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Hydrophobic or Hydrophilic Fumed Silica

as Filler of Polyurethane Adhesives
a a a
T. G. Maciá-Agulló , J. C. Fernández-García , A. Torró—palau ,
a b
A. C. Orgilés Barceló & J. M. Martín-Martínez
a
INESCOP, Footwear Research Institute , 03600, Elda, Alicante,
Spain
b
Adhesion & Adhesives Laboratory, Department of Inorganic
Chemistry , University of Alicante , 03080, Alicante, Spain
Published online: 24 Sep 2006.

To cite this article: T. G. Maciá-Agulló , J. C. Fernández-García , A. Torró—palau , A. C. Orgilés

Barceló & J. M. Martín-Martínez (1995) Hydrophobic or Hydrophilic Fumed Silica as Filler of
Polyurethane Adhesives, The Journal of Adhesion, 50:4, 265-277, DOI: 10.1080/00218469508014557

To link to this article: http://dx.doi.org/10.1080/00218469508014557

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 J . Adhesion, 1995, Vol. 50, pp. 265-211 Q 1995 OPA (Overseas Publishers Association)
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Hydrophobic or HydrophiIic Fumed Si Iica

as Filler of Polyurethane Adhesives*
T. G. MACIA-AGULLd, J. C. FERNANDEZ-GARCfA, A. TORRd- PALAU, and
A. C. ORGILES BARCELd
INESCOP, Footwear Research Institute, 03600 Elda, Alicante, Spain
J. M. MARTiN-MARTiNEZ**,
Downloaded by [Moskow State Univ Bibliote] at 11:29 03 February 2014

Adhesion &Adhesives Laboratory, Department of Inorganic Chemistry,

University of Alicante, 03080 Alicante, Spain

(Received September 13,1994: i n j n a l form February 28, 1995)

Two hydrophilic and two hydrophobic fumed silicas of different characteristics were added to solvent-based
polyurethane adhesives (PU). IR spectroscopy, contact angle measurements and rheology (viscosity
measurements, determination of viscoelastic properties) were used to monitor the variation of properties of
PU adhesives produced by addition of silica. Immediate (green)adhesion was determined by T-peel testing of
halogenated synthetic rubber/PU adhesive/halogenated synthetic rubber joints. Silica addition produced a
noticeable increase in the PU adhesive viscosity which can be related to the variation of viscoelastic
properties. Viscosity of PU adhesives containing hydrophilic silica slightly increased with time after
preparation; the increase was less significant in PU adhesives with hydrophilic silica. In the rheological
studies, silica imparted shear thinning and negative thixotropy to PU adhesives due to a better dispersion of
the silica in the polyurethane during shearing. The addition of silica produces an increase in the storage
modulus (G’) of PU adhesives, the values obtained being independent of the hydrophilic or hydrophobic
nature of the fumed silica. The increase of G’ and the changes in tan 6 of PU adhesives containing silica
corresponded to an improvement in the green adhesion properties of chlorinated rubber/PU adhes-
ive/chlorinated rubber joints. In general, in disagreement with previous results,’ the presence of silica did
affect the properties of solvent-based PU adhesives, but these properties were not dependent on the type of
silica (hydrophobic or hydrophilic) used in this study.

KEY WORDS: hydrophobic and hydrophilic nature; fumed silica; solvent-based polyurethane adhesives;
rheology; viscoelastic properties; green strength; contact angle; infra-red spectroscopy.

1 INTRODUCTION

Inorganic mineral fillers are generally used to modify the rheological properties and
adhesion behaviour and to decrease the cost of manufacture of sealants, coatings and
adhesives. Specifically, fumed silicas are often used as a component in the formulation
of epoxy’ and PU3 adhesives, among others, to improve their rheological behaviour,
their stability to elevated temperature and their adhesion properties.

*Presented at Adhesion ’93, the Fifth International Conference of the Adhesives Section of the Polymer
Industry Division of The Institute of Materials, held at The University of York, York, UK, September 6-8,
1993.
**Corresponding author.

265
 266 T. G . M-AGULLO et al.

