See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/225107957

Study of Chromium Activity in the Cr-Fe-N System by Galvanic Cell Method

Article  in  Metallurgical and Materials Transactions A · January 2009

DOI: 10.1007/s11661-009-0053-5

CITATIONS READS

2 106

4 authors, including:

Lidong Teng Nanxian Chen

KTH Royal Institute of Technology Tsinghua University
68 PUBLICATIONS   528 CITATIONS    97 PUBLICATIONS   1,325 CITATIONS   

SEE PROFILE SEE PROFILE

Seshadri Seetharaman
KTH Royal Institute of Technology
467 PUBLICATIONS   4,607 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

high-temperature properties of solid solutions View project

structure and property of molten slag View project

All content following this page was uploaded by Seshadri Seetharaman on 30 January 2015.

The user has requested enhancement of the downloaded file.

Study of Chromium Activity in the Cr-Fe-N System
by Galvanic Cell Method
JIAYING XIE, LIDONG TENG, NANXIAN CHEN, and SESHADRI SEETHARAMAN

In the present work, the Cr-Fe-N alloys with different compositions were synthesized by
nitriding the Cr-Fe powder mixtures in the purified nitrogen gas (101,325 Pa) at 1473 K for
2 weeks. The phase relationships in the synthesized alloys and the alloys equilibrated at 1173 K
were carried out by X-ray diffraction (XRD) and scanning electron microscopy (SEM) tech-
niques. The nitrogen content in the alloys equilibrated in the nitrogen gas (101,325 Pa) at
1173 K was analyzed using the inert-gas fusion thermal conductivity (IGFTC) method. The
thermodynamic activities of Cr in Fe-Cr-N alloys were measured in the temperature range 973
to 1123 K using the solid-state galvanic cell technique with CaF2 single crystal as the solid
electrolyte. Based on the measured EMF values, the chromium activities in the alloys were
calculated with respect to pure Cr with bcc structure as the standard state. The effect of nitrogen
on Cr activities in the Cr-Fe-N system was examined by comparing the experimental results of
the Cr activities in the Cr-Fe and Cr-Fe-C systems.

DOI: 10.1007/s11661-009-0053-5

The Minerals, Metals & Materials Society and ASM International 2009

I. INTRODUCTION experimental information is significantly essential to

THE role of nitrogen in stainless steels and other
alloy steels containing Cr is an important subject in view
of the fact that the addition of a small amount of
nitrogen can improve the hardness of the alloys. The
knowledge of the thermodynamics of the Cr-Fe-N
system is essential for the understanding, as well as the
predicting the chemical and physical behaviors of these
alloys in various environments. The Cr-Fe-N system has
been investigated a number of times,[1–4] with Adcock[5]
and Blix[6] among the first to study this system.
Hertzman and Jarl[7] analyzed the available experimen-
tal information of the Cr-Fe-N system by the use of
thermodynamic models with which isothermal sections
of phase diagram were computed between 1173 and
1573 K. It should be pointed out that the liquid phase
has not been involved in Herzman and Jarl’s assessment.
By considering the new experimental information car-
ried out by Feichtinger et al.,[8] a reassessment including
liquid phase has been carried out by Frisk,[3] and the
assessment results are now available in the TCFE6[9]
database of the Thermo-Calc software.[10] As reported
in Frisk’s work, there are some differences in the
experimental results on locations of phase bound-
aries between different works. Reliable and consistent
JIAYING XIE, Research Scholar, is with the Department of
Wide and Heavy Plate Research, Shougang Technology Institute,
Beijing 1000 43, P.R. China. Contact e-mail: jyxie2005@hotmail.
com LIDONG TENG, Senior Researcher, and SESHADRI
SEETHARAMAN, Professor, are with the Department of Materials
Science and Engineering, Royal Institute of Technology, SE-100 44
Stockholm, Sweden. NANXIAN CHEN, Professor, is with the
Department of Physics, Tsinghua University, Beijing, 1000 84,
P.R. China.
Manuscript submitted June 5, 2009.
Article published online October 30, 2009
clarify the phase relations in the Cr-Fe-N system. To the
knowledge of the present authors, there is no experi-
mental data of the chromium activity in the Cr-Fe-N
system available in the literature. The purpose of the
present work is to investigate the activities of chromium
and the phase relations in the Cr-Fe-N alloys. In this
work, an electromotive force (EMF) method involving
CaF2 solid electrolyte was employed in order to measure
the chromium activity in Cr-Fe-N alloys in the temper-
ature range 973 to 1123 K. It is generally known that the
CaF2 galvanic cell technique is reliable for the genera-
tion of thermodynamic activity data in high-temperature
systems,[11,12] except at high PO2 ; and has recently been
used to investigate the thermodynamic properties of the
Mn-Ni-C-N system.[13] The nitrogen content in the
Cr-Fe alloys equilibrated at 1173 K in pure N2 gas
(101,325 Pa) was measured using the inert-gas fusion
thermal conductivity (IGFTC) method.
II. EXPERIMENTAL
In the present work, EMF measurements with CaF2
as the solid electrolyte were performed in order to
investigate the chromium activities in the Fe-Cr-N
alloys. The experimental details are presented in
Sections A through D.
A. Principle of EMF Measurements
The galvanic cell used in the present work can be
represented as follows:
ð
ÞPt j N2 ; Cr alloy þ CrF2 þ CaF2 k CaF2 k CrN þ
CrF2 þ CaF2 ; N2 j PtðþÞ ½1

