Surfaces and Interfaces 21 (2020) 100683

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Surfaces and Interfaces

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Synthesis of meso-porous gamma-alumina membrane: effect of yttria T

addition on the thermal stability
Shirin Khanmohammadia, Ehsan Taheri-Nassaja, , Morteza Farrokhi-Radb
⁎

a
Department of Materials Engineering, Faculty of Engineering, Tarbiat Modares University, P.O. Box 14115-143, Tehran, Iran
b
Department of Materials Engineering, Faculty of Engineering, Azarbaijan Shahid Madani University, P.O.Box: 53751-71379, Tabriz, Iran

ARTICLE INFO ABSTRACT

Keywords: In this study supported meso-porous gamma-alumina membrane with a thickness of 2.5µm was synthesized on a
Gamma-alumina macro-porous alpha-alumina substrate via colloidal sol-gel route. To evaluate the improvement in the thermal
Membrane stability of alumina by yttria addition, unsupported alumina membranes with various amounts of yttria (0, 2.5, 5
Sol-gel and 10%mol) were investigated by XRD and TG-DTA analyses. Based on XRD results and considering transitional
Thermal stability
alumina stabilization effect, the optimum concentration of yttria was determined to be 5%mol. The results of
Yttria
Porous
DTA analysis showed that 5%mol yttria addition shifted the gamma to alpha phase transformation to higher
temperatures.

1. Introduction as gamma (γ), delta (δ) and theta (θ) phases. All these polymorphs can
be produced by the sequential transformations as follows:
Porous materials have momentous applications in the fields of op-
boehmite(AlOOH) Al2 O3 Al2 O3 Al2 O3
tics, catalysis, gas separation, drug delivery, membranes, energy and
health [1–5]. The application is strongly dependent on materials com- Al2 O3
position and structure such as the pores size, shape, distribution and
Among these polymorphs, γ phase has found applications in the
connectivity [6]. Among diverse porous materials, ceramic membranes
field of membranes and catalyst supports because of its high surface
due to their high temperature and pressure resistance have found ex-
area and catalytically active surface sites [18–20]. γ-alumina mem-
tensive applications in the fields of gas and liquid separations and
brane can be formed by the coating of boehmite colloidal sol on the
membrane reactors. The sol-gel method is regarded as the most inter-
macro-porous substrates, followed by heat treatment leading to the
esting method for the fabrication of porous inorganic membranes owing
transformation of boehmite into γ-Al2O3. The morphology of boehmite
to its simplicity and cost-effectiveness [7–11]. Among ceramic mem-
sol particles and deposition conditions influence the eventual mem-
branes, alumina is one of the most commonly used materials and it is
brane microstructure and the smallest pore size is determined by the sol
used almost exclusively as a meso-porous intermediate layer prior to
particle size distribution [21,22]. For the membrane applications in
the coating of micro-porous silica membranes [12]. Supported and
gas-separation, water-gas shift reaction, coal gasification and specially
unsupported micro-porous silica is desirable to be applied is catalysis,
methane steam reforming (around 800°C), using high temperatures is
waste water treatment and optics as antireflective coating and etc.
inevitable. Therefore at these high temperatures, γ to α phase trans-
[13–15]. Graded composite membranes consisting of mesoporous alu-
formation occurs above 1000°C and affects the thermal stability of the
mina accompanied by microporous silica layer on top can be good
membrane. This phase transformation is not desirable due to the micro
candidate as membrane reactor utilized in steam reforming of methane.
crack formation, loss of specific surface area, increasing pore sizes and
Steam reforming of methane is a reaction which is used to produce
finally the destruction of porous structure [23,24].
hydrogen as clean fuel for energy systems. In the aforementioned
Generally Al2O3 structure can be divided into two categories: a face-
graded membrane reactor, hydrogen producing reaction and hydrogen
centered cubic (FCC) or a hexagonal close-packed (HCP) arrangement
separation can occur simultaneously [16,17].
of oxygen anions. Cations distribution also results in different alumina
Aluminum oxide is known to exist in various polymorphs including
polymorphs. For example in γ, δ and θ structures with FCC–packed
thermodynamically stable alpha phase (α) and metastable phases such
oxygen sublattice, Al3+ cations occupy both octahedral and tetrahedral