Solvent-based polyurethane adhesives (PU) are often employed to join styrene-

butadiene rubber materials (SBR) in the footwear industry. Hydrophilic fumed silica
can be added to impart thixotropy and to adjust the rheological behaviour of such PU
adhesives. In a previous study,3 we analyzed the influence of the addition of a
hydrophilic fumed silica (AerosiI-200)(5-25wtY0) to solvent-based PU adhesives on
their adhesion properties through un-chlorinated and chlorinated rubbers; the halogen
precursor was trichloroisocyanuric acid in 2-butanone solution. In general, the addi-
tion of silica produced an increase in the adhesive viscosity and an improvement of
green (immediate) peel strength (especially with chlorinated rubber); the best results
were obtained for a silica content of 10-20 wt%. There appears to be no chemical
interaction between silica and polyurethane polymer, although the presence of silica
resulted in the improvement of the resistance of the PU adhesive to degradation by
chlorinated species on the rubber surface.
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Hydrophilic fumed silica may interact with polar solvents (ketones, ethyl acetate)
leading to a continuous variation of viscosity with time. To avoid these drawbacks, the
use of hydrophobic fumed silica was proposed by Degussa4.The proposal was that the
use of hydrophobic fumed silica prevents specific interactions with water, produces an
increase in adhesion and a “true” enhancement of viscosity, which is usually constant
over time. (The creation of hydrogen bonds between OH surface groups on the silica
and polar groups of solvent and/or adhesive is avoided).
Fumed silicas are manufactured by high-temperature hydrolysis of silicon tetrach-
loride in a flame.’ Silanol functional groups (which are responsible for the hydrophilic
character of fumed silica) and siloxane groups (which are responsible for the hydropho-
bic character of fumed silica) are thus created on the silica surface. Through continuous
development of flame technology and chemical after-treatment, it became possible to
produce numerous different hydrophilic and hyal q h o b i c silicas. In fact, the silanol
groups present on the hydrophilic fumed silica surface may be chemically modified
using halosilanes,alkoxysilanes,silazanes or siloxanes? leading to a chemical bond on
the silica surface. The resulting product (generally called hydrophobic fumed silica) has
a similar particle size but a reduced specific surface area, reduced water vapour
adsorption and, of course, a reduced silanol group density, compared with hydrophilic
silica.
Hydrophobic fumed silicas have been successfully used as rheological aids to provide
effective and stable thickening, and thixotropy of epoxy systems.’32The nature of the
epoxy determines the effectiveness of the hydrophobic silica, although, in general, an
increase in viscosity (which is maintained over time) and an increase of adhesion to steel
films have been reported.2 A comparison among different hydrophobic and hy-
drophilic silicas was carried out, showing different effects depending on the nature of
the fumed silica.
To our knowledge, no further studies related to the addition of silica to PU adhesives
have been carried out. For this reason, the objective of this work is to extend our
previous study3 to a larger number of fumed silicas. We deal specifically with the
influence of particle size, specific surface area and the hydrophilic or hydrophobic
nature of fumed silica on the rheological properties of PU adhesives and on their
adhesion to synthetic rubber.
 FUMED- SILICA-FILLED ADHESIVES 261

EXPERIMENTAL

11.1 Materials
A polyester-urethane polymer based on E-polycaprolactone (Pearlstick 45-4011 5 ) was
used to prepare the solvent-based P U adhesives. This polyurethane, supplied by
MERQUINSA S.A. (Barcelona, Spain), has a medium thermoplasticity (reversible
tendency to melt under temperature), short open time and very high crystallization
rate.
Four fumed silicas (two hydrophobic-Aerosil R805 and R8 12- and two hydrophilic-
Aerosil200 and 300),provided by DEGUSSA AG (Hanau, Germany) of specificsurface
areas between 200 and 300m2/g were selected for this study. Some of the properties of
the silicas are given in Table 1.
PU adhesives (with the nomenclature given in Table 11) were prepared by mixing
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18 wt% PU and 2 wt% fumed silica in 2-butanone. This mixture was placed in a
laboratory mixer (1500 rpm) and stirred for 2 hours at room temperature until a
homogeneous dispersion was obtained. The adhesive solutions were kept in an
hermetic container until used.
PU adhesives were characterized by using contact angle measurements and infrared
spectroscopy. The Brookfield viscosities of the adhesives (at 25°C) using spindle no. 3
and a speed of 20rpm were measured in an RVT Brookfield Viscometer. The
measurements were taken after 1 min. Brookfield viscosities provide incomplete
information about the viscous characteristics of adhesives because they do not provide
any information related to the rheological behaviour (Newtonian, pseudoplastic) of

TABLE I
Properties of Aerosil fumed silicas (taken from Reference 3)

