International Journal of Adhesion & Adhesives 21 (2001) 411–422

Silicone sealants and structural adhesives$

Franc,ois de Buyl*
Dow Corning s.a., Industrial Park, area C, B-7180 Seneffe, Belgium
Accepted 27 March 2001

Abstract

The mode of preparation of silicones, their use and typical performances are reviewed. Particular attention is given to their use as
sealants and structural adhesives in construction and building applications where adherence properties for assembling two substrates
are important. An important part of this paper has been previously published ten years ago in French (Colas, Chimie Nouvelle 8(30)
(1990) 847–852) however the purpose with this paper is to bring some more up-to-date information’s on the above subject. r 2001
Elsevier Science Ltd. All rights reserved.

Keywords: A. Silicones; A. Sealants

1. Introduction: nomenclature and brief history
By analogy with ketones, the name silicone was given
in 1901 by Kipping to describe new compounds of the
formula R2SiO. These were rapidly identified as being
polymeric and corresponded to polydialkylsiloxanes,
with the general formula:
simultaneous presence of ‘‘organic’’ groups attached to
an ‘‘inorganic’’ backbone gives silicones a combination
of unique properties and allows their use in sealants and
adhesives compositions in fields as different as aerospace
(for their low and high temperature behaviour), electro-
nic (for their electrical resistance), medical (for their
excellent biocompatibility) and the building industries
(for their capability to seal materials of various nature,
and their good resistance to weathering) [1].
The most common silicones are the PDMS terminated
with trimethylsilyloxy groups, with the following structure:

The name silicone was adopted by the industry and most
of the time refers to polymers where R ¼ Me (poly-
dimethylsiloxanes, abbreviated as PDMS). Many other
groups, e.g. phenyl, vinyl or trifluoropropyl group, can
substitute the methyl group along the chain. The
These are linear polymers and liquids, even for large values
of n. The main chain unit, a(SiMe2O)a, is often shortened
by the letter D referring to the 2 oxygen atoms bonded to
the silicon atom. In a similar way, M, T and Q units can be
defined relative to the number of oxygen atoms as [2]:

$ This nomenclature allows an easy and fast description

This review is based on a lecture presented at a seminar on
Reactive Adhesives held in Loughborough on 29 November 2000. of polysiloxanes. The structure of the trimethylsilyloxy-
*Tel.: +32-64-888-333; fax: +32-64-888-950. terminated polydimethylsiloxane depicted above can
E-mail address: francois.debuyl@dowcorning.com (F. de Buyl). therefore be expressed as MDnM. It is possible to

0143-7496/01/$ - see front matter r 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 1 4 3 - 7 4 9 6 ( 0 1 ) 0 0 0 1 8 - 5
412 F. de Buyl / International Journal of Adhesion & Adhesives 21 (2001) 411–422

simplify the description of various structures like
(Me3SiO)4Si or tetrakis(trimethylsilyloxy)silane, which
becomes M4Q. Superscripts are used to indicate groups
other than methyl attached to the silicon atoms of the
polymeric backbone. For example vinyl-, longer alkyl-
chain, or simply hydrogen.
by hydrolysis of PDMS. Redistribution reactions
can be used to convert the other silanes and increase
the commercial yield of the production equipment
[4].
It is also possible to replace the chlorine groups by
alcoholysis:

2. From quartz to silicone

In this way, various silanes with different functionalities
Silicones are obtained in a three steps synthesis:
can be prepared, e.g. alkoxy and vinyl: these allow
1. Chlorosilane synthesis, coupling reactions to take place between inorganic
2. Chlorosilane hydrolysis, surfaces and polymers in composite manufacturing
3. Polymerisation and polycondensation. [5,6].

2.1. Synthesis of chlorosilanes 2.2. Hydrolysis of chlorosilanes

Today, silicones are obtained commercially from
chlorosilanes prepared following the direct process of
Rochow [3] and using Si metal obtained from the
xMe2 SiCl2 - yHOðMe2 SiOÞn Hþ
ðmainly 4Þ: linears
ð1Þ ð2Þ
PDMS are then obtained by the hydrolysis of the
dimethydichlorosilane in presence of an excess of water
according to the following reaction [2]:
zðMe2 SiOÞm with n ¼ 20250 and m ¼ 3; 4; 5; y
cyclics
ð3Þ

reduction of quartz at high temperature:
SiO2 þ2C-Si þ 2CO
and methylchloride obtained by condensation of metha-
nol with hydrochloric acid:
cat
CH3 OH þ HCl - CH3 Cl þ H2 O:
The reaction giving chlorosilanes takes place in a
fluidised bed of silicon metal powder in which flows a
stream of methylchloride, usually at temperatures of
250–3501C and at pressures of 1–5 bars. A mixture of
different silanes is obtained containing mainly the
dimethydichlorosilane, Me2SiCl2 [2]:
This heterogeneous and exothermic reaction gives
formally a disilanol intermediate [Me2Si(OH)2], which
readily and rapidly condenses with HCl acting as a
catalyst to give a mixture of so-called linears (2) and
cyclics (3) oligomers by inter- or intramolecular
condensation. This mixture separates from the aqueous
acid phase, the ratio between the two types of oligomers
depending on the hydrolysis conditions (concentrations,
pH, solvents).
These oligomers are water-washed, neutralised and
dried. The HCl is recycled and reacted with methanol to
give the methylchloride used in the direct process
described above.

