Authors Copy

Diffusion Modeling of the Carburization -48?

Process

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

Mathematical models have been developed for simulating the carburization process.
One model simulates carburization in low alloy steels tvhere temperature, time, surface
carbon content, and diffusion coefficient vary during the process. Two step and vacuum
carburization are among the treatments considered. The other model simulates the ef
fect of major ternary alloying additions such as Mn. Cr, Ni and Si during carburization.
The importance of the off diagonal or cross diffusion coefficient D on carbon diffusion
is calculated. The Crank-Nicolson finite difference equations are used to provide numeri
cal stability and flexability. Calculated carbon profiles for low alloy steels were com
pared with experimental data available in the literature. Agreement between calculated
and measured data was very good. Chromium and silicon have large cross coefficient ef
fects and it is predicted that they have a large influence on the amount of carburization
which will occur. Experimental data for carburization treatments of Fe-C-Cr alloys are
in excellent agreement with model predictions of major increases in effective surface
carbon content and the formation of carbides in austenite at the carburization tempera
ture. These computer models are relatively easy to apply and can be used to design car
burization treatments for specific alloy steels.

C ARBURIZATION is one of the oldest industrial C = surface concentration of carbon,

processes in which mass transport-diffusion plays a Co = initial carbon level in Fe.
major role. A source of carbon is provided at the D = diffusion coefficient for C in the y phase, D,
surface of a low carbon steel. The carbon diffuses which is assumed to be independent of concen
into the steel at high temperatures usually 1600 to tration, and
1800°F (871 to 982°C), for time periods generally C = carbon concentration as a function of distance
from a few hours to a day. A carbon gradient is pro X and time / from the surface at X = 0.
duced in which the carbon content decreases from the
It is assumed that no volume changes occur in the lat
surface into the steel.
tice during diffusion. This is a valid assumption for
In the pack or gas carburizmg process the carbon
interstitial diffusion processes. Figure 1 shows car
concentration at the surface of the steel is controlled
bon profiles for varying times at 17 00°F and fig. 2
by the CO/CO2 ratio in the gas atmosphere, the tem
shows carbon profiles at 1600, 1700 and 1800°F for 8
perature and the solubility of carbon in the steel.
h carburization treatments all calculated using Eq.
Gurry’ has considered the thermodynamic aspects of
the heat treatment of plain carbon steels in CO/CO2 DISTANCE t 001)
gas mixtures produced in endothermic or exothermic 80 20
generators. Using the analysis of Gurry the composi
tion of the gas mixture in equilibrium with a specified
surface carbon content can be calculated. Recently
Harvey2 has described a similar calculation scheme I
z
for the heat treatment of alloyed steels. 0
The simplest carburization process, tvhereby car cc
U]
0.
bon diffuses into a plain carbon steel at one tempera
ture can be described by the Van-Ostrand Dewey 3
solution to the diffusion equation: z
0
I

CC — Cs_ cc
erf(X/2 ‘I) [1] z
Co — cs_ U]
U
z
0
where U
z
0
cc
.1
U
J. I. GOLDSTEIN is Professor of Metallurgy and Materials Engineering, Lehigh
University. Bethlehem, PA 18015, and A. E. MOREN. formerly Graduate Assist.
ant, Metallur’ and Materials Engineering Department. Lehigh University, is now
Asaistant Professor. Physics Department. Wheeling College, Wheeling, WV 26003.
This paper is based on a presentation made at a symposium on “Carburizing 20 30 40 5.0
and Nitriding: Fundamentals. Processes and Properties held at the Cincinnati DISTANCE 1mm)
Meeting of the Metallurgical Society of AIME. November Il and 12. 1975 under fig. 1—Carbon concentration vs distance curves for varying
the sponsorship of the Heat Treatment Committee. times at 1700’F, 1) f(C), Binary Fe—C.
ISSN 0360.2133/781I1I3-I5ISSOO.75/0
METALLURGICAL TRANSACTIONS A © 1978 AMERICAN SOCIETY FOR METALS AND VOLUME 9A. NOVEMBER 1978—15 15
THE METALLURGICAL SOCIETY OF AIME