172—VOLUME 41A, JANUARY 2010 METALLURGICAL AND MATERIALS TRANSACTIONS A

The individual electrode reactions can be written as where R is the gas constant and T is the temperature.
The standard state for the activity of chromium, aCr alloy
Left-hand-side electrode: in Eq. [10], is pure Cr with bcc structure.
Cr alloy þ 2F
$ CrF2 þ 2e ½2
B. Alloy and Electrode Preparations
Right-hand-side electrode:
1 The raw materials used in this work for the prepara-
2e þ CrF2 þ N2 $ CrN þ 2F
½3 tion of alloys and electrodes are presented in Table I.
2 The compositions of starting Cr-Fe powder mixtures for
the Cr-Fe and Cr-Fe-N alloys, as well as the corre-
Overall:
sponding sample numbers, are listed in Table II (CFN
1 donates the Cr-Fe-N system, and CF, the Cr-Fe
Cr alloy þ N2 $ CrN ½4
2 system.). The compositions of starting Cr-Fe powder
mixtures are also illustrated in the Cr-Fe phase diagram
The change of molar Gibbs energy in Reaction [4] is
(Figure 1) calculated by the use of Thermo-Calc soft-
given by Eq. [5]:
ware with the TCFE6 database, in which a is bcc-
Dr Gð4Þ ¼
nEF ½5 structured solid solution and c is fcc-structured solid
solution. Furthermore, the Fe-Cr-N phase diagram
where n denotes the number of electrons taking part in (Figure 2) was also calculated at 1473 K using Ther-
the reaction, E the EMF of the cell, and F the Faraday¢s mo-Calc software. The prepared powder Cr-Fe samples
constant. Reactions [3] and [4] are written with respect in 20-g batches were mixed thoroughly and then
to the most stable nitride of chromium at a nitrogen compacted into shallow alumina crucibles. Nitrogen
pressure of 101,325 Pa at the experimental tempera- was introduced into the specimens by exposing the
tures, as shown by the thermodynamic calculations in powder mixtures to purified N2 gas (101,325 Pa) at
Section B on alloy and electrode preparations. 1473 K for 2 weeks. The thickness of a Cr-Fe powder
In order to calculate the Cr activity in the alloys, the mixture bed packed in the alumina crucible was less than
standard Gibbs energy change for Reaction [6] needs to 5 mm in order to get sufficient in-depth nitridation. The
be considered. synthesized alloys were then cooled in the N2 gas in the
furnace. It should be pointed out that nitrogen uptake
1
Cr (bcc) þ N2 $ CrN ½6 could take place during the cooling of the alloy in N2 gas
2 since the solubility of nitrogen increases with decreasing
According to the thermodynamic data,[14] the Gibbs temperature.
energy of formation corresponding to Eq. [6] can be Further, in order to investigate the equilibrium phase
expressed as assemblages of these alloys at 1173 K, the samples had
o
to be heat treated in nitrogen gas (101,325 Pa) at this
Df Gð6Þ ¼
111; 892 þ 72:351  T ð800 K  T  1500 KÞ temperature for sufficiently long period in order to
ensure the attainment of equilibrium. A consideration of
½7
diffusion of nitrogen in bcc-Cr reveals that the time for
Equation [6]
[4] give diffusion of 2 mm at 1173 K is approximately
180 hours,
pffiffiffiffiffiffiffiffiffiffiffiwhich is estimated by the diffusion equation
Cr (bcc) $ Cr alloy ½8 S ¼ 2DN t; where S is the diffusion distance, DN is the
Thus, diffusivity of N in bcc Cr (3.16 9 10
12 m2/s
1 at
1173 K) at the given nitriding temperature,[15] and t is
o
Dr Gð8Þ ¼ Df Gð6Þ
Dr Gð4Þ ½9 the nitriding time under consideration. Hence, synthe-
sized alloys in the form of plates with the thickness of
4 mm were held at 1173 K in the purified N2 gas
The activity of chromium in the alloy can be obtained (101,325 Pa) for two different time intervals, viz. 240
by Eq. [10], viz. and 720 hours before being quenched into liquid nitro-
gen. The nitrogen content and phase relationships in the
Dr Gð8Þ ¼ RT ln aCr-alloy
quenched alloys were examined by the IGFTC method
¼
111; 892 þ 72:351  T þ nEF ½10 and X-ray diffraction (XRD), respectively.

