A comparative study of heat treatment temperature inuence on the thickness of

zirconia solgel thin lms by three different techniques: SWE, SEM and AFM
Esmaiel Nouri
a
, Mohammad Shahmiri
a
, Hamid Reza Rezaie
a,
, Fatemeh Talayian
b
a
Department of Materials and Metallurgical Engineering, Iran University of Science and Technology (IUST), Narmak, Tehran 16846-13114, Iran
b
Department of Materials Engineering, Sahand University of Technology, Tabriz 11111-53317, Iran
a b s t r a c t a r t i c l e i n f o
Article history:
Received 26 July 2011
Accepted in revised form 18 November 2011
Available online 26 November 2011
Keywords:
ZrO
2
thin lm
Solgel
316L SS
Heat treatment
Thickness
A clear ethanol based precursor sol obtained using zirconium acetate hydroxide was utilized for the deposi-
tion of nanometer ZrO
2
thin lms on 316L stainless steel substrates by a solgel dip coating process. The in-
uence of heat treatment temperature on the structural evolution of the lms was examined using X-ray
diffractometry (XRD) and Fourier transform-infrared spectroscopy (FT-IR). The results indicated that the
adopted production route led to the formation of an amorphous structure at 200300 C and surface tetrag-
onal (t-ZrO
2
) and monoclinic (m-ZrO
2
) zirconia phases at 700 C and 900 C temperatures, respectively.
Microstructural studies by a scanning electron microscopy (SEM) showed that the morphology and size of
the particles of ZrO
2
lms depend upon the heat treatment temperature. The effect of ring temperature
on the thickness of ZrO
2
nanometer thin lms was studied by three different techniques: single-
wavelength ellipsometry (SWE), SEM and atomic force microscopy (AFM). The lm thickness measured by
the SWE and SEM techniques, as a function of heat treatment temperature, was in close agreement, elucidat-
ing a major decrease when heated up to 700 C, and a slight increase between 700 and 900 C. As determined
by the AFM studies, the thickness changes were similar to those of SWE and SEM results during the former
step, up to 700 C, but it appeared to be constant in the later temperature interval. The AFM prole images
showed an increase in surface roughness of the lms with rising of the heat treatment temperature.
2011 Elsevier B.V. All rights reserved.
1. Introduction
Various ultra thin solid lms of ZrO
2
, TiO
2
, SiO
2
, etc., have been
previously prepared on different metal substrates such as magnesium
alloys [1], aluminum [2] brass [3], low carbon steel [4], mild carbon
steel [5,6], galvanized steel [7,8] and stainless steels specially 316L
[913], using several techniques including physical vapor deposition
(PVD) [14], chemical vapor deposition (CVD) [15], electrodeposition
[12], spray pyrolysis [7,8], plasma spray [11,16] and solgel process
[1,2,46,9,10,13]. Solgel is one of the most promising techniques
for the synthesis of various coating lms, because it possesses a num-
ber of advantages over other techniques, such as low processing tem-
perature, easy coating of large surfaces, excellent control of the
precursor solution stoichiometry, possible formation of porous lms
and homogeneous multicomponent oxide lms, inexpensive equip-
ment and good control of lm thickness [9,17]. The solgel lms
were used in order to improve some properties of metallic substrates
like corrosion resistance [1,2,4,5,9,10,13], oxidation behavior [6],
thermal barrier [18] and optical applications [19,20].
It is well known that further improvements of these properties de-
pend strongly on the thickness of solgel thin lms. For instance, it is
found that the thickness of ZrO
2
coatings is a crucial factor affecting
the corrosion and oxidation behaviors, i.e., a multi-layer coating is
much more effective than the single-layer one [46,9,13]. The lm
thickness by itself and/or by affecting on the other microstructural
features, like cracking, may control the structural behavior of the
coatings. In a more detailed description, cracking onset temperature
depends on lm thickness and thicker lms tend to crack at lower
temperatures, in fact the thickness can affect on the tensile stresses
generated during the heating-up and isothermal heating (annealing)
stages of solgel thin lms [21].
