Journal of Alloys and Compounds 577 (2013) 360369

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Journal of Alloys and Compounds

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Electrical resistivity of YSZ-coated stainless steel electrodes. A study

by response surface methodology
Jos Mangas-Murillo a, Eduardo M. Cuerda-Correa a,, Joaqun R. Domnguez b, Antonio Macas-Garca c,
Elena Bernalte d
a
Department of Organic and Inorganic Chemistry, Faculty of Sciences, University of Extremadura, Avda. de Elvas, s/n, E-06071 Badajoz, Spain
b
Department of Chemical Engineering and Physical Chemistry, Faculty of Sciences, University of Extremadura, Avda. de Elvas, s/n, E-06071 Badajoz, Spain
c
Department of Mechanical, Energetic and Materials Engineering, School of Industrial Engineering, University of Extremadura, Avda. de Elvas, s/n, E-06071 Badajoz, Spain
d
Department of Analytical Chemistry, Faculty of Sciences, University of Extremadura, Avda. de Elvas, s/n, E-06071 Badajoz, Spain

a r t i c l e i n f o a b s t r a c t

Article history: Ceramic-coated electrodes with minimum electrical resistivity have been prepared using AISI 304 stain-
Received 8 November 2012 less steel as a substrate for the deposition of Yttria-Stabilized Zirconia (YSZ) coatings. SEM-EDX, XPS, FT-
Received in revised form 4 May 2013 IR, GIXRD and EIS have been used to characterize the samples. The tetragonal phase of zirconia has been
Accepted 13 May 2013
successfully stabilised. A statistical design of experiments has been used to analyze the inuence of
Available online 30 May 2013
withdrawal rate, sintering temperature and dopant percent on the electrical resistivity of the coatings.
ANOVA analysis indicates that all factors exert a statistically signicant effect on the electrical resistivity
Keywords:
at 95% of condence. A non-linear polynomial equation (r2 = 0.9481) has been obtained in order to cor-
YSZ coatings
Electrical resistivity
relate electrical resistivity with the analyzed factors. Withdrawal rate and sintering temperature
Dip coating resulted to be the most important factors inuencing the electrical resistivity, R. Interactions appear
Solgel methodology between all the pairs of variables. Hence, modifying one of the variables signicantly affect the other
Response surface methodology ones.
2013 Elsevier B.V. All rights reserved.

1. Introduction
Zircona-, alumina- and titanium carbide- and/or nitride-based
ceramic materials are receiving a great deal of attention along the
last two decades due to their promising properties and technolog-
ical applications. Among the most interesting properties corrosion
and thermal shock resistance [1], chemical stability and electrical
conductivity [2] and mechanical resistance [3] are to be mentioned.
Zirconia is a material showing excellent properties such as large
values of hardness and elastic modulus, low friction coefcient,
high boiling point and high tenacity when compared with other
ceramic materials [4,5]. Zirconia is stable in chemically aggressive
media and it resists abrasion and high temperatures. All these
characteristics make zirconia a very attractive material from the
industrial standpoint. In fact, zirconia-based ceramics constitute
a group of highly demanded materials [6]. In the last few years a
number of papers have been published in connection with the
use of zirconia as the starting material for the preparation of new
ceramics [7,8]. Pure zirconia in solid state exhibits three stable
polymorphic phases as a function of temperature, namely
monoclinic (below 1170 C), tetragonal (between 1170 and
Corresponding author. Tel.: +34 924 289300x86121; fax: +34 924 289395.
E-mail address: emcc@unex.es (E.M. Cuerda-Correa).
2370 C) and cubic (between 2370 C and the melting point, ca.
2680 C). Addition of different proportions of certain metallic oxi-
des such as yttria, magnesia or ceria are frequently used to attain
stabilization of the tetragonal and/or cubic phase at room temper-
ature [9].
The interest on the design and development of zirconia-based
coatings and thin lms has grown signicantly owing to their wide
range of potential uses. In fact, this kind of coatings may provide an
excellent protection towards the chemical attack of different sub-
strates [6]. They may also act as thermal barriers in turbines and
combustion chambers of engines, as magnetic memories coating
or as ionic conduction lms deposited onto semiconductor lms
in gas sensors [10].
Recent research trends and specic application elds of YSZ
coatings include but are not restricted to solid oxide fuel cells
(SOFCs) [11,12], prosthetics [13], odontology [14], refractory mate-
rials [15,16], electroceramics [17] or jewellery [18]. On the other
hand, YSZ is commonly used as a thermal barrier coating with
the aim of protecting different alloys against high temperatures.
This oxide has a low thermal diffusivity as well as a good
coefcient of thermal expansion [19]. Porosity plays an important
role in the ability of YSZ to act as thermal insulator. Hence, the
control of the pore size in porous YSZ ceramics is a topic of current
interest [20,21].