⁎
Corresponding author.
E-mail addresses: khanmohammadishirin@yahoo.com (S. Khanmohammadi), taheri@modares.ac.ir (E. Taheri-Nassaj).

https://doi.org/10.1016/j.surfin.2020.100683
Received 30 April 2020; Received in revised form 6 August 2020; Accepted 5 September 2020
Available online 10 September 2020
2468-0230/ © 2020 Elsevier B.V. All rights reserved.
S. Khanmohammadi, et al.
sites in various proportions, while α phase with HCP packing is iden-
tified with octahedral sites occupied by Al3+ cations [25–27]. γ-Al2O3
is accepted to have spinel structure of AB2O4 with FCC-packed oxygen
sublattice in which divalent cations (A) occupying tetrahedral and the
trivalent cations (B) occupying octahedral sites. In order to maintain
electroneutrality in the spinel structure of Al2O3, it requires vacancies
and because cations reside on two distinct positions, vacancies are
considered to exist either in tetrahedral or octahedral positions ran-
domly [26]. By γ to α transformation, the packing of oxygen ions re-
mains unaffected but Al3+ cations rearrange from their octahedral and
tetrahedral sites to new octahedral sites. Rearrengement of octahedral
Al ions can take place just by simple jumping of cations to other vacant
octahedral sites, but tetrahedral cations migrate into octahedral sites of
HCP structure [28].
The effect of dopants such as La, Ce, B and silica on the inhibition or
retardation of γ to α phase transformation has been extensively in-
vestigated. The most suitable elements are lanthanide or rare earth
metals [23,28–32]. Research conducted by Zhang et al. [33] showed
the optimal thermal and hydrothermal stabilities for silica-doped alu-
mina as catalyst support. Chen et al. [34] indicated the enhancement of
crystallization temperature of γ-alumina and also γ to α transformation
for mesoporous γ-alumina by incorporation of phosphorous. According
to Tran et al. [35], La2O3 could promote CH4 and CO2 conversion for
methane reforming application of mesoporous alumina.
The change in the phase transformation mechanism can be justified
by two principals: altering the activation energy and the kinitics of
transformation. Activation energy is connected to oxygen ions re-
arrengement but not to the rearrengement of cations. Therefore the
activation energy for transformation is unaffected by the presence of
dopants. But oppositely, the kinetics of transformation is influenced in
two different ways by the presence of dopant ions. Dopant ions occupy
the available vacancies in the spinel structure of alumina and decrease
the velocity and kinetics of the transformation by affecting cations ar-
rangement. Furthermore, due to the solubility limitation of dopant ions
in alumina structure and their segregation, nucleation sites and diffu-
sion process reduces and leads to the decrease of transformation ki-
netics [36].
In this study, γ-alumina and yttria-doped alumina thin films were
prepared by colloidal sol-gel method. The aim of yttria addition was to
shift γ to α phase transformation to higher temperatures and improves
γ-alumina's thermal stability. Supported and unsupported membrane
properties were characterized by XRD, TG-DTA and FESEM analyses.
DLS analysis was used in order to investigate colloidal sol properties.
The phase transformation mechanism and yttria's role in this me-
chanism have also been discussed briefly.
2. Experimental
2.1. Support preparation and characterization
α-alumina disks as the substrate with dimensions of 4.5cm diameter
and 2mm thickness were fabricated using uniaxial pressing method. For
this purpose, α-alumina powder with average particle size of 0.3μm and
8%Wt distilled water were utilized. The obtained green disks were
dried at room temperature and subsequently sintered at 1400°C. Prior
to coating procedure, sintered substrates were polished with sand pa-
pers up to 1200 grade and washed with distilled water and dried at
room temperature. The microstructure of the substrate was inspected
by FESEM images taken by MIRA-TESCAN field emission scanning
electron microscope. The apparent porosity of the substrate was mea-