According to some previous investigations on the lms thickness
produced by solgel dip coating process [22]; it was found that vari-
ous parameters can affect the coating thickness. These parameters in-
clude the coating cycles, withdrawal speed and angle, which is
normally 90 and the lm thickness is different on both sides of the
sample for other angles, the concentration of the solution, heating
rate and soaking time. Solution properties affecting the lm thickness
are pH, viscosity, surface tension, vapor pressure and relative humid-
ity above the coating bath [23].
There are many reports investigating the how effecting of the
aforementioned parameters on the thickness of solgel lms deposit-
ed on non-metallic substrates, but a few, dealing with the effect of
Surface & Coatings Technology 206 (2012) 38093815
Corresponding author. Tel.: +98 21 77240540; fax: +98 21 77240480.
E-mail address: hrezaie@iust.ac.ir (H.R. Rezaie).
0257-8972/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2011.11.030
Contents lists available at SciVerse ScienceDirect
Surface & Coatings Technology
j our nal homepage: www. el sevi er . com/ l ocat e/ sur f coat
heat treatment temperature on the thickness of solgel thin lms de-
rived on metallic substrates. In addition, a few attempts have been
made to study microstructural evolution of the thin lmcross-sectional
views, deposited on non-metallic and brittle substrate like kinds of
glasses such as silica [2428] and sodalime glasses [19]. However, to
the best of our knowledge, there is no paper that reports a microscopic
study on the cross section of the solgel derived nanometer thin lm
deposited on metallic substrate.
In the present study an attempt is made to develop a new procedure
for microscopic characterization of the solgel thin lm cross-sectional
views, prepared on metallic substrates. For this purpose, ZrO
2
thin lms
were deposited by the solgel dip coating route on 316L stainless steel
using the ethanol solution of zirconium acetate hydroxide as precursor.
The inuence of heat treatment temperature on the crystallization,
phase transformation, thickness and morphology of thin lms was inves-
tigated and characterized by XRD, FT-IR and SEM. The 2 range of XRD
patterns was selected based on our previous study [9], in which the
peaks belonging to ZrO
2
phases have only appeared. The thickness of
the nanometer and nanostructure thin lms as a function of heat treat-
ment temperature was measured by three different techniques: SWE,
SEM and AFM, for a comparative investigation on the measured values.
2. Experimental procedures
2.1. Substrate preparation
In this study a 316L austenitic stainless steel (sample, hereafter)
sheet with a thickness of 2 mm was used as a substrate for surface
treatments. The composition of sample has been reported in the pre-
vious study [9]. The sheet was cut into 20 mm10 mm plates for coat
driving, and then the surface and cross sectional characterizations.
The samples were polished with SiC abrasive papers of successively
ner grit down to 2500 grit and then were mirror polished with dia-
mond paste (1 and 0.5 m particles). Finally, the samples were
degreased with acetone using an ultrasonic cleaner.
2.2. Preparation of ZrO
2
stable sol
The ZrO
2
sol was prepared using 3 g zirconium acetate hydroxide
((CH
3
CO
2
)
x
Zr(OH)
y
, Sigma-Aldrich) which was gradually solved in
50 ml ethanol (C
2
H
5
OH). The solution was mixed with 2.5 ml acetone
(CH
3
COCH
3
) to prevent the formation of zirconium hydroxide. Zeta
potential of ZrO
2
solution as a function of pH was measured using a
zeta potential analyzer (Model 3000 Zetasizer, Malvern Instruments,
Malvern, U.K.) and the obtained prole is shown in Fig. 1. According
to these measurements, the pH of the nal solution set is 3.2 by drip-
ping nitric acid. The solution was homogenized with a magnetic stir-
rer for 1 h at room temperature until a transparent sol was obtained.
No precipitate or turbidity was observed even after 6 months.