Yield Bp (1C)
(weight %) 2.3. Polymerisation and polycondensation
xSi þ Me2SiCl2 (1) >50 70.0
cat
yCH3 Cl - The linear (2) and cyclic (3) oligomers obtained by
MeSiCl3 10–30 66.4 hydrolysis of the dimethyldichlorosilane have too short
Me3SiCl o10 57.9 chains for most applications. They must be condensed
MeHSiCl2 o5 41.0 (linears) or polymerised (cyclics) to give macromolecules
other silanes 5 F of sufficient length [7–9].
Opening and polymerising cyclics, (R2SiO)m, to form
The reaction, exothermic, proceeds in the presence long linear chains is catalysed by many acid or base
of a copper-based catalyst and has a yield of compounds [4] and gives at equilibrium a mixture of
85–90%. The various silanes are separated by dis- cyclic oligomers plus a distribution of polymers. The
tillation: as the boiling points are close together, proportion of cyclics will depend on the substituants
long distillation columns are always seen at sili- along the chain, the temperature and the presence of a
cone plants. The dimethyldichlorosilane (1), which is solvent. Polymer chain length will depend on the
separated, becomes the monomer for the preparation presence of substances capable of giving chain ends.
 F. de Buyl / International Journal of Adhesion & Adhesives 21 (2001) 411–422
Polymer chain end functionality will depend on the
presence of end-blocking agents of various natures.
Linear condensation is an equilibrium reaction
catalysed by many acids or bases [4,7]:
to give long chains by intermolecular condensation of
terminals SiOH. A distribution of chain length is
obtained and longer chains are favoured when working
under vacuum and/or at elevated temperatures to reduce
the residual water concentration. Acid catalysts are
more efficient when the organosilanol carries electron-
donating groups, base catalysts when it carries electron-
withdrawing groups. Some catalysts can induce redis-
tribution by attacking the polymer chain with the
formation of cyclics. This will be important when
condensing a mixture of linear oligomers such as
dimethyl- and methylphenylpolysiloxanes: a sequential
HO2ðMe2 SiOÞx 2H þexc: MeSiðOAcÞ3 -@2AcOH ðAcOÞ2 MeSiOðMe2 SiOÞx OSiMeðOAcÞ2
ð5Þ
polymer will be obtained in the absence of redistribution
while a random polymer will result if a catalyst capable
of opening the main chain is used.
Apart from the above polymers, reactive polymers
can also be prepared. This can be achieved when re-
equilibrating oligomers or existing polymers:
to obtain a poly(dimethyl-co-methylhydrogenosiloxane)
terminated with trimethylsiloxy groups. This polymer
can be further functionalised using an addition reaction:
The above polymers are all linear apart from the cyclics,
but these are also made up of difunctional units, D.
Apart from these, branched polymers or resins can be
prepared if, during hydrolysis, a certain amount of T or
Q units are included, which will allow a three-dimen-
sional expansion of the material. This can be achieved if
considering the hydrolysis of the methyltrichlorosilane
in the presence of trimethylchlorosilane.
3. Silicone crosslinking
The silicone polymers are easily transformed into a
three dimensional network and an elastomer via a cross-
linking reaction, which allows the formation of chemical
413
bonds between adjacent chains. This is achieved
according to one of the following reactions: cross-
linking by condensation, addition or radical reaction.
3.1. Crosslinking by condensation
This method is used in sealants such as the ones
available from Do-it-yourself shops. Silicone sealants
are also widely used by professionals in original
equipment manufactories for glazing sealing windows
and doors for either residential or public buildings.
These products are ready to use and require no mixing:
cross-linking starts when the product is squeezed from
the cartridge and comes into contact with moisture from
the atmosphere and/or present at the surface of the
substrate.
Most silicone sealants are formulated from a reactive
polymer prepared from a hydroxy-endblocked-polydi-
methylsiloxane and a large excess of methyltriacetox-
ysilane:
:
As a large excess of silane is used, the probability of 2
different chains reacting with the same silane molecule is
remote and all the chains are endblocked with 2 aOAc
functions (5). The resulting product is still liquid and
can be stored in sealed cartridges or aluminium foils
sausages.
Upon opening and contact with the ambient
moisture, the acetoxy groups are hydrolysed to
give silanols, which allow further condensation to
occur:
In this way, 2 chains, (5)+(6) have been linked, and the
reaction will proceed further from the remaining acetoxy
groups on (7). An organometallic tin catalyst is typically
414 F. de Buyl / International Journal of Adhesion & Adhesives 21 (2001) 411–422
used. This cross-linking requires that moisture diffuses
within the product and the cure will proceed from the
outside surface, towards the inside. These sealants
are called 1-part sealant RTV (room temperature
vulcanisation) but actually require moisture as a
second component. Acetic acid is released as a by-
product of the reaction and corrosion problems are
possible on substrates like concrete, with the formation
of a water-soluble salt at the interface (and loss of
adhesion at the first rain!). To overcome this, other
systems have been developed: 1-part sealants releasing
less or non corrosive by-products, e.g. oxime using the
oximosilane RSi(ON ¼ CR20 )3 or alcohol using the
alkoxysilane RSi(OR0 )3 instead of the above acetoxysi-
lane.
Condensation curing is also used in 2-part systems
where cross-linking starts upon mixing the two
components, e.g. an hydroxy endblocked polymer
and an alkoxysilane such as tetra n-propoxysilane
[7]:
Here, no atmospheric moisture is needed. Although
residual moisture presents in filler helps condensation
reaction to occur, organotin salt is usually used as
catalyst but it also limits the stability of the resulting
elastomer at high temperatures (reversion reaction).
Alcohol is released as a by-product of the cure leading to
a slight shrinkage upon cure: this precludes the
fabrication of very precise objects (0.5–1% linear
shrinkage).
3.2. Crosslinking by addition
The shrinkage problem encountered with both 1- and
2-parts condensation systems can be eliminated when
using an addition reaction to achieve cross-linking.
Here, cross-linking is achieved using vinyl endblocked
polymers and reacting