Organosilicon Chemistry I I

Edited by Norbert Auner and Johann Weis

Copyright 0VCH Verlagsgesellschaft mbH. 1996

Fumed Silica - Production, Properties, and Applications

H. Barthel*, L. Rosch, J . Weis

Wacker-ChemieGmbH
Gescha$sbereich S - WerkBurghausen
Johannes-HeJ-Str. 24, 0-84489 Burghausen, Germany

Summary: Since its first production in the early forties of this century, fumed silica has found
widespread use in industrial applications. Due to its pyrogenic manufacturing process by
combustion of silicon tetrachloride in an oxygen-hydrogen flame, fumed silica offers a variety
of fascinating properties. It consists of finely dispersed amorphous silicon dioxide and its
surface is covered by highly reactive silanol groups which are available for chemical
reactions. Additionally, fumed silica shows a space-filling particle structure related to a high
surface area and lacking micropores. These characteristics enable fumed silica to act as a free
flow additive in powder-like solids, as a thickener in various liquids and as a powerful
reinforcing filler in elastomers. The aim of this paper is to combine results from surface
chemistry and particle characterizationin order to understand the basic mechanisms of fumed
silica applications. Recent investigations in the field of surface characterization and
interactions are reported.

Introduction

Fumed silica is a highly dispersed synthetic silicon dioxide product. Finely divided silicas may be
classified according to their manufacturing process: natural products, byproducts and synthetic products.
The product origin implies distinct differencesof the properties of these silicas. Natural products as quartz
powders or diatomaceous earth, and by-products that include, e.g. fused silica, silica fume, or fly ashes
from metallurgy and power plants are mostly cristalline silica products of micron size particles or larger
and have surface areas up to 1 m2g-', rarely 10 m2g-'. In contrast, synthetic silicas from wet processes or
thermal pyrogenic reactions are typically amorphous silica products with a high surface area of 100 m2g-'
and larger. Wet processes, that are based on the reaction of soluble silicates with aqueous acids, lead to
762 H. Barthel

silica-gels or precipitated silica. By far the most important thermal pyrogenic path is the flame pyrolysis
of silanes, which gives access to the product of interest - fumed silica. To better understand the properties
and applications of this fascinating product, a detailed discussion of the production process will help.

Production

Fumed silica is produced by burning volatile silanes, such as silicon tetrachloride, in an oxygen-
hydrogen flame. Ulrich [ 11 gave a description of the flame process based on the immediate formation of
protoparticles directly related to the chemical reaction - rather than surface deposition. At high flame
temperatures collision and coalescence of protoparticles lead to the formation of primary particles. The
rate of coalescence depends on the viscosity of the molten oxide, which is exceedingly high for silicon
dioxide at a flame temperature of about 1500 K. Therefore, the size d of the fumed silica primary
particles, i.e., the surface area SA = 6/6rrSilicais strongly related to the flame temperature. At lower
temperature, collision and sticking of primary particles only results in partial fusion and stable particle
aggregates are formed. The silica aggregates leave the flame and cool, but they still collide. As their
surfaces are now solid, agglomerates of aggregates are formed, that are held together by physico-chemical
surface interactions (Fig. 1).

Fig. 1. Production of fumed silica in a flame process

A very helpful approach to understand the formation of particle clusters was given by Meakin [2], who
uses the concept of mass fractal dimension D, which relates the size d of a particle cluster to its mass M
(Eq. 1).
 Fumed Silica - Production, Properties, and Applications 763

M=dDmwithl<D,<3
Eq. 1.

At high temperature the tacky primary particles adhere to each other to form aggregates at the moment
they collide, i.e., the sticking coefficent is near 1. Thus, the formation of fumed silica aggregates in the
flame is dominated by diffusion limited aggregation of primary particles (DLA), which gives an aggregate
mass fractal dimension of Dmaggregate
= 2.5. Values close to this result from small angle neutron scattering

(SANS), Dm= 2.6 [3], and small angle X-ray scattering (SAXS) or nitrogen adsorption at 78 K, with D,
from 2.6 to 2.7 [4]. At lower temperature the agglomeration of aggregates follows a reaction limited
cluster aggregation (RLCA), as the aggregates may collide, and they will also rearrange their positions in
order to optimize surface interactions. RLCA provides an agglomerate mass fractal dimension of
Dmagglornerate -
- 2.1, taking into account polydispersity of aggregate sizes.