—
 Authors Copy
DISTANCE t
80
U)
UI
0
z
C
z
UI
C-)
z
0
z NUMERICAL ANALYSIS
0
C Binary Diffusion
U)
0 20 30
DISTANCE (mm)
Fig. 2—Carbon concentration vs distance curves, calculated
for 8 h carburization treatments at 160O 1700 and 180OF,
D f(C), Binary Fe-C.
[iJ. An average diffusion coefficient3 D = 0.12
exp (— 32,000/RI) cm2/s, was used in the calcula
tions. The value of C was set at the maximum solu
biUty of carbon in the y phase at the temperature of
interest.4 These calculations are restricted however
to simple carburization processes and Fe-C alloys.
‘rris5 has developed an empirical technique, using
hon profile data from carburized steels, for de
termining the effect of time and temperature on the
case depth, the maximum distance of carbon diffusion
from the surface, and on the carbon gradient. This
technique has been applied with adequate results to
carburization treatments in plain carbon and in alloy
steels as well.
Three major complications to the previous descrip
tion of the carburization process should however be
noted.
A) D is a function of concentration. According to
the measurements of Wells and Mehl,3 the diffusion
coefficient increases with carbon content. Carbon
profiles will therefore differ in detail from those cal
culated from Eq. [ij. Limited calculations accounting
for this effect have been made.5
B) In many carburization treatments temperature T
and/or surface carbon concentration C5 may vary with
time. After an initial period of carburization, C5, and
possibly T, is usually lowered. The latter part of the
treatment is called the diffusion step. C5 may also
vary with time in this diffusion step. These opera
tional variations are often made to insure that maxi
mum hardenability will be obtained at the steel sur
face after the quench.
C) Major ternary solute impurities (Mn, Cr, Si,
Ni, and so forth) may have a major effect on carbon
diffusion during the carburization process. If any of
solute impurities are inliomogeneously thstri
.ted in the alloy, for example by grain boundary
segregation or by surface or internal oxidation, the
carbon flux can be modified by the effect of the off-
15 16—VOLUME 9A, NOVEMBER 1978
diagonal or cross diffusion coefficients.8 The carbon
flux can be either increased or decreased by this ef
fect.
These 3 major complications to the standard car
burization process discussed above cannot be simu
lated by Eq. [1 although Harris5 has developed a
technique to account for the diffusion period tvhen cal
culating total case depth. The purpose of this paper
is to describe computer models which will allow the
calculation of carbon gradients for conditions where
T, / and C5 vary and for ternary alloys as well. Cal
culated carbon gradients will also be compared to
available experimental data.
The diffusion of carbon in iron can be described by
Fick’s second law:
ac DIBC [2
at ax ax )
For the case where 13 is not a function of concentra
tion Eq. [21 reduces to:
ac 13aC [31
at ax
The most useful methods for solving differential
equations such as the diffusion equation are the
finite difference techniques. One of these, the Crank
Nicolson finite difference analog, as described by von
Rosenberg,9 is second-order correct with respect
to both independent variables X and t and, in addition,
stable over a large range of increments of the varia
bles.
The finite difference technique employs a one di
mensional space grid. The composition distribution
of carbon in the y phase is shown schematically
within such a space grid in Fig. 3(a). L is the total
length of the grid. C represents the carbon concen
tration at any grid point i or node along the grid. The
diffusion problem is bounded spatially by a constant
carbon concentration at the surface of the steel at
grid point i = 2, and a zero mass transfer boundary
where the carbon gradient ac/’ax 0 at X L, that
is at grid point 1 =113. The size of each grid spacing
is equal to L/(ID 2). —
The finite difference equations used in the Crank
Nicolson method to solve Eq. 131 are presented below:
C— C [4j
at
2 C7 ‘ +
a2c
—
1/2
— I
Cz_il
+ Ct+1 —2 C +
[51
()2
At any time step, C1, C’, and C.1 are known values
and C’, C’ and C11 .re unknown values.
The subscript I and superscript n refer to the space
position of a particular grid point (Fig. 3) and the
time step respectively. The time increment between
METALLURGICAL TRANSACTIONS A
 Authors Copy
time step n and n + us given by t. Substituting c
,
from the old ones, e.g. C. The specification
Eqs. [4] and [5] into Fick’s second law, Eq. [31 and of X and t is relatively flexible in the Crank
collecting terms for points n and n ÷ I on opposite Nicolson method. In the forward finite difference
sides of the equation gives: technique’ stability requires that
((.X) “ ,z+ Dt 17
C°’[ 2 1/2 I
j-1 + I —
— ‘Dtt 11+ 1+1 ()2 -

In this work we take our initial value of t so that Eq.

(fv)S)
= —C’_1 ÷ C’ [2— 2 1 C’+, [6] [71 is satisfied. After each carbon profile generation
we increment t by 10 pet so that relatively large
for each of the grid points I. heat treatment times can be handled with a minimum
Applying Eq. [6] to all the grid points i yields a of computer time. After each carbon profile genera
tridiagonal matrix of equations. A Thomas algorithm9 tion, a new value of surface carbon concentration and
can be used to solve for all the concentration values temperature (diffusion coefficient) can be used for the
at the n + 1 time step provided the boundary condi next time increment. The accuracy of the finite dif
tions as described above are specified. The zero ference technique was established by comparison of
mass transfer boundary condition can be satisfied by the results with the analytic solution, Eq. [1].
setting CID = CID
+,
at X = L. The value of C at I
-,

= 2 is specified by the carbon concentration at the Ternary Diffusion

surface.
The calculation of a carbon gradient proceeds in the The diffusion of carbon in ternary Fe-C-M alloys,
following manner. An initial carbon profile is speci where M represents a metallic solute element such
fied. Using the appropriate diffusion coefficient, and as Cr, Ni, Si or Mn, may be determined with the aid
the specified boundary conditions, the Thomas al of Onsager’s extension of Fick’s first law.’° For a
gorithm solves for the new concentration terms, e.g. ternary system” the generalized Fick equations for
the flux of elements I and 2 in terms of the concentra
ZERO MASS TRANSFER tion gradients in a given phase are:
CiZ).CONSTANT, MASS
BOUNDARYC5 BOUNDARY C(ID-l).C(ID*l7
3C1 OC, rL8a
J, -—D,,-—D,,-
—

‘PHASE

CARBON CONTENT I-i (t,Xt.L/(ID_2)

—
—
—
-‘22 —
3
21
ad

D and D, are measures of the effect of the concen

tration gradient of a given component on its own
flux, whereas D, and D1 reflect cross-effects usually
iD.IJIO referred to as the ternary diffusional interaction.
I 2 L3
Combining Eq. [8] with the continuity equation and as
x.O DISTANCE X.L suming that the ternary coefficients are composition
(a) independent, the Fick’s second law for a ternary sys
C(2)CONSTANT, MASS ZERO MASS TRANSFER tem is:
\RNsFER BOUNDARY • C9 BOUNDARY CtID-I)•Ct7
2
[9aj
J’PHASE
-
= D,
-; ÷ D12
(IC2 3 3 a-C1 [9b
f C1
- —
—-