Table I. Raw Materials Used in the Present Work for Alloy and Electrode Preparations

Name Purity (Wt Pct) Particle Size Origin

Pure Cr powder 99.95
200 mesh Alfa Aesar
Pure Fe powder 99.9 <10 lm Alfa Aesar
Nitrogen gas 99.9999 AGA, Stockholm
CrF2 powder 97 fine Aldrich, Stockholm, Sweden
CaF2 powder 99.95 fine E. Merck, Darmstadt, Germany
Cr2N analytical reagent
325 mesh Sigma-Aldrich, Stockholm, Sweden

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 41A, JANUARY 2010—173

Table II. Sample Numbers, Compositions (Weight Percent),
and Mole Fraction of Cr (XCr) in the Starting Cr-Fe Powder
Mixtures for the Cr-Fe-N and Cr-Fe Alloys

Sample Sample Cr Fe XCr

CFN-1 CF-1 80 20 0.812
CFN-2 CF-2 60 40 0.618
CFN-3 CF-3 40 60 0.418
CFN-4 CF-4 20 80 0.212
CFN-5 CF-5 92 8 0.925
CFN-6 CF-6 94 6 0.944

Fig. 3—XRD patterns of the original Cr2N and the final sample
obtained by heat treating Cr2N at 1273 K for 2 weeks in 101,325 Pa
purified N2 gas.

(101,325 Pa) before being mounted in the galvanic cell.

Fig. 1—Compositions of the starting Cr-Fe powder mixtures
presented in the Cr-Fe phase diagram calculated using Thermo-
Calc software.[10]
Earlier experiments carried out in the present laboratory
have shown that CrF2 and CaF2 do not dissolve in each
other in the solid state.[16]
According to the thermodynamic data of chromium
nitrides,[14] Cr2N phase would transform into CrN phase
below 1350 K in 101,325 Pa N2 gas. Thus, CrN used in
the reference electrodes was prepared by heating the
Cr2N powder in the purified N2 gas at 1273 K for
2 weeks. The XRD patterns (Figure 3) corresponding to
the original Cr2N sample and final sample indicated that
the original Cr2N phase was totally transferred into CrN
phase after heat treatment. The reference electrode,
consisting of CrN, CrF2, and CaF2 powders with a
weight ratio of 75:15:10, was prepared in a similar
fashion as the working electrode.
As CaF2 is a well-known electrolyte with high fluoride
ion conduction ðtF
 0:99Þ and low electronic con-
duction[17] in the temperature range 963 to 1193 K,
CaF2 single crystal (supplied by Alfa Aesar, Karlsruhe,
Germany) has been used as the electrolyte in this work.
The electrolyte was in the form of an optical disc 22 mm
in diameter and 4 mm in thickness and both sides were
polished.