Properties
Particle Structure

Fumed silica appears as a fluffy white powder characterized by an extremly low bulk density down to
the range of about 20-50 g 1-I. In contrast, the submicron fumed silica particle consists of amorphous
silicon dioxide and, hence, its true density is about 2200 g 1-l.
Any discussion of fumed silica particle structure has to take into account this enormous difference. The
approach of mass fractal dimension may provide a rough but helpful estimation. A real mass fractal is
limited by the size of the cluster as an upper limit and the size of the particles as a lower limit. Then, the
may be calculated from the true density of the particle pparticle,
density of the cluster pciuSter the ratio of the
cluster size dcluster and the mass fractal dimension 0, of the cluster (Eq. 2):
to the particle size dparticie

Pciuster = Pparticle *
. )Dm-3
( dcluster / dparticle
Eq. 2.

By electron microscopy the size of the primary particles in the aggregates is estimated to be about 10
nm. Particle size measurements using a nanosizer show the size of aggregates dispersed in a well wetting
solvent to be in the range of 100 nm. Laser diffraction of fumed silica dispersed in air provides sizes of
agglomerates larger than 5 pm.
764 H. Barthel

Fig. 2. Fumed silica (surface area 200 m2g-') - Transmissionelectron microscopy (TEM)

Fig. 3. Fumed silica (surface area 125 m'g-') - Scanning electron microscopy (SEM)
 Fumed Silica - Production, Properties, and Applications 765

By Eq. 2 and D = 2.5 from DLA we estimate the apparent density of the aggregate to be 700 g 1-'. This
is the density found experimentally,when powdered fumed silica is pressed to a solid disc. Dm= 2.1 from
RLCA then gives an agglomerate density of about 20 g 1-' - close to the bulk density of the freshly
produced fluffy product.
From scanning electron microscopy (SEM) and transmission electron microscopy (TEM) (see Fig. 2
and 3) the predominant particle structures of fumed silica are aggregates, that consists of firmly attached
and partially fused primary particles. Some characteristic features of these silica aggregates are
summarized in Fig. 4.

4 particle size aggregate 100 nm *

Fig.4. Characteristic features of fumed silica aggregates

Fumed silica aggregatesare obviously linear and branched particle structures with a mean size of about
100 to 200 nm. By TEM we derive the size of the partially fused primary particles of about 10 nm. This
very small particle size correlates well with the high surfaces area of fumed silica which usually is larger
than 100 m2 g-' as determined by nitrogen adsorption at 78 K according to BET [5]. Adsorption
techniques and electron microscopy provide very close values of surface areas. This indicates that fumed
silica exhibits a smooth particle surface in the range of nanometers, apparently its surface is free of
micropores.
This lack of micropores is further confirmed by SAXS and nitrogen adsorption data. Again a very
helpful concept is fractality, in this case the surface fractal dimension D,. A smooth, non-porous surface is
described by a surface fractal dimension of D, = 2.0, but a totally porous body will reach a D, of up to
nearly 3. SAXS and adsorption measurements on fumed silica result in a surface fractal dimension D,
very close to 2.0 L:,.The fact of a nonporous smooth surface of the fumed silica particles is a most
766 H. Barthel

important characteristic, as it will simplify the interpretation of chemical surface reactions [7].
Additionally, surface microporosity would markedly decrease the interaction efficiency of the silica
surface [6].

