Communications
sults. Notably, a COF of 0.19 was obtained, which is similar
to the COF obtained for IFs/tetradecane, reflecting the
dominant role of the WS2 transfer layers formed in situ
during sliding in this system.
In conclusion, we have used the surface forces apparatus
to characterize the normal and lateral forces of WS2 IFs
dispersed in tetradecane and confined between mica sur-
faces. The IFs particles were found to be present between
the surfaces even at very high pressures, to minimize adhe-
sion, and to decrease the friction coefficient of mica sur-
faces lubricated with tetradecane by at least 35 %. The
mechanism of friction and wear reduction was shown to in-
volve in situ deposition of highly oriented, ultrathin WS2
layers without exposure to the ambient air. While further
studies are required to investigate the relevance to more
general metal and ceramic surfaces, the results of this work
point out potential advantages of friction-induced material
transfer from IF additives as an efficient method for spe-
cific and localized deposition of oriented solid lubricant
films in shearing contacts.
Received: February 15, 1999
Final version: April 15, 1999
[1] L. Rapoport, Y. Bilik, M. Homyonfer, S. R. Cohen, R. Tenne, Nature
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ture 1996, 382, 520.
[3] G. Luengo, S. E. Campbell, V. I. Srdanov, F. Wudl, J. Israelachvili,
Chem. Mater. 1997, 9, 1166.
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[18] E. A. Dukhovskoi, A. N. Ponomarev, A. A. Silin, V. L. Tal'roze,
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[22] D. N. Dunn, K. J. Wahl, I. L. Singer, Mater. Res. Soc. Symp. Proc.
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oue, Tribology Int., in press.
[25] R. Tenne, L. Margulis, M. Genut, G. Hodes, Nature 1992, 360, 444.
[26] Y. Feldman, E. Waserman, D. J. Srolovitz, R. Tenne, Science 1995, 267,
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lis, H. Cohen, G. Hodes, J. L. Hutchison, R. Tenne, J. Am. Chem. Soc.
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[29] L. Rapoport, Y. Feldman, M. Homyonfer, H. Cohen, J. Sloan, J. L.
Hutchison, R. Tenne, Wear 1999, 229, 975.
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vili, Wear, in press; C. Drummon et al., unpublished.
Fabrication and Characterization of Carbon
Nanotube/Poly(vinyl alcohol) Composites**
By Milo S. P. Shaffer and Alan H. Windle*
There is considerable interest in fabricating composite
materials containing carbon nanotubes, both from the point
of view of fundamental property determination and the de-
velopment of applications.[1] While one might expect the ax-
ial elastic modulus of carbon nanotubes to approach that of
the basal plane of graphite crystals (1 TPa), some theoretical
predictions have suggested that nanotube stiffness may be
even higher.[2,3] Initial experiments performed on micro-
scopic samples broadly support these suggestions;[4] how-
ever, due to the difficulties of manipulating nanoscaled ob-
jects, the experimental measurements have been made
indirectly or do not represent the loading conditions that
would be experienced in a practical composite material.
Manipulations of individual nanotubes indicate a high
strength,[5] but again it is unclear whether or not this prop-
erty could be exploited in a macroscopic composite. More
immediate applications may arise from the electrical proper-
ties of nanotubes, for example in flat screen displays.[6] This
work describes the fabrication of nanotube composite films,
and the resulting thermo-mechanical and electrical proper-
ties are discussed. Successful fabrication depended crucially
on maintaining stable colloidal mixtures of nanotubes and
polymer. The stiffness of the composites measured at room
temperature was relatively low and was interpreted using
short-fiber composite theory; however, the high temperature
properties showed considerable promise. The electrical con-
ductivity of these composites shows the type of percolation
behavior observed in other fiber-filled systems.
Arc-grown nanotubes, although preferred for micro-
scopic studies due to their relatively high perfection, are
not readily available in large quantities. Therefore, in this
[*] Prof. A. H. Windle, M. S. P. Shaffer
Department of Materials Science and Metallurgy
University of Cambridge
Pembroke Street, Cambridge, CB2 3QZ (UK)
[**] Grateful thanks to Dr. George Z. Chen for assistance with the impe-
dance spectroscopy and to Hyperion Catalysis International for the
supply of material.
0935-9648/99/1108-0937 $ 17.50+.50/0 937