Property H ydrophilic Hydrophobic

A200 A300 R805 R812

BET surface area (m2/g) 200 f 25 300 f 30 150 25 260 30

Average primary particle size (nm) 12 7 12 I
Moisture content (%) < 1.5 < 1.5 < 0.5 < 0.5
Surface group -%OH -Si-OH -Si-C,H,, -Si(CH,),
Bonded carbon (wt%) - - 5 2.5
PH 3.6-4.3 3.6-4.3 5-1 1.O-2.5

TABLE I1
Nomenclature of solvent-based PU adhesives

PU adhesive Fumed silica

A0 None
A1 Aerosil200
A2 Aerosil300
P1 Aerosil R805
P2 Aerosil R812
 268 T. G. M-AGULL6 et a/.

adhesives. Thus, rheological studies (viscosity measurements and viscoelastic proper-

ties) were also conducted on the PU adhesives.

11.2 Experimental Methods

11.2.I Contact angle measurements. Adhesive films were prepared by placing the
P U adhesive solutions in a rectangular mould and allowing the solvent to evaporate
slowly to prevent the formation of bubbles. Contact angles were determined with a
Rame-Hart 100 goniometer. Single sessile drops (2 pl) of water (doubly distilled) and
ethanediol(99Oh minimum purity) were placed on the surface of the above-mentioned
adhesive film in an hermetic, isothermal (25°C)and solvent-saturated chamber, and the
contact angles on both sides of the drops were measured. The measurements were taken
15 minutes after the drops were placed on the adhesive film. Average values of at least
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three drops on three different batches of the same adhesive film were taken and the
standard deviation was always less than 2".

11.22 fT1R studies. A Nicolet 510 FTIR spectrophotometer was used with a
signal/noise ratio of 0.04% T (at 2000 cm- '). A KBr:silica (300: 1) mix was pressed to
prepare a pellet and then was analyzed by transmission; 80 scans per experiment were
carried out.

11.2.3 Rheological measurements. Rheological tests were conducted using a Physica

MClOO rheometer. Viscosity measurements were carried out in the rotational mode
using concentric cylinders type 2 2 (according to DIN 53019) with the following
technical characteristics: Radius of measuring bob = 2.25 cm; radius of measuring
cup = 2.44 cm; radius of shaft = 0.35 cm; measuring cone angle = 120"; length of
measuring bob = 6.75 cm; distance of lower edge of measuring bob from bottom to
cup = 3.5 cm; immersion of measuring shaft = 2.25 cm. 100cm3 of P U adhesive sol-
utions were used in the measurements and a solvent trap device assured that minimal
evaporation of solvent occurred during the experiments. Controlled shear stress (CSS)
experiments were carried out as follows: Shear stress was increased to 200 Pa in one
minute, maintained at 200 Pa for three minutes, and finally decreased to 0 Pa in one
minute. Previous experiments showed that these experimental conditions produced
complete disorder of the PU structure. Some experiments were repeated and an
excellent reproducibility was always obtained.
Viscoelastic properties were measured in the oscillatory mode, first by varying the
amplitude of a sinusoidal signal between 0.01 and 10 (amplitude sweep)- the frequency
selected was 1 Hz- and second by varying the frequency between 1 and 100Hz- the
amplitude selected was 6.

11.2.4 feel Strength measurements. Peel strength of adhesive joints created

between strips (150 x 30mm) of vulcanized styrene-butadiene rubber (SBR)- about
3 mm thick- was measured by a standard T-peel test. The rubber selected in this study is
one of the most commonly used in the footwear industry as a reference material to test
the peel strength of adhesive joints. Table 111 includes the SBR formulation.
 FUMED- SILICA-FILLED ADHESIVES 269