sured based on ASTM C20-92 standard. For this purpose, dry weight (D)
of samples was measured and then kept for hours in boiled water. After
that the weight of the immersed samples (S) was determined. In the
next step the water drops removed from the surface of samples by
moisturized cotton and saturated weight (W) was measured. Apparent
porosity was calculated according to the following equation.
2
Surfaces and Interfaces 21 (2020) 100683
P=
W D
W S (1)
Image J analysis was also utilized to estimate the porosity of the
substrate according to the SEM image.
2.2. Sol preparation and characterization
Boehmite sol was prepared using aluminum tri-sec-butoxide (ATSB,
Merck), distilled water and nitric acid (65%, Merck). ASTB was added
into the preheated water at 80°C by the molar ratio of
water:ASTB=100. After 1 hour stirring, HNO3 was added drop wise to
the solution. Finally boehmite sol got prepared after stirring for 12
hours under reflux condition. In order to dip-coat the substrates, the
prepared boehmite sol was mixed with of 3.5wt% polyvinyl alcohol
solution (PVA, Merck, MW=7200) prior to coating procedure. For
preparing yttria (5%mol) doped boehmite sol, 50g/L of yttrium nitrate
(Y(NO3)3.6H2O, 99.99%, Dae Jung) solution and the boehmite sol were
mixed 3 hours in the molar ratio of yttrium nitrate to boehmite of 0.05.
A dynamic light scattering analyzer (DLS) by Malvern- ZEN3600 in-
strument was used to measure the particle size distribution of boehmite
sols.
2.3. Supported membrane preparation and characterization
The substrate was coated with dipping and withdrawal rate of
10mm.min−1 and holding time of 10s. After coating procedure, mem-
brane was calcined for 3 hours at 600°C with the heating and cooling
rate of 0.5°C/min. The coating and calcination cycles were repeated
twice in order to increase the thickness and cover the defects and un-
coated areas of the membrane layer.
The microstructures of γ-alumina membrane on α-alumina support
were observed using a MIRA-TESCAN field emission scanning electron
microscope (FESEM). The thickness of the layer was determined using
cross-sectional FESEM image. Same like substrate, Image J analysis was
also conducted in order to estimate the porosity level of the coating.
Atomic force microscope (AFM, CP-Research) was used to determine
the surface topography and the roughness of coating.
2.4. Unsupported membrane preparation and characterization
The resultant sols were dried in the petri dishes as xerogel powders
(unsupported membrane). Characterizations were carried out on un-
supported membranes by assuming that their properties are similar to
those of supported membrane layers. The thermal stability of the un-
supported alumina and yttria-doped alumina membranes was in-
vestigated by thermo gravimetric/differential thermal (TG/DTA) ana-
lysis using STA 1640 thermogravimetric analyzer. For this purpose, the
xerogels calcined at 1200°C for 1 hour were used as the samples. X-ray
diffraction (XRD) analysis was also conducted for the aforementioned
samples by X’ Pert MPD operating at 40KV and 30mA with Cu-Kα ra-
diation of wavelength 1.54°A in the 2θ range from 10° to 90°.
3. Results and discussion
3.1. α-alumina support characteristics
The FESEM images from the microstructure of the substrate are
shown in Fig. 1-a,b. The apparent porosity based on the method ex-
plained in the experimental section calculated to be 50% which is al-
most in accordance with the result estimated by Image J analysis
(Fig. 1-c). The calculated porosity by Image J is around 41%. According
to the substrate structure and porosity level, it can be considered as a
macro-porous membrane support. The porosity level is in accordance
with the acquired amount of porosity (35-50%) for membrane supports
to ensure permeability and sufficient mechanical strength
S. Khanmohammadi, et al. Surfaces and Interfaces 21 (2020) 100683

Fig. 1. FESEM image of α-alumina structure sintered at 1400°C at (a) high, (b) low magnifications and (c) image obtained by Image J analysis.

simultaneously [37].

