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DOI : 10.2240/azojomo0172
Structural Transformations of the
Pseudoboehmite to ĄAlumina
Written by AZoM Dec 15 2005
J. Zárate, G. Rosas and R. Pérez
Copyright ADTECH; licensee AZoM.com Pty Ltd.
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AZojomo (ISSN 1833122X) Volume 1 December 2005
Topics Covered
Abstract
Keywords
Introduction
Experimental
Results and Discussion
Conclusions
Acknowledgements
References
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Structural Transformations of the Pseudoboehmite to Ą-Alumina
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Abstract
A study has been carried out on the structural transformations of the pseudoboehmite.
The pseudoboehmite is one of the main precursors of the αalumina. However, the
thermal route to obtain αalumina, gives rise to intermediate crystalline phases such as
the: γAl2O3, θAl2O3 and αAl2O3. In this investigation pseudoboehmite has been
synthesized through a desulphatation of the commercial Al2(SO4)3 using an ammonia
solution. The obtained pseudoboehmite has been annealed at different temperatures to
obtain the intermediate crystalline phases. Xray diffraction patterns, scanning and
transmission electron microscope techniques and dilatometer measurements have been
used in the microstructural characterization.
Keywords
Ceramics, Structural Materials, Chemical Synthesis, Electron Microscopy, XRay
Diffraction
Introduction
Alumina (Al2O3) is one of the best ceramic structural materials. This nonmetallic
material has been widely studied in recent years [1, 2]. These studies have been
prompted due to a large number of characteristic physical properties and also to different
type of applications. These include properties such as: high wear resistance, resistance
against high temperature corrosion, high electrical resistivity, high thermal conductivity
and an already established ceramicmetal joining technology. This ceramic is already
used as a structural sections subjected to mechanical loads usually at high
temperatures. Alumina is also used as an effective electrical insulator. Different
applications of this material usually requires particular associated properties design,
therefore, studies to improve the mechanical strength, the electrical conductivity, the
thermal diffusion, the resistance under corrosion environments etc., have been carried
out in recent years. Most of these properties are strongly dependent on the processing
route to obtain the thermodynamic stable αalumina. The aluminum hydroxides (HA)
and the oxyhydroxides (OHA) are the main resource materials to obtain the alumina.
The most used names for these compounds are related with the mineralogical
nomenclature [3]. Thus, for example, crystalline compounds such as Al2O3.xH2O where
1<x<2 are known as boehmite, however, when this compound has a poor crystallinity,
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Structural Transformations of the Pseudoboehmite to Ą-Alumina
the material is known as pseudoboehmite. The pseudoboehmite under heat similar to
the transformations of the boehmite [4]. Few investigations have been carried out on the
role of the pseudoboehmite as the structural induced phase of the α alumina. To get an
insight on these structural heat induced transformation, a morphological and structural
characterization of the heat induced intermediate phases is required. In this
investigation the nature of these transformations are studied. Also, the shrinkage
characteristics of the crystalline phases which are obtained under these transformations
are explored.
Experimental
The pseudoboehmite was obtained using the U. G. process of the alunite [5]. This
process is related with the alkaline desulphatation of the basic compounds [6]. Also, this
compound can been obtained with the desulphatation of the Al2(SO4)3 using an
ammonia solution. The obtained pseudoboehmite has a chemical composition of
Al4O3(OH)6. Furthermore, the compound derived from the commercial sulphate with a
chemical composition (wt%) given by: Al2O3 (98.9010), SiO2 (0.5560), CaO (0.4960),
Fe2O3 (0.0259), ZnO (0.0061), CuO (0.0053), SO3 (0.0048), NiO (0.0032) and K2O
(0.0015) [7]. The powders were annealed at 250, 550, 1000 and 1200°C. The
crystalline phases were obtained using Xray diffraction techniques (Siemens D5000).
Morphological characteristics of the powders have been obtained using the scanning
electron microscope SEM (Jeol 6400) also some microstructural characteristics were
obtained with a transmission electron microscope TEM (Jeol 2010). TEM specimens
were obtained from a suspension of the powders in isopropyl alcohol. Drops of this
suspension were deposited on a copper grid (3 mm in diameter) with an amorphous
carbon film. Dilatometer measurements (Dilatronic theta 6548) have also been used to
determine the nature of the structural transformations of the pseudoboehmite. The
specimens for the dilatometer measurements were small bars of 1cmX0.5cmX0.5cm.
These bars were obtained using an axial pressing instrument. The velocity of the
dilatometer experiments were carried out at 5oC/minute.