2.3. Preparation of ZrO
2
thin lms
The deposit of the ZrO
2
thin lms on the samples is achieved by a dip-
coating device. This device (a homemade design) is constitutedof a sealed
piston in a steel cylinder to surmount its limps, a surrounding wall
squared in glass as a humidity controller and an electrical motor permit-
ting us to control the immersion and withdrawal speeds of the sample in
the sol. After 24 h aging, the samples were dip coated in the ZrO
2
solution
witha rate of 4 cm/min, andthenpulledout withthe same rate. However,
in each case (SWE, SEM and AFM studies); particular processes were ap-
plied for the measurement of the thickness of thin lms, which included
the lm derived area and number of coated samples.
2.3.1. SWE studies
In this case, the whole area of each sample surface was dip coated
as mentioned earlier. After suitable drying and heat treatment
processes (explained later on), the thickness and refractive index of
ZrO
2
nanometer thin lms were measured by an ellipsometer
(model DVA-36VMW, Mizozojiri Optical Co., Ltd.) using a HeNe
laser as the light source with a wavelength of 632.8 nm.
2.3.2. SEM studies
A new procedure was developed to view and measure the thick-
ness of thin ceramic lms on metallic substrates with SEM. We called
this preparation and observation method as FSCF process, which is
an acronym of its four main stages: xation, sealing, coating and frac-
ture. A schematic illustration of the FSCF process is shown in Fig. 2.
First, two prepared substrates were xed to each other with a x-
ative frame of 316L stainless steel, the same material with the sub-
strate to avoid thermal expansion problems (Fig. 2(a) and (b)). In
this step, the top faces of samples and xative frame should be at
the same level. Then, the gap generated between two xed samples
was lled (Fig. 2(c)) by using a sealer which was a mixture of polyes-
ter and CaCO
3
, as a ller resin, and benzoyl peroxide as a hardener.
The sealed samples were slightly polished using that 0.5 m particles
diamond paste and degreased with acetone by the ultrasonic cleaner
before deriving solgel thin lms. In the next step, as shown in
Fig. 2(d), dip coating process was carried out on the samples and
then dried and heat treated (Fig. 2(e)) with a procedure, explained
in the following section. The last step included the fracture of nal
coated and synthesized samples along the sealed line which was car-
ried out after unxing the samples from the xative frame. The frac-
ture process should be taken place on a prop, located on the
backside of the samples; along two directions shown in Fig. 2(f).
After separating the samples, the cross sectional view and lm thick-
ness measurement were achieved by a SEM (WEGA\\TESCAN).
2.3.3. AFM studies
Both the surface roughness and thickness of the ZrO
2
lms on
samples were measured by an AFM (DME A/S, SPM, DS M95 series,
Denmark). We operated the instrument in the AC mode: the cantile-
ver is oscillated at the resonance frequency and the tip to sample sep-
aration is regulated in order to obtain a constant reduction in
oscillation amplitude. The cantilever and tip units, are made from sil-
icon. For AFM imaging, a part of substrate surface was covered with a
refractory banderole and then a 3-layered lm was applied on the
specimen. After detaching the banderole, the height of generated
step on one side, i.e., difference between the uncoated surface and
coated surface was measured as the lm thickness.
Fig. 1. Zeta potential curve of ZrO
2
solution.
3810 E. Nouri et al. / Surface & Coatings Technology 206 (2012) 38093815
In all three studies, after dip coating, the soaked substrates were
hung in the open air for the sake of lm drying. After drying in an am-
bient atmosphere, they were further dried in an oven at 80 C for 1 h
followed by furnace heating at 400 C for 30 min in order to remove
most of the organic load, except those samples which were heat
treated at 200 C and 300 C. The above process of dip-coating, drying,
and heating at 400 C was repeated three times to minimize the pro-
duced defects such as cracks and pores, which resulted from shrink-
age of wet thin lms. The 3 layer coated samples were nally
calcined in a quartz-tube furnace at 200, 300, 400, 500, 600, 700,
800 and 900 C with a heating rate of 5 C/min and a soaking time
of 50 min. Heating above 700 C was carried out under an argon
atmosphere.