3.2. Boehmite sol characteristics

The results for particle size distribution of boehmite sol obtained by

DLS method are shown in Fig. 2. As can be seen, the particle size for
boehmite sol is in the range of 3-11.7nm. The particle size distribution
for boehmite sol containing 3.5wt% of PVA shifted to 24.8-80.4nm. As
it is observed, with the addition of PVA to the boehmite sol, particles
get coarser which is in agreement with the results reported by Ecsedi
et al. [38]. This effect not only makes suitable sol particles to create a
meso-porous layer, but also prevents the infiltration of the particles into
the macro-porous substrate. PVA is a semicrystalline polymer with
hydroxyl groups, which gives rise to hydrogen bonds between sol par-
ticles [38] or in other words, it promotes agglomeration of the ceramic
particles. The creation of hydrogen bonds between boehmite particles
and PVA molecules is shown schematically in Fig. 3.

3.3. Supported membrane characteristics

Fig. 3. Schematic illustration of hydrogen bonds creation between boehmite

Fig. 4 shows the surface microstructure of γ-alumina coating before
and after the addition of PVA into the boehmite sol. As it is seen, the
absence of PVA in the sol resulted in the cracked surface. Beside the
benefits outlined earlier for PVA addition, one more reason is that it
prevents crack formation while drying and calcination procedure. As far
as is known, binders have major role in increasing the strength and
preventing the crack generation [39–41]. Development of hydrogen
bonding between sol particles and PVA leads to the reduction in surface
tension [42,43]. According to the Laplace equation (Eq. (2)) in the
following, capillary pressure is controlled by the surface tension of li-
quid (γlv), pore size (Rp) and also wetting angle between pore wall and
liquid (θ). Thus the capillary pressure descends in proportion to the
surface tension reduction [44].
Fig. 2. Particle size distribution of boehmite sol with and without PVA.
particles and PVA molecule.
2 lv Cos
Pc =
Rp (2)
Another acceptable explanation for the role of PVA is that, it pro-
vides internal lubrication among particles which avoids crack appear-
ance [45]. Therefore PVA addition could act as a factor capable of
controlling either the particle size distribution and coating quality.
Fig. 5-a shows the cross sectional FESEM image of the γ-alumina
membrane on the α-alumina substrate. As can be seen the thickness of
the twice-coated γ-alumina layer is about 2.5µm and has good contact
with the support. The FESEM image from the top view of the γ-alumina
membrane is shown in Fig. 5-b,c. As it is seen, no defect can be observed
on the surface of the layer formed on the α-alumina support. In addi-
tion, the synthesized membrane has good surface uniformity. Particle
size obtained from the surface FESEM image is in good agreement with
the particle size distribution of the sol shown in Fig. 2. Thus the sol
particle size distribution is important parameter to determine the final
microstructure of the membrane and its particle and pores size. The
porosity level of the alumina layer based on the Image J analysis of SEM
image of Fig. 5-c is estimated to be approximately 25%.
Fig. 6-a,b shows the 3-D and 2-D images from the surafce of doped
alumina membrane. According to the images, the dark areas represents
pores among the particles. The average roughness from the different
areas of membrane suraface according to AFM images is 5.3nm.

3
S. Khanmohammadi, et al. Surfaces and Interfaces 21 (2020) 100683

Fig. 4. FESEM images from sintered alumina surface (a) without and (b) with PVA addition in the sol.

