Acc. Chem. Res.

2007, 40, 874–884

Three-Dimensional Core-Shell
Superstructures: Mechanically
Strong Aerogels
NICHOLAS LEVENTIS
Department of Chemistry, University of Missouri,
Rolla, Missouri 65409
Received October 26, 2006

ABSTRACT
Nanocasting conformal polymer coatings on preformed three-
dimensional assemblies of nanoparticles, macroscopically classified
as aerogels, reinforces the interparticle necks and increases the
strength of the bulk material dramatically. For example, specific
compressive strengths are reported to be higher than those for mild
steel and aluminum, while the ability to store energy may surpass FIGURE 1. Scanning Electron Micrographs (SEM) at random spots
that of armor grade ceramics. Specific chemistries have been in the interior of fractured monoliths of: (A) a native base-catalyzed
developed for cross-linking skeletal nanoparticles with polyureas silica aerogel with bulk density Fb ) 0.169 g/cm3; and, (B) a similar
and polyurethanes, epoxies, and polystyrene, while the technology sample whose skeletal framework has been coated conformally with
has been demonstrated with 30 different nanoparticle networks a diisocyanate-derived polymer by a process referred to herewith
in addition to silica. as cross-linking, Fb ) 0.380 g/cm3. Reprinted in part with permission
from ref 16. Copyright 2002 American Chemical Society.

1. Introduction polymer coating around the filler, fusing the filler particles
together. For reasons that become evident below, we refer
From a materials perspective, nanotechnology uses mo-
to this process as cross-linking, and as such a “filler,” we
lecular science (chemistry and physics) to manipulate
identified silica in its lowest bulk-density form, the silica
matter in the 1–100 nm size regime in order to furnish
aerogel.
useful macroscopic properties. In that regard, improve-
Silica aerogels are mesoporous materials5 made by
ments in performance in terms of strength, modulus, and
supercritical fluid (SCF) drying of wet gels..6–9 The latter
wettability are accomplished by, for example, introducing
are prepared via the so-called sol–gel process,6–8 which
nanoparticles as fillers in plastics.1 Materials compatibility
usually involves acid- or base-catalyzed hydrolysis and
is improved by chemical bonding of the filler with the
condensation of silicon alkoxides:
polymer, enhancing properties beyond what is obtained
by simple mixing.2,3 Going a step further, that is if both
the dopant and the matrix consist of particles with similar
sizes, we may realize distinct advantages in certain ap-
plications, for example, in catalysis.4 On the basis of this
background, if the dopant and the matrix (i.e., the filler
and the polymer) are not only sized similarly, but also if
the relative amounts are comparable, their roles can be
reversed. Then, if the filler, or one of its forms, possesses where R is CH3 for TMOS and R is CH3CH2 for TEOS.
interesting properties of its own, those properties could
Just before drying, gelation solvents filling the meso-
be enhanced by chemical nanocasting of a conformal
pores are exchanged with liquid CO2 in an autoclave,
whose temperature is then raised above the critical point
Nicholas Leventis was born in Athens, Greece, in 1957. He received his B.S. of CO2 (32 °C, 73.8 bar), turning the entire volume of the
degree in chemistry from the University of Athens in 1980 and his Ph.D. in organic liquid into a SCF, which is vented off isothermally (e.g.,
chemistry/photochemistry from Michigan State University (East Lansing, MI) with at 40 °C). That process circumvents evaporation and
Peter Wagner in 1985. He spent three years as postdoctoral fellow with Mark
Wrighton at the Massachusetts Institute of Technology (Cambridge, MA), and
prevents formation of a liquid–gas interfacial meniscus
he worked for six years in the private sector before coming to the Chemistry retreating through the pores of the wet gel. Hence, since
Department of the University of Missouri—Rolla (UMR) as an Assistant Professor no surface tension forces are ever exerted on the skeletal
in 1994, advancing to Associate Professor in 1999 and to Professor in 2007. Dr.
framework, as for example via evaporation during ambi-
Leventis was introduced to aerogels by Debra Rolison at NRL where he spent
the summer of 1998 as a Senior Faculty Fellow. During an extended leave from ent-pressure drying, SCF drying leaves the geometric
UMR (September 2002 to February 2006), Dr. Leventis joined as a Civil Servant dimensions of the wet gel unchanged, and the resulting
(GS-14 promoted to GS-15 in June 2005) the Polymers Branch of the NASA Glenn materials are very low density objects (0.003–0.8 g/cm3).
Research Center (Cleveland, OH), where he directed research on polymer-cross-
linked aerogels. Dr. Leventis has been the recipient of the ACS Arthur K. Doolitte Microscopically, typical base-catalyzed silica aerogels
Award (1992), the NASA Exceptional Scientific Achievement Medal (2005), and consist of randomly distributed pearl-necklace-like strings
one of the 2005 Nano50 Awards. Besides aerogels, his interests include physical
organic chemistry, electrochemistry, polymers, and inorganic materials. * Telephone: (573) 341-4391. E-mail: [email protected].