2.4. XRD and FTIR studies
Structural evolution and phase composition of the annealed ZrO
2
thin lms were determined by XRD and FT-IR techniques. The XRD
results obtained using a PHILIPS-PW1800 diffractometer with Cu K
radiation source (=1.5406 ) in the range of 2561 with 0.02
step. The ICCD les were used to identify the crystalline phases of
XRD patterns. X-ray diffraction data along with the following
DebyeScherrer's formula was used for an understanding of the crys-
tallite size changes in synthesized nanostructured ZrO
2
lms accord-
ing to heat treatment temperatures:
d
kcos

where d is the crystallite size (nm), k=0.9 is a correction factor to ac-

count for particle shapes, is the wavelength of Cu target equals
1.54056 , is the full width at half maximum intensity (FWHM)
and is the diffraction peak angle (the Bragg's angle).
The FT-IR spectra of the lms were recorded by a spectrometer
(SHIMADZU-IRsolution, 8400S series, Japan) in the wave number
range between 200 and 4000 cm
1
.
3. Results and discussion
Fig. 3 shows the XRD patterns of 3 layers coated samples with ZrO
2
nanostructured thin lms and heat treated from 200 to 900 C in the
2 ranges of 2561, and ranges of 2 in which the peaks belonging to
ZrO
2
phases appeared [9]. As observed in this gure, there are two
more intensive distinct peaks at (111) and (200) planes that corre-
spond to the Chromium+Iron+Nickel cubic phase (ICCD le 33-
0945). It can be seen that the calcined nanocoatings that are amor-
phous at 200 and 300 C may be due to organic compounds contained
in the lms. However, the threshold temperature for the appearance
of crystallinity in the lms seems to be in the range of 300400 C.
The crystallinity improved with increasing heating temperature, so
the heat treated samples at 400 and 500 C show a weak peak at
(111) plane corresponding to tetragonal and/or cubic phases of ZrO
2
.
Hence, it is difcult to distinguish the t-ZrO
2
phase from the c-ZrO
2
at
these temperatures. The intensity of the (111) diffraction peak became
stronger and four more peaks at (002), (200), (202) and (311) planes
appeared when the lms were red at 600 and 700 C, suggesting the
high crystallization of t-ZrO
2
phase (corresponding to the ICCD le
number 17-0923). Three more peaks appeared at (111), (111) and
(200) planes, corresponding to m-ZrO
2
phase (ICCD le 17-1484),
when samples were heat treated at 800 C. In other words, as the tem-
perature rises, the amount of monoclinic phase increases on the ex-
pense of the tetragonal phase, thus the t-ZrO
2
and m-ZrO
2
phases co-
exist at 800 C. After heat treatment at 900 C, there was no trace of
t-ZrO
2
phase and the monoclinic was the only form of ZrO
2
.
As mentioned earlier, the (111) peak intensity increased with an in-
crease in the annealing temperature. However, the full width at half-
maxima (FWHM) of the (111) peaks was decreased with ring tem-
perature between 400 and 700 C. Hence, based on DebyeScherrer's
formula, the crystallite sizes of thin lms would increase with temper-
ature in tetragonal form.
The evolution of the ZrO
2
nanostructure lms formed on the sam-
ples up to crystallization and phase transformation processes as a
function of heat treatment temperature was studied by FT-IR spec-
troscopy in the wave number range between 200 and 4000 cm
1
and the results are shown in Fig. 4. The spectra of unheated lm
showed the characteristic bands of (OH)/H
2
O and organic groups.
The absorption peaks at 2931 and 2881 cm
1
before heat treatment
may be ascribed to the chelating H-bridge of the O\H, and the
peaks at 1448 and 1537 cm
1
belong to the Zr\O\C [29]. These
bands disappeared after heating the sample at or beyond 500 C.
The broad peak centered at about 3566 cm
1
is due to the OH
stretching vibration indicates the presence of molecular water.
Fig. 2. A schematic illustration of the FSCF process.