3.4. Unsupported membrane characteristics
Fig. 7 shows the XRD patterns of boehmite xerogels at different
temperatures. As the temperature increases to 600°C, the boehmite to γ-
alumina phase transformation occurs. According to XRD patterns, the
identified phase is mainly boehmite (AlOOH) at room temperature and
only small quantities of bayerite (Al(OH)3) phase also present. At
400°C, the mixture of boehmite and γ–alumina could be identified
which demonstrate the initiation of boehmite to desirable γ-alumina
transformation. Due to the completion of phase transformation, only γ
phase related peaks are visible at 600°C. The average crystallite size of
boehmite based on Scherrer equation is estimated to be 2.4nm and
3.2nm at room temperature and 400°C, respectively. At 600°C there is
no boehmite phase and the average obtained γ-alumina crystallite size

Fig. 5. FESEM images from (a) cross section, (b,c) surface of the sintered γ-alumina membrane and (d) Image J analysis of surface.

4
S. Khanmohammadi, et al.
Fig. 6. 3-D (a) and 2-D (b) AFM topographical images from the membrane surface.
is 7.8nm.
The XRD patterns of the unsupported alumina membranes con-
taining various amounts of yttria calcined at 1200°C are shown in
Fig. 8. For the pure alumina sample, only α phase is detected and there
is no other phase. The sample having 2.5mol% of yttria also transforms
to α phase after calcination at 1200°C and some amounts of delta and
theta phases also present. Yttria addition up to 5 and 10mol% stabilizes
mainly delta and theta phases, however small amount of α phase still
exists. Some peaks also correspond to crystalline phase of Y3Al5O12
(YAG). Despite the expectations, increasing yttria amount up to 10%
cannot reduce considerably or vanish α phase compared to the sample
with 5mol% yttria. The calculated crystallite size of formed α phase is
76nm for pure alumina, while it decreased by the yttria addition. The
crystallite size shifted to approximately 55, 25 and 32nm for alumina
containing 2.5%, 5% and 10% mol yttria, respectively. As it is seen,
yttria addition successfully could lower α phase amount, either by de-
creasing crystallite size or decreasing related peaks intensity. These
results indicate that the retarding effect of yttria on the γ-Al2O3 to α-
Al2O3 phase transformation occurs at its optimum concentration of
5mol%. The smallest crystallite size also achieved at 5% mol yttria,
indicating the lowest amount of α phase for this sample.
Fig. 7. XRD patterns of alumina gels at (a) RT, (b) 400 and (c) 600°C.
5
Surfaces and Interfaces 21 (2020) 100683
Additional information over the thermal stability of the un-
supported membranes was provided by TG/DTA analysis. Fig. 9 shows
the TG/DTA curves for the unsupported alumina gels containing 0 and
5mol% of yttria. The DTA curve for the both samples shows an en-
dothermic peak around 100-250°C related to the removal of physical
water adsorbed on the particles, decomposition of organic groups and
also removal of water presents in the pores. The weight loss of 20wt%
can be measured from TG curve in this region. Second endothermic
peak around 350-500°C is due to the dehydroxylation of boehmite
(AlOOH → γ-Al2O3+H2O) which was also seen in other previous
published works [46]. The related weight loss of this region according
to TG analysis is about 20%. The weight loss is negligible above 500°C
and it is halted around 600°C. The DTA curves of both samples are
similar and the only difference is seen around 1200°C. Above 1150°C an
exothermic peak is observed for pure alumina attributed to the for-
mation of α-alumina from γ phase. This exothermic peak is not ap-
peared for the sample with 5mol% of yttria. These observations prove
the shift of phase transformation temperature and stabilizing effect of
yttria which makes this membrane applicable at higher temperatures.
As it was explained earlier, dopant addtition lowers the velocity and
transformation kinetics through (1) affecting cations arrangement and
S. Khanmohammadi, et al.
Fig. 8. XRD patterns of (a) 0%, (b) 2.5%, (c) 5%, (d) 10%mol yttria doped alumina gels calcined at 1200°C.
Fig. 9. TG-DTA diagrams of (a) alumina, (b) 5% yttria doped alumina gels calcined at 1200°C.
(2) reducing nucleation sites. Yttrium retards the transformation from γ
to delta and theta alumina and its succeeding transformation to α. The δ