TABLE I11
Formulation of vulcanized styrene-butadiene rubber

Compound Percentage

SBR 1502 100

Carbon Black (N330) 23
Silica 25
Sulphur 1.76
Curnarone-indene resin (85°C) 3.52
Zinc oxide 3.81
Stearic acid 0.76
N-cyclohexyl-2-benzothiazole sulphenamide 1.14
Phenolic antioxidant 0.78
Dibenzothiazyl disulphide 0.16
Polyethylene glycol 1.13
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SBR samples were cleaned in an ultrasonic bath of doubly-distilled water for 15 min
and stored in vacuum for 60 minutes to remove any retained water. After the cleaning
process, SBR was halogenated by brushing its surface with 2-butanone solution
containing 1 wt% TCI (trichloroisocyanuricacid -1,3,5-trichloro-l,3,5- triazin-2,4,6-
trione). After 18 hours, the reaction of TCI with rubber was complete.6 Subsequently,
100mg of PU adhesive was applied to the rubber surface and left to dry for 40 min. The
PU adhesive film was heated to 80°C using infrared radiation in order to facilitate
contact of the adhesive applied to the two identically-surface-treated SBR strips. The
strips were then placed in contact and a pressure of 3 atm was immediately applied for
10 seconds to achieve a suitable joint.
The green (immediate) peel strength was measured 30 seconds after the two strips
were joined. The T-peel strength was measured on an Instron 1121 (peel rate:
0.1 m/min). The values obtained were the average of three tests (standard deviation was
less than 5%). More details are given el~ewhere.~

111 RESULTS AND DISCUSSION

111.1 Characterizationof Fumed Silica

According to Table I, Aerosil A200 and R805 silicas have the same average primary
particle size (12nm) and similar BET surface areas (175-225 m2/g), although the
hydrophobic silica Aerosil R805 has a lower moisture content and is less acidic. BET
surface areas were calculated by applying the Brunauer-Emmett-Teller equation* to
N2/77K adsorption isotherms of the silicas; BET plots were linear in the range of
relative pressure between 0.05 and 0.30. Aerosil R805 has a smaller number of surface
silanol groups than Aerosil A200 because a fraction of those were chemically reacted
with a silane to form -Si-C,H,, surface groups. A similar situation applies to Aerosil
A300 and R812, although the average primary particle size of these silicas is smaller
(7 nm) and the BET surface area is higher (260-330 m2/g). Aerosil R812 was prepared
by reaction of Aerosil A300 with a silane to form -Si(CH,), surface groups; the nature of
the silane groups and the experimental treatment conditions results in an acidic silica.
 270 T. G. M-AGULLO et al.

Consequently, the selection of these four fumed silicas enables the influence of several
properties (specific surface area, particle size, hydrophiliclhydrophobic nature) to be
studied when the silica is added to solvent-based PU adhesives.
IR spectra of the fumed silicas, Figure 1, show typical 3-0-bands: 9* l o
- Stretching due to hydrogen bonded OH groups (3245-3658 cm- '),
- Bending of OH groups (1 632 cm- ').
- Bending and stretching bands of Si-0-Si groups (1045-1209 cm- ').
- Asymmetric stretching of Si-0-Si groups (979 cm- ').

- Symmetric stretching of Si-0-Si groups (808 cm- I).

In addition, IR spectra of hydrophobic fumed silicas (Figure lb) show stretching

bands of CH, and CH, between 2929 and 2820cm- '. The IR spectrum of Aerosil R812
shows a less marked band due to CH, groups than that of Aerosil R805 (in agreement
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with the different kinds of surface groups in these silicas -Table I).
A relative measurement of the amount of surface silanol groups in the fumed silicas
can be obtained from IR spectra by taking the ratio, R,, of the areas under the bands at
3438cm-' (OH group) and llOOcm-' (Si-0-Si group). Aerosil A200 ( R , = 4.1) is
around 25% more hydrophilic (i.e. there is a greater amount of silanol groups) than
Aerosil A300 ( R , = 3.1). The hydrophilic fumed silicas possess 20-30% less silanol
groups than the hydrophobic ones, indicating a reduced tendency to form tridimen-
sional aggregates among particles by hydrogen bonding between silanol groups.
Following the same argument, the "degre'e of hydrophobicity" in fumed silica can be
obtained from R,, the ratio of the areas under the bands at 2929 cm- (CH, group) and '
3438cm- (OH group); Aerosil R805 ( R 2 = 0.20) is around 60% more hydrophobic(i.e.

Ivanumara l c r l l I
FIGURE 1 IR spectra of fumed silica. a) Hydrophilic silica. b) Hydrophobic silica.
 FUMED- SILICA-FILLED ADHESIVES 27 1

there is a smaller amount of silanol groups) than Aerosil R812 ( R , = 0.12). The larger
value of R, for Aerosil R805 is in good agreement with the ratio of bonded carbon
atoms to silanol groups in those silicas (Table I). Therefore, Aerosil A200 is the most
hydrophilic and Aerosil R805 is the most hydrophobic fumed silica used in this work.