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 J. Mangas-Murillo et al. / Journal of Alloys and Compounds 577 (2013) 360369 361

There are many different procedures for the preparation of cera-
mic coatings. Among these procedures Chemical Vapor Deposition
(CVD) [22], Physical Vapor Deposition (PVD) [23], Pulsed Laser
Deposition (PLD) [24], Electrophoretic Deposition (EPD) [25], ther-
mal sputtering [26] or solgel [9] are to be mentioned. The useful-
ness of each of these methods depends on the kind of substrate as
well as on the desired coating. The solgel route is one of the most
interesting alternatives to obtain oxide thin lms due to its sim-
plicity and versatility [27]. Solgel solutions may be deposited
through different methods (e.g., spraying, spin-coating, dipping,
etc.) [28]. The dipping method exhibits some advantages as, for
instance, the feasibility of coating large surfaces, the simplicity of
the required equipment and its low cost. Micrometric coatings
may be obtained by the deposition of successive layers (i.e., the
so-called multi-layer process) despite the fact that each monolayer
is constituted by a sub-micrometric thin lm [27].
It is worth noting that the structure and properties of thin lms
can differ signicantly from those of the bulk material. In particu-
lar, thin lm properties depend on porosity and thickness, making
the control of both characteristics during the densication pro-
cesses a critical issue in solgel lm preparation. Likewise, in addi-
tion to the dopant proportion, the withdrawal rate of the sample
from the solgel solution as well as the sintering temperature used
in the process have a noticeable inuence on the structure and -
nal properties of the lms. The aim of this work was to analyze,
through an adequate design of experiments, the inuence of these
three parameters on the electrical conductivity of stainless steel
electrodes coated with YSZ by the dip-coating procedure.
2. Materials and experimental procedure
2.1. Materials
2.2. Experimental methods
2.2.1. Statistical design of experiments
Typically, the one-factor-at-a-time approach has been used to study the inu-
ence of several operation variables (factors) on a parameter (response). Neverthe-
less, this classical methodology involves a large number of experiments and some
important conclusions on the interaction among factors can be missed. To avoid
these important disadvantages, statistical design of experiment (DOE) constitutes
an efcient alternative since it offers the possibility of analyzing the effect of vari-
ables and their responses minimizing the number of experiments. In the present
study, a routine DOE previously optimized by our research group [29,30] has been
used. StatGraphics software provides a useful and powerful mathematical and
statistical tool in order to develop the experimental planning, to analyze the results
and to draw conclusions on a rigorous basis. StatGraphics Plus was used to design
and analyze the experimental results. A factorial central composite orthogonal and
rotatable design (CCORD) was used with nine replicates of the central experiment.
This design involves the use of a two-level factorial design with 2k points combined
with 2k axial points and n replicates of the central experiment, k being the number
of factors. N, the total number of experiments with k factors is obtained according to
Eq. (1):
N 2k 2  k n 1
In this study k was equal to three and n-as indicated above-was considered to be
nine. Hence, according to Eq. (1), the total number of experiments resulted to be
23. The axial distance was 1.681 in order to guarantee an orthogonal and rotatable
design.
To evaluate the inuence of the yttria percent (YP) used as dopant, withdrawal
rate (WR) of electrodes from the solgel solution and sintering temperature (ST)
and their concomitant effects on the electrical resistivity (R) of the electrodes, dif-
ferent levels were set for these factors. Table 2 summarizes the operating levels
used in the present study.
Additionally to the operating levels indicated in Table 2, in order to guaranty
the rotatability of the design, a set of experiments with coded values of variables
equal to 1.681 was performed. Hence, this specic study involves a range com-
prised between 19 and 171 mm/min in withdrawal rate, 398902 C in sintering
temperature, and 0.3013.70 in yttria percent. Table 3 shows the experimental
planning in DOE, and the response obtained in each of the experiments performed
in this study.

Stainless steel AISI 304 was used as the substrate for the YSZ coating deposition.
2.2.2. Preparation of the samples
Among the 300-series, AISI 304 is the most versatile and one of the most used stain-
For the preparation of the precursor solgel solutions the following procedure
less steels. It exhibits excellent properties for forming and welding and may be used
was conducted. Firstly, stoichiometric amounts of n-propanol (n-PrOH), nitric acid
for deep drawing, rolling and cutting. AISI 304 steel does not require annealing after
and zirconium n-propoxide (ZNP), were added to a beaker and kept under stirring
welding to be used in a wide range of corrosive conditions. The corrosion resistance is
for 1 h, until obtaining a clear and transparent solution (solution 1). Meanwhile,
excellent, exceeding that of the 302 type in a wide range of corrosive environments.
stoichiometric amounts of isopropanol (i-PrOH), nitric acid and yttrium acetate tet-
Some of the most important properties of this steel are summarized in Table 1.
rahydrate (ACY) were added to another beaker and kept under stirring for 15 min,
For the preparation of the YSZ coatings deionized Milli-Q water was used. Yt-
until it had a clear and transparent appearance (solution 2). Once this time was
trium acetate tetrahydrate (99.9%, Alfa-Aesar) nitric acid (69%, Panreac), 1-propanol
elapsed, solution 2 was added to solution 1 and the mixture was subjected to stir-
(99.5%, Panreac), 2-propanol (99.5%, Panreac) and zirconium (IV) n-propoxide (70%
ring for one additional hour. Finally, the stoichiometric amount of water was slowly
w/w in propanol, Alfa-Aesar) were used, all of them of analytical grade.
added dropwise, thus initiating the hydrolysis process. This solution (solution 3)
was kept under stirring for half an hour.
In order to perform the coating of metal substrates a computer-controlled de-
Table 1 vice was used. The electrode to be coated was held by a clamp and dipped into
Some properties of the AISI-304 stainless steel. the solgel solution 3. Next, the electrode was extracted from the solution at a pro-
Physical properties grammed withdrawal rate comprised between 19 and 171 mm/min as described
Density 7.8 g/cm3 above.
Thermal expansion (20 C) 17.2  106 C1 Once the specimens were coated they were sinterized inside an oven (Naber-
Specic heat capacity 502 J/(kg K) therm LH 60/12) under controlled inert atmosphere by heating at temperatures
Thermal conductivity 16.2 W/(m K) between 398 and 902 C according to the planned design of experiments. In all
Electric resistivity 7.2  107 X cm2 cases, temperature was increased at a constant rate of 3 C/min until the preset
temperature was reached. This temperature was maintained for 2 h in all cases
Chemical properties (composition) and samples were next cooled down to room temperature inside the oven.
C 0.08% (minimum)
Mn 2.00%
Si 1.00%
Table 2
Cr 18.020.0%
Operating levels in the preparation of YSZ-coated stainiless steel electrodes.
Ni 8.010.5%
P 0.045% Variable Central Step Minimum Low High Maximum
S 0.03% value level level level level
Mechanical properties (0) (1.681) (1) (+1) (+1.681)
Fluence resistance 310 MPa Withdrawal 95 45 19 50 140 171
Maximum resistance 620 MPa rate, WR
Elongation 30% (in 50 mm) (mm/min)
Modulus of elasticity 193 GPa Sintering 650 150 398 500 800 902
Tensile strength 586 MPa temperature,
Yield strength 241 MPa ST (C)
Elongation 55% Yttria percent, 7 4 0.3 3 11 13.7
Hardness 80 RB YP (%)
362 J. Mangas-Murillo et al. / Journal of Alloys and Compounds 577 (2013) 360369