and θ formation before growing into α (XRD results in Fig. 8) suggests
that the transformation kinetics is relatively low.
Phase diagram in Fig. 10 [47] shows that yttria has very low solu-
bility in alumina. Former investigations have shown that the solubility
of yttria in alumina is in the range of ppm [36,48]. Solid solubility
happens because trivalent yttrium ions substitute aluminum ions inside
alumina structure. Octahedral vacancies are larger than tetrahedral
ones, so it is predicted that yttrium ions occupy octahedral vacancies of
γ-alumina structure and decrease the concentartion of available octa-
hedral sites below the value required for α phase transformation. The
cations are positioned only at the octahedral sites in the α structure. So
the drop in the concentration of octahedral vacancies prevents the
migration of Al cations toward the octahedral sites and therby inhibits
the α phase formation. Therefore the diffusion of Al cations at elevated
temperatures cause them to distribute in both tetrahedral and octahe-
dral vacancies in different portions and result in δ and θ formation
instead of pure α.
The significant decrease in the γ→α transformation velocity for the
sample with high amounts of yttria caused by the fact that yttria is
6
Surfaces and Interfaces 21 (2020) 100683
relatively insoluble in alumina which provides evidence that these large
ions can affect the diffusional process in alumina. Due to the limited
solubility, yttria segregation and consequently the precipitation of
garnet occur at higher concentration of yttria. Garnet is formed through
reaction between alumina and segregated yttria. The garnet particles
present in the transformation interface reduce the possible nucleation
sites. It can also block the diffusion sites. Garnet particles can prevent
the growth of metastable α alumina nuclei and exceeding their critical
size needed for the formation of stable α nucleuses [49]. The rate of α
nucleation decreases due to the lower surface area of alumina grains
which garnet particles laid on. Therefore yttria additive increases the
transformation temperature and changes phases sequence during
transformation through affecting transformation kinetics.
4. Conclusion
Because of destructive impact of γ-α phase transformation on
membrane's porous structure, stablizing transitional alumina is vital
factor in high temperature applications. The effect of yttria addition on
the thermal stability of meso-porous γ-alumina has been investigated.
The results showed that doping 5 mol% of yttria is sufficient to enhance
S. Khanmohammadi, et al.
Fig. 10. Equilibrium phase diagram of Al2O3-Y2O3 [32].
the thermal stability of alumina. This remark is in agreement with the
DTA data which indicates phase transformation shifts to higher tem-
peratures. The higher thermal stability of Y2O3-added gel is related to
the retarded γ to α phase transformation. This effect could be explained
by (1) solubility and incorporation of yttrium ions in the defective
spinel structure of alumina, (2) formation of second phase and grain
boundries segregation of additive which reduce α nucleation sites.
In the following, the applicability of the produced yttria-doped γ-
alumina as an intermediate layer for H2-permselective ceramic based
membranes (such as microporous silica) in the field of steam reforming
reaction can be further investigated.
Author statement
Dear Dr. Hong Deng,
We have submitted the revised manuscript entiteled “Synthesis of
meso-porous gamma-alumina membrane: effect of yttria addition on
the thermal stability” and claim that all authors participated sufficiently
in this work and all meet authorship criteria.
Sincerely yours,
E. Taheri-Nassaj
Conflict of Interest
Dear Editor,
The authors whose names are listed below certify that they have no
affiliations with or involvement in any organization or entity with any
financial interest, or non-financial interest in the subject matter or
materials discussed in this manuscript titled “Synthesis of meso-porous
gamma-alumina membrane: effect of yttria addition on the thermal
stability”.
Authors names:
Shirin Khanmohammadi
Ehsan Taheri-Nassaj
Morteza Farrokhi-rad
7
Surfaces and Interfaces 21 (2020) 100683
Declaration of Competing Interest
None.
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