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Zirconium Oxide Structure Prepared by the Sol-Gel Route: I, The Role of the
Alcoholic Solvent

Article  in  Journal of the American Ceramic Society · February 2004

DOI: 10.1111/j.1151-2916.2000.tb01200.x

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Zirconium Oxide Structure Prepared by the Sol–Gel Route:
I, The Role of the Alcoholic Solvent
Marı́a C. Caracoche,† Patricia C. Rivas,‡ and Mario M. Cervera‡,§
Departamento de Fı́sica, FCE, Universidad Nacional de La Plata, 1900 La Plata, Argentina
Ricardo Caruso, Edgardo Benavı́dez,‡ and Oscar de Sanctis*
Laboratorio de Materiales Cerámicos, FCEIyA, IFIR, UNR, 2000 Rosario, Argentina
Departamento de Ciencia y Tecnologı́a, Universidad Nacional de Quı́lmes, 1864 Bernal, Argentina
Sol– gel-derived powder samples of zirconia (ZrO2) prepared
via the dissolution of zirconium n-propoxide in methanol,
ethanol, and 2-propanol have been characterized mainly using
perturbed angular correlations spectroscopy, as a function of
temperature. Results indicate that the nanostructures and
subsequent thermal evolution are alcohol dependent: the
shorter the alcohol chain, the more hydrolyzed the product.
ZrO2 powder that has been obtained using ethanol as the
solvent is the product that exhibits the better stabilization of
the metastable tetragonal phase (t-phase). It undergoes a clear
and detailed t1-form 3 t2-form 3 monoclinic ZrO2 thermal
transformation and shows the highest activation energy
against the transformation to the monoclinic phase.
I. Introduction
Z IRCONIA (ZrO2) has attracted much attention in the science
community. This focus is due to its superior properties of
mechanical strength, chemical resistance, and ionic conductivity.
The sol– gel route offers several advantages, such as low-
temperature processing and control of the microstructure for the
preparation of monodispersed powders and multicomponent ce-
ramics and coatings. An oxide network is obtained from metal
alkoxide molecular precursors through hydrolysis and subsequent
condensation reactions. Controlling the kinetics of the hydrolysis
and condensation reactions can alter the polymeric structure of the
oxide precursor gels. The effect of these molecular structural
changes in the gels is maintained in the derived materials (ceramic
and glasses), which allows modification of their properties within
a given composition.
In the hydrolytic condensation of zirconium alkoxides, the alkyl
group of the alkoxide has a very important role. The alkyl group
affects the morphology and particle size of the resultant ZrO2 and
the monoclinic–tetragonal (m 3 t) transformation.1
Zirconium is known to have a tendency to expand its coordi-
nation with alcohol molecules instead of with alkoxy-bridging
K. J. Bowman—contributing editor
Manuscript No. 189754. Received November 11, 1998; approved August 5, 1999.
Supported by Comisión de Investigaciones Cientı́ficas de la Provincia de Buenos
Aires (CICPBA) and Consejo Nacional de Investigaciones Cientı́ficas y Técnicas
(CONICET).
*Member, American Ceramic Society.
†
‡
Member, CICPBA, Argentina.
Member, CONICET, Argentina.
§
Now with Siemens, Argentina.
377
J. Am. Ceram. Soc., 83 [2] 377– 84 (2000)
‡
Marta E. Escobar‡
groups.2 Moreover, to prepare ceramics via sol– gel processing, the
precursor alkoxide generally is dissolved in alcohol, and it seems
sensible that this solvent is far from being an inert medium that is
not involved with the chemical process.3 When a zirconium
alkoxide is dissolved in an alcohol, the product of its interaction
with the solvent is an alkoxide that is different from the starting
alkoxide. Thus, the molecular structure of the precursor alkoxide
will be dependent on the nature of the solvent.
The ZrO2 syntheses conducted in this work use zirconium
n-propoxide that has been dissolved in different alcohols; there-
fore, we expect to obtain zirconias with alcohol-dependent prop-
erties. The intent of this paper is to focus the attention on the
effects of the alcohol that is used as the solvent on ZrO2 powders
prepared via the sol– gel technique, through the investigation of the
resulting structures and nanostructures and their thermal evolution
from room temperature (RT) up to ⬃1000°C.