Table 3 The acquisition of the SEM images together with the EDX spectra was carried
Experimental planning in DOE and obtained response in each experiment. out using a 3D Quanta FEG equipment (FEI Company, Hillsboro, USA). Measure-
ments were made in the high vacuum working mode, using an accelerating voltage
Run WR ST YP Coded Coded Coded Surface of 15 kV. The secondary detector (DTE) was used and the working distance was
(mm/ (C) (%) WR ST YP resistivity 10 mm.
min) (X cm2) The application of the XPS technique allows an estimation of the stoichiome-
1 50 800 3 1 1 1 10.19 try, the chemical state and electronic structure of the elements existing on the sur-
2 95 650 7 0 0 0 9.50 face of the sample. Assays were performed on a Thermo Fisher equipment, model
3 95 650 13.7 0 0 1.681 13.11 K-Alpha, equipped with load balancing device. In all cases 20 scans were per-
4 50 800 11 1 1 1 11.24 formed and the analysis was carried out at two points on the electrode surface un-
5 19 650 7 1.681 0 0 0.81 der study.
6 95 650 7 0 0 0 10.03 The FT-IR spectra were registered on a Nicolet equipment provided with an IS10
7 140 500 11 1 1 1 13.54 DTGS detector. For each sample 32 scans were recorded in a wavenumber range
8 140 500 3 1 1 1 12.56 comprised between 4000 and 525 cm1 with a resolution of 0.48 cm1. It is note-
9 95 902 7 0 1.681 0 14.08 worthy that the use of attenuated total reectance mode (ATR, according to its acro-
10 171 650 7 1.681 0 0 6.29 nym) involves that the technique is not destructive and that the samples do not
11 140 800 3 1 1 1 10.34 require any previous preparation.
12 95 650 7 0 0 0 7.59 The GIXRD patterns were acquired with the aid of a Bruker D8 ADVANCE dif-
13 50 500 3 1 1 1 6.25 fractometer equipped with a PSD Vantec detector within the 2h range comprised
14 140 800 11 1 1 1 7.71 between 20 and 80 (step = 0.02) using a Kamedia = 1.54184 radiation.
15 95 650 7 0 0 0 9.90 The response variable in this study was the electrical resistivity (R) of the coat-
16 95 650 7 0 0 0 9.54 ings. To determine it, Electrochemical Impedance Spectrosocpy (EIS) was used. Elec-
17 95 650 7 0 0 0 10.52 trochemical impedance measurements were carried out using a three-electrode
18 95 650 7 0 0 0 7.82 conguration in which the YSZ-coated stainless steel pieces were used as working
19 50 500 11 1 1 1 11.62 electrodes and silver/silver chloride (Ag/AgCl) and platinum electrodes were used
20 95 398 7 0 1.681 0 17.09 as reference and counter electrode, respectively. The impedance spectra were ob-
21 95 650 7 0 0 0 9.28 tained using a CH Instruments 660D equipment controlled by the software pro-
22 95 650 7 0 0 0 8.94 vided by the supplier, CHI (CH Instruments, Inc., USA). The frequency range from
23 95 650 0.3 0 0 1.681 10.07 65 kHz to 0.1 Hz was scanned logarithmically with an applied sinusoidal perturba-
tion of 10 mV rms amplitude in 12 steps per frequency decade, superimposed on
the chosen applied potential (0.0 V). Data tting to equivalent circuits was per-
formed also with CHI analyzer program.
2.2.3. Characterization of the samples For electrochemical impedance measurements a 0.1 M KCl solution prepared
The coatings prepared as described above were characterized by Scanning Elec- from KCl suprapure reagent (Merck, Germany) and ultrapure water (Wasserlab,
tron Microscopy coupled with X-Ray Energy Dispersive Spectroscopy (SEM-EDX), Spain) was used as supporting electrolyte. Solutions were not deaerated before
X-Ray Photoelectron Emission Spectroscopy (XPS), Fourier-Transform Infrared recording the impedance spectra. All experiments were carried out at room temper-
Spectroscopy (FT-IR), Grazing Incidence X-Ray Diffraction (GIXRD) and Electro- ature (25 1 C). The coated area of the electrode that was kept in contact with the
chemical Impedance Spectroscopy (EIS). solution during the EIS measurement experiments was equal to 1 cm2.