Surface Chemistry

The chemistry of a finely divided solid with high surface area is at the borderline between molecular
chemistry and physics of solid surfaces. The surface of a finely divided amorphous silica may be
understood as a two-dimensional projection of the three-dimensionally linked silicon dioxide tetrahedra.
By this the chemistry of the fumed silica surface is dominated by Si-0-Si units and, in particular,
dangling surface Si-0 bonds, which will create silanol groups under the influence of humidity at ambient
temperature.
The density of the silica surface silanol groups strongly depends on the production process of silicon
dioxide. There is no evidence that fumed silica contains internal silanols. In contrast to silica products
from wet processes, hmed silica shows only a low surface density of surface silanols. Approximatively
every second silicon atom on its surface bears a silanol group. A large part of these silanols are not
hydrogen-bonded but isolated and give rise to a IR band at 3750 cm-’. Additionally, surface silanols on
fumed silica are statistically distributed over the surface [8]. For these reasons, the surface of fumed silica
is highly reactive to chemical reactions. Due to its surface silanols but also from its oxide nature, fumed
silica exhibits a high surface energy y and is wettable by water - untreated silica therefore usually shows a
hydrophilic character.
Many industrial applications of fumed silica basically depend on its high surface energy and the
existence of surface silanol groups. But there are also a variety of systems where reactive silanol groups
and water adsorbed on the hydrophilic surface will import serious disadvantages. In consequence, one of
the most important reactions on fumed silica is the silylation of these surface silanol groups. The
desactivation of the surface silanols groups will additionally lower the surface energy y of the oxide.
Thus, the surface is rendered hydrophobic, as it will no be longer wettable by water. Most common
silylating agents are alkylchlorosilanes, as dichlorodimethylsilane, or alkylsilazanes, as hexamethyl-
disilazane (Eq. 3).

SiO,,-Si-OH + 1/2 [(CH,),Si],NH + H20

hydrophilky > 72 mJ m-’
- SiO,,-Si-O-Si(CH,), + 112 NH,
hydrophobic:y < 30 mJ m-’
Eq. 3.
 Fumed Silica - Production, Properties, and Applications 767

Due to its high surface area, surface chemistry and physics dominate the properties of fumed silica.
The 0-Si-0 being 0.3 to 0.4 nm let estimate about only 20 silicon dioxide units spanning the diameter of
a primary particle of amorphous silica. Fumed silica therefore has an extremely high surface to bulk ratio
up to about 10 %. This is why even bulk methods of chemical analysis are suitable to follow chemical
reactions on its surface: elemental analysis, IR or NMR methods, etc.
The chemical reaction of the silica surface with hexamethyldisilazane leads to a coverage with
trimethylsiloxy groups. The molecular area of a trimethylsiloxy group has been reported to be
= 0,38 nm2[9]. The limiting carbon content % C at full surface coverage will then be %C = 1.6 per
aMegSiO
100 m2 g-' of surface area - the completion of the reaction is easily followed by standard carbon analysis.
Additionally, the disappearence of the band of isolated silanol groups at 3750 cm-', as monitored by
DRIFT, is a convenient method to determine the yield of silanol conversion. Suitable methods for
estimating the surface energy y of hydrophilic or silylated silica are wetting tests or gas adsorption
techniques.
Essential for silylation is the activation of the silica silanol groups. To accelerate the reaction of silica
with hexamethyldisilazane molar amounts of water have to be added. But water may be omitted, without
losing reaction activity, if a methyl group of the trimethylsilyl unit is substituted by a
3,3,3-trifluoropropyl group. DRIFT shows the isolated silanol groups at 3750 cm-' to disappear in the
course of silylation with trimethylsiloxy groups, but a broad band at 3650 cm-l always remains. It belongs
to hydrogen-bonded, associated and less active silanol groups being unavailable for reaction. On a
3,3,3-trifluoropropyldimethylsiloxysilylated silica surface the band of H-bonded, associated silanol
groups is only shifted to 3690 cm-' which indicates a weakening of the H-bonds. It is likely that the polar
3,3,3-trifluoropropyl group interacts with the less active, associated silanol groups in order to activate
them.
Acid-base reactions are of particular analytical interest [lo]. Titration of fumed silica with sodium
hydroxide seems not to be a very exciting reaction. But the advantage of a acid-base reaction is that it
distinguishes easily between the acidic silanols of silica and any other kind of monomeric, polymeric or
resinous silanols. Titration may be a helpful tool to follow the degree of reaction of silica silanol groups
with a variety of silylating agents.

Eq. 4.
SiO,,-Si-OH + NaOH - SiO,,-Si-O- Na' + H 2 0
768 H. Barthel

Under suitable reaction conditions the acid-base reaction provides a hydroxyl capacity or silanol group
density of fumed silica of about 2 SiOH per nm2.This value falls well between the total amount of silanol
groups on fumed silica of about 2.5 SiOH per nm2[1 13 and 1.7 SiOH per nm2 as reported for the content
of reactive isolated silanol groups [12]. Titration seems to give a good estimation about the content of
chemically reactive and available silanol groups.

