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The Journal of Supercritical Fluids 134 (2018) 228–233

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The Journal of Supercritical Fluids


journal homepage: www.elsevier.com/locate/supflu

Aerogel production: Current status, research directions, and future T


opportunities

Irina Smirnova , Pavel Gurikov
Institute of Thermal Separation Processes, Hamburg University of Technology, Eißendorfer Straße 38, 21073 Hamburg, Germany

A R T I C L E I N F O A B S T R A C T

Keywords: Being the lightest solid materials known, and given the great variety of possible chemistries capable of yielding
Aerogels wet-gels, aerogels and composite aerogel materials have a tremendous potential in a wide range of applications,
Applications where high pore volume and high surface area play major roles. Today, the main commercialized application of
Aerogel production aerogels is thermal insulation, although aerogels can be used for a huge variety of applications such as elec-
trochemistry (super capacitors), carrier of catalysts and other active agents, filling materials, materials for tissue
engineering etc. However, industrial production of aerogels is so far mostly limited to silica-based systems,
limiting the possibility to prove the potential application by prototyping. In this paper first the state of the art of
the aerogel manufacturing and applications are briefly discussed. Based on the current status, main knowledge
gaps and challenges are identified and the future research directions from the point of view of the authors are
derived. In the next future, we expect significant further development in the area of the organic and hybrid
aerogel aerogels, optimization of their manufacturing processes and their transfer to the market.

1. Introduction target application. Other way around, if the properties of aerogels are
improved, new applications, which were impossible in the past (for
Aerogels are low-density nanoporous solids with a fine, open-pore instance due to poor mechanical properties, sensitivity to moisture or
structure resulting in low densities (0.003–0.15 kg/m3), high porosity low sorption capacity) would be enabled in the future. Accordingly, the
and large surface areas (500–1000 m2/g). This combination of proper- main focus of this paper is to point out and shortly discuss the most
ties makes them unique in many senses, opening a possibility to a huge promising research directions towards this goal.
number of applications, some of which have been commercialized al-
ready. The definition of aerogels has been discussed a lot in the last 2. Aerogels: current state
years [1]. According to Smirnova and Gurikov [2] an aerogel is an open
colloidal or polymeric network consisting of loosely packed, bonded 2.1. Availability of aerogels
particles or fibers that is expanded throughout its volume by a gas and
therefore exhibits very low density and high specific surface area. Aerogels can be generally produced in different forms, included
Although the method of preparation is not included in this defini- complex customized monoliths, since the original liquid starting mix-
tion, aerogels are usually formed by removing all swelling agents from ture can be shaped during the gel formation. For thermal insulation,
an initial gel without substantial volume reduction or network com- Cherenkov detectors, and supercapacitors, often monoliths are needed.
paction or degradation. Initial gel can consist of virtually any material At the same time, certain flexibility along with the pre-shaped forms
or combination of different ones (hybrid aerogels). Therefore the can be desired as realized through the incorporation of aerogels into
chemistry of aerogels is very flexible: their pore size and surface area textiles and other matrices. However for many applications (for in-
can be tailored; furthermore, different functional groups can be im- stance filler materials, carrier for pharmaceuticals and cosmetics)
plemented in order to provide desired mechanical and physico-che- monolithic or matrix-supported form is not necessary needed. Here
mical properties. Although a large number of aerogels exist, the authors granules or powder is the desired shape of the aerogel product, which
are convinced that a lot more new aerogel types are going to be dis- has been realized by several suppliers already. Fig. 1 represents ex-
covered in the next years, since especially hybrid aerogels enable to amples of different forms of commercially available aerogel materials.
modify the properties and add new functionalities depending on the Recently, production of aerogel fibers was suggested, although not


Corresponding author.
E-mail address: smirnova@tuhh.de (I. Smirnova).

https://doi.org/10.1016/j.supflu.2017.12.037
Received 23 October 2017; Received in revised form 26 December 2017; Accepted 26 December 2017
Available online 27 December 2017
0896-8446/ © 2018 Elsevier B.V. All rights reserved.
I. Smirnova, P. Gurikov The Journal of Supercritical Fluids 134 (2018) 228–233