3811 E. Nouri et al. / Surface & Coatings Technology 206 (2012) 38093815
These bonding vibrations gradually disappear with increasing the cal-
cination temperature. The presence of molecular water in the sample
calcined at 300 C may be due to the absorption of ambient moisture
during the test. As the temperature increases to around 500 C, they
are almost undetected. A band at 1387 cm
1
which also disappeared
after heating at 500 C corresponds to NO
3

group originated from the

addition of HNO
3
. The absorption peaks at 1614 cm
1
belong to C_O
bond vibration and that their intensity decreases with temperature
rising.
The lms annealed at 100 and 300 C exhibit a relatively broad
band centered at 450 cm
1
assigned to the amorphous ZrO
2
(a-
ZrO
2
). It is known that the a-ZrO
2
is appeared at wavenumber of
470 cm
1
[30]. The intensity of the band assigned to the a-ZrO
2
phase, in the 500 C annealed lm is stronger in comparison to the
300 C, afrming thereby the XRD investigations (Fig. 3), which
have conrmed the presence of crystallinity in the former. It should
be remarked that the bonds at wave numbers around 450 cm
1
also correspond to ZrO bond in tetragonal structure as reported in
the literatures [13,3033]. As observed in the gure, there is a peak
of t-ZrO
2
around 455 cm
1
at 700 C, but with increasing tempera-
ture, it splits to ve 336, 398, 479, 555 and 720 cm
1
bands at
900 C. Based on L. Shi et al. studies [30], this set of peaks corresponds
to the m-ZrO
2
phase.
As a consequence, the spectra of the thermal treated samples
showed that the intensity of absorption peaks due to the characteris-
tic bands of (OH)/H
2
O, organic groups and Zr\O\C, most of which
decreases and eventually vanished while that of Zr\O increases
strongly with heating temperature.
All the 3 layer coated samples were visually transparent and uni-
formover the surface. The SWE measured refractive index (n) and av-
erage thicknesses of the lms (t
f
) with the experimental errors () as
a function of heat treatment temperature are given in Table 1. It can
be seen that the lm thickness steadily decreases with increasing
the temperature up to 700 C, and then increases between 700 and
900 C. However, the refractive index of the lms increases slightly
with increasing heat treatment temperature.
Fig. 5 shows the cross-sectional views of the 3 layer ZrO
2
coated
samples with different thicknesses which resulted from ring at
200800 C. The pictures are taken from fractured surfaces of the
lms which were prepared using FSCF process. Based on XRD
(Fig. 3) and FT-IR (Fig. 4) studies, Fig. 5(a) and (b)(d) must Fig. 4. FT-IR spectra for solgel ZrO
2
-coated on samples at 25900 C.
Fig. 3. X-ray diffraction patterns of ZrO
2
-coated samples at 200900 C.
3812 E. Nouri et al. / Surface & Coatings Technology 206 (2012) 38093815
respectively belong to the amorphous and crystallized ZrO
2
thin lms
in which all of them consist of particles. A comparison of Fig. 5(a)(d)
shows that in the lm heated at 200 C, Fig. 5(a), there are some
spaces at regular intervals between particles which are lled by a ma-
terial. According to XRD and FT-IR analysis, it may be the organic
compounds that remained in the lms. Fig. 5(b) shows some gaps be-
tween the particles, presumably left behind after evaporation of the
organic compounds at 400 C treatment. When the temperature
increased up to 600 and 800 C, the packing density of the lm in-
creased due to the disappearance of those gaps between the particles.
This densication of layers with temperature may be the cause of in-
creasing the refractive index of the lms as given in Table 1.
It can be seen that the particle morphology and size of the ZrO
2
lms depends upon the heat treatment temperature. The microstruc-
ture of the lms consisted of elongated and angular shaped particles
at 200 C, and then they appeared as round shape at 600 and
800 C. In addition, the average particle size increased from 78
5 nm at 200 and 400 C (Fig. 5(a) and (b)) up to 1089 nm at
800 C (Fig. 5(d)). The particle size increasing with temperature con-
rms the results obtained fromthe XRD studies and DebyeScherrer's
formula. A larger difference in size was observed between the large
and small particles at higher temperatures which is attributed to
the growth of the nanoparticles in the interior region of lms.