Surface Area

The surface area is one of the most important and most commonly used parameters to characterize a
highly dispersed oxide. To quantify and to normalize chemical surface reaction data or physico-chemical
properties usually the surface area rather than the oxide mass is used as a reference.
The most reliable technique to determine surface areas above 100 m2 g-' has turned out to be the
adsorption of gases, e.g. nitrogen at 78 K, to calculate the BET surface area. This calculation bases on the
monolayer capacity as evaluated from the adsorption isotherm and the molecular area of the adsorbate.
When working with silylated silica samples this may lead to questionable results. Silylation and various
other surface treatments of fumed silica clearly will change its surface properties, among them silanol
content and surface energy. Koberstein [131 reported that even the so thought inert molecule of nitrogen
may exhibit specific polar interactions due to its quadrupolmoment. Kiselev [I41 pointed out that the
apparent molecular area of the adsorbate may depend on its surface interactionswith the adsorbent.
A more detailed study on silylated fumed silica that used nitrogen and argon at 78 K and also neo-
pentane at 273 K as adsorbates revealed a distinct decrease of the BET surface area with growing carbon
loading and decreasing content of surface silanol groups (Fig. 5) [151.
This decrease of the BET surface area is markedly larger than determined from TEM or as expected
from the particle growth by the silylation layer. Obviously, the apparent molecular area of the adsorbate
strongly depends on the surface energy of the solid as determined by wetting tests or the equilibrium
spreading pressure from gas adsorption. On a high energy surface, as hydrophilic fumed silica, the
molecular area of nitrogen aN2= 0,162 nm2 (adopted from the liquid density) and, therefore, the related
BET surface area from nitrogen adsorption, will provide reliable values. Whmeas it seems that on a low
energy surface, as for example silylated silica, no ordered monolayer is formed and therefore the
monolayer capacity and consequently the BET surface area are evaluated markedly too low. In general it
turns out that a good compromise is to use the nonsilylated hydrophilic surface area as a reference.
 Fumed Silica - Production, Properties, and Applications 769

surface area [m'/g]

300

200

100

0
-
0 2 4 6 8 10
carbon content I"/.]

Fig. 5. Surface area of silylated silica: N,-adsorption BET-surface area (M); Ar-adsorption BET-surface area ( 0 ) ; surface
area from TEM analysis (0);decrease of surface area according to mean thickness of silylation layer (V) [IS]

Applications

Fumed silica finds wide use in a variety of industrial applications. Most important are reinforcement of
elastomers as active filler and thickening of liquids as a rheological additive, both applications cover more
than two thirds of the market volume. Smaller volumes of fumed silica are used as free - flow additive in
powder-like solids, for example, in toners for copiers and printers, in fire extinguishers, or even food. It
also finds use in anti-foam agents, as anti-blocking, in cable insulation, catalysis, cosmetics, adsorbents,
paper coating, pharmaceuticals, polishes etc. All these applicationsprofit from the two basic properties of
fumed silica that result from its pyrogenic origin: a structure of finely dispersed, aggregated particles and
a large surface area of high activity. Exemplarily, this fascinating interplay of fumed silica particle
structure and particle surface shall be discussed for the free flow of toners, the thickening of liquids, and
the reinforcement of elastomers.
770 H Barthel

Free flow of toners

The ability of fumed silica to support and maintain the free flow of solid-like powders is directly
related to the small particle size of its aggregates. The silica aggregates will cover the surface of the
powder particle and thus prevent the powder particles to lump together and will additionally act as a ball
bearing to let the powder flow (Fig. 6).
The free flow of a toner in a copy machine is essential to accurate toner flow and image quality.
Without silica the free flow of the toner will diminish after multiple copies and the image quality breaks
down. Highly hydrophobic silica as a free flow additive sustains the toner flowability. Additionally, any
additive has to be compatible with the chargeability of the toner system. It turned out that the toner
requires the addition of a silica type of same polarity and chargeability. The chargeability of the silica is
controlled by surface chemistry - silylation and hydrophobization will retain the negative polarity of the
silicon dioxide, but surface modification by amino or ammonium organosilicon compounds result in
positive chargeability [161.