111.2. Characterizationof Solvent-Based PU Adhesives Modified with Silica

Brookfield viscosity (25°C) of the P U adhesives was monitored with time after their
preparation (Fig. 2). Addition of silica to the adhesives produced an increase of at least
50% in Brookfield viscosity. The Brookfield viscosities are similar and do not vary with
time in adhesives A1 and P1 (containing Aerosil 200 and R805, respectively), except
that there is a slight increase of viscosity during the first week after preparation of
adhesive A l . However, adhesives A2 and P2 show an increase of around 10% in
viscosity with time, which is more gradual in the adhesive containing hydrophobic
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silica, P2. The increase of viscosity with time shown by these PU adhesives can be
ascribed to the larger BET surface areas and the smaller particle size compared with
adhesives A1 and P1. A more comprehensive study of the influence of such properties of
silica on the flow properties of the P U adhesives has been assessed with rheological
studies.
Previous results'. ' ' related to the addition of different fumed silicas to liquid systems
and epoxy adhesives showed a different trend. Hydrophilic fumed silica interacted by
hydrogen bonding with solvent and/or polymer leading to higher viscosity than was
found with hydrophobic silica. The fact that, under the experimental conditions used in
this study, the hydrophobic or hydrophilic silicas gave similar results indicated a lack of
chemical interaction with the P U adhesives.
Flow curves were obtained in the rheometer under controlled shear stress (CSS).
Figure 3 shows the variation of viscosity as a function of shear rate obtained for all P U
adhesives. Adhesive A0 (without silica) gives Newtonian behaviour, and the addition of
silica partially modifies this behaviour towards pseudoplastic. The addition of silica to
the P U adhesives produces an increase of viscosity for a given shear rate, this increase
being more marked for the adhesives containing silica with high BET surface area and

Brookfield Viscosity (Pa I Brookfield Viscosity (Pa )

4F= +
5 1 51

1
' 3
3 - .
+ A0

-t2
3 A1
0 A o P1

A A2 1 A P2
l t
0 " " " 0 ' " ' ' .
0 10 20 30 40 50 6 0 0 10 20 3 0 40 5 0 6 0

t (days) t (days)

FIGURE 2 Variation of Brookfield viscosity (25°C) of silica-modified, solvent-based PU adhesives with

time after preparation. a) PU adhesives containing hydrophilic silica. b) PU adhesives containing hydropho-
bic silica.
 272 T. G. M-AGULLO et ul.

0
0 20 40 60 80 0 20 40 60 80

D (l/s) D (l/s)
FIGURE 3 Flow curves of silica-modified PU adhesives. a) PU adhesives containing hydrophilic silica. b)
PU adhesives containing hydrophobic silica.
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small particle size; the hydrophilic or hydrophobic nature of fumed silica does not seem
to modify the flow curves of the adhesives, probably because no chemical interaction
(i.e. hydrogen bond formation between silanol groups of silica and OH groups of
polyurethane) between silica and polyurethane polymer occurs.
The flow curves of Figure 3 were recorded with increasing as well as with decreasing
load. Between both sections there was a short holding time (three minutes) under
constant load. Whereas for the P U adhesive without silica both curves were coincident,
in the case of P U adhesives containing silica the viscosity for any given shear rate was
higher when the decreasing load experiment was carried out (negative thixotropy). The
area between the up and down curve as a measure of thixotropy has proven usefui.”
Flow curves in Figure 3 show a slightly higher degree of negative thixotropy in PU
adhesives containing hydrophilic silica with high surface area (Aerosil300).Negative
thixotropy can be attributed to a disordering of the physical structure of polyurethane
in the solvent by increasing the load (shear stress) during the rheological experiment, in
such a way that a higher resistance to deformation is obtained upon reduction of the
load. In fact, this kind of modification is quite stable because a second rising-decreasing
load experiment carried out immediately after the first run provides a flow curve
without any thixotropy and which is coincident with the decreasing curve obtained in
the first rheological run. Therefore, the modification of P U adhesive structure during
the rheological experiment probably consists of a better dispersion of the silica particles
in the adhesive matrix, in such a way that a more effective contact between poly-
urethane and/or solvent and silica is produced. Although the nature of such interaction
needs further study, perhaps negative thixotropy can be explained by a competition
between solvent and polyurethane to interact with silica.
Viscoelastic properties of the solvent-based P U adhesives have been assessed using
the rheometer operating in an oscillatory mode. Amplitude sweep studies were carried
out at a frequency of 1 Hz and the variations of storage modulus (G’),loss modulus (G”)
and loss factor (tan 6) were monitored. Figures 4 and 5 show the variation of G’ and tan
6, respectively, as a function of the strain for a frequency of 1 Hz. Addition of silica
increases the storage modulus and decreases the loss factor of the P U adhesives due to
an improvement of their viscous properties. The loss modulus (G”)is much larger than
 FUMED- SILICA-FILLED ADHESIVES 213