874 ACCOUNTS OF CHEMICAL RESEARCH / VOL. 40, NO. 9, 2007 10.1021/ar600033s CCC: $37.00  2007 American Chemical Society
Published on Web 05/09/2007
 Mechanically Strong Aerogels Leventis

of nanoparticles (Figure 1A).6–8 Because of that microstruc-

ture, silica aerogels can be considered as quasi-stable three-
dimensional assemblies of nanoparticles pursued because
of useful properties above and beyond those of their
individual building blocks. Those properties are traced to
the internal voids (dark areas in Figure 1A) and include a
very low thermal conductivity (<0.020 W m-1 K-1),8 a low
dielectric constant (as low as 1.5),10 and a high impedance
to acoustic waves (with speeds of sound as low as 100 m/s).11
Despite those attractive properties, however, aerogels
have found only limited use in some very specialized
features in the SEM of a native sample (Figure 1A) are still
environments, for example, as Çerenkov radiation detec-
visible in the SEM of the corresponding cross-linked sample
tors in certain nuclear reactors, as collectors of hyper-
(Figure 1B), leading to the conclusion that the new material
velocity particles in space (NASA’s Stardust program), and
covers the skeletal nanoparticles conformally.15–17 Nitrogen
as thermal insulators of the electronic boxes aboard all
sorption porosimetry yields typical type IV isotherms for both
three NASA Mars rovers (Sojourner in 1997, Spirit in 2004,
native and cross-linked samples, ensuring that the material
and Opportunity also in 2004). Wider commercial use of
remains mesoporous. As demonstrated in Figure 2, this
aerogels has been difficult because of their fragility,
environmental instability (hydrophilicity), and the need
for SCF drying.8 We could conceivably survive with the
first two issues, but the fragility problem imposes severe
limitations in terms of handling and long-term use.
This account summarizes our efforts to improve the
mechanical properties of aerogels with minimal penalty
in the internal void space.

2. Mechanically Strong Silica Aerogels by

Cross-Linking with Isocyanate-Derived
Polymers
Formally, aerogels are low-density foams, and as such, they
comprise a subcategory of cellular solids, the strength of
which is related to their pore size,12 increasing with the wall
thickness and decreasing with pore diameter. However, the
pore walls of base-catalyzed silica aerogels have well-defined
weak points, the interparticle necks (Figure 1A). Therefore,
although grafting material on the surface of the skeletal
nanoparticles will increase stiffness (resistance to bending),
to impart a significant increase in strength the grafting
material should also bridge the particles at the necks with
covalent bonds. This line of reasoning is akin to processes
taking place during aging of wet gels, where Ostwald ripening FIGURE 2. N2 sorption isotherms and the corresponding BJH
with dissolution and reprecipitation of silica at surfaces with (desorption) pore size distribution data for typical native and cross-
negative curvature (i.e., at surfaces that cross all tangent linked aerogel monoliths: (b) adsorption and (O) desorption. The
planes at every point of those surfaces, e.g., the necks) result specific data are for Gd aerogels (see Section 3.b), where before
cross-linking, Fb ) 0.18 g/cm3 and σ ) 383 m2/g, while after
in mechanically stronger frameworks.13,14 In our first attempt
crosslinking, Fb ) 0.44 g/cm3 and σ ) 171 m2/g).
to address the aerogel fragility issue, this logic was applied
by bridging nanoparticles using polyurethane chemistry behavior is typical for all types of aerogels investigated in
where the hydroxyl-rich surface of a preformed (from TMOS) these studies. The pore size distribution of silica aerogels
silica framework plays the role of a polyol that reacts with a determined by the BJH method shows a shift toward larger
di- and a triisocyanate (e.g., Desmodur N3200 and N3300A, average pore diameters (from 13.4 nm for native aerogels
respectively, from Bayer) dissolved in the pore-filling solvent, with a bulk density Fb of 0.17 g/cm3 to 21.9 nm for cross-
forming carbamate (urethane).15–17 As it turns out, the cross- linked samples with a Fb of 0.39 g/cm3), suggesting that
linking reaction requires heating at whatever temperature access to the smaller crevices on the superstructure has been
is allowed by the solvent (e.g., 50 °C with acetone, 70 °C with blocked.15–17 Consistent with this model is also the decrease
CH3CN, and 100 °C with propylene carbonate); results, in the BET surface area (969 ( 30 m2/g before to 277 ( 30
however, do not seem to depend on the cross-linking solvent m2/g after cross-linking at a Fb of 0.399 g/cm3) with a
or the specific temperature. At the end, after SCF drying and simultaneous decrease in the C parameter (from 80–90 to
despite a bulk density increase by a factor of 2.2, the smallest 46–48), indicating a decrease in surface polarity, as expected
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 Mechanically Strong Aerogels Leventis