Fig. 6. Scanning electron microscopy of toner particles without silica (left) and with 0.4 %weight of fumed silica (right)

Thickening of liquids

Many industrial and manufacturing processes face the requirement to apply a liquid solution, resin or
polymer onto vertical substrates as coatings, paints, lacquers, etc. During application, the liquid should be
 Fumed Silica - Production, Properties, and Applications 771

thin and easy to paint or spray but consecutively the applied liquid film should stay on the substrate the
time needed to accomplish hardening.
Fumed silica bears the properties of an effective thickener which will not undergo swelling and
exhibits chemically inertness. Additionally, thickening by fumed silica results in a non Newtonian system
commonly accompanied by a yield point, shear thinning and thixotropy. Thus, fumed silica solves in an
excellent manner the requirements of reversible shear thinning under high shear stress but a distinct yield
point or high viscosity at lower shear stresses.
These rheological effects that fumed silica imposes on a liquid system may be understood by a
fascinating interplay of particle structure and surface interactions, as depicted in Fig. 7. According to
Eq. 1 a space-filling particle network will be possible at a loading of fumed silica at about 1 wt. % (with a
primary particle size of 10 nm, an aggregate size of 100 nm and a size of agglomerates of 10 pm as
measured by laser diffraction in liquids). Reality is not far from such a rough estimation, typical industrial
loads of fumed silica as a thickener are in the range from 0.5 to about 2 wt. %.

viscosity [Pa - s] shear stress [Pa]

shear rate [ 1/s]

shear thinning *
Fig. 7. Thickening of liquids by fumed silica

This space-filling network of percolating and interacting fumed silica particles may result in an
enormous high viscosity or even a yield point. The thickened liquid gets a gel-like consistence and will
resists shear stress until the shear stress overcomes the strength of the particle-particle interactions and
772 H. Barthel

starts to break the particle network and large agglomerates to smaller clusters of aggregates. With
increasing shear rate more and more particle linkages are broken. By this the particle network is destroyed
and the size of the agglomerates will diminish - the liquid is thinned under the stress of shear. At the
moment the shear stress is decreased or stopped, then aggregates and small agglomerates will rearrange
and restart to interact and grow to larger agglomerates - the liquid is thickened again by the silica, but as
the rearrangement of particles requires time the system behaves thixotropic.
The origin of the linkage of silica aggregates to agglomerates and to particle networks are particle-
particle surface interactions. Interparticle hydrogen-bonds have been discussed as a main force to bind
fumed silica particles together [ll]. The study of the thickening effect of hydrophilic and silylated
hydrophobic fumed silica in liquids of different polarities revealed a more generalized picture of particle
interactions and thickening ability. It turned out, that a similar system of silica surface and liquid medium
will not show pronounced thickening whereas if the surface of the silica is markedly different from the
liquid then in consequence a high thickening effect will occur (Table 1).
Hydrophilic fumed silica aggregates will very strongly interact in a nonpolar medium by hydrogen-
bonds between surface silanol groups of neighbouring particles. For that, hydrophilic silica is an excellent
thickener and rheological additiv for nonpolar liquids. Less than 5 wt. % of hydrophilic fumed silica will
thicken a liquid alkane or silicone oil to a cuttable rubber-like gel.
The importance of surface silanol groups for linking silica particles and for thickening is demonstrated
when fumed silica is silylated. Its thickening ability in a nonpolar liquid will sharply decrease when the
silanol groups are blocked, the oxide surface is shielded and the silica is rendered hydrophobic. There
seems to be no resulting energy of interaction for hydrophic particles in a nonpolar medium. A silicone oil
may be loaded up to 30 wt. YO with highly hydrophic fumed silica but always retains its liquid
consistence.

