6
Nanostructure synthesis using surfactants and copolymers
Wolfgang Meier
Self-assembled structures of surfactants and block
copolymers provide a valuable tool for controlling
nanostructure formation in polymers and inorganic solids.
The past year has seen a huge number of different new
nanoparticles and mesostructured solids. A high level of
control of the mesoscopic and macroscopic morphologies
has been reached for both polymer nanostructures and
mesoporous inorganic materials.
Addresses
Physikalische Chemie, Departement Chemie, Universitat
Institut fur
Basel, Klingelbergstrase 80, 4056 Basel, Switzerland
Current Opinion in Colloid & Interface Science 1999, 4:6]14
Electronic identifier: 1359-0294-004-00006
Q 1999 Elsevier Science Ltd. All rights reserved. ISSN 1359-0294
Introduction
An extremely active and prolific field in modern colloid
chemistry is finding ways to control size and mor-
phology of colloids at the nanometer level. One main
objective is to manipulate the properties of the result-
ing materials thus enabling the introduction of new
material properties into well-known standard com-
pounds, for example the quantum size effects that occur
in particles that have become too small to exhibit bulk
properties. This concept is largely inspired by biominer-
alization where Nature displays that, with only a few
simple inorganic minerals like CaCO 3 , SiO 2 or hydrox-
yapatite which are molded into an appropriate shape, an
extremely large variety of different materials properties
e.g. mechanical properties. can be realized w1,2x. Simi-
lar to Nature, self-organized systems are usually used as
structure guiding media. In this context the aggregates
of surfactants and block copolymers have proven to be
valuable tools; micelles, microemulsions, vesicles, ly-
otropic liquid crystalline phases or the mesostructures
of block copolymers offer a huge variety of microphase
textures which may be used as structural templates, the
size and structure of which is to be captured in the
newly-formed material. These concepts are currently
applied in polymer chemistry as well as in inorganic
materials science. Although the frontiers between these
two different streams become more and more diffuse,
this review is divided into several subsections based on
this classification: polymeric and inorganic nanoparticles
and mesostructured solids, depending on the chemistry
used and the structure obtained during the templating
process, respectively.
A whole series of recent reviews already summarizes
the main developments achieved in this field or certain
subsections of it w3]11x, so that here only a short
overview will be given covering some aspects of the
period from mid-1997 to the mid-1998.
Polymeric nanoparticles
Microemulsions are thermodynamically stable emul-
sions and consist of nanometer-sized water and oil do-
mains and have spherical, cylindrical or sponge-like
morphologies. These hydrophilic and hydrophobic do-
mains have attracted increasing interest of polymer
chemists during the past two decades w3,4x. The con-
cept of polymerization in microemulsions has devel-
oped into a rapidly growing field of research and there
is a wide variety of different applications for the result-
ing materials, such as drug delivery, catalysis or separa-
tion processes.
Ultrasmall spherical latex particles in the range of 5]100
nm are usually obtained from this polymerization tech-
nique, the size of which is controlled by the surfactant-
to-monomer ratio. These particles possess a relatively
narrow size distribution and consist of only a few high
molecular weight chains. The molecular weight, molec-
ular weight distribution and particle diameter is additio-
nally controlled in the polymerization using all of the
following: surfactant w12x, monomer w13x or initiator w14x.
The polymerization rate is very high in microemulsions
and can, for example, be influenced by the hy-
drophobicity of the monomers w13x.
The restricted volume available to the growing polymer
chain within a microemulsion droplet does not seem to
be of considerable influence; the tacticity of, for exam-
ple, polymethylmethacrylate. produced in a mi-
croemulsion does not differ from that of bulk polymer-
ization w15x. Furthermore, the large internal interface
may catalyze polymerization of monomers which usu-
ally do not lead to significant conversions under compa-
rable conditions w16x.
Although the fundamental processes which determine
the reaction kinetics and latex properties have been
investigated, most of the results can only be interpreted
at a qualitative level except for some attempts to quan-
tify the reaction kinetics. Recently, however, a mecha-
nistic model has been proposed which, for the first
time, allows an analytical expression for the molecular
weight distribution and particle size w17 x. Using this
vv
model some of the assumptions from Morgan and Kaler
w17 x could be verified for one system using on-line
vv
small-angle neutron scattering measurements w18 x. vv
 Nanostructure synthesis using surfactants and copolymers Meier 7

One problem concerning the applications of microemul-

sion polymerization is the usual, rather low polymer
content of the resulting latex dispersions. This can be
overcome, for example, by slow continuous addition of
the monomer to the reaction mixture w19x.