For this purpose, we have characterized the different sol– gel-
derived zirconias, using the highly nanoscopic perturbed angular
correlations (PAC) technique,4 which allows investigation of the
Zr-ion nearest neighborhoods, as a function of temperature. The
technique is based on the fundamental principle of the conserva-
tion of angular momentum. This principle dictates that, if a nucleus
decays through a radiation process, the angular momentum of the
emitted gamma ray plus the angular momentum (nuclear spin) of
the ending nuclear state should be equal to the nuclear spin of the
starting nuclear state. Considering the fact that the angular mo-
mentum of a radiation is related to its angular distribution, one
easily can realize that, when a nucleus decays through a ␥–␥
cascade, information about the intermediate nuclear state can be
obtained by measuring the angular distribution of the cascade, i.e.,
the distribution of one gamma ray with respect to the other. During
its life in the intermediate state, between the emission of both rays,
the nucleus may be perturbed by the crystalline field, which
changes its orientation in space, therefore changing the above-
mentioned distribution. This phenomenon is called hyperfine
interaction, in which the nuclear states are modified by the
environment. The nonperturbed case (an isolated nucleus) has a
well-known angular correlation that is dependent on the spins of
the nuclear states and the multipolarity of the radiation involved.
The goal of the PAC technique is to determine the hyperfine
interaction (and, thus, the perturbing field) that is experienced by
a nucleus immersed in a real crystal by measuring the departure
from the nonperturbed angular correlation. Zirconium-containing
materials such as ZrO2-based ceramics have a natural hafnium
impurity of 1%–3%; because of chemical similarity, these Hf
atoms occupy Zr sites. Radioactive 181Hf isotopes are obtained
when the materials are subjected to neutron irradiation. These
isotopes, in turn, disintegrate by ␤⫺ to excited levels of 181Ta
nuclei and then to its ground state through two gamma rays in
378 Journal of the American Ceramic Society—Caracoche et al.
cascade (␥1 ⫽ 133 keV and ␥2 ⫽ 482 keV).5 The intermediate
level of this cascade—the I ⫽ 5⁄2⫹ level, with adequate values of
the quadrupole moment Q and the half-life ␶N (the “nuclear
probe”)—reflects the effect of its interaction with the nearest
neighborhood very efficiently, thus giving information of the
lattice electric field gradients (EFGs) at the probe sites.
If an EFG exists at the site of the 181Ta nucleus, the angular
correlation will be modified within the time that the intermediate
level lives. This effect is revealed by the so-called “perturbation
factor,” G2(t). Calculation of the experimental ratio R(t), which is
given as6
C共180⬚,t兲 ⫺ C共90⬚,t兲
R共t兲 ⫽ 2 ⫽ A 2 G 2 共t兲
C共180⬚,t兲 ⫹ 2C共90⬚,t兲
allows determination of the G2(t) factor (because A2 is a tabulated
constant that is related to the unperturbed correlation) and,
consequently, the quadrupole parameters that describe the EFGs at
the 181Ta (Zr) sites. This ratio is obtained from the measured ␥1–␥2
coincidence spectra C(␪,t), where ␪ is the angular separation
between ␥1 and ␥2 and t is the time elapsed between both
emissions. This procedure is performed by fitting the A2G2(t)
function (which also is called the PAC spectrum or spin-rotation
curve), using a nonlineal least-squares fitting procedure with
appropriate theoretical G2(t) functions of the general form
冋
G 2 共t兲 ⫽ s 20 ⫹ 冘
n⫽1,3
册
s 2n 关cos ␻ n t兲 exp共⫺␦␻ n t兲 exp共⫺␭t兲
where the transition frequencies ␻n between the sublevels of the
intermediate nuclear state are functions of the quadrupole interac-
tion frequency ␻Q (which is proportional to the major component
Vzz of the EFG) and the asymmetry parameter ␩ (which is defined
as (Vxx ⫺ Vyy)/Vzz), the value of which varies between 0 (noting an
axially symmetric EFG) and 1 (noting a completely asymmetric
EFG). The geometrical coefficients s20 and s2n are dependent on ␩
and are very sensitive to the sample texture. Whenever disorder
and/or impurities or defects are present in the lattice, the fitting
procedure accounts for them through the inclusion of the addi-
tional quantity ␦ or a Lorentzian distribution width around the
mean value of the quadrupole frequency. Furthermore, the method
also is sensitive to atomic or defect movements that occur around
the Zr sites. The dynamic EFG that is involved manifests through
a measurable damping of the spin-rotation curve, which is repre-
sented by the factor exp(⫺␭t) in Eq. (2), for which different fitting
theoretical models have been proposed.7 Given the short range that
is inherent to the quadrupole hyperfine interaction (⬃r⫺3), the
PAC technique generally can resolve different neighborhoods;
thus, a relative fraction or intensity (f) and the corresponding EFG
parameters (␻Q, ␩, ␦) can be determined for each neighborhood,
where each set of parameters characterizes a particular probe
location in the sample.
The EFGs of the three equilibrium phases of ZrO2, which
transform according to
1170⬚C 2300⬚C
m-ZrO2 |
- 0 t-ZrO2 -
| 0 c-ZrO2
already have been determined.8,9 The corresponding well-known
hyperfine quadrupole parameters are listed in Table I.
