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The influence of hydrothermal-reaction parameters on the formation of chrysotile nanotubes

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INSTITUTE OF PHYSICS PUBLISHING NANOTECHNOLOGY
Nanotechnology 17 (2006) 25–29 doi:10.1088/0957-4484/17/1/005

The influence of hydrothermal-reaction

parameters on the formation of chrysotile
nanotubes
Bostjan Jancar and Danilo Suvorov
Jozef Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia

E-mail: bostjan.jancar@ijs.si

Received 6 July 2005, in final form 3 October 2005

Published 25 November 2005
Online at stacks.iop.org/Nano/17/25
Abstract
X-ray diffraction and transmission electron microscopy were used to
investigate the hydrothermal formation of chrysotile Mg3 [Si2 O5 ](OH)4
nanotubes from amorphous SiO2 and nanocrystalline Mg(OH)2 . The results
show that nanotubes form readily in a highly basic hydrothermal
environment via the curling of flake-like nanocrystallites with a
serpentine-type Mg–Si bilayer crystal structure. The curling occurs in a
helical manner, which introduces chirality into the structure of the resulting
tubes. The diameter and length of the nanotubes can be controlled by
varying the temperature and time of the hydrothermal reaction.

1. Introduction have been synthesized via solvothermal and hydrothermal

Since the discovery of nanotubes based on carbon [1] and MoS2
[2] at the beginning of the 1990s, it has become widely accepted
that the formation of such tubular-shaped single crystals is a
generic property of compounds with a layered crystal structure,
where individual layers are bound together by weak secondary
chemical bonds. Tenne et al [2, 3] postulated that nanotubes
form when such structures exist in the form of nanocrystallites
that do not grow beyond a certain size. According to their
hypothesis, the driving force behind the formation of tubular
crystals can be ascribed to the tendency of a system to saturate
highly energetic dangling bonds inherent in these 2D crystal
structures.
To date, several different methods have been utilized to
synthesize nanotubes from compounds exhibiting a layered
structure. Among the most frequently employed are arc
discharge, laser ablation, chemical vapour deposition (CVD),
electron-beam irradiation and different types of gas-phase
reactions [3–8]. All these methods involve either the
evaporation and redeposition of a material or its formation
in the gaseous phase and subsequent deposition. In both
cases the formation of a solid substance must proceed via a
nucleation and subsequent growth of crystallites. Apparently,
under certain conditions the formed crystallites of layered
compounds tend to adopt tubular structures. A common
drawback of most of these gas-phase processes is the low yield.
Recently, however, larger quantities of different nanotubes
reactions [9–12]. Under solvothermal and hydrothermal
conditions the material either dissolves in the solvent and
subsequently re-precipitates or the solvent acts as a medium
for a reaction in the liquid state, which results in a solid
material [13, 14]. As with vapour-phase processes, this can
lead to the formation of nanotubes from compounds with a
layered crystal structure.
The formation of nanotubes also occurs as a result of the
natural hydrothermal processes that take place in the earth’s
crust. An example is phyllosilicate chrysotile, a member of
the serpentine mineral group [15]. The basis of the crystal
structure of the serpentine minerals is bilayer sheets that consist
of a brucite-type Mg(OH)2 layer joined to a sheet of linked
SiO4 tetrahedra. The Mg and Si layers are joined in such a
way that the apical oxygens of the SiO4 tetrahedra replace two-
thirds of the hydroxyl groups on one side of the brucite layer.
Such electrically neutral sheets are bound together by hydrogen
bonding. There is a mismatch in the lateral dimensions
between the Mg and Si layers, which can be compensated
in several different ways, resulting in a variety of serpentine
structures. In the case of antigorite the mismatch results in a
wave-like modulation of the sheets, which yields a corrugated
structure [15, 16]. Lizardite forms different polytypes by
varying the stacking of individual layers, whereas chrysotile
accommodates the structural mismatch by forming tubular
crystals [15, 17, 18]. Furthermore, in natural environments
the strain associated with the difference in size between the