A similar procedure has been used to condense mix-

tures of methyltrimethoxysilane and dimeth-
yldimethoxysilane in water in the presence of surfactant
w20 ,21,22 x. This highly interesting method allows the
v v

preparation of spherical micronetworks with a narrow

size distribution and particle sizes ranging from 5 to 30
nm. Analogous to a living polymerization, subsequent
addition of two monomers with different functional
groups may lead to core-shell particles in which, for
example, noble metal ions can be entrapped. or to
hollow polymer spheres in the nanometer range w21,22 x. v

Another elegant approach for forming hollow spherical

polymer particles is the polymerization of hydrophobic
monomers dissolved in the hydrophobic domain of a
lipid bilayer w23 ,24 ,25 ,26x. The polymerization does
v vv vv

not affect the size of the templating vesicles probably

because of the very slow lipid exchange between dif-
ferent bilayers. Parachute-like morphologies w24 x or
vv

closed spherical polymer shells w25 ,26x have been

vv

reported; the type of morphology formed depends on

their mutual miscibility for different combinations of
monomer, polymer and surfactant. The details of the
mechanisms behind this still need to be clarified. Nev-
ertheless, this method does not only allow control over
the inner and outer radius of the polymer shell, but the
(a) SEM micrograph of a polymer hollow sphere obtained by a
polymer scaffold within the bilayer also leads to con-
cross-linking polymerization of alkylmethacrylate monomers in the
siderable mechanical stabilization without loss of the bilayer of a giant vesicle after isolation from the bilayer. The
lateral mobility of the lipids, thus enabling such po- diameter of the sphrere is approximately 250 mm. (b) SEM
lymer-containing membranes to self-repair see Figure micrograph of a semispherical fragment of a polymer hollow sphere
1. w26x. obtained by shearing the polymer particle. The thickness of the
shell could be

