Materials Science and Engineering A 415 (2006) 21–32

Relation between the oxidation mechanism of nickel, the microstructure

and mechanical resistance of NiO films and the nickel purity
I. Oxidation mechanism and microstructure of NiO films
A.M. Huntz a,∗ , M. Andrieux a , R. Molins b
a LEMHE, CNRS UMR 8647, Université Paris XI, Centre d’Orsay, F-91405 Orsay, France
b ENSMP, Centre des Matériaux, CNRS UMR 7633, BP 87, F-91003 Evry, France

Received in revised form 1 May 2005; accepted 1 August 2005

Abstract
The effect of impurities on the oxidation mechanism of nickel and on the mechanical characteristics of NiO films was studied on two industrial
nickel grades compared to a pure nickel. In this part, influence of impurities on the oxidation mechanism and on the NiO film microstructure
will be detailed. The oxidation mechanism, especially studied at 800 ◦ C in air, was clarified using complementary techniques, SEM and STEM
microstructural and analytical investigations, XPS analyses, profilometry, oxygen isotopic exchange and SIMS. Depending on the Ni purity, the
morphology of the oxide scale and the porosity amount differs. Duplex oxide layers and internal oxidation are observed on industrial grades, while
a simple NiO film grows on pure nickel without internal oxidation. An oxidation mechanism, which differs according to the presence or not of
impurities in the nickel substrate, is proposed. The mechanical characteristics will be characterised and discussed in the following paper (part II)
in relation with the microstructural modifications induced by changing the nickel purity.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Oxidation; Nickel; Impurities; NiO; Microstructure; Diffusion

1. Introduction interpret mechanical results displayed in part II. Moreover, such

Though nickel oxidation has been largely studied [1–17], the
oxidation mechanisms of nickel are not really clarified and dis-
crepancies still exist in the literature data. This is probably due to
the differences in purity of studied nickel grades, in the surface
preparation and roughness, in furnace atmosphere and in heating
procedures . . .. Indeed, all these parameters may have an influ-
ence on the oxidation behaviour, but, at this date, the effect of
impurities on the oxidation mechanism and on the morphology
of the oxide scale is not yet clarified.
The characterisation of oxide morphology and of the
oxidation mechanisms depending on many parameters such
as the oxidation conditions, the porosity of the oxide films,
the initial surface roughness and the nickel purity, is of great
importance to explain mechanical behaviour and deduce
mechanical characteristics of thin films. This part will help us to
∗ Corresponding author. Tel.: +33 1 69 15 63 18; fax: +33 1 69 15 48 19.
E-mail address: am.huntz@lemhe.u-psud.fr (A.M. Huntz).
a study presents an interest not only for a fundamental meaning
of environmental aggression phenomena, but also as Ni-based
materials can behave similarly to nickel after depletion in more
oxidising elements.
So, this work was focused on the effect of impurities in
a nickel substrate on both the oxidation mechanisms and the
mechanical characteristics of NiO scales. The purpose of the
first part is related to the determination of the oxidation mech-
anism, while the second part will be allocated to the deter-
mination of the mechanical characteristics depending on the
film microstructure and growth mechanism. In order to point
out the effect of impurities, the oxidation in laboratory air of
three nickel grades was studied, two industrial grades, while the
third one, qualified of pure (so called “pure”), was elaborated
in “Ecole Nationale Supérieure des Mines de Saint Etienne,
France” (ENSMSE). The oxidation behaviour was followed
by thermogravimetry in isothermal conditions and the oxide
films were analysed using many techniques allowing to evi-
dence their microstructure and their chemistry at various scales.
A particular attention was paid to the first oxidation stages,