G' (Pa)

:::
10 10
+ A0
1
C) A 1

0.1 0.1
A2 A P2
.,.cw:
0.0 1 0.0 1
0.1 1 10 0.1 1 10

Strain Strain

FIGURE 4 Variation of storage modulus (G') as a function of amplitude. Frequency = 1 Hz. a) PU

adhesives containing hydrophilic silica. b) PU adhesives containing hydrophobic silica.
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10000
+ A0

c' A 1

A2
1000

100

10
.
+ A0

A
P1

P2

1
0.1 1 10 0.1 1 10

Strain Strain
FIGURE 5 Variation of loss factor (tan 6) as a function of amplitude. Frequency = 1 Hz. a) PU adhesives
containing hydrophilic silica. b) PU adhesives containing hydrophobic silica.

the storage modulus (G') because of the essentially viscous nature of the PU adhesive
solutions. There is a continuous decrease of G' with strain (Fig. 4) which becomes more
marked for strain values between 1 and 3 in the PU adhesive without silica. The
addition of silica retards the strain value at which the sudden decrease of G' occurs
(between 2 and 4), and at the same time that decrease of G' is more abrupt. Therefore,
the addition of silica improves the viscous properties of the adhesives and facilitates the
maintenance of such viscous properties in a broader range of strain. The most
noticeable modification of viscoelastic properties of the adhesives is produced by
addition of hydrophilic fumed silica Aerosil A300 (adhesive A2), the fumed silica with
the largest specific surface area and smaller particle size among those selected in this
study. However, variations in G' (and in tan 6) for adhesives P1 and P2 (prepared with
hydrophobic silica) and A l , are very similar, such variations being independent of the
specific surface area and particle size of silica.
Figure 6 shows the variation of G' for PU adhesives as a function of frequency; a
strain of 6 (where G' was found to be independent of the strain, according to Figure 4)
 214

100

10
1
0.1
~

:I
:I
:I
~ ~

-irZ-

-A- A 2
A1
':;;!m
T.G. M-AGULLO et a / .

10

0.1
~

;:
1 :
+ A0 A

- 4 -P1

-A-- P 2
o

20 40 60 80 100 20 40 60 80 100

Frequency (Hz) Frequency (Hz)

FIGURE 6 Variation of storage modulus (C) as a function of the frequency. Amplitude = 6. a) PU
adhesives containing hydrophilic silica. b) PU adhesives containing hydrophobic silica.
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was chosen to carry out the experiments. G' (and tan 6) values are similar for all the
adhesives, the presence of silica in the PU adhesives being irrelevant. For frequencies
lower than 40-50 Hz, tan 6 ( = G"/G') is very high (tan 6 --t co)because the viscous
properties predominate over the elastic properties of adhesives; for higher frequencies,
however, tan 6 is very small (tan 6 --t 0) and the elastic properties predominate over the
viscous ones. The addition of silica to the PU adhesives increases the frequency at
which the change from viscous to elastic properties is produced. Thus, whereas this
change is produced at 47 Hz for adhesive AO, the frequency is displaced to 53 Hz
(adhesive A l ) and 58 Hz (adhesive A2) for PU adhesives containing hydrophilic silica
(Fig. 6a). In the case of the adhesives containing hydrophobic silica, the change from
viscous to elastic properties is produced at 54 and 57Hz for adhesives P1 and P2,
respectively. Thus, the addition of the fumed silica with high specific surface area and
small particle size modifies more effectively the viscous properties of the PU adhesives.
In summary, the addition of silica to PU adhesives enhanced their viscoelastic
properties (increase of G and decrease of tan 6). No differences between the PU
adhesives containing hydrophobic or hydrophilic silica were found, but those silicas
with high specific surface area and small particle size produced a more noticeable effect.
Furthermore, although Aerosil A200 possesses the largest amount of silanol groups
among all the fumed silicas selected in this study, Aerosil A300 has a more marked effect
upon the rheological properties. This may indicate that no hydrogen bond between
silica and polyurethane is produced. This can also be confirmed with IR spectroscopy.
Figure 7 shows the IR spectra of all PU adhesives. All the IR spectra are very similar
and present bands typical of urethane and 0 - S i - 0 groups. There are no new bands or
noticeable modification in the intensity of those bands, indicating that no chemical
interaction between silica and polyurethane is produced. Furthermore, the nature of
the fumed silica added to the PU adhesive. does not affect the IR spectra of the
adhesives.
Table TV shows the contact angles of ethanediol and water on PU adhesive films.
Contact angles measured with water are higher than those obtained with ethanediol,
although the trend followed by the different adhesives is similar. Addition of silica to
 FUMED- SILICA-FILLED ADHESIVES 275
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FIGURE 7 IR spectra of PU adhesives. a) PU adhesives containing hydrophilic silica. b) PU adhesives

