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Synthesis of lanthanum aluminate by reverse chemical precipitation using

pseudoboehmite as alumina precursor

Article  in  Applied Radiation and Isotopes · January 2016

DOI: 10.1016/j.apradiso.2016.01.026

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 Applied Radiation and Isotopes 117 (2016) 96–99

Contents lists available at ScienceDirect

Applied Radiation and Isotopes

journal homepage: www.elsevier.com/locate/apradiso

Synthesis of lanthanum aluminate by reverse chemical precipitation

using pseudoboehmite as alumina precursor
Hernández Muñoz Wilson a,n, Serrato Rodríguez Juan a, Muñoz Saldaña Juan b,
Zárate Medina Juan a
a
Instituto de Investigación en Metalurgia y Materiales, Universidad Michoacana de San Nicolás de Hidalgo, C.P. 58060 Morelia, Michoacán, México
b
Centro de Investigación y de Estudios Avanzados del IPN, Unidad Queretaro, Libramiento Norponiente No. 2000, Fracc. Real de Juriquilla,
Queretaro CP 76230, México

H I G H L I G H T S

Lanthanum aluminate was synthesized by reverse precipitation out of pseudoboehmite.

Pseudoboehmite proved to be an advantageous lanthanum aluminate synthesis precursor.

A mechanism of formation of lanthanum aluminate is proposed.

art ic l e i nf o a b s t r a c t

Article history: Lanthanum aluminate was synthesized by using reverse precipitation. A lanthanum nitrate salt in so-
Received 30 October 2015 lution allowed the precipitation of lanthanum hydroxide onto the surface of the pseudoboehmite par-
Received in revised form ticles. Pseudoboehmite was previously synthesized out of aluminum sulfate which after characterization
25 January 2016
presents a poor crystallized structure. A Perovskite-type lanthanum aluminate was obtained at different
Accepted 26 January 2016
Available online 27 January 2016
temperature and calcination time. When calcination was set up to 1500 °C to 3 °C/min pure, high crys-
tallinity and highly agglomerated lanthanum aluminate is obtained, relative density of 94% was reached.
Keywords: & 2016 Elsevier Ltd. All rights reserved.
Lanthanum aluminate
Psuedoboehmite
Reverse precipitation

1. Introduction al,2008). These techniques use expensive precursors to synthesize

Nowadays multi-functional advanced materials have enormous
impact on technology due to its favorable combination of prop-
erties, one interesting group are ceramics based on the Ln2O3–
Al2O3 system (ln¼lanthanide element) which exhibits out-
standing mechanical, optical, electronic, and electrical properties
(Luo and Wang, 2008; Yu et al., 2009). In the past, much research
has been devoted to dosimetry applications. In particular, ultra-
violet dosimetry relies on thermoluminescent (TL) materials; such
as lanthanum aluminate (LAO), that provides a good combination
of thermal stability and mechanical durability in service (Oliveira
et al., 2011; Alves et al., 2014). LAO belongs to the perovskites
group and can be obtained by co-precipitation-calcination tech-
nique (Brylewski and Bućko, 2013) of lanthanum oxide and alu-
minum oxide. LAO can also be synthesized by a variety of methods
including, combustion (Tian et al., 2007), high energy ball milling
(Zhang and Saito, 2000), precipitation (Kuo et al., 2009; Behera et
n
Corresponding author.
pure LAO, therefore it needs an economic way to produce LAO.
A low-cost alumina precursor is the pseudoboehmite (PB)
which is an hydrated aluminum oxihydroxide, that can be readily
synthesized (Zárate et al., 2005) and can be easily dispersed in
order to obtain non agglomerate nanometric particles (Zheng
et al., 2014). Therefore the aim of the present work is synthesize
single-phase LAO using solid-phase synthesis method, which is
modified by the special method of the precursor preparation. The
LAO physical characterization was presented and a model of for-
mation of LAO based on a thermally activated diffusion process is
proposed.
2. Materials and methods
PB was obtained dissolving reactive grade aluminum sulfate
(Meyer 99.9%) in destilled water (300 gr/L). Then this solution was
stirred and after 24 h it was filtered. Ammonium hydroxide (J.T
Baker 68%) was heated at 60 °C and stirred, then aluminum sulfate
solution was injected at 0.1 mL/min, simultaneously ammonium