0921-5093/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2005.08.225
22 A.M. Huntz et al. / Materials Science and Engineering A 415 (2006) 21–32
which can have a great influence on crack initiation in the
oxide film.
2. Experimental
Three nickel grades were studied; two of them are industrial
grades “Imphy and MSX nickel”, whose composition given by
the industry is gathered in Table 1. Note that for Imphy nickel, all
the impurities are not mentioned. For instance, for Imphy nickel,
Mn is not given as impurity by the industry, but was detected after
oxidation in the oxide layer. The third nickel grade “ENSMSE
nickel” was provided as a very pure single crystal and contains
less than 10 ppm of impurities.
The nickel grade provided by Imphy S.A. is as-hot-wired
drawn, while nickel provided by MSX was previously hot-
rolled. Both industrial grades are polycrystalline with a grain
size around 30–50 ␮m containing a sub-structure of dislocation
cells resulting from the elaboration process. These grades con-
tain various impurities, but they differ according to their type
and content, namely silicon, titanium and manganese which are
more present in MSX nickel (see Table 1).
In order to obtain a pure polycrystalline nickel, the single
crystal of ENSMSE Ni was cold-rolled, then heat-treated for
24 h at 920 ◦ C in an argon-hydrogen mixture. Observations by
electron microscopies and analyses (EDX, energy dispersive X-
ray analysis and XPS, X-ray photo-electron spectrometry) did
not reveal any impurity and the resulting grain size of this pure
nickel was about 100 ␮m. However, a substructure of dislocation
cells was still remaining, the annealing treatment having not been
long enough.
Prior to oxidation tests, all the samples were mechanically
polished using SiC paper down to 1200 grade, then ultrason-
ically cleaned in ethanol. The oxidation kinetics tests were
performed in a high sensibility SETARAM thermobalance (sen-
sitivity ±1 ␮g), in air between 700 and 900 ◦ C, but at 800 ◦ C for
most experiments. This allowed to choose adequate oxidation
treatments for the specimens to be studied by bending-tests, so
that oxide scales of the same thickness for the three nickel grades
could be obtained.
After oxidation tests at 800 ◦ C, all samples were observed
using scanning electron microscopy (SEM) on surface and cross
section, and EDX analyses were performed to detect impurity
rich precipitates. Cross-sectional thin foils were also prepared on
the three oxidised nickel grades and characterized using a trans-
mission electron microscope (Tecnai F 20 ST) equipped with
analytical spectrometers. The analytical resolution was 1 nm,
allowing a better detection of segregated impurities.
Table 1
Composition of nickel provided by Imphy S.A.
Ni grade Element (wt%)
Ni Co C Ti Si
Imphy Ni 99.700 0.01 0.058 0.01
MSX Ni 99.480 0.014 0.089 0.102
The first oxidation stages were studied by in situ XPS analyses
and by interferometric profilometry (performed in “laboratoire
de physico-chimie de l’état solide” in University Paris Sud,
France). For in situ XPS experiments, the sample surface was
carefully polished. Then, once introduced into the XPS cham-
ber, it was cleaned by an Ar+ sputtering and heated up to 600 ◦ C
in ultra-vacuum. At last, oxygen was introduced at 10−5 atm for
1, 5 or 15 min and spectra were recorded during dwell time at
600 ◦ C and after cooling at room temperature.
3. Results
3.1. Kinetics
Fig. 1a collects the weight gain versus time obtained for
Imphy industrial nickel at three temperatures. In each case, the
oxidation kinetics can be represented by a parabolic law. Curves
obtained at 800 ◦ C for the three nickel grades are given in Fig. 1b
and indicate that pure nickel oxidizes faster than nickel of indus-
trial grades. Similar observations were made at 700 and 900 ◦ C.
There is no significant difference between the two industrial
nickel grades. Fig. 1c shows that the oxidation kinetics can be
fitted to a parabolic law:

2
M
= a + kp · t (1)
S
where a is a small constant term, kp is the parabolic constant
whose values are reported in Table 2, and t is the oxidation
duration. The oxide thickness xNiO was calculated from:
M/S · MNiO
xNiO = (2)
MO · ρNiO
where MNiO and MO are the molar mass of NiO and O respec-
tively, and ρNiO is the volumetric mass of NiO (taken as
6.85 g/cm3 ). Eq. (2) assumes that all oxygen is incorporated
in the scale (no internal oxidation) and that the oxide film is
compact.
3.2. Morphology of the oxide layers
Fig. 2 shows that the oxide scales formed on specimens of
industrial grades (Fig. 2a and b) are duplex, consisting in two
distinct films, an outer film made up of columnar NiO grains,
and an inner one of equiaxed NiO grains. On the contrary, the
oxide formed on pure nickel is simple, only composed of one
oxide layer. Contrary to references [3,4], the duplex structure
for the two industrial grades and the simple structure for the
pure nickel were observed whatever the oxidation duration and
S P Mo Mn Cu Fe
0.003 0.084 0.005 0.01
<10 ppm <10 ppm 0.266 0.034 0.016
 A.M. Huntz et al. / Materials Science and Engineering A 415 (2006) 21–32 23

Fig. 1. Evolution of the weight gain per surface unit by oxidation in air of (a) Imphy nickel at three temperatures, (b) the three nickel grades at 800 ◦ C and (c) same
as (b) in quadratic coordinates.

