M A TE RI A L S C H A RAC TE RI ZA T ION 5 9 ( 2 00 8 ) 1 5 8 01 5 8 6

SEM, EDS, EPMA-WDS and EBSD characterization of carbides in

HP type heat resistant alloys

J. Laigo a,b , F. Christien a , R. Le Gall a , F. Tancret a,, J. Furtado b

a
Universit de Nantes, Nantes Atlantique Universits, Polytech'Nantes, LGMPA, Rue Christian Pauc, BP 50609,
F-44306 Nantes Cedex 3, France
b
Air Liquide, Centre de Recherche Claude-Delorme, 1, chemin de la Porte des Loges, 78354 Jouy-en-Josas, France

AR TIC LE D ATA ABSTR ACT

Article history: The microstructure of centrifugally cast heat resistant alloys of the HP-series (Fe35Ni25Cr
Received 16 January 2008 0.4C, wt.%) contains several minor phases, like carbides (M7C3, M23C6 and MC). Several alloys
Received in revised form are characterized by means of scanning electron microscopy in back-scattered electron
31 January 2008 imaging and energy dispersive spectroscopy, of electron probe micro-analysis by X-ray
Accepted 1 February 2008 wavelength dispersive spectroscopy, and of electron back-scattered diffraction. On the one
hand, scanning electron microscopy imaging in the back-scattered mode, associated with
Keywords: energy dispersive spectroscopy analysis and electron back-scattered diffraction, can lead to
Cr7C3 the identification of all phases, but with a lack of accuracy in certain cases. On the other
Cr23C6 hand, electron probe micro-analysis by X-ray wavelength dispersive spectroscopy alone can
NbC always provide a strict identification of all phases, with additional precise information on
EDX phase composition, including for light elements, which is important in the case of carbides.
Castaing microprobe 2008 Elsevier Inc. All rights reserved.

1. Introduction transformations, it is important to be able to fully characterize

Heat resistant steels of the HP-series have widespread uses in
the petrochemical industry in pyrolysis and reformer fur-
naces. These HP-series (Fe35Ni25Cr0.4C, wt.%, plus minor
and micro additions like Mn, Nb, Si and Ti) have replaced the
traditional nickel based superalloys with a substantial reduc-
tion of cost and have equivalent properties under conditions
of creep, with excellent resistances to high temperature ox-
idation and metal dusting. In most cases, these complex alloys
are used in their as-cast condition but, during service, ageing
and phase transformations occur. The typical microstructure
of as-cast HP alloys is an austenite matrix with intergranular
eutectic-like primary chromium-rich carbides (M7C3 and/or
M23C6 types) and niobium carbides (MC type). During service at
temperatures of 8501050 C, all the primary chromium car-
bides eventually transform into M23C6; intragranular second-
ary M23C6 carbides also precipitate [1]. To understand phase
the microstructure of both as-cast and aged alloys. Several
techniques are used in the present study, alone or in com-
bination, and their performances compared, to identify minor
phases: scanning electron microscopy (SEM) in back-scattered
electron imaging mode and with X-ray energy dispersive
spectroscopy (EDS), electron back-scattered diffraction (EBSD)
and electron probe micro-analysis with X-ray wavelength
dispersive spectroscopy (EPMA-WDS). Transmission electron
microscopy (TEM) technique is a priori not well adapted to
these materials. Indeed, in addition to the fact that specimen
preparation is difficult and delicate, the observed area is
extremely small. Given the large grain size of HP alloys
(hundreds of m) and sometimes the modest quantities of
certain carbides, only very few precipitates would be likely to
be studied, if any.
Hence, the objective of this work is to find the best tech-
nique or combination of different techniques to identify all

Corresponding author. Tel.: +33 2 40 68 31 97; fax: +33 2 40 68 31 99.

E-mail address: franck.tancret@univ-nantes.fr (F. Tancret).