work, catalytically grown nanotubes have been used as a
starting material, despite a higher defect concentration.
The starting material was long and entangled, although free
from contaminating nanoparticles. A chemical treatment
described elsewhere[7] was used to produce an electrostati-
cally stabilized dispersion of nanotubes in water, with an
average length of 1.1 mm.
Composite films with a wide range of nanotube loadings
were made by careful mixing of aqueous poly(vinyl alcohol)
solutions, [CH2CH(OH)]n (PVOH), with carbon nanotube
dispersions followed by subsequent casting, and controlled
water evaporation. Equal concentrations for the two solu-
tions ensured that the overall volumes of each sample as-
mixed were identical, regardless of the nanotube loading.
Since gelling of both nanotube and polymer solutions oc-
curred at around the same concentration (~5 vol.-%), all
composite films should have experienced equal contraction
on drying and hence have a similar degree of nanotube align-
ment to the plane of the film. This conclusion was confirmed
by an analysis of transmission X-ray diffraction patterns.
Careful mixing of the components was required in order
to prevent aggregation. To form a stable mixture each nano-
tube must become covered with an adsorbed layer of poly-
mer before it is able to interact with a significant number of
other nanotubes. In colloidal terms, the adsorbed polymer
then sterically stabilizes the nanotube dispersion, and pro-
tects it against bridging flocculation and depletion aggrega-
tion caused by the free polymer.[8] A similar effect can be
observed during the preparation of pigment suspensions for
paper-marking when the aggregation is termed shock.[9]
The thickness of the dry films varied from 53 mm down
to 44 mm, following the trend with increasing nanotube
loading. This behavior was to be expected since all the
films had approximately the same mass of material, whilst
the density of nanotubes (~1.75 g cm3) is higher than that
of PVOH (~1.3 g cm3). The densities of both the compo-
sites and the pure materials were measured by a liquid im-
mersion technique,[10] and found to obey a linear law of
mixtures; the results are shown in Figure 1.
Fig. 1. Plot of the densities of pure PVOH, pure individual nanotubes, and
the intermediate composites, showing a linear interpolation.
938 WILEY-VCH Verlag GmbH, D-69469 Weinheim, 1999
Communications
The composites were examined in a scanning electron
microscope (SEM) in order to determine the quality of the
structure. Unfortunately, the samples with less than about
20 wt.-% nanotubes were insufficiently conductive to pre-
vent charging, and could not be imaged directly. Imaging
composites with higher loading was possible, although hin-
dered by the low contrast between nanotubes and matrix,
and the sensitivity of the matrix to beam damage. In the
samples examined, the nanotubes were found to be evenly
dispersed (see Fig. 2) and voids were only observed in the
60 wt.-% composites. After coating with chromium, there
was no significant contrast on the surfaces of the films, but
nanotubes could be readily observed on the fracture sur-
faces, confirming the uniform quality of the dispersion.
Pull-out lengths of around 100 nm suggested fracture of
the individual nanotubes.
Fig. 2. Scanning electron micrograph of a 50 wt.-% PVOH/nanotube com-
posite.
In order to obtain additional confirmation of both the
nanotube content and of the structure of the material, as
well as to investigate the effects of the nanotubes on the
thermal stability of the matrix, thermo-gravimetric analysis
(TGA) was performed on composites at all concentrations.
The TGA was carried out under a nitrogen atmosphere
which minimized the mass loss due to nanotube oxidation,
whilst allowing the PVOH to thermally decompose almost
completely. The resulting curves are shown in Figure 3.
The masses remaining at 700 C are almost entirely due to
the remaining nanotubes, and are consistent with initial
nanotube loading. On observation under the SEM, all the
films appeared indistinguishable, regardless of the original
nanotube loadings, and no evidence of any non-uniformity
of the nanotube distribution was observed. The final thick-
ness of the residue films was proportional to the nanotube
content, and thus the densities of all the films were equal to
1.3 g cm3. Since the nanotubes are relatively well-isolated
by the matrix, they do not form a stable structure once the
matrix is burnt-out, but collapse to form a layered film,
similar to those formed by simple drying of nanotube dis-
persions.[7] Comparison of the curves in Figure 3 reveals
that although there is a retardation of the onset of PVOH
0935-9648/99/1108-0938 $ 17.50+.50/0 Adv. Mater. 1999, 11, No. 11
Communications
decomposition for the composites with low nanotube load-
ings (peaking at around 20 wt.-%), there is no noticeable
effect on the subsequent progress of the degradation, which
was completed at the same temperature for all samples.
The retardation is likely to be a result of absorption, by the