temperature, in the range 700–900 ◦ C. It could be noted that
Haugsrud and Pedraza [15,16] worked with pure nickel grades
and observed duplex structures for the oxide scale. By com-
paring their nickel purity to ours, it appears that their nickel is
less pure than ENSMSE Ni of this study. It clearly shows that
the oxide morphology is very sensible to the degree of nickel
purity. On the industrial nickel grades, the thicknesses of the
two layers are always near the ratio 1:1, and for a same oxi-
dation time, the oxide scale formed on industrial nickel grades
is nearly twice thinner than the oxide formed on pure nickel.
On industrial grades, the porosity of the inner layer increased
with time and seemed slightly more important on MSX Ni
than on Imphy Ni. On the contrary, as shown by SEM sur-
face observations, the porosity of the outer layer decreased
with the oxidation time [5–8]. For industrial grades, under the
oxide layers, internal bulk and intergranular oxidation were
observed (Fig. 3). Internal oxidation is slightly more pronounced
for MSX nickel (Fig. 3b) than for Imphy Ni (Fig. 3a and d),
whereas intergranular oxidation seems to develop deeper in
Imphy grade. This can be related to a higher carbon content.
As shown on Figs. 2c and 3c, there is no internal oxidation for
pure nickel.

Table 2
Kinetics constants deduced from parabolic law
Nickel T (◦ C) kp (mg2 cm−4 s−1 ) Oxidation time (h) Oxide thickness (␮m) calculated
with ρ = 6.85 g/cm3

Imphy 700 6.2 × 10−7 93 3.1

800 4.6 × 10−6 66 7.4
900 3.2 × 10−5 22 10.7
MSX 800 7.3 × 10−6 66 9.3
ENSMSE 800 6.3 × 10−5 46 22.2
24 A.M. Huntz et al. / Materials Science and Engineering A 415 (2006) 21–32

Fig. 2. Transverse sections of NiO scales formed at 800 ◦ C on (a) Imphy Ni, (b) MSX Ni and (c) pure Ni.

Fig. 3. Transverse sections and observation of the underlying substrate with or without internal oxidation. Oxidation at 800 ◦ C: (a) Imphy Ni, (b) MSX Ni, (c) pure
Ni and (d) STEM general view of the scale (dark field image, DF, Imphy grade).
 A.M. Huntz et al. / Materials Science and Engineering A 415 (2006) 21–32
Fig. 4. EDX analysis of precipitates in industrial nickel.
3.3. EDX chemical analyses
After oxidation sequences allowing to develop oxide films of
1–10 ␮m, only Ni and O were detected at the surface of the sam-
ples by EDX. No outer diffusion of impurities was evidenced.
On the contrary, when analysing cross-sections, many internal
precipitates were observed (see Fig. 3a, b and d) in the sub-
strate and especially along grain-boundaries of industrial nickel
grades. As shown in Fig. 4, these precipitates were mainly com-
posed of Ti and Mn oxides, with some Si. A higher content
of precipitates was present in MSX grade than in Imphy grade
(compare Fig. 3a and b).
3.4. Transmission electron microscopy (TEM)
Cross-sections of specimen of the three studied Ni grades
oxidised for 3 h at 800 ◦ C were investigated through the oxide
layers and along the interfaces, oxide–metal interfaces but also
oxide–oxide interfaces in the case of oxide films formed on
industrial grades, and finally in the underlying substrate. Ele-
mental EDX profiles were performed with a probe size of 1 nm
and a step size of 1 nm in order to detect any interfacial or inter-
granular precipitation and segregation.
On both oxidised industrial grades, the duplex structure of
the oxide scale was confirmed with an outer columnar layer
1–2 ␮m thick, with grains 300 nm large, and an inner layer made
of equiaxed grains (Fig. 3a and 5) whose thickness varies (from
0.5 to 1.5 ␮m), due to large convolutions of the internal Ni/NiO
interface.
For MSX nickel grade, some tiny precipitates enriched in
Si and/or Mn were detected in the outer layer, but neither seg-
regation nor precipitation were detected along columnar grain
boundaries or at the interface between the two oxide layers
(Fig. 6a). Through the inner oxide layer whose grain size is
about 100 nm, many pores were observed (Fig. 6b). Large cav-
ities are also present at the oxide–metal interface, associated to
metallic nickel areas between the cavities (Fig. 6c, see arrows).
No segregation was detected at a nanometric scale at the NiO–Ni
interface. Note that the grain size of nickel, under the oxide scale
is about 1 ␮m while the grain size of nickel in the bulk is around
50 ␮m.
25
Fig. 5. Duplex structure of NiO (STEM-DF image, Imphy grade).
Concerning the oxidised Imphy nickel, there is no specific
microstructural difference compared to oxidised MSX nickel.
The oxide scale is duplex with a planar interface between outer
and inner layers, neither segregation nor precipitation occurs
at oxide grain boundaries or along oxide/oxide interface and a
great amount of porosity is observed through the inner layer.
Contrary to the observations made on the MSX grade, silicon
and a few Mn were sometimes detected at the Ni/NiO interface
(Fig. 7) as segregated elements or as precipitated in oxidized
particles.
For both industrial grades, the inner NiO/outer NiO inter-
face is rather flat (Fig. 8a) as previously shown by SEM, and
without any segregation, while the Ni/NiO interface is very con-
voluted and irregular with large cavities (Fig. 8b). Below the
NiO/Ni interface, in the underlying nickel, transgranular pre-
cipitates essentially rich in Mn, Si, Mg and O (Fig. 9a) were
observed, while precipitates enriched in Mn, Si, Mg, Ti and
O were observed (Fig. 9b) along the grain boundaries, as the
result of important internal bulk and intergranular oxidation.
Always for both industrial grades, large cavities were observed
at the metal/oxide interface after limited oxidation time (Fig. 10).
Under the oxide, the substrate displays the same microstructure
than in its as-received state. No recrystallisation occurred, per-
haps due to a pinning effect by precipitates.
The observed microstructure is quite different in pure nickel.
Only one NiO layer, 5 ␮m thick, is observed with large equiaxed
grains varying between 200 and 500 nm (Fig. 11). The Ni/NiO
interface is rather flat, only facetted by the grain shape (Fig. 12a).
This facetted interface is possibly related to some crystallo-
graphic orientation relationship between Ni and NiO, resulting
from initial stages of oxidation. No cavities were detected at
this interface. However, there are many pores through the oxide
layer (Fig. 12b) often with a geometrical shape. Other chemical
elements were detected neither within the oxide layer, nor at
the oxide/metal interface and internal oxidation was evidenced
26 A.M. Huntz et al. / Materials Science and Engineering A 415 (2006) 21–32