Table I. Hyperfine Parameters of the Zirconia Equilibrium Phases
Phase †
Temperature, T (°C)
m-ZrO2 20
t-ZrO2 1150
c-ZrO2 1950
†
Data for the m-ZrO2 and t-ZrO2 phases are from Caracoche et al.,8 and data for the c-ZrO2 phase are from Forker.9
Vol. 83, No. 2
More recently, PAC has been used to investigate metastable
nanometric configurations in very fine pure zirconias and doped
zirconias that have been prepared using different methods.6,10 –13
The determination of two very different sets of quadrupole
parameters that correspond to two EFGs at the Zr sites indicates
that the technique allows us to establish that two forms of the
metastable tetragonal phase coexist in pure and yttria-doped
zirconias (YSZs); the XRD patterns of these tetragonal phases are
hardly distinguishable from that of the high-temperature t-ZrO2
phase. The difference between the two varieties has been inter-
preted based on a different distribution of vacancies around the
probe. One variety, which is present in most ceramics at low
temperatures, is the strongly distorted tetragonal t1-form, where
(1)
␩ ⬎ 0.5 and oxygen probably is defectively coordinated, as in the
stabilized cubic phase.14 This structure, when obtained via the
sol– gel method,6,10 –12 is very disordered and exhibits a very broad
diffraction signal, where the most-intense (111) cubic or tetragonal
peaks must appear. Before the gel– oxide transformation is com-
pleted, the structure is believed to be composed of Zr environments
entrapping hydroxides and aquo residue groups, in addition to
structural defects. The other structure is the slightly distorted (␩ ⱕ
0.2) and ordered (␦ ⱕ 3%) tetragonal t2-form, which is predomi-
nant at high temperatures; this structure has quadrupole parameters
that are very similar to those of the equilibrium tetragonal phase.
Table II lists the quadrupole parameters that have been fitted for
both the t1- and t2-forms in tetragonal zirconias. The t13 t2
(2)
transformation and the movement of the oxygen vacancies, which
occur as the temperature increases, prove that a redistribution of O
atoms occurs. In YSZs, the t13 t2 transformation partially reverts
upon cooling.
In most zirconias that have been prepared via the sol– gel
method starting with an organic precursor, in addition to the
previously described tetragonal t1-form, some of the as-obtained
products that are amorphous (as determined via X-ray diffractom-
etry (XRD)) are described by another disordered hyperfine inter-
action; this phase is labeled the x-phase,10,12 and its parameters
also are included in Table II. The disappearance of the x-phase at
approximately the organic firing temperature suggests that the
x-phase probably describes Zr environments that still contain
residue from organic preparation.
II. Experimental Procedure
(1) Sample Preparation
The starting solution was prepared by adding zirconium
n-propoxide (ZNP) (70 wt% of zirconium in n-propanol, Product
22989, Alfa Products, Danvers, MA) to methanol, ethanol, or
2-propanol with nitric acid (HNO3), under an anhydrous nitrogen-
gas atmosphere. Subsequently, a mixture of distilled water and
acetic acid (3:1 ratio by weight) was added carefully to each of the
preparations while stirring. After 10 h, the resulting solutions were
quite transparent and pale yellow and had a pH of 0.5. The
powders were prepared by gelling the solutions in an open flask at
a temperature of 60°C and subsequently drying the obtained gels at
100°C. Samples were designated as G1 (using methanol), G2
(using ethanol), and G3 (using 2-propanol).
(2) X-ray Diffraction Measurements
Room-temperature XRD analyses were performed on the as-
obtained powders and after heat treatments for 2 d at several
temperatures (in the range of 150°–1000°C). Powder XRD data
Frequency, ␻ (Mrad/s) Asymmetry parameter, ␩ ␦ (%)
1261 0.331 ⱕ3
1674 0 ⱕ3
0 0 ⱕ3
February 2000 Zirconium Oxide Structure Prepared by the Sol–Gel Route: I, The Role of the Alcoholic Solvent
Table II. Hyperfine Parameters of the Precursor x-phase and Metastable Tetragonal t1- and t2-Forms in
Sol–Gel-Derived Zirconias†
x-phase
Measured temperature,
Tmeas (°C) ␻Q (Mrad/s) ␩ ␦ (%)
150 21515 0.655 253
1150
20‡
†
After Rivas et al.13 ‡After cooling from high temperature.