ax2 ax’
cit
Components 1 and 2 may be taken as carbon and solute
+ I

element M respectively. Component 3 is the iron sol

vent.
The Crank-Nicolson finite difference technique can
also be used to solve Eq. [9] for both C1 and C,. The
czt Czxi.L/(tD2) one dimensional space grid used to describe the dis
tribution of C, and C, in the y phase is shown in Fig.
3(b). The finite-difference nomenclature is the same
as that used for the binary case, F 1g. 3(a). The dif
ID-I--’tD LIO+I
IJ 2 i-I—a fusion problem is bounded spatially by a constant C,
XO DISTANCE XL and C2 concentration at the surface of the steel at grid
(I’) point I = 2 and a zero mass transfer boundary where
Fig. 3—(a) Schematic diagram of the space—composition ac,/ax = ac,/aX = 0 at X = L at grid point I = ID. The
grid for the numerical model of binary carburization. (1,) finite difference equations used in the Crank-Nicolson
Schematic diagram of the space—composition grid for the method to solve Eqs. [8] and [91 are given by Eqs. [4 1
numerical model of carburization in a ternary Fe—C—M al—
and [5]. By combining Eqs. [4], [5], [8] and [9] one ob
by. Schematic composition profiles of element 1 and Z (C1
and C,) in ‘ are shown for one time level. tains a bi-tridiagonal matrix of the form:

VOLUME 9A,NOVEMBER 1978—1517

METALLURGICAL TRANSACTIONS A
 Authors Copy
a’ 1C?,’ —1 + j
)ç,?l+ 1
—1 + b’
1
+ b2
1
= [0.07 ÷ (0.06 C)l exp (—32,000/RI) cm2/s [12]
-2, j

(l),—fl+ 1 (2)ç.fl *1 I1) 0 where C is the carbon content in ;vt pct. Since D& is
+ C1 ‘—,+i I-c1
—

tOj [iGa]
‘—‘2,j+Y
not a strong function of composition, the value of the
—

(3),-.?? +1 (4)ç,fl+ 1 (3)ç.fl* 1 , (1)r’0 1 second term in Eq. [ii] is much smaller than the first
a1 ‘1,j—1 + Cli ‘-‘Z,j—l + Ui °.‘1,j + Uj —‘2,j term and can be neglected. To account for variations
* 1 (4 Ic0’ 1 — (2),fl
[lob] of 13 with composition, values of D are calculated from
+ C 6..-i,j+i + C ‘—‘2,j+1 —
Eq. [12 for each carbon content C along the grid and
for each time increment n. These diffusivities are sub
The coefficients a1, b1, c and the term d1 are con stituted in Eq. [61 for the solution of the carbon con
stants determined at each time interval. The matrix
centration gradient. Figure 4 shows the calculated
is solvable using a standard algorithm1 provided the
carbon gradients at 1700°F for 13 .1(C) and 13 = f(C)
boundary conditions for C1 and C2 are specified. The
and for two times, 2 and 16 Ii. The effect of the varia
zero mass transfer boundary conditions for C1 and C2
tion of diffusion coefficient with composition is small
can be satisfied by setting C1,113+1 = C1,113_1 and allowing slightly less carbon diffusion. No measur
C2,113 +1 = C27113 -r at X = L. The value of C1 and C2 at
able change in the shape of the carbon gradient is
grid point I = 2 is specified by the value of C1 and C2 predicted. In subsequent binary calculations the
at the surface. variation of carbon diffusivity with composition is in
The calculation of the carbon and element M gradient cluded.
proceeds in the same way as in the binary diffusion
case. An initial C1 and C2 profile is specified as well
as the appropriate ternary diffusion coefficients, D, DISTANCE COOl”)
1322, 1312, D, and boundary conditions. For each
new 0 40 80 120 160
time step n + 1 of At s, a new set of concentrations
C1, C’,’ are obtained for each grid point in the ‘3
phase.
I— A TEMP
z .6 (680 0
w 0 09—
CALCULATIONS OF THE CARBURIZATION U
a: (670 08 u’
PROCESS a 07
‘I
I— 06
Binary Diffusion 12
z
A) Variation of Diffusion Coefficient With Com a
position. Fick’s second law, Eq. [2 can be expanded, a:
I
if 13 is a function of composition, to: z
w 0.8
U
z
aC 32C / aD ‘ / aC 11 0
U
T
—

3X2&A’ ‘. ax
z
0
cr 04
In this expression 13 ftc) and will vary along the dif 4
U
fusion gradient. According to the measurements of
Wells and Mehl;3
DISTANCE t 0011
0
80 ‘20 0 (0 20 30 40 50
DISTANCE (mm)
(11)

DID 7671(1 00Il

O 20 •O 60 40 00 20 40 60
I—
z
U
U
a:
U
0 ALADuNID

I — CALCULATED

0 70

a:
I
z
U
U
z
0
U
z
0
a:
*1
U

0i5O02l03(0’40

DISTANCE

(hi
DISTANCE (mm) fig. 5—ta) Carbon concentration us distance curves calcu
Fig. 4—Carbon concentration us distance curves calculated lated for a two step carburization treatment 13 =f(C). (b)
for 2 and 1Gb treatments at 1700°F, 13 =f(C) and 13 ftc), Comparison of calculated and measured carbon profiles for
Binary Fe-C. the two step carburization treatment, Fig. 5(a).