1044-5803/$ see front matter 2008 Elsevier Inc. All rights reserved.
doi:10.1016/j.matchar.2008.02.001
 M A TE RI A L S C H A RAC TE RI ZA T ION 5 9 ( 2 00 8 ) 1 5 8 01 5 8 6
precipitates: chromium carbides (M7C3 and M23C6) and nio-
bium carbides (MC) in as-cast and aged alloys.
2. Materials and Characterization Techniques
2.1. Materials
Two specimens are studied: an as-cast alloy (A) and a
laboratory-aged alloy (B). Alloys A and B come from the same
melt, with B being aged in air for 100 h at 950 C. Average
chemical composition is presented in Table 1.
2.2. Characterization Techniques
2.2.1. Scanning Electron Microscopy (SEM) in the Back-
Scattered Electron Imaging Mode with X-ray Energy Dispersive
Spectroscopy (EDS)
In a scanning electron microscope, a focused electron beam
scans the surface of the specimen, and generates a variety of
signals, resulting from beammatter interactions. The three
most common modes of operation in SEM are secondary
electron imaging (SE), back-scattered electron imaging (BSE),
and EDS chemical analysis. Backscattered electrons are pro-
duced by the elastic interactions between the specimen and
the incident electron beam. The production efficiency of these
high-energy electrons roughly correlates to the mean atomic
number, so that BSE offers a visual contrast between phases
based on their electron density. For example, a niobium par-
ticle (atomic number 41) would appear significantly brighter
than a chromium particle (atomic number 24).
The elemental composition of a phase is determined using
the characteristic X-ray spectrum of the examined specimen.
The EDS scintillation detector is capable of identifying ele-
ments with atomic numbers equal to or greater than five
(boron) although the quantification is very difficult for ele-
ments with atomic number below eight (oxygen). In this study,
all detected elements with atomic numbers higher than eight
were quantified from the EDS spectra using the classical ZAF
model. All the spectra were recorded under a 20 kV accelerat-
ing voltage and a standard-less quantification procedure was
followed. The summation of all the quantified elements was
normalized to 100%. It must be noted that this quantification
procedure is not very accurate for carbides: indeed, the ZAF
corrections are not absolutely right since one major element
(carbon) is not taken into account. Nevertheless this procedure
gives a reasonable estimation of the relative concentrations of
the quantified elements with respect to each other. Addition-
ally, the carbides chosen for analysis were sufficiently large
(typically 3 m in width) to avoid any significant contribution
from the surrounding matrix. Indeed, both the diameter of the
beammatter interaction zone and the X-ray emission depth
Table 1 Initial chemical composition, in weight percent
(wt.%), of investigated alloys
Cr Ni Nb Si C Mn Fe + others
27 35 1.2 0.8 0.36 0.6 Bal
Remainder is Fe and other minor alloying elements.
1581
for all the analysed radiations are smaller than 1.5 m under
an accelerating voltage of 20 kV.
For SEM observation and EDS analysis, specimens are
mounted in an epoxy resin and polished with 240, 400, 800,
1200, 2400 grit silicon carbide papers, then polished with 1 m
diamond paste and finally cleaned with distilled water and
ultrasonically cleaned in ethanol. A LEO Stereoscan 440 scan-
ning electron microscope, equipped with a LINK-ISIS X-ray
energy dispersive spectroscopy analyzer from Oxford Instru-
ments, is used. In this study, all observations and EDS ana-
lyses are performed at a voltage of 20 kV (corresponding to an
approximate analysis volume of 1 m3). Probe currents be-
tween 150 and 250 pA, and between 1 and 2 nA are used,
respectively for BSE imaging and EDS analysis. The elemental
analysis is performed in a spot mode in which the beam is
focused on a chosen point of the specimen.
2.2.2. Electron Back-Scattered Diffraction (EBSD)
EBSD is based on the acquisition of electron diffraction pat-
terns from bulk specimens in the scanning electron micro-
scope. A beam of highly accelerated electrons strikes a titled
specimen. The diffracted electrons form a set of paired large
angle cones corresponding to each diffracting plane. The re-
gions of enhanced electron intensity between the cones pro-
duces the Kikuchi bands of the electron back-scattered
diffraction pattern (EBSP), which are then used to form an
image on a fluorescent screen. Kikuchi bands can be inter-
preted in terms of crystallographic structure. More detailed
discussion of the technique can be found, for example, in the
review of Humphreys [2].
The first step of specimen preparation is the same as for
SEM observation and EDS analysis. Afterwards specimens are
polished using colloidal silica for 10 h to remove any strain
hardening due to mechanical polishing, and then cleaned with
distilled water.
The equipment employed for EBSD is the LEO Stereoscan
440 microscope associated with Nordlys 2 camera and Chan-
nel 5 EBSD software from HKL Technology. EBSD is carried out
on a specimen which is tilted 70 from horizontal. An
accelerating voltage of 20 kV is used for these operations.
The software controls the beam location on the specimen, as
well as data acquisition and treatment. In the present work,
electron back-scattered patterns (EBSP) are recorded in spot
mode for specific locations on precipitates. HKL Technology
Flamenco software is used to analyse the patterns. The EBSP is
indexed and the best matching phase is determined auto-
matically by the software, based on its crystal structure and
lattice parameters.
2.2.3. Electron Probe Micro-Analysis (EPMA) by X-ray Wave-
length Dispersive Spectroscopy (WDS)
The principle of EPMA-WDS (also known as Castaing electron
probe) is the following: as for EDS analysis, a beam of highly
accelerated electrons strikes a small surface (approximately
1 m2) of the specimen. The emerging X-rays are then selected
on the basis of their wavelength, using Bragg diffraction con-
ditions on an adapted crystal. The intensity of each radiation is
then measured using a gaseous proportional counter. Moreover,
it is possible to quantify the information by comparing the
intensities of X-ray characteristic of each element present in the
1582 M A TE RI A L S C H A RAC TE RI ZA T ION 5 9 ( 2 00 8 ) 1 5 8 01 5 8 6