Stabilization by a colloidal template also plays an impor-

tant role in alleviating the poor processibility of con-
ducting polymers. For example, thin polyparaphenylene
films can be prepared from microemulsions w27x,
nanoparticles of polypyrrole w28x or polyaniline w29x by
polymerization in the presence of stabilizing copo-
lymers. Coating preformed polystyrene latexes with a
thin overlayer of polyaniline leads to core-shell struc-
tures w30 x. Removing the polystyrene core allows the
v tributed to quantum confinement or surface effects.
isolation of partially broken conducting polymer shells.
Similarly, gold-polypyrrole core-shell particles of various
shapes can be obtained by polymerization of pyrrole
within gold ions containing polystyrene-block-poly2-
vinylpyridine. micelles w31 x. Polymerization of pyrrole
v
within the polar domains of a lamellar sulfonated
polystyrene-block-polyethylene-alt-propylene. me-
sostructure yields nanocomposites which display
anisotropic electric conductivity w32 x.
vv
Inorganic nanoparticles
The synthesis of metallic and other inorganic nanoparti-
cles has become a topic of increasing interest w3]5x
because of the wide range of optical and electronic
properties that are accessible in the nanometer regime.
The unique properties of such nanoparticles are at-
Similar to microemulsion polymerization, the droplet
structure of microemulsions can also be used as a tem-
plate for the preparation of such inorganic nanoparticles.
Most of the papers in this field are mainly concerned
with particle synthesis and the characterization of their
interesting material properties. The knowledge about
the underlying mechanisms of the synthesis controlling,
for example, shape and size of the particles is, however,
8 Self-assembly
rather poor and further efforts to clarify these open
questions are required. Although a certain control over
size and shape of the particles is possible, as shown by
the preparation of cylindrical copper particles or copper
networks w33 x, it is still impossible to predict the
vv
properties of the resulting particles a priori.
Reversed micelles have been used to obtain nanoparti-
cles of Cd 1y y Mn y S a magnetic semiconductor. w34x,
Cd 1y y Zn y S w35x, Ag 2 Se w36x, Cu 2 S, CuS w37x and AgCl
w38x. Similarly Fe]Cu alloys w39x with superparamag-
netic properties or alkylthiole covered Ag and Ag 2 S
particles which can be self-assembled at surfaces have
been prepared w33 ,40x. Hydrolysis of TiiPrO.4 or
vv
SiOEt.4 in water-in-oil microemulsions yields nanome-
ter-sized TiO 2 w41x or SiO 2 w42x, respectively.
Metal nanoparticles, however, can also be prepared
within the nanostructures of polyelectrolyte gels con-
taining oppositely charged surfactants w43x and disk-like
CdS nanoparticles have been shown to be available by
H 2 S treatment of Cd-arachidate multilayers w44x.
Because of their lower dynamics, compared with con-
ventional surfactants, there has been an increasing in-
terest in block copolymer aggregates as matrices for the
formation of inorganic nanoparticles in the past few
years. This field has recently been reviewed w6,7x and
examples of block copolymer templating can be found
in nearly every section of this review. Two interesting
papers should be mentioned at this point, Moffitt et al.
w45 x and Colfen
v
and Antonietti w46 x. Recently, the
v systems.
formation of spherical assemblies of CdS containing
block copolymer reversed micelles has been reported in
w45 x. These semiconductor-doped so-called large com-
v
pound micelles can be prepared in the presence of an
additional stabilizing copolymer and offer, for example,
interesting possibilities in the optics of catalysis.
Precipitation of CaCO 3 in the presence of so-called
double hydrophilic block copolymers, consisting of one
hydrophilic polyoxyethylene. block and a second hy-
drophilic block which is able to strongly interact with
the growing inorganic particle, allows control of the
morphology and crystal modifications of the CaCO 3
w46 x. Although the structures reported in w46 x are in
v v
the micrometer range, such polymers seem to be highly
promising as new templates in the field of inorganic
nanostructure formation.
Polymeric mesostructured solids
Mesoporous polymeric materials can be obtained using,
for example, a thermally w47x or photochemically initi-
ated free radical polymerization within the sponge-like
structure of bicontinuous microemulsions. In most cases,
however, the polymer structures obtained are larger
than the original system. Nevertheless, they have highly
interesting properties due to their continuous, high
surface pore system. Recently, it could be shown that
using a high-molecular-weight polyoxyethylene-based
surfactant macromonomer may lead to materials with
pore sizes ranging from 1 to 10 nm which are probably
direct casts of the water channels of the precursor
bicontinuous microemulsion w48 x. This might be the
v
result of the very slow dynamics of the polymeric
surfactant preventing rearrangements in the reaction
mixture during polymerization. In contrast, acrylamide
polymerization in the aqueous domains of lyotropic
phases of counterion-coupled gemini surfactants does
not preserve the original length scales. Despite the
lamellar architecture of the resulting gels, the character-
istic size of this lamellar structure was approximately
two orders of magnitude larger than that of the templat-
ing lyotropic liquid crystalline phase w49 x. This in-
vv
crease in size has been explained to be the result of a
