COLLOIDS

Colloidsand Surfaces SURFACES

A
ELSEVIER A: Physicochemicaland EngineeringAspects 101 (1995) 217-226

Surface interactions of dimethylsiloxy group-modified fumed silica

H. Barthel
Wacker-Chemie GmbH, Werk Burghausen, D-84480, Burghausen, Germany
Received 15 October 1994; accepted 29 March 1995

Abstract

Fumed silica is widely used in industry as a rheological additive. Produced by a flame process, fumed silica consists
of aggregates of hydrophilic primary particles. The thickening effect is related to particle-particle interactions leading
to agglomerates and particle networks. These particle-particle interactions depend heavily on the liquid medium.
Hydrophilic silica, whose surface is covered by silanol groups, shows greatest thickening in low polarity systems owing
to strong hydrogen bonds. In polar media, wetting of the hydrophilic surface weakens particle interactions and breaks
down thickening. In contrast, silylated hydrophobic silica is an effective rheological additive in high polar media. This
effect is related to hydrophobic interactions between silica particles. Additionally, silylation of the silica surface by
dimethylsiloxy groups results in greater thickening than silylation by trimethylsiloxy groups. Gas adsorption data
reveal particle-particle interactions arising from interpenetration of the polymer-like silylation layer.

Keywords: Dimethylsiloxy groups; Modified fumed silica; Surface interactions

1. Introduction Particle-particle interactions and, consequently,

Control over the rheological properties of liquid
systems is of enormous industrial importance.
Fumed silica has the advantage of being an effective
rheological additive which will not undergo
swelling and also exhibits chemical inertness.
Additionally, thickening by fumed silica results in
a non-Newtonian system commonly accompanied
by a yield point, reversible shear thinning and
thixotropy. An understanding of the parameters
which control thickening is of great technical
interest.
In liquid media, the interactions of finely
dispersed particles lead to the formation of agglom-
erated structures and space-filling particle net-
works. Studies of the rheological behaviour of the
dispersed system can, therefore, provide informa-
tion about its state of agglomeration [1-4].
the formation of agglomerates or larger particle
networks are related to a non-linear increase in
the apparent particle size and effective volume
fraction. This is because particle dusters are usually
less dense in mass than the primary particles
themselves [5]. Therefore, the rheology of a dis-
persed solid phase in a liquid medium will depend
both on its ability to undergo particle-particle
interactions and on its specific particle structure.
Fumed silica is a finely divided amorphous sili-
con dioxide produced by high temperature hydrol-
ysis of silicon tetrachloride in an oxygen-hydrogen
flame. In the flame process, protoparticles directly
formed during the chemical reaction collide and
coalesce to give primary particles at high flame
temperatures [6]. At lower temperatures, collision,
sticking and partial fusion of primary particles
result in the formation of stable aggregates. While

0927-7757/95/$09.50 © 1995ElsevierScienceB.V. All rights reserved

SSDI 0927-7757(95)03179-0
218 H. Barthel/Colloids Surfaces A: Physicochem. Eng. Aspects 101 (1995)217 226
leaving the flame and cooling, the silica aggregates
continue to collide, but their surfaces are now solid
and agglomerates of aggregates are formed by
physicochemical surface interactions.
The formation of aggregates may be understood
as a diffusion-limited aggregation (DLA) of pri-
mary particles, since the sticking coefficient is
virtually unity. Reaction-limited cluster aggrega-
tion (RLCA) controls the agglomeration of aggre-
gates, as aggregates will rearrange after collision
in order to optimize surface interactions. DLA and
RLCA provide mass fractal dimensions of--mODLA=
2.5 for aggregates and DRCLA= 2.1 for agglomerates,
taking into account polydispersity of aggregate
sizes [5]. Small-angle neutron scattering (SANS),
Dm=2.6 [7], and small-angle X-ray scattering
(SAXS) or nitrogen adsorption at 78 K, Dm 2.5-2.7
[8], confirm aggregate mass fractal dimensions as
revealed by DLA.
Interactions of fumed silica particles are
dominated by the surface siloxane bonds of the
oxide backbone and the surface silanol groups.
Approximately every second silicon atom on the
fumed silica surface bears a silanol group [9]. A
large number of these silanols are not hydrogen-
bonded but are isolated and statistically distributed
over the surface [ 10]. Owing to its surface silanol
groups and its oxide nature, fumed silica is
hydrophilic and exhibits a high surface energy, ~.
Deactivation of the surface silanol groups by silyla-
tion with alkylchlorosilanes or alkylsilazanes
strongly decreases the surface energy, ~,, of the
oxide, and its surface becomes hydrophobic [ 11 ].
In this paper, we will investigate the thickening
behaviour at low shear rates of hydrophilic and
silylated fumed silica in liquid media of different
polarity. By carefully silylating the same hydrophi-
lic silica grade as the basis for different degrees of
silylation, the structure of the primary particles
and silica aggregates remains preserved. However,
the size of the silica agglomerates, arising from
particle-particle interaction, will strongly depend
on the liquid medium. Therefore, we can use the
thickening of liquids to gain a qualitative under-
standing of particle interactions in relation to
surface properties and characteristics of the liquid
media used. Additionally, the enhanced thickening
effect of fumed silica modified by a high loading
of dimethylsiloxy groups will be studied.