C. Gas Purification System

Fig. 2—Isothermal Fe-Cr-N phase diagram calculated at 1473 K by
using Thermo-Calc software.[10]
Synthesized alloy powders, mixed with CrF2 and
CaF2 powders in a weight ratio of 75:15:10, were used as
working electrodes. The mixtures were ground and
compacted into cylindrical pellets with diameter 16 mm.
The pellets were placed in boron nitride crucibles, dried
under vacuum at 373 K for 12 hours, and then sintered
at 1123 K for 4 hours in the purified nitrogen gas
From Section A, it is understood that the galvanic cell
must be kept in the nitrogen gas at 101,325 Pa pressure
in order to keep the nitrogen potential in the system to
be constant. The phase stability diagram of ternary
system Cr-O-N at 1173 K was calculated from thermo-
dynamic data[14] and presented in Figure 4 (the PO2
and PN2 represent the partial pressure of oxygen and
nitrogen, respectively, and P0 is defined as 101,325 Pa).
Commercial nitrogen gas ordered from AGA has an
oxygen impurity level of less than 0.101 Pa. The cell
components would be oxidized significantly under this
oxygen pressure. Hence, the nitrogen gas must be
purified extensively in order to meet the experimental
requirement.
A gas purification train was developed, standard-
ized, and successfully used in the thermodynamic