1518—VOLUME 9A,NOVEMBER 1978 METALLURGICAL TRANSACTIONS A

 Authors Copy
3) Two Step Carburizing Treatments. A two step
carburizing treatment (Example 4, Cycle 1) is de
scribed in the gas carburizing article in the Metals
Handbook.’2 A 4815 steel is carburized in a continu
ous carburizing furnace at 1690°f for 22 h and then
given a final diffusion heat treatment at 1670°F for
13 h. The carbon potential is 1.25 wt pct during car
burization and then varies in the diffusion step from
1.25 wt pct to 0.80 tvt pct at the center of the zone to
0.6 wt pct at discharge. The diffusion treatment
helps develop a relatively flat carbon distribution
near the surface. The variation of temperature, and
surface carbon content with time is shown in Fig. 5(a).
This two step carburization process was simulated
using the binary diffusion model with D =1(C) and a
uniform initial carbon concentration of 0.15 wt pct.
The values of temperature and surface carbon poten
temperature and surface carbon content from 1500
to 1700°f.’4 The resulting C vs time relationship is
shown in Fig. 6(a) and is approximated by a series of
straight line segments.
The carburization process was simulated using the
binary diffusion model with D = 1(C) and a uniform
initial carbon concentration of 0.15 wt pct. The val
ues of temperature and surface carbon potential were
varied during the computer simulation as shown in
Fig. 6(a). This figure also shows the predicted car
bon profiles at the various indicated time periods. At
t,, after heat up, the C5 value is a maximum. The
curve at I gives the carbon profile at the end of the
carburization cycle. from time t3 to /, decarburization
occurs, and a hump in the carbon profile develops due
to the fact that C5 decreases faster than the diffusion
process can ma hit am the shape of (lie norma I ca rhour —

tial were varied during the computer simulation as ization curve. At time t, at the cud of the cliffuNtun
shown in Fig. 5(a). The surface carbon potential is
DISTANCE C 001’)
changed in linear segments throughout the final treat 40 60
ment cycle. Figure 5(a) also shows the predicted
carbon profiles at three time periods, 1,, at the end
of the carburizing cycle, t2 in the middle and t at the
end of the final diffusion treatment at 1670°F. The I
unusual profile developed after carburization and z
La
during the diffusion treatment is caused by the lower U

ing of C at the steel surface. The decrease in the 0

surface carbon potential after 1,, causes carbon to

diffuse out of the sample (decarburization) at the sur
z
face. Decarburization continues throughout the re 0
I
mainder of the cycle. The hump in the carburization ‘1

curves at t2 and t3 represents the position where I

z
ac/ax = 0: beyond this position carbon continues to La
U
z
diffuse into the steel. This hump moves gradually 0
U
away from the surface as diffusion time increases. 0
z
Relatively minor additional carbon diffuses into the
sample beyond the position where ac/ax = 0 after
•0
L)

the carburization cycle is completed, at 1,.

The final calculated carbon profile, for the two step
treatment (time t3) is replotted on fig. 5(b) along with
the measured carbon data.’2 The shape of the calcu
DISTANCE (mm)
lated curve and the predicted case depth are very (a)
similar to the measured data. The carbon contents D’S tANC! C 001
match within 0.05 wt pct carbon although the calcu 2 .0 20 30 40 50 60 70 00 90

lated curve falls somewhat below the measured curve.

00
C) Variation of Surface Carbon Potential and Tem
perature During the Carburizmg Treatment. 1) One — 000

type of complex carburizing treatment is given by

Example 36 from the gas carburizmg article in the 5 080

Metals Handbook.’3 In this example the long carburi 0

— 0 70
zing cycle of the carburization-diffusion process re
sults in a high surface carbon content and a large o’0

distance from the surface to the eutectoid carbon 000

composition. Figure 6(a) shows the variation of T
and C adopted for carburizing 8620 steel shafts in a 0 00

vestibule-type furnace having an enclosed quench.

0 30
The 8 h thermal cycle involved a heat up from 1500°F
to the carburization temperature, 1700°F, a car 0 20
burization treatment of approximately 6 it, a cool 0 05 0 5 20 25
down in just under an hour to the diffusion tempera
ture of 1550°F and a diffusion treatment taking just (h)
fig. 6—ta) Carbon concentration vs distance curves calcu—
under an hour. The C values were roughly deter
lated for a complex carburization—diffusion treatment in a
mined using the recorded Dew point and temperature vestibule type furnace, D = ftc). tb) Comparison of calcu
values for the carburizing cycle’3 and the equilibrium lated and measured carbon profiles for the carburization
curves which give the relationship between dew point, treatment, fig. 6(a).

METALLURGICAL TRANSACTIONS A VOLUME 9A, NOVEMBER 1978—1519

 Authors Copy
by turning
DISTANCE 001) cycle, as shown in Fig. 7(a), is achieved
off the enriching gas in the furna ce.
( • The carburization process was simu
lated using the
binary diffusion model with D = f(C) and a uniform
tion of 0.2 tvt pct. The values
initial carbon concentra
re and surfa ce carb on pote ntial were
of temperatu
varie d durin g the com pute r simulation as shown in
z
el the slow
Fig. 7(a). No attempt was made to mod
UI
U

the samp le after carb uriza tion. This figure

UI
cooling of
0
les at the vari
also shows the predicted carbon profi
rburi zatio n occu rs after
ous indicated times. Deca
z the enric hing gas is turne d off. In this
0 time /3 when
urably after
example. the case depth increases meas
turne d off since the temperature
I
z the enriching gas is
cons tant. The surfa ce conc entra tion C de
UI
U remains
z r than the diffu sion process
0 creases only slightly faste
U
the shap e of the norm al carb urization
z can maintain
smal t hump in
curve. This process leads to a very
0
0