0957-4484/06/010025+05$30.00 © 2006 IOP Publishing Ltd Printed in the UK 25

B Jancar and D Suvorov
Mg and Si layers is often minimized by a partial substitution
of both cations with Al3+ , which is larger than Si4+ and smaller
than Mg2+ [15].
One of the first systematic studies regarding the formation
of serpentine minerals under artificially created hydrothermal
conditions was published in the 1950s by Roy and Roy [19].
They investigated the influence of the substitution of Mg2+
with other cations, such as Mn2+ , Zn2+ , Ni2+ , Al3+ , and the
substitution of Si4+ with Ge4+ and Al3+ , on the morphology
of serpentine crystals. Their conclusions supported the idea
that the structural misfit due to the difference in the cation
size between the octahedral and tetrahedral layers is the basic
reason for the formation of the tubular-shaped crystals. Further
investigations in the 1960s and 1970s dealt with studies of
hydrothermal-reaction conditions that led to the formation of
Mg3 [Si2 O5 ](OH)4 chrysotile tubules. For the case of MgO and
SiO2 as starting materials, Yang [20] described the optimum
hydrothermal conditions as a temperature between 300 and
350 ◦ C, a pH in the range 10.3–10.7 and a time from 5 to
10 days, with the presence of NH4 F as a mineralizer. Yamai
et al [21] studied the effect of using different combinations
of starting components, such as brucite, quartz, sintered
magnesia and silica sand, on the hydrothermal formation
of chrysotile, and found that it formed in all cases. Yada
et al [22] followed the serpentinization of mineral olivine
and concluded that it can be transformed to tubular chrysotile
in the pH range 3–13 at temperatures between 300 and
400 ◦ C. In more recent literature, the hydrothermal synthesis
of chrysotile has been revisited primarily for the purposes of
obtaining pure material suitable for ongoing investigations of
its cytotoxicity and carcinogenicity, and furthermore to study
it as a possible candidate for applications in the developing
field of nanotechnology [23–29]. Falini et al [23, 24] reported
that the optimum hydrothermal conditions, at 82 atm (300 ◦ C),
for obtaining single-phase chrysotile with a Si/Mg molar ratio
between 0.66 and 0.68, using SiO2 and MgCl2 as reagents,
are a pH of 13.0 and a reaction time of longer than 24 h. They
observed that lower pH values as well as shorter reaction times
adversely affected the crystallinity of the material. Foresti et al
[25] studied the hydrothermal synthesis of Fe-doped chrysotile
by applying a modified method of that reported by Falini
et al [24]. They found that the incorporation of Fe reduces
the crystallinity and results in a flatter morphology of the
product. A more detailed investigation of the hydrothermal-
reaction mechanism, leading to the chrysotile nanotubes, was
performed by Korytkova et al [26]. They followed reaction
products after exposing different combinations of reagents,
such as MgO, SiO2 , MgSiO3 and Mg3 [Si4 O10 ](OH)2 , to
several temperatures between 100 and 450 ◦ C, and a highly
basic medium (pH > 13). The results of their experiments
indicate that the formation of nanotubular chrysotile proceeds
most quickly in the temperature range 350–400 ◦ C with SiO2
and MgO as reactants. Furthermore, they found that lamellar
Mg3 [Si2 O5 ](OH)4 forms prior to nanotubes, regardless of the
reagents used.
The renewed interest in chrysotile, which is a result of the
rapid developments in nanostructured materials, has shown