silica polar-hydrophilic nonpolar-hydrophobic

liquid

polar no interaction hydrophobic interaction

no thickening high thickening

nonpolar H-bonding no interaction

high thickening no thickening

Table 1. Principles of particle-particle interactions

 Fumed Silica - Production, Properties, and Applications 773

The thickening ability of hydrophilic fumed silica in a highly polar liquid is also rather low. In a polar
medium the hydrophilic silica surface will be effectively wetted, the particles are shielded from each other
and their interaction is prevented. Hydrogen-bonds and other polar interactions within the liquid, between
surface and liquid molecules or between particle surfaces are of the same order of strength - no energy
results from hydrophilic particles that interact in a polar medium and consequently no thickening is
reached.
In contrast, if accurately dispersed highly hydrophobic fumed silica is in a polar liquid medium then
strong thickening of the dispersion is achieved. The origin of the underlying particle interactions are so
called hydrophobic interactions [17], which result from strong polar interactions in the liquid itself, for
example intermolecular hydrogen-bonds. Polar liquids tend to build up rather stable supermolecular
structures - water or aqueous solutions of alcohols are known to be well clustered and structured by
hydrogen-bonding. A particle of hydrophobic surface will disturb this network. Therefore, the contact
surface of the nonpolar hydrophobic particles towards the polar liquid will be minimized. This forces the
hydrophobic particles to contact each other and this results in a rather strong particle-particle interaction.
By this indirect interaction the hydrophobic silica particle build up stable agglomerates and particle
networks. Highly hydrophobic fumed silica thickens a liquid polar medium as excellently as a hydrophilic
silica thickens a nonpolar one. It has to be mentioned that the interpretation of particle interactions in
different media is not restricted to hydrogen-bonding. Qualitatively the interaction of particles on the
basis of London dispersion forces in general also leads to particle interactions in a medium which differs
in its Hamaker constant from that of the particle, but the interaction energy will tend to zero if the
Hamaker constants of particles and medium are equal [18). The rough principles of particle interactions as
discussed above seem to be a general and helpful approach to understand thickening of liquid by fumed
silica. It may depend on the particular system which types of interaction forces are quantitatively
dominant, whether hydrogen-bonds, electrical charges or van-der-Waals interactions including London
dispersion interactions of fluctuating dipoles, and Keesom forces from dipole-induced dipole or Debye
forces from dipole-dipole interactions.

Reinforcement of Elastomers

From a rubber it is essentially demanded to elongate under stress, to withstand stress without breaking
and to reversibly find back to its original shape after the stress ceases. An unfilled, cured polymer will
rarely fulfill these requirements; this is a fact, which is true for most rubber-like systems. The industrial
development of elastomers therefore is strongly related to the production of active reinforcing fillers.
774 H. Barthel

The high mechanical strength of natural and organic rubbers as used in tires is due to the incorporation
of pyrogenic carbon blacks as active fillers. Elastomers of a more polar polymer backbone, such as
polyacrylates, polyurethanes or polysulphides, require fillers of higher polarity. In particular the
performance of polydimethylsiloxane elastomers (silicone rubber) is basically related to the addition of
fumed silica.

stress [Pal
break

10

50 500 strain [%I

deformation +
Fig. 8. Reinforcement of elastomers by fumed silica

The bare vulcanized silicone polymer, a polydimethylsiloxane network, shows only a low mechanical
strength. Adding 30 wt. YOof fumed silica by mixing and dispersing increases the elongation and stress at
break by a factor larger than 10 (Fig. 8).
It is not the aim of this paper to discuss in detail theories of rubber elasticity, starting from the unfilled
entropic polymer network of Kuhn and Flory [19] to the filled van der Waals network of Kilian [20].
Also, the experimental observation of hysteresis particular found in the first stress-strain cycles will not
be followed further.
To understand elastic mechanical properties, the discussion of the storage of energy of deformation
provides a powerful approach. Dynamic mechanical measurements at higher strain on filled silicone
elastomers show that the energy of deformation may be related to an entropic and an enthalpic part. The
entropic part is mainly due to the restriction of the conformational space of the polymer chain by the
presence of the solid silica particles. Whereas the enthalpic part of the energy of deformation is related to
 Fumed Silica - Production, Properties, and Applications 775

