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Structural and magnetic characterization

of a carburized cast austenitic steel
I.C. Silva,
a
J.M.A. Rebello,
a
A.C. Bruno,
b
P.J. Jacques,
c
B. Nysten
d
and J. Dille
e,
*
a
Federal University of Rio de Janeiro, Cidade Universita ria, PO Box 68505, Rio de Janeiro, Brazil
b
Department of Physics, Pontical Catholic University of Rio de Janeiro, Rua Marques de Sa o Vicente 225,
Rio de Janeiro, RJ 22451-900, Brazil
c
Universite Catholique de Louvain, De partement des Sciences des Mate riaux et des Proce de s, IMAP,
Place Sainte Barbe 2, 1348 Louvain-la-Neuve, Belgium
d
Unite de Chimie et de Physique des Hauts Polyme` res (POLY) and Research Center for Micro- and Nanoscopic
Materials and Electronic Devices (CeRMiN), Universite catholique de Louvain Croix du Sud 1, B-1348 Louvain-la-Neuve, Belgium
e
Chemicals and Materials Department, Universite Libre de Bruxelles, Avenue F. Roosevelt 50, 1050 Brussels, Belgium
Received 16 May 2008; revised 7 July 2008; accepted 7 July 2008
Available online 22 July 2008
A magnetic ux measurement technique was used to correlate the magnetic response of carburized cast austenitic steel tubes with
the volumetric fraction of chromium carbides in the tube wall. Two dierent types of chromium carbides were identied by back-
scattered electron diraction: Cr
23
C
6
in the outer part and Cr
7
C
3
in the inner part of the tubes. Magnetic force microscopy and
energy-dispersive X-ray analysis reveal a correlation between the ferromagnetic behavior of the tubes and chromium depletion in
the matrix.
2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: Austenitic steels; Magnetic force microscopy (MFM); Electron backscattering diraction (EBSD); Carburization; Non-destructive
magnetic test
The classical industrial process for manufacturing
ethylene is based on the thermal cracking of a mixture of
hydrocarbons in the presence of steam in a pyrolysis fur-
nace. Nowadays, the alloys used to manufacture the ser-
pentine tubes of a pyrolysis furnace are of the high-
pressure (HP) type. These materials guarantee corrosion
and creep resistance at the working temperatures of
>1000 C that are encountered in specic regions of the
tubes [1,2]. Based on the ASTM composition [3], manu-
facturers of HP alloys have developed alloys via addition
of other elements to achieve improved mechanical prop-
erties at high temperatures. For example, the addition of
Nb and Ti leads to the formation of more stable carbides,
improving the creep resistance [4].
The high-temperature conditions during the cracking
process, together with the characteristics of the uids
present, lead to carbon diusion into the tube walls from
the internal surface towards the external one, resulting
in carburization. This detrimental eect leads to metal-
lurgical alterations and brittleness, aecting the reliabil-
ity of the tubes and reducing their lifetime.
The carburization process has been studied by vari-
ous authors [1,2,46]. At the beginning of the operation,
with temperatures between 850 and 1000 C, a protec-
tive oxide layer (Cr
2
O
3
) begins to form. This layer acts
as a barrier to carbon diusion. At temperatures above
1000 C the oxide layer becomes thermodynamically
unstable, allowing the diusion of carbon. Initially, the
carbon deposited on the internal wall of the coils is ab-
sorbed by the internal surface. In a second stage, the car-
bon diuses into the austenitic matrix, precipitating as
M
7
C
3
and M
23
C
6
carbides [2]. Carbide precipitation
brings about a decrease in the Cr concentration in the
matrix [5,7], reducing tensile strength and creep resis-
tance [4].
Therefore, there is an interest in developing nonde-
structive methods in order to evaluate quantitatively
the degree of carburization in pyrolysis furnace tubes.
