Vacuum 86 (2011) 448e451

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Vacuum
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The kinetics of low-pressure carburizing of alloy steels

R. Gorockiewicz*
Faculty of Mechanical Engineering, University of Zielona Gra, Podgrna 50, 65-246 Zielona Gra, Poland

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 26 March 2011
Received in revised form
15 September 2011
Accepted 16 September 2011

In the article the author analyzed the kinetics of low-pressure carburizing of alloy steels, based on steel
16MnCr5 and CSB 50NIL. It was found that an active radical-carbon layer (carbon deposit) deposits on the
surface of austenite grains or austenite and carbides during boost steps. This layer mediates in moving
the carbon deeper into the austenite grains. During the diffusion steps the layer deposited on the carbide
surfaces transfers into the austenite grains. Both this layer and the one previously deposited on the
austenite grains surface now undergo another catalytic decomposition into atomic carbon and hydrogen,
other types of radicals and ne-crystalline graphite. The resulting carbon atoms are absorbed by surface
austenite grains and next diffuse deeper into the austenite grains, and, alternatively, into the carbide
surface, making the carbides grow and contributing to the increase in the carburized layer thickness.
2011 Elsevier Ltd. All rights reserved.

Keywords:
Low pressure carburizing
Kinetics
Alloy steels
Structure

1. Introduction
Low pressure carburizing (LPC) of steel means a diffusive ow of
carbon mass from the carburizing atmosphere to the surface layer
of the items carburized. The process continues under the temperature of austenite existence, usually within the range of
850e1000
C and consists of two steps: boost and diffusion. In the
boost step the carburizing atmosphere, consisting of aliphatic
hydrocarbons e acetylene, ethylene, propane additionally diluted
with hydrogen or nitrogen [1e6], is let into the process chamber
under a lowered pressure (within the range of several or even
several hundred Pa). It is thought that the carburizing process of Fe
and carbon steels in the boost step is a result of a catalytic reaction
of the carburizing atmosphere with the charge surface, which leads
to carbon release in the form of atoms, the absorption of it by the
surface and precipitation in the form carbon deposit and diffusive
transport deeper into the material. The carbon deposit is composed
of hydrocarbon radicals and ne-crystalline graphite and constitues
a source of carbon atoms [8,9]. On the surface of the carburized
parts the limit of carbon solubility in austenite is reached in a very
short time (according to [5] only after 5 min under the temperature
of 950
C) which is then followed by precipitation of carbon deposit
[7]. The carburized layer after the boost steps contains high level of
carbon on the surface. Further absorption of carbon atoms by the
austenite from the radical-carbon layer occurs at the beginning of
the diffusion steps, subsequently followed by their transformation
into ne-crystalline graphite until all radicals are absent [10]. This
* Tel.: 48 683282547; fax: 48 683243540.
E-mail address: marotti_goro@interia.pl.
0042-207X/$ e see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.vacuum.2011.09.006

results in additional carbon mass increase in the carburized layer.

Simultaneously, as a result of carbon atom diffusion in the
austenite, the carbon mass progresses deeper into the surface layer.
The thickness of the carburized layer increases and the concentration prole of carbon decreases around the edge area.
The aim of this paper was to analyze the mechanism of lowpressure carburizing of alloy steels based on carburizing of low
alloy steel 16MnCr5 used in the machine industry as well as high
alloy steel CSB 50NIL used in heavy-laden engine elements (has
successfully been used in the most reliable bearings in aircraft
engines [11]). Both steels, while carburized, differ in the diffusion
process of carbon and alloy components. 16MnCr5 has a lowered
limit of carbon solubility in the austenite than pure iron and carbon
steels. While this steel is being carburized, the carbon diffusion
occurs initially only in the austenite, and when the carbon
concentration exceeds the limit of solubility, a nucleation process
takes place as well as the increase of carbides in the austenite,
accompanied by diffusion in austenite-carbide area. In the case of
CSB 50NIL the austenite with carbides is found during the process
of annealing at the temperature of 850e1050
C. Hence, during
carburizing the diffusion will occur in the austenite-carbide area.