the particle-polymer interactions at the silica surface. This enthalpic part of storage of defomational
energy might be explained if the optimum number of polymer-on-particle surface interactions will
decrease while stress is applied to the elastomer. The polymer chain may be drawn away from the particle
surface or may loose its optimized position relative to the particle surface. When the strain is relaxed, the
optimization and reorientation of the silicone chain to active adsorption sites of the particle surface will
release interaction energy.
In order to achieve excellent mechanical properties of silicone elastomers the absolute amount of silica
surface and additionally the surface activity of fumed silica should be as high as possible. To realize this
aim high loadings of the filler are used which directly will lead to a large particle-polymer interface. A
high quality silicone rubber requires a silica loading up to 30 wt.%. But the incorporation of highly active
polar hydrophilic silica directly involves thickening of the unvulcanized rubber - crepe hardening will
occur.
This is understandable by Eq. 2 that predicts that a filler loading of 30 wt. % establishes a percolating
particle network of silica, even at a very small size of the silica agglomerates of about
= 250 nm, i.e., at an agglomerate size being only 2-3 times larger than the size of the
dagglomerate
= 100 nm. Going back to the thickening ability of silica, we know from Table 1, that a
aggregates daggregate
silica of high polarity exhibits strong particle-particle interaction in a nonpolar medium such as the
silicone rubber.
In order to suppress thickening we are forced to silylate the silica surface and block surface silanol
groups, to prevent the formation of hydrogen-bonds and interactions of the oxide surfaces between fumed
silica particles. Consequently, as measured by wetting tests or gas adsorption this again will generally
decrease the surface activity. As Litvinov [21] could clearly demonstrate by NMR, the strength of fumed
silica particle-polymer interaction is distinctly decreased when silylating its surface. In order to optimize
the compromise between reinforcement and thickening, it turns out that a key to further improvement is
the investigation at the interactions of silicones on a fumed silica surface.
Adsorption measurements may provide helpful data in this field. In particular the adsorption of pure
gases gives access to the interaction adsorbate - adsorbent without any interference from solute
molecules. Fig. 9 shows the adsorption isotherms of hexamethyldisiloxane on a hydrophilic, a silylated
but yet reinforcing and an over-silylated, no longer reinforcing silica at T = 303 K.
The total amounts of adsorbate adsorbed show no large differences near saturation pressure at
po = 73.3 hPa. All three samples base on fumed silica of surface area SA = 300 m2 g-' referring to a
hydrophilic surface. In the high-pressure, multilayer and capillary condensation region the adsorption
isotherm is dominated by particle size and aggregate interparticle voids in the mesopore range. But in the
low-pressure submonolayer region of the isotherm at plpo < 0.07, the adsorbate uptake is controlled by
776 H. Barthel

the strength of the adsorption sites. Compared to the hydrophilic silica sample the amount adsorbed of
hexamethylsiloxane on both silylated silica samples is markedly diminished. The loss of adsorption
capacity by silylation is also confirmed by adsorption of neo-pentane, argon and nitrogen [15]. As
mentioned above, this reveals a sharp decrease of surface energy for both silylated silica samples -
despite the differencesof their reinforcing activity.

siloxane adsorbed [mmol/g] energy distribution

7 I

-
calculation

.. ..
i over-silylated

relative pressure energy of adsorption sites

Fig. 9. Gas adsorption of hexamethyldisiloxane on hydrophilic, silylated reinforcing and over-silylated non-reinforcing
fumed silica at T = 303 K, 0 < p/po < 0.07;po = 73.3 hPa: adsorption isotherm (left) and calculated energy
distribution (right)

Hines developed an analytical equation for an adsorption isotherm on a heterogeneous surface [22].
His analytical equation provides the advantage to more clearly interpret the shape of the adsorption
isotherm by replotting it as a calculated energy distribution. By this helpful approach of high and low
energetic sites of adsorption, we may at least qualitatively see differences between reinforcing and
nonreinforcing silylated silica samples.
The hexamethyldisiloxane molecules probe adsorption sites of lower and higher energy on the
hydrophilic fumed silica surface. When silica is silylated, the adsorption energy of the low-energy sites
are consecutively shifted to lower values. Surprisingly the high-energy sites remain for the reinforcing
silylated silica, but vanish for the non-reinforcing one.
For the moment we have no clear model to relate these low and high energetic adsorption sites to
chemical groups such as silanols or the oxide backbone. Such an interpretation will need further
investigations in order to achieve more quantitative data describing this picture of a heterogeneous silica
surface.
 Fumed Silica - Production, Properties, and Applications 777