Traditionally, magnets are used to qualitatively evaluate
the carburization of the tubes. Indeed, the as-cast HP
1359-6462/$ - see front matter 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.scriptamat.2008.07.015
*
Corresponding author. Tel.: +32 2 650 27 23; fax: +32 2 650 27 86;
e-mail: jdille@ulb.ac.be
Available online at www.sciencedirect.com
Scripta Materialia 59 (2008) 10101013
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alloy is paramagnetic and gradually becomes ferromag-
netic as carburization progresses. In a previous paper [8]
the carburization level in samples extracted from HP al-
loy tubes was characterized through measurements of
the magnetic eld over their external surface. The mag-
netic measurements were then correlated with the vol-
ume fraction of chromium carbides in each sample. In
this paper, the objective is to characterize the structural
evolution in the tubes during carburization and to corre-
late this with their ferromagnetic behavior. The para-
magnetic as-cast microstructure consists of an
austenitic matrix with M
23
C
6
carbides, and the purpose
of this work is to investigate which structural change in-
duces the ferromagnetic evolution of the alloy.
The composition of the HP alloy investigated is pre-
sented in Table 1. Three HP alloy samples (S1, S2, S3)
with dierent operating times were extracted from the
highest-temperature regions of pyrolysis furnace tubes.
A fourth sample (S0) corresponding to the as-cast con-
ditions was also analyzed. This sample treatments are
summarized in Table 2.
The level of carburization of the samples was deter-
mined by nondestructive magnetic ux density measure-
ments before they were removed from the tubes [9]. This
technique measures the magnetic ux density near the
external surface of the tubes by means of a magnetore-
sistive sensor biased by a small ferrite magnet. Chro-
mium carbide volumetric fraction measurements were
carried out by scanning electron microscopy (SEM) at
selected points of the samples in accordance with the
ASTM E 562 standard. Electron back-scattered dirac-
tion (EBSD) analyses were performed in order to iden-
tify the phases present in the samples at dierent
carburization levels.
After polishing with diamond paste down to 1 lm,
the specimens were further polished with a 0.03 lm col-
loidal silica suspension for 1 h. The EBSD measure-
ments were carried out with a eld emission gun
scanning electron microscope operating at 20 kV and a
working distance of 15 mm. Step sizes ranging from
0.1 to 5 lm were used.
Magnetic force microscopy (MFM) imaging allowed
the identication of the ferromagnetic regions in the
cross-section of the tubes after carburization. MFM
analyses were performed on cross-sectioned sample S2
under ambient conditions with a PicoPlus microscope
(Agilent Technologies) using PointProbe

MFM probes
(NanoSensors
TM
) with a resonance frequency around
75 kHz and a typical spring constant value of
3 N m
1
. The magnetic images were acquired in the
so-called Lift Mode. During a rst pass, the topogra-
phy of a scan line was acquired in the standard intermit-
tent-contact mode (Tapping

mode). Then the tip was

lifted to a specic height above the surface (75 nm in
the present study) and the magnetic proles (phase-shift
and cantilever vertical deection) were acquired while
the tip scanned the same line at constant tipsurface dis-
tance, following the previously recorded topography.
This method yields images free of topographic artifacts.
The cantilever vertical deection is proportional to the
magnetic force acting on the magnetic tip. If the oscillat-
ing cantilever is considered as a linear harmonic oscilla-
tor, the phase-shift is roughly proportional to the second
derivative of the vertical component of the local mag-
netic induction of the sample.
After extraction, a cross-section was prepared for
each of the four samples. Figure 1 shows a macroscopic
view of sample S2. Going from the internal wall to the
external wall, two dierent regions can clearly be distin-
guished. These two regions can be found on all three
carburized samples although the transition zone posi-
tion varies with the operating time. The longer the oper-
ating time, the farther away from the internal wall is the
transition zone position.
Back-scattered electron imaging by SEM allows the
chromium carbides to be distinguished from other pres-
ent phases. In Figure 2A, the chromium carbides appear
in black. The corresponding energy-dispersive X-ray
analysis (EDX) spectrum is given in Figure 2C. Nio-
bium-rich compounds are colored in white (niobium
carbides) or pale gray (nickelniobium silicide Ni
16
Nb
6-
Si
7
, named the G phase). The G phase precipitates in HP
alloys above 900 C [10]. Figure 2B shows an EDX spec-
trum of an NbC particle, and the EDX analysis of the
matrix is presented in Figure 2D.