2. Experimental
A hydrophilic fumed silica with a surface area
of 200m 2 g-~ (WACKER H D K N20), exhibiting
a smooth non-microporous surface (surface fractal
dimension Ds = 2.0 [ 12]), was used. Silylation was
achieved by reaction of the silica with dichlorodi-
methylsilane (Silan M2) and hexamethyldisilazane
(Silazan HMN), respectively, in the presence of
molar amounts of water. This was followed by
drying at 300°C (Silan M2) or 150°C (Silazan
HMN) for 1 h. Silica and silanes were supplied by
Wacker-Chemie GmbH, Germany, and used as
received. In order to avoid damage to the particle
structure, silylation was performed by spraying the
silanes onto the carefully fluidized and stirred silica.
Silica was analyzed for carbon content (%C)
using a CS/244, Leco, USA. The contents of silanol
groups were determined by acid-base titration of
the silica against aqueous sodium hydroxide [13]
(Titroprozessor 682, Metrohm, Switzerland). The
titration revealed a silanol group density of about
1.9 SiOH pernm 2, which seems to be a good
estimation of the content of chemically reactive
and available surface silanol groups on fumed silica
[9,14]. Relative contents of residual silanol groups
are calculated by dividing the silanol content of
the silylated silica sample by the silanol content of
the hydrophilic silica.
Three liquid media (Newtonian viscosity) of
different polarity were used; as follows.
(1) High polarity: mixture of 66 wt.% glycerin,
25 wt.% 2-propanol, 9 wt.% water (hydrophobic
silica required pre-wetting by 2-propanol).
(2) Medium polarity: unsaturated polyester
resin; viscosity ~/o= 1 Pa s at a shear rate of 1 s-1
and at 25°C. (In this study we used two technical
grades of commercially available resins: Ludopal
P6, BASF AG, Germany, and Roskydal W15,
Bayer AG, Germany. Composition of both resins:
35 wt.% of styrene and 65 wt.% of a polyester
which is a co-condensation product of phthalic
acid anhydride (35 mol%) and maleinic acid
 H. Barthel/Colloids Surfaces A: Physicochem. Eng. Aspects 101 (1995) 217-226
anhydride (65 mol%) with 2-propandiol; acid
number of 30 according to DIN 53182.)
(3) Non-polar: polydimethylsiloxane (PDMS)
with trimethylsiloxy end groups, viscosity t/o=
1Pa s at a shear rate of l s -1 and at 25°C
(Silicone Fluid AK 1000, Wacker-Chemie GmbH,
Germany).
Dispersion of silica samples in the liquid media
was performed by a dissolver (LD 50, Pendraulik,
Germany) with a stirrer disc of 0.04 m in diameter
at 2800 r.p.m, followed by degassing. After 15 min,
viscosity was recorded by a Rheolab MC 20 visco-
simeter with a UM measuring head using a
MB-Z3/UM coaxial sensor system along with a
constant temperature circulatory device (25°C)
(Physica, Germany). The shear rate was varied
continuously from 0.5 to 50 s- 1.
Gas adsorption data were recorded on an
Omnisorp 100 analyzer (Omnicron, Berkeley
Heights, N J, USA), modified by Grimm
Labortechnik (Ainring, Germany) and by the
author, in a static-volumetric mode. All silica
samples were evacuated for 4 h at 105°C at a
pressure of less than 10 -5 hPa. Nitrogen and argon
were at least 99.995% pure and adsorbed at 78 K;
2,2-dimethylpropane (neo-pentane) and hexameth-
yldisiloxane were at least 99.5% pure and adsorbed
at 273 K and 303 K, respectively.
Surface energies, 7, of the hydrophilic and sily-
lated silica were estimated from wetting tests in
water with increasing content of methanol: equal
volumes of the fluffy silica (apparent density 40 g
1-1) and the water/methanol mixture were vigor-
ously agitated; the silica only became immersed if
it was wetted by the liquid. The surface tension, 71,
of the just-wetting water/methanol mixture was
taken as a measure of the surface energy, V,, of
the silica.
Particle sizes of silica below 1 ~tm were eval-
uated from transmission electron microscopic
(TEM) images (CM 12, Phillips, Germany) and
above 1 lam by light scattering (Helos, Sympatec,
Germany). SAXS data were provided by a Kratky
camera, Paar, Austria, at the Consortium for
Elektrochemische Industrie, Munich, Germany,
and analyzed in slit-smeared form [ 15-1.29Si N M R
spectra were recorded on an AC 300, Bruker,
Germany.
219
3. Results and discussion
3.1. Characterization of hydrophilic and silylated
silica
Silylation of fumed silica samples was performed
by reaction with hexamethyldisilazane up to a
carbon content of 3% C and by reaction with
dichlorodimethylsilane up to a carbon content of
6% C, corresponding to relative contents of resid-
ual silanol groups ranging from 1.0 (hydrophilic
silica) down to 0.15 (highly hydrophobic silica), as
shown in Fig. 1.
In the presence of water, silylation with hexa-
methyldisilazane leads to a silica surface modified
by trimethylsiloxy groups, which are monofunc-
tional and, therefore, will cover the silica surface
like a monolayer. Silylation with dichlorodimethyl-
silane in the presence of water results in difunc-
tional dimethylsiloxy groups. At carbon contents
higher than 3% C, an additional increase in the
carbon content is observed, indicating the forma-
tion of a polymer-like silylation layer on the silica
surface. However, TEM analysis shows that the
size of the silica particles is not substantially
affected by the silylation layer.