Fig. 1. SEM images of samples prepared with different dopant proportions. Coded YP equal to 1.681 (upper left), 0 (upper right) and 1.681 (down).
 J. Mangas-Murillo et al. / Journal of Alloys and Compounds 577 (2013) 360369 363

3. Results and discussion X-Ray energy dispersive spectroscopy (EDX) is also a semi-
quantitative technique, which allows to estimate the percentage
3.1. Characterization of the samples of atoms of a particular element that exists in the sample under
analysis. The values for samples 3, 6 and 23 are shown in Table 4.
In order to test the efciency of the doping process, three sam- From the data summarized in this table it may be observed that, for
ples containing different amounts of Y2O3 as dopant were chosen sample number 3, the atomic ratio of Y and Zr in the coating equals
for the characterization. Such samples were 3, 6 and 23, which con- 0.286, which corresponds to a molar ratio Y2O3/ZrO2 equal to 0.143
tain 13.7, 7 and 0.3 mol% of Y2O3 (i.e., coded values equal to 1.681, or, in percent, 14.3%. This value is very close to the theoretical
0, and 1.681, respectively) with WR and ST kept constant in their 13.7%. In the case of samples 6 and 23 the Y to Zr mole ratios are
central (0) value (namely, 95 mm/min and 650 C). 8.69% and 0.27% respectively. Again, these values are very close
to the theoretical values, which suggests that the doping process
3.1.1. Scanning electron microscopy-X-Ray energy dispersive was carried out in an efcient manner.
spectroscopy (SEM-EDX) analysis
Fig. 1 depicts the SEM images of the three selected samples.
3.1.2. X-Ray emission photoelectron spectroscopy (XPS)
From such images it is apparent that, in all cases, the surface of
Fig. 3 shows the XPS analyses of samples 3, 6 and 23. Since most
the substrate is coated with a ceramic layer. Residuals of non-sin-
of the peaks of Zr and Y are located in the region between 0 and
tered YSZ on such surface can also be appreciated. The ceramic
600 eV, the XPS spectra have been restricted to this binding energy
layer clearly exhibits cracks or defects in some areas. This is partic-
range. The low-intensity peaks appearing at low values of binding
ularly evident in samples prepared with a coded YP equal to 0 and
energies (i.e., between 0 and 30 eV) are caused by the photoemis-
1.681. In this regard it is noteworthy that, in the form of massive,
sion of the valence electrons (outermost orbitals).
YSZ has high mechanical stability and resistance to fracture. How-
It may be clearly appreciated that, in the case of sample 23,
ever, as coatings these properties are limited [31]. A similar behav-
which contains a very low percentage of Y2O3 as dopant (0.3%)
ior was recently described in the literature and is attributed to the
the peaks at 403 eV (corresponding to the emission of electrons
hardening effect that involves the transformation from tetragonal
from the 3s level of yttrium), 312 and 303 eV (assigned to the emis-
to monoclinic phase. Such a transformation is in turn conditioned
sion of electrons from the 3p levels of the aforesaid element) are
by the percentage of Y2O3 introduced as dopant [24].
negligible. In contrast, in the case of sample 6 (which contains 7%
X-Ray energy dispersive spectroscopy (EDX) patterns of sam-
of doping agent) such peaks can be clearly observed. Finally, for
ples 3, 6 and 23 are shown in Fig. 2. From these spectra it may
sample 3, which has been doped with 13.7 mol% of yttria, the peaks
be concluded that the technique is capable of detecting the pres-
are of high intensity. The relative position of the peaks is coincident
ence of zirconium and yttrium, even though this latter occurs in
very low percentages. This is the case of sample 23, in which the
mole percent of yttria to zirconia is as low as 0.30%. Table 4
In the coated samples several signals corresponding to yttrium Elemental analysis by EDX.
appear around 1.62.4 keV. This region is shown in Fig. 2 in an en-
Element Sample 3 Sample 6 Sample 23
larged manner. Furthermore, a large peak corresponding to the
Weight% Atom % Weight % Atom % Weight % Atom %
iron present in the stainless steel may be appreciated. The intensity
of this peak clearly indicates that this technique is able to see be- C 0.01 0.04 0.01 0.06 0.01 0.07
O 0.09 0.34 0.33 1.15 0.21 0.75
yond the layer of ceramic material covering the surface of the sub-
Si 0.05 0.10 0.05 0.10 0.04 0.07
strate. In contrast, the EDX spectrum for bare steel does not exhibit Y 0.10 0.06 0.06 0.04 0.02 0.02
at all the signals corresponding to zirconium and yttrium as ex- Zr 0.34 0.21 0.37 0.23 0.61 0.37
pected although some alloying metals present in AISI 304 (such Cr 10.94 11.75 7.28 7.75 10.44 11.17
as chromium and nickel) are present in the EDX spectra. Fe 70.29 70.25 82.81 82.11 71.90 71.66
Ni 18.17 17.28 9.08 8.57 16.77 15.90
Total 100.00 100.00 100.00 100.00 100.00 100.00