activated carbon surface, of free-radicals generated during
polymer decomposition.[11] At higher temperatures or load-
ing the decomposition of the oxidized nanotube surface it-
self negates the stabilizing effect.
Fig. 3. TGA of PVOH, nanotubes and composites, in a nitrogen atmo-
sphere.
The tensile elastic modulus and damping properties of
the composite films were assessed in a dynamic mechanical
thermal analyzer (DMTA) as a function of nanotube load-
ing and temperature. Below the glass transition of the ma-
trix, there was an increase in modulus due to the carbon
nanotubes, which can be analyzed using Krenchel's expres-
sion for short-fiber composites (Eq. 1),[12] where Ef, Em are
the moduli of the fiber and matrix, and Zo, Zl are efficiency
factors relating to fiber orientation and length, respectively.
E = ZoZlVfEf + (1 Vf) Em (1)
The fiber length efficiency factor is given by Cox's equa-
tions, which are derived on the assumption of an elastic ma-
trix and a gradual stress transfer between fiber and matrix
along the fiber length, according to the shearlag model.[13]
The value of Zo is calculated assuming strain continuity,
and taking only the axial stiffness of the fibers to be signifi-
cant. The first assumption is reasonable for the intertwined
nanotubes in these composites; the second is more uncer-
tain but since none of the elastic properties of catalytically
grown tubes is well-established, it is an acceptable first ap-
proximation. The fiber orientation efficiency factor calcu-
lated from Krenchel's equation, on the basis of the nano-
tube distribution determined by X-ray analysis, was 0.33,
which is close, in any case, to that for a random planar ar-
rangement (0.38).[12]
Adv. Mater. 1999, 11, No. 11 WILEY-VCH Verlag GmbH, D-69469 Weinheim, 1999
The best fit to the experimental data for the in-plane
stiffness of the composite films, as a function of nanotube
concentration, was obtained using values of 150 MPa for
the axial modulus and a reduced effective length of 35 nm.
This first determination of the stiffness of nanotubes in a
macroscopic composite is well below values reported for
isolated nanotubes. It is not yet clear whether this result is
chiefly a consequence of the imperfections in the graphitic
layers within the catalytically grown nanotubes used, or
whether it relates to a fundamental difficulty of shear stress
transfer between the shells of multi-walled nanotubes. A
recent measurement of the individual stiffness of catalyti-
cally grown nanofibers in an atomic force microscope
(50 GPa) appears to be for much more defective nano-
tubes than those used in this study, but does highlight the
potential impact of defects.[14] On the other hand, theoreti-
cal predictions of stiffness are almost all for single-wall
nanotubes, whilst calculations based on experiment have
not yet addressed the possibility of relative slippage of the
shells of a multi-wall nanotube. Under tensile axial load, it
is possible that the inner shells carry little load; indeed,
telescopic rupture of nanotubes has been observed.[15] This
suggestion is further supported by a recent report on arc-
grown nanotubes embedded in epoxy resin in which nano-
tube strain was measured using Raman spectroscopy, and
shown to be much larger with the matrix under compres-
sion than under tension; the result was attributed to poor
load transfer in tension.[16] The low effective length of the
nanotubes required by the fitting to the Krenchel model, in
this study, is seen as a reflection of both the nanotube cur-
vature and the reduced efficiency of shear stress transfer.
Although catalytically grown nanotubes are intrinsically
curved, even arc-grown nanotubes have been shown to be
bent after being embedded in a matrix[17] and thus are like-
ly to suffer a reduction in effectiveness.
Above the glass transition temperature of the matrix, the
nanotubes had a much more significant effect, resulting in
the retention of a large proportion of the stiffness seen be-
low the transition. The nanotubes themselves would not be
expected to soften if the temperature were raised further,
though of course, the matrix would begin to decompose.
An even larger relative improvement would be expected if
an amorphous matrix were used in place of the semicrystal-
line PVOH; recent work on cellulose nanofibers in an
amorphous latex rubber matrix revealed similar trends to
those reported here, but with greater softening at low fiber
loading.[18] The tangent of the ratio of the complex to real
modulus (tan d) is a measure of the damping, and in this
case, the peak in tan d corresponds to the glass transition
(see Fig. 4). The presence of the nanotubes did not signifi-
cantly affect the peak position, which lay at a temperature
between 75 C and 80 C, for all samples. The decreasing
peak height with increasing nanotube loading is to be ex-
pected due to the reducing fraction of polymer matrix. The
onset of the glass transition was not affected by the nano-
tubes, but the higher temperature side was significantly
0935-9648/99/1108-0939 $ 17.50+.50/0 939