Wetting tests reveal that silylation of the hydro-
philic silica decreases its high surface energy
from 7>72 mJ m -2, being wettable by water, to
?<33 mJ m -2, being hydrophobic and wettable
only by water with high methanol content (Fig. 1).
Carbon content% SurfaceenergymJim2
7
8O
6 hydrophobic
70 hydrophobic
5 ! i)ica
5060 s i l i c a /
4
~. hydrophilic
2 40 ~'~ hydmphilic
30 ~ silica
1
O" ' 20 . 0.2
. . . . .0.4
. . 0.6 0.8
Relative SiOHcontent RelativeSiOHcontent
Fig. 1. Carbon content (left) and surface energy (right) versus
relative content of residual silanol groups of dimethylsiloxy-
modified ( 1 ) and trimethylsiloxy-modified ([]) fumed silica.
220 H. Barthel/Colloids Surfaces A: Physicochem. Eng. Aspects 101 (1995)217-226
3.2. Thickening behaviour of hydrophilic and
silylated fumed silica in non-polar, medium polarity
and high polarity liquid media
Concentrated dispersions of non-colloidal silica
particles in Newtonian liquids have been reported
to show a distinct increase in viscosity, associated
with pseudoplastic flow behaviour [16-20]. The
rheological effectivity of colloidal silica is markedly
higher, providing greater thickening at lower load-
ing levels. However, the highest thickening of liquid
media is achieved by fumed silica [21-24].
The rheological effectiveness of fumed silica
results from an interplay of space-filling particle
structures and strong particle-particle interactions.
A rough estimation of the particle structure will
demonstrate that the well-known concept of silica
structures as mass fractals provides a helpful
approach. A real mass fractal is limited by the size
of the cluster as an upper limit and the size of its
primary particles as a lower limit. The density of
the cluster Peluster may be calculated from the true
density of the particle Pparticle, the ratio of the
cluster size deluste r to the particle size dparticle , and
the mass fractal dimension D m of the cluster:
Pcluster = Pparticle(dcluster/dparticle) Dm- 3 ( 1)
TEM provides primary particle sizes of about
10 nm and aggregate sizes in the range of 100 nm.
Light-scattering measurements of fumed silica dis-
persed in air show agglomerate sizes of about
5 Ixm. Given that the density of the primary particle
Pparticle: 2200 g 1-1 and DmDLA= 2 . 5 (aggregates of
primary particles), Eq. (1) yields an apparent aggre-
gate density of 700 g 1-1, which is observed experi-
mentally when pressing fumed silica into a solid
disc. With DRm LcA= 2.1 (agglomerates of aggregates)
an agglomerate density of about 20g 1-1 is
obtained. Indeed, this is the extremely low bulk
density, p, of freshly prepared fumed silica: a fluffy
white powder with p = 20-30 g 1-1.
Therefore, owing to its specific particle structure,
fumed silica will be able to form a space-filling
particle network of percolating aggregates and
agglomerates even at a very low loading of 2 wt.%
(Eq. 1), provided that there is a sufficiently strong
particle-particle interaction of the silica dispersed
in the liquid. Indeed, typical industrial loadings of
fumed silica as a thickener are in the range of
0.5-3 wt.%. At such low loadings, the thickening
effect of the silica particles should be predomi-
nantly due to particle-particle interactions, while
the increase in particle sizes by adsorption layers
seems to be negligible.
Thickening effects on the basis of particle-
particle interactions are strongly dependent on the
shear rate applied. The system usually behaves as
a pseudoplastic. At low shear rates, formation of
large agglomerates is dominant. With increasing
shear rate, agglomerates are broken down. Finally,
at high shear rates, the behaviour is predominantly
Newtonian with small interparticle effects as com-
pared to hydrodynamic forces. In this paper, we
investigate thickening data at low shear rates to
study particle-particle interactions in the liquid.
Particle-particle interactions are controlled by
surface chemistry, but surface structure also has
an influence. It has been shown elsewhere that
microporosity of silica surfaces decreases particle-
polymer interactions [12]. Further studies have
revealed a distinct loss of the thickening effect of
silica with a fractally rough surface [8]. Usually,
commercial grades of fumed silica up to a surface
area of 200 m 2 g- 1 have smooth non-microporous
particle surfaces [12,25]. Consequently, in our
studies we used silica of a grade with smooth
particle surfaces; this will simplify our discussion
of particle-particle interactions.
Among particle-particle surface interactions,
hydrogen bonds have been discussed as one of the
main driving forces for the attachment of fumed
silica particles [26]. In consequence, hydrophilic
silica has been ascertained as the most effective
silica thickener. However, hydrophobic silica par-
ticles have been reported to cause thickening
and pseudoplastic flow in highly polar liquids, aris-
ing from particle agglomeration and flocculation
[16-19,22,23].