Fig. 6. STEM transverse sections, MSX grade (a) outer/inner NiO interface, (b) grain size and porosity through the inner layer, (c) interfacial cavities (marked by
arrows) and Ni extrusion (EDX analysis performed between the two cavities).

neither in the bulk nor along grain boundaries of the underlying
substrate.
3.5. First oxidation stages and in situ XPS chemical
analyses
It was observed that the spalling at the oxide/oxide inter-
face was easier for Imphy nickel than for MSX and segregation
of impurities at the initial surface of nickel was suspected to
have an influence. Thus, “in situ” XPS analyses were performed
before oxidation, after heating at 600 ◦ C in ultra-vacuum and
after a limited oxidation duration. Note that the XPS device
cannot heat over 600 ◦ C, and analyses at 600 ◦ C only indicates
what occurs at the very beginning of oxidation and what can
be the consequence of the first oxidation stages. Contrary to
“accelerated tests” which are generally performed in most stud-
ies in order to simulate the life-time of systems, our XPS tests,
that can be considered as “delayed tests”, give information on
first oxidation stages. In the case of commercial materials, no
segregation was detected before oxidation. After oxidation at
600 ◦ C, for instance, up to 15 min or even one hour at an oxygen
pressure of 1 Pa, it was surprising to observe that, for indus-
trial grades, the experimental peak of nickel was composed of
Ni2+ (peak at 854.6 eV) and Ni0 (peak at 852.6 eV) [11], while

Fig. 7. STEM view of NiO/Ni interface and associated EDX silicon profile (Imphy grade).
 A.M. Huntz et al. / Materials Science and Engineering A 415 (2006) 21–32 27

Fig. 8. STEM images (Imphy grade, bright field, BF), (a) outer/inner NiO interface and (b) inner NiO/Ni interface.