Table 2 Analysis crystals used in EPMA-WDS technique

Crystal name Type 2d ()

TAP Thallium acid phthalate, C8H5O4Tl 25.745

PC1 W/Si multilayer 60
PET Pentarythriol, C5H12O4 8.742
LIF Lithium fluoride, LiF 4.027
PC2 Ni/C multilayer 95.131

specimen (Is) with the intensity of the same radiation emitted by

a standard (Istd), in which the concentration (Cstd) is known. The
concentration of each element in the specimen (Cs) is calculated
from the k-ratios (I/Istd) using the PAP model [3].
The peak positions on the spectrometer obey the Bragg law
(Eq. 1):

nk 2d sin h
where is the wavelength of the X-ray, n is the order of
diffraction, d is the interplane distance in the crystal (or the
interlayer distance in the case of a multilayer crystal), and
the diffraction angle. The peak positions are usually expressed
in sin 105, which is proportional to the wavelength.
Unlike EDS, EPMA-WDS analysis allows the detection and
quantification of light elements like carbon, which should
allow, in the present case, the analysis of carbides.
Specimen preparation is the same as for SEM observation
and EDS analysis. EPMA-WDS is carried out with a Cameca
SX50 electron probe equipped with four spectrometers con-
taining several analysis crystals. In the present case, the
crystals listed in Table 2 are used.
The phases to be analysed are first identified using the BSE
detector of the microprobe. In our case, EPMA-WDS analyses
are performed in the spot mode, under an accelerating voltage
of 10 kV and a probe current of 10 nA. The beam diameter in
these conditions is approximately 1 to 2 m. The SAMx
software suite [4] is used to control the spectrometer and to
process the experimental data. The experimental conditions
are summarized in Table 3. More details concerning the setup
of the microprobe are given in appendices 1 and 2.
3. Results and Discussion
3.1. Scanning Electron Microscopy (SEM) and X-ray Energy
Dispersive Spectroscopy (EDS)
Alloys A and B have been investigated with these techniques.
Figs. 1 and 2 present micrographs of alloys A and B respec-
1
Fig. 1 SEM micrograph of alloy A in the BSE mode.
tively. Tables 4 and 5 present examples of compositions of
different phases in alloys A and B, respectively.
These results (Fig. 1 and Table 4), show that alloy A is
constituted of an austenite matrix with a niobium-rich phase
(white phase) and a chromium-rich phase (dark grey phase).
According to the existing literature on HP alloys [1], the
niobium-rich phase should correspond to niobium carbides of
the NbC type and the chromium rich phase should correspond
to chromium carbides of the M7C3 type or M23C6 type.
Fig. 2 and Table 5 show SEM observation and EDS analysis
for alloy B (i.e. alloy A aged 100 h at 950 C). Alloy B is
constituted of an austenite matrix, with a niobium-rich phase
(white phase), probably niobium carbides of the MC type, and a
chromium-rich phase (dark grey phase).
Using the SEM and EDS, it is easy to observe differences
between chromium-rich carbides (M23C6 and M7C3) and
niobium-rich carbides (MC). Indeed, on back-scattered elec-
tron images, the bright niobium-containing phases can be
distinguished easily from the dark grey chromium-rich
phases. Nevertheless, this technique cannot differentiate
M23C6 from M7C3, because they have similar electronic
densities (1.96 electrons/3 for Cr23C6 and 1.92 electrons/3
for Cr7C3) and therefore similar chemical contrasts in BSE.
Additionally, it should be reminded that EDS analysis does not
lead to the determination of carbon content and that, con-
sequently, the above results should only be considered as
(very probable) assumptions.