Fig. 2. EDX spectra of stainless steel and samples prepared with different dopant Fig. 3. XPS spectra (0600 eV) of samples prepared with different dopant
proportions. The 1.62.4 keV range is shown in a detailed manner. proportions.
364 J. Mangas-Murillo et al. / Journal of Alloys and Compounds 577 (2013) 360369
with previously reported data for YSZ coatings on Nicalon bers
[32]. These data corroborate that the doping procedure of zirconia
with yttria has been quite effective. Hence, it may be stated that yt-
tria has been successfully incorporated into the lm that consti-
tutes the coating on the surface of the stainless steel.
As EDX, XPS makes it possible to determine the semi-quantita-
tive elemental analysis of the samples (data not shown for brevity).
The Y to Zr ratios for samples 3 and 6 are 14.2 and 7.8 mol%,
respectively, which are in good agreement with the theoretical val-
ues. It is worth noting that for sample 23 (i.e., that including
0.3 mol% of yttria) the peak corresponding to yttrium was too weak
and it could not be quantied by the XPS-equipment.
3.1.3. Fourier transform infrared spectroscopy (FT-IR)
The FT-IR spectra corresponding to the samples analyzed in
this study are shown in Fig. 4. In these spectra clear differences
between samples may be observed. Firstly, as the percentage of
yttria rises from 0.3% to 13.7%, the complexity of the spectrum
and the number of bands increases. The band observed around
3380 cm1 can be assigned to the stretching and deformation
vibration of the OH bond of water. The band centered around
740 cm1 is attributable to vibration of the ZrO bond in the
ZrO2, specically in the tetragonal phase of zirconia [33,34]. Fur-
thermore, in samples containing higher percentages of yttria as
a dopant especially in sample 3, which contains 13.7% of yttria
the bands centered at 1640 and 1520 cm1 can be appreciated.
Such bands are assigned to yttrium-containing bonds [35]. Two
small shoulders centered at 470 cm1 and 621 cm1 are also
appreciated in the spectra. These shoulders are usually associated
with the monoclinic and cubic phases of zirconia, respectively
[36].
The FT-IR spectra also show that, at the sintering temperature
here used (650 C in all cases) a complete removal of organic sol-
vent employed in the preparation of coatings occurs. According
to previously published data, this has a signicant effect on the
properties of the coatings. For example, if the sintering tempera-
ture is below 573 K, Dominguez-Crespo et al. [37,38] have shown
that the solvent remaining in the coating has a detrimental effect
on corrosion resistance. It also hinders the adhesion of the coating
onto the substrate.
3.1.4. Grazing incidence X-Ray diffraction (GIXRD)
The GIXRD patterns are shown in Fig. 5. The disadvantages of
conventional XRD measurements of thin lms (i. e., below
1000 nm) are well-known. Particularly, a weak signal from the lm
and an intense signal from the substrate are commonly observed.
Fig. 4. FT-IR spectra of samples prepared with different dopant proportions.
GIXRD spectra of Fig. 5 exhibit the occurrence of a peak at values
of 2h equal to 43 that are attributable to the austenitic substrate.
However, a wide variety of peaks corresponding to different poly-
morphs of YSZ may also be appreciated. An adequate study of these
spectra has made it possible to identify the different crystalline
phases present in the samples as well as to determine the semi-
quantitative phase analysis. All this information is summarized
in Table 5. From these results it may be concluded that a noticeable
stabilization of the cubic and tetragonal phases of YSZ has been
achieved by the introduction of yttrium in the crystalline structure
of ZrO2. Additionally, for sample 3 large percents (up to 42.34% in
total) of phases containing 1316 mol% of yttrium have been ob-
tained. For sample 23, up to 67.3% of the sample appears as un-
doped zirconia and approximately 7% contains 34 mol% of
ytrium. Finally, for sample 6 the foreseeable occurrence of phases
containing 68 mol% of yttrium has not been conrmed by GIXRD.
The occurrence of an undoped rhombohedral phase has been
detected for samples containing 13 and 0.30 mol% Y2O3. In this
connection, it has been previously reported in the literature that
the rhombohedral phase (r-phase) is produced on the abraded sur-
face of partially-stabilized zirconia (PSZ) [39]. Nevertheless, it was
also reported that the r-phase may also appear in alloys showing
compositions as low as 34 mol% Y2O3 without mechanical treat-
ments [40]. This seems to be the case in the present study. Accord-
ing to the referred authors, this phase tends to disappear with
annealing at 1000 C or by removing the surface layer by polishing
[40].
Taking into consideration the different ctrystalline fases in-
cluded in Table 5 and their respective composition in percent,
the average stoichiometry of each of the three samples here re-
ported resulted to be Zr0.90Y0.10O1.95, Zr0.94Y0.06O1.97 and Zr0.98Y0.02-
O1.99 for samples 3, 6 and 23, respectively. If these formulae are
referred to 100% Zr, the doping percents of yttria result to be
11.7, 6.3 and 1.7 mol%. These data are, in general, in good agree-
ment with those provided by the XPS and EDX local microanalyses.
3.2. Analysis of the electrical resistivity by response surface
methodology
Design of Experiments (DOE) is a useful tool to verify the effects
of different variables and their interactions on the process response
within a certain range and with a minimum number of experi-
ments. Table 2 shows the operating levels of the DOE whereas Ta-
ble 3 summarizes the experimental planning in the DOE and the
obtained response in each experiment (i.e., electrical resistivity of
the electrodes in X cm2).
3.2.1. Numerical analysis
The ANOVA analysis provides the signicance of the different
parameters. The results of the ANOVA test are summarized in Ta-
ble 6. According to the RSM, nine factors are considered. All of
them exhibit a p-value below 0.05 (signicance limit), which indi-
cate that all factors exert a statistically signicant effect on the re-
sponse variable, electrical resistivity, at 95% of condence.
Non-linear polynomial regression was carried out and the fol-
lowing expression was obtained accordingly:
RX cm2 9:23 1:03  WR  0:69  ST 0:72  YP  1:98
 WR2  1:45  WR  ST  1:01  WR  YP 2:27
 ST 2  0:99  ST  YP 0:86  YP 2 2
An excellent correlation factor r2 equal to 0.9481 was obtained. For
each experiment, the difference between experimental R and calcu-
lated R (according to Eq. (2)) is represented in Fig. 6 (left) versus the
specic run number. No correlation can be appreciated since resid-
uals are located in a random order at both sides of the 0 axis. Hence,
 J. Mangas-Murillo et al. / Journal of Alloys and Compounds 577 (2013) 360369 365