Further investigations of the thickening behavi-
our of hydrophilic and silylated hydrophobic
fumed silica in liquids of different polarities have
now resulted in a better understanding of thicken-
ing and particle-particle interactions. It turns out
that the physicochemical similarity between the
silica surface and the liquid medium will not result
in thickening of the liquid. In fact, the contrary is
 H. Barthel/Colloids Surfaces A: Physicochem. Eng. Aspects 101 (1995) 217-226 221

Table 1 content of residual silanol groups, the thickening

Principles of particle-particle interactions in liquid media effect of the silica decreases pronouncedly. Equally,
Polar hydrophilic silica in Hydrogen bonding, high the pseudoplastic behaviour of the dispersion
non-polar liquid medium thickening becomes less distinct. At relative contents of resid-
Polar hydrophilic silica in Weak interactions, low ual silanol groups of less than 0.3, the thickening
polar liquid medium thickening effect of the hydrophobic silica in the silicone fluid
Non-polar hydrophobic Weak interactions, low nearly vanishes and the liquid shows Newtonian
silica in non-polar liquid thickening
medium flow.
Non-polar hydrophobic Hydrophobic forces, high The viscosity, ~/, of a dispersion of solid particles
silica in polar liquid thickening can be related to the viscosity of the pure liquid,
medium ~/o, and the volume fraction of the dispersed solid,
q~, by a modified relation of Einstein [27], taking
into account the polydispersity of the particles:
found: if the chemical structures and polarity of
the silica surface are different from those of the ,7/~o = (1 - • )-2.5 (2)
liquid, then a high thickening effect will be observed The true density of the fumed silica primary
(Table 1). particles p,iuca=2200g 1-1 (amorphous silicon
In a non-polar liquid, hydrophilic fumed silica dioxide) and the density of the silicone fluid
aggregates strongly interact via hydrogen bonds PPDus = 970 g 1-1 yield a volume fraction of q~ =
between surface silanol groups of neighbouring 0.009 at a loading of 2 wt.% fumed silica in the
particles [21]. The liquid media of low polarity silicone fluid. However, dispersed in air, fumed
used are polydimethylsiloxanes (silicone fluids). silica agglomerates show a markedly lower density
Owing to the high flexibility of the polymer chain, of pagglorn,rate=20 g 1-1 (Eq. 1). Therefore, assum-
the polar siloxane backbone is effectively shielded ing that the silica agglomerates show a similar
by the extremely non-polar methyl groups [24]. fractally space-filling mass structure in the silicone
Fig. 2 shows the viscosities of a silicone fluid fluid to that in air, and assuming that the agglomer-
thickened by hydrophilic and silylated silica at a ates behave like rigid spheres at the applied shear
shear rate of 1 s-1. The addition of 2 wt.% hydro- rate owing to hydrogen bonds between the hydro-
philic silica enhances the viscosity of the silicone philic fumed silica aggregates, a much higher effec-
fluid by a factor of 35. The thickening effect of the tive agglomerate volume fraction of • > 0.9 has to
hydrophilic silica is associated with pronounced be considered at a loading of 2 wt.% silica.
pseudoplastic flow behaviour. With decreasing Indeed, higher loadings of hydrophilic silica than
2 wt.% lead to a gel-like consistency accompanied
Relative viscosity "q/rio by a yield value, indicating a percolating particle
50 structure and an effective volume fraction of virtu-
30 hydrophilic s i l ~ ; ¢ = ally unity. At a silica loading of 2 wt.%, resulting
20
in a relative viscosity t/It/o= 35 at a shear rate of
10 1 s -1, Eqs. (1) and (2) provide a mean size of
hydr°phobic spherical agglomerates of about 4 lam, which is
5
close to values obtained from light scattering. An
increase of the shear rate to 10 s-1 decreases ~//~/o
to about 7, revealing a reduction in the mean
1
0 0.2 0.4 0.6 0.8 agglomerate size to 2-3 gm. The reduction in the
Relative content of residual silanol groups relative content of residual silanol groups to less
than 0.3 by silylation with trimethylsiloxy groups
Fig. 2. Relative viscosity ~//t/oversus relative content of residual
silanol groups of dimethylsiloxy-modified (Is) and trimethylsi- decreases r//t/o to <1.2 (Fig. 2), related to an
loxy-modified ([]) fumed silica (2 wt.%) in a silicone fluid (qo = agglomerate size of less than 250 nm. Hence, even
1 Pa s, shear rate 1 s -1, temperature 25°C). at a low shear rate of 1 s-1, highly hydrophobic
222 H. Barthel/Colloids Surfaces A: Physicochem. Eng. Aspects 101 (1995) 217-226
silica aggregates are barely agglomerated in the
silicone fluid. The loss of active silanols diminishes
the interaction between the silica particles. Finally,
no particle-particle interaction results when highly
hydrophobic silica is dispersed in the hydrophobic
silicone fluid.
It is evident that agglomeration due to particle-
particle interactions rather than adsorption of
PDMS layers provides a helpful model of thick-
ening effects. Silanol groups on the surface of
hydrophilic silica lead to direct particle-particle
interactions on the basis of strong hydrogen bonds.
Additionally, weaker hydrogen bonds between
silica silanols and the silicone fluid may occur.
However, PDMS adsorption onto the silica par-
ticles will lead to steric repulsion 1-28] rather than
to particle bridging in the silicone fluid.