Table 3 Setup for EPMA system

Element Standard Crystal X-ray line Spectrometer positions (105 sin ) Counting time (s)
used for
microanalysis Peak Background (with respect to peak position) Peak Background

Ni Pure Ni TAP L 56,688 2500; 1500 20 5

Cr Pure Cr PC1 L 34,863 3000; 3000 10 5
Fe Pure Fe TAP L 68,169 2500; 1500 20 5
C Fe3C PC2 K 45,778 7000; 9000 10 5
Ti Pure Ti LiF K 68,261 2000; 3000 10 5
Nb Pure Nb PET K 65,430 750; 750 10 5
 M A TE RI A L S C H A RAC TE RI ZA T ION 5 9 ( 2 00 8 ) 1 5 8 01 5 8 6 1583

Table 5 EDS analysis of phases in alloy B

Element (at%) Fe Ni Cr Nb Ti

Dark grey phase 9.5 3.25 87.25

White phase 3.69 2.69 6.74 82.54 4.36

Relative compositions are given (in atomic percent, at.%), since EDS
analysis does not provide carbon content.

lies between 96% and 99%. The fact that this summation
does not exactly reach 100% may be due to slight chemical
effects (change in peak shape and position between the
specimen and the standard material) on carbon (K lines) or
even on chromium and iron (L lines). Anyway, this does not
strongly affect the atomic fractions (deduced from weight
fractions).
Fig. 2 SEM micrograph of alloy B in the BSE mode.

3.2. Electron Back-Scattered Diffraction (EBSD)

According to the existing literature, two types of chromium

carbides can be found in HP alloys: M7C3 and M23C6. Since these
phases have different crystal structures, it should be possible to
distinguish them using EBSD. M7C3 carbides have an orthor-
hombic structure with lattice parameters a ~ 4.53 , b ~ 6.99
and c ~ 12.11 and a Pnma space group [5], and M23C6 carbides
have a cubic structure with a lattice parameter a ~ 10.64 and a

Fm3 m space group [6].
Alloys A and B are investigated. Examples of electron back-
scattered patterns (EBSP) of chromium carbides in alloys A and
B are presented in Fig. 3. In all cases, the EBSD automatic
indexing software has attributed the EBSP of chromium
carbides (see examples in Fig. 3) to M7C3 in alloy A and to
M23C6 in alloy B. To sum up, since the distinction between
M7C3 and M23C6 type is not possible using SEM nor EDS
analysis, the EBSD technique can be used to solve this type of
problem.

3.3. Electron Probe Micro-Analysis (EPMA) by X-ray

Wavelength Dispersive Spectroscopy (WDS)

Chromium-rich carbides in alloys A and B have been

investigated with the EPMA-WDS technique. Examples of
average chemical compositions in atomic percent (at.%) of
chromium rich carbides in alloys A and B are presented in
Tables 6 and 7 respectively. Each of the four analyses
corresponds to one precipitate, with an average of four to six
analyses on each precipitate. For all the precipitates, the
summation of the measured elemental weight fractions