Fig. 1. Different forms of available aerogel materials


(examples) [4–7].

commercialized yet [3]. Table 1, we provide a list of the commercial aerogel suppliers estab-
Aerogels have been for a long time seen as a curious material ex- lished today (to the best of author’s knowledge).
isting mainly in the labs. However, today at least silica aerogels as well Generally organic and carbon aerogels can be ordered in small
as some organic and carbon aerogel are commercially available. In amounts for academic purposes (e.g., via [8]). Besides that, several

Table 1
Commercial aerogel suppliers established today (to the best of author’s knowledge). Producer of aerogel-based products, which do not manufacture the aerogels themselves are not
included.

Region Country Producer Chemical nature of the aerogel Aerogel form

North America USA Aspen Aerogel Mainly silica incorporated in textiles Blankets
American Aerogel Diverse Diverse
NanoPore Inc Silica Thin films and related products
Aerogel Technologies Organic aerogels, other types on demand Panels, particles, customized
TAASI Mainly silica-based Powder, granules, beads, small monoliths, customized
Marketech International Inc. Customized Mainly small monoliths, customized
CDT Systems Inc. Carbon, composite materials Monoliths and solutions for water purification and
electrochemistry
Dow Corning (Head quarter in USA) Silica Powder
Cabot Corp. (aerogel production in Mainly silica incorporated in support matrix; Blankets/sheets/ granulates
Germany) Hydrophobic silica
Europe Germany BASF SE Polyurethane Monolithic panels
Sweden Airglass Transparent silica Monoliths
Svenska Aerogel Silica Powder, granules
Portugal Active Aerogels Silica composites Sheets
Spain Green Earth Aerogels Silica from rice wastes and husks Powder, granules
Enersens SAS Silica Powder/small monoliths
Keey Aerogels Mainly silica, silica incorporated in support Particles
matrix
Switzerland Nexaero Hydrophobic silica Particles
Asia China NanoHigh-Tech Co. Ltd Silica, organic, diverse Diverse
South Korea JIOS Aerogel Corp Mainly silica Powder
Japan Tiem Factory Inc. Silica (ambient drying) Powder/Granules/ Monoliths

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I. Smirnova, P. Gurikov The Journal of Supercritical Fluids 134 (2018) 228–233

academic groups have developed their own aerogel products and offer

Low energy costs; well established process; extensive use of

Significant energy costs due to CO2 compression (may be


improved by process optimization); so far bath process;
them also on request. The aerogel market is seen as having a high

High energy costs to maintain low temperature; batch

(heating); batch process, High explosion and toxicity


growth potential, as lab scale process breakthroughs described in the

lower explosion risk due to low T and CO2 nature


Moderate energy costs to reach critical conditions
scientific literature, show potential of being translated into industrial
scale processes.

2.2. Current state of production process

Aerogel production process is traditionally divided in 3 steps: gel


formation (chemical reaction, crosslinking, sol-gel transformation),

hydrophobization agents
Main energy costs/Risks
solvent exchange (if required by the following drying) and drying.
Sometimes, some post-processing (hydrophobization, coating etc.) is
needed. The shape of the final aerogel (monolith, granules, powder) is
mainly formed during the gel formation (for example by molding). At

hazards
the same step, the microstructure of the later aerogel arises. Thus, the

process
main requirement to the following solvent exchange and drying is to
preserve this microstructure as well as shape from compaction and

in/out the matrix; Well compatible with all kind of gels


further changes. The gel formation as such uses mainly the well-known

Drying kinetics depend on the CO2/solvent transport


Temperature > 100 °C often not compatible with the
organic gels; possible side reactions with the solvent
Target density below 0.03 g/cm3 hardly achievable;
reactions of organic and/or inorganic materials and can be realized

density > 0.1 g/cm3 are reported; Not possible for


Compaction of the matrix: mainly aerogels with
based on the corresponding principles provided by chemistry. At the
same time, the preservation of the microstructure formed by the reac-
tion is the key and the main challenge of the aerogel production. All
aerogels commercially available at large scale presently use the sol-
vents, which are directly applicable for drying and therefore do not

fragile and hydrophilic matrices


Limitations for the gel matrix
involve the solvent exchange. Therefore we can conclude that there is
actually no state of the art for the solvent exchange on industrial scale.