that it can be successfully employed as a template material for
the synthesis of nanowires [27–31]. It has also been shown that
structure tolerates cation substitution [25, 32], which leads to
26
the possibility of nanotubes with semiconducting or magnetic
properties. For this reason it is of great importance to study
the mechanism of formation of nanotubular chrysotile in order
that we can develop techniques to control the diameter and
length of the tubes synthesized under artificial hydrothermal
conditions. Furthermore, we need to know whether chrysotile
can serve as a model system for studying the mechanism and
conditions that lead to the formation of nanotubes from other
materials with a layered crystal structure.
There is plenty of literature on the subject of finding the
optimum conditions for hydrothermal syntheses that lead to
the formation of chrysotile nanotubes. There is, however, a
lack of more detailed investigations into the influence of the
reaction parameters on the curling of layered serpentine sheets.
With this in mind, we have investigated how the hydrothermal-
reaction conditions, such as the pH, temperature and time,
influence the propensity of serpentine-type structures with the
Mg3 [Si2 O5 ](OH)4 chemistry to curl the Mg–Si bilayers as a
mode of accommodating the structural mismatch, leading to
the formation of nanotubes.
2. Experimental details
Tetra-ethyl-ortho-silicate (TEOS; 99%+, Alfa) was hydrolysed
in a basic water–ethanol solution with the composition
CTEOS = 0.17 M, CNH3 = 1.3 M, CEtOH = 14.8 M and
CH2 O = 1.3 M. The hydrolysis yielded amorphous silicon
oxide spheres with an average diameter of 300 nm and a narrow
size distribution. These were used as a silicon source for the
hydrothermal reaction. A separate hydrolysis of magnesium
ethoxide (Mg 21–22%, Alfa) resulted in the formation of
Mg(OH)2 crystals with an average size of 20 nm, which were
used as a source of Mg. Both powders were weighed to produce
approximately 0.3 g of the mixture with a Mg/Si ratio that
satisfied the Mg3 [Si2 O5 ](OH)4 serpentine mineral chemistry,
and placed into an INCONEL-alloy or PTFE autoclave. Water
was added to fill 40 vol% of the autoclave capacity and the pH
value was adjusted either with HCl or NaOH. The reaction
temperatures were between 150 and 300 ◦ C and the times
from 5 h to 5 days. The solid product of the reaction was
separated from the liquid phase by centrifuging and thoroughly
washed with water. The obtained powders were analysed with
a Bruker AXS Endeavor D4 powder diffractometer, utilizing
Cu Kα radiation, and with a JEOL 2010F transmission electron
microscope (TEM). Prior to both analyses the powders were
dispersed in acetone. In the case of the x-ray analysis the
suspension was dropped on the Si-monocrystal holder, whereas
for the TEM analysis a lacy carbon film on a copper grid was
used.
3. Results and discussion
The suspension of the reagent powder in the distilled water
at room temperature exhibited a pH of 9.5, which can be
attributed to the partial solubility of Mg(OH)2 . Subjecting
such a mixture to five days of hydrothermal conditions, as
can be seen from the x-ray powder diffraction (XRD) patterns
shown in figure 1, results in the disappearance of Mg(OH)2
and the appearance of at least one new crystalline phase.
The XRD reflections of the newly formed crystalline phase(s)
become sharper with an increase in the hydrothermal-reaction
 Hydrothermal synthesis of chrysotile nanotubes