2. Method
Low pressure carburizing was carried out in a vacuum furnace
manufactured by Seco/Warwick by means of FineCarb method.
The FineCarb method is based on atoms conducting a xed
number of boost and diffusion steps within a specied period of
time. During the boost step the carburizing atmosphere, consisting

R. Gorockiewicz / Vacuum 86 (2011) 448e451

Table 1
Nominal chemical composition of the steel grade 16MnCr5 and CSB 50NIL, % of the
mass.
Steel grade

Chemical composition, % of the mass

C

Mn

Cr

Ni

Mo

Si

16MnCr5
CSB 50NIL

0.16
0.13

1.15
0.25

0.95
4.20

e
3.40

e
4.25

0.40
0.20

e
1.20

of a mixture of acetylene, ethylene and hydrogen, is let into

a process chamber. The boost step was carried out at a temperature
of 950
C and at a pressure uctuation of 6e7 h Pa. The charge
consisted of the ballast e low-carbon steel sheets with a dened
surface and samples of 16MnCr5 and CBS 50NIL steel. Chemical
composition of the steels is listed in the Table 1 above. The samples
were of F 20  10 mm with a polished at face surface. Carburizing
parameters: low-pressure (4Pa) heating up to the temperature of
950
C at a speed of 10
C/min, heating under low-pressure
conditions for 30 min at a temperature of 950
C, performing
a dened number of boost and diffusion steps at this temperature
and then cooling down to the room temperature in nitrogen stream
under a pressure of 0.5 MPa. Seven processes were carried out:
process 2 n (2 min of boost), process 5n (5 min of boost), process
10n (10 min of boost), process 5n1w (5 min of boost 1 min of
diffusion), process 10n1w (10 min of boost 1 min of diffusion),
process 10n2w (10 min of boost2 min of diffusion).
The carburized surfaces were observed with a scanning electron
microscope Jeol 5600 JV and the measurements of changes in
carbon concentration were taken with the use of the EDS method.
The observations and measurements were conducted at an accelerating voltage of 12 and 15 kV. The ndings are presented in
Figs. 1e4.

449

3. Results and discussion

The surface structure of the sample matrix of 16MnCr5, carburized at various saturation times, visible in Fig. 1, indicates the
presence of carbon deposit on the surface. It is visible both at
shorter times than when the limit of solubility of carbon in the
austenite is reached- Fig. 1, and at longer times- Fig. 1 b, c. Hence, as
in the case of carburizing iron and carbon steels [6,8], the carbon
deposit occurs on the surface of samples at the moment when the
carburizing atmosphere contacts the surface of the steel charge.
Further carburizing of this steel, as seen in Fig. 1 b, c, leads to
carbide precipitation on the surface, especially on the edges of the
austenite grains. A delicate coat of carbon deposit can be seen on
the surface of the carbide precipitation. In the surface structure of
CSB 50NIL samples, carburized at similar durations- Fig. 2 a, b, one
can notice a very large contribution of carbide precipitation. The
surfaces of both the matrix and the carbides are covered in a carbon
deposit.
The low-pressure annealing of previously saturated samples of
both 16MnCr5 steel- Fig. 4, and 50NIL- Fig. 2 c, d, leads to the
decrease in carbon deposit on the matrix surface. This nding was
conrmed by the results of assessing changes in carbon concentration on the surface of 16MnCr5 samples, visible in Fig. 3 (samples
5n, 5n1). The surface structure of 16MnCr5 samples after the
saturation steps suggests that when carbon concentration exceeds
the limit of its solubility in the austenite, which depends on the
times of saturation and low-pressure annealing, a nucleation
process occurs, accompanied by the increase or dissolution of
carbides- Fig. 2 aec. In 50NIL samples (Fig. 2) the nucleation and
increase/dissolution processes run simultaneously.
In this case, the active carbon layer deposits mainly on the
austenite grain surface, though it is also present on the carbide
surfaces (most probably in the form of radicals), which may be seen

Fig. 1. The photographs of 16MnCr5 steel samples carburized with the low-pressure method at a temperature of 950
C at various boost times: a) 2 min - the carbon deposit against
former austenite grains; b) 5 min - the carbon deposit against former austenite grains and a considerable amount of ne carbides precipitation on the edges of the former austenite
grains; c) 10 min - the carbon deposit against the matrix and considerably increased contribution of the carbides on the edges of the former austenite grains with minor carbon
deposit.

450

R. Gorockiewicz / Vacuum 86 (2011) 448e451

Fig. 2. The photographs of CSB 50NILsteel samples after various steps of low-pressure carburizing at a temperature of 950
C: a), b) 5 min of boost - almost the whole sample
surface, both the matrix area and the carbides, are covered in carbon deposit; c), d) 5 min of boost 1 min of diffusion e the carbon deposit covers the matrix and partly the
carbides, mainly in their central areas. The brighter carbide edges suggest the translocation of the deposit into the matrix.