Table 4 EDS analysis of phases in alloy A Fig. 3 Examples of EBSP with the indexing of (a) chromium
Element (at%) Fe Ni Cr Si Nb carbide in alloy A and (b) chromium carbide in alloy B. The
three Euler angles (1, , 2) are = 63.2, 1 = 23.1 and
Dark grey phase 7.94 92.06
White phase 4.51 3.87 8.00 1.87 81.75 2 = 72.9 from (515) plane as the SEM frame of reference for
the chromium carbide in alloy A and = 345.1, 1 = 29.2 and
Relative compositions are given (in atomic percent, at.%), since EDS 2 = 3.1 from (035) plane as the SEM frame of reference for the
analysis does not provide carbon content.
chromium carbide in alloy B.
1584 M A TE RI A L S C H A RAC TE RI ZA T ION 5 9 ( 2 00 8 ) 1 5 8 01 5 8 6

Table 6 Composition of chromium-rich phase in alloy A Table 8 Composition of niobium-rich phase in alloy A
(at.%), determined by EPMA-WDS (at.%), determined by EPMA-WDS
Analysis C Cr Fe Ni Cr + Fe + Ni Average Analysis C Ti Nb Cr + Fe + Ni Average
composition composition

1 30.59 58.89 8.35 2.17 69.36 M7C3.07 1 46.09 8.10 40.90 4,91 M0.55C0.45
2 32.63 58.96 7.91 0.50 67.37 2 44.62 7.99 43.03 4.36
3 28.98 63.58 6.59 0.85 71.02 3 45.19 1.84 45.94 7.03
4 29.63 62.81 6.89 0.67 70.37 4 44.75 2.57 45.21 7.47

According to our results, there are two types of chromium
carbides in these alloys. In the as-cast alloy (alloy A), chromium
carbides are of M7C3 type but in the aged alloy (alloy B) only M23C6
carbides are found. So, after exposure to high temperatures,
M7C3 chromium carbides transform into M23C6 chromium
carbides, which occurs in less than 100 h at 950 C. The EPMA-
WDS results are therefore consistent with the EBSD results.
Indeed, the latter have also shown that chromium carbides are
of M7C3 type in the as-cast alloy and of M23C6 type in aged alloys.
Moreover, the niobium-rich phase has been investigated
in alloy A. An example of average chemical composition in
atomic percent (at.%) of this phase in alloy A is presented in
Table 8. As for chromium carbide analysis, the summation of
the measured weight fractions is not exactly equal to 100% but
varies between 99% and 104%.
These results show that the stoichiometry of the niobium-
rich phase is not exactly of type MC but rather of type MC1 x
where x = 0.18. This is consistent with the NbC binary phase
diagram [7] and with thermodynamic calculations of phase
composition in this alloy [8].
Consequently, since EPMA-WDS is a rather accurate
analysis technique, able to measure the concentrations of
light elements, it can be used to determine the chemical
composition of precipitates and thus identify each phase. In
the present case, it has been successfully used to distinguish
between M7C3, M23C6 and MC, and to evidence the transfor-
mation of M7C3 into M23C6 during high temperature ageing.
the ability of each technique (or combination of techniques) to
identify all phases: The SEM with back-scattered electron imaging
and EDS, EBSD and EPMA-WDS. In conclusion, there are two
groups of techniques that allow the identification of all the
carbides in HP alloys, on the one hand a combination of SEM, EDS
and EBSD, and on the other hand EPMA-WDS alone. Indeed:
A combination of SEM, EDS and EBSD (as they are often
found in the same equipment) is a rather good way to
identify diverse precipitates: first, BSE imaging contrast can
easily make a difference between chromium-rich carbides
(M23C6 or M7C3) and niobium-rich carbide (MC). EDS can also
differentiate between chromium-rich phases (M23C6, M7C3)
and MC carbides. Finally, in the case of M23C6 and M7C3,
which cannot be differentiated neither by SEM nor by EDS,
EBSD can be used to identify the two different lattice sym-
metries of M23C6 and M7C3. This combination of techniques is
less expensive than EPMA-WDS, but specimen preparation is
rather difficult in the case of EBSD, and specific to each
different alloy. Moreover, even if the nature and approximate
composition of phases are obtained, no precise information
is given on the chemical composition of phases.
The EPMA-WDS technique alone can be used to obtain the
chemical composition of all precipitates, including carbon
content, with a much better precision and level of con-
fidence than EDS. Although the equipment is relatively
expensive, it is an excellent technique to identify exactly all
precipitates in HP alloys.