S
S
S
S
S pH = 13
o
300 C

pH = 9.5
o
200 C
pH = 7
o
150 C
pH = 4.5
Reagent
M powder
M M
10 15 20 25 30 35 40 45 50 55
10 15 20 25 30 35 40 45 50 55 2θ [Deg]
2θ [Deg]
Figure 3. XRD spectra of the reaction product after 5 days under
Figure 1. XRD spectra of the reagent powder and reaction product hydrothermal conditions at different pH values of the reaction
after 5 days under hydrothermal conditions at different temperatures medium (T = 200 ◦ C).
(pH = 9.5). M = Mg(OH)2 , S = serpentine.

Figure 2. Flake-like nanoparticles formed after 5 days under

hydrothermal conditions at pH = 9.5: (a) 200 ◦ C and (b) 300 ◦ C.
Arrows mark the curled edges.

temperature, which can be attributed to an increase in the

particle size (figure 2). The positions of the reflections in
the XRD spectra match well with those recorded for three
serpentine minerals, lizardite, antigorite and chrysotile. The
breadth of the reflections in the XRD spectra, shown in figure 1,
however, hinders the unambiguous determination of the exact
nature of the phase(s) present after the hydrothermal treatment.
The TEM analysis was employed to investigate the mor-
phology of the reaction product. Figure 2(a) shows that the
particles formed during the five-day hydrothermal reaction at
200 ◦ C are thin and slightly anisotropic with average lateral di-
mensions of approximately 30 nm × 10 nm. These flake-like
nanoparticles appear thicker along the edges, which suggests
that partial curling of the Mg–Si bilayers has occurred. A
further inspection of figure 2(a) reveals that some of the parti-
cles exist in the form of a tubular structure. With an increase
of the reaction temperature to 300 ◦ C the size of the formed
particles increases, while their morphology remains similar
(figure 2(b)). The curling of the edges becomes more evident.
According to the XRD spectra shown in figure 3, raising
the pH of the reaction medium has a similar effect on
the reaction product as does raising the temperature. The
Figure 4. Nanotubes formed after 5 days under hydrothermal
conditions at pH = 13 and 200 ◦ C. The arrow marks the step
growth.
powder obtained in the acidic environment (pH = 4.5) exhibits
broad reflections of poor intensity that become sharper at
a higher pH, similar to the case with an increase in the
reaction temperature. The TEM imaging, however, reveals
that the pH of the reaction medium exhibits a more profound
effect on the particle morphology compared to the reaction
temperature. Under strongly basic conditions, instead of flake-
like particles, nanocrystals with a tubular geometry are formed
(figure 4). These nanotubes formed under artificially created
hydrothermal conditions closely resemble natural chrysotile,
which was investigated in detail by Yada [18] in the early
1970s. Figure 4 further reveals that some of the nanotubes
synthesized at 200 ◦ C and pH = 13 exhibit features such as
a conical shape and step growth, which have already been
described elsewhere [18, 23].
By increasing the hydrothermal-reaction temperature to
300 ◦ C and maintaining a highly basic reaction medium with

27
B Jancar and D Suvorov
Figure 5. Nanotube formed after 5 days under hydrothermal
conditions at pH = 13, T = 300 ◦ C and its SAED pattern.
a pH of 13, the average length of the synthesized nanotubes
exceeds 1 µm, whereas their diameter remains below 50 nm.
An example of such a synthesized nanotube, together with its
selected-area electron diffraction (SAED) pattern, is shown in
figure 5. The SAED pattern reveals that the nanotube possesses
pseudohexagonal symmetry and that the reflections streaked in
the direction away from the tube axis can be indexed with the
(hk0) planes of chrysotile. Furthermore, the distances between
