Biomaterials
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Corresponding author: m_gabriela2004@yahoo.com
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Zn and Mg metallic nanotubes have attracted the
interest of researchers due to their fundamental importance
and potential applications as nanodevices and medicine
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The technique applied for obtaining metallic nanotubes
was to penetrate an ultrasonic vibration porous
semiconductor (matrix), through the pores of a template.
To obtain metallic nanotubes with Zn and Mg substrate,
anodized aluminum oxide (AAO) was used the sol-gel
method. The sol penetrated the AAO pores through
ultrasonic vibration. The AAO template, which
incorporated the sol into its pores, was then taken out and
the template was heated from room temperature to 400ºC,
at a heating rate of 1.0 ºC minï, in air. Finally, metal
nanotubes were formed by further annealing at 550 ºC in
hydrogen atmosphere for 1.5 h.
The morphology of the AAO template was analyzed
on a SEM environmental scanning electron microscope.
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(AAO), sol-gel
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In recent years, the theoretical and experimental
investigations on nanostructure synthesis and
characterization witnessed an unprecedent
development. Preparation of new nanostructured
materials, alongwith the theoretical and
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provide new opportunities in the evolution of
nanosystems, for various applications (electronic
detection, mechanical and magnetic devices at
nanometric scale [1, 2], information storage
systems [3-6], medical devices).
The simplest technique for nanostrcuture
synthesis is the pattern method [7-12]. Metallic
nanotubes attracted special attention, if
considering their electric conductivity, catalytic
activity, magnetism, etc [13, 14].
260
The practical importance of nanotubes lies in
the fact that the metabolic processes developed
inside the human organism are based on ionic
transfers through nanotubes [15-18].
Some researchers focused on the magnetic
properties of metallic nanotubes, respectively of
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of metallic nanostructure formation [23-29],
however the growth mechanism is still
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challenge for the authors of the present
investigation.
Consequently, discussed in the following will
be the synthesis of some Zn and Mg metallic
nanotubes using an aluminium oxide template
(AAO), as well as their growth mechanism. The
synthesized nanostructures may contribute to
obtaining new nanocomposites with unique
physical properties.
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Metallic Zn and Mg nanotubes have been
synthesized by the sol-gel method, the pioneering
approach of Martin [7,8]. The porous membrane
is obtained through aluminium anodization in
a special acid solution, at some difference of
potential. As the pores are spontaneously
developed, as a result of field-assisted
dissolution, the obtained membrane is defined
as a self-assembled template. Under such
circumstances, the pores form a compact,
almost periodical hexagonal network, so that
they may be selectively filled with metals,
semiconductors, insulating agents, respectively
superconductors, through electrodeposition.
vROXPH18‡iVVXH2FWREHU'HFHPEHU‡ pp. 260-264
 Zn AND Mg NANOTUBES FOR POSSIBLE MEDICAL APPLICATIONS

Each pore is a cylinder with constant diameter. 6\QWKHVLV RI PHWDOOLF QDQRWXEHV ZLWK $$2
The length-diameter ratio may be varied WHPSODWHV
within quite large limits, without provoking The colloidal solutions were obtained using
modifications in diameter along its lenght. ethylene-glycol as a solvent, tricaboxylic acid
as a corrosion agent and the solvable salts of
2EWDLQLQJRIDOXPLQDSRURXVPHPEUDQHV the corresponding metals as solutes.
Surface rugosity represents an important The metallic salts employed for Zn and Mg
factor in obtaining an ordered pore distribution. solution obtaining are: zinc acetate and
7KH DOXPLQLXP IRLO ² SUHYLRXVO\ GHJUHDVHG magnesium acetate. The solution was thermally
with acetone - was subjected to mechanical treated at a temperature of 60ºC, for 8 hours,
polishing for reducing surface rugosity to a by means of a thermostate.
few nm, after which the aluminium foil (Al) Nanotubes were obtained through thermal
was once again degreased and thermally decomposition, followed by reduction, under
treated at a temperature of 550 qC for hydrogen atmosphere, of the sol-gel precursor
approximately 6 hrs. The thus treated foil is from the pores of the AAO substrate. Figure 2
used as an anode in an aqueous solution of plots schematically the process of metallic
oxalic acid with a concentration of 0.4%, and nanotube manufacture.
subjected to a constant potential of 40 V, at a
temperature of 30ºC., for 12 hrs, after which
the rests of the aluminium layer still present
on the back of the anodized aluminium oxide
layer (AAO) substrate are corroded in an
aqueous CuCl2 solution.