4. Conclusions
HP alloys are complex materials, since they can contain different
phases (austenite, M7C3, M23C6, MC), with high temperature phase
transformations. In the present work, two HP alloys (~Fe35Ni
25Cr0.4C1Nb) have been studied, with two different micro-
structural states: an as-cast alloy and a laboratory-aged alloy.
Different phases with various stoichiometries are present in
these alloys: chromium rich-phases (M23C6 and M7C3) and nio-
bium carbides (MC). Complete characterization of precipitates has
been performed, using several techniques, in order to evaluate
Table 7 Composition of chromium-rich phase in alloy B
(at.%), determined by EPMA-WDS
Analysis C Cr Fe Ni Cr + Fe + Ni Average
composition
Appendix A. Justification of Experimental Conditions
Used for EPMA-WDS
Standards
For elements Cr, Fe, Ni, Nb and Ti, pure metals were used as
standards. For carbon, Fe3C (cementite) was used. Fe3C was
obtained by carburising an iron specimen for 2 h at 900 C. After
carburising, the specimen contained large areas (~50 m) of
cementite in a pearlite (Fe/Fe3C lamellar eutectoid structure)
matrix. Fe3C is conductive and perfectly stoichiometric. More-
over, chemical effects (change in carbon peak shape and
position) are expected to be small between the specimen and
the standard since carbon is in the form of carbides both in the
specimen and in the standard.

1 20.73 47.56 18.07 13.64 79.27 M23C6.41 Choosing the X-ray lines to be analysed
2 21.67 44.69 17.85 15.79 78.33
3 22.67 56.27 13.17 7.39 77.33 For the microanalysis of transition metal elements, K lines are
4 22.15 55.46 14.14 8.25 77.85
usually preferred to L lines to avoid chemical effects (change
 M A TE RI A L S C H A RAC TE RI ZA T ION 5 9 ( 2 00 8 ) 1 5 8 01 5 8 6 1585

in peak shape and position). Nevertheless, we chose here to
work on L lines to quantify Cr, Fe and Ni in the analysed
secondary phases. The reason for that is explained below.
It is shown in this study that the secondary phases
analysed in this work can contain large amounts of iron (up
to ~20 at.%) and nickel (up to ~15 at.%). Iron and nickel K lines
are strongly absorbed by chromium and are likely to induce
the fluorescence of the chromium K line. Indeed, iron and
nickel K lines (EK K
Fe = 6.40 eV and ENi = 7.48 eV respectively) can
ionize the chromium K level (EK Cr = 5.99 eV) with a high
probability according to the criterion proposed in [9]:
Some authors [11] have proposed to use an area/peak factor
(APF) in order to correct the error that one makes when mea-
suring peak heights instead of peak areas. Nevertheless, this
APF depends on composition and should then be determined for
each phase to be analysed, which in turn is equivalent to
working in an integral mode. That is why no APF was taken into
account in this work. Nevertheless, because of the poor spectral
resolution of the Ni/C crystal, we estimate that the error on the
intensity of the carbon K line should not exceed 5%.
Background measurement

EKCr bEKFea or Ni b1:25EKCr 2 The position of background measurement is indicated in Table 3