the sharp reflections extending perpendicular to the tube axis
correspond to the separation between adjacent bilayers in the
serpentine structures and can thus be indexed with 00l indices.
Such a combination of streaked hk0 and sharp 00l reflections
additionally confirms that the synthesized crystals are indeed
nanotubes [33, 34]. Streaking occurs as a direct result of the
tubular geometry due to a gradual decrease of the projected
spacing between the (hk0) planes in the direction toward the
circumference of the tube. Sharp 00l reflections, on the other
hand, indicate that the tube walls are composed of several
parallel sheets of Mg–Si bilayers, which is confirmed by the
image of the lattice fringes shown in figure 6. Furthermore, the
SAED patterns of the synthesized nanotubes exhibit splitting of
(hk0) reflections which suggests that curling occurred around
an arbitrary axis and not parallel to either the [100] or [010]
directions. Such a helical curling renders the nanotubes
chiral [33, 34].
The influence of the reaction time on the curling process
and thus the formation of chrysotile nanotubes was determined
at 200 ◦ C and pH = 13. Figure 7 shows the XRD spectra of
the sample powder collected after several different times of the
hydrothermal treatment; these reveal that the serpentine-type
structures are already formed after 5 h. As was the case with
increasing temperature and pH, an increase in the time results
in sharper reflections, which indicates a larger average particle
size. Furthermore, figure 7 reveals that after 5 and 15 h of
hydrothermal reaction some Mg(OH)2 is still present in the
system, indicating an incomplete conversion.
An insight into the evolution of the particle morphology
is provided by the TEM images shown in figure 8. A 5 h
hydrothermal reaction yields flaky nanoparticles (figure 8(a))
that appear to grow as the time of the hydrothermal treatment
is prolonged to 15 h (figure 8(b)). After 30 h, however, the
flake-like nanoparticles exhibit curling similar to that observed
after a five-day reaction at pH = 9.5. Furthermore, as can
be seen from figure 8(c) some of the particles already adopt
28
Figure 6. Lattice fringes in the nanotube formed at pH = 13,
T = 300 ◦ C.
120 hours
30 hours
15 hours
5 hours
Reagent
powder
10 15 20 25 30 35 40 45 50 55
2θ [Deg]
Figure 7. XRD spectra of the reaction product after several different
times under hydrothermal conditions at T = 200 ◦ C and pH = 13.
nanotubular structures with an approximate diameter of 20 nm.
On average the length of these nanotubes formed after 30 h of
reaction rarely exceeds 60 nm. Prolonging the reaction to five
days (120 h) results in a complete conversion to nanotubular
shapes, with an average length of over 120 nm. A comparison
of figures 8(c) and (d) further reveals that compared to the
increase in the length the average diameter does not change
significantly with an increase in the reaction time.
These results suggest that a hydrothermal treatment of the
mixture of amorphous silica and crystalline Mg(OH)2 , with
a ratio Mg:Si = 3:2, first results in the formation of flake-
like nanocrystallites, which exhibit a serpentine-type Mg–
Si bilayer crystal structure. As the reaction proceeds these
nano-flakes grow, and beyond a certain threshold size they
begin to curl, which ultimately results in the formation of
nanotubes. The curling process is strongly influenced by the
pH of the reaction medium. While their formation seems to
be hindered in an acidic environment, the nanotubes readily
form under basic conditions. After the serpentine sheets have
curled, the growth of the resulting tubes occurs primarily in
the direction parallel to the tube axis, which allows control

