Oxidation of Metals, Vol. 40, Nos.

5/6, 1993
The Growth and Structure of Thi n Oxi de
Fi l ms on Ceri a- Sol - Coat ed Ni ckel
F. Cz e r wi n s k i * t and W. W. Sme l t z e r *
Received February 11, 1993; revised June 22, 1993
The influence of 14-nm thick ceria ceramic coatings deposited by the sol-gel
technique on the early-stage oxidation of polycrystalline nickel at 973 K was
studied by analytical electron microscopy, Auger electron spectroscopy,
Rutherford backscattering spectrometry and X-ray diffraction. The size of the
ceria particles in the coating was modified prior to oxidation by vacuum
annealing. It was f ound that ceria particle size is a crucial factor affecting the
oxidation kinetics, oxide microstructure, and distribution of cerium within the
oxide film. Coarse ceria particles applied to the nickel surface were ineffective
in the inhibition of oxidation and were spread throughout the whole oxide.
Coatings with small ceria particles markedly improved the oxidation resis-
tance. After oxidation such particles were present in the surface region of
nickel oxide, acting as the sources of cerium ions segregated at the nickel-
oxide grain boundaries. The stereological analysis of oxide microstructure as
well as microchemical examination supported the predominant role of grain-
boundary segregation of cerium ions decreasing the oxidation rate. The
results are discussed in terms of reactive-element effect on the development of
microstructure of nickel oxide film during initial stages of oxidation.
KEY WORDS: reactive-element effect; nickel oxide; ceria/cerium; sol-gel coating.
I N T R O D U C T I O N
Sol - ge l p r o c e s s i n g u s i n g c o l l o i d a l d i s p e r s i o n s o f h y d r o u s o x i d e wa s d e v e l -
o p e d i n i t i a l l y t o p r e p a r e s p h e r i c a l p a r t i c l e s o f o x i d e n u c l e a r f ue l a n d
*Institute for Materials Research, McMaster University, Hamilton, Ontario, Canada,
L8S 4M1.
tPermanent address: Institute of Metallurgy, Academy of Mining and Metallurgy, 30-059,
Cracow, Poland.
503
0030-770X/93/1200-0503507.00/0 9 1993 Plenum Publishing Corporation
504 Czerwinski and Smeltzer
eliminate the grinding and sieving steps. ~ Currently, the direct calcination
of gels is also being utilized to produce ceramics with high purity and
homogeneity. Although sols are a relatively expensive source of oxides f or
fabrication of bulk ceramic materials, their use to produce the thin surface
coatings is highly cost effective. Compared to the other precursors for the
reactive-elements oxides in coating technology for high-temperature-corro-
sion protection, i.e. the nitrate salts in solutions or molten2 or the oxide
slurry, 3 the sol coatings are characterized by having the :smallest and
best-controlled oxide particle size.
Although the early patent by Pfeil 4 dealt with surface-applied, reac-
tive-element oxides, most of the first three decades of research analyzed
mainly the reactive element as an alloy addition. The studies in the last 25
years have focused also on other types of additions including ion implanta-
tion and coatings. 5 There is a considerable literature dealing with the
influence of reactwe-elements-oxide coatings on the high-temperature-oxi-
dation behavior of NiO-formers, 6 Cr2 03 -formers, 7 and A1203-formers. 8
The beneficial effect of this mode of applying of reactive elements is
reported for NiO and Cr203-formers. The latest study of thin coatings of
nitrate-converted, reactive-element oxides showed no beneficial influence at
all, however, on scale adhesion of A12 03 -formers. 8
In our previous papers 9,1~ we discussed the effect of ceria-sol coatings,
their thickness, substrate pretreatment, preoxidation before coating and
reaction temperature on the oxidation kinetics and growth morphology of
nickel oxide. In this study we consider the role of ceria particle size in
sol-gel coatings and analyze the development of the microstructure of thin
oxide films formed at 973 K on sol-coated polycrystalline nickel.
E X P E R I ME N T A L P R O C E D U R E
Subs t rat e, Coat i ngs , Ox i da t i o n Te s t
Specimens with thicknesses of 1 mm and diameters of 9.5 mm were
prepared from 99.99% purity of polycrystalline nickel rod supplied by A.
D. MacKay, Inc. After grinding through 600-grit SiC paper, the samples
were mechanically polished to a 1-#m diamond finish, cleaned ultrasoni-
cally and annealed at 1173 K for 1 hr in a vacuum of 10 - 7 torr. This
procedure resulted in an average nickel-grain diameter of 100 #m. As a
final step a chemical polish was performed for 40 s at 363 K in a solution
composed of 30 ml nitric acid, 10 ml sulphuric acid, 10 ml orthophosphoric
acid, and 50 ml glacial acetic acid. it To improve surface wetness before
coating, the substrates were preoxidized at 673 K for 2 hr in 1 atm oxygen.