were collected with a diffractometer (Model PW1700, Phillips
Electronic Instruments, Eindhoven, The Netherlands), using CuK␣
radiation and a graphite monochromator; the 2␪ step size was
0.02°, and the time per step was 5 s. Diffractograms of the samples
were obtained in the 2␪ range of 20°–105°. The low-angle region
(2␪ ⫽ 27°–32°), at which the most-intense peaks of all the ZrO2
polymorphs appear, and the high-angle region (2␪ ⫽ 72°–76°),
which allows us to discern between tetragonal and cubic ZrO2
(t-ZrO2 and c-ZrO2, respectively) structures, were inspected care-
fully. Powder XRD data were used to calculate the average sizes
of the tetragonal crystallites from the magnitude of the half-width
of the (111) peak, using Scherrer’s equation.15
(3) Differential Thermal Analysis and
Thermogravimetric Analysis
Simultaneous differential thermal analysis/thermogravimetric
analysis (DTA/TGA) studies were conducted (Model STA 409,
Netzsch, Selb, Germany) on ⬃50 mg of the as-obtained powders,
under normal atmospheric conditions and over the temperature
range from RT to 1350°C. Magnesia (MgO) crucibles and an
␣-alumina (␣-Al2O3) reference were used, and the system was
calibrated against the melting point of gold (1063°C). The heating
and cooling rates were 10°C/min. The temperatures of the DTA
events were determined using the usual method, based on the
intersection of the DTA baseline with the extension of the linear
region of the peak rising slope. The temperature uncertainty was
estimated to be ⬍5°C.
(4) The PAC Experiment
The powder gels were encapsulated in air at atmospheric
pressure in sealed quartz tubes (volume of 0.5 cm3) and then
neutron-irradiated with a flux of 1013 neutrons/(cm2䡠s) for ⬃1 d to
achieve the desired 181Hf activity (⬃200 ␮Ci). The hyperfine
interaction was determined using two cesium fluoride (CsF)
detectors with a temporal resolution of ␶R ⫽ 0.75 ns. Coincidence
spectra (C(␪,t)) were collected for 1 or 2 d for each gel at
increasing temperatures up to 1150°C (except for sample G1, for
which the highest measurement temperature was 950°C) and then
at temperatures that gradually decreased to RT. The mean temper-
ature uncertainty was 5°C. Then, the experimental A2G2(t) data
derived from Eq. (1) were fitted to a theoretical function, using a
nonlineal least-squares fitting procedure. Various sets of quadru-
pole parameters (f, ␻Q, ␩, ␦), which depict the lattice EFGs, were
obtained from the best fits that were achieved.
III. Results
Results for all the samples, taken from the different experi-
ments, are shown in Figs. 1–7. Figure 1 shows the diffraction
patterns of the as-obtained gels, and Fig. 2 shows the XRD-derived
sizes for the tetragonal crystallites, as a function of the annealing
temperature. Figure 3 presents the DTA heating and cooling
curves, and Fig. 4 shows the TGA heating curves. Figures 5 and 6
present the PAC results; Fig. 5 shows PAC spectra at selected
temperatures, and Fig. 6 shows the thermal evolution of the
hyperfine quadrupole parameters, which fit all the PAC spectra
that have been obtained better. Figure 7 shows the thermal
behavior of the monoclinic fraction, as a function of reciprocal
temperature. Finally, Fig. 8 is a plot of the calculated partial charge
379
t1-form t2-form
␻Q (Mrad/s) ␩ ␦ (%) ␻Q (Mrad/s) ␩ ␦ (%)
1603 0.534 253 1823 0.173 31
1374 0.352 111 1584 0.163 21
1673 0.496 162 1902 0.102 11
distribution of zirconium and propoxide species, as a function of
the number of solvent molecules added.
(1) X-ray Diffractometry
Figure 1 shows that the XRD patterns of the as-obtained gels are
those of an amorphous material and are superimposed over some
broad signals at the main tetragonal diffraction positions (2␪ ⬵
30°, 50°, and 60°). Also, the definition of the tetragonal peaks was
observed to improve, according to the sample sequence G3 3 G2
3 G1. RT diffractograms, after the samples were heated for 2 d at
increasing temperatures above 250°C, revealed the gradual defi-
nition of t-ZrO2 peaks. After heating at 450°–500°C, the predom-
inance of the crystalline tetragonal phase was unambiguous and
traces of monoclinic ZrO2 (m-ZrO2) appeared in all the gels. At
850°C, the monoclinic phase was dominant, and at 1000°C,
m-ZrO2 was the only phase. The tetragonal crystallite sizes that are
plotted in Fig. 2 (which could not be calculated at temperatures
⬍150°C for sample G1 and ⬍350°C for samples G2 and G3) show
that, for all temperatures, the tetragonal crystallite sizes of sample
G1 are smaller than those of sample G2, and those of sample G2,
in turn, are smaller than those of sample G3.