In a highly polar medium with a strong tendency
to form hydrogen bonds, as in a mixture of
water, glycerin and 2-propanol, the situation is
different. As depicted in Fig. 3, the ability of hydro-
philic fumed silica to thicken a highly polar liquid
is rather low. At a loading of 3 wt.%, the flow
behaviour is nearly Newtonian. In a polar medium,
the hydrophilic silica surface is effectively wetted,
and the particles are shielded from each other and
prevented from interacting. As assumed in the
foregoing section, strong adsorption of the liquid
onto the particle surface and blocking of the silanol
groups suppresses the thickening effect of the silica
rather than enhancing it. Hydrogen bonds and
Relative viscosity rl/q0
30
20
3 i.e. hydrophobicity, rather than to different
2 structures of the silylating layer. The origin of the
hydrophilic silica
10 . . . 0.2. 0.4 0 i6 0.:8 1'
Relative content of residual silanol groups
Fig. 3. Relative viscosity ~//~/oversus relative content of residual
silanol groups of dimethylsiloxy-modified (IN) and trimethylsi-
loxy-modified ([]) fumed silica (3 wt.%) in glycerin-2-propanol-
water (66 : 25 : 9, wt. OYo), (shear rate 10 s - 1 , temperature 25°C).
other polar interactions within the liquid, between
surfaces and liquid molecules or between particle
surfaces are at a similar level. Consequently, no
strong attraction of hydrophilic silica particles
results, to give rise to a thickening of the polar
liquid medium.
In contrast, if hydrophobic fumed silica is uni-
formly dispersed in a polar liquid medium, then
extensive thickening of the dispersion occurs
and, additionally, pseudoplastic flow is observed.
As shown in Fig. 3, the enhancement of viscosity
even starts at rather high relative contents of
residual silanol groups of about 0.8. However,
thickening is most pronounced for highly hydro-
phobic silica with a relative silanol content of 0.2,
providing a value of ~//~/oof nearly 30 and exhibit-
ing pseudoplastic flow behaviour. Again, Eqs. (1)
and (2) reveal mean agglomerate sizes of 2-3 ~tm
at a shear rate of 10 s -1. Obviously, the agglomer-
ate structures of hydrophilic silica in a silicone
fluid and of hydrophobic silica in the polar glycerin
mixture are rather similar.
Pseudoplastic flow of non-colloidal hydrophobic
silica dispersions in liquids of high polarity has
been related to hydrophobic particle coagulation
as a result of non-wettability by the liquid [16],
high hydrophilic/lyophilic balance values of the
liquid 1-18] and protruding polymer chains from
the silylation layer [ 19]. The thickening behaviour
of colloidal hydrophobic fumed silica in water has
been explained by dispersion interactions between
alkyl chains grafted onto the silica surface 1-22,23].
As shown in Fig. 3, fumed silica bearing a
monolayer of trimethylsiloxy groups on the surface
shows the same efficiency of thickening in the
glycerin mixture as silica modified by a polymer-
like layer of dimethylsiloxy groups. Thickening of
the polar liquid by the hydrophobic particles is
related to the content of residual silanol groups,
underlying particle-particle interactions is so-
called hydrophobic interactions [29]. Polar liquids
tend to build up rather stable supermolecular
structures - - water or aqueous solutions of alco-
hols are known to be well clustered and structured
by hydrogen bonding. Hydrophobic particles will
disturb this network. Therefore, polar liquids tend
 H. Barthel/Colloids Surfaces A: Physicochem. Eng. Aspects 101 (1995) 217-226
to minimize the contact interface towards the non-
polar hydrophobic particles. The hydrophobic par-
ticles are forced to make contact with each other,
thus resulting in an apparently strong particle-
particle "interaction". By means of this solvent-
mediated interaction, the hydrophobic silica par-
ticles build up stable agglomerates and particle
networks. Highly hydrophobic fumed silica thick-
ens a polar liquid medium as effectively as a
hydrophilic silica thickens a non-polar one.
It has to be mentioned that the understanding
of particle interactions in liquid media is not
restricted to hydrogen bonding. Qualitatively,
London dispersion forces also lead to particle-
particle interactions, and thickening [20], if the
medium and the particles differ in their Hamaker
constants, but the London dispersion interaction
energy will tend to zero if these Hamaker constants
become equal [30]. The particular system may
determine which type of interaction force is quanti-
tatively dominant, i.e. hydrogen bonds, electrical
charges or Van der Waals interactions, including
London, Keesom and Debye forces.
Given a primary particle radius of R = 5 nm and
Hamaker constants of A l t = 1 2 x 10-2° J (silica)
and A22=6.3 x 10-2° J (PDMS), the interaction
of two silica particles, separated at a distance
d = 0.1 nm (surface to surface distance) by a silicone
fluid, yields a non-retarded dispersion energy of
attraction, AGd21=-At21R/12d [30], of about
5-15kT, where kT is the thermal energy at a
temperature of 298 K. The interaction energy due
to hydrogen bonding of hydrophilic silica particles
in a silicone fluid may be roughly estimated as
follows. A primary particle of R = 5 nm with a
silanol density of 2 SiOH nm -2 [9] bears about
600 silanol groups. However, owing to the particle
structure and steric constraints at the solid surface,
only a minor part of these silanol groups partici-
pate in strong hydrogen bonds with a neighbouring
particle. Assuming that 1% of the total amount of
silanol groups interact provides an interaction
energy of two particles, AG~ion, of about 50-
100kT. In water, the hydrophobic interaction
energy of two particles, hydrophobized by hexade-
cyltrimethyl ammonium bromide (CTAB), was
reported to be ztG~AB = --40Re -a/d°, where do =
1 nm [29]. A particle distance d=0, i.e. particles
223
in contact, yields a hydrophobic interaction energy
of about 80 kT. Taking into account the higher
solubility of CTAB in water, compared to that of
a silicone fluid, the silylation of the surface (PDMS
layer) should result in more pronounced hydro-
phobicity than CTAB coverage. Thus, hydrophobic
thickening by silylated silica should be greater than
hydrogen-bond thickening by hydrophilic silica.