The carbon concetration, % of the mass

especially on CBS 50NIL steel samples (Fig. 2a, b). Low-pressure

annealing of 16MnCr5 samples, in the structure of which a large
amount of precipitated carbides were present after the saturation
step (Fig. 1- sample 10n), leads to their dissolution and coalescenceFig. 4. At sufciently long times of annealing the carbides dissolve
in the austenite completely.
The observations of carbide surfaces of CBS 50NIL samples
saturated for 5 min and subsequently annealed with a low-pressure
method for 1 min- Fig. 2 c, d- indicate considerable decrease in
carbon deposit versus the sample without diffusion annealing.
Furthermore, the carbide surface areas adjacent to the matrix show

60
50
40
30
20
10
0

5n

5n_1w

10n

10n_1w

10n_2w

The type LPC step

Fig. 3. The change in carbon concentration of 16MnCr5 steel samples depending on
the type of low-pressure carburizing step. Step 5n1w stands for 5 min of boost and
1 min of diffusion. The carbon concentration was measured with the EDS method.

less deposit than the central areas. Carbide coalescence is also

visible.
It may be presumed that during the low-pressure annealing the
undissolved radicals progress from the carbide surface to the
austenite, where they undergo catalytic dissociation, and the
resulting carbon atoms are absorbed by the surface austenite
grains. Subsequently they diffuse to the carbide surfaces, making
them grow, and deeper into the austenite grains, contributing to
the increase of the carburized layer thickness.
4. Conclusions
The kinetics of low-pressure carburizing of alloy steels may run
as follows: in the boost steps, at the moment when the atmosphere contacts the charge surface, the molecules of gases forming
the atmosphere (e.g. actylene e C2H2, ethylene C2H4) are absorbed
by active surface centers, and subsequently they dissociate, as
a result of catalytic reaction of the surface with simultaneous
chemisorption of the dissociation products. The rst stage of the
dissociation is formation and a deposit process of different types
of radicals on the surface. Inuenced by iron atoms, the radicals
undergo another catalytic decomposition into atomic carbon and
hydrogen, other kinds of radicals and ne-crystalline graphite. The
carbon atoms are attracted by the iron atoms and deposit on the
austenite grain surface. With simultaneous dissolution in interstitial spaces of the austenite, they diffuse deeper. The hydrogen
atoms, in turn, link into molecules and leave the surface. This
order of absorption and catalytic dissociation steps hampers the
opposite processes, leading to formation of the initial gas molecules. The resulting radical-carbon layer, mediates in the carbon
transportation from the atmosphere to the austenite. When the
concentration of carbon in the austenite exceeds the limit of
solubility, the nucleation process occurs accompanied by carbide
growth. Put simple, these processes are controlled by the level of

R. Gorockiewicz / Vacuum 86 (2011) 448e451

451

Fig. 4. The photographs of 16MnCr5 steel samples carburized with the low-pressure method at a temperature of 950
C: a) 5 min of boost, 1 min of diffusion e decreased amount of
carbon deposit against the former austenite grains and mild carbide precipitation of the edges and inside the former austenite; b) 10 min of boost, 1 min of diffusion - thickened
carbide precipitation and decreased amount of carbon deposit against the former austenite grains; c) 10 min of boost, 2 min of diffusion e thickened and decreased carbides
precipitation against the matrix, partly covered in carbon deposit.

austenite saturation and the pace of carbon and alloy component

diffusion from the austenite to the carbides. The formation of
carbides on the saturated surface changes its crystalline properties. Due to saturation of covalent bonds, the carbide surfaces do
not show such catalytic activity as the austenite surface, therefore
they do not cause the dissociation of the atmosphere components
(or they cause it to a small extent). The radicals which resulted
from partial decomposition of the molecules deposit on the
carbide surfaces, and the undecomposed gas molecules undergo
desorption and move out of the vacuum chamber. During the
initial stage of the diffusion steps the carbon atoms are further
absorbed by the austenite from the radical-carbon layer deposited
on it. The layer transforms into ne-crystalline graphite until the
radicals are absent. In the case of any precipitated carbides
present in the austenite, the radicals deposited on their surfaces as
a result of surface diffusion progress to the austenite grain areas
where they undergo dissociation. The resulting carbon atoms are
absorbed by the austenite grain surfaces, diffuse to the austenite
and further to the carbide surfaces, causing the carbides to grow.
The gradient of the chemical potential as well as the diffusion of
carbon and the alloy components in the austenite, as well as the
phenomena connected with dissolution/precipitation of carbides,
lead to a progression of the carbon mass into the material and

thickening of the carburized layer with a simultaneous decrease in

the carbon concentration prole in the edge area.
Acknowledgments
The research was carried out under the programme R&N of
Seco/Warwick Poland.
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