FIGURE 3. Cross-sectional MRI of (A) a cylindrical native silica wet

gel monolith [diameter of ∼1 cm, bulk density of the resulting aerogel
(Fb) of ∼0.18 g/cm3] and (B) a similar isocyanate polymer-cross-
linked wet gel monolith (diameter of ∼1cm, Fb of ∼0.55 g/cm3), both
solvent-exchanged and filled with acetone. Smaller dark circles (at
two different sizes) surrounding the wet gels are empty capillary
tubes helping the monoliths stand straight up. The bright circle at
the top is a capillary tube filled with water. The average dark pixel
density around the perimeter of the native gel is 160 ( 8 and that
of the cross-linked gel 152 ( 8. The background is 193 ( 10.
Reprinted from ref 17, Copyright 2004, with permission from Elsevier.

for the coating of silica with an organic polymer.18 It should

be pointed out though that in spite of the apparent sub-
stantial changes taking place at the nanoscopic level, the
accessible (i.e., useable) porosity from a macroscopic view-
point has not been compromised significantly: NMR imaging
(MRI, Figure 3) followed by gray scale analysis shows that
the void space available to a solvent (acetone) has been
reduced by only ∼5%.17 FIGURE 4. Mechanical properties (by a short beam three-point
bending, see the inset) of isocyanate-cross-linked aerogels and their
The amount of material incorporated into silica can be
non-cross-linked (native) counterparts: (A) (a) 0.63, (b) 0.44, (c) 0.38,
controlled to a certain extent by the concentration of the and (d) 0.28 g/cm3. Native samples are not shown because they do
isocyanate in the cross-linking bath, and although the not register on the load force scale shown. (B) Cumulative data.
density of a typical cross-linked aerogel monolith may Blue triangles and the dark blue line concern two-step aerogels
increase by a factor of 3, the strength at breakpoint through (see the text). All other samples use one-step base-catalyzed silica.
a short beam three-point bent test method increases by a Multiple lines for cross-linked samples correspond to different di-
factor of up to 300.19 Typical load-deformation curves and and triisocyanate cross-linkers. Reprinted from ref 17, Copyright 2004,
cumulative strength data are summarized in Figure 4. Thus, with permission from Elsevier.
a typical native sample fails with less than 100 g of vertical density with a silica–polymer combination rather than with
force, while a cross-linked sample can withstand in excess silica alone.
of 30 kg (Figure 4A). In fact, cross-linked wet gels can Chemically, the situation turned out somewhat more
withstand capillary forces, and they can be dried from low- complex than originally planned. CP-MAS 13C NMR
surface tension solvents (e.g., pentane) under ambient (Figure 5) shows that the accumulated material contains
pressure, practically without loss of porosity or surface area.19 both carbamate and urea, and Scheme 1 summarizes the
Now, as the density (i.e., the amount of material ac- mechanistic interpretation: cross-linking involves not only
cumulated) increases, cross-linked monoliths become not formation of carbamates with surface silanols but also
only stronger (they can withstand more load before reaching formation of urea by hydrolysis of dangling isocyanates
the breakpoint) but also stiffer (the initial slope of the load- into amines, which in turn react with more isocyanate in
deformation curve increases) and tougher (they can store the mesopores.17 On the basis of density increase con-
more energy as the area under the load-deformation curve siderations, the average polymeric tether (from N3200) is
also increases). Figure 4B shows that strength increases faster ∼5 monomer units long. The hydrolysis of dangling
by addition of cross-linker onto the preformed skeletal isocyanates is carried out by gelation water remaining
framework than by use of more TMOS in the sol. In other adsorbed on silica even after numerous solvent exchange
words, in terms of strength, it is better to achieve a given steps. No unbound polymer is formed in the cross-linking
876 ACCOUNTS OF CHEMICAL RESEARCH / VOL. 40, NO. 9, 2007
 Mechanically Strong Aerogels Leventis

FIGURE 5. CP-MAS 13C NMR characterization of the carbonyl region of (A) N3300A (CDCl3), (B) the product of the reaction of N3300A with
methanol (CDCl3), (C) the product of the reaction of N3300A with isopropylamine (solid sample), (D) the product of the reaction of N3300A and
water (solid sample), and (E) the N3300A cross-linked aerogel with a Fb of ∼0.38 g/cm3 (solid sample). Reprinted from ref 17, Copyright 2004,
with permission from Elsevier.
Scheme 1. Mechanism of Cross-Linking a Silica with a Diisocyanatea bonding between the two components.22 By the same
token, however, it is also noted that the benefit from
developing even weak hydrogen bonding between an
interpenetrating polymer (e.g., poly-2-vinylpyridine) and
surface silanols has not gone unnoticed.23 On the other
hand, polymer cross-linking as defined here is conceptu-
ally related to Einarsrud’s work on reinforcing aerogels
by rendering interparticle necks wider via postgelation
treatment of silica with TEOS.24 Nevertheless, although
silica itself has a high compressive strength, reinforcing
silica with silica does not realize the synergistic benefit of
reinforcing necks with a high tensile strength material like
a polymer. In this context, rubbery materials produced
by reactive incorporation of hydroxyl-terminated poly-
dimethylsiloxane (PDMS) in both xerogels and aerogels
have been discussed by Mackenzie in terms of three
a Reprinted from ref 17, Copyright 2004, with permission from Elsevier. models; at one extreme, silica particles separated from one
another are yet connected by PDMS, while at the other
bath under the same conditions. All containers develop extreme, silica particles are in contact with each other and
pressure during the cross-linking reaction, and the identity also bridged (cross-linked in our terminology) with
of the evolving gas (CO2) was confirmed by FTIR. In PDMS.25,26 The shortcoming of using a sol incorporating
certain experiments involving two-step gels (acid-cata- a cross-linker that competes for the same functional
lyzed hydrolysis followed by base-catalyzed gelation20), groups (Si-OH) involved in gelation is that it provides no
reducing the amount of gelation water hampered the control for tuning-in high stiffness and strength versus
ability of wet gels to cross-link.17 On the other hand, rubbery behavior. This kind of issue was encountered
cutting down the number of postgelation wash steps had when the isocyanate was included in our sol: gelation was
the opposite effect, yielding denser gels with a progressive retarded tremendously (days instead of minutes), while
loss of porosity.21 Of course, our data do not exclude the the mechanical properties of the resulting aerogels did not
possibility that a certain amount of polymer is surface- improve significantly.16
bound by one end only. Cross-linked aerogels, however,
do not contain free isocyanate (by 13C NMR and IR),
suggesting that all dangling tethers are eventually hydro-
3. Three Degrees of Freedom in the Design of
lyzed and terminated with amine. Cross-Linked Aerogels
The cross-linked aerogels described above are distinctly Once it was evident that interparticle tethers consist of
different from reinforced sol–gel materials by interpen- polyurea, the immediate question became whether urea
etrating organic polymers with no provisions for covalent formation can be induced from the attachment point on
VOL. 40, NO. 9, 2007 / ACCOUNTS OF CHEMICAL RESEARCH 877
 Mechanically Strong Aerogels Leventis

interior or located at the particle surface.29 The fact,

however, that gelation of the TMOS/APTES system is
extremely fast while APTES itself apparently hydrolyzes
on a time scale of TEOS (10–50 min) suggests that APTES
in our TMOS/APTES system is simply grafted on the
surface of TMOS-derived particles. The BET specific
surface areas, σ, of standard TMOS/APTES aerogels (top
of Figure 9, Fb ) 0.190 ( 0.014 g/cm3) are ∼740 m2/g,
larger than values reported for TEOS/APTES gels (<300
m2/g).32 On the basis of skeletal densities of TMOS/APTES
aerogels (Fs ) 1.74 g/cm3), the particle radius (r ) 3/Fsσ)
FIGURE 6. Design space of crosslinked X-aerogels. is calculated to be 2.3 nm, which is significantly smaller
than what has been reported based on SAXS for the TEOS/
the skeletal framework. Of course, that requires amine- APTES system (6.0-6.3 nm). The reaction-limited mono-
rich mesoporous surfaces, but once we found ourselves mer–cluster growth mechanism for gelation in basic media
willing to consider modification of the surface functional- prescribes fast condensation and large particles.7 The
ity, we also realized that actually there are three degrees small particles observed herewith are attributed to hy-
of freedom in the design of cross-linked aerogels (Figure drogen bonding stabilization of the relatively more acidic
6): (a) the nanoparticle surface chemistry, (b) the chemical TMOS-derived Q-hydroxyls by APTES amines.32
identity of the cross-linker, and (c) the network morphol-
3.a.1. Cross-Linking with Isocyanates.27–29 Wet gels
ogy. Surface and cross-linking chemistries are intimately
made using the standard TMOS/APTES formulation fol-
related and are reviewed together in section 3.a, while
lowed by (a) four CH3CN washes to remove excess gelation
section 3.b discusses the effect of the network morphology.
water, (b) equilibration in a concentrated isocyanate bath
3.a. Cross-Linking of Amine-Modified Silica. Amines
(24 h) and oven heating in fresh CH3CN for 3 days at 71
were introduced into silica by cogelation of TMOS with
°C, and (c) SCF CO2 drying resulted in translucent (as
aminopropyltriethoxysilane (APTES) in a 3:1 volume ratio
opposed to opaque) aerogels with densities in the range
of 0.48 ( 0.01 g/cm3 (Figure 9, middle), thermal conduc-
tivities (∼0.041 ( 0.001 W m-1 K-1) comparable to that
(4.8:1 molar ratio). The amount of gelation water was left of glass wool, and an average specific compressive strength
at approximately the same ratio that was used for the one- at ultimate failure (77% strain, Poisson ratio ) 0.18) at
step base-catalyzed TMOS gels of the previous section, 3.89 × 105 N m kg-1, that is 2.8 and 3.2 times higher than
namely at a 2.2:1 H2O:(TMOS+APTES) molar ratio. The that of 4031 steel and of 2024 T3 aluminum, respectively.33
preferred gelation solvent was acetonitrile. We will refer Clearly, the combination of mechanical and thermal
to this sol formulation as “standard”. The resulting amine- properties of those materials is promising for practical
modified silica wet gels were cross-linked with iso- applications. More recent studies have focused on two
cyanates,21,27–29 epoxies,30 and styrene31 as outlined in objectives: (a) exploring properties of low-density cross-
Figure 7. Cross-linked wet gels were dried with SCF CO2.
linked aerogels (Fb < 0.1 g/cm3) and (b) studying the effect
APTES amines catalyze the sol–gel process, and our
of the preparation protocol on the properties of the final
TMOS/APTES system gels almost instantaneously upon
product. To minimize the number of samples required for
mixing. To allow time for pouring into molds, sol precur-
those studies, we made extensive use of statistical design-
sors are cooled in an ice/water or dry ice/acetone (pre-
of-experiments (DoE) methods, whereas a subset of
ferred) mixture. Gelation into clear gels takes place in less
experimental runs fully capable of capturing with a high
than a minute while the sol is still cold. It is known that
degree of confidence the relationships between properties
under basic conditions hydrolysis of R-Si(OCH3)3, where
and preparation conditions is computer-generated from
R is a nonbase group, is slower than hydrolysis of TMOS,
all possible candidate experiments.30 Here we summarize
resulting in a stepwise sol–gel process, whereas R is grafted
results that shed light on the chemical composition of the
onto TMOS-derived silica particles.7 However, because of
the fast reaction (reported as precipitation) of TMOS in materials.
the presence of APTES, the TEOS/APTES system has been Low-density APTES-modified aerogels were prepared
studied more thoroughly, and it has been reported that by reducing the concentration of total silica (TMOS and
hydrolysis of TEOS and APTES take place at similar rates, APTES) while keeping the TMOS:APTES volume ratio at
resulting in gels in which APTES is incorporated into the 3:1. Since APTES-modified silica reacts with isocyanate
silica network.32 In our CP-MAS 29Si NMR studies (Figure even at ambient temperature, cross-linking was carried
8), silicas derived from the TMOS/APTES system show out and investigated at two temperature extremes: 71 and
clearly that silicon from TMOS is divided between Q4, Q3, 25 °C.28 Low-density cross-linked aerogels (∼0.05 g/cm3),
and Q2 sites (participating in four, three, and two Si–O–Si irrespective of preparation conditions, are flexible, and
bridges, respectively), while practically all the APTES/ microscopically, they include more empty space than
silicon form is bound through three Si–O–Si bridges (T3 denser versions (bottom vs middle of Figure 9) with
silicon at -65.1 ppm) and could be either buried in the porosities in excess of 95%. It is instructive to consider
878 ACCOUNTS OF CHEMICAL RESEARCH / VOL. 40, NO. 9, 2007
 Mechanically Strong Aerogels Leventis

FIGURE 7. Selected cross-linking possibilities for amine-modified silica.

FIGURE 8. CP-MAS 29Si NMR of aerogels made with TMOS (A) and
a 3:1 TMOS:APTES volume ratio (B).

the DoE-predicted variation of strength with density for

the same initial TMOS/APTES concentration at the two
processing temperatures (Figure 10).28 As dimensions do
not change during processing, aerogels made with the
same amount of silica and having the same final density
contain the same amount of polymer, but aerogels cross-
linked at 71 °C are consistently weaker (by up to 40%) than
those made at room temperature (albeit making the latter
takes longer). Therefore, the chemical makeup of the two
polymers should be different. Given that native APTES-
FIGURE 9. Comparative SEM of a standard (see the text) native
modified silica carries via TMOS Q3 silicon atoms with TMOS/APTES aerogel (top), a higher-density cross-linked sample
hydroxyl groups (Figure 8B), and that TMOS-derived silica (middle), and a lower-density cross-linked sample (bottom). Middle
reacts with isocyanate reasonably fast only at elevated and bottom panels reprinted from ref 28, Copyright 2006, with
temperatures,16,17 it is suggested that under standard permission from Elsevier.
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 Mechanically Strong Aerogels Leventis

Scheme 2. Cross-Linking APTES-Modified Silica with a Triepoxidea

FIGURE 10. Predicted plots of maximum stress vs density using

model-generated data points at 12% (red) and 24% (blue) of total
silane (TMOS/APTES) (v/v) in CH3CN. Empty symbols depict data
for aerogels made at 25 °C; filled symbols depict data for aerogels
made at 71 °C. Monoliths produced at 71 °C are predicted to be
always weaker than monoliths of the same density (i.e., along the
vertical lines) made at 25 °C. Reprinted from ref 28, Copyright 2006,
with permission from Elsevier.
a Reprinted with permission from ref 30. Copyright 2005 American

processing conditions (∼70 °C) isocyanate most probably Chemical Society.

binds to APTES-modified silica via both carbamates and
ureas.
density for any formulation. This is rather expected as
Studies of the effect of the preparation conditions on
interparticle necks become stiffer when material ac-
the properties of cross-linked aerogels were partly moti-
cumulates on the particles. On the other hand, however,
vated by the practical need to reduce the preparation time
the stress at failure shows a clear maximum, presumably
by reducing or eliminating the number of postgelation
corresponding to the maximum degree of interparticle
washes. In one school of thought, this may be ac-
cross-linking. Strength and modulus data taken together
complished by reaching a balance between the (TMOS/
have been considered as strong evidence of the role of
APTES):isocyanate and (TMOS/APTES):H2O ratios. CP-
building interparticle tethers for strength. Similar trends
MAS 13C NMR of cross-linked aerogels has shown that as
with analogous inferences have been reported recently for
the number of postgelation washes is decreased from four
aerogels cross-linked with isocyanate derived polymers.21b
to none, the length of the polymer may increase from
3.a.3. Cross-Linking with Polystyrene. Although iso-
three hexamethylene repeat units (four washes) to more
cyanate and epoxy-cross-linked aerogel monoliths are much
than 600 repeat units (no washes).21 The porosity (by SEM)
may also decrease as the amount of material taken up less hydrophilic than native silica, they are not hydrophobic:
increases,21 supporting the role of the gelation water in for instance, in contact with water, they are quickly filled
the cross-linking process. with the liquid and sink within minutes. This is not surpris-
3.a.2. Cross-Linking with Epoxies. In analogy to iso- ing because both polyurethanes and epoxies have polar
cyanate cross-linking that mimics polyurethane chemistry, groups able to hydrogen bond with water. To impart
we have also imitated “epoxy glue” chemistry where hydrophobicity, nonpolar cross-linkers such as polystyrene
amine-modified silica plays the role of the hardener and polypentafluorostyrene were considered.31 The cross-
reacting with a multifunctional epoxide.30 Epoxy-cross- linking process was rather lengthy (Scheme 3). First, amines
linked aerogels based on the standard TMOS/APTES of standard APTES-modified silica reacted with p-chlorom-
formulation may have a density of up to 0.49 g/cm3 with ethylstyrene; subsequently, styrene or pentafluorostyrene
a BET surface area of 314 m2/g and an average pore and a free radical initiator (AIBN) were introduced into the
diameter of 14.7 nm. CP-MAS 13C NMR excludes inter- mesopores, and the samples were heated. The free radical
particle tethers from ring opening homopolymerization process initiated in the mesopores engages surface-bound
of epoxides, supporting the cross-linking mechanism of styrene, and when radicals at the tips of polymer chains
Scheme 2. Again DoE studies were used to investigate the growing out from the surface meet, the radical process is
role of parameters such as the “valency” of the epoxide terminated, yielding molecular interparticle tethers. In fact,
in materials properties. Figure 11 summarizes data for this process is not in principle different from the peroxide-
density, ultimate strength, and modulus (by a three-point initiated copolymerization of methacrylate with surface-
bend test) as a function of preparation conditions. Con- bound methacrylate [introduced by cogelation of an ep-
sistently, triepoxide-cross-linked aerogels exhibit higher oxysilane, methacryloxysilane, and T(OR′)4], described in the
density, strength, and stiffness for almost all preparation mid-1980s by Schmidt for contact lens applications.34 In our
conditions. This may be related to either the reactivity of case, however, unbound polymer formed in the mesopores
the epoxide or its structure. Interestingly, for all epoxides, was removed by post-cross-linking washes, and wet gels
density and modulus vary in a similar fashion, indicating were dried to aerogels.31 Polystyrene-cross-linked aerogels
that the elastic modulus increases monotonically with are strong mechanically in analogy to their isocyanate and
880 ACCOUNTS OF CHEMICAL RESEARCH / VOL. 40, NO. 9, 2007
 Mechanically Strong Aerogels Leventis

Scheme 3. Cross-Linking of APTES-Modified Silica Nanoparticles

with Polystyrene31

reflecting a bimodal radical termination process in which

surface–surface and surface–solution radical combination
events form shorter and longer polymer chains, respectively.
Water droplets on isocyanate-cross-linked aerogel disks
form a contact angle of 59.7 ( 1.3° and are absorbed by
the pores within 5 min. With polystyrene-cross-linked
disks, the contact angle is 121.4 ( 0.9°, and with poly-
pentafluorostyrene, it is 151.3 ( 1.8°. Those contact angles
FIGURE 11. Response surface models for density, modulus, and do not change with time, and polystyrene-cross-linked
stress at failure (via a short-beam bending test method) of epoxy- aerogel monoliths float on water for months.31
cross-linked silica aerogels vs APTES and epoxide concentration 3.b. Effect of the Network Morphology on Strength.
with cross-linking time and bath temperature held constant at the
Acid-catalyzed silica aerogels have a polymer-like (fi-
predicted optimum value for stress at failure.
brous), as opposed to the colloidal (particulate) texture
of their base-catalyzed counterparts,6 and they are twice
epoxy counterparts. Typical monoliths with a bulk density as stiff.35 Therefore, it was reasoned that by varying the
of 0.47 g/cm3 show a relative high BET surface area chemical identity of the aerogel framework, we could
(370 m2/g), pore diameters of ∼11.5 nm, and a thermal potentially realize not only materials with variable optical,
conductivity of 0.041 W m-1 K-1. The average surface-bound electrical, magnetic, and chemical (e.g., catalytic) proper-
polymeric tether consists of 15 monomer units (determined ties without a need for external doping,36 but also different
by both 13C NMR and density change considerations) with elements that would yield network morphologies that
a polydispersity of 2.05 (determined by GPC), which is higher could dissipate load forces differently, resulting in yet
than that of the free polymer formed in the mesopores (1.50), stronger materials. In that context, we were aware of the
VOL. 40, NO. 9, 2007 / ACCOUNTS OF CHEMICAL RESEARCH 881
 Mechanically Strong Aerogels Leventis

wormlike texture of vanadia aerogels.37 Thus, in addition

to silica, we prepared and isocyanate-cross-linked aerogels
based on 30 other elements from the periodic table (Al,
Sc, Ti, V, Cr, Mn, Fe, Y, Zr, Nb, Ru, In, La, Pr, Nd, Sm, Eu,
Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, and Re). As it
turns out, even gels prepared from hydrated metal chlo-
rides via a nonhydrolytic route38 are surface-terminated
with OH groups and retain coordination water so that they
are able to develop conformal polymer coatings by reac-
tion with di- and triisocyanates in analogy with silica. Rare
earth (RE) aerogels were studied in greater detail because
of their dielectric and paramagnetic properties.40 They are
nonstoichiometric amorphous materials with moderately
high surface areas (368 ( 14 m2/g before and 156 ( 19
m2/g after cross-linking). The percent metal content (58.0
( 2.3%, w/w) is significantly lower than that of pure oxides
(85.4–87.9%, w/w). Even native RE aerogels contain a
significant amount of carbon, mostly as carbonate (9.0 (
2.4%, w/w), presumably formed during SCF drying. The
gram magnetic susceptibility, χ, is a sensitive probe of the
skeletal contribution to the materials properties. Aerogels
have χ values lower than those of the corresponding
xerogels, because of the higher carbonate content. Cross-
linked aerogels exhibit χ values lower than those of both
xerogels and aerogels, reflecting spin dilution by the
polymer (Figure 12A). Despite their stoichiometric com-
plexity, the magnetic susceptibility of RE aerogels varies
FIGURE 12. Room-temperature gram magnetic susceptibilities, χ,
linearly with the susceptibility of the pure oxides (Figure
of rare earth sol–gel materials as a function of the atomic number
12B), as if RE aerogels were pure compounds themselves, showing the expected trend for pure compounds (A). Those χ-values
a property potentially very useful from an applications in fact correlate linearly with the susceptibilities of the pure oxides
design perspective. (B), reflecting the stoichiometric similarity within each series of
Microscopically, with the exception of vanadia, all non- materials. Slopes are proportional to the relative abundance of the
silica aerogels look very similar to one another, consisting metal ions. The inset in panel A shows the X-dysprosium aerogel
powder picked up by a 1 cm diameter Nd-Fe-B magnet. Reprinted
of nanoparticles, pretty much like the base-catalyzed silica
with permission from ref 40. Copyright 2007 The Royal Society of
of Figure 1, and the mechanical properties track those of Chemistry.
cross-linked silica. Vanadium aerogels consist of entangled
wormlike nanosized objects assembled into a bird nest-
like structure (Figure 13A). 37 Cross-linking vanadia aero-
gels with isocyanate yields a conformal coating (Figure
13B).
Cross-linked vanadia aerogels possess very interest-
ing mechanical properties (Figure 14).41 Isocyanate-
cross-linked APTES-modified silica aerogels (0.48 g/cm3)
fail at 77% strain under ∼30 ksi compression, but
vanadia (0.38 g/cm3) does not fail even at 95% com-
pressive strain under 100 ksi. Samples do not buckle,
and swell only at the very last stages of compression
(Poisson ratio ) 0.18). The material is practically
absorbed by its own porosity. Samples recovered after
testing show a complete loss of their internal surface
area. From an applications perspective, a very important
property of those materials is their ability to store FIGURE 13. SEM of (A) a native vanadia aerogel (Fb ) 0.078 g/cm3)
energy, particularly at high strain rates. Thus, the and (B) a vanadia aerogel cross-linked with diisocyanate (Fb ) 0.428
specific energy absorption density of isocyanate-cross- g/cm3).
linked vanadia (0.52 g/cm3) is 1.3 × 106 N m kg-1. By
comparison, the energy absorption density at the fail ceramics is 3.5 × 104 N m kg-1, namely ∼50 times lower
point of isocyanate-cross-linked silica (0.48 g/cm3) is than that of the 0.52 g/cm3 cross-linked vanadia aero-
7.3 × 104 N m kg-1, and that of armor grade SiC-N gels.39
882 ACCOUNTS OF CHEMICAL RESEARCH / VOL. 40, NO. 9, 2007
 Mechanically Strong Aerogels Leventis

Capadona, Joe Counsil, Paul Curto, Amala Dass, Eve Fabrizio,

Abigail Hobbs, U. Faysal Ilhan, J. Chris Johnston, Jim Kinder,
Hongbing Lu, Linda McCorkle, Mary Ann Meador, Sudhir Mulik,
Anna Palczer, Abdel-Monem Rawashdeh, Samit Roy, Dan
Scheiman, Jennifer Schnobrich, Chariklia Sotiriou-Leventis, Jeff
Thomas, Plousia Vassilaras, Xiaojiang Wang, and Guohui Zhang.

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