From the electron backscattered images, it was
possible to calculate the volume fraction of chromium
Table 1. Composition of the alloy investigated (wt.%)
C Cr Ni Si Mn Nb Ti Mo Fe
0.45 26.0 34.6 2.4 1.0 1.0 0.15 0.2 Bal.
Table 2. Sample operating time
Sample Operating time (h)
S0 0
S1 6800
S2 25,600
S3 >90,000
Figure 1. Macroscopic view of a cross-section of sample S2.
I. C. Silva et al. / Scripta Materialia 59 (2008) 10101013 1011
Author's personal copy
carbides through the tubes cross-section by image anal-
ysis. These results are shown in Figure 3. As expected,
the chromium carbide volume fraction increases with
the exposure time at high temperature. In each cross-sec-
tion, there is also an increase in the chromium carbide
volume fraction from the outer wall to the inner wall.
In Figure 3, the magnetic ux density values are also dis-
played for each sample.
Taking into account the chromium carbide volume
fraction curves (Fig. 3), it is possible to establish a linear
relationship between the magnetic ux density and the
areas under these curves. This is shown in Figure 4.
The measurement of the magnetic ux can therefore
be considered as a valid non-destructive method for a
quantitative determination of the degree of carburiza-
tion in pyrolysis furnace tubes and for the prediction
of their remaining life.
EBSD analyses were performed in order to dierenti-
ate the various phases based on their crystal structures.
Two dierent zones were observed. For each carburized
sample, they are identical to the two macroscopic re-
gions shown inFigure 1. In the outer region of the tubes,
the microstructure is similar to the as-cast microstruc-
ture. It consists of a face-centered cubic (fcc) austenitic
matrix (a = 0.36 nm) containing Cr
23
C
6
carbides having
a fcc structure (a = 1.064 nm). In the inner part of the
tubes, the Cr
23
C
6
carbides are replaced by carbon-rich
Cr
7
C
3
carbides in the austenitic matrix. These Cr
7
C
3
carbides exhibit a hexagonal structure (a = 1.398 nm;
c = 0.452 nm). These results are shown in Figure 5. This
clear dierentiation between Cr
23
C
6
and Cr
7
C
3
carbides
by EBSD was not possible by traditional back-scattered
electron imaging in the SEM. Indeed, with this method,
both types of carbide appeared in black in the matrix
(see Fig. 2).
Figure 2. (A) Back-scattered electron image; (B) EDX analysis of point 1; (C) EDX analysis of point 2; (D) EDX analysis of point 3.
Figure 4. Area under the chromium carbide volume fraction curves
(arbitrary units) versus the measured magnetic ux density.
Figure 3. Chromium carbide volume fraction through the tube
thickness. The depth is measured from the external wall.
Figure 5. EBSD phase identication: red, austenite; blue, Cr
23
C
6
;
yellow, Cr
7
C
3
.
1012 I. C. Silva et al. / Scripta Materialia 59 (2008) 10101013
Author's personal copy
Finally, a MFM study was carried out in order to
determine which structural component is responsible
for the ferromagnetic behavior of the carburized
tubes. Figure 6 shows six MFM images obtained from
dierent areas on a cross-section of sample S2, from
the external wall (region a) to the internal wall (re-
gion f). On these images, a negative phase-shift, i.e.