containing hydrophobic silica.

PU adhesives produces a decrease in contact angle (more marked with water) but there
are no great differences between the contact angles of PU adhesives containing silica.
Dispersion (yf), polar (yx), and total (y,) surface energies of PU adhesive films were
calculated by applying the Owens and Wendt method13*l4

Surface tension values of test liquids were:

0 Water:ye = 51.0mN/m; yi = 21.8mN/m; y L = 72.8mN/m.
Ethanedio1:yi = 19.0mN/m; yf = 29.3 mN/m; y L = 48.3 mN/m.
According to Table IV, adhesive A0 has a relatively important polar component of
the surface energy, due to the polar nature of polyurethane polymer. Addition of silica

TABLE IV
Total (y,), polar (y:) and dispersive ( y 3 components of the surface.free energy of PU adhesive films

A0 78 50 12.4 16.3 28.7

A1 69 48 27.9 6.3 34.2
A2 70 47 24.6 8.2 32.8
P1 68 47 29.1 6.1 35.2
P2 65 41 36.3 3.5 39.8
 216 T. G . M-AGULL6 et al.

increases the surface free energy of PU adhesive films, and a decrease of dispersive
component and an increase of the polar components of the surface free energy 01
adhesive are produced. Thus, the addition of silica might affect the orientation of the
polyurethane and, thus, an increase of polarity of the surface is produced. On the other
hand, in general, the specific surface area, the particle size and the hydrophilic/
hydrophobic nature of silica do not seem to modify greatly the surface free energy of
PU adhesives.
Consequently, the addition of silica to PU adhesives modifies their viscosity,
enhances their viscous properties and increases their surface free energy.The nature of
different silicas influences the viscoelastic properties of PU adhesives, but does not
affect their surface free energy.

111.3 Adhesion Properties of PU Adhesives to Surface Chlorinated Rubber

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Immediate (green)T-peel strength of synthetic SBR rubber/PU adhesives containing

silica/syntheticSBR rubber joints are given in Figure 8. Silica definetly has an effect on
adhesion, The adhesion to rubber of PU adhesivescontaining silica is nearly twice that
of the PU adhesive without silica. However, the specific surface area, particle size and
hydrophilicity/hydrophobicity of fumed silica do not affect green T-peel.
The improved adhesion of PU adhesives containing silica can be related to the
enhancement in viscosity and the modification of viscous properties, and with the
increased surface free energy produced when silica is added to PU adhesives.

IV CONCLUSIONS

1. Addition of silica to solvent-based PU adhesives increases their viscosity and

modifies their viscous properties and their wettability. Furthermore, the addition
of silica to PU adhesives increases the immediate adhesion to chlorinated rubber.
The presence of silica imparts “negative thixotropy” to the polyurethane/2-
butanone system.

P U Adhesives
FIGURE 8 Immediate T-peel strength for chlorinated SBR/PU adhesiw/ehlorinated SBR joints.
 FUMED- SILICA-FILLED ADHESIVES 277

2. Four fumed silicas were selected in this study with different specific surface area,
particle size and hydrophobic/hydrophilic nature. Differences in properties, in
general, do not greatly affect the viscosity, viscoelastic properties, surface free
energy and adhesion properties of PU adhesives.

Acknowledgements
Financial support from ClCYT (Projects no. MAT92/0067 and MAT92/0522) and from Generalitat
Valenciana (a grant was given to purchase the rheometer Physica MC100) is gratefully acknowledged.

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