Fig. 6(a), (c), (e) and (g) shows the AFM three-dimensional (3D)
images of the ZrO
2
lms on one side coated and heat treated samples.
The height difference between the upper surface of each lm and its
substrate surface indicates the thickness of the lm. Images of height
proles, in three different regions, corresponding to the AFM's tip
scanning on the surfaces of those one side coated samples at different
temperatures are shown in Fig. 6(b), (d), (f) and (h). These proles
were produced by scanning the tip on the stepped surface of heat
treated lms, from substrate toward the lm using a cross-section
analysis program of the AFM. It can be seen that after crossing the
tip over the step and just before dropping into the stable thickness
of the lm, the tip encounters a few micrometer shoulder in all the
lms which were formed during the sol immersion of the samples
containing a banderole. In addition, the height prole images of
lms showed an increase in roughness with rising of the heat treat-
ment temperature.
The effect of heating temperature on the thickness of ZrO
2
nano-
structure thin lms was studied using SWE, SEMand AFMtechniques.
Resulting thickness values are the average values of the ten indepen-
dent measurements performed at the same environmental conditions
at each temperature to get the reliable thickness values. The average
error between measurements within each series is shown by error
bars on the plots of Fig. 7. The SWE and SEM measurements, in a
good agreement, elucidated that the thickness decreases with
Table 1
The thickness (t
f
) and refractive index (n) of ZrO
2
thin lms according to the heat
treatment temperature (T), measured by SWE technique.
T (C) t
f
(nm) n
200 2532 1.79
300 2053 1.91
400 1754 1.97
500 1603 2.08
600 1453 2.16
700 1352 2.21
800 1422 2.18
900 1514 2.14
Fig. 5. SEM images of cross sectional view of ZrO
2
-coated samples at (a) 200 C, (b) 400 C, (c) 600 C and (d) 800 C.
3813 E. Nouri et al. / Surface & Coatings Technology 206 (2012) 38093815
different rates up to 700 C treated samples, and then increases be-
tween 700 and 900 C. The AFM measured thickness also decreases
like those of SWE and SEM up to 700 C, but then no remarkable
changes are observed. Moreover, the measured lm thicknesses by
AFM are slightly more than those measured by SWE and SEM,
which may be attributed to the some parameters such as the AFM
tip quality and magnitude of surface loads aggregated between tip
and sample.
Fig. 6. 3D and height prole AFM images of ZrO
2
thin lm on the samples at (a, b) 200 C, (c, d) 400 C, (e, f) 600 C and (g, h) 800 C.
3814 E. Nouri et al. / Surface & Coatings Technology 206 (2012) 38093815
It is known that the solgel coatings are strongly dependent on
the heat treatment conditions, because the substratelm and the
lm body interactions progress by heating. As represented in the lit-
erature [24,26], each heat treatment process is performed rst to
dry the deposited lms to a porous oxide layer (here, ZrO
2
) and sec-
ond to densify the lm body by modifying the original pore size.
The point to be noted here is that the applied lm dries to a porous
structure layer (like that one shown in Fig. 5(b)) having a general
composition of ZrO
2(x+y)/2
(OH)
y
(OR)
x
. OH and OR groups consti-
tute about 25%; of the total weight, whose OH groups make up
about 20% of the total weight, while OR groups contribute perhaps
2%4% [24]. Hence, the largest contraction should be occurred in the
drying stage and this may be the period when cracking in the lms
is most likely to occur. The slop of thickness vs. heat treatment tem-
perature plots in SWE, SEM and AFM measurements, as shown in
Fig. 7, conrms this opinion. It can be seen that the drying and densi-
cation of the lms are not smooth functions of temperature and the
largest reduction of thickness occurred in the lms heat treated
below or at 400 C.