on pure nickel, the Ni2+ peak only was present. It was verified,
by thermogravimetry performed in pure argon at 600 ◦ C, that
the oxide thickness, developed in these in situ oxidation tests,
was greater than the XPS analysis depth. Indeed, after oxida-
tion for 1 h in pure argon, the NiO scale thickness was equal to
290 nm whereas the allowed depth analysed by XPS was about
5 nm. Then, the appearance of the oxide surface was observed
by interferometric profilometry and 3D images were obtained
on industrial and pure nickel after 15 min oxidation at 600 ◦ C
in 10−5 atm O2 in the XPS chamber. It clearly appeared that
walls of about 100 nm thick were present along grain bound-
aries of the underlying metal in the case of industrial nickel
(Fig. 13a) as also along some grain sub-boundaries (Fig. 13b),
while the surface of pure nickel remained flat [11] (Fig. 13c).
EDX analyses allowed to detect that these walls were only made
of metallic nickel, while nickel oxide was present on the bulk of
Ni grains [11]. Further sputterings by Ar+ ions in the XPS cham-
ber were successively repeated. Observations by interferometric
profilometry after each sputtering showed that the height of
nickel walls along Ni grain boundaries progressively decreased,

Fig. 9. STEM views, Imphy grade: (a) internal precipitate (arrows) and EDX spectrum showing the presence of Si, Mn and O; (b) intergranular precipitate along
grain boundaries of Ni and associated EDX profile showing Mn, Si, Mg and O.
28 A.M. Huntz et al. / Materials Science and Engineering A 415 (2006) 21–32

Fig. 10. BF-STEM view (Imphy grade) of an interfacial cavity and EDX analysis of precipitate hung to the cavity (rich in Mg, Si, Mn and O).

the observations made at 600 ◦ C. Moreover, the Ni walls along

grain and sub-grain boundaries were also observed after a short
oxidation time at 800 ◦ C in air [7].

4. Discussion on the oxidation mechanism

Concerning the order of magnitude of the parabolic constants

(Table 2), our values are in the range of values given in the litera-
ture [1,3–6,15–17]. Haugsrud and Pedraza [15,16], who worked
with pure nickel (clearly purer than our industrial grades), found
parabolic constants of the same order of magnitude than the kp
value of our pure nickel. So, it is important to note that the pure
nickel oxidation constant is greater than that of industrial grades
and, simultaneously, the oxide scale thickness is about twice
greater.

4.1. Initial stages

At first, let us consider the initial oxidation stages, as pre-

Fig. 11. Pure Ni, DF-STEM view of the simplex layer.
and, simultaneously, precipitates identified by SEM–EDX as
Mn or Ti rich oxides appeared along the grain boundaries, as
seen in Fig. 14. These precipitates were also viewed by TEM.
Post-mortem examinations by XPS of the surface of the oxidised
samples after treatment at temperatures of 800 ◦ C always agree
viously mentioned and studied by “in situ” XPS experiments
associated to interferometric profilometry and EDX analyses.
In the case of industrial grades, impurities such as Mn, Mg,
Ti, Si, which have a strong affinity for oxygen were present
mostly as intergranular precipitates in the underlying metal.
These impurities promoted inward oxygen diffusion, and, during
the initial stage of oxidation, internal oxidation of manganese