Figure 8. Bright field TEM images of the reaction product after
(a) 5, (b) 15, (c) 30 and (d) 120 h at T = 200 ◦ C and pH = 13.
of the tube size at a constant diameter. A comparison of
figures 4 and 5, on the other hand, reveals that the tube
diameter is affected by the hydrothermal-reaction temperature.
Higher temperatures yield tubes with larger diameters, which
is reflected in a larger number of Mg–Si bilayers in the
tube walls. These observations imply that the tube diameter
depends on the number of Mg–Si bilayers that are stacked
together in the direction normal to the (001) basal plane of
the pseudohexagonal structure prior to the commencement of
curling. A larger diameter of tubes is synthesized at 300 ◦ C
compared to those synthesized at 200 ◦ C (figures 4 and 5),
which therefore suggests that at higher temperatures more Mg–
Si bilayers are stacked together within the nanoflake before the
curling threshold is reached.
4. Conclusions
Chrysotile nanotubes form readily when a precursor composed
of a mixture of amorphous silica and nanocrystalline Mg(OH)2
is subjected to hydrothermal conditions in a strongly basic
environment (pH ≈ 13). In the first stage of the reaction,
flake-like nanocrystals with a serpentine-type crystal structure
are formed. After exceeding a certain threshold size these
nanoflakes tend to curl, which results in the formation of nan-
otubes. The curling is neither parallel to the [100] nor to the
[010] axes, which introduces chirality into the tube structure.
The average length and diameter of the nanotubes can be con-
trolled by the reaction temperature and time. By extending the
reaction time at a certain temperature the tube length increases,
whereas the average diameter is not significantly affected. An
increase in the reaction temperature multiplies the number of
Hydrothermal synthesis of chrysotile nanotubes
tube walls, thus increasing the average nanotube diameter. Fur-
thermore, an increase in the temperature speeds up the growth
rate. After 5 days the 300 ◦ C average tube length exceeds
1 µm, while the average diameter remains smaller than 50 nm.
References
[1] Ijima S 1991 Nature 354 56
[2] Tenne R, Margulis L, Genut M and Hodes G 1992 Nature
360 444
[3] Feldman Y, Wasserman E, Srolovitz D J and Tenne R 1995
Science 267 222
[4] Ebbesen T W and Ajayan P M 1992 Nature 358 220
[5] Guo T, Nikolaev P, Thess A, Colbert D T and
Smalley R E 1995 Chem. Phys. Lett. 243 49
[6] Lourie O R, Jones C R, Bartlett B M, Gibbons P C,
Ruoff R S and Buhro W E 2000 Chem. Mater. 12 1808
[7] Tenne R 2001 Prog. Inorg. Chem. 50 269
[8] Nath M N, Govindaraj A and Rao C N R 2001 Adv. Mater.
13 283
[9] Kasuga T, Hiramatsu M, Hoson A, Sekino T and
Niihara K 1998 Langmuir 14 3160
[10] Krumeich F, Muhr H J, Niederberger M, Bieri F,
Schnyder B and Nesper R 1999 J. Am. Chem. Soc.
121 8324
[11] Liu X Y, Zeng J H, Zhang S Y, Zheng R B, Liu X M and
Qian Y T 2003 Chem. Phys. Lett. 374 348
[12] Fan W, Sun S, You L, Cao G, Song X, Zhang W and
Yu H 2003 J. Mater. Chem. 13 3062
[13] Dawson W J 1988 Am. Ceram. Soc. Bull. 67 1673
[14] Mambote R C M, Reuter M A, Krijgsman P and
Schuiling R D 2000 Miner. Eng. 13 803
[15] Deer W A and Howie R A 1992 An Introduction to the
Rock-Forming Minerals (Harlow, Essex, UK: Longman
Scientific and Technical) p 344
[16] Dodony I, Posfai M and Buseck P R 2002 Am. Mineral. 87
1443
[17] Dodony I and Buseck P R 2004 Int. Geol. Rev. 46 507
[18] Yada K 1971 Acta Crystallogr. A 27 659
[19] Roy D M and Roy R 1954 Am. Mineral. 39 957
[20] Yang J C S 1961 Am. Mineral. 46 748
[21] Yamai I and Saito H 1974 J. Cryst. Growth 24/25 617
[22] Yada K and Iishi K 1974 J. Cryst. Growth 24/25 627
[23] Falini G, Foresti E, Lesci G and Roveri N 2002 Chem.
Commun. 14 1512
[24] Falini G, Foresti E, Gazzano M, Gualtieri A F, Leoni M,
Lesci I G and Roveri N 2004 Chem. Eur. J. 10 3043
[25] Foresti E, Hochella M F, Kornishi H, Lesci I G, Madden A S,
Roveri N and Xu H 2005 Adv. Funct. Mater. 15 1009
[26] Korytkova E N, Maslov A V, Pivovarova L N,
Drozdova I A and Gusarov V V 2004 Glass Phys. Chem.
30 51
[27] Poborchii V V, Ivanova M S and Salamatina I A 1994
Superlatt. Microstruct. 16 1994
[28] Ivanova M S, Kumzerov Y A, Poborchii V V,
Ulashkevich Y V and Zhuravlev V V 1995 Micropourous
Mater. 4 319
[29] Romanov S G, Torres S, Yates H M, Pemble M E,
Butko V and Tretijakov V 1997 J. Appl. Phys. 82 380
[30] Poborchii V V, Al’Perovich V I, Nozue Y, Ohnish N,
Kasuya A and Terasaki O 1997 J. Phys.: Condens. Matter
9 5687
[31] Metraux C, Grobety B and Ulmer P 2002 J. Mater. Res. 17
1129
[32] Korytkova E N, Maslov A V, Pivovarova L N,
Polegotchenkova Yu V, Povinich V F and
Gusarov V V 2002 Inorg. Mater. 41 743
[33] Amelinckx S, Devouard B and Baronnet A 1996 Acta
Crystallogr. A 52 850
[34] Amelinckx S, Lucas A and Lambin P 1999 Rep. Prog. Phys.
62 1471
29