The thickness proles, shown in Fig. 7, also indicate the thickness
reduction by 43% (for SWE and SEM measurements) and 33% (for
AFM measurement), when the lms are completely densied, which
is comparable with other investigations on solgel lms [24]. This
implies that in the present study, the elimination of about 2/3 of the
pore space was achieved during the densication.
The most noticeable feature in Fig. 7 is an increase of approxi-
mately 5% in thickness of treated lms above 700 C which was ob-
served in SWE and SEM measured thicknesses. Based on the XRD
and FT-IR results, the t-ZrO
2
phase transform to m-ZrO
2
phase
above 700 C. On the other hand, researchers have previously
reported that this phase transformation of ZrO
2
is associated with in-
creasing in volume [34]. Since the m-ZrO
2
phase occupies a larger vol-
ume compared with the t-ZrO
2
. The positive change in volume during
the transformation may be the cause of increasing the lm thickness
in heat treated samples at 800 and 900 C. In the case of AFM mea-
surements no increase in volume or thickness was detected. So it
sounds that the SWE and SEM measurement are more reliable than
AFM results.
As discussed earlier, the ZrO
2
lms tend to shrink as heat treat-
ment proceeds, resulting in pore disappearance and densication.
This, in turn, produces tensile stresses in the lms, the magnitude of
which should increase as the densication proceeds. Therefore, it
may be concluded that the crystallization into m-ZrO
2
phase is sup-
pressed by the tensile stress arising in these thin lms.
Based on the present results, the more densication of ZrO
2
thin
lms was obtained at higher temperatures such as 700 C, but the
highest corrosion resistance was observed in heat treated samples
at 500 C (our previous study [9]). It sounds that the remaining
trace of organic compounds in the lms is useful to improve corrosion
resistance of the samples. Maybe it was related to the tensile stresses
which rise in the lms with increasing heat treatment temperature
and accelerate the corrosion rate of the samples coated at higher tem-
peratures. It is also possible that the lm has a compromised compo-
sition between good densication and retained part of the organic
structure that could act giving hydrophobic characteristic to the
structure.
4. Conclusions
A solgel dip coating process has been employed to derive ZrO
2
nanostructure thin lms on 316L SS using zirconium acetate hydrox-
ide as precursor. The inuence of heat treatment temperature on lm
thickness was studied using SWE, SEM and AFM techniques. The re-
sults obtained in the present study are as follows:
1. The amorphous, tetragonal and monoclinic phases of ZrO
2
appeared
in the nanostructure thin lms.
2. With increasing heat treatment temperature, the lm thickness
decreases and refractive index increases.
3. It sounds that the SWE and SEM studies are more reliable than
AFM, because it could not detect the lm thickness increasing
above 700 C which may be a result of the tetragonalmonoclinic
phase transformation in ZrO
2
thin lms.
4. The amorphous and crystallized ZrO
2
thin lms were consisted of par-
ticles in which their size and morphology change with temperature.
References
[1] Q. Li, X. Zhong, J. Hu, W. Kang, Prog. Org. Coat. 63 (2008) 222.
[2] X.F. Yang, D.E. Tallman, V.J. Gelling, G.P. Bierwagen, L.S. Kasten, J. Berg, Surf. Coat.-
Technol. 140 (2001) 44.
[3] J.P. Holgado, M.P. Sanchez, F. Yubero, J.P. Espinos, A.R.G. Elipe, Surf. Coat.Technol.
151152 (2002) 449.
[4] L. Fedrizzi, F.J. Rodriguez, S. Rossi, F. Deorian, R.D. Maggio, Electrochim. Acta 46
(2001) 3715.
[5] M.A.D. Crespo, A.G. Murillo, A.M.T. Huerta, C.Y. Zamora, F.J.C. Romo, J. Alloys
Compd. 483 (2009) 437.
[6] H. Li, K. Liang, L. Mei, S. Gu, Mater. Sci. Eng. A 341 (2003) 87.