Measured oxygen uptake was 7.7 #g/cm 2 which corresponds to a NiO
thickness of 54 nm.
Thin Oxide Films 505
Ceria sol having a concentration of 5 g CeOE/dm 3 in 0.1 M nitric acid
and containing a nonionic surfactant was prepared using the 20 wt.% colloi-
dal dispersion supplied by Johnson Matthey, Ltd. and the surfactant Triton
X-100 supplied by Aldrich Chemical Co. Inc. Coating deposition by cold
dipping was followed by drying at 363 K for 20 hr in a desiccator and cal-
cination at 573 K for 1 hr in 1 atm oxygen. The weight of coatings after drying
and calcination was 35 and 10 # g/cm 2, respectively. Annealing was performed
for 5 hr in the temperature range of 673-1173 K in a vacuum of 10 -7 torr.
For all samples annealing followed calcination. The thermal evolution of the
ceria grain size was determined by X-ray diffraction (XRD) using nickel-
filtered CuK~ radiation on powder specimens prepared from about 15-/~m
thick ceria films deposited on and stripped after drying from a glass substrate.
Oxidation kinetics at temperature of 973 K in oxygen at a pressure of
5 x 10 -3 torr and for times up to 4 hr were measured in an ultrahigh-vac-
uum manometric apparatus. The samples were heated to the oxidation
temperature in oxygen. Details regarding the oxidation-kinetics measure-
ments were reported previously. 1~
Oxide Composition and Microstructure
The combination of Auger electron spectroscopy (AES) and Rutherford
backscattering spectrometry (RBS) was utilized to characterize the compo-
sition of oxide films. The measurements by a scanning Auger microprobe
(Perkin Elmer PHI 600) were performed while simultaneously sputtering the
oxide film with Ar + ions. The oxide was sputtered from an area of 2 mm a,
and a small part ( < 1%) of this region was analysed. The RBS depth profiles
of oxide films were measured using 1 MeV 4He+ ions at a scattering angle
of 160 ~ and an energy calibration of 1.016 keV/channel. The sample-tilt angle
was 0 ~ A maximum current of 2 nA was used to ensure that the detector
dead time was less than 5% and that beam-heating effects were negligible.
The morphology of coatings and growth surface of oxide was observed
by scanning electron microscopy (SEM). The oxide microstructure was
analyzed in details by transmission electron microscope (TEM-Philips
CM12). Thin foils were prepared parallel to the oxide-metal interface by
two different techniques. For routine analysis the oxide was stripped from
the substrate using a saturated solution of iodine in methanol, la For
high-magnification analysis of the films near the gas-oxide interface, the
samples were prepared by ion thinning using the technique described by
Pint. 13 Ion thinning of oxide from the metal side only was conducted in a
Gatan 600 duomill with an Ar beam at 4-4.5 keV. The TEM images and
selected area diffraction (SAD) patterns, if not otherwise indicated, were
taken at an angle of 0 ~ off the sample normal. The individual ceria particles
506 Czerwinski and Smeltzer
and the segregation of reactive element to NiO grain boundaries were
analyzed by a field-emission gun scanning transmission electron microscope
(STEM, Vacuum Generator Microscopes Ltd. model HB5) with a 3.5 nm
electron probe and windowless Link detector (EDX).
RESULTS
The Modification of Ceria Grain Size in Coatings by Vacuum Annealing
To examine the effect of particle size in a surface-applied, reactive-ele-
ment oxide on the inhibition of high-temperature corrosion, the ceria-grain
diameter in 14-nm thick coatings on nickel substrates was modified by
vacuum annealing before oxidation. Because of the difficulties in determin-
ing the dimensions of extremely small particles (about 5 nm in size) in thin
coatings, the analysis of thermal growth of ceria grains was carried out
separately on 15-#m thick ceramic films produced from the same precursor
by sol-gel technology. The crystallite size calculated according to Sherrer's
equation, 14'15 plotted as a function of annealing temperature is shown in
Fig. 1 together with values derived from SEM and TEM observations. The
error bars for XRD results were calculated assuming a 5% experimental
error in measuring the diffraction breadth.
A high-magnification TEM image of a coating stripped from non-
preoxidized nickel substrate after calcination is given in Fig. 2a. It is seen
from microscopical observations that for 14-nm thick coating the ceria
particles uniformly cover the substrate. The SAD pattern indicates the
presence of small amounts of NiO formed during calcination. Traces of Ni
were also detected, due to incomplete dissolution of the substrate during
thin-foil preparation. The surface morphology of a coating after annealing
at 973 K is shown in Fig. 2b. The mean linear size of ceria particles of
40 nm found after this treatment is about two times larger than the value
obtained from XRD. The XRD method was quite insensitive to variation
in particle size for annealing temperature above 1000 K due to the coarsen-
ing of ceria particles.