h is quite close to the surface

‘1
U the carbon profile whic
(time t4).
this treat
The final calculated carbon profile for
tted on Fig. 7(b) alon g with the
0 ment (time t) is replo
profi le.’3 Ther e is gene rally good agree
measured
e and the meas ured
ment between the calculated curv
uptu rn in the C profi le near the
data. The predicted
steel is also obse rved in the meas ured
surface of the
data.
vacuum carburiza
D) Vacuum Carburization. In the
steel parts are place d in the furnace
tion process, the
tion tempera
and the sample heated to the carburiza
ped down to a vacuum of
3 ture while the furnace is pum
ific amo unt of carb urizi ng gas.
‘10 Torr. A spec
purif ied natu ral gas, is then back filled into
usually
lly has a car
the furnace. The gas atmosphere usua
initia lly satur ates the sample in
bon potential which
uriza tion gas is
carbon at the surface. Once the carb
ient prod uced earli er in the
used up, the carbon grad
redis tribu te. None of the carb on leaves the
cycle will
on cont ent will de
sample although the surface carb
amo unt of carb urizi ng gas is
DIStANCE I,,,.,) crease with time. The
d in orde r to prod uce spec ific carbon
th) therefore varie
um carb uriza
surface contents and case depths. Vacu
distance curves calcu
Fig. 7—ta) Carbon concentration vs in a pit
carbur ization —diffu sion treatm ent er temp eratu res and shor ter
lated for a complex tion usually employs high
ted and meas
furnace, D =f (C). (1,) Comparison of calcula ment, fig. times, than thos e used for gas carb uriza tion.
treat
ured carbon profiles for the carburization An example of the vacuum carburizi
ng process is
7(a). e 1 in. diam ground bars
described by Jindal” wher
prog ramm ed for 1.00 pet surface
le has been evened of 8620 steel were
cycle, the hump in the carbon profi carb on and 0.020 in. case dept h. The l)roc eSs in
lated carbon
out by further diffusion. The final calcu volved heating to 1900°F for 45 mm, carb urizm g at
ment
profile for this complex carburization treat 1900°F for 45 mm, and gas quen chin g.
g with the
(time t,) is replotted on Fig. 6(b) alon This vacuum carburization process was
simulated
agre emen t betw een
measured carbon profile.’3 The using the binary diffusion mod el with D f(C) and an
particu
the calculated curve and measured data is initial uniform carb on conc entra tion of 0.20 wt pot.
larly good. ture was held cons tant at 1900°F for the en
urizmg treat Tem pera
2) Another example f a complex carb time of 45 min.
by Exam ple 34 from the gas carb urizing tire carburization/diffusion process
ment, is given porti on of the 45 mm process,
shows For the carburization
article in the Metals Handbook.’3 Figure 7(a) ce carb on conc entra tion was held constant
ng 8620 t,, the surfa
the variation of T and C5 used for carburizi valu e of auste nite at
ce. at approximately the saturation
steel ring gears in a metallic-retort pit furna on. For the diffu sion portion
ased 1900°F, 1.67 wt pet carb
Starting from 1500°F the temperature is incre ess, t2 (whe re ÷ = 45 mm) a zero flux,
and held of the proc (j /2
linearly to 1700°F in approximately 30 mth ce. In the com
there for over 5 h. The samp le is then slow cool ed in ac/ax = 0, was imposed at the surfa at X 0. In this simu
puter model, Fig. 3(a), C, C3 =
ured dew
the cooling pit from 1700°F. Using meas lation t, is 30 mm and t2 is 15 mm.
the variation
point data, as in the previous example, The simulated profile is shown in Fig.
8(a) at the
entra tion durin g the cycle can
of surface carbon conc end of carburization t, and at the end of the diffusion
urizthg
be obtained. The drop in C, after the carb
METALLURGICAL TRANSACTIONS A
1520—VOLUME 9A, NOVEMBER 1978
 Authors Copy
cycle 12. The profile at t, shows how the carbon gradi therefore assumed for the calculation. There are a
ent at 11 is redistributed with no loss of carbon from variety of other combinations of initial surface car
the sample. The case depth increases while the sur bon concentrations and cycle time t, and t2 that yield
face carbon concentration, C5, decreases. The most similar carbon profiles.
critical factors determining the resultant surface
carbon content are the initial surface carbon concen
tration and the diffusion cycle time t2, where a zero Ternary Diffusion
flux at X = 0 is present. A) General Considerations. It is apparent that cal
Figure 8(b) shows a comparison between the pre culations of carburization profiles for low alloy
dicted profile and the measured profile.’5 The agree steels, using the binary computer model, are satis
ment is excellent. It should be pointed out, however, factory in many respects. However the addition of
that both the initial surface carbon concentration and ternary solute elements such as Ni, Mn, Cr and Si
the times t, and t2 were not given by Jindal’5 and were influence both the solubility limits of C in austenite,
DISTANCE (0.001)
t.e., C, and the mass fluxes of carbon as shown in
Eqs. 181 and [9 I. The effect of cross coefficienis on
carbon diffusion may be important as pointed out by
Boize, et at.8 They considered the carburization of
a manganese steel and assumed a negligible Mn con
centration at the surface. The reason for the Mn de
pletion at the surface was not explained. The practi
cal result of such a Mn depletion near the surface is
to increase the effective surface carbon concentra- -