broadened. It is likely that the unconstrained segments of
the polymer molecules retained the glass transition temper-
ature of bulk PVOH but that those segments near to the
nanotube surface were less mobile and showed an in-
creased glass transition temperature. Similar effects have
been observed in other polymer systems filled with finely
divided materials.[19]
Fig. 4. Dynamic mechanical analysis of PVOH and composites. a) Log mod-
ulus with temperature. Note that the 60 wt.-% samples were brittle. The sam-
ple with the highest initial modulus is shown. b) tan d with temperature. Nano-
tube loadings increase in 10 wt.-% steps between 10 wt.-% and 60 wt.-%.
The electrical conductivity of the composites was mea-
sured using impedance spectroscopy, in a four-point config-
uration, and is shown in Figure 5. The percolation threshold
for these composites clearly lies between 5 and 10 wt.-%.
This behavior is typical of polymers filled with conductive
fibers and the results closely resemble those in the litera-
ture for polyethylene filled with carbon fiber.[20] The results
are also very similar to those obtained for smaller-scale
composites based on nanotubes and conducting polymers,
studied primarily for their opto-electronic properties.[21]
For a given loading, all these sets of composites have a
rather low conductivity in comparison to composites based
940 WILEY-VCH Verlag GmbH, D-69469 Weinheim, 1999
Communications
on very low loading of nanotubes in epoxy resins.[22] This
contrast is almost certainly a consequence of an adsorbed
layer of polymer which reduces the quality and quantity of
electrical contacts between the nanotubes.
Fig. 5. Plot of the electrical conductivities of PVOH/nanotube composites.
The conductivity of the lowest loading fraction (5 wt.-%) represents the lim-
it of what was measurable on the equipment used, and the value plotted for
the pure matrix is taken from the literature [23]. Lines are visual aids.
This report describes a successful route for the fabrica-
tion of large composite films containing nanotubes, based
on the formation of a stable colloidal intermediate, which
should be broadly applicable to a range of nanotube mate-
rials and polymers. The densities of the composites follow a
linear law of mixtures, and the electrical conductivities
show typical percolation behavior. The presence of the
nanotubes stiffens the material, particularly at high temper-
ature, and in some cases retards the onset of thermal degra-
dation. The indications from this work are that nanotubes
may not ideally be suited to a straightforward reinforcing
role, but that they could find application as a modifier for
polymers, particularly as an improved matrix for conven-
tional fiber composites for service at high temperatures.
Experimental
The PVOH which was supplied by Aldrich was 9899 % hydrolyzed with
a molecular weight between 85 000 and 146 000. Solutions of PVOH were
made by stirring appropriate quantities of polymer and distilled water at
>90 C for at least 4 h. The nanotube materials was supplied, under contract,
by Hyperion Catalysis International, and oxidized as described elsewhere.
The nanotube dispersions were added dropwise to the PVOH solution, both
at 1 wt.-%, whilst stirring continually at 480 rpm. After a further 20 min,
the solutions were cast into 10 cm by 2 cm Teflon troughs. The thermogravi-
metric analysis (TGA) was performed under a nitrogen atmosphere using a
heating rate of 10 C min1 from room temperature up to 700 C. The electri-
cal conductivities were measured in a four-contact configuration using a So-
latron SI 1260 Impedance/Gain Phase Analyzer, with data collected by a PC
running Z-60 software. The samples were all dried in a vacuum dessicator
for 1 week before measurement, and then scanned in a frequency range of
1 MHz to 1 Hz, under voltage control with an amplitude of 2 V. DMTA, un-
der tensile loading was performed using Perkin Elmer equipment and sam-
ples 1 cm by 50 mm, with a length of 2 cm between the clamps. A 5 N static
tensile load and a displacement oscillation amplitude of 16 mm, frequency
0935-9648/99/1108-0940 $ 17.50+.50/0 Adv. Mater. 1999, 11, No. 11
Communications