Oxidation Kinetics
The oxidation kinetics of pure and ceria-coated nickel are illustrated in
Fig. 3. The oxidation of all samples followed a parabolic relation after an
early transient stage lasting 20-40 rain. The average values of the parabolic
rate constants after 4 hr of exposure at 973 K are listed in Table I. Since the
oxygen uptake during preoxidation at 673 K for 2 hr was from 10 to 100%
of the total oxygen uptake during subsequent oxidation at 973 K, the rate
constants were calculated assuming that the average oxygen uptake is
Thi n Ox i d e Fi l ms 5 0 7
I00
8-
~'~ 4 -
~
2-
. r-(
1 0 -
Q,) e -
~ = ~ s X R D
I l l i i S E M
~ u u ~ u TEM
+
e - v" D / a f t e r d r y i n g
2 7 5 4 7 5
T e m p e r a t u r e (K)
Fi g. 1. Cer i a cryst al l i t e size as a f unct i on of anneal i ng t emper at ur e
det er mi ned by XR D a nd mi cr oscopy. TEM- c oa t i ng st r i pped f r om ni ckel
s ubs t r at e. SEM: sur f ace coat i ng mor phol ogy (973 K) , f r act ur e cross-sec-
t i on of 15- #m t hi ck films (1173 K) .
Ta bl e I. The Par abol i c Oxi dat i on Rat e Con-
s t ant s Cal cul at ed f r om Oxygen Up t a k e Af t er
4 hr Oxi dat i on at 973 K in 5 x 10 - 3 Tor r Oxy-
gen ( Anne a l i ng Ti me 5 hr)
Speci men t r e a t me nt kp (g2 c m- 4 s - 1)
Unc oa t e d 1.80 10 - I 3
Coa t e d una nne a l e d 3.43 10 -14
Anne a l e d at 723 K 2.85 10-13
Anne a l e d at 823 K 2.66 x 10 -13
Anne a l e d at 873 K 2. 30 10 -13
Anne a l e d at 973 K 2. 00 x 10 -13
508 Czerwinski and Smeltzer
Fig. 2. Microscopical observations of ceria coatings: (a) the TEM image and SAD pattern
of a coating stripped from a nonpreoxidized nickel substrate after calcination at 573 K for
1 hr and (b) SEM surface morphology of the coating after annealing at 973 K for 5 hr,
grain boundary in nickel substrate (arrow).
Thin Oxide Films 509
60-
~ 50-
~8
20
010-
0-
~ e e e o u n c o a t e d
-" "--" -" -" c o a t e d u n a n n e a l e d
~-~=== ann. 723 K
r ann. 8 2 3 K
~--'~.~'~ a n n . 873 K
ann. 973 K
0 50 100 150 200 250
Time (rain)
Fig. 3. Oxidation kinetics at 973 K of CeO 2 sol-coated nickel without and after
vacuum annealing for 5 hr prior to the exposure to oxygen (723-923 K).
the mean of the values at the start and finish of oxidation at 973 K. Details
regarding calculations are described elsewhere. 9,1~ The unannealed coating,
which consisted of ceria particles about 5 nm in size, markedly decreased
the oxidation rate of nickel. The difference in parabolic rate constants is
about one order of magnitude. Vacuum annealing resulted in an increase in
ceria particle size and a higher oxidation rate compared to uncoated nickel.
All values of kp for annealed samples are higher than that for uncoated
nickel and the kp values decrease gradually with increase of annealing
temperature in the range of 723-973 K (Table I).
The effect of ceria coatings on reduction of oxidation rate was
characterized by the ratio R defined as:
R = kpi blank/kpi coat ed (1)
where kpi blank and kpi coated are the instantaneous parabolic rate constants
for samples uncoated and ceria-coated, respectively. The values of kpi were
calculated as 2w dw/dt, where w is oxygen uptake per unit area and t is the
time of oxidation. Plots of R as a function of oxidation time are given in
510 Czerwinski and Smeltzer
16
15-
14-
o 131
121
~ 11
9 -~ 10
~ a--
~ 7 -
" 6--
~ a 2
4-
II a--
~ e 2
t
J
/
/
pr eoxi di zed/ anneal ed
0 50 100 i 50 200 250
Ti me ( r ai n )
Fi g, 4. The rat i os o f t he i nst ant aneous values o f par abol i c rat e cons t ant s kpi f or
uncoat ed nickel t o t hat f or cer i a- coat ed nickel as a f unct i on o f oxi dat i on t i me at