http://dx.doi.org/10.1016/j.apradiso.2016.01.026
0969-8043/& 2016 Elsevier Ltd. All rights reserved.
 H.M. Wilson et al. / Applied Radiation and Isotopes 117 (2016) 96–99
Fig. 1. IR spectrum of pseudoboehmite.
Fig. 2. XRD spectrum of PB.
hydroxide was dropped in order to keep pH above 11.
Gel-like precipitates were obtained after injection followed by
aging that was carried out for 1 h. Subsequently the precipitated
was filtered and washed with deionized water at 60 °C many times
until no gel formation in barium chloride was observed after re-
acting few drops collected from the last filtering. Gels were dried
at 80 °C for 24 h. Finally, powders were milled in an alumina
mortar.
Lanthanum nitrate hexahydrate 0.5 M solution (J.T Baker 99.9%)
was prepared in deionized water to obtain lanthanum aluminate;
PB was subject to mechanochemical treatment consisting of mil-
ling in alumina mortar and adding nitric acid until formation of a
peptized PB. Both lanthanum nitrate solution and peptized PB
were mixed and stirred, then ammonium hydroxide was dropped
maintaining pH above 11 producing gel-like precipitates. Then
they were stirred for 1 h, washed in distilled water and filtered.
Gels were dried at 100 °C for 24 h to render the LAO powders.
Calcination was carried out at different temperature and time in
air. Powders were finally pressed uniaxially at 550 MPa and sin-
tered at 1600 °C for 5 h.
IR measurements were collected in a Bruker Tensor 27 spec-
trometer with 1 cm  1 resolution and 1.6 mm/s scanning rate. X
97
Fig. 3. XRD spectra of LAO powders calcined at different conditions of temperature
and heating rate.
ray spectra were acquired using Siemens D5000 using Cu Kα ra-
diation. SEM and TEM examinations were conducted in a JEOL
6400 microscope and Philips Technai F-20, respectively. Density
measurements were done by the Archimedes' method.
3. Results
IR spectroscopy was used to identify the PB bonding according
to the characteristic bands in terms of vibration intensity and
frequency. Fig. 1 represents IR spectrum of PB, firstly one can see
broad peaks showing PB structure is disordered; 3300, 3000 and
1069 cm  1 bands correspond to hydroxyl groups while 1638 cm  1
peak represents water (Cobo et al., 2006; Rodríguez-páez et al.,
2001).
The pseudocristalline structure of PB and the phases in the
calcined precursor of LAO powders were analyzed by XRD. Fig. 2
presents XRD patterns of pseudoboehmite dried after 24 h, it
shows lower intensities and peak broadening meaning that PB is a
poor crystallized aluminum oxyhydroxide. Peaks were indexed
using the PDF chart JCPDS 211307 corresponding to boehmite,
such peaks are characteristics of PB and were reported by Zyl et al.
(1993) and Zárate et al. (2005).
Fig. 3 shows XRD spectra of LAO powders calcined at different
temperature, time and heating rate. At 800 °C peaks of perovskite
LAO phase (JCPDS 031-0022) are observed, which can be assigned
to rhombohedral structure with R3c spatial group, also peaks of
additional phases can be observed i.e. LaAl11O18 and La10Al4O21.
These additional phases do not disappear at 1000 °C, 1300 °C and
1500 °C when the heating rate is 5 °C/min, however if heating rate
decreases to 3 °C/min and temperature rises to 1500 °C, LAO is the
only phase observed by XRD. Presumably, the low heating rate
allows for a better diffusion of atoms, and better homogenization
takes place leading to the LAO desired phase.
Fig. 4 presents SEM and HRTEM micrographs of LAO powders
calcined at 1500 °C for 10 h. Agglomeration of individual rounded
particles within the size range of 0.25–1 mm as well as the onset of
abnormal grain growth can be seen in Fig. 4(a). Fig. 4(b) shows
crystallites randomly oriented where two interplanar distances
were measured corresponding to the (110) and (012) planes ac-
cording to JCPDS 031-0022. The inserts in the HRTEM figure are
the Fourier transform, FT and the inverse Fourier transform, IFT, of
the (012) planes.
98 H.M. Wilson et al. / Applied Radiation and Isotopes 117 (2016) 96–99

2.68 Å
(110)

3.57 Å
(012)

5 nm

Fig. 4. SEM (a) and HRETM (b) micrographs of LAO powders calcined at 1500 °C for 10 h-3 °C/min.