Fig. 12. Pure Ni: (a) DF-STEM view of NiO/Ni interface and (b) pores through the NiO layer.
 A.M. Huntz et al. / Materials Science and Engineering A 415 (2006) 21–32
Fig. 13. Surface of the oxidised samples observed by interferometric profilometry after 15 min oxidation at 600 ◦ C: (a and b) Imphy nickel, grain boundaries and
sub-boundaries, respectively, and (b) pure nickel.
and titanium occurred along the grain boundaries of nickel while
NiO crystallites formed at the nickel grain surface. The increase
in volume due to internal oxidation induced an outward flow
of metal and extrusion of metallic nickel on the outer surface
(Fig. 13), extrusion which appeared as walls on grain bound-
aries of the underlying nickel, while the surface of grains were
Fig. 14. SEM observation of intergranular oxide precipitates found after sputter-
ing of the previous metallic nickel walls formed along grain boundaries during
the first oxidation stages.
29
covered of NiO islands. Thermo-elasto-plastic calculations were
performed using finite element methods to verify the possibility
to form nickel extruded walls. Taking into account the volume
of each phase and the mechanical properties of NiO, Ni and pre-
cipitates, calculations confirm such extrusion of nickel which
were indeed observed using TEM (cf. Fig. 6c). Such a particular
reactivity induced an additional driving force for oxygen.
4.2. Comparison of oxide thickness calculated from
thermogravimetric results or measured in SEM
When comparing the oxide thickness calculated according
to Eq. (2) from thermogravimetric data (Fig. 1b) and the oxide
thickness determined by SEM observations (see all the related
micrographs), a slight scattering can be remarked. This is not
surprising as values deduced from thermogravimetric data do not
take into account several phenomena discussed in the following:
(i) The calculations were made considering the volumetric
mass given for the massive oxide (i.e. 6.85 g/cm3 deduced
from crystallographic data). As a great density of pores
were detected through the oxide films, the real volumetric
mass is smaller and the oxide thickness greater than the cal-
culated value. This is sometimes the case, but not always.
30 A.M. Huntz et al. / Materials Science and Engineering A 415 (2006) 21–32
(ii) As shown in Fig. 3, internal oxidation occurred in the bulk
(particularly for MSX nickel, Fig. 3b) and especially along
grain boundaries of both industrial nickel grades. Thus,
the oxygen content of the film was overestimated in the
calculation from thermogravimetric data and consequently
the oxide film thickness also. This parameter induces an
opposite variation when compared to the previous one.
(iii) In fact, calculation from thermogravimetric data cor-
responds to an oxide free growth in the direction
perpendicular to the substrate surface (the surface of the
oxide film is taken as S, the surface of the substrate). Thus,
it corresponds to an anisotropic formation of the oxide film
by nickel ions piling up at the outer surface of the scale [6].
In such a theoretical case, a nickel layer of 1 ␮m would give
an oxide layer of 1.65 ␮m (taking 6.85 and 8.9 g/cm3 for
the volumetric mass of NiO and Ni, respectively). In this
case also, the oxide film would be stress-free. Such events
could correspond to the growth of NiO on pure nickel, but
cannot satisfy the case of industrial nickel for which, as it
will be detailed further on, a non negligible part of the oxide
growth is associated to inward growth by oxygen diffusion.
It means that, at least for industrial substrates, the thickness
calculated from thermogravimetric data is overestimated.
Consequently, it appears that, according to the importance of
each of these three phenomena, differences can appear in the
oxide thickness measurement.
4.3. Oxide growth mechanism
After these considerations, it is important to discuss about
the oxidation mechanism according to the nickel purity. Pure
nickel developed one simple film, while the industrial grades
developed, at the same time, two oxide layers, one outer colum-
nar layer and an inner one with equiaxed grains (see Fig. 2).
The size of equiaxed grains for pure nickel was higher than
those of inner scales for industrial grades. It is expected that
the oxide growth on industrial grades is controlled by counter-
current diffusion, the outer columnar layer being due to outward
cationic diffusion, and the inner one to inward anionic diffusion.
Such an assumption agrees with the shape of the interfaces: the
oxide/oxide interface, from which the outer layer is growing by
cationic diffusion, has a flat surface corresponding to the ini-
tial surface of nickel prior to oxidation. As observed for other
systems (alumina or zirconia forming materials [18,19]), the
oxide/metal interface is convoluted due to the oxygen reactivity
at the inner interface. Such convoluted shapes correspond to a
minimisation of the energy of the system in relation with the
stresses generated by the inner growth of an oxide layer. In the
case of pure nickel, the oxide layer made of equiaxed grains
seems to be related to a cationic growth mechanism. Moreover,
the facetted morphology of the interface seems to be due to a
recession of this later, thus avoiding cavity formation.
In order to verify the assumption concerning the growth
mechanism of NiO on industrial grades and to determine the
growth mechanism on pure nickel, isotopic exchange tests were
made by successive 16 O2 and 18 O2 treatments (Roberval Labo-