1000

800
s)
Intensity (count

600

400

79
73
200 68
63
57
52

()
47
0 41

2
O3 36
Y2
.7% 31
13 O3 25
Y2
7% 20
O3
Y2
0%
0.3

Fig. 5. GIXRD patterns of samples prepared with different dopant proportions.

Table 5
Crystalline phases determined by GIXRD and semi-quantitative analysis. also corroborates that the randomization of the design has been
properly planned and performed, so that accumulation of experi-
Phase Crystal system Composition (%)
mental error may be discarded.
Sample 3 Sample 6 Sample 23
ZrO2 Cubic 2.37 19.34 29.58 3.2.2. Graphical analysis
ZrO2 Rhombohedral 19.50 0.00 30.94
Modelization was made on the basis of the nine factors included
ZrO2 Tetragonal 0.00 3.29 6.78
Zr0.97Y0.03O1.985 Tetragonal 6.55 13.99 4.75 in Eq. (2). The so-called Pareto plot (see Fig. 7, left) is a graphical
Zr0.96Y0.04O1.98 Tetragonal 0.00 7.10 2.58 expression of the ANOVA test results. Bars represent the standard-
Zr0.87Y0.13O1.935 Tetragonal 6.69 2.67 0.00 ized effects of each involved factor, considering them as WR, ST
Zr0.85Y0.15O1.925 Cubic 8.91 1.95 6.38 and YP and combinations of all of them. Gray bars are a graphical
Zr0.84Y0.16O1.92 Tetragonal 26.74 6.69 0.00
representation of positively-affecting factors, such as WR, YP, the
Zr0.79Y0.21O1.895 Tetragonal 0.00 1.23 0.00
Zr0.76Y0.24O1.88 Cubic 1.81 3.60 0.68 square of ST and the square of YP. This means that these factors ap-
Substrate (austenite) Cubic 0.00 36.52 18.32 pear in Eq. (2) behind a positive sign. On the other hand, blue bars
represent negatively-affecting factors, such as ST, the square of
WR, and the combinations of WRST, WRYP and STYP. It may
be observed that these factors appear in Eq. (2) behind a negative
Table 6 sign. The vertical rule that stands close to 2 is related with the sig-
ANOVA results.
nication level of ANOVA test, which is equal to 95% of condence.
Factor Sum of squares Degrees of freedom F-ratio p-values Since all factors reach this vertical rule, all of them are within the
A:WR 14.4879 1 15.76 0.0016 signicant region. The Pareto plot also provides an idea on how
B:ST 6.68122 1 7.27 0.0183 factors inuence the nal response, R. Positive bars indicate that
C:YP 7.15148 1 7.78 0.0153 by varying a given variable the value of R increases. Negative bars
AA 62.5127 1 68.00 0.0000
indicate the contrary.
AB 16.849 1 18.33 0.0009
AC 8.14061 1 8.85 0.0107 The application of the CCORD model also makes it possible to
BB 81.9864 1 89.18 0.0000 analyze the main effects of the involved variables. Such effects
BC 7.86061 1 8.55 0.0118 can be observed in Fig. 7 (right). Three curves are drawn represent-
CC 11.7266 1 12.76 0.0034 ing the effect of varying each variable (from 1 up to +1) while the
Total error 11.9518 13 0.919368
Total (corr.) 230.292 22
other ones are kept constant in their respective central values. A
maximum is shown in the nal part of the curve in the case of
WR. On the contrary, two minima are appreciated for ST and YP.
This will be clearly appreciated in the response surface and contour
it may be concluded that the randomization of the design is fully plot gures that will be discussed below.
working and no accumulation of experimental error is observed. Fig. 7 (right) also illustrates that the plots corresponding to WR
Also, for each experiment Fig. 6 (right) represents the observed and ST exhibit remarkably steep slope. This mean that WR and ST
R versus the values of R calculated according to Eq. (2). A good cor- are the main factors governing the electrical resistivity, R, whereas
relation between both parameters may be observed. This latter the inuence of YP is less remarkable.
366 J. Mangas-Murillo et al. / Journal of Alloys and Compounds 577 (2013) 360369