pores partly destroyed


At the lab-scale the solvent exchange is mainly needed for the pro-
duction of all types of aerogels based on hydrogels, since water is poorly
miscible with CO2 at reasonably low pressures and temperatures.
Obviously, the scale-up of the solvent exchange needs to be established
in the future. The drying itself can be conducted in three different ways:
at ambient conditions, at supercritical conditions or at low pressure and
temperature below the melting point (freeze drying). Specific features
Chemical hydrophobization of the matrix is

of these processes are summarized in Table 2.

Solvent should be reasonably mixable with


Addition of modifier (e.g. tert-butanol) to

CO2 at process conditions; For hydrogels


It is obvious that each drying process has its own advantages and
disadvantages. However, in authors’s opinion, supercritical drying by
No solvent exchange needed; direct
conversion of the solvent to critical
Preparation steps prior to drying

CO2 extraction is the most general, safe and environmentally friendly


way of drying, suitable for virtually all kinds of gels. Still, a lot of efforts
avoid structure compaction

are needed to reduce the drying time and the energy costs associated
solvent exchange needed

with this process. Freeze drying seems to be an alternative, if hydrogels


can be directly dried without severe loss of the pore volume and surface
area, what is for instance the case for high density gels. Moreover,
often needed

freeze drying is usually a long process (tens of hours) leaving a room for
conditions

process intensification. However, realization of all drying types at large


scale for aerogel manufacturing is currently almost exclusively limited
to the silica-based matrices and should be further extended for other gel
types.
T > 31 °C P > 74 bar Typically 40 °C,
Over critical point of organic solvent
Ambient pressure, room or slightly

used for gel formation T > 100 °C

2.3. Raw materials for the aerogel production

Obviously, the diversification and scale up of the aerogel production


Vacuum (P < 100 mbar);

is closely associated with the availability and costs of the raw materials
elevated temperature

−70 < T < −20 °C

used for their manufacturing. Concerning silica aerogels, organic sili-


cates and water glass (Na2SiO3)n are established precursors. However,
100–150 bar
Drying technologies for aerogel production.

P > 30 bar
Conditions

silica can be found in different types of biomass (inorganic ash).


Recently, ashes of various (industrial) biowastes containing silica spe-
cies, such as rice husk [9,10], bagasse [11], oil shale [12], fly [13], and
wheat husk [14], have been used as a silica source for aerogel pro-
duction. The company “Green Earth Aerogels” has commercialized the
Direct supercritical drying
(high temperature)

Supercritical drying by

production of silica aerogels from rice husks already.


CO2 extraction

In the last decade low-molecular-weight gelators have been con-


Ambient drying

sidered as precursors [15,16], which could give a new opportunity to


Freeze drying

integrate the experience from supramolecular chemistry into aerogel


technology. In the case of organic aerogels, biopolymers from various
Table 2

renewable sources can be used (alginate, pectin, chitosan, and pro-


teins). Lignocellulosic biomasses that are another source of cellulose

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I. Smirnova, P. Gurikov The Journal of Supercritical Fluids 134 (2018) 228–233

Table 3
Main aerogel applications.
(adopted from [2]).