tion by about 20 pct. This effect allows much more

carbon to enter the steel than would be calculated
from binary considerations alone. Therefore, the dif
fusion of carbon may be changed if there is a gradi
z ent of the ternary addition M in the steel.
0
One of the mechanisms by which ternary steel ad
‘2
ditions may redistribute during carburization is oxi
dation. Both surface and internal oxidation may occur
I-; during the carburization process. Modified Richard
son diagrams in which the logarithm of the ratio
Pco2 is plotted as a function of temperature for
oxides, which could form in alloy steels, are given by
Harvey.2 These diagrams show that at CO/CO2 ratios
which are necessary to saturate the steel with carbon,
oxides such as SiO,, Cr,O3 and MnO should form.
Under the same conditions Fe and Ni will not oxidize.
The formation of such oxides will cause a depletion
of the metallic element in the surrounding steel ma
trix. The oxide compositions and the amount of metal
depletion in the steel are a function of the composition
0 0.5 (.0 (.5 2.0 2.5 3.0 of the steel, the Co/Co2 ratio and the carburization
DISTANCE (mm) temperature. The metal depletion could be quite large
tu) and C2, the concentration of element M in the Fe-C-M
DISTANCE (0.001’) alloys, could approach zero. The formation of a co
herent oxide layer on the surface may however com
plicate carbon control and prevent exchange of carbon
between the carburizing gas and the solid. Simultane
1.0
ous oxide formation normally occurs during heat
treatment of chromium bearing steels2 and we have
z 06
0 observed internal oxidation in silicon bearing steels.
4
Segregation of solute elements to interfaces as a
0.6
18
result of heat treatment is a well known phenomenon
in metallic systems. Solute atoms exhibit both equi
0.4
librium and nonequihbrium segregation to free sur
faces and both types of segregation have been ob
0.2
served. During annealing of Fe-i pct Mn in the fer
rite range and in high purity hydrogen, surface segre
0 0.2 0,4 0,6 0.8 1.0 1.2 1.4 1.6 1.8 20 gation of Mn occurs with the formation of a Mn-de
DISTANCE (mm) pleted zone below an enriched surface layer where
(I,) (FeMn)O forms.’6 Surface segregation was however
fig. 8—ta) Carbon concentration vs distance curves calcu
lated for a vacuum carburizing treatment, D =1 (C). (b) not observed in Fe-i pct Ni alloys under the same
Comparison of calculated and measured carbon profiles for conditions.16 In an Auger electron spectroscopy study
the carburization treatment, Fig. 8(a). of oxidation of modified 440C steel, a thin film of

METALLURGICAL TRANSACTIONS A VOLUME 9A,NOVEMBER 1978—1521


chromium oxide was observed at temperatures above
700°C.’7 Other studies confirm the formation of
oxide’8 during carburization although we know of no
studies which have described this phenomenon in de
tail.
The following calculations of ternary carburiza
tion effects show the possible influence of the ele
ments Cr, Si. Mn and Ni in Fe-C-M alloys. Thin
relatively incoherent oxide layers are assumed to
form on the surface of Fe-C-M alloys where M is
Cr, Si and Mn. Depletion of these elements at the
surface of the steel in contact with the CO/CO2 at
mosphere is assumed. Calculations of C, and C2, the
carbon and solute element concentrations respec
tively, will be made using the ternary diffusion com
puter model previously described.
B) Input Parameters. The initial carbon content for
all the Fe-C-M steels was assumed constant at 0.15
wt pct. The initial metal solute concentration of vari
ous Fe-C-M alloys was assumed constant at 2.5 wt
pet Si, 5.0 wt pct Ni, 2.0 wt pot Cr or 1.0 wt pet Mn.
These concentrations represent the maximum solute
contents generally found in carburizing steels. Stain
less steel compositions were not considered in these
calculations. The carbon surface concentration, C,
was assumed to be the saturation value in the y phase
at 1700°F (1200 K) for the Fe-C-M system of interest.
These values were obtained directly or by extra
polation from the appropriate ternary phase dia
grams.4 The values of C used were: 1.28 wt pet C
for a Fe-C-1.0 wt pet Mn alloy, 1.1 wt pet C for a
fe-C-5 wt pet Ni alloy, 1.0 wt pet C for a Fe-C-2.0
, wt pet Cr alloy and 1.0 wt pet C for a Fe-C-2.5 wt
pet Si alloy.
Four ternary coefficients, D,, D2, D12 and D,, are
necessary to describe the three element diffusion
problem. Element 3 is the solvent iron and elements
1 and 2 are carbon and solute M respectively. Since
the value of D, is iO to 10 times larger than that of
D22, the amount of diffusion of component 2 during
carburization is very limited. As discussed by Brown
and Kirkaldy,’° the experimental effect produced by
the cross coefficient D, is very small. In the ternary
calculations which follow D, is set equal to zero.
Table I. Calculated Values of D2/D, for Ternary Carburization Calculations°
System e,,
Fe-C-Si 9.5 8.9
Fe-C-Ni 4.6 8.9
Fe-C-Mn —4.2 8.9
Fe-C-Cr —10.7 8.0
*12 and e1 values from Ref. 19.
Table II. Values of Ternary Diffusivities Used for the 1700°F Ternary
Carburization Calculations
System D,(cm2/s) Di(cm2fs)
Fe-C-Si 1.78 X l0 5.43 X
Fe-C-Ni 1.78 X l0 2.63 X
1.78 X I0 —2.40 X
Fe-C-Mn
1.78 X l0 —6.11 X
Fe-C-Cr
1522—VOLUME 9A, NOVEMBER 1978
Authors Copy
According to Brown and Kirkaldy/° in dilute ter
nary austenite the variation of D12 to D can be given
by the relation:
[131
D2/D, 1 + e11N,
where N, is the mole fraction of element 1. carbon
and e,, and C13 are the thermodynamic Wagner inter
action parameters which relate the activity of ele
ment 1 to the mole fraction of elements 1 and 2. Ex
perimental evidence for Fe-C-M alloys has been
presented” to show that one can calculate the ratio
D/D4 from purely thermodynamic data. The ratio
D2/D, is a strong function of the concentration of
element 1, Eq. 131. Since a gradient of element 2.
ac2/ax, only occurs close to the steel surface, the
effect of cross coefficient on carbon diffusion will
only be important close to the surface. Therefore,
D12 is calculated at a point where the carbon content
approaches C, approximately 1.0 wt pet carbon at
1700°F. Table I lists the data and values of diffusion
coefficients obtained. The cross coefficients for the
carbide formers Cr and Mn are negative while the
cross coefficients for Si and Ni are positive. The
D/D, ratios for Si and Cr are quite high >1 0.3 and
will have a large influence on carbon diffusion.
The value of D, was assumed to be the average
diffusion coefficient for the Fe-C system.3 Since D2
approaches the interdiffusion coefficient D for the bi
nary 2—3 or Fe-M at small amounts of element 1.
carbon, we have used interdiffusion data for Fe-Ni at
5 wt pet Ni2° to evaluate DNj, tracer diffusion data
for Mn’4 in an alloy of 1.04 at. pet Mn in Fe2’ to evalu
ate DMfl,[fl , tracer diffusion data for Cr°’ in pure
yFe22 to evaluate Dcr, and interdiffusion data for
Fe-Si from an Fe vs 2 at. pet Si-98 at. pot Fe diffu
sion couple23 to evaluate D Table II lists the
values of D1, D12, and D22 used for the 1700°F car
burization calculations in the ternary diffusion model.
C) Solutions, Ternary Effects in the Carburization
Process. Figure 9 shows predicted carbon profiles as
a function of time at 1700°C in a Fe-2.0 wt pet Cr-
0.15 wt pet C alloy. The chromium is assumed initially
constant at 2.0 wt pet. At the beginning of the calcu
lation the Cr content at the steel surface is set equal
2StArCE I OO’I
N1
0.0449 0.305
0.0449 0.148
0.0449 -0.135
00.449 —0.343
0
D2(cm2 /s)
10° 7.61 X 10-Is
10° 4.97 X l0- DISTANCE
I -8 7.67 X 10-fl Fig. 9—Carbon concentration us distance curves calculated
L0 2.18 l0’ for an Fe—2.0 wt pet Cr—0.15 wt pct C alloy and for varying
times at 1700° F. CC,. = 0 at the surface.
METALLURGICAL TRANSACTIONS A
 Authors Copy
‘to zero (note Fig. 3(b)). The effect of the cross co measured surface carbon content.25 A lotv carbon skin
efficient D2 = is significant. It raises the C observed metallographically was also produced in
value from 1.0 wt pct carbon at the surface to almost the samples and increased in size with time. All of
1.7 wt pct less than 12 jim (0.0005 in.) from the sur these observations are consistent with those predicted