Results and Discussion
In order to obtain the structural transformation temperatures associated with this
compound, dilatometer measurements have been carried out. Figure 1 shows the linear
shrinkage (1a) and the corresponding derivative (1b) which represent the changes of the
pseudoboehmite structure. The maximum transformation velocity of the
pseudoboehmite to the γalumina is obtained at 500°C. The velocity of shrinkage is
higher at 1200°C. This corresponds to the θ to αalumina transformation. The initial
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Structural Transformations of the Pseudoboehmite to Ą-Alumina
features of the sintering process can be observed at 1500°C. These experimental
dilatometer results were used for the setting of the annealed temperatures of the
pseudoboehmite powders. Figure 2 shows a bright field image and its corresponding
electron diffraction pattern. The image contrast shows the characteristic spike
morphology of the pseudoboehmite. Figure 3 shows the Xray diffraction patterns
obtained from the pseudoboehmite and also from the annealed specimens at 550°C,
1000°C and 1200°C (c, b and a) respectively. Figure 3d shows the typical spectra of the
boehmite. However, the peaks are appreciably wide in shape. This effect is related with
the poor crystallization of this phase. This is the main reason for the name
pseudoboehmite. Figure 3c shows the spectra which correspond to the γalumina
obtained at 550°C. Furthermore, Figure 3b shows the θ alumina obtained at 1000°C.
Figure 1. Linear shrinkage of the pseudoboehmite sample (1a) and its corresponding
derivative (1b). Structural transformations are obtained at 500°C and also at 1250°C.
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Structural Transformations of the Pseudoboehmite to Ą-Alumina
Figure 2. Bright field image and its corresponding electron diffraction pattern of the
pseudoboehmite. The characteristic spike morphology of the pseudoboehmite can
clearly be seen.
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Structural Transformations of the Pseudoboehmite to Ą-Alumina
Figure 3. Xray diffraction pattern of the αphase (3a), the θphase (3b), the γphase
(3c) and the pseudoboehmite (3d). The θ, γ and pseudoboehmite phases present
poor crystallinity properties. However, the αphase spectrum has clear indications of a
enhanced crystallinity.
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Structural Transformations of the Pseudoboehmite to Ą-Alumina
Figure 4. TEM images of the γ and θ phases and their corresponding electron
diffraction patterns. The images illustrate the nanometric nature of the alumina
crystals and also their whisker morphology.
Both of these phases (γ and θ) still show appreciably wide peaks which indicates poor
crystalline conditions. It’s important to note that the crystalline state of the γ and θ
phases is lowest in comparision with the pseudoboehmite phase. However, Figure 3a
shows the spectra which corresponds to the αalumina. This spectrum was obtained
from the pseudoboehmite powders annealed at 1200°C. The peaks in the spectra are
narrow in shape, suggesting good crystalline conditions. Some reflections in the γ
alumina spectra are also obtained in the θ alumina spectra. This result is related with
the structural transformation of the cubic structure (γphase) to the monoclinic (θphase)
structure. The crystalline nature of the different phases is strongly dependent on the
annealed process. It is important to point out that both, the dilatometer experimental
results and the X ray diffraction patterns do not show any evidence of the δ alumina
presence. The Table 1 shows the Xray crystallographic values and also those obtained
after a minimum square refinement of the experimentally measured values. The lattice
parameters show a slight increment in their values, consequently there is also an
increment in the unit cell volumes. These variations could be related to impurities
obtained during the processing route. TEM observations of the annealed powders of the
pseudoboehmite have also been carried out. Figure 4 shows the TEM images and also
the diffraction patterns which corresponds to the γ and θ alumina phases. These images
illustrate the nanometric nature of the alumina precursors and also the whiskers
characteristic shapes. Both, the XRD results and the TEM observations show the
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Structural Transformations of the Pseudoboehmite to Ą-Alumina
presence of nanometric crystals in the pseudoboehmite phase. X ray diffraction results
and TEM observations obtained from the γ and the θ phases suggest an apparent
dependence on the structural characteristics of the pseudoboehmite. Figure 5 shows
the bright and dark field images of an alumina crystal. Also, its corresponding diffraction
pattern is illustrated. In contrast to Figure 4, these αalumina images shows larger
crystalline grains with sizes of a few hundred nanometers.
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Figure 5. Bright and dark field image of an α alumina crystal. Its diffraction pattern is
also illustrated. The crystal size is higher than 500 nanometers.
This result seems to be in agreement with the Xray spectra corresponding to this
crystalline phase (Figure 3a). Some annealed specimens show the presence of different
crystalline structures. This is illustrated in Figure 6. This figure shows a dark field image
and its corresponding diffraction pattern from a specimen annealed at 550°C.