Fig. 5 shows the sintered free surface of LAO powders pressed

at 550 MPa and sintered at 1600 °C-5 h-3 °C/min. It can observed
normal grown grains of about 5 mm due to sintering. Red arrows
show the presence of terracing effects which may indicate high
surface diffusion during sintering. The relative density was 94%
73, which is in good agreement with results obtained by Li (95%)
(Li et al., 2004), Lano (94%) (Lano et al., 2014).

4. Discussion

In order to obtain pure LAO at low temperature, it is necessary

Fig. 5. SEM micrograph of LAO sintered at 1500 °C for 10 h-3 °C/min and pressed at
550 MPa. (For interpretation of the references to color in this figure legend, the
reader is referred to the web version of this article.)
to have homogeneous component distribution and to control hy-
droxides formation as a function of pH, this can be done by using
La and Al salts or chlorides as precursors, as was demonstrated
by Li et al. (2004), Kuo et al. (2007), Behera et al. (2008) who
obtained LAO at temperatures as low as 600°C. However, in the
case of the PB precursor it is difficult to maintain homogeneous
component distribution mainly due to the ample particle size
distribution so diffusion paths can be large for the reaction which

Fig. 6. Schematic representation of the proposed mechanism of formation of LAO.

 H.M. Wilson et al. / Applied Radiation and Isotopes 117 (2016) 96–99
produces LAO (Li et al., 2004). On the other hand the thermal
parameters, heating rate and time, can be adequately designed to
obtain pure LAO.
Presence of additional phases during thermal treatment could
be explained analyzing LAO formation mechanism schematically
presented in Fig. 6, at beginning of reaction PB particles are sur-
rounded by lanthanum hydroxides formed during precipitation
(Fig. 6a), rising of temperature facilitates both La and Al ions dif-
fusion which in turns produces LAO and other compounds for-
mation (La10Al4O21 and LaAl11O18) (Barrera et al., 2007), LAO for-
mation with perokskite-type implies changes on coordination
shell of Al ions, whereas other compounds formation involves Al
and La interdiffusion (Barrera et al., 2007). Besides LAO formation
requires perfect mixing of both constituent cations in the pre-
cursor powders (Djoudi et al., 2012) which is proved by no de-
tection of La2O3 and Al2O3 in XRD spectra (Fig. 6d). Presence
LaAl11O18 indicates LAO reacted with Al2O3 (Ropp and Carroll,
1980) possibly due to PB segregation while presence of La10Al4O21
indicates lower La quantity (Krishnan et al., 2015) possibly due to
PB segregation or inaccuracies of La precursor, respectively
(Fig. 6c).
Oliveira and Alves (Oliveira et al., 2011; Alves et al., 2014) have
proved that LAO can be doped with Ce and Dy increasing TL re-
sponse to UV radiation as compared to undoped LAO, so the
synthesis of LAO using PB as an alumina precursor could be seen as
an alternative technique for doping LAO.
5. Conclusion
Reverse precipitation of lanthanum precursor on top of the PB
particles proved to be a suitable technique to synthesize LAO since
it allowed to obtain a pure crystalline phase. Even though addi-
tional phases were detected when LAO powders were submitted
to low temperature thermal treatments or high rates of heating,
the remnant phases could be eliminated through low heating rates
and by increasing calcination temperature at 1500 °C.
Acknowledgments
The authors would like to thank CIC-UMSNH and Conacyt
Projects 223069, 254932 for its support.
References
Alves, N., Ferraz, W.B., Faria, L.O., 2014. Synthesis and investigation of the lumi-
nescent properties of carbon doped lanthanum aluminate (LaAlO3) for appli-
cation in radiation dosimetry. Radiat. Meas. 71, 90–94, Available at 〈http://
View publication stats
99
www.sciencedirect.com/science/article/pii/S1350448714000341〉 [accessed
14.10.15].
Barrera, a, et al., 2007. Structural properties of Al2O3–La2O3 binary oxides prepared