(2) Thermal Events
The DTA curves of Fig. 3 are similar for all the gels. They
revealed subtle slope changes at temperatures that are known to
correspond to the elimination of the adsorbed water and solvent. In
the temperature range of 250°–350°C, a double and broad peak
that is associated to bound water and organics elimination12 could
be observed. At a temperature of ⬃485°C, a rather sharp and large
asymmetric exothermic peak appeared, which has been reported as
being due to dehydroxylation12 that occurs at the oxide crystalli-
zation temperature. The very wide peak, starting at 600°C and
centered at ⬃760°C, corresponds to the elimination of the last
(OH)⫺ groups,16 oxygen absorption, and the t 3 m metastable
transition.12 The slope changes observed near 1100°C are indica-
tive of the m 3 t equilibrium phase transition.
Fig. 1. XRD patterns for the as-obtained gels.
380 Journal of the American Ceramic Society—Caracoche et al.
Fig. 2. Tetragonal average crystallite sizes, as derived from XRD
information.
Fig. 3. DTA heating and cooling curves, taken at 10°C/min.
In correspondence with the DTA results, the TGA data in Fig.
4 reveals a continuous mass loss from RT up to 450°C. Between
this temperature and 530°C, the mass loss becomes more pro-
nounced. The change in the slope of the TGA curves that occurs at
⬃600°C can be interpreted as the onset of oxygen absorption. This
change, in addition to removal of the last residual hydroxyl groups,
leads to the net mass gain that is plotted in detail in the figure,
extending over the 600°–1000°C region. Samples G1 and G3
gained almost twice as much weight as sample G2.
Upon cooling, the DTA curves showed exothermic peaks at
⬃910°C, which correspond to the t 3 m equilibrium reverse phase
transition. TGA results did not show any appreciable change for
any of the gels.
(3) Structures at Nanometer Scale: PAC Results
The PAC spectra shown in Fig. 5 were fitted for the already-
known four interactions: x-phase, the t1- and t2-forms, and m-ZrO2
(also see Fig. 6 ). No dynamic interactions had to be considered to
fit the spin-rotation curves of all the gels satisfactorily. As Fig. 6
suggests, the gels must be analyzed separately.
Vol. 83, No. 2
(A) Powder Gel G1: The as-obtained powder gel presents
two hyperfine interactions, which are assigned to the noncrystal-
line x-phase (15%) and the metastable highly distorted tetragonal
t1-form (45%). A third interaction, which corresponds to a disor-
dered (␦ ⬵ 10%) m-ZrO2 phase, also is present in a relevant
amount (40%).
At 150°C, both the quadrupole frequency and the asymmetry
parameter of the t1-form reveal substantial changes: the former
increases, and the latter decreases.
At 350°C, the x-phase interaction has disappeared. In the
temperature range of 350°– 450°C, the t1 3 m transformation
begins to occur, whereas the t1-form shows a noticeable decrease
in its quadrupole frequency.
At 550°C, the decrease of the distribution width (␦) of the
disordered monoclinic phase to 5% indicates that the crystalliza-
tion of this structure increases. At 950°C, ⬎90% of the sample is
composed of the monoclinic phase.
(B) Powder Gel G2: The as-obtained gel presents only two
interactions: x-phase and the t1-form. The x-phase is the dominant
phase.
At temperatures between RT and 250°C, the x 3 t1 transfor-
mation and, simultaneously, some variations in the hyperfine
parameters of the corresponding interactions can be observed. At
350°C, the x-phase has disappeared.
In the temperature range of 350°– 650°C, the t1 3 t2 transfor-
mation occurs. The parent t1 interaction exhibits a decrease in its
quadrupole frequency. The interaction that describes the t2-form is
dominant from temperatures ⬎450°C.
At 650°C, after the t1-form has disappeared, a small amount of
distorted m-ZrO2 phase (compare its ␩ value with that given by
Caracoche et al.8) is needed to give an account of the hyperfine
pattern. The evolution continues through a progressive t2 3 m
transition, and the monoclinic phase achieves its proper parameters
over the temperature range of 850°–1050°C.
At 1050°C, the m 3 t equilibrium phase transition can be
observed clearly through the variation of the relative fractions.
(C) Powder Gel G3: The as-obtained gel G3 is depicted
entirely by the x-phase interaction. This situation is unaltered up to
a temperature of 250°C.
At 450°C, the x-phase interaction has disappeared and the
sample is 100% tetragonal, exhibiting almost the same hyperfine
pattern as gel G2 at 350°C. However, the subsequent behavior of
the hyperfine interaction is different. At 650°C, an incipient
increase of the t2-form and the appearance of m-ZrO2, both at the
expense of the tetragonal t1-form, can be observed concomitant
with the decrease of the quadrupole frequency of the parent
interaction.