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Structural Transformations of the Pseudoboehmite to Ą-Alumina
Figure 6. Dark field image of a pseudoboehmite specimen annealed at 550°C. The
diffraction pattern suggests the presence of pseudoboehmite and also γalumina.
Figure 7. HREM image of an αalumina specimen. The HREM image shows
interplanar distances which correspond to this crystalline structure (αalumina).
The indexation of the diffraction pattern suggests the presence of pseudoboehmite and
also γalumina. The presence of αalumina has also been obtained from the high
resolution electron microscope (HREM) images. This is illustrated in Figure 7 which
correspond to the specimen annealed at 1200°C. The HREM image shows interplanar
distances from the αalumina crystalline specimen.
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Structural Transformations of the Pseudoboehmite to Ą-Alumina
The XRD results and the TEM observations suggest a high crystallinity nature of the α
alumina phase. The precursor phases of the αalumina have nanometric crystalline
structures. Therefore, these phases have a strong influence on the structural nature of
the αalumina phase. The heat treatments or sintering of the precursors powders have
suggested the processing routes to obtain αalumina with nanometric crystalline sizes,
which will improve the mechanical properties of this material. The absence of the δ
phase and the less energy used to produce nanometric crystals of αalumina, could have
also some commercial implications along the production costs of αalumina.
Table 1. Lattice parameters variations of the different phases in comparison with the
values from the Xray crystallographic tables.
Lattice Parameters (Å) Lattice Parameters refinement (Å)
Phase a b c Vc a B c Vc
Conclusions
The microstructural characteristics of the polymorphic phases during the transformation
and the crystallization of the pseudoboehmite to the αalumina phase (PγθαAl2O3)
have been studied. The α alumina precursor phases (pseudoboehmite, γ phase and θ
phase) have crystal sizes in the nanometric range. The nanometric crystalline sizes of
the precursors phases suggest the control of microstructural evolution during the
formation of αalumina phase. Also, an increment in the lattice parameters of the
alumina phases has been obtained. This increment could be related with the presence
of impurities which have been produced during the synthesized process.
Acknowledgements
G. Rosas thank the UMSNH and CONACYT (38410U) for financial support.
References
1. D. Lee William and W. Mark Rainforth, “Ceramic microstructures. property control by processing”, Chapman & Hall, (1994) 3.
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Structural Transformations of the Pseudoboehmite to Ą-Alumina
2. J. Alexander Chediak, “Ceramic Engineers in the 21st Century”, The American Ceramic Society Bulletin, 75 [1] (1996).
3. R Tertian, and D. Papee, “Thermal & Hidrothermal Transformations of Alumina”, J. Phys. Chem., 55 (1958) 341353.
4. K. Wefers and C. Misra, “Alcoa Tech Reporte # 9”, Alcoa Tech Center, PA, USA (1987).
5. López W. X., “Three methods to produce alumina from alunite”, Light Metals., 2 (1977) 4958.
6. H. JuárezM, J. M. MartínezR. and J. M. RuvalcabaL., “Obtención y Caracterización de Pseudoboehmita a Partir de Sulfato de
Aluminio Comercial", IV Congreso Iberoamericano de Química Inorgánica y XI Congreso Mexicano de Química Inorgánica,
Guanajuato, Gto., México, (1993) 256260.
7. S. D. De la Torre, A. Kakitsuji, H. Miyamoto, K. Miyamoto, H. BalmoriR., J. ZárateM. and M. E. Contreras, “Seeding with α
Alumina for Transformation and Densification of BoehmiteDerived γ and δAlumina by Spark Plasma Sintering”, Ceramic
Transactions, 94 (1999) 8389.
Contact Details
J. Zárate G. Rosas
Instituto de Investigaciones Metalúrgicas Instituto de Investigaciones Metalúrgicas
Universidad Michoacana de San Nicolás Universidad Michoacana de San Nicolás
de Hidalgo de Hidalgo
Edificio U, C. U., C. P. 58000, Morelia, Edificio U, C. U., C. P. 58000, Morelia,
Michoacán Michoacán
Mexico Mexico
Email: [email protected]
R. Pérez
Instituto Mexicano del Petróleo
Programa de Investigación y Desarrollo de
Ductos
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Structural Transformations of the Pseudoboehmite to Ą-Alumina
Eje Central Lázaro Cárdenas 152, Col.
San Bartolo Atepehuacan
Gustavo A. Madero, 07730 México D. F.
Mexico
This paper was also published in print form in “Advances in Technology of Materials and
Materials Processing”, 7[2] (2005) 181186.
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