Fig. 15. 18 O2 penetration profiles in NiO scales formed at 800 ◦ C on the three
nickel grades (16 O2 , 1 atm, 7 h then 18 O2 , 10−2 atm, 2 h).
ratory, UTC, France), at 800 ◦ C, in the same conditions for the
two industrial grades and the pure nickel [11]. The depth profiles
were established by secondary ions mass spectrometry (SIMS),
CNRS Bellevue, France, with a Cs+ primary beam. The sputter-
ing rate of the nickel oxide was determined from the depth of
the crater measured by profilometry. The obtained profiles are
gathered in Fig. 15 and show that the oxidation mechanism is
different according to the nickel purity. Indeed, it clearly appears
from these depth profiles of 18 O, that in case of pure nickel, 18-
oxygen is just localised at the outer part of the scale due to its
reaction with Ni2+ ions coming from the nickel sample, while,
for the industrial samples, its penetration in the oxide is very
deep, down to the two interfaces (oxide/oxide then metal/oxide)
where it laterally extends. This verifies that, for industrial grades,
the NiO scale grows by simultaneous counter-current diffusion
of Ni2+ cations and O2− anions or gaseous oxygen, while for
pure nickel, the NiO layer grows only by cationic diffusion. Due
to this growth mechanism, the Ni/NiO interface on pure nickel
is fairly flat, only facetted by the oxide grains.
Several questions arise from this result. The first one concerns
the correlation between the growth rate and the diffusion data of
NiO. According to Ref. [1], at 800 ◦ C, the nickel diffusion in the
bulk of NiO is somewhat 109 times higher than the oxygen bulk
diffusion, and along grain boundaries, DNiO Ni ∼ 104 –106 DO .
NiO
Moreover, the comparison of parabolic oxidation constants val-
ues and diffusion coefficients of nickel in NiO indicates that the
oxide scale growth cannot be controlled by bulk diffusion only,
but is ensured by an effective diffusion taking into account bulk
and grain boundary diffusions. The effective diffusion coeffi-
cients can be calculated according to Hart equation [20]:
Deff = (1 − f )Db + fDgb
where f is the fraction of atoms diffusing along grain boundaries,
calculated as f = 3δ/Φ (δ being the grain boundary width conven-
tionally taken as 10−7 cm) and Φ the oxide grain size, varying
between 100 and 300 nm in our case. Considering the pure nickel
with a scale growth ensured only by cation diffusion, it leads to
an effective diffusion coefficient around 3 × 10−11 cm2 s−1 , i.e.
 A.M. Huntz et al. / Materials Science and Engineering A 415 (2006) 21–32
to an oxide thickness, approximately calculated by x2 = 4Deff t,
of the order of 20 ␮m after 48 h oxidation. Such approximating
considerations agree with the microstructural observations and
confirm that on pure nickel, at 800 ◦ C, the oxide scale grows by
cationic diffusion in the bulk and along grain boundaries of the
NiO film.
Now, considering the NiO scale on industrial nickel, two
questions have to be answered: how can oxygen reach the inner
interface of the scale when the diffusion coefficient of O2− ions
is smaller than the diffusion coefficient of Ni2+ ions by several
order of magnitudes and, secondly, why the oxide film is thin-
ner when two counter-current diffusions have to be taken into
account. The first question can be solved if gaseous diffusion
is considered instead of, or simultaneously to, ionic diffusion
for oxygen. This is given possible due to the great porosity in
the oxide films and it is confirmed by the presence (Fig. 15) of
oxygen peaks along the interfaces (oxide/oxide and oxide/nickel
interfaces). Thus, while Ni2+ ions ensure the outward growth of
the oxide scale, gaseous oxygen goes through the porous oxide
film and allows the inward growth of the scale. This gaseous
oxygen diffusion was already suggested by Graham et al. [17].
Moreover, it is important to note that, in the case of industrial
nickel grades, impurities in the substrate which have a great
affinity for oxygen (Si, Ti, Mn) act as a driving force promoting
inward diffusion of oxygen during the first stage of oxidation,
and initiating anionic growth of equiaxed NiO film. This oxide
film progressively formed into the metallic substrate is subjected
to compressive stresses [21] which must induce a decrease of the
diffusion coefficients, enhancing the barrier effect when com-
pared to that of the oxide film formed by cationic diffusion (on
pure nickel). Ni cations have now to go through this barrier
and consequently the oxide growth is reduced. Thus, the whole
thickness of the duplex scale is smaller than the thickness of the
simple scale. Such a difference of behaviour of the oxide layers
formed on the two types of nickel grade will be encountered also
when considering the mechanical characteristics. Nevertheless,
an effect of silica precipitated along the nickel/oxide interface
[22] cannot be completely excluded though TEM observations
did not evidence a continuous silica film.
Another question subsists: why the oxide layer growing by
cationic diffusion on pure nickel is equiaxed while it is columnar
on industrial grades? In the present case, it can be noticed that the
diameter of the columnar grains is of the order of magnitude of
the diameter of the sub-grains initially observed in the substrate.
In the case of industrial nickel grades, the grain sub-boundaries
are marked with tiny metallic precipitates (some nanometers
in size), as are the grain boundaries, and it can be suggested