2.3 18

15
1.3
12

Observed
Residuals

0.3 9

6
-0.7
3

-1.7 0
0 3 6 9 12 15 18 0 3 6 9 12 15 18
Predicted Predicted

Fig. 6. Residuals plot (left) and observed versus calculated values of R (right).

BB 14.2
+
AA -

Electrical resistivity
AB 12.2
A:Coded WR
CC 10.2
AC
BC
8.2
C:Coded YP
B:Coded ST
6.2
0 2 4 6 8 10 -1.0 1.0 -1.0 1.0 -1.0 1.0
Standardized effect Coded WR Coded ST Coded YP

Fig. 7. Pareto plot (left) and main effects plot (right).

With regard to the interaction between variables, Fig. 8 shows 15.3

the interaction between each two of the three variables studied. +
Each pair of curves represents the evolution of R by varying one
13.3
variable in the extremes of the CCORD model, that is, with its pair
-
Electrical resistivity

variable equal to +1 (upper plot) and equal to 1 (lower plot). The

fact that the curves do not present a parallel behavior involves that
-
11.3 - +
interaction occurs and the modication of one of the variables af-
fects the other one. Accordingly, from Fig. 8 it may be concluded
that interaction clearly appears between all the pairs of variables, 9.3 + -
AB, AC and BC. Thus, it may be assumed that interaction takes place + +
+
in all cases and the modication of one of the variables signi- -
cantly affect the other one. 7.3

3.2.3. Response surfaces and contour plots

The response surface plot is the most important graphical rep- 5.3 -
resentation in the RSM. It represents Eq. (2) and makes it possible -1.0 1.0 -1.0 1.0 -1.0 1.0
to evaluate the behavior of the whole system under study from a AB AC BC
qualitative point of view.
Fig. 8. Interaction between variables.
Fig. 9 depicts the response surface and contour plots obtained
when each pair of variables is modied and the third one is kept
constant and equal to its central value (i.e., 0.0). As it can be appre- sented by the presence of red areas in the contour plot. This, again,
ciated, within the region here studied the response is represented is in good agreement with the information provided by the main
by a convex surface. Fig. 9a shows the inuence of the two vari- effects plots.
ables exerting a more remarkable effect, namely WR and ST. It Finally, Fig. 9c corroborates the scarce inuence of YP on the
may be clearly appreciated that the trend pointed out by the main electrical resistivity of the samples and clearly points out the trend
effects plot (see Fig. 7, right) is corroborated by the response sur- to an optimum (i.e., a value of R very close to zero represented by the
face plot. Furthermore, Fig. 9a suggests the trend to reach an opti- dark blue area in the contour plot) at low values of both, WR and YP.
mum (i.e., a minimum in R represented by blue areas in the
contour plot under the surface) at low values of WR and interme- 3.3. Physical meaning of the experimental results
diate values of ST.
On the other hand, Fig. 9b reveals that the combination of low The purpose of this section is far from questioning the results of
values of ST and high values of YP yields to an increase in R, repre- the statistical analysis above detailed. The statistical criteria of
 J. Mangas-Murillo et al. / Journal of Alloys and Compounds 577 (2013) 360369 367

(a) Coded Y2O3 percent=0.0

Electrical resistivity
0.0
2.0
4.0
20 6.0
8.0

Electrical resistivity
15 10.0
12.0
14.0
10
16.0
18.0
5
1.68 re
tu
0.84 ra
0 0 pe
m
-1.68 -0.84 te
-0.84 0 ing
0.84 1.68
-1.68
t er
sin
Coded withdrawal rate d
de
Co

(b) Coded withdrawal rate=0.0

Electrical resistivity
0.0
2.0
4.0
25 6.0
8.0
Electrical resistivity

20 10.0
12.0
15 14.0
16.0
10
18.0

5 1.68
t
0.84 en
0 erc
0 p
-1.68 -0.84
-0.84 O3
0 0.84 -1.68 Y2
1.68 d
de
Coded sintering temperature Co

(c) Coded sintering temperature=0.0

Electrical resistivity
0.0
2.0
4.0
20 6.0
8.0
Electrical resistivity

15 10.0
12.0
14.0
10
16.0
18.0
5
1.68
0.84 nt
0 0
erce
-0.84 p
O3
-1.68 -0.84 0 0.84 1.68
-1.68
Y2
d
de
Coded withdrawal rate Co

Fig. 9. Response surface plot and contour curves.