© face. Such a large cross coefficient effect allows

much more carbon diffusion to occur than in the bi
nary case tvhere no ternary interactions occur. As
time increases, the maximum carbon content also in
creases.
In the standard chemical analysis technique used
to measure carbon gradients, the spatial resolution
along the gradient is typically greater than 25 p.m or
0.001 in. (Figs. 5(h), 6(b), 7(b)). If the calculation for
8.31 h (Fig. 9) in the Fe-C-Cr alloy is assumed to be
correct, the carbon concentration closest to the sur
face, which is measured by standard chemical tech
niques, would be reported to be 1.6 wt pct carbon.
The actual surface concentration C is of course 1.0
in Fig. 9, namely that the maximum carbon content
increases with time and that a low carbon area be
tween the surface and the maximum carbon content,
of limited depth —°0.001 in., should be formed. The
result of this increase in carbon content has been
demonstrated by the formation of carbide at the car
burizing temperature.
Figure 10 shows the calculated chromium and car
bon gradients close to the surface of the Fe-2.O wt pct
Cr-0.15 wt t)ct C alloy carburized at 1700°F for 8.31
h. The carbon gradient calculalçd when D2 = 0 can
also be compared. The D12 = Dc = 0 curve is the
same as a calculated binary diffusion curve with C5
= 1.0 wt pct C. An extrapolation of the Dr curve

wt pct. It has been reported that steels containing
more than about 0.5 wt pct Cr have surface carbon
contents far above austenite saturation values.24’25
A 5120 steel containing 0.8 wt pct Cr, for example,
carburized at potentials which will saturate austenite
yields 1.7 tvt pct C for the effective C5 at the surface.
The curve for Cr redistribution demonstrates that a
very small amount of Cr diffusion actually occurs.
DISTCE 001’)

and for heat treatments of 9 to 10 h at 1700°F, had a

measured carbon content of 1.75 wt pct, 0.0025 in. be
low the carburized surface.21 This value is well above
C5 of °1.0 wt pct C. It is interesting to note that our
calculations indicate C contents in excess of 1.6 wt
pct C up to 0.0025 in. below the carburized surface.
It was also observed in the Cr containing steels that
the longer the carburization time the higher was the

DISTANCE (.001’)
0 I 2 3 4 5 6 7

-; ISO

I7OO F 05 ‘5
Z
Ft 2.0 Co -O.ISC OIST4NCE
.25
-

0 2.99 .(0 SEC.

8.31 HRS.)
fig. 11—Carbon concentration vs distance curves calculated
4
for an Fe—2.0 wt pet Cr—0.15 wt pet C alloy carburized at
1700°F for 8.31 h. The surface concentration of Cr is varied
from 0.0 to 2.0 wt pci.
IoOrt-o

075 0CCo -
3lST0’CE

4
1)

0.10-

z
0

0
U

03 0 IS 20 25 30
0.10 0.20 DISTOOCt I,,..I
DISTANCE (“““I Ftg. 12—Comparison of carbon penetration curves calculated
Fig. 10—Carbon and chromium vs distance curves calcu— for 2 alloys (Fe—2.0 wt pet Cr—0.15 wt pet C, and Fe—2.5 tvt
lated for an Fe—2.0 wt pct Cr—0.15 svt pct C alloy carburized pet Si—0.15 wt pet C) carburized at 1700F for 8.31 Ii. C5 = 1.0
at 1700°F for 8.31 h. The surface concentration of carbon is wt pet C. CCT = C = 0 for the ternary alloys at the surface.
1.0 vt pct and of chromium is 0.0 wt pct. The near surface One curve is calculated for D12 = 0, no cross coefficient ef
region of the C—Cr gradient is plotted. fects.

