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CERAMICS
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Ceramics International 40 (2014) 1370313707

www.elsevier.com/locate/ceramint

Short communication

Fabrication of biomorphic Al2O3 ceramics with hierarchical architectures

by templating of cotton bers
Tao Zhang, Yuming Zhoun, Xiaohai Bu, Yongjuan Wang, Muyang Zhang, Jingang Hu
School of Chemistry and Chemical Engineering, Southeast University, Jiangsu Optoelectronic Functional Materials and Engineering Laboratory,
Nanjing 211189, China
Received 30 April 2014; received in revised form 2 May 2014; accepted 2 May 2014
Available online 11 May 2014

Abstract
This work presents an effective method for fabricating hierarchical Al2O3 ceramic bers with high surface-to-volume ratios. To do this, the
microscaled Al2O3 bers are fabricated via a simple biotemplate method employing cotton bers as bio-templates. The hierarchical architectures
are designed by in situ growth of AlOOH nanocrystal on surface of Al2O3 microtube walls in a closed hydrothermal system. The developed facile
route is highly valuable and feasible for hierarchical porous Al2O3 ceramic materials for applications in research and industrial elds.
& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Keywords: Al2O3 ceramics; Biomorphic ceramics; Cotton bers; Hierarchical structure

1. Introduction
Alumina (Al2O3) is an important functional material that has
attracted considerable attention in a variety of applications
including ceramic materials, adsorbents, catalysts, catalyst
supports, refractory materials, etc. To date, various morphologies of nanoalumina materials, such as nanobers [1],
nanorods [2], nanobelts [3], nanowires [3], nanoplates [4],
hollow and self-encapsulated microspheres [5], have been
successfully prepared. The properties of these alumina materials can be signicantly improved by special nanostructures.
However, the high surface energy of nano-Al2O3 makes them
extremely reactive, and most systems undergo aggregation
without protection of their surfaces [6], which limits their
industrial application in catalysis and adsorption. Additionally,
the separation and recycling of nano-Al2O3 from solutions can
be a problem due to the small sizes. There are two general
methods to overcome the limitations: one is through hierarchical assembly, where preformed, individual origami structures
are assembled to form larger structures [7], the other one is

Corresponding author. Tel./fax: 86 25 52090617.

E-mail address: fchem@163.com (Y. Zhou).

http://dx.doi.org/10.1016/j.ceramint.2014.05.005
0272-8842/& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

through the use of hierarchical templates to fabricate micro/

nanostructured alumina.
Hierarchically structured Al2O3 ceramic materials, which
possess dual or multiple morphologies and structures, are
attracting considerable attention owing to its synergism and
coupling effect on micro-nanoscales. It is remarkable that
many exploratory researches in this led have started to
fabricate hierarchically structured Al2O3 with various methods
including anion-mediated method [8], microwave-assisted
method [9], assembly method [10], template method [11],
etc. However, these methods either require elaborated equipment or need complex operational process. Cai et al. [12,13]
prepared a series of hierarchical Al2O3 by a non-template
hydrothermal synthesis and sequential calcination route using
aluminum nitrate or aluminum chloride as precursors. Fan
et al. [14,15] prepared the biomorphic Al2O3 with hierarchical
architectures using natural plant as bio-templates. The hierarchical structures down to the nanometer level, especially the
pore structures, were retained in the biomorphic Al2O3.
However, the structures of biomorphic Al2O3 are highly
dependent on biological templates. Hence, it should be
interesting to fabricate new structural Al2O3 with hierarchical
architectures based on the biotemplates. This may give rise to
new structural features, physical properties, and multifunctions

T. Zhang et al. / Ceramics International 40 (2014) 1370313707

from the synergy of the individual nanostructures and biological structures.

Although the template method is reliable, easy to implement
and cost effective to fabricate biomorphic materials, the
potential applications of biomorphic materials are limited due
to their limited microstructures. In this work, we combine the
biological template method with in situ growth technique and
design a novel route to fabricate biomorphic Al2O3 with
hierarchical architectures. In this route, the morph-Al2O3 with
ber structure is prepared by template-directed synthesis
employing cotton bers as bio-templates. Then, the hierarchical architecture is fabricated based on the controlled crystal
growth on the surface of Al2O3 bers in a closed hydrothermal
system. The advantage of this strategy is that the well-ordered
nanoparticles can be xed on surface of biomorphic Al2O3
bers to form the hierarchical architectures.

Al2O3 fibers
AlOOH fibers
hierarchical Al2O3 fibers

c
Intensity (a.u)

13704

b
a
15

30

45

60

75

2 Theta (degree)

Fig. 1. XRD patterns of Al2O3 bers, AlOOH bers and hierarchically

structured Al2O3 ceramic bers.