At higher temperatures, m-ZrO2 grows at the expense of the two
metastable tetragonal forms t1 and t2. At 1050°C, 90% of the
material is t2-form and the t1-form has disappeared.
During cooling, PAC spectra were fitted with a mixture of
m-ZrO2 and t2-ZrO2. The powders are fully monoclinic at temper-
atures of 800°, 250°, and 600°C for samples G1, G2, and G3,
respectively.
(4) Thermal Behavior of the Monoclinic Fraction
Information about the growing of the monoclinic phase was
obtained by plotting the monoclinic fractions against the reciprocal
absolute temperature during the thermal evolution of the gels.
Figure 7 clearly shows that the metastable t 3 m transformation is
a thermally activated process that obeys an Arrhenius dependence.
The figure also shows the values of the activation energies that
have been calculated from the slopes of a lineal fit; the smallest
activation energy corresponds to sample G1 and the highest
activation energy corresponds to sample G2.
IV. Discussion
(1) As-Obtained Gels
The starting gels, which were almost amorphous, according to
XRD, have been described by three hyperfine interactions. Two of
February 2000 Zirconium Oxide Structure Prepared by the Sol–Gel Route: I, The Role of the Alcoholic Solvent 381

Fig. 4. TG heating curves, taken at 10°C/min.

Fig. 5. Selected PAC spectra; the measurement temperatures are

indicated. Solid curves correspond to the best fits obtained.

Fig. 6. PAC relative fractions and quadrupole parameters thermal

them are very disordered—the x-phase and the t1-form. The PAC
relative fraction of the t1-form increased in the following order:
sample G3 3 sample G2 3 sample G1. This order matched that
of the increasing sharpness of the tetragonal diffraction signal at 2␪
⬵ 30°. The third interaction, which corresponded to a disordered,
nondiffractable m-ZrO2, is present exclusively in sample G1.
Considering the interpretation given for the x-phase and t1-form
zirconium hyperfine configurations, the initial t1-form:x-phase
evolution ((ƒ) x-phase, (F) t1-form, (E) t2-form, and (䡺) m-ZrO2).
intensity ratio could give some idea of the degree of hydrolysis that
was achieved during the synthesis of the gels. This ratio, which
was 3.3, 0.3, and 0 for powder gels G1, G2, and G3, respectively,
shows that the extent of hydrolysis decreases as the length of the
chain of the alcohol used as solvent during the synthesis increases.
382 Journal of the American Ceramic Society—Caracoche et al.
Fig. 7. Relative fraction of monoclinic phase, as a function of reciprocal
absolute temperature. Activation energies, calculated assuming an Arrhe-
nius thermal dependence, are indicated.
The presence of a considerable amount of disordered monoclinic-
like ZrO2 from the lowest temperatures in sample G1 also is
indicative of the major degree of hydrolysis that has been achieved
in this gel.
These experimental results can be explained using the reactions
that could occur between the nucleophilic molecules of the solvent
and the electrophilic and nonsaturated coordinated Zr atoms of the
ZNP. Any nucleophilic substitution can be described by the
following three-step process:
␦⫹
H Consequently, one can conclude that the addition of solvent
␦⫺ ␦⫹ P ␦⫺
R⬘OH ⫹ Zr OPr 3 R⬘O O OZrO O Pr
step 1 step 2
⫹ ⫹
␦ ␦
3 R⬘OO ZrO Pr OH 3 R⬘OOZr ⫹ PrOH
step 3
For the substitution to be successful, the Zr atoms and the leaving
HOPr species must be positively charged. The entire process is
dependent on the charge distribution in the alkoxide and the
complex of the transition state [(HOR⬘)-Zr-(OPr)n] that is formed
during step 2. However, the R⬘ radicals in step 1 will have a
marked influence on the process. A simple theoretical calculation
that is based on the partial charge model,17 in which steric
hindrance effects are neglected, can provide a reasonable expla-
nation of the different chemical reactivity of ZNP when dissolved
in methanol, ethanol, and isopropanol. The results are shown in
Fig. 8, where the behavior of the partial charge distributions of Zr
(␦Zr) and OPr (␦OPr) are plotted as a function of the number of
molecules of the solvent added to ZNP. Figure 8(a) shows that a
high increase of ␦Zr is observed when methanol is used, and no
appreciable changes can be observed when isopropanol is used. In
Fig. 8(b), ␦OPr generally is negative but becomes positive when
three molecules of methanol are added. As in the model used, the
alkoxy bridging does not promote any charge distribution over the
atoms; this simple calculation indicates that the Zr(OPr)4 in HOPri
would have a high tendency for alkoxy bridging. Figure 8(b) also
shows the calculated ␦OPr values when water molecules are added.