Conclusion

Fumed silica is a highly dispersed silicon dioxide of large industrial importance and a wide spectrum
of applications. Due to its production in a flame process fumed silica exhibits a smooth and nonporous
particle surface. Additionally to its high surface area fumed silica bears isolated and statistically
distributed surface silanol groups that render this product hydrophilic. A most important technical
reaction, therefore, is the silylation and hydrophobization of the hydrophilic surface.
In the flame process firm aggregates are formed from primary particles by DLA followed by
agglomeration of these aggregates by RLCA, according to mass fractal dimensions of Dmaggregate
- 2.5 and
Dmagglomerate -
- 2.1. The fractal approach to the spatial particle structure of fumed silica has been shown to
explain the low bulk density of the product just as the loading needed to build up a percolatiqg particle
network to thicken liquid media. A model of particle-particle interactions has been evolvea to interpret
the high thickening ability of silanol group-free hydrophobic silica in polar media by hydrophobic forces.
Fumed silica acts as a highly reinforcing filler in silicone elastomers. Its activity results from its highly
dispersed particle structure, high surface area and surface energy. To better understand the interplay of
these properties first studies on gas adsorption of hexamethylsiloxane on hydrophilic and silylated silica
have been conducted. The shape of the adsorption isotherm revels the existence of low- and high-energy
adsorption sites, the latter qualitatively seem to be related to reinforcement of the silicone elastomer.
Further quantitative studies in this field are needed.

Acknowledgements: The authors thank Dr. Achenbach and Dr. Heinemann, Wacker-Chemie GmbH, for
providing elastomer and toner data and greatly appreciate the many interesting and helpful discussions.

References:

[l] G. D. Ulrich, J. W. Riehl, J. Colloid Sci. 1982,87(1), 257; G.D. Ulrich, Chem. Eng. News, 1984,
8,22.
[2] P. Meakin, in: The Fractal Approach to Heterogeneous Chemistry, Surfaces, Colloids, Polymers
(Ed.: D. Avnir), Wiley, New York, 1989,p. 131.
[3] T.Freltoft, J. K. Kjems, S. K. Sinha, Phys. Rev. 1986,33B,269.
[4] H. Barthel, unpublished results.
[5] S. Brunnauer, P. H. Emmett, E. Teller, J. Am. Chem. SOC.1938,60,309.
778 H. Barthel

[6] A. J. Hurd, D. W. Schaefer, J. E. Martin, Phys. Rev. 1987, 35(5)A, 2362; H. Barthel,
F. Achenbach, H. Maginot, Proceedings of Mineral and Organic Functional Fillers in Polymers,
International Symposium,Namur, 1993.
[7] D. Avnir, P. Pfeifer, J. Chem. Phys. 1983, 79(7), 3558; D. Avnir, D. Farin, P. Pfeifer, J. Chem.
Phys. 1983, 79(7), 3566.
[8] E. Papirer, A. Vidal, M. Wang, J. B. Donnet, Chromatogr. 1987,23(4), 279; Legrand, Adv. Colloid
Int. Sci. 1990,33,91.
[9] P. Larsen, 0. Schou, Chromatogr. 1982,16,204.
[lo] G. W. Sears, Anal. Chem. 1956,28(12), 1981.
[111 G. Michael, H. Ferch, Schriftenreihe Pigmente, Degussa AG, Nr. 11.
[12] B. Evans, T. E. White, J. Catalysis 1968,II, 336; W. Hert1,J. Phys. Chem. 1968, 72(12), 3993.
[131 E. Koberstein, M. Voll, Phys. Chem. 1970, 71,275.
[14] A. V. Kiselev, A. Y. Korolev, R. S. Petrova, K. D. Shcherbakova, Kolloid. Zh. 22,1960,671.
[151 H. Barthel, Proceedings of the Fourth Symposiumon ChemicallyModified Surfaces, Chadds Ford,
(Eds.: H. A. Mottola, J. R. Steinmetz), Elsevier, 1992, p. 243.
[16] M. G. Heinemann, R. H. Epping, Japan Hardcopy, Yokohama,1993.
[17] J. N. Israelachvili, Chemica Scripta, 1985,25,7.
[18] S. Ross, I. D. Morrison, ColloidSystemsand Interfaces, Wiley, New York, 1988, p. 205.
[19] W. Kuhn, F. Griin, Kolloid-Z. 1942,101,248; J. P. Flory, Princbles of Polymer Chemistry, Cornell
University Press, Ithaca, 1953.
[20] G. Kilian, Progr. Coll. Polym. Sci. 1987, 75,213.
[21] V. M. Litvinov, Polymer Science U.S.S.R. 1988, 30(10), 2250; V. M. LiWinov, Organosilicon
ChemistryZZ (Eds.: N . Auner, J. Weis), VCH, Weinheim, 1995, p. 779.
[22] L. Hines, S.-L. Kuo, N. H. Dural,Separation Sci. Techn. 1990,25(7&8), 869.