973 K. Vacuum annealing: 973 K, 5 hr.
Fig. 4. In this Figure, an addi t i onal pl ot of R is present ed f or a ceria
coat i ng deposi t ed on non- pr eoxi di zed nickel. The base f or R cal cul at i on in
this case was kpi val ue f or non- pr eoxi di zed nickel substrate. Oxi dat i on
kinetics f or this met hod of subst rat e pr et r eat ment are given elsewhere. 9'~~
An essential difference is seen bet ween pl ot s of R f or unanneal ed and
anneal ed samples. Values of R f or anneal ed samples are less t han 1 at all
oxi dat i on times, which indicates t hat ceria coatings consisting of coarse
particles, (l arger t han 10 nm in size) are ineffective in inhibiting oxi dat i on.
Values of R f or unanneal ed coatings are in the range bet ween 10 and 15;
however, a hi gher r educt i on of oxi dat i on rat e is observed f or the coat i ng
deposi t ed directly on t he pure-ni ckel subst rat e r at her t han on a pr ef or med
54-nm-thick, nickel-oxide film.
O x i d e - D e p t h C o m p o s i t i o n
The dept h l ocat i on of ceri um in nickel-oxide films was exami ned by
RBS and AES. The surface area anal yzed f or RBS was about ! mm 2. The
Thin Oxide Films 511
RBS spect r a f or coat ed nickel bef or e and aft er oxi dat i on are shown in Fig.
5a. The concent r at i on profiles deri ved f r om these spect ra are pr esent ed in
Fig. 5b. The spect r um f or a sampl e oxi di zed wi t hout anneal i ng exhi bi t s a
di st i nct cer i um peak. Thi s peak, however in compar i s on to t he unoxi di zed
case, is l ower in i nt ensi t y and has shifted t o l ower energies. The spect r um
for oxi de wi t h the coat i ng anneal ed before oxi dat i on at 973 K does not
show the distinct cer i um peak. I n this case, ceri um is not l ocal i zed in the
vicinity of t he out er surface of oxide, as in t he unanneal ed sampl es, but is
spr ead t hr oughout in the oxi de (Fi g. 5b).
The above RBS spect ra were conf i r med wi t h AES studies. Wher eas t he
RBS spect r um was deri ved f r om oxide film gr own on over 100 grai ns of
nickel subst rat e, the AES signal was gener at ed f r om oxide gr own on one
nickel grain. The results obt ai ned by these t wo met hods were fully consis-
tent. For oxi de f or med on nickel wi t h unanneal ed coat i ngs (ceri a part i cl es
2000
=
O
cJ
(P
c~
(9
CQ
C~
%o
x
1500 x ~)
ooo x
500 ~)
ox 0
o o
) o o o o u n a n n e a l e d/ , unoxi di z e d 9 o
9 * 9 9 u n a n n e a l e d / o x i d i z e d
%
x x x anne al e d/ ox i di z e d x o
~s .%.
i i i i i i i i i I i i i i i i i ~ i I i i i i i t ~ i i I , = ] ~ ,
150 250 350 4:50
Cha nne l numbe r
(a)
Fig. 5. Results of RBS measurements: (a) energy spectrum of l MeV 4He ions
backscattered from ceria-coated before and after oxidation for 4 hr without
and with annealing at 973 K for 5 hr, and (b) cerium concentration vs. depth
profiles, as derived from RBS spectra shown in (a).
5 1 2 C z e r w i n s k i a n d S m e l t z e r
14
~ 1 2
9
9
9
9
v
9
( b )
9
/ 9
/
4- /
- . t 9
/
2- J
: X / x x X X x x X x
4 ~ 9
O-q
o t o
o o o o _ . o unanneal e d/ / unoxi di zed
9 9 9 9 9 unanneal ed/ oxi di zed
x x x anneal ed/ oxi di zed
est i mat ed
dept h r esol ut i on
i " " , .
XxXXxx ~
q]l~ , ~ 0. 0 X
e I ~ X X X
X X X X X
O o % O O o ; ~ t , o ~ o i
20 30 40
D e p t h ( n m )
50
Fi g. 5. Co n t i n u e d .
of 5 nm) the cerium was also concentrated in the surface region of nickel
oxide (Fig. 6). This was not the case for oxide formed on nickel with
annealed coatings, composed of coarse ceria particles.