174—VOLUME 41A, JANUARY 2010 METALLURGICAL AND MATERIALS TRANSACTIONS A


Fig. 4—Cr-O-N phase stability diagram at 1173 K calculated based
on thermodynamic data.[14]
investigations for some transition metal systems
containing carbon and nitrogen in the present labora-
tory.[13,16,18] In this purification train, the nitrogen gas
was further purified before passing through the nitrid-
ation (during the synthesis of the alloys) and equilibra-
tion furnaces, as well as the furnace containing the
galvanic cell during activity measurements. In this
purification method, traces of H2O in the gas were
removed by passing gas through silica gel and magne-
sium perchlorate, CO2 by ascarite and O2 by copper
turnings at 873 K, and magnesium chips at 773 K. The
oxygen partial pressure in the gas stream was monitored
throughout the EMF measurement by passing the
outgoing gas from the cell furnace through an oxygen
sensor involving partially stabilized zirconia electrolyte
with a slow stream of dry air as the reference electrode.
The oxygen partial pressure in the outing gas had to
be maintained at a value less than 10
17 Pa throughout
the measurement. It was necessary to point out that the
exact oxygen partial pressure value in the outgoing gas
was probably lower than the value measured by the
oxygen sensor, since the measured value was likely to be
below the ionic conduction region of the ZrO2-
7.5 mol pct CaO electrolytic tube used in the oxygen
sensor. The electrodes of the galvanic cell were examined
by optical microscope after the EMF measurements and
were found to be free from oxidation.
D. Experimental Apparatus and Procedure
A schematic diagram of the galvanic cell arrangement
used in this work is presented in Figure 5. As can be
seen from this figure, the single-crystal electrolyte is kept
sandwiched between the two electrodes in an open cell
arrangement. The cell was placed in a vertically
mounted alumina reaction tube inside a Kanthal A1
resistance furnace (Hallstahammar, Sweden) and posi-
tioned in the uniform temperature zone of the furnace
(±0.5 K over a length of 6 cm). The temperature of the
cell was measured by a K-type thermocouple positioned
under the cell that had been earlier calibrated against the
METALLURGICAL AND MATERIALS TRANSACTIONS A
Fig. 5—Schematic diagram of the apparatus used for the EMF mea-
surement.
melting point of pure gold. The reaction tube was closed
at both ends with water-cooled copper lids provided
with O-ring seals. The cell leads, the gas inlet, and the
outlet tubes, as well as the thermocouple sheath, were
taken out of the reaction tube through O-ring seals.
In order to remove the moisture absorbed in the
ceramic components around the cell, the reaction tube of
the furnace as well as Al2O3 components in the cell
arrangement were dried at 423 K under a pressure of
1.0 Pa for 10 hours and then flushed with the purified
nitrogen gas for 2 hours. This vacuum drying and
cleaning process was repeated 3 times before the cell
was positioned into the reaction tube in the furnace. The
reaction tube with cell was also dried at 373 K under a
pressure of 1.0 Pa for 12 hours and then flushed with
purified nitrogen gas for 4 hours in order to improve the
accuracy of the EMF measurements. When the partial
pressure of oxygen in the outgoing gas monitored by
oxygen sensor was less than 10
17 Pa, the furnace was
turned on. The cell temperature was raised to 973 K at a
rate of 6 K/min. The time needed for the cells to obtain
equilibrium during the first heating was more than
3 days. The equilibrium time thereafter was dependent
on the temperature. The EMF measurements were
carried out in the purified nitrogen gas at 101,325 Pa
pressure, and the values were measured by a high
impedance digital Newport millivoltmeter (Stevenage,
England) within an accuracy of ±0.01 mV. The revers-
ibility of the cell was verified by polarizing the cell in both
directions and ascertaining that the EMF returned to its
original value. The cell was taken through temperature
cycles and the values were found to be reproducible. The
galvanic cell measurements were repeated in a number of
cases in order to confirm the reliability of the results.
III. RESULTS AND DISCUSSION
A. Phase Compositions and Microstructures
The main phases of the synthesized alloys, CFN-1,
CFN-2, CFN-3, and CFN-4, were examined by XRD
and are presented in Figure 6 (M represents the Cr or
VOLUME 41A, JANUARY 2010—175
Fe). As can be seen from this figure, (Cr, Fe)2N nitride
has been formed during the nitridation procedure; the
main phases in these alloys are (Cr, Fe)2N and a solid
solution phase. A comparison of the XRD patterns
among CFN-1, CFN-2, CFN-3, and CFN-4 indicates
that the intensity of (Cr, Fe)2N nitride peaks decreases
with increasing Fe content in the alloys, while the
intensity of a solid solution phase peaks increases. It
should be pointed out that the main phases in the
Fig. 6—XRD patterns of CFN-1, CFN-2, CFN-3, and CFN-4 alloys
synthesized at 1473 K in purified N2 gas (101,325 Pa) for 2 weeks.
Fig. 7—SEM micrographs of the CFN-1, CFN-2, CFN-3, and CFN-4 alloys synthesized at 1473 K (the dark-gray phase is identified as
(Cr, Fe)2N phase, and the light-gray one as a solid solution phase).
176—VOLUME 41A, JANUARY 2010
synthesized alloys are not exactly the equilibration
phases corresponding to the synthesized temperature
1473 K, since the alloys were cooled in the furnace in
pure nitrogen gas. As mentioned in Section II–B,
nitrogen pickup would even take place during the
cooling of the alloy in N2 gas.
The microstructures of these alloys were examined
by SEM and presented in Figure 7. Combining with
the XRD results, the dark-gray phase in Figure 7 is
identified as (Cr, Fe)2N phase and the light-gray one as
a solid solution phase. Since the nitrogen content in the
various phases could not be determined accurately in
view of the limitations of the EDS analysis, the
chemical compositions of synthesized alloys were
analyzed for Fe and Cr only. The results are shown
in Table III in which the chemical compositions are
Table III. Chemical Compositions of Synthesized Alloys Are
Given in Site Fraction of the Metallic Components, yCr
and yFe (yi 5 xi/(xCr + xFe), Where xi is the Molar
Fraction of Element i)
CFN-1 CFN-2 CFN-3 CFN-4
Phase YCr YFe YCr YFe YCr YFe YCr YFe
M2 (C, N) 0.91 0.09 0.96 0.04 0.91 0.09 0.83 0.17
a solid solution 0.22 0.78 0.18 0.82 0.18 0.82 0.15 0.85
METALLURGICAL AND MATERIALS TRANSACTIONS A
 Fig. 9—XRD patterns of CFN-1 alloy held at 1173 K for different
Fig. 8—Dependence of standard Gibbs energy of formation of periods, viz. 240 h (CFN-1-240) and 720 h (CFN-1-720).
various nitrides (per mole nitrogen gas) on the temperature.