phase separation in the system induced during gel
formation.
Amphiphilic polymer networks with a layer spacing of
approx. 20 nm., the structure of which is a direct cast of
the templating liquid crystalline phase, can be prepared
in a magnetic-field-aligned ternary parental system in
the presence of polymerizable triblock copolymers
w50 x. The lamellar structure is preserved even after
vv
extraction of the templating matrix and reswelling these
elastomers in water leads to a mainly one-dimensional
swelling, reflecting the high degree of order in these
Another highly interesting approach to nanoporous ma-
terials which allows an exact control over the resulting
morphology has been described by Hashimoto et al.
w51 x. Here the polyisoprene blocks of a polystyrene]
vv
block]polyisoprene gyroid phase have been selectively
degraded by ozonolysis. The resulting nanochannels in
the glassy polystyrene do not perturb the original
symmetry of the system see Figure 2..
Inorganic mesostructured solids
Since the discovery of mesoporous silicate materials of
the M41S family, the synthesis and investigation of
mesoporous inorganic solids with uniform tunable pores
in the range from 2 to 30 nm has developed into a
rapidly expanding field. This is reflected in a tremen-
dous number of papers appearing in this field which
have recently already been reviewed in several articles
w7]11x. Therefore, only a short overview over some
recent developments will be given here.
The synthesis of regular mesoporous materials usually
proceeds via templating a lyotropic liquid crystalline
phase. One possibility is to start with a dilute micellar
 Nanostructure synthesis using surfactants and copolymers Meier
SEM micrograph showing the bicontinuous nanochannels in a
polystrene matrix. The channels have been formed by ozone
polystrene. The channels have been formed by ozone degradation
of the polyisoprene blocks of a cubic gyroid phase of a
polystrene]block polyisoprene block copolymer. Figure courtesy
surfactant solution. Electrostatic or hydrogen bonding
interactions between the surfactant and the growing
inorganic species usually leads to a phase separation
into a surfactant-rich gel phase and a dilute isotropic
solution in which polymerization to the final product
occurs. The structure of the resulting inorganic solid
depends sensitively on the reaction conditions such as
concentration, temperature and pH w52,53x. Moreover,
during the synthesis phase transitions may occur in the
surfactant assembly thus complicating the situation even
more w54x. As a consequence, the structure of the result-
ing mesoporous solid usually cannot be predicted a
priori. To do this would require knowledge about the
relation between synthetic conditions, polymerization,
growth and curvature of the inorganic]surfactant liquid
crystalline phase. Obviously, certain efforts have been
made to clarify these questions. They were, however,
successful only in a few cases up to now. For example, a
model for aluminophosphate formation via a linear chain
aluminophosphate intermediate has been proposed
w55 x. The molecular and mesoscopic organization in
v
alkylammonium phosphate w56 x and alkaline hexagonal
v
and lamellar silica-surfactant liquid crystals w57 x have
vv
also been investigated. In the latter case the use of
unreactive silica species at high pH and ambient tem-
perature allowed the decoupling of the self-assembly
9
process from the interfacial silicate polymerization.
Compared with the surfactant in solution the silicate
surfactant aggregates reveal a significantly lower curva-
ture because of the electrostatic binding of the head-
groups. This has been modeled in a recent study using
cationic gemini surfactant aggregates on anionic mica
planes w58 x.
vv
A higher control over the architecture of the inorganic
nanostructures can be achieved using the mesostructure
of lyotropic liquid crystalline phases or amphiphilic
block copolymers as a template. In this case the inor-
ganic precursor is directly incorporated in the hy-
drophilic domains of the respective mesostructure. The
resulting materials are a direct cast of the parental
mesostructure. This approach also allows the use of
non-ionic surfactants or disordered L 3 sponge phases
w59 x and may lead to large transparent, up to centime-
v
ter-sized monoliths w60,61 x while the classic method
vv
usually yields fine precipitates with particle sizes in the
sub-micrometer range.
Interestingly, it is also possible to prepare mesoporous
platinum in the form of small particles w62 x or films
vv
w63 x by reducing platinum salts in the aqueous do-
v
mains of a non-ionic surfactant liquid crystalline phase.
This method can thus be extended to metallic materials
with a tailored nano-architecture which proposes appli-
cation as catalysts or sensors.
Recently, the microphase-separated block copolymer
morphology of a polyisoprene]block]polyethylene ox-
ide. has been used to prepare lamellar and hexagonal
aluminosilicate]polymer mesostructures that are highly
ordered w64 x. Applying well-known concepts of block
v
copolymer technology allows control over the length
scale and the alignment of the microstructures.
Compared with low molecular weight surfactants, am-
phiphilic block copolymers do not only allow the real-
ization of mesoporous silica with larger pore sizes up to
approx. 30 nm. w65 x and improve the ductility and
vv
elasticity of the resulting composite leading, for exam-
ple, to crack-free monoliths. w61x but the slower relax-
ation times of copolymers also lead to an even higher