Application Type of aerogel involved Decisive aerogel properties

Thermal insulation of buildings, pipelines, Silica; polyurethane; biopolymers (cellulose, alginate, pectin); Thermal conductivity: main importance to the homogeneity of
packaging, winter apparel products, carbon aerogels the pore size distribution to ensure Knudsen diffusion,
textiles. Composites: interpenetrated aerogel networks, macropores should be avoided; high mechanical stability;
granulate + aerogel network, nonporous material + aerogel hydrophobicity
granulate; textile + aerogel granulate; clay-containing aerogels
Drug delivery Native silica; biopolymers: alginate, pectin, starch, chitosan, High surface area, accessibility of the pores for the drugs
cellulose, and hybrids thereof (micropores may be a hindrance), affinity to specific drugs
(surface modification may be needed)
Tissue engineering Mainly biopolymers: alginate, pectin, starch, chitosan, cellulose, Combination of meso- and macroporosity in the same material,
and hybrids thereof biocompatibility
Medical implants Polyurea crosslinked aerogels, natural biopolymers: alginate, Pore structure suitable to applications (usually micropores to
alginate-starch, gellan gum, hybrids with gelatin be avoided), biocompatibility, stability in liquids,
biodegradability
Cosmetics Silica particles Amorphous aerogel backbone, potential to adsorb liquid,
flowability
Catalysts and carrier materials for catalysis SiO2, various metal oxides (TiO2, Al2O3, CuO-CoO-MnO/SiO2, High surface area, stability in corresponding gaseous or liquid
and Electrocatalysis Fe2O3, ZrO2), graphene oxide, Ru/graphene, gold, chalcogenides phases, transport through large meso- and macropores
and their mixtures, carbon (fuel cells), polysaccharides, (chitosan,
alginate), noble metals and bimetals, Pt-Ni, hybrids of metal and
semiconductor nanoparticles, photovoltaics
Biocatalysis Mainly silica Compatibility with enzymes, absence of toxic gelation by-
products, pore sizes adjusted to molecular size of reaction
products/adducts
Energy/hydrogen storage devices Carbon, graphene-oxide, combinations thereof, including those Large surface area, electrical conductivity
with functionalized pores
Sorbents for liquids, hazardous ions (heavy Carbon, graphene-oxide, combinations thereof, including those Surface functionalization to ensure the selectivity to target
metal ions) (e.g., water treatment), with functionalized pores; functionalized/hydrophobized silica molecules, open porosity, hydrophobicity, or oleophobicity
sorbent for oil spills aerogels; magnetic cellulose aerogel, titania, clay aerogels
(Bio)sensors Au-carbon aerogel (doped with nanoparticles), graphene, silica, Surface functionalization to ensure the selectivity to target
zirconium phosphate–carbon, carbon/metal hybrids, N-doped molecules, open porosity
graphene, graphene/alginate, tungsten oxide, graphene-ZnO,
resorcinol-formaldehyde aerogels, MoS2/graphene, boron nitride
aerogel
Sorbents for gases (CO2, hazardous gases, Silica, amino-modified silica, carbon, graphene-oxide, Surface functionalization to ensure the selectivity to target
VOC) combinations thereof including functionalization (e.g., N-doping) molecules, open porosity
Cherenkov detectors Silica Refractive index
Ballistic protection Crosslinked silica aerogels Mechanical strength
Fillers (paints) Silica particles Hydrophobicity, particle size
Separation technologies (membranes) Carbon, fiber-aerogel hybrids, graphene, graphene oxide, chitosan Selectivity to target molecules, pore size tuning,
hydrophobicity
Miniaturized gas (μ-Knudsen) pump Hydrophobized silica aerogel Low skeletal and gas thermal conductivities, open-porous
structure (rarefied air flow)
Foundry Resorcinol-formaldehyde, carbon Pore structure, open porosity
Construction material Silica aerogels in high performance aerogel concrete Mechanical properties and density of composites
Space applications Mainly silica and hybrids Transparency, thermal conductivity