Table IV. Nitrogen Content (Weight Percent) in the Alloys definitely reach equilibrium with nitrogen gas. Further,
Kept at 1173 K for 240 Hours (Alloy 240) or 720 Hours the nitrogen content increases with the increasing
(Alloy 720) and the Equilibrium Phases in the Alloys chromium content in the alloys, which indicates the
at 1173 K Measured by XRD presence of nitrogen as compounded with Cr.
The phases coexisting in these alloys after equilibrium
Nitrogen Content treatment at 1173 K at different time intervals (240 and
Sample Alloy-240 Alloy-720 Main Phases by XRD
720 hours) were determined by XRD analysis. The
results in the case of CFN-1 are shown in Figure 9. The
CFN-1 9.5 10.3 (Cr, Fe)2N, (Cr, Fe)N, equilibrium phases are the same in these two samples
a solid solution and they are (Cr, Fe)2N, (Cr, Fe)N, and a solid solution.
CFN-2 7.1 (Cr, Fe)2N, (Cr, Fe)N, Thus, the XRD analysis results and nitrogen analysis
a solid solution indicate that 720 hours is long enough for the alloys to
CFN-3 2.89 2.62 (Cr, Fe)2N, a solid solution
reach equilibrium state at 1173 K. The equilibrium
CFN-4 0.93 (Cr, Fe)2N, a solid solution
CFN-5 (Cr, Fe)2N, (Cr, Fe)N, phases of alloys at 1173 K are listed in Table IV. The
a solid solution XRD spectra of some alloys are presented in Figure 10.
CFN-6 (Cr, Fe)2N, (Cr, Fe)N,
a solid solution B. Activities of Chromium in the Cr-Fe-N Alloys
The EMF measurements were performed as described
given in site fractions of the metallic components, in Section II–D in the temperature range 973 to 1123 K.
i.e., yCr and yFe (yi = xi/(xCr + xFe), where xi is the Based on Eq. [10] and the measured EMF values, the Cr
molar fraction of element i). As can be seen from this activities in the Cr-Fe-N alloys were obtained and
table, the main metallic element in (Cr, Fe)2N nitride is presented in Table V. As shown in this table, chromium
chromium, while iron is the main metallic element in a activities in the Cr-Fe-N alloys are very low and the
solid solution phase. values in different alloys are very close to each other in
A comparison of standard Gibbs energies of forma- the measured temperature range, which indicates very
tion of Cr-N and Fe-N are presented in Figure 8. The strong interaction between Cr and N. Further, the Cr
Df G deg values in this figure were taken from the activities have been found to increase with the increase
Reference 14. In this figure, only the nitrides in in temperature. This can be attributed partly to the
equilibrium with pure nitrogen gas have been consid- decrease of nitrogen solubility in the alloys and partly to
ered. It is seen that the DfG deg of CrN has the negative the increase of the Gibbs formation energy of nitrides
value, while iron does not form a stable nitride. This is with the increasing temperature.[14] The chromium
in conformity with the SEM-EDS observations. activities in the corresponding matrix alloy Cr-Fe were
In this work, the equilibrium nitrogen contents in also calculated by using the TCFE6 database in the
some selected Cr-Fe-N alloys at 1173 K were measured Thermo-Calc software. The comparisons show that
using the IGFTC method. The nitrogen content in the addition of nitrogen into the Cr-Fe-N alloys decreases
alloys held at 1173 K at different time intervals (240 or the chromium activities significantly.
720 hours) is presented in Table IV. It can be seen that
the nitrogen contents in the alloys between 240 and
720 hours are quite close within analytical error limits C. Effect of Nitrogen on the Activity of Chromium
(usually ±5 pct), which indicates that the alloys with In the industrial applications, the Fe-Cr alloys often
4-mm thickness kept at 1173 K for 720 hours would contain carbon and nitrogen. It would be interesting to

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 41A, JANUARY 2010—177

Fig. 10—XRD patterns of the CFN-1, CFN-2, CFN-3, and CFN-4 alloys held at 1173 K in purified N2 gas for 720 h and then quenched in
liquid nitrogen.

Table V. Chromium Activities (Exp.) in the Cr-Fe-N Alloys Obtained by EMF Measurements in the Present Work,
as well as Chromium Activity (Noted as Calc.) in the Cr-Fe Alloys Calculated Using Thermo-Calc Software;
the Standard State for Cr Activity is Pure Bcc-Cr

aCr aCr aCr

CFN-1 CF-1 CFN-2 CF-2 CFN-3 CF-3

T (K) Exp. Calc. T (K) Exp. Calc. T (K) Exp. Calc.
983 0.016 0.851 988 0.010 0.777 983 0.009 0.632
1023 0.017 0.848 1031 0.015 0.745 1023 0.012 0.617
1073 0.022 0.844 1083 0.020 0.734 1073 0.024 0.615
1123 0.031 0.837 1120 0.032 0.707 1118 0.032 0.599

aCr aCr aCr

CFN-4 CF-4 CFN-5 CF-5 CFN-6 CF-6

T(K) Exp. Calc. T(K) Exp. Calc. T(K) Exp. Calc.
993 0.007 0.534 983 0.010 0.932 993 0.012 0.945
1024 0.009 0.502 1023 0.017 0.932 1023 0.024 0.944
1072 0.022 0.453 1073 0.028 0.931 1073 0.030 0.944
1123 0.035 0.421 1123 0.039 0.930 1123 0.036 0.944

examine if the stability of separate nitride phases is compare the standard formation Gibbs energies of the
consistent with the stability of carbides in the transition carbides of Cr and Fe. Such a comparison using the Df G
metal alloys. In order to understand the relative stability deg from the literature[14] is presented in Figure 11. In
of the transition metals carbides, it may be useful to this figure, only the carbides in equilibrium with