dark color level, corresponds to ferromagnetic regions,
while a zero phase-shift, i.e. bright color level, corre-
sponds to paramagnetic regions. These measurements
show that M
23
C
6
and M
7
C
3
carbides are both para-
magnetic. On the other hand, it can be seen that the
matrix becomes more and more ferromagnetic when
moving from the external surface towards the internal
one. It is clear from these results that the austenitic
matrix, close to the external wall, is paramagnetic with
only thin ferromagnetic domains in the areas adjacent
to the chromium carbides. The ferromagnetic areas
progressively widen and, nally, the whole matrix be-
comes ferromagnetic. On image f of Figure 6, the
magnetic domains are clearly visible in the entire ma-
trix. EDX analyses were also performed in dierent
regions of Figure 6 in order to measure the chromium
content. The results are given in Table 3. Whereas the
global chromium content is constant between each re-
gion, the chromium content of the matrix decreases
appreciably when moving from the external wall to
the internal one. These results conrm that the magne-
tization of the carburized tubes is due to chromium
depletion in the matrix, as proposed by Stevens et
al. [7,11]. On a ternary phase diagram, the position
corresponding to HP alloy composition is located near
the boundary between the paramagnetic domain and
the ferromagnetic domain [12]. This fact can explain
why even slight chromium depletion makes the austen-
itic matrix ferromagnetic instead of paramagnetic.
In conclusion, a linear relationship between the de-
tected magnetic ux density and the total area under
the chromium carbide volume fraction curve through
the thickness of the tube was found. This result conrms
the adequacy of magnetic non-destructive evaluation as
a tool to characterize the carburization and the subse-
quent mechanical degradation of the tubes. The EBSD
analysis shows a transition from Cr
23
C
6
carbides in
the external part of the tubes to Cr
7
C
3
carbides in the
internal part. The position of the transition zone de-
pends on the carburization level. MFM analysis con-
rms that the magnetization of the HP steel is due to
chromium depletion in the matrix, resulting from car-
bide precipitation.
The authors thank CNPq, CAPES, FAPERJ for the
Grants given to support this work and TSEC LTDA for
providing the HP carburized samples. B.N. is Senior Re-
search Associate of the Belgian Funds for Scientic Re-
search (FRS-FNRS). P.J.J. acknowledges the FNRS
and the FRFC.
[1] T.F. da Silveira, M.Sc. Thesis, COPPE/Federal University
of Rio de Janeiro, 2002.
[2] H.J. Grabke, Materials at High Temperature 17 (2000)
483.
[3] ASTM, Standard Specication ASTM A 297/A 297M 97
(Re-approved 2003).
[4] H.J. Grabke, I. Wolf, Materials Science and Engineering
87 (1987) 23.
[5] S.B. Parks, C.M. Schillmoller, Hydrocarbon Processing
International Edition 75 (1996) 53.
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(2003) 288.
[7] K.J. Stevens, A. Parbhu, J. Soltis, D. Stewart, Journal of
Physics D: Applied Physics 36 (2003) 164.
[8] I.C. Silva, A.C. Bruno, J.M.A. Rebello, L.L. Silva,
Scripta Materialia 56 (2007) 317.
[9] I.C. Silva, A.C. Bruno, J.M.A. Rebello, R.S. da Silva,
T.F. Silveira, NDT& E International 39 (2006) 569.
[10] G.D.A. Soares, L.H. de Almeida, T.L. da Silveira, I. Le
May, Materials Characterization 29 (1992) 387.
[11] K.J. Stevens, A. Parbhu, J. Soltis, Current Applied
Physics 4 (2004) 304.
[12] A.K. Majumbar, P. van Blanckenhagen, Physical Review
B 29 (1984) 4079.
Figure 6. MFM phase-shift images acquired on a cross-section of
sample S2. The images (a)(f) were successively acquired at dierent
locations from the external wall (a) to the internal wall (f). In (a) and
(f), the insets are the magnetic force images given for comparison.
Table 3. Chromium content (wt.%) measured by EDX analysis of
dierent regions shown in Figure 6
Region on sample
S2 cross-section
Matrix Cr
content
Global Cr
content
Region a 17.1 0.1 25.6 0.1
Region d 9.8 0.4 26.0 0.1
Region f 5.2 0.3 26.2 0.1
I. C. Silva et al. / Scripta Materialia 59 (2008) 10101013 1013