However, Figs. 2 and 3 reveal rather similar thick-
ening effectiveness from both types of interactions.
Actually, the glycerin mixture shows lower polarity
than pure water, surface tensions 7g~y~nn< Ywatcr,
and, additionally, adsorption of 2-propanol may
weaken the hydrophobicity of the silylation
(PDMS) layer. The latter effect is supported by
some experimental evidence: immersion of highly
hydrophobic silica in glycerin requires pre-wetting
with pure 2-propanol.
A very interesting result is observed when fumed
silica of varying silanol content is dispersed in
a liquid of medium polarity. In this study, two
commercially available unsaturated polyester
resins of different sources have been used, contain-
ing 65 wt.% of the polyester in styrene. The thicken-
ing effects of hydrophilic and silylated silica turned
out to be virtually equal in both resins. Owing to
the high polarity of the polyester and the non-
polar properties of styrene, the resin may be classi-
fied as being of medium polarity. Fig. 4 shows the
viscosity of the resin as a function of the relative
Relative viscosity TI/~qo
10
5
3 hyd ilic
silica silica
20 0.2
L ,
0.4
i
0.6
i
08 1
i
Relative content of residual silanol groups
Fig. 4. Relative viscosity ~//~/oversus relative content of residual
silanol groups of dimethylsiloxy-modified (11) and trimethylsi-
loxy-modified ([2) fumed silica (3 wt.%) in an unsaturated
polyester resin (65 wt.% in styrene; ~/o= 1 Pa s; shear rate 1 s -1,
temperature 25°C).
224 H. Barthel/Colloids Surfaces A: Physicochem. Eng. Aspects 101 (1995) 217 226
content of residual silanol groups at a loading of
3 wt.% silica.
Hydrophilic fumed silica turns out to be a rather
effective thickening agent in the unsaturated poly-
ester resin, enhancing the viscosity of the latter by
a factor of about 7. Silylating the silica surface to
50% conversion of the silanol groups destroys
thickening action. However, on going to highly
hydrophobic silica, the thickening action increases
again and, finally, will reach viscosity values similar
to those found for hydrophilic silica. Obviously, a
silica surface covered half by hydrophilic silanols
and half by hydrophobic methyl groups shows a
polarity similar to that of the mixture of polyester
and styrene and, therefore, particle-particle inter-
actions are weak and thickening breaks down. Full
coverage with polar silanol groups or full coverage
by the non-polar silylation layer imposes a suffi-
ciently large difference on the properties of silica
surface and liquid medium. According to Table 1,
strong particle-particle interactions and high thick-
ening result.
3.3. Particle-particle interactions due to a polymer-
like silylation layer of dimethylsiloxy groups
In the foregoing section, the silylation layer has
been regarded as behaving as a dense and rigid
monolayer of methyl groups on the solid silica
surface. As a consequence, silica particles modified
by monofunctional trimethylsiloxy groups and
silica particles modified by difunctional dimethyl-
siloxy groups should interact in the same manner.
There should not be a pronounced difference in
the thickening effect of differently silylated silica
surfaces. As shown in Figs. 2 and 4, this concept
seems to be correct only for low carbon content.
At higher carbon content, fumed silica modified
by dimethylsiloxy groups shows a greater thicken-
ing ability than the trimethylsiloxy-modified silica.
This greater thickening is found in particular when
a silicone fluid is used as a medium (Fig. 2), but
in an unsaturated polyester resin it occurs pro-
nouncedly only for a silica carbon content higher
than 3% C (Fig. 4) and vanishes in a highly polar
liquid (Fig. 3).
At the highest coverage of the silica by dimethyl-
siloxy groups (carbon content of 6% C, i.e. a
siloxane content of about 18 wt.%), the mean
thickness of the silylation layer is about 0.6 nm.
Even at this high siloxane content, the mean chain
length of grafted siloxane oligomers is not larger
than four or five dimethylsiloxy units. Therefore,
particle bridging by polymer chains or polymer
entanglements should be of minor importance.
In this paper, we propose that the underlying
additional particle-particle interactions arise from
interpenetration of particle silylation layers. A sily-
lation layer of dimethylsiloxy groups at low cover-
age will behave like a rigid surface layer, as does
a layer of trimethylsiloxy groups. However, with
increasing loading, the silylation layer will consist
more and more of polymer-like chains of dimethyl-
siloxy groups, and will thus behave like a bonded
phase of quasi-liquid silicone.