178—VOLUME 41A, JANUARY 2010 METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 11—Standard formation Gibbs energy of Cr and Fe carbides
(per mole carbon).
Fig. 12—Interatomic pair potentials of Cr-C, Mn-C, Fe-C, Cr-N,
and Mn-N acquired by using the lattice inversion method.[19]
graphite have been considered. It is seen that the DfG
deg for Cr3C2 carbides has the larger negative value than
Fe3C carbides. Hence, Cr carbides are likely to precip-
itate out preferentially.
It is interesting to examine if the order of carbon
affinities is consistent with nitrogen affinities for Cr, Mn,
and Fe. This is clarified by interatomic pair potentials of
Cr-C, Mn-C, Fe-C, Cr-N, and Mn-N. These pair poten-
tials have been calculated based on the lattice inversion
method[19] and ab-initio cohesive energies at 0 K and used
to study the properties of the carbides in the present
group.[20,21] In Figure 12, the order of interaction inten-
sity, ICr-N >IMn-N >ICr-C >IMn-C >IFe-C (I donates the
intensity of interatomic interaction), could be estab-
lished, which indicates that both carbon and nitrogen
affinities for Cr, Mn, and Fe atoms decrease with the
increase in atomic number.
The values of DfG deg for Cr carbide and nitride
presented in Figures 8 and 11 and the interatomic pair
potentials of Cr-N and Cr-C presented in Figure 12
indicate that the formation of carbides in the Cr-Fe-C
alloys and the formation of nitrides in the Cr-Fe-N
alloys will decrease the chromium activity. Further, the
METALLURGICAL AND MATERIALS TRANSACTIONS A
Fig. 13—Comparison of Cr activities between the Cr-Fe, Cr-Fe-C,
and Cr-Fe-N systems (the weight ratio of Fe is the same, while the
weight ratio of Cr is slightly different between the Cr-Fe-C and
Cr-Fe-N alloys in each comparison group).
stronger negative effect of nitrogen than carbon on the
chromium activity can be foreseen.
In this work, the chromium activity was compared
between the Cr-Fe and Cr-Fe-N systems and presented
in Table V, in which the data of Cr activities in the
Cr-Fe alloys are calculated by using Thermo-Calc
software.[10] As shown in Table II, the weight ratios of
Cr and Fe in the powder mixtures for the Cr-Fe-N
system are the same as those for the Cr-Fe system. Due
to the strong interaction of Cr and N, addition of
nitrogen into the Cr-Fe-N alloys decreases the chro-
mium activities significantly in comparison to those in
the Cr-Fe alloys. The difference of Cr activity between
the Cr-Fe and Cr-Fe-N alloys decreases with the
decreasing Cr content in the alloys.
The effect of nitrogen on the chromium activity was
further investigated by comparing the Cr activities in the
Cr-Fe-C and Cr-Fe-N alloys. The data of Cr activities in
the Cr-Fe-C alloys are taken from the earlier work.[18]
The comparison is presented in Figure 13 (CCF denotes
VOLUME 41A, JANUARY 2010—179
the Cr-Fe-C system. CCF-13: Fe 60 wt pct, Cr
38.6 wt pct; and CCF-14: Fe 80 wt pct, Cr 19.3 wt pct).
The weight ratio of Fe is the same, while the weight ratio
of Cr is slightly different between the two ternary
systems in each comparison group. The comparison
indicates the strong negative effect of nitrogen on the Cr
activity in the Fe-Cr-N alloys, which is consistent with
the results of Fe-Cr-C-N alloys achieved in the earlier
work.[22]
IV. CONCLUSIONS