METALLURGICAL TRANSACTIONS A VOLUME 9A,NOVEMBER 1978—1523

 Authors Copy
oo
Little diffusion beyond 10 .im or 0.0005 in. from the
surface tvill occur during the diffusion process. The
ratio of to is 1.22 x 10. Figure 11 shows
the relative effects of assuming a Cr content at the
steel surface of 0.0, 0.5, 1.0 and 2.0 wt pct Cr.
Q Clearly the Cr content has a very significant effect
on the effective carbon content at the surface.
is
The sign of the cross coefficient of silicon,
positive. If the Si content in the Fe-2.5 wt pct Si,
0.15 wt pct C alloy is assumed equal to zero at the
surface, the effect of the cross coefficient is to
severely limit carburization. Figure 12 shows the
calculated carbon profile for a carburization treat
ment of 8.31 h at 1700°F. The carbon profiles for the
fe-2.0 wt pct Cr-0.15 wt pct C alloy and the case
where D = 0 are also shown for comparison pur 20 23 30

poses. The effect of Si is rather dramatic limiting
carburization and producing an effective C of 0.25
wt pct C instead of the saturation value of 1.0 wt pct
C. The absolute value of the cross coefficient D2 of
both Cr and Si are approximately the same but the
sign change from negative for Cr to positive for Si
causes very different carburization effects.
Figure 13 shows the results of the ternary carburi
zation calculation for an Fe-1.0 wt pct Mn-0.15 wt pct
C alloy at 1700°F for an 8.47 h treatment. The surface
carbon content of 1.28 wt pct C is raised about 10 pct
relative to an effective value of 1.4 wt pet C. The ef
fect of the cross coefficient is smaller than that of
Cr primarily because the value of D1 is about one
third that of Dr. Boize et at8 also show an effec
tive increase in surface carbon content in their cal
Fig. 14—Comparison of carbon penetration curves 0
= ÷0.148) for an fe—5.0 wt pet Ni—0.15 vt pct
and
C alloy carburized at 1700F for 8.31 h. CNI = 5.5 wt pet at
the surface.
of -5 pet relative was calcutated. A larger Ni in
crease at the surface would bring about a correspond
ingly higher effective value of C.
SUMMARY AND CONCLUDING REMARKS
Computer models have been developed to simulate
the effects of variations of temperature, time and
surface carbon concentration during gas or pack car
burization of low alloy steels. The computer models

. culations of ternary carburization for an Fe-4.58 wt

pct Mn-0.25 wt pct C alloy. The Mn content was also
assumed to be zero at the steel surface.
predict that the variation of surface carbon content
during the diffusion cycle causes decarburization
close to the surface and prevents any significant
increase in case depth. The vacuum carburization
As discussed previously Ni will not oxidize in the
process was also modeled assuming that the process
normal co/Co2 atmospheres used for carburization.
consisted of ttvo steps: carburization with a specific
The surface Ni content will remain constant or per amount of gas backfilled into the chamber and dif
haps increase somewhat if surface oxidation of another fusion after the gas is used up in which the initial
solute element occurs. Figure 14 shows the effect of carburization profile is redistributed and no carbon
a slight increase in Ni content, from 5.0 to 5.5 wt pet is allowed to leave the sample.
at the surface, on the carbon gradient in a nominal Calculated carbon profiles were also compared to
Fe-5.0 wt pet Ni-0.15 wt pet C alloy. The carburiza experimental data available in the literature. Agree
tion calculation was carried out for a carburization ment between calculated and measured data was very
time of 8.31 h at 1700°F. Only a small carbon increase good. Unfortunately very little experimental data
where carbon profiles are measured close to the sur
35TNCt 30)

face or where temperature and surface carbon poten

tials are closely monitored is available. Until such
data is obtained the models cannot be thoroughly
tested.
Computer models were also developed to simulate
ternary solute element effects on the carburization
process. The case where solute element depletion
or enrichment occurs by oxidation at the surface was
studied. Chromium and silicon have large cross co
efficient effects and it is predicted that they have a
large influence on the amount of carburization which
will occur. Experimental data from fe-C-Cr alloy
carburization treatments are in excellent agreement
with our ternary predictions of major increases in ef
fective surface carbon content and the formation of
STC
carbides in austenite at the carburization tempera
O Fig. 13—Comparison of carbon penetration curves fDin=O
and D1/D = —0.135) for an Fe—1.0 wt pct Mn—0.15 vt
pct C alloy carur1zed at 1700°F for 8.47 h. CMn = 0 wt pet
ture.
The computer models developed in this study are
at the surface. relatively easy to program and to apply to specific

METALLURGICAL TRANSACTIONS A
1524—VOLUME 9A, NOVEMBER 1978
 Authors Copy
alloys and carburization treatments. They ;vill allow
complex carburizing cycles to be modeled and will
significantly decrease the amount of trial and error
often associated with designing the processing steps.
A CIOWLEDGMENTS
The authors wish to acknowledge the partial financial
support of this work by the National Science Foundation
Grant No. DES 74-22518. The authors wish to thank
Dr. E. Randich (Sandia Labs) for assistance in the
computer modeling.
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VOLUME 9A,NOVEMBER 1978—1525