Morphology of Oxi de Surface
The surface of oxide formed on uncoated chemically-polished nickel is
non-uniform. Differently-oriented nickel grains oxidize selectively. Prefer-
ential oxide formation at nickel grain boundaries was also observed. On
coated nickel, the oxide surface is more uniform; however, preferential
oxide growth is still observed at nickel grain boundaries. The development
of surface morphol ogy of oxide formed on ceria-coated non-preoxidized
nickel during the very initial stages of exposure to oxygen is illustrated in
Figs. 7a- c. It is seen that after 3 rain of oxidation, small grains of nickel
oxide are present on the coating surface (Fig. 7b). Longer exposure to oxy-
gen resulted in an increase of number and size of individual oxide grains
growing on the top of the coating. After approximately 40 rain of oxida-
Thi n Oxi de Fi l ms 513
- - - : - .
i i i i i i J
8i '
6
, i
i i T i - i - i ! ~
0 2 4 6 8 10 12 14 16 18
Z
S P U ' I T E R T I M E ( M I N )
F i g . 6. T h e A E S s p u t t c r - d e p t h profile o f c o a t e d n i c k c l after
o x i d a t i o n at 9 7 3 K for 4 h r ( w i t h o u t annealing).
tion, these changes are relatively small, suggesting that the subsequent
growth process takes place mainly under the coating.
In Fig. 7d is shown the morphology of oxide formed on coated nickel,
annealed before oxidation at 973 K for 5 hr. The coating, composed of
ceria particles with diameters about 20-40 nm, did not protect the sub-
strate against oxidation. After 4 hr of exposure, the oxide film is 380 nm
thick, which is greater than that formed on pure nickel after the same
oxidation time. Also the oxide gram size is much smaller. Once again, the
thickness of oxide grown over the nickel grain boundaries is much higher
than that observed for unannealed coatings (Fig. 7d).
TEM Microstructure of Oxide
The typical microstructure for 360-nm thick oxide formed on uncoated
nickel after 4 hr of oxidation at 973 K presented in Fig. 8 indicates that the
thickness and microstructure of oxide depends on the oxide growth direc-
tion. In addition to well-defined subgrains and dislocation substructures,
areas are present showing Moir~ fringes produced by overlap which occurs
between two NiO crystals. The arrowed Moir6 fringes in Fig. 9, with a
measured spacing of 17 A, are produced due to angular rotation. Assuming
the NiO {220} interplanar spacing as 1.476 A (from ASTM index), a value
of 5 ~ is found for the rotation angle in this region (16).
A bright-field image of oxide formed on ceria-coated nickel annealed
at 973 K for 5 hr before oxidation is shown in Fig. 10. The SAD pattern
514 Czerwinski and Smeltzer
Fig. 7. Surface morphology of nickel oxide: (a), (b), (c) unannealed coatings: (a) after
calcination at 573 K for 1 hr, (b) oxidation for 3 min, (c) oxidation for 30 min, (d) coating
annealed at 973 K for 5 hr--oxi dat i on at 973 K for 4 hr.
Thin Oxi de Films 515
Fig. 8. TEM mi crograph and SAD pat t erns of 360-nm thick nickel oxide formed on
uncoat ed nickel at 973 K. SAD from region 1 was t aken at an angle 28 ~ of the sample
normal .
516 Czerwinski and Smeltzer
Fig. 9. High-magnification TEM image and SAD pattern of oxide formed on uncoated nickel.
indicates the presence of randomly-oriented Ni O and Ce O a phases. Some
of the coarse ceria particles with diameters of about 50 nm are marked.
The TEM microstructure of 165 nm thick oxide grown at 973 K on
coated nickel without additional annealing before oxidation is shown in
Fig. 11. In comparison to oxide formed on pure nickel, coatings with 5-nm
Thin Oxide Films 517
Fig. 10. TEM micrograph and SAD of oxide formed on ceria-coated
nickel, annealed at 973 K for 5 hr before oxidation. Some of the coarse
ceria particles are marked.
ceria particles markedly inhibited preferential oxide formation at nickel
grain boundaries. However, the nickel oxide formed at these sites still seems
to be thicker than that observed at grain faces. Also the thickness of oxide
is still dependent on the grain orientation of the nickel substrate. The SAD
patterns of NiO formed on the two nickel grains 1 and 2, are composed of
rings which are superimposed on the intense spots. The comparison of these
patterns with those obtained for oxide formed on pure nickel suggests that
these maxima are produced by a portion of nickel oxide having an epitaxial
relationship with the nickel substrate. The rings expected for CeO 2 are also
present (Fig. 11).
The high magnification TEM bright-field image of the near-surface
region of this oxide film is presented in Fig. 12a. The structure is composed
of nickel-oxide grains and small ceria particles distributed randomly, at grain
boundaries and within grains. As is seen from SAD pattern (Fig. 12b), bot h
phases in this port i on of oxide are oriented randomly. The nickel-oxide grain
boundaries in this region of oxide film were also examined by STEM/ EDX
to detect the segregation of reactive element. Typical results in Fig. 13
demonstrate the segregation of cerium to NiO grain boundaries.