Although water is the more-reactive molecule, which explains the
high reactivity of the zirconium alkoxides with water under neutral
media, the strong acid medium reduces the nucleophilic water
reactivity, which allows other nucleophilic additions (such as
alcohol solvating or alkoxy bridging) to occur before hydrolysis.
Vol. 83, No. 2
Fig. 8. Partial charge distribution of Zr and propoxide (OPr) species as
a function of the number of solvent molecules added.
molecules to ZNP produces more-reactive molecules in the case of
methanol than that with ethanol or isopropanol. This fact is
consistent with the different t1-form:x-phase PAC population
ratios and can explain the decreasing degree of hydrolysis in
samples G1, G2, and G3.
(2) Thermal Evolution
The lack of dynamic effects in the hyperfine patterns at all
temperatures suggests that oxygen vacancies that are introduced by
the sol– gel synthesis and/or eventually caused by the thermal
removal of residues are not sufficient to cause any observable
movement. This observation is contrary to what has been reported
for structural-charge-compensating vacancies that are inherent to
doped stabilized zirconias.12,13,18
The DTA/TGA and XRD results can be correlated to some
extent with the evolution of the structure of the Zr environments
that are revealed in detail by the PAC experiments. This correla-
tion can be performed despite the dissimilar thermal treatments of
the experiments that have been conducted in this work (10°C/min
in DTA/TGA, at least 2 d at each temperature in in situ PAC
measurements and after annealing at increasing temperatures in
XRD).
At moderate temperatures, the tetragonal phase in either or both
of its two configurations (the t1- and t2- forms) erupts (in the case
of powder gel G3) or grows (in the case of powder gels G1 and
G2). This observation is consistent with the XRD data. The
tetragonal phase forms at the expense of the x-phase interaction,
which disappears in all gels at temperatures at which the elimina-
tion of the organic groups is known to occur. In addition, the
hyperfine characteristics of the interactions that are involved
change while the transformation develops, thus reflecting the
evolution of the nanostructures as the preparation residues are
eliminated.
Dehydroxylation and crystallization, which is observed at a
temperature of ⬃480°C via DTA/TGA, is revealed using PAC in
February 2000 Zirconium Oxide Structure Prepared by the Sol–Gel Route: I, The Role of the Alcoholic Solvent
powder gel G1 by the appearance of the perfect and ordered
monoclinic-phase hyperfine interaction. The pre-existence of dis-
ordered precipitates of nondiffractable monoclinic-like material
from the lowest temperatures seems to facilitate crystallization of
the monoclinic phase, rather than the t2-form, because of destabi-
lization of the t1-form. This fact leads one to consider the
as-obtained powder gel G1 as a tetragonal matrix with dispersed
monoclinic-like particles in the form of small nondiffractable
clusters that, despite the smallest crystallite size of the parent
tetragonal phase (see Fig. 2), promote early appearance of the
crystalline monoclinic phase. The smallest activation energy
against the t 3 m transition that has been determined for this gel
(see Fig. 7) contributes to the preceding interpretation. On the
other hand, and consistent with the XRD information, in powder
gels G2 and G3, the tetragonal phase is the form that crystallizes
at ⬃450°C. Although in powder gel G2, the t2-form grows at the
expense of the t1-form at temperatures of ⱖ350°C, both tetragonal
forms are present simultaneously in powder gel G3 from 450°C; in
addition, a slight t13 t2 conversion is revealed only at 550°C,
along with the appearance of ⬃20% of m-ZrO2. The reduction of
the quadrupole frequency of the t1-form remaining configurations
that have been observed at temperatures ⬎350°C in the case of
powder gels G1 and G2 and at ⬎550°C in powder gel G3 indicates
that some defect redistribution occurs as the transformation from
t1-form to other structures occurs. To understand the different
crystallization behavior that has been observed, a hypothesis that a
fraction of x-phase is composed of at least two types of Zr
surroundings that are nonresolvable via PAC has been imagined.
One of them—monomeric (hereinafter called x1) and, thus, pre-
dominant in powder gel G1—fires at low temperatures and results
in the t1-form. The other type—polymeric and firing at higher
temperatures (hereinafter called x2)—is structurally more related
to the t2-form and results in this latter tetragonal form. This
assumption helps to explain the crystallization process in powder
gels G1 and G2: although, in sample G2, the t1-form initially
grows at the expense of the x1-phase interaction and the t2-form
appears at higher temperatures at the expense of the late-
disappearing x2-phase, only t1-form tetragonal configurations are
present in sample G1. This interpretation, if considered with the
pre-existence of monoclinic “seeds” in powder gel G1, favors
direct and easy crystallization of the monoclinic phase. The lack of
PAC data for powder gel G3 at the temperature of appearance of
the tetragonal phase prevents the authors from speculating about
the crystallization aspects in this gel.