robustness of the method have already been sufciently demon- With respect to the inuence of the withdrawal rate on the
strated in the previous section. This section will attempt to explain electrical resistivity of the samples, not much information can be
and justify the results, comparing them when possible with found in the literature. DellAgli et al. [41] have reported that with
other previously published ones. the solgel technique, homogeneous lms may be obtained at low
368 J. Mangas-Murillo et al. / Journal of Alloys and Compounds 577 (2013) 360369
and high withdrawal rates. It should be noted that this parameter
is closely related to the thickness of the coating layer that is depos-
ited onto the substrate. Thus, high extraction rates lead to the for-
mation of a large meniscus between the surface of the substrate
and the solution where it is dipped when performing the dip-coat-
ing process. This implies that the coating formed after sintering is
thicker. In contrast, slow withdrawal rates result in a less pro-
nounced meniscus and, therefore, in thinner coatings. The results
found in the literature regarding the inuence of the coating thick-
ness on the electrical resistivity show that R increases progres-
sively with increasing thickness [42]. In fact, once the coatings
reach thicknesses above 30 lm the resistivity of the coating is vir-
tually equivalent to that of the bulk YSZ [4345]. According to the
statistical analysis here reported, both the ANOVA test and its
graphical expression Pareto plot show that if the withdrawal
rate increases (and, therefore, the thickness of the coating in-
creases as well) the electrical resistivity of the sample rises. How-
ever, the model itself clearly shows that both, the square of the
withdrawal rate and its interaction with the sintering temperature
and the percentage of yttria used as dopant result in a remarkable
decrease in electrical resistivity.
On the other hand, YSZ coatings have been employed widely
as a material for the preparation of thermal barriers and as elec-
trodes or electrolyte in solid oxide fuel cells (SOFCs). Hence, a
large number of works focused on the inuence of sintering tem-
perature on connectivity/electrical resistivity of YSZ can be found
in the literature. It is commonly accepted that an increase in
temperature results in a decrease in electrical resistivity
[38,4648].
A possible explanation for this fact is the porosity of the sam-
ples. Thus, increasing treatment temperature will result in a
change in the microstructure of the coating, which implies a poros-
ity evolution. Pore size and porosity could be controlled by adjust-
ing sintering temperature [49]. Usually, the average pore size
becomes progressively smaller [50]. Other authors [38] have dem-
onstrated that increasing the sintering temperature leads to a tri-
ple effect resulting in the decrease in resistivity. Specically,
there is a progressive stabilization of the cubic phase of zirconia,
a complete removal of organic precursors used and an increase
in the crystallinity of the lm. Furthermore, the use of such coat-
ings enhances the protection against corrosion. According to the
referred authors, such a protection is in turn more effective as
the sintering temperature increases.
The experimental results obtained in this work point out in the
same direction. Thus, a decrease in the resistivity of the coating has
been observed when the sintering temperature rises.
Finally, the results suggest that the percentage of yttria as a
dopant exerts a signicant inuence on the values of electrical
resistivity determined by EIS. Specically, an increase in the per-
centage of yttria results in a slight increase in resistivity. A biblio-
graphic review suggests that the information that can be found in
this connection is scarce. According to Zhang et al. [51], the con-
ductivity of samples prepared with a molar ratio of 8% yttria is
around 50% higher than that of other samples containing 4.5 mol
% of dopant. In principle, this fact is consistent with the appearance
of O2 anion vacancies in the zirconia network. Such vacancies oc-
cur to maintain electrical neutrality of the lattice when Zr4+ cations
are progressively replaced by Y3+ cations. Therefore, as the percent-
age of yttria used as dopant rises, the number of O2 vacancies
should also increase. This latter would lead to a subsequent in-
crease in the electronic and ionic conductivity of the samples. On
the contrary, Heiroth et al. [52] have demonstrated that the electri-
cal conductivity of 3 mol% YSZ is comparable or slightly higher
than that obtained for 8 mol% YSZ, which is in good agreement
with the results obtained in this study.
4. Conclusions
According to the results obtained in this work, the following
conclusions may be drawn:
 YSZ coatings have been successfully deposited onto the surface
of stainless steel AISI 304 as corroborated by the SEM images
and the EDX spectra. XPS and GIXRD analyses indicate that
yttria has been sucessfully incorporated into the lm that con-
stitutes the coating on the surface of the stainless steel. FT-IR
and GIXRD spectra reveal that the tetragonal phase of zirconia
has been adequately stabilized by the introduction of yttria in
the original structure of ZrO2.
 A statistical design of experiments has been performed in order
to analyze the inuence of withdrawal rate, sintering tempera-
ture and dopant percent on the electrical resistivity of the coat-
ings. The ANOVA analysis indicate that all factors here studied
exert a statistically signicant effect on the response variable,
electrical resistivity, at 95% of condence. Non-linear polyno-
mial regression has been carried out and the correlation factor
r2 of the so-obtained equation is equal to 0.9481.
 The main effects plot illustrates that withdrawal rate and sin-
tering temperature are the most important factors governing
the electrical resistivity, R, whereas the inuence of yttria per-
cent is less remarkable. The interaction plot clearly shows that
interactions appear between all the pairs of variables. Hence,
the modication of each one of the variables signicantly affects
the response attained for the other ones and the optimal is dis-
placed accordingly.
 The response surface plot conrms that the withdrawal rate
supposes the most important affection on the target variable,
R, whereas the yttria percent exerts an intermediate inuence
on R.
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