2. Materials and methods

The Al2O3 bers were prepared based on structure replication of cotton bers. In a typical preparation, 7.50 g of Al
(NO3)3  9H2O was dissolved in 200 mL ethanol solution to
prepare the precursor of alumina sol. Then 0.2 g of cleaned
cotton was immersed into the precursor sol for 3 h, followed
by ultrasonic treatment for 1 h. The inltrated cotton bers
were washed with distilled water to remove non-adsorbed
metal ions. After being dried at 80 1C for 12 h, the sample was
calcined at 550 1C for 4 h to obtain Al2O3 bers.
The hierarchically structured Al2O3 bers were prepared
based on the controlled crystal growth on the surface of Al2O3
bers. The detailed preparation process was described as
follows: 0.102 g of Al2O3 bers and 0.14 g of hexamethylenetetramine (HMT) were dissolved in 25 mL of distilled water
in a 30 mL autoclave Teon vessel. The reaction vessel was
further treated under a hydrothermal condition at 180 1C for
10 h. The obtained product was ltered, washed thoroughly
with distilled water for several times. After being dried at
80 1C for 12 h, the sample was calcined at 550 1C for 4 h to
obtain hierarchically structured Al2O3 bers.
The general structure of the samples was investigated using
an X-ray diffraction measurement on a Bruker-AXS D8 X-ray
diffractometer system with Cu K radiation at 40 kV and
40 mA. The morphologies and microstructures of prepared
samples were characterized by obtaining scanning electron
microscope (SEM) images using a Hitachi S-3400N SEM at an
acceleration voltage of 20 kV. The surface areas and pore-size
distributions of prepared products were analyzed by nitrogen
adsorption measurements, operated at 77 K on a Micromeritics
ASAP 2020 adsorption analyzer.
3. Results and discussion
Fig. 1 presents the XRD patterns of starting Al2O3 bers, the
products obtained by hydrothermal treatment of the starting
Al2O3 bers and the nal products of hierarchically structured
Al2O3 ceramic bers. In XRD patterns, the Al2O3 bers
(Fig. 1a) show only very broad and diffuse patterns, indicating

the amorphous nature of the Al2O3 bers obtained by a

sacricial template method. The hydrothermal treatment leads
to the change of structure of Al2O3 bers and the transformation of the phase from amorphous to crystalline boehmite
phase (Fig. 1b). No obvious XRD peaks arising from other
crystalline forms of alumina are observed, indicating the high
purity and crystallinity of the as-prepared AlOOH bers. The
XRD pattern of hierarchically structured Al2O3 ceramic bers
(Fig. 1c) shows weak reections at 2 theta of 45.781 (d400)
and 67.121 (d440), conrming the phase transformation from
-AlOOH to -Al2O3 after being calcined at 550 1C for 4 h.
During the hydrothermal process, the HMT decomposes to
formaldehyde and ammonia as primary products and the
decomposition is dependent on the solution pH [16]. According to previous studies, the morphology and structure of
AlOOH are determined by solution pH and inorganic anions.
Hence, the hydrothermal time may play a critical role in the
crystal growth of AlOOH in the hydrothermal process and
further determines the structure of the Al2O3 bers. Fig. 2
illustrates the morphology evolution of AlOOH bers at
various reaction times. Fig. 2A shows the overall morphology
of AlOOH bers prepared with a hydrothermal time of 3 h,
and indicates that the obtained products consist of ber
morphology with hierarchical architectures. It can be seen
from Fig. 2A and C that the outer diameter of the AlOOH
bers can be up to 57 m, and the surfaces of the inorganic
bers are covered by irregular nanoparticles. Compared with
Fig. 2A, the surfaces of inorganic bers (Fig. 2C) are
composed of numerous randomly ordered nanoparticles as
the hydrothermal time increased from 3 h to 12 h. Fig. 2D
shows the magnied image of the surfaces of inorganic bers
(Fig. 2C). It can be seen more clearly that the nanoparticles
exhibit a smooth surface and uniform diameter of  150 nm.
The hierarchical architectures are formed by epitaxial growth
of AlOOH nanoparticles on the surface of inorganic bers,
indicating that the mechanism of AlOOH growth process was
governed by in situ crystallization.

T. Zhang et al. / Ceramics International 40 (2014) 1370313707

13705

Fig. 2. SEM images of the AlOOH bers obtained at various hydrothermal reaction times: (A, B) 3 h and (C, D) 12 h.

Fig. 3. SEM images of the Al2O3 bers (A, B) and hierarchically structured Al2O3 ceramic bers (C, D).