There is some experimental evidence of a poly-
mer-like quasi-liquid silylation layer on a dimethyl-
sitoxy group-modified surface. As mentioned
above, greater thickening by the dimethylsiloxy-
modified silica decreases from non-polar (Fig. 2)
to less polar (Fig. 4) and polar (Fig. 3) liquid
medium. Solid-state 2H NMR techniques have
shown that octadecyl chains grafted onto silica are
highly mobile in a wetting non-polar solvent, but
are forced to lie flat on the solid silica surface
when immersed in water [31].
29Si NMR spectra of silylated silica dispersed in
deuterated chloroform show a single broad signal
at 10ppm of the surface-bonded trimethylsiloxy
group, but a broad signal superposed by a sharp
signal at - 2 2 ppm for dimethylsiloxy-modified
silica with a carbon content > 5% C, indicating
that a measurable amount of the silylation layer is
quasi-liquid.
SAXS provides a fractal surface dimension of
Ds= 2.0, as the surface of fumed silica is smooth
and free of micropores. Silica surfaces modified by
long alkyl chains have been reported to give values
of Ds markedly below 2. It has been demonstrated
that these unexpected data do not result from
surface fractal character; they may be explained by
not a sharp but rather a fuzzy particle boundary
due to silylation [32]. Our own SAXS measure-
ments also yielded a value of Ds<2 for highly
silylated dimethylsiloxy-modified silica (carbon
content 6% C, D~=l.8), but, as expected, Ds=2.0
 1t. Barthel/Colloids Surfaces A: Physicochem. Eng. Aspects 101 (1995) 217-226
for a trimethylsiloxy layer. Again, this can be
explained by a quasi-liquid state of the polymer-
like dimethylsiloxy silylation layer.
Gas adsorption techniques are suitable methods
for studying adsorption phenomena of a single
pure adsorbate on a solid surface. The most famous
application is the determination of the surface area
of highly dispersed solids: the monolayer capacity,
as evaluated by the BET equation from the adsorp-
tion isotherm, is multiplied by the molecular area
of the adsorbate [ 33]. It has been shown elsewhere
that the monolayer capacities of nitrogen (at 78 K),
argon (at 78 K) and neo-pentane (at 273 K) on
fumed silica decrease distinctly with increasing
silylation [34]. Surprisingly, the monolayer capac-
ity of neo-pentane on silica increases again at high
loadings of dimethylsiloxy groups. Recently, a
similar increase in the monolayer capacity was
found when hexamethyldisiloxane at 303 K was
used as an adsorbate (Table 2).
This increase is observed with neither nitrogen
nor argon, nor with a trimethylsiloxy-modified
silica. It is assumed that absorption effects addi-
tional to adsorption are responsible for the increase
in sorption capacity. A silylation layer of dimethyl-
siloxy groups can be compared to a grafted phase
of short PDMS chains. PDMS shows a melting
point at 210 K and a glass transition temperature
of about 150 K. At a temperature of 78 K, nitrogen
or argon is, therefore, adsorbed onto a solid surface
of silylated silica, regardless of the thickness of the
grafted PDMS layer. However, at the adsorption
Table 2
BET surface areas from monolayer capacities of fumed silica
silylated by dimethylsiloxy groups: adsorption of nitrogen
(78 K), argon (78 K), neo-pentane (273 K) and hexamethyldisi-
loxane (303 K), using molecular areas of 0.162, 0.138, 0.37 and
0.55 nm 2, respectively
Adsorbate BET surface area (m2 g - t ) of silica
Hydrophilic Silylated
0.0% C 2.0% C 6.0% C
Nitrogen 200 171 109
Argon 157 141 86
neo-Pentane 116 59 74
Hexamethyldisiloxane 142 52 86
225
temperatures of neo-pentane and hexamethyl-
disiloxane, 273 and 303 K, a thick PDMS layer
will be quasi-liquid and, thus, able to solve adsorb-
ate molecules. Both absorption and adsorption
will occur and enhance the apparent monolayer
capacity.
N M R and SAXS confirm the foregoing assump-
tion of a polymer-like, quasi-liquid silylation layer
on fumed silica modified with dimethylsiloxy
groups at carbon contents greater than 3% C. Gas
adsorption data additionally provide evidence that
the dimethylsiloxy layer also has an absorption
capacity. Enhancement of the thickening action
of dimethylsiloxy- versus trimethylsiloxy-modified
fumed silica is also observed at high carbon
content. Therefore, we propose the occurrence of
additional particle-particle interactions arising
from the interpenetration of silylation layers of
neighbouring particles.
4. Conclusion
Fumed silica is a highly dispersed silicon dioxide
of great industrial importance. Controlling the
rheology of liquid media is one of its most impor-
tant applications. The thickening action of fumed
silica can be related to its production from a flame
process leading to a particular space-filling particle
structure and an active surface covered with silanol
groups. Besides particle structure, particle-particle
interactions are the main basis of the thickening
effects in liquid media. A general model of particle-
particle interactions has been developed which
proposes a thickening ability of fumed silica if the
silica surface and the liquid medium differ in their
physicochemical properties. In particular, the high
thickening of silanol group-free hydrophobic silica
in polar media has been explained by hydrophobic
forces. Additionally, an enhanced thickening action
of dimethylsiloxy- versus trimethylsiloxy-modified
fumed silica is observed in liquid media of low and
medium polarity. Gas adsorption studies suggest
particle-particle interactions arising from inter-
penetration of silylation layers of neighbouring
particles. The understanding of the origin of this
interaction requires further investigation.
