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CONTROL OF DECARBURIZATION OF STEEL

Paul Shefsiek

Introduction
Historically, heating steel for forming, forging or rolling, was done in electrical resistance
or natural gas heated furnaces. It was inevitable that these furnaces contained Oxygen and
Decarburization of the steel surface occurred. This decarburization was either ignored or
minimized by coating the steel with stopoff . Also, this decarburization was minimized
through the use nitrogen atmosphere furnaces. But, decarburization could not be reduced
to acceptable limits until the Chemical Potential of the Carbon in the furnace atmosphere
matched the dissolved Carbon in the steel.
The Furnace Industry that provides Equipment for the processing of steel, because of the
temperature ranges involved, divided itself into two categories, namely, Reheat and Heat
Treating. Each has its own special Technology. But, because of this division, quite often
one division does not know the Technology of the other. In some cases this has been
unfortunate. If the Reheat side of the Industry had the Carburizing Technology of the
Heat Treating side, this Technology could have been applied to applications where
preventing Decarburizing was a requirement.
Therefore, the purpose of the following discussion is to separate out that part of
Carburizing Technology that is applicable to preventing Decarburization in Reheat
applications.

Fundamentals
Control of the Decarburization of Steel has been standardized to the monitoring of
- The Metal Temperature (Furnace Temperature)
- The Atmosphere Concentration of Carbon Monoxide (CO)
- The Atmosphere Concentration of Carbon Dioxide (CO2).
Knowing the values of these three (3) parameters and the knowledge of
- Saturated Austenite in Iron
- The Alloy Content of the Steel
- The Equilibrium Constant for the Controllable Chemical Reaction
between the Steel and the Gas Atmosphere
it can be determined if the Atmosphere will prevent Decarburization of the Steel.
The Reversible Controllable Reactions that are present when Methane ( CH4 ) is the
Hydrocarbon added to control the Carbon content of the Atmosphere are
2CO = ( C ) + CO2
CH4 = ( C ) + 2H2
CO + H2O = CO2

-----------------------------------------------------------------

+ H2

---------------------------------

(1)
(2)
(3)

where
( C ) is the Carbon content of Saturated Austenite at Metal Temperature ( T ).

Reactions ( 1 ) and ( 2 ) indicate the addition of Carbon to Steel from Carbon Monoxide
and Methane to form a solution of Carbon in Austenite and also to form Carbon Dioxide
and Hydrogen, respectively . Both are reversible and the Gas Concentrations required to
maintain Equilibrium with a particular Surface Carbon Concentration at a definite
Temperature can be calculated from thermochemical data.
Reaction ( 3 ) results from the presence of H2 due to reaction ( 2 ).
Equation ( 1 ) represents the reaction between the Atmosphere and the Steel and through
the thermochemical equilibrium data and knowing the Concentrations of the reactants,
the Carbon Concentration - Carbon Potential can be determined.
The Equilibrium Constant for reaction ( 1 ) is as follows:
K = (Partial Pressure of CO) 2
(Partial Pressure of CO2)

-------------------- ( 4 )

and
Log10 K =

- 15,966
T(R)

+ 9.060

---------------------- ( 5 )

where
T (R)

= T ( in deg F

460.)

When using Equation ( 4 ) and ( 5 ) to determine the Carbon Potential of the Furnace
Atmosphere, it is necessary to define an Activity Function [ A ] as the percentage of
Saturated Austenite at Temperature T ( R ), that is,
[A]

= % Carbon in the Atmosphere


% Carbon in Saturated Austenite

-----------

(6)

and [ A ] must be incorporated in Equations ( 4 ) and ( 5 ) for Carbon Potential values


less than Saturated Austenite as shown in Equation ( 6 ).
K =

1 ( P.P. of CO ) 2
[ A ] (P.P. of CO2 )

--------------------------

(7)

This is a straight-line approximation of Carbon Activity, but this assumption does not
produce any significant error in the evaluation of Carbon Potential. A & B
Curve fitting of published data for Saturated Austenite in Iron at different Temperatures
yields within 1 % accuracy the following relationship for Saturated Austenite : A
Log 10 ( S.A.)

1 -

1950
T(R)

--------------------------

(8)

And, the following Equation gives the relationship between the Carbon in the Alloy and
the Carbon Potential of an Equilibrium Atmosphere based on the Iron Carbon SystemC:
Log 10 ( % C FE ) = +
(%CA)
+
where

% Si (0.058)
% Ni(0.012)
% Mn(0.018)
% V(0.123)
% Cr(0.038)

+ % Al(0.0394)
- % W(0.014)
- % Mo(0.0176)
- % Ti(0.194)
------

(9)

% C A = Carbon in the Alloy


% C FE = Carbon Potential of the Atmosphere
based on the Iron-Carbon System

Application
The use of these Equations will be illustrated for M1 Steel having the composition as
follows:
C 0.85 %; Si 0.30 %; Mn 0.40%; Cr 4.50%; Mo 9.00%; W 1.30%; V 1.75%
Applying this composition to Equation ( 9 ), yields, that the Carbon Potential of a
atmosphere that would be in equilibrium with M1 steel based on the Iron - Carbon
System, is 0.372 %. Knowing this value, Equation ( 6 ) & ( 8 ) will yield the Activity [A]
as a function of Temperature. Equation ( 5 ) gives the Value of K as a function of
Temperature.
Combining the results of Equation ( 5 ) & ( 6 ) with Equation ( 7 ) yields a relationship
that gives a value for the [ (CO)2 / (CO2) ] Ratio as a function of Temperature for M1
steel. This Ratio is called PDR -- Prevent Decarb Ratio
The result of this evaluation is shown in Figure 1. Figure 1. is a plot of the Prevent
Decarb Ratio vs. Temperature for M1 steel. Also shown in Figure 1. is a plot of the
required Carbon Monoxide Percentage( % CO ) vs. Temperature for M1 steel if the
concentration of the Carbon Dioxide ( CO2 ) has a value of 0.01 %, a practical lower
limit control value.

Conclusion
A method for the Prevention of Decarburization of steel during the Reheat process for
Forging and Rolling has been presented. It incorporates the accepted procedure for
controlling the Carbon Potential of the Furnace Atmosphere and the relationship between
Carbon in Alloy Steel and the Iron Carbon System.

References
A. Metals Handbook, Vol. 2 , 8th Edition, pp 113,114,
(1964) American Society for Metals
B. Shefsiek,et.al., U.S. Patent, No. 4,228, 062 (1981)
C. Moiseev,et.al., Thermodynamic Activity of Carbon in Recarburizing
Central Scientific-Research Institute of Metallurgy, Translated from
Metallovedenie i Termicheskaya Obrabotka, No.1, pp 21-26, Jan, 1974,
UDC 536.777:669.784:699.14.018.298

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