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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