226 H. Barthel/Colloids Surfaces A: Physicochem. Eng. Aspects 101 (1995) 217-226
Acknowledgements
The author thanks Dr. Achenbach and Dr.
Heinemann, Wacker-Chemie GmbH, for the many
interesting and fruitful discussions.
References
[1] T. Dabak and O. Yucel, Rheol. Acta, 25 (1986) 527.
[2] R. Lapasin, Susp. Rheol., Chem. Biochem. Eng. Q., 1(4)
(1987) 143.
[3] W.M. Jiao, A. Vidal, E. Papirer and J.B. Donnet, Colloids
Surfaces, 40 (1989) 279.
[4] M. Chen and W.B. Russel, J. Colloid. Interface. Sci.,
141(2) (1991) 564.
[5] P. Meakin, in D. Avnir (Ed.), The Fractal Approach to
Heterogeneous Chemistry, Surfaces, Colloids, Polymers,
Wiley, New York, 1989, p. 131.
[6] G.D. Ulrich and J.W. Riehl, J. Colloid Interface Sci.,
87(1) (1982) 257.
[7] T. Freltoft, J.K. Kjems and S.K. Sinha, Phys. Rev. B,
33(1) (1986) 269.
[8] H. Barthel, unpublished results, 1994.
[9] V.A. Tertykh, V.M. Mashchenko and A.A. Chuiko, Dokl.
Akad. Nauk SSSR, 200(4) (1971) 865.
[10] M. Zaborski, A. Vidal, G. Ligner, H. Balard, E. Papirer
and A. Burneau, Langmuir, 5 (1989) 447.
[11] J.B. Donnet, M.J. Wang, E. Papirer and A. Vidal,
Kautsch. Gummi, Kunstst., 39(6)(1986) 510.
[12] H. Barthel, F. Achenbach and H. Maginot, Proc. Int.
Symp. on Mineral and Organic Functional Fillers in
Polymers (MOFFIS 93), Universit~ de Namur, Belgium,
1993, p. 301.
[13] G.W. Sears, Anal. Chem., 28(12) (1956) 1981.
[14] L. Boks~my, O. Liardon, E.sz. Kov~its, Adv. Colloid
Interface Sci., 6 (1976) 95.
[15] D.W. Schaefer, J.E. Martin, P. Wiltzius and D.S. Cannell,
Phys. Rev. Lett, 52(26) (1984) 2371.
[16] S.V. Kao, L.E. Nielsen and C.T. Hill, J. Colloid Interface
Sci., 53(3) (1975) 358.
[17] A.J.G. van Diemen and H.N. Stein, J. Colloid Interface
Sci., 86(2) (1982) 318.
[18] A.J.G. van Diemen, F.W.A.M. Schreuder and H.N. Stein,
J. Colloid Interface Sci., 104(1) (1985) 87.
[19] F.W.A.M. Schreuder and H.N. Stein, Rheol. Acta, 26
(1987) 45.
[20] S.C. Tsai and K. Zammouri, J. Rheol., 32(7) (1988) 737.
[21] Y. Otsubo, M. Horigome and K. Umeya, J. Colloid
Interface Sci., 83(1) (1981) 240.
[22] G. Lee and H. Rupprecht, J. Colloid Interface Sci., 105(1)
(1985) 257.
[23] G. Lee, S. Murray and H. Rupprecht, Colloid Poly. Sci.,
265 (1987) 535.
[24] H. Kobayashi and A. Tazawa, Kobunshi Ronbunshu,
44(9) (1987) 675.
[25] A.J. Hurd, D.W. Schaefer and J.E. Martin, Phys. Rev. A,
35(5) (1987) 2361.
[26] G. Michael and H. Ferch, Schriftenreihe Pigmente,
Degussa AG (F.R.G.), 11 (1991) 63.
[27] P.C. Hiemenz (Ed.), Principles of Colloid and Surface
Chemistry, Dekker, New York, 1977, p. 69.
[28] P. Auroy, L. Auvray and L. L6ger, J. Colloid Interface
Sci., 150(1) (1992) 187.
[29] aJ.N. Israelachvili, Proc. Symp. on Complex and
Supermolecular Fluids N.A. Clark and S. Safran) (Eds.),
Wiley, New York, 1987, p. 101.
[29] bJ.N. Israelachvili and R.M. Pashley, J. Colloid Interface
Sci., 98(2) (1984) 500.
[30] S. Ross and I.D. Morrison (Eds.), Colloid Systems and
Interfaces, Wiley, New York, 1988, p. 205.
[31] R.C. Zeigler and G.E. Maciel, J. Am. Chem. Soc. 113(17)
(1991) 6349.
[32] P.W. Schmidt, D. Avnir, D. Levy, A. H6hr, M. Steiner
and A. R011, J. Chem. Phys., 94(2) (1991) 1474.
[33] S. Brunauer, P.H. Emmett and E. Teller, J. Am. Chem.
Soc., 60 (1938) 309.
[34] H. Barthel, Proc. Fourth Symp. on Chemically Modified
Surfaces, H.A. Mottola and J.R. Steinmetz (Eds.), Elsevier,
Amsterdam, 1992, p. 243.