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For increasing pore diameter, the AAO
template was dipped in a phosphoric acid
First step the AAO matrix was immersed in
solution with a 5% mass concentration, for 20
the colloidal solution for 15 min. Penetration of
min, at a temperature of 30ºC.
the colloidal solution inside the pores of the
Formation of the aluminium oxide layer
AAO substrate was made through ultrasonic
occurs as a result of aluminium oxidation by the
vibrations.
ions containing oxygen, when a difference of
In the second etaps the AAO support which
potential is applied.
incorporates the colloidal solution in its pores
The electrolyte nature, the applied tension and the
was taken out from the colloidal solution, the
duration of anodization control pores ordering.
excess of solution being wipped out, after which
7HPSHUDWXUH RI WKH HOHFWURO\WH LQÁXHQFHV SRUH
it was heated from room temperature up to
structure during anodization, even if to a lower
400ºC, at a heating rate of 1.0 ºC, in air.
extent [30].

International Journal of Medical Dentistry 261

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6LPRQD1,&+,78û(OHQD)2/(6&8

After the second stage, nanotubes of metallic

oxides were formed in the pores of the AAO
substrate.
In the next stage the ”dip-anneal-dip”
process was repeeted 3 times for each sample
in part, for obtaining nanotubes with a certain
wall thickness.
In the end of the process, the nanotubes
were obtained through additional treatment
at 600ºC, under hydrogen atmosphere, for 1
hr.
In stage four the metallic nanotube/AAO
composite was partially included into a
SRO\PHULFÀOP
b)
In the last stage the AAO template was )LJ6(0LPDJHVRID=QQDQRWXEHVSUHFLSLWDWHG
dissolved in an aqueous sodium hydroxyl IURPDFHWDWHLQDPDWUL[RIDOXPLQLXPDQRGL]HGLQ
solution. R[DOLFDFLGIRUKDWDWHQVLRQRI9EVL]HRIWKH
Formation of metallic nanotubes in the =Q$$2QDQRWXEHV
anodized aluminium (AAO) matrix was
investigated by SEM and EDX techniques.

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SEM images of the templated anodized matrix

in which the Zn and Mg nanotubes were formed
are plotted graphically in Figures 3 and 4. SEM
micrographs evidenced that the diameters of the
obtained metallic nanotubes range between 60
and 75 nm (Figs. 3-4), these dimensions being
LQÁXHQFHGE\WKRVHRIWKHPDWUL[SRUHV
D

b)
D )LJ6(0LPDJHVRID0JQDQRWXEHVSUHFLSLWDWHG
IURPWKHSUHFXUVRU0JDFHWDWHLQDPDWUL[RI
DOXPLQLXPDQRGL]HGLQR[DOLFDFLGIRUKDWDWHQVLRQ
RI9EVL]HRIWKH0J$$2QDQRWXEHV

262 vROXPH18‡iVVXH2FWREHU'HFHPEHU‡ pp. 260-264

 Zn AND Mg NANOTUBES FOR POSSIBLE MEDICAL APPLICATIONS

6RPH PRUSKRORJLFDO PRGLÀFDWLRQV LQ WKH EDX analysis evidenced small amounts of
DVSHFW RI VDPSOHV LQGLFDWH SRUHV PHWDO ÀOOLQJ copper, most of it being retained in the treatment
1DQRWXEHVVL]HLVLQÁXHQFHGE\WKHQDWXUHRIWKH of the AAO matrix with CuCl2.
employed metal and by the deposition time.

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Elements Series [wt.-%] [norm. wt.-%] [norm. at.-%] Error, as %

Aluminium K-series 53.16 54.86 44.14 1
Carbon K-series 0.14 0.15 0.26 0.11
Phosphorous K-series 0.77 0.78 0.55 0.07
Zinc K-series 0.39 0.41 0.07 0.04
Oxygen K-series 41.07 43.80 56.00 5.22

7DEOH&RQWULEXWLRQRIWKH(';VSHFWUXPHOHPHQWVWRWKH0J$$2QDQRWXEHV

Elements Series [wt.-%] [norm. wt.-%] [norm. at.-%] Error, as %

Aluminium K-series 49.35 55.15 42.71 2.50
Carbon K-series 0.14 0.15 0.27 0.091
Phosphorous K-series 1.27 1.315 0.95 0.08
Magnesium K-series 0.57 0.58 0.17 0.04
Oxygen K-series 38.39 42.81 55.90 4.63

The AAO matrix was dissolved with an
aqueous NaOH solution. The metallic nanotubes/
AAO system was partially included into a
SRO\PHULFÀOP
Nanotubes morphology was analyzed after
dissolution of the pattern support.
&21&/86,216
Zn and Mg Metal nanotubes were obtained by
a sol-gel template method. SEM micrographs
evidenced that the diameters of the obtained
metallic nanotubes range between 60 and 75 nm
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