In the present work, the nitrogen content and
equilibrium phases in the Cr-Fe-N alloys equilibrated
at 1173 K were investigated using the IGFTC method
and XRD analysis. The experimental results show that
the solubility of nitrogen in the alloys decreases with
decreasing chromium content. The activities of chro-
mium in these alloys were obtained using the EMF
method with CaF2 solid electrolyte in the temperature
range 973 to 1123 K. It is found that, in the Cr-Fe-N
system, the activities of chromium are very low due to
the strong interaction between Cr and N. The activity
values increase with increasing temperature. The com-
parison of Cr activities between the Cr-Fe and the
Cr-Fe-N systems indicates a strong negative effect
of nitrogen on the Cr activities in the Cr-Fe-N alloys.
A comparison of Cr activities between the Cr-Fe-N and
Cr-Fe-C systems implies stronger Cr-N interaction than
that of Cr-C.
ACKNOWLEDGMENTS
The authors thank Professor Jiang Shen for his help
on the acquirement of the interatomic pair potentials.
Financial support from the Swedish Environmental
Research Foundation (Mistra) and the scholarship
180—VOLUME 41A, JANUARY 2010
View publication stats
from the Foundation for Applied Thermodynamics are
gratefully acknowledged.
REFERENCES
1. V. Raghavan: Phase Diagrams of Ternary Iron Alloys, ASM
INTERNATIONAL, Metals Park, OH, 1987, Part 1, pp. 171–82.
2. J. Sopousek, J. Vrestal, J. Kunze, B. Beyer, and I. Baecher:
Z. Metallkd., 1998, vol. 89 (3), pp. 192–99.
3. K. Frisk: Metall. Trans. A, 1990, vol. 21A, pp. 2477–88.
4. B. Ozturk, R. Matway, and R.J. Fruehan: Metall. Mater. Trans.
B, 1995, vol. 26B, pp. 563–67.
5. F. Adcock: J. Iron Steel Inst., 1926, vol. 114, pp. 117–26.
6. R. Blix: Z. Phys. Chem., 1929, 3B, pp. 229–39.
7. S. Hertzman and M. Jarl: Metall. Trans. A, 1987, vol. 18A,
pp. 1745–52.
8. H. Feichtinger, A. Satir-Kolorz, and Z. XiaoHong: HNS 88, Int.
Conf. on High-Nitrogen Steels, Lille, France, Institute of Metals,
London, 1989.
9. J.-O. Andersson and B. Sundman: CALPHAD, 1987, vol. 11,
pp. 83–92.
10. J.-O. Andersson, T. Hekander, L. Höglund, P. Shi, and
B. Sundman: CALPHAD, 2002, vol. 26, pp. 273–312.
11. J.W. Hinze and J.W. Patterson: J. Electrochem. Soc., 1973,
vol. 120, pp. 96–100.
12. K. Kiukkola and C. Wagner: J. Electrochem. Soc., 1957, vol. 104,
pp. 308–16.
13. L.D. Teng, R. Aune, and S. Seetharaman: J. Alloys Compd., 2005,
vol. 388, pp. 250–57.
14. I. Barin: Thermochemical Data of Pure Substances, VCH
Verlagsgesellschaft mbH, Weinheim, Federal Republic of
Germany, 1993, Part I.
15. B. Jönsson: Trita-Mac-0514, Royal Institute of Technology,
Stockholm, 1993.
16. L.D. Teng: Ph.D. Thesis, Royal Institue of Technology,
Stockholm, 2004.
17. R.W. Ure: J. Chem. Phys., 1957, vol. 26, pp. 1363–73.
18. L.D. Teng, R. Aune, M. Selleby, and S. Seetharaman: Metall.
Mater. Trans. B, 2005, vol. 36B, pp. 263–70.
19. N.X. Chen, Z.D. Chen, and Y.C. Wei: Phys. Rev. E, 1997, vol. 55,
pp. R5–R8.
20. J.Y. Xie, N.X. Chen, J. Shen, L.D. Teng, and S. Seetharaman:
Acta Mater., 2005, vol. 53, pp. 2727–32.
21. J.Y. Xie, N.X. Chen, L.D. Teng, and S. Seetharaman: Acta
Mater., 2005, vol. 53, pp. 5305–12.
22. J.Y. Xie, L.D. Teng, N.X. Chen, and S. Seetharaman: Metall.
Mater. Trans. B, 2007, vol. 38B, pp. 93–100.
METALLURGICAL AND MATERIALS TRANSACTIONS A