Stereological Quantitative Analysis of Microstructure
The quantitative analysis of the surface portion of nickel oxide pro-
duced on coated nickel after 4 hr oxidation at 973 K, was performed using
518 Czerwinski and Smeltzer
Fig. 11. TEM micrograph and SAD patterns from regions 1 and 2 indicated, of 165-nm
thick oxide formed on ceria-coated nickel at 973 K. Oxidation time 4 hr.
Thin Oxide Films 519
Fig. 12. High-magnification TEM image (a), and SAD pattern (b) of the surface region
of NiO formed during 4 hr at 973 K on ceria-coated nickel.
images obtained by TEM. Images for exami nat i on by the Leco 20001
image analyser were prepared manual l y from TEM micrographs. Figure
14a gives a schematic representation of the oxide microstructure, manual l y
created on the basis of the bright-field image. The ceria particles seen as a
black phase, are superimposed on the net work of nickel-oxide grain
520 Czerwinski and Smeltzer
3. 0
2. 5
o- -
c"
-I
2. 0
_6
>~1.5
.4--1
o B
t-
tO
.4..a
1.0
0,5 a n a I u n u n u I I n n u a I u I n I I n n n n u u n u I u u u n n u a I
- 20 - 10 0 10 20
Di st ance nm
Fig. 13. TEM bright-field image (a), and corresponding STEM/EDX
analysis of cerium segregation in a NiO grain boundary (b).
Thin Oxide Films 521
ap-
8.88
rllll @o
17.14~.
15.43~.
1 3 . 7 1 Z
3.8. ag~
S. 57~.
6. B6~,
5. 14~.
3.4,3~,
1.71W,
12.e0 e4. ~ mS. ~ 4S.~a 6e. ~
Cm~6TH . m
28. 3C~.
a 5 . 5 ~ .
pp.. 6 ~ .
19.
17'. 01~.
II. 3 4 ~
8.51X
5.61'X
2. f14~.
0.gl~ 4.8~ 8.8~ 12.8~ 16.~ 2B.88
LENGTH nm
Fig. 14. Results of stereological quantitative analysis
of Ce-rich port i on of nickel oxide after 4 hr oxidation
at 973 K: (a) microstructure with elements analyzed
(nickel-oxide-grain-boundary network and ceria par-
ticles as black phase), (b) distribution of Ni O grain
diameters, (c) distribution of ceria particle diameters.
522 Czerwinski and Smeltzer
Table II. Results of Analysis of Near-Surface Region of Oxide Formed on Ceria-Coated
Nickel After 4 hr Oxidation at 973 K
Phase Parameter Value Remarks
Nickel oxide Mean linear grain size of oxide 29.1 nm 6 = 12.9 nm
Surface area of grain boundaries 13.7 105 cm i Assuming a one phase
per unit volume of specimen structure
Ceria Mean linear particle size 5.5 nm ~ = 3.3 nm
Volume fraction 17.3%
Mean linear spacing 12.4 nm 6 = 6.1 nm
between particles
boundaries. A simple, visual assessment of this microstructure supports the
random distribution of ceria particles. The stereological parameters evalu-
ated for NiO and CeO2 are listed in Table II. The distribution of the size
of Ni O grains and CeO: particles are illustrated in Figs. 14b and c,
respectively. Ni O grains in this region are characterized by an average size
of 29.1 nm with higher fractions at 24 and 36 nm. The average diameter of
ceria particles was measured to be 5.5 nm, however, a high percentage of
the particles had a diameter of about 4 nm. The volume fraction of ceria
approximating to 17.3% is relatively high in comparison to the volume of
5- 10% found by Moon 6 after long-time oxidation of nickel at 1173 K. The
spacing between particles of 12.4 nm is much smaller than the nickel-oxide
grain size of 29.1 nm.
DI SCUSSI ON
The Rol e of Ceria Particle Si ze in Sol -Gel Coating
It was stated by George e t a l . 17 that several different reactive elements
produce a similar effect. From the literature it is seen that the effectiveness
of reactive elements can also depend on the element itself and on the
met hod of application. Some of the important factors affecting the
efficiency for a given element seem to be the size and dispersion of reactive
element oxide particles.