control over the structure thus allowing the exploitation
of even kinetically hindered structures or micellar ag-
gregates as templates w66 x. Unlike conventional sur-
vv
factants the properties of amphiphilic block copolymers
can be continuously tuned to adjust the composition,
the molecular weight or the architecture to the desired
purpose see Figure 3. w6,7x.
Applications of mesoporus silica often requires materials
with a well-defined macroscopic shape. Such systems
can be synthesized, for example, using a procedure
described by Ryoo et al. w67 x. This process allows the
v
10 Self-assembly
Silica monoliths obtained by templating from a lyotropic liquid
crystal polymer template. The backround lines are 5 mm apart. (b)
The transmission electron micrograph of the calcined silica of Fig.
3a. The sample was embedded in epoxy resin and ultramicrotomed.
Figure courtesy of CG Gother et al.
formation of transparent, single-crystal-like mesoporous
silica in the form of films, plates and wires from a
largely non-aqueous solution. Hollow tubular morpholo-
gies have also been realized using bacterial filaments
w68 x as substrates and even in a narrow composition
vv
range using cetyltrimethylammonium bromide as sur-
factant w69x. Mesoporous silica lamines and hollow
spheres can be prepared in the presence of alkylamines
as structure guiding components w70,71x. So far there
does not appear to be any great disadvantages. As this is
a young field, however, these structures have only re-
cently been synthesized.
Thin films of surfactant-templated mesoporous silica
have been prepared by a simple dip-coating method
w72 x. Interestingly, this procedure can be extended to
v
laminated organic]inorganic hybrid coatings mimicking
nacre by using a combined organic and inorganic po-
lymerization technique w73 x.
vv
Mesoporous thin films are expected to have high poten-
tial as separation membranes. In this context it is quite
important to achieve a macroscopically uniform orienta-
tion of the pores. This can be realized, for example, by
orientational ordering of the pores by magnetic field
alignment of the lyotropic silicate]surfactant liquid
crystal w74 x or by mechanically shearing the crystal in
vv
the presence of high KBr concentrations w75 x. Subse- v
quent polymerization freezes the orientation of the
pores. Another approach has been used to prepare long
oriented continuous silica tubules w76 x; microcapillar-
vv
ies serve as a substrate whereby an applied electric field
induces electro-osmotic flow from the reaction mixture
into the capillaries and enhances polymerization by
local Joule-heating.
This orientation problem, however, can be bypassed
using isotropic three-dimensional continuous pore struc-
tures like the disordered L 3 sponge phase which has
been developed by McGrath et al w59 x or cubic MCM48
v
materials w72 ,77,78x.
v
The potential applications of these mesoporous materi-
als has not only led to the development of a series of
non-silica materials, based on, for example, AlPO4
w79,80x, Al 2 O 3 w81 x, SnO 2 w82,83x, ZrO 2 w84x, TiO 2 ,
v
NbO 2 w85x and even metallic platinum w62 ,63 x, but vv v
also has led to forming materials in which the Si in silica
is partially replaced by Ti w77x or Al w78x, the encapsulat-
ing transition metal complexes w86]88 x in the pore
vv
system and so incorporating the organic functional
groups w89x. This last development is, for example,
accessible by an elegant one-pot synthesis using organo-
trialkoxy silanes as co-monomers w89x.
The preparation of a mesoporous V2 O5 with an excep-
tional ribbon structure using a water-in-oil microemul-
sion has been reported w90x. The structure is formed by
slow intermicellar agglomeration and is not a direct cast
of the parental microemulsion. Nevertheless, the result-
ing material has potential in catalysis or rechargeable
batteries.
An interesting approach, especially from an applications
point of view, is the recently reported preparation of
mesoporous silica in the presence of environmentally
friendly non-surfactant templates, like sugars, which
allow control over pore diameters in the range from 2 to
6 nm w90x.
Conclusions
The recent years have seen tremendous progress in the
preparation of nanostructured materials using surfactant
 Nanostructure synthesis using surfactants and copolymers Meier
and copolymer templates. A huge variety of different
organic and inorganic compounds can be molded into a
wide range of different mesostructures and macroscopic
shapes. Applications of the resulting materials are
presently extensively explored in a plenitude of re-
search areas and they certainly have not fully achieved
their potential. Commercial applications of all these
different nanostructures, however, call for a high degree
of control over the processibility as well as the structure
and composition of the resulting materials. This re-
quires a much better understanding of the underlying
mechanisms and physics behind the templating
processes occurring during synthesis. The development
of this knowledge is currently still in its infancy and
clearly much more work needs to be done in this area in
the near future.
Acknowledgements
The author would like to acknowledge the support of the Swiss
National Science Foundation.
References and recommended reading
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review, have been highlighted as:
v of special interest
vv of outstanding interest
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12 Self-assembly
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