with respect to the peak position. A linear shape of background
It must be noticed that, according to this criterion, nickel K
was assumed to calculate the background at the peak position.
line is also expected to induce the fluorescence of the iron K
The background was then subtracted to the X-ray intensity at
line. Of course, the fluorescence due to the characteristic X-ray
the peak position in order to get a net peak height.
lines is taken into account in the PAP model used for
quantification, but this model assumes a homogeneous con-
Peak interferences
centration all over the specimen, which is not the case here
since the material contains several phases with different
It is important to notice that the peak corresponding to the
compositions. Since the secondary phases are rather small (a
second order diffraction of the chromium L line is very close to
couple of microns), the iron and nickel K lines produced in the
the carbon K peak (105 sin = 46,140 and 45,778 respectively).
analysed phase are likely to easily go out of this phase, that-is-
So the carbon K peak height may be affected by the presence of
to-say into the metal matrix or in other phases (see the
this chromium second order peak. Nevertheless, the energy of
Appendix B for the absorption calculations). The composition
the chromium L line is about twice the one of the carbon K line.
is not the same in the different secondary phases and in the
It is then possible to discriminate those two lines in energy and
matrix. Then the fluorescence corrections made in the quanti-
reject the chromium L line by correctly adjusting the PHA (Pulse
fication model are not correct. An example of microanalysis
Height Analyser) parameters of the spectrometer.
artefacts due to the fluorescence induced in one phase by the X-
ray emission produced in another phase is given in [10].
Anti-contamination system
To avoid fluorescence in a phase different from the analysed
phase, one has to work with low energy lines in order to promote
It is well known that in secondary vacuum the surface of the
absorption in the analysed phase and prevent X-ray to go out of
analyzed specimen gets contaminated through a combined
this phase. Let us consider the case of the chromium L line: its
effect of the electron beam and the residual hydrocarbon
fluorescence can be induced by the iron and the nickel L lines
molecules of the atmosphere. This contamination is a problem
(but not by the iron and the nickel K lines that are too high in
for light elements microanalysis because their radiation can be
energy) according to Eq. (2). Nevertheless, this fluorescence is
strongly absorbed by the contamination layer. Furthermore,
very likely to occur entirely inside the analysed phase because
this is also a problem for carbon microanalysis since the
the iron and the nickel L lines will be totally absorbed inside the
contamination layer, that is carbon-rich, leads to overestimate
analysed phase (see Appendix B for the absorption calculations).
the carbon content in the specimen. In order to prevent surface
The situation is then similar to a massive material and the
contamination, we used the liquid nitrogen cold finger located
fluorescence corrections are correct. That is why we chose to
near the specimen (this device is available on most Cameca
work with the L line (rather than K) for Cr, Fe and Ni.
SX50 microprobes). It was checked in this work that the oxygen
micro-jet device (also available on SX50 microprobes and
Peak shape and peak position alteration
sometimes used for carbon microanalysis) brought no appreci-
able improvement to the anti-contamination system.
It is well known that K lines of light elements like carbon is
subjected to peak shape and peak position alteration due to
chemical effects. That is why it is normally necessary to perform
Appendix B. Estimating the Absorption of the Iron
intensity measurements in an integral fashion: the whole peak
K and L Lines in a 3 m Diameter Carbide
area and not only the peak height should be recorded. Never-
theless, we chose in this work to record only peak heights, rather
We consider as an example the absorption of the iron K and
than peak areas. The reasons for that are the following:
L lines in a carbide containing 20 at.% C, 20 at.% Fe, 15 at.% Ni
Working in an integral mode is very time consuming and and 45 at.% Cr (~M23C6). The absorption is described by [12]:
considerably increases the risk of surface contamination
I I0 exp Ax 3
during analysis.
The Ni/C crystal that was used for carbon analysis has very where I0 is the X-ray intensity produced in the carbide under
poor spectral resolution and is then not much sensitive to the electron beam, I is the X-ray intensity after travelling a
peak shape and peak position alteration. distance x in the carbide and is the linear absorption
1586 M A TE RI A L S C H A RAC TE RI ZA T ION 5 9 ( 2 00 8 ) 1 5 8 01 5 8 6
Fig. 4 Microanalysis of a 3 m diameter carbide. The
distance that the X-rays have to travel to go out of the carbide
is around 1 m.
coefficient of the considered line in the carbide. From mass
absorption coefficients (m2 kg 1) tabulated in the literature for
a variety of X-ray lines and absorbents [13], we calculated the
linear absorption coefficients (m 1) of the iron K and L lines
in the carbide. Using a carbide density of 7280 kg m 3 (we
assumed the same lattice parameter as Cr23C6 [6]), we found:
AKa 1:9  105 m1
ALa 7:0  106 m1
Let us consider now a carbide on which the electron beam
is focused as described on Fig. 4. We assume a hemispherical
shape with a diameter of 3 m, which corresponds to the size
of the smallest phases that were analyzed in this work. It can
be seen on Fig. 4 that the X-ray emitted in the carbide have to
travel around 1 m on average to go out of the carbide and
reach the metal matrix. According to the linear absorption
coefficients presented above, it can be calculated using Eq. (3)
that the iron L line will be absorbed at 99.9% before reaching
the metal matrix whereas the iron K line will be absorbed at
17.3% only.
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