and lignin have recently attracted a great deal of attention as starting 2.5. Knowledge Gaps/Needs in aerogel technology
materials for aerogel preparation [17]. Principally, all these biopoly-
mers can also be a source for carbon aerogels produced by pyrolysis. An The numerous existing and potential applications of different types
alternative way to find new raw materials for organic aerogels is based of aerogels developed in academia clearly show that the existing
on recycling of used materials, analogous to paper or plastic recycling; aerogel production, being mostly limited to inorganic aerogels needs to
the use of waste newspaper [18] and waste cotton fabrics [19] to pre- be further developed. In the last decades organic aerogels of different
pare cellulosic aerogels support this idea. For sure, further synthetic origins have been intensively studied in academia and further devel-
routes are possible, even taking into account that waste materials are oped within several EU projects. It was shown, that a number of dif-
always a mixed fraction of different polymers. ferent organic precursors (biopolymers) can be utilized to produce
aerogels from sustainable sources and with specific functions, which
can be successfully used in different emerging areas (adsorption, cos-
2.4. Current state of applications metics, biocatalysis, drug delivery etc.). Due to such properties like
mechanical elasticity, presence of diverse functional groups, biode-
In the following, we discuss the existing and potential applications gradability, biocompatibility, they can successfully find the way to the
of different aerogel types, although only a part of them are commer- market. Nevertheless, in order to prove the real applicability of these
cialized today. Currently, the main market application of aerogels is new types of aerogels in industrial settings, significant amount of ma-
thermal insulation, since aerogels are the best thermal insulating ma- terials are needed for prototyping. Organic aerogels (besides Slentite
terial besides vacuum insulation panels. However, further applications produced at the pilot scale in Lemförde, Germany) are available only in
as carrier and filler material (cosmetics, pharmaceutics), supercapacitor small amounts, mainly for academic purposes, although polymeric and
(electronic) and absorber (environmental area) are already developed. biopolymeric aerogels offer many beneficial properties, especially for
Those and further application areas are summarized in Table 3 adapted the applications in the life science field (e.g. mechanical elasticity, di-
from [2]. verse functional groups, biodegradability, biocompatibility). In the