by sol–gel. Mater. Res. Bull. 42 (4), 640–648, Available at 〈http://linkinghub.
elsevier.com/retrieve/pii/S0025540806003199〉 [accessed 09.10.13].
Behera, S.K., et al., 2008. Phase evolution in gel-precipitated LaAlO3 ceramics. J.
Phys. Chem. Solids 69 (8), 2041–2046, Available at 〈http://linkinghub.elsevier.
com/retrieve/pii/S0022369708000619〉 [accessed 09.10.13].
Brylewski, T., Bućko, M.M., 2013. Low-temperature synthesis of lanthanum
monoaluminate powders using the co-precipitation–calcination technique.
Ceram. Int. 39 (5), 5667–5674, Available at 〈http://www.sciencedirect.com/sci
ence/article/pii/S0272884212014447〉 [accessed 14.03.14].
Cobo, Q.J., et al., 2006. Síntesis de nanopartículas de Al2O3 a partir de Al2(SO4)3 
18H2O: estudio de los mecanismos de formación de partícula. Revista Latio-
namericana de Metalurgia y Materiales 26 (2), 95–106.
Djoudi, L., Omari, M., Madoui, N., 2012. Synthesis and characterization of lantha-
num monoaluminate by co-precipitation method. EPJ 00016, 29.
Iano, R., et al., 2014. Single-step combustion synthesis of LaAlO3 powders and their
sintering behavior. Ceram. Int. 40 (40), 7561–7565.
Krishnan, T.R., Sherly, K.B., Moothedan, M., 2015. Structural characterization of nano
lanthanum aluminium oxide synthesized by the sol-gel method. Universe of
emerging technologies and science II (II), 1–5.
Kuo, C.-L., et al., 2007. Low temperature synthesis of nanocrystalline lanthanum
monoaluminate powders by chemical coprecipitation. J. Alloy. Compd. 440 (1–
2), 367–374, Available at 〈http://linkinghub.elsevier.com/retrieve/pii/
S092583880601471X〉 [accessed 05.12.13].
Kuo, C.-L., Chang, Y.-H., Wang, M.-C., 2009. Crystallization kinetics of lanthanum
monoaluminate (LaAlO3) nanopowders prepared by co-precipitation process.
Ceram. Int. 35 (1), 327–332, Available at 〈http://linkinghub.elsevier.com/re
trieve/pii/S027288420700380X〉 [accessed 05.12.13].
Li, W., Zhuo, M.W., Shi, J.L., 2004. Synthesizing nano LaAlO3 powders via co-pre-
cipitation method. Mater. Lett. 58 (3–4), 365–368, Available at 〈http://linkin
ghub.elsevier.com/retrieve/pii/S0167577X03005020〉 [accessed 09.10.13].
Luo, X., Wang, B., 2008. Structural and elastic properties of LaAlO from first-prin-
ciples calculations. J. Appl. Phys. 104 (7), 104–112, Available at 〈http://link.aip.
org/link/JAPIAU/v104/i7/p073518/s1&Agg ¼doi〉 [accessed 09.10.13].
Oliveira, V.H., et al., 2011. Study of TL properties of LaAlO3:Ce,Dy crystals for UV
dosimetry. Radiat. Meas. 46 (10), 1173–1175, Available at 〈http://www.science
direct.com/science/article/pii/S1350448711004379〉 [accessed 14.10.15].
Rodríguez-páez, J.E., Villaquirán, C., Cobo, J., 2001. Estudio de la formacion de los
complejos intermedios durante la sintesis de alumina. Mater. Res. 4 (4),
255–264.
Tian, Z.-Q., Yu, H.-T., Wang, Z.-L., 2007. Combustion synthesis and characterization
of nanocrystalline LaAlO3 powders. Mater. Chem. Phys. 106 (1), 126–129,
Available at 〈http://linkinghub.elsevier.com/retrieve/pii/S0254058407003483〉
[Accessed 09.10.13].
Yu, H.-F., et al., 2009. Thermochemical behavior of metallic citrate precursors for
the production of pure LaAlO3. J. Phys. Chem. Solids 70 (1), 218–223, Available
at 〈http://linkinghub.elsevier.com/retrieve/pii/S002236970800468X〉 [Accessed
09.10.13].
Zárate, J., Rosas, G., P, P., 2005. Estructural transformations of the pseudoboehmite
alumina to a-alumina. Adv. Technol. Mater. Mater. Process. 7 (2), 181–186.
Zhang, Q., Saito, F., 2000. Mechanochemical synthesis of lanthanum aluminate by
grinding lanthanum oxide with transition alumina. J. Am. Ceram. Soc. 41
(189189), 439–441.
Zheng, Y., et al., 2014. Peptization mechanism of boehmite and its effect on the
preparation of a fluid catalytic cracking catalyst. Am. Chem. Soc. 53,
10029–10034.
Zyl, A., et al., 1993. Synthesis beta alumina from aluminium hydroxide and oxy-
hydroxide precursors. Mater. Res. Bull. 28, 145–157.
Ropp, R.C., Carroll, B., 1980. Solid state kinetics of LaAl11O18. J. Am. Ceram. Soc. 63
(7–8), 416–419.