that the oxidation mechanism along sub-boundaries is the same
as for grain boundaries: in the initial oxidation stages, oxygen
penetrates in sub-boundaries leading to impurity oxidation and
nickel outward flow and extrusion. This was observed in some
cases along dislocation alignment by profilometry (see Fig. 13b).
Such phenomena correspond to anisotropic oxidation and induce
a columnar growth of the oxide grains. In the case of pure nickel,
as the sub-boundaries or grain boundaries are not marked by
precipitates, the oxide nucleation is homogeneous which leads
to an equiaxed oxide film structure.
31
In all cases, due to cationic diffusion, cation vacancies are
created and can coalesce to form the pores observed through
the oxide layers (see Figs. 6b and 12b). Vacancies can also
arrive at the oxide/metal interface. For the pure Ni, creep of the
substrate is allowed and the interface recession seems to com-
pensate the vacancies, as no interfacial pore was detected. This
justifies the facetted interface. In the case of industrial grades,
most of the vacancies resulting from cationic growth (diffu-
sion in the outer oxide layer) are injected in the inner oxide
layer (see Figs. 5, 6b, 8a) and creep of the substrate is avoided
by grain boundary pinning by precipitates. In this case, vacan-
cies can condense at the metal/oxide interface to form voids
(Figs. 6c and 10). This formation of interfacial cavities can then
enhance the anionic contribution. Moreover, some pores can
result from the oxidation of carbon and gaseous release (CO,
CO2 ). Indeed, the effect of carbon, even in small amount, was
already mentioned by other authors [13,14], and carbon can also
be responsible for the important voids, i.e. cavitation, which are
observed in the industrial nickel substrates (Figs. 3d and 6c).
This was not observed for pure nickel, may be because our pure
nickel contains less than 10 ppm impurities.
Concerning the internal oxidation into the industrial nickel
substrates, it is clearly related to the presence of oxidisable
impurities as Si, Mn and Ti. Indeed, no internal oxidation was
observed in pure nickel. The internal oxide deepness slightly
differs between the two industrial grades as also the localisa-
tion of the oxide precipitates (Fig. 3). In case of MSX nickel,
internal oxide particles are present in the bulk and along grain
boundaries while they are mainly localised along grain bound-
aries (but at a deeper extent) in the Imphy nickel. This can be
due to the carbon content higher for Imphy grade whereas metal-
lic impurity content is higher for MSX grade. According to the
order of magnitude of the internal intergranular oxidation depth,
it leads to a grain boundary diffusion coefficient of oxygen in
nickel of the order of magnitude of 10−11 cm2 s−1 which agrees
with literature data [23] concerning oxygen diffusion in nickel
at 800 ◦ C.
5. Conclusion
The oxidation behaviour of nickel is well-known to depend
on many parameters such as surface preparation, atmosphere,
heating procedure, oxidation temperature, presence of impurity,
etc. But, at this date, the effect of impurities on the oxidation
mechanism of nickel is not yet clarified. It was the objective of
this first part to clarify the influence of impurities on the mor-
phology of the NiO scales and on the oxidation mechanisms. It
was possible by coupling microstructural observations at various
scales, analytical techniques and kinetics studies. Three nickel
grades were selected, two industrial ones and a very pure nickel
for which no impurity was detected, even on thin foils, neither at
the initial state, nor after thermomechanical treatments or oxi-
dations performed mainly at 800 ◦ C in air.
Both the scale morphology and the oxidation mechanism are
clearly modified according to the presence or not of impurities.
For pure nickel, without any impurity detected, a NiO film grows
by outward diffusion of nickel, leading to the presence of a sim-
32 A.M. Huntz et al. / Materials Science and Engineering A 415 (2006) 21–32
ple oxide layer with equiaxed grains. The growth rate of this
oxide layer is controlled by effective diffusion of Ni2+ , i.e. con-
tribution of bulk and grain-boundary diffusion. When impurities
are present, i.e. case of commercial nickel grades, two oxide lay-
ers are formed: an outer one with columnar grains due to cationic
diffusion, and an inner one with equiaxed small grains formed
by anionic diffusion. The growth rate is controlled by diffusion
of Ni2+ through the equiaxed inner oxide layer which acts as a
good barrier, so that the growth rate of NiO is slower on industrial
nickel than on pure nickel. Simultaneously gaseous diffusion of
oxygen occurs and ensures the formation of the inner layer. As
a consequence, a duplex scale is formed.
Under the oxide scale, internal oxidation, especially along
grain-boundaries, extends on distances greater than the oxide
scale thickness. The duplex structure of the NiO films is related
to the great affinity for oxygen of elements present in the nickel
substrate as precipitates (Mn, Mg, Ti, Si). These elements react
with oxygen inducing, in the first oxidation stages, an outward
flow and extrusion of nickel along grain boundaries and sub-
boundaries on account of the stresses created by the volume
increase.
Acknowledgements
Thanks to C. Sévérac for XPS experiments and to LPCES
(laboratoire de Physico-chimie de l’Etat Solide), Orsay, for opti-
cal interferometry.
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