The particle-size effect was analysed by Rhys-Jones e t a l . 18 using an
internally oxidized Fe- 20Cr - 0. 02Ce alloy. Increased spacings of CeO2
particles at the alloy surface gave less chromia with more time being
required to form a continuous oxide layer. In this work, the ceria-particle
size in 14-nm thick coatings was modified in the range of 5- 40 nm by
vacuum annealing before oxidation. The experiment clearly demonstrates
Thin Oxide Films 523
t hat the ceria-particle di amet er in the sol coatings is the critical f act or
affecting the oxi dat i on process. It is seen in Fig. 3 t hat a coat i ng cont ai ni ng
ceria particles wi t h di amet ers larger t han 10 nm is ineffective in t he i nhi bi t i on
of oxi dat i on. The oxi de-growt h rat e and oxygen upt ake aft er 4 hr of
exposure are even hi gher t han t hat observed f or uncoat ed nickel. This higher
oxi dat i on rat e is believed to be due to the refi nement of t he nickel-oxide
grai n size and an increase of gr ai n- boundar y density as easy-diffusion paths.
Thi s f act or is pr obabl y the mai n reason r epor t ed in the l i t erat ure f or hi gher
oxi dat i on rates observed for some alloying addi t i ons of reactive elements.
A weight gain in excess of 4 0 - 5 0 % in compar i son t o pur e nickel aft er 142 hr
exposure in 1 at m oxygen at 1173 K was not ed by Moon 6 f or nickel with
alloying addi t i on of 0.6 wt . % Ce. Coat i ngs cont ai ni ng large reactive-ele-
ment -oxi de particles deri ved f r om ni t rat e solutions or slurry are oft en
r epor t ed to exhibit low efficiency or no effect of the reactive elements. 2
The same f act or seems t o be responsible for l ow-prot ect i on propert i es
of t hi ck or non- uni f or m coatings. Thi cker coatings are not so easily
i ncor por at ed i nt o growing oxi de and remai n f or a longer time on the
surface. The size of a reactive-element-oxide particle also increases and
reaches a size, which is ineffective in inhibiting oxi dat i on. Thi s effect is
mor e clearly seen for l ower oxi dat i on t emperat ures, as was observed f or
ceri a-sol -coat ed nickel oxidized at 873 K. 1~ Also, as demonst r at ed in Fig. 4,
the higher efficiency of coatings deposi t ed on nonpr eoxi di zed substrates is
due to the rapi d i ncor por at i on of ceria particles in the growing oxi de film.
A coat i ng deposi t ed on pr ef or med oxide remains on the surface f or a
l onger time as is seen f r om kinetics measurement s. 9,1~
It is clear f r om the dept h l ocat i on of ceri um in an oxide film t hat a
general correl at i on exists bet ween t he l ocat i on of ceri um in the oxide and
t he r educt i on in oxi dat i on rates. 19'2~ Some aut hor s det ect ed t he maxi mum
concent r at i on of reactive el ement at the gas - oxi de interface, 2~ whereas the
ot hers find it at the oxi de- met al interface. 2~,22 Ther e is also l i t erat ure
showing reactive elements disseminated regul arl y in oxide scales. 6,23 Hussey
et al. 24 not ed t hat the l ocat i on of ceri um in an oxidized sput t er-coat ed
i r on- c hr omi um alloy depends on coat i ng thickness. For ineffective, thin-
ceria coatings, the ceri um maxi mum was present at t he al l oy- oxi de inter-
face. Wi t h increasing coat i ng thickness, the maxi mum was shifted t owar d
the out er surface of t he oxide film. In the present case when the coarse ceria
particles are spread t hr oughout the oxide t hey do not reduce the oxi dat i on
rat e compar ed to the uncoat ed nickel (Figs. 3 and 5b). Fr om a compar i son
with t he mi crost ruct ure shown in Fig. 10 and the cor r espondi ng oxi dat i on
kinetics (Fig. 3) coarse CeO2 particles seem to be ineffective as a source of
Ce ion segregants. The size of a CeO2 particle det ermi nes its effectiveness as
a source of Ce ions for segregation at the oxi de boundari es.
524 Czerwinski and Smeltzer
The plot of the ratio R of instantaneous parabolic rate constants
indicates that the effect of a reactive element on the inhibition of nickel
oxidation increases with time (Fig. 4). Two phenomena taking place in the
surface portion of oxide affect these characteristics. During the early stages
of oxidation, very small ceria particles deposited on the surface are
incorporated into the growing nickel oxide. During further oxidation,
nickel-oxide grain boundaries in this region become saturated with Ce
ions, inhibiting the flux of Ni 2 along these boundaries. The principal
nickel oxidation mechanism at 973 K is by outward diffusion of Ni 2
cations via grain boundaries. It is believed that the mechanism of the
reactive-element effect is the blocking of these paths by large Ce 4+ cations.