Fig. 3 shows SEM images of typical starting Al2O3 bers and

the nal products of hierarchically structured Al2O3 ceramic
bers. Fig. 3A shows the overall morphology of Al2O3 bers,
which consist of bers with an average diameter of 8 m,
approaching the diameters of the paper-based Al2O3 bers
reported in previous research [16]. The magnied SEM images

are displayed in Fig. 3B; the exact microstructures of cotton

bers are retained in inorganic replicas. However, the microscaled Al2O3 ceramic bers are not sufcient to meet the
demands of various applications. The sub-micrometer structures
may meet the demand of potential applications such as
adsorption and catalysis. Fig. 3C and D shows the morphologies

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T. Zhang et al. / Ceramics International 40 (2014) 1370313707

500

AlOOH fibers
hierarchical Al2O3 fibers

400

Volume absorbed (cc/g)

However, the broad pore size distributions in the range of

420 nm are observed in AlOOH bers and hierarchically
structured Al2O3 ceramic bers. It is noteworthy that the AlOOH
bers and hierarchical Al2O3 ceramic bers have similar pore
size distribution and isotherm, implying the similar structural
and textural properties of two samples.

Al2O3 fibers

300

200

4. Conclusions
100

0
0.0

0.2

0.4

0.6

0.8

1.0

Relative pressure (P/P0)

Fig. 4. N2 adsorptiondesorption isotherms and BJH pore size distributions

(inset) of Al2O3 bers, AlOOH bers and hierarchically structured Al2O3
ceramic bers.

and microstructures of the calcined AlOOH bers. After the

phase structure change from boehmite phase to -Al2O3 phase,
the ber morphologies are well preserved. It should be noted
that nanoparticles are maintained on the surface of inorganic
bers as the microstructures of AlOOH bers (Fig. 2C and D).
The surfaces of the Al2O3 bers are covered by nanoscaled
Al2O3 particles, indicating that the prepared Al2O3 ceramic
bers show a hierarchical structure at scales ranging from
micro- to nanoscales. The structural design of biomorphic
Al2O3 bers can be extended to other biomorphic materials
for the purpose of obtaining largely enhanced physical and
chemical properties.
The Al2O3 bers have a hollow structure by removing the
cotton ber template, which allow the growth of the nanoparticles on the surface of inorganic bers. These nanoparticles
can provide high specic surface areas and porous structures.
The thickness of the Al2O3 microtube walls was reduced by
the growth of the nanoparticles. Hence, the surface structures
of Al2O3 bers are changed greatly by hydrothermal treatment.
To further conrm the structural changes, nitrogen adsorption
and desorption measurements are performed to estimate the
texture properties. The nitrogen adsorptiondesorption isotherm and the BJH pore size distribution of as-fabricated
materials are shown in Fig. 4. It shows that all the sorption
isotherms are of type IV according to IUPAC classication
with a sharp capillary condensation step at intermediate P/P0,
indicating the presence of mesopores in all the samples. The
calculated BET surface areas are 79.11, 180.98, and 203.27 m2/g
and the calculated total pore volumes are 0.13, 0.62 and
0.72 cm3/g for Al2O3 bers, AlOOH bers and hierarchically
structured Al2O3 ceramic bers, respectively. The increased
BET surface areas and pore volumes are attributed to the
formation of nanoparticles on the surface of Al2O3 bers. The
corresponding pore size distributions of as-fabricated materials
calculated from the BJH method are shown in the inset of Fig. 4.
The results reveal that the Al2O3 bers have a narrow pore size
distribution centered at 3.88 nm, implying that the sample
possesses uniform pore channels in the mesoporous region.

In this work, we developed a new approach for the

fabrication of the hierarchically structured Al2O3 ceramic
bers by combining the biological template method and the
hydrothermal method. The Al2O3 bers are prepared by
template-directed synthesis employing cotton bers as biotemplates. The hierarchical architectures are designed by
crystal growth on surface of microtube walls of Al2O3 bers
in a closed hydrothermal system. The surfaces of the microscaled bers are covered by nanoscaled Al2O3 particles,
forming the hierarchical structure at scales ranging from microto nanoscales. It is found that the as-fabricated materials
exhibit high surface area (203.27 m2/g) and large pore volume
(0.7214 cm3/g). This approach provides a facile and simple
way to fabricate the hierarchically structured Al2O3 ceramic
bers for use in elds such as adsorbents, catalysis, porous
ceramics, and catalyst supports.
Acknowledgments
The authors are grateful for the nancial support from the
National Natural Science Foundation of China (No. 51077013)
and Fundamental Research Funds for the Central Universities
(CXZZ13-0091, CXLX13-107 and CXLX12-0107).
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