c a r b o n flux can be modified by the effect of the off- t i m e step r e s p e c t i v e l y . The t i m e i n c r e m e n t between

1516-VOLUME 9A, NOVEMBER 1978 METALLURGICALTRANSACTIONSA