1 Hz, were applied. The temperature was ramped from 0 C to 120 C, at a
rate of 2 C min1. Films were dried in a vacuum dessicator for at least a
week before use, and dry nitrogen flowed through the DMTA oven to pre-
vent water uptake.
Received: January 20, 1999
Final version: April 30, 1999
[1] T. W. Ebbesen, Carbon Nanotubes, CRC Press, Boca Raton, FL 1997.
[2] G. Overney, W. Zhong, D. Tomnek, Z. Phys. D 1993, 27, 93.
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R. P. H. Chang, Appl. Phys. Lett. 1998, 72, 2912.
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[8] D. H. Everett, Basic Principles of Colloid Science, Royal Society of
Chemistry, London 1988.
[9] K. Tsunemitsu, Y. Murakami, in Polyvinyl Alcohol (Ed: C. A. Finch),
Wiley, Chichester, UK 1973.
[10] N. A. Pratten, J. Mater. Sci. 1981, 16, 1737.
[11] T. Kelen, Polymer Degradation, Van Nostrand Reinhold, New York
1983.
[12] H. Krenchel, Fibre Reinforcement, Akademisk Forlag, Copenhagen
1964.
[13] A. Kelly, Strong Solids, Clarendon, Oxford 1966.
[14] J.-P. Salvetat, A. J. Kulik, J.-M. Bonard, G. A. D. Briggs, T. Stckli,
K. Mtnier, S. Bonnamy, F. Bguin, N. A. Burnham, L. Forr, Adv.
Mater. 1999, 11, 161.
[15] H. D. Wagner, O. Lourie, Y. Feldman, R. Tenne, Appl. Phys. Lett.
1998, 72, 188.
[16] L. S. Schadler, S. C. Giannaris, P. M. Ajayan, Appl. Phys. Lett. 1998,
73, 3842.
[17] O. Lourie, D. M. Cox, H. D. Wagner, Phys. Rev. Lett. 1998, 81, 1638.
[18] V. Favier, D. Dendievel, G. Canova, J. Y. Cavaille, P. Gilormini, Acta
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[19] G. Tsagaropoulos, A. Eisenberg, Macromolecules 1995, 28, 6067.
[20] Y. Agari, A. Ueda, S. Nagai, J. Appl. Polym. Sci. 1994, 52, 1223.
[21] J. N. Coleman, S. Curran, A. B. Dalton, A. P. Davey, B. McCarthy,
W. Blau, R. C. Barklie, Phys. Rev. B 1998, 58, 1.
[22] J. Sandler, M. Shaffer, T. Prasse, W. Bauhofer, K. Schulte, A. H.
Windle, Polymer, in press.
[23] W. J. Roff, J. R. Scott, Fibres, Films, Plastics, and Rubbers, Butter-
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ten observed in either isolated molecules or macroscopic
solids. The current approaches to nanomaterials include
gas-phase synthesis,[1a] solution-phase synthesis,[1b,1c,24] sol-
id-state preparation,[1b,1d] and template synthesis.[2,5] Sol-
vents, other chemicals (such as surfactants or templates),
complex process control, or high reaction temperatures
may be required for these approaches. Here we report a
general and effective approach based on one-step solid-
state metathesis reactions of hydrated transition metal salts
or hydroxides to yield nanocrystals of oxides, sulfides,
oxalates, carbonates and insoluble 8-hydroxyquinoline
(HOxin) compounds with uniform sizes and shapes in high
yields at ambient temperatures.[6]
Nanocrystals of oxides (CuO), sulfides (CuS, ZnS, CdS,
PbS), oxalates [M2(C2O4)3 3H2O (M = Nb, La);
M(C2O4) 2H2O (M = Cu, Ni, Mn, Co, Zn)], carbonates
(MCO3, M = Ca, Ba), and salts of 8-hydroxyquinoline
(HOxin) [M(Oxin)x (M = La, x = 3; M = Zn, x = 2)] are
prepared at ambient temperatures through rapid (10 s to
30 min), self-propagating solid-state metathesis reactions
of hydrated transition metal salts and NaOH, Na2S
9H2O, H2C2O4 2H2O, Na2CO3, and HOxin, respectively.
Such reactions were found to give spherical products of
uniform size and shape [10(2)80(7) nm] in over 90 %
yields. Most reactions were found to proceed at room
temperature. In some cases, the reaction temperatures
rose to ca. 80 C. The results and analyses by inductively
coupled plasma quantometer (ICP) are summarized in
Table 1.
Table 1. Nanocrystals prepared at ambient temperatures by one-step solid-
state reactions [a].