In regard to the coincident temperature of the onset of the broad
DTA exothermic peak and the relative mass gain that is attributed
to oxygen adsorption in TGA (at ⬃600°C), it has been suggested
that the elimination of the last (OH)⫺ groups is concomitant with
oxygen absorption.16 In fact, removal of the hydroxyl groups
yields a nonstoichiometric structure that is thermodynamically
unstable and has an affinity for oxygen. These chemical modifi-
cations seem to be reflected in powder gels G1 and G3 through the
changes exhibited in the quadrupole parameters of the t1-form
within the temperature range of 650°–950°C (see Fig. 6). In
powder gel G2, in which the t1-form does not exist in the thermal
range that has been considered, the monoclinic product exhibits
variations in its hyperfine parameters in the temperature range of
650°– 850°C. The eight-O-coordinated t2-form shows no apprecia-
ble changes; therefore, it is reasonable to infer that the loss of
(OH)⫺ groups and oxygen absorption must involve the highly
defective t1-structure (in samples G1 and G3) or the incipient
monoclinic product (in sample G2). The smaller relative mass gain
that is revealed via TGA for sample G2 might be associated with
a lower degree of nonstoichiometry of the lattice here, which can
be ascribed to the distorted monoclinic phase.
Upon cooling, it can be clearly recognized that sample G2 is the
gel that retains the t2-form down to the lowest temperature. In
contrast to what occurs in doped zirconias, the t1-form does not
definitively appear in any of the gels, which indicates that oxygen
vacancies that are derived from synthesis and residue removal
have been eliminated during the previous thermal heating.
383
In regard to the influence of the alcohol on the stability of the
tetragonal phase, it can be concluded that ethanol yields a
condensed product that evolves with temperature clearly as
x-phase 3 t1-form 3 t2-form 3 m-ZrO2. In comparison with the
other gels, in sample G2, the t2-form attains its larger abundance
and is retained during a larger thermal range both during heating
and cooling, it absorbs less oxygen, and the activation energy for
the t 3 m metastable transition has its highest value. These
observations indicate that the use of ethanol leads to better
stabilization of the tetragonal phase.
V. Conclusions
Substitution between the alkoxy groups of the starting zirco-
nium n-propoxide and the alkoxy groups of the different alcohols
used as solvent has a relevant role in the sol– gel product that is
obtained and its subsequent thermal evolution. Results indicate the
following:
(1) The shorter the alcohol chain, the more hydrolyzed the gel.
This situation seems to originate in a major alkoxy interchange and
result in an increased relative fraction (via perturbed angular
correlation, PAC) of the t1-form. As a consequence of extreme
hydrolysis, methanol, which has the shortest alcohol chain, leads to
a relevant amount of precipitated pseudomonoclinic “seeds.”
(2) Zirconia (ZrO2) crystallization occurs via a two-step
process. In the first step, the organic groups are fired, which leads
to a different appearance of the two tetragonal forms in gels
formed using ethanol and 2-propanol (samples G2 and G3,
respectively) and monoclinic ZrO2 (m-ZrO2) in gels formed using
methanol (sample G1). The dissimilar crystallization behavior of
powder gels G2 and G3 has been explained using the hypothesis
that the parent x-phase compounds contain organic groups of
different sizes that fire at different temperatures and produce one
of the two tetragonal zirconia forms predominantly. In contrast, in
powder gel G1, the pre-existing monoclinic seeds promote direct
crystallization to m-ZrO2, which involves the lowest activation
energy. The second step occurs after the last (OH)⫺ groups have
been eliminated and the lattice absorbs oxygen to achieve the
major stoichiometry, which leads to m-ZrO2 in samples G2 and
G3.
(3) Ethanol seems to be the alcohol that best stabilizes the
tetragonal phase. The PAC method allows unambiguous establish-
ment of the following thermal sequence for the transformations
that this gel undergoes: x-phase 3 t1-form 3 t2-form 3 m-ZrO2.
Here, the tetragonal phase attains its maximum abundance and
exhibits the greatest reluctance to make the transition to m-ZrO2
upon heating, as well as cooling.
(4) Oxygen vacancies that are introduced via sol– gel synthe-
ses of zirconia do not cause any observable movement and become
cancelled as the gels incorporate oxygen at temperatures ⬎600°C.
(5) The PAC technique has been shown to be highly efficient
in determining the local structure and the thermal evolution of
zirconia gels that initially are amorphous via X-ray diffractometry.
This technique also has made it possible to determine relevant
differences between zirconia products that are obtained using
different alcoholic solvents.
Acknowledgment
The authors are very grateful to Dr. D. Quattrini (Centro Atómico Bariloche,
Comisión Nacional de Energı́a Atómica) for his cooperation with the thermal
analyses.
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