[7] R. Romero, R.L. Ibanez, F. Martin, J.R.R. Barrado, D. Leinen, Surf. Coat. Technol. 200
(2006) 6606.
[8] R. Romero, F. Martin, J.R.R. Barrado, D. Leinen, Surf. Coat.Technol. 204 (2010) 2060.
[9] E. Nouri, M. Shahmiri, H.R. Rezaie, F. Talayian, Surf. Coat.Technol. 205 (2011)
5109.
[10] M. Atik, P. Neto, L.A. Avaca, M.A. Aegerter, Ceram. Int. 21 (1995) 403.
[11] I. Gurappa, Surf. Coat.Technol. 161 (2002) 70.
[12] I.E. Cabrera, H.O. Hernandez, R.T. Sanchez, M.E.C. Garcia, P.B. Perez, L. Martinez,
Mater. Lett. 58 (2003) 191.
[13] S.K. Tiwari, J. Adhikary, T.B. Singh, R. Singh, Thin Solid Films 517 (2009) 4502.
[14] B.K. Jang, Surf. Coat.Technol. 202 (2008) 1568.
[15] Z. Xu, J. Sankar, S. Yarmolenko, Surf. Coat.Technol. 177178 (2004) 52.
[16] S.H. Cho, B.H. Park, J.M. Hur, H.S. Lee, K.C. Song, J.H. Lee, Corros. Sci. 52 (2010)
2353.
[17] C.J. Brinker, G.W. Scherer, SolGel Science: The Physics and Chemistry of SolGel
Processing, Academic Press, Inc., London, 1990.
[18] C. Viazzi, J.P. Bonino, F. Ansart, Surf. Coat.Technol. 201 (2006) 3889.
[19] S.S. Kim, S.Y. Choi, C.G. Park, H.W. Jin, Thin Solid Films 347 (1999) 155.
[20] M.J. Alam, D.C. Cameron, Surf. Coat.Technol. 142144 (2001) 776.
[21] S. Sakka, H. Kozuka, Handbook of SolGet Science and Technology: Processing,
Characterization and Applications, SolGel Processing, Volume I, Kluwer Academic
Publishers, 2005.
[22] H. Schroeder, Physics of Thin Films, Volume 5, Academic Press, New York, 1969.
[23] L.C. Klein, Solgel Technology for Thin Films, Fibers, Preforms, Electronics, and
Specialty Shapes, Noyes Publications, New Jersey, 1988.
[24] B.E. Yoldas, D.P. Partlow, Thin Solid Films 129 (1985) 1.
[25] C.C. Yang, J.Y. Josefowicz, L. Alexandru, Thin Solid Films 74 (1980) 117.
[26] L. Hu, T. Yokot, H. Kozuka, S. Sakka, Thin Solid Films 219 (1992) 18.
[27] J.H. Lee, B.O. Park, Thin Solid Films 426 (2003) 94.
[28] T. Ohya, M. Ito, K. Yamada, T. Ban, Y. Ohya, Y. Takahashi, J. Sol-Gel. Sci. Technol. 30
(2004) 71.
[29] K. Izumi, M. Murakami, T. Deguchi, A. Morita, J. Am. Ceram. Soc. 72 (1989) 1465.
[30] L. Shi, K. Tin, N. Wong, J. Mater. Sci. 34 (1999) 3367.
[31] H. Wang, G. Li, Y. Xue, L. Li, J. Solid State Chem. 180 (2007) 2790.
[32] Y. Gao, Y. Masuda, H. Ohta, K. Koumoto, Chem. Mater. 16 (2004) 2615.
[33] W. Qin, C. Nam, H.L. Li, J.A. Szpunar, Acta Mater. 55 (2007) 1695.
[34] J.F. Shackelford, R.H. Doremus, Ceramic and Glass Materials: Structure, Properties
and Processing, Springer, 2008.
Fig. 7. The SWE, SEM and AFM measured ZrO
2
lm thickness vs. temperature.
3815 E. Nouri et al. / Surface & Coatings Technology 206 (2012) 38093815