The distribution of the ceria-particle sizes after 4 hr oxidation in Fig. 14,
depicts that in comparison to relatively uniform size of particles before
oxidation (Fig. 2a), after 4 hr exposure the ceria particle size is rather
non-uniform. It is characteristic that the highest number of particles have
a diameter of approximately 3-4 nm suggesting the preferential dissolution
of smaller particles. Some coarse particles, with a diameter of about 15 nm
are produced in thicker regions of a coating and lead to its non-uniformity.
Development of Oxide Microstructure During the Early Stages of Exposure
to Oxygen
It was possible to deduce the cross-sectional image of an oxide film
formed on ceria-coated nickel after 4 hr of oxidation at 973 K on the basis
of SEM and TEM planar observations (Fig. 15). The total thickness of
oxide, including preoxidation, is 165 nm as estimated from oxygen uptake.
The ceria-rich portion is located in the vicinity of the outer surface. As
estimated from oxygen uptake during the very initial, transient stage of
oxidation, this film should have a thickness of about 30 nm. Some surface
overgrowth of nickel oxide is present at the location of the grai n
boundaries of the nickel substrate. The major part of the oxide film is
present beneath the ceria-modified portion of NiO. After long-time oxida-
tion these overgrowths form a continuous outer film of nickel oxide19;
however, even after 120hr oxidation at 973K the ceria-rich region is
located close to the oxide surface. In this three-layer structure, the thickness
ratio of the outer to inner part, as evaluated from cross-sectional TEM
observations, is about 0.1.
If we assume that ceria particles act as inert markers, their location
indicates the transport mechanism leading to the oxide-structure development
as illustrated schematically in Fig. 16. At the beginning of oxidation, a ceria-
modified nickel oxide film is formed by outward Ni 2+ diffusion. The nuclea-
tion of small NiO grains on the top of ceria coatings after a few minutes of
Thin Oxi de Films 525
Oxidation temperature 973 K
OxidatiOn time 4 h
02 - gas
Ni Oovergrowth
- ~ NiO+CeO2
E= randomly oriented
NiO oriented
epitaxially
with Ni substrate
grain boundary
Ni substrate
Fig. 15. Schematic diagram of cross-sectional microstructure de-
velopment of NiO grown on ceria-coated nickel at 973 K for 4 hr.
Oxidation temperature 973 K
02 - gas
i i i i l l l l l I I i i i i I ~ I I / I
Nickel
C e O 2
NiO from preoxidation
02 - gas
/
2 e / N i 2 + 2 e - l l O 2 "
i
, ,
I
Nickel
NiO overgrowth
NiO+CeO 2
NiO
Fig. 16. Schematic diagram of mechanism of NiO
growth on ceria-sol-coated nickel during the initial
stages of oxidation.
526 Czerwinski and Smeltzer
oxidation (Fig. 9) supports this mechanism. This oxide layer contains ceria
particles and cerium ions segregated at boundaries. Subsequent growth of
nickel oxide occurs above and beneath this ceria-modified layer probably by
outward Ni 2+ cations and inward 0 2- anions diffusion. The present
measurements and observations do not distinguish whether oxygen diffusion
occurs only in the ceria-modified layer or completely through the oxide film.
CONCLUSIONS
1. In surface-applied, sol-gel coatings on polycrystalline nickel, the
size of ceria particles is a decisive factor affecting the oxidation
kinetics, oxide microstructure and distribution of cerium within the
oxide film. Coarse ceria particles with diameters higher than 10 nm
in a coating are ineffective in decreasing the nickel oxidation rate
and are spread throughout the oxide. Small particles with a mean
size of 5 nm markedly inhibit the oxidation rate and after 4 hr
oxidation at 973 K are located in the surface region of the oxide
film and act as sources of cerium-ion segregation in NiO
boundaries.
2. The analyses of oxide microstructure and microchemistry supported
the predominant role of grain-boundary segregation of cerium ions
in decreasing the nickel oxidation rate at 973 K.
3. Examination of oxide-growth surface, microstructure and cerium
location indicates that the following mechanism can be proposed
for oxide growth on ceria-sol-coated nickel during the initial 4 hr
oxidation at 973 K: (i) during very early stages of exposure to
oxygen, a ceria-modified nickel oxide film is formed by outward
Ni 2+ diffusion; this portion of oxide with ceria particles and
cerium-ion segregant in grain boundaries is believed to be transport
controlling for steady-stage oxide growth, and (ii) oxide growth,
following this transient period takes place predominantly under the
ceria-modified portion of nickel oxide probably by inward oxygen
diffusion.
ACKNOWLEDGMENTS
The authors express their appreciation to the Natural Sciences and
Engineering Research Council of Canada for financial support of this
research. We also wish to thank Dr. R. G. Macaulay-Newcombe for
skillful assistance with the RBS analysis and Dr. A. Perovic for the EDX
examination.
Thin Oxide Films 527
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