One-Step Solid-State Reactions at Ambient

TemperaturesA Novel Approach
to Nanocrystal Synthesis**

By Xiang R. Ye, Dian Z. Jia, Jian Q. Yu, Xin Q. Xin,* and

Ziling Xue*

The development of novel methods for producing mate-

rials at the nanometer scale is of intense current inter-
est.[13] The unique properties of nanomaterials are not of-

[*] Prof. X. Q. Xin, Dr. X. R. Ye

State Key Laboratory of Coordination Chemistry, Nanjing University
Nanjing, 210093 (PR China)
Professor Z. Xue
Department of Chemistry, University of Tennessee
Knoxville, TN 37996 (USA)
Professor D. Z. Jia, J. Q. Yu
Department of Chemistry, Xinjiang University
Wurumuqi, 840046 (PR China)
[**] The research was supported by the National Natural Science Founda- [a] acac = acetylacetonate; Ac = acetate. [b] The analyses were conducted by
tion of PR China, National Science Foundation of the USA, and the ICP. Impurities were as follows: Al < 10 ppm; Ca < 200 ppm; Na < 500 ppm,
Camille and Henry Dreyfus Foundation. except [c] Na = 2000 ppm.

Adv. Mater. 1999, 11, No. 11 WILEY-VCH Verlag GmbH, D-69469 Weinheim, 1999 0935-9648/99/1108-0941 $ 17.50+.50/0 941