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opinion of the authors, these facts clearly indicate the direction of a high potential for a wide spectrum of applications (see Table 3).
further developments in this area. At the same time, making the aero- Biopolymer characteristics (molecular weight, composition, degree of
gels to competitive products requires not only further scale-up of the branching) have a significant effect on both bulk properties of the
production process, but also the critical consideration of the raw ma- aerogels as well as on their porous network on molecular level.
terials. Based on these considerations, following critical gaps and needs Thus, the major scope of research in biopolymer aerogels is the
in fundamental and process-related could be identified1: establishing of quantitative relations between aerogel properties and
chemical nature of the raw materials as well as materials’ combinations.
• Critical assessment and strategies towards diversification of raw Further, the search for suitable raw materials with better sustainability
materials for the aerogel production in terms of availability, en- and lower prices must continue, especially for commodity applications.
vironmental footprint, and later recycling (including the use of re-
cycled polymers as raw materials). 2.6.2. Hybrid aerogels
• Understanding/tailoring of hybrid aerogels: structure-properties Hybrid materials offer an almost unlimited potential for the further
relations between the characteristics of the individual polymers and development. Combinations of different polymer matrices, modification
the properties of the final matrix. of inorganic ones, and combinations with third materials (fibers, par-
• General upscale of the organic aerogels production, including sol- ticles, textiles) are the most promising ways to fulfill the requirements
vent exchange. of specific applications and to transfer the chemically promising aero-
• Establishing and upscale of the manufacturing process for organic gels into a real product. If the final properties cannot be reached by the
and hybrid aerogels directly in form of particles or fibers with well- co-gelation of different materials, post-treatment is a promising alter-
defined size distribution and controlled porosity. native. Post-treatment can include coating, hydrophobization or even
• The majority of the operations involved in the current manu- pyrolysis (in case of carbon aerogel production) and offers an oppor-
facturing process are based on empirical optimization. For further tunity to can further broaden the final properties of aerogels. However,
improvement and scale up of the process, multi-scale modelling of the development of hybrid materials cannot be purely empirical, since
all process steps (gel formation, especially for hybrid systems; sol- the number of possible combinations is too high. Synergetic effects
vent exchange; swelling and shrinkage of the gel matrix; drying, between different precursors and additives need to be understood and
especially supercritical one) is needed. modelled on the molecular level. Generally, this is the only way to the
• Aerogels are currently produced only batch-wise. Here the transfer rational design of new hybrid materials. Especially the modelling of
to the continuous processes would bring a significant advantage, aerogel mechanical properties entirely based on their molecular struc-
although the solutions are not obvious due to depressurization steps. ture is beneficial and should be thereby further developed.
• Standardization of the characterization methods for aerogels (e.g.
measurements of pore size distribution, density of irregularly 2.6.3. Conductive aerogels
shaped samples or powders, thermal conductivity, mechanical On the borderline between electrochemistry, biochemistry, and re-
properties) could improve the comparability of the results from newable energies highly porous conductive materials are rapidly de-
different sources. Therefore guidelines for such measurements is- veloping, whereas this high interdisciplinary leads to new requirements
sued in collaboration of the corresponding institutions may be to be fulfilled. In this sense, all types of carbon-based aerogels, in-
useful. cluding carbon nanotubes, graphene, and graphene oxide as well as
aerogels derived from different metals and their hybrids have received a
2.6. Future Directions/Perspectives lot of attention. Such aerogels can be produced from several different
organic gels via pyrolysis, whereas the structure of the initial gel mainly
The authors are convinced that the aerogel field will continue its predetermines the structure of the final carbon aerogels, enabling sig-
rapid development in the coming years. Thereby the key factor is the nificant variations in pore size. Original electrical conductivity of the
simultaneous development of the material aspects and corresponding material can be increased via appropriate additives/coatings. Most
production process to decrease aerogel prices and enable practical ap- probably the application in (electro)catalysis, hydrogen storage, su-
plications apart from pure academic research. At the same time, de- percapacitors, fuel cells will further promote the development of
velopment of new aerogel types should be application driven and target aerogels in the future.
product properties and restrictions should be known from the begin-
ning. This can be realized only by close cooperation between academic 2.6.4. Process development
groups and industrial partners, which should be further encouraged. The chances of the different aerogel-based products to be trans-
Following directions of research in the opinion of the authors are ferred to the market heavily depend upon further reduction of cost
the most promising and highly needed: associated with the production process. Overall decrease in aerogel
production time will significantly contribute to this goal. To reach this
2.6.1. Polymer based aerogels purpose, fundamental understanding of the thermodynamics and ki-
There is currently a great interest in using of synthetic polymers and netics of the solvent exchange and the drying process as well as its
biopolymers for aerogel production. Biopolymers from various sources translation into the corresponding multiscale modelling is required. The
such as polysaccharides (alginate, cellulose, pectin, chitosan, chitin), choice of the working solvent, its interaction with the matrix and it
lignin, proteins and others have been used as precursors. Exemplary, influence on the drying process should be rationalized. Here corre-
the EU project “Aerowood” aims to use different fractions from of lig- sponding models on the molecular level, including all the solvent ex-
nocellulose (different C5 and C6 sugars) for aerogel production [20]. change steps and the corresponding gel behavior (swelling/shrinkage)
Resulting aerogels exhibit both specific functions of the starting bio- need to be developed. Importantly, the issues of the energy consump-
polymer and typical features of aerogels (open porous structure with tion of all process steps should be then derived on the macroscopic
high specific surface and pore volume). This synergy of properties offers level. Here such issues as flow profiles in the reactors, reactor design
and effective use of the reactor volume (gel/volume ratio) should be
taken into account. An example of such a modelling is given in the work
1
Partly based on the roadmap (Strategiepapier) for aerogel development in Germany,
of Lebedev et al. [21], who have published CFD modelling of super-
written in collaboration with the members of Aerogel Cluster of the German Federal
Ministry for Economic Affairs and Energy (BMWI), including L.Ratke, B.Milow,
critical drying step.
G.Reichenauer, W.Lölsberg, M.Fricke and their colleagues and coworkers (submitted In the future the main focus should be on the transition from batch
September 2015). to (semi)continuous processes. For production of monoliths, semi-

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I. Smirnova, P. Gurikov The Journal of Supercritical Fluids 134 (2018) 228–233

continuous manufacturing seems to be the only possible way, because recommendation or endorsement by the authors or by the Journal of
the depressurization step for taking the monoliths out of the autoclave Supercritical Fluids.
is needed. In the case of particle and fiber production more options
seem to be available. The production of aerogels directly in the form of Conflict of interest
particles or thin fibers has a tremendous advantage: the solvent ex-
traction time for small particles is much shorter than that for monoliths, The authors have no conflict of interest with the companies men-
allowing for significant reductions in process costs. In this case, the tioned in the manuscript.
numbering-up strategy using relatively small autoclaves with fixed beds
or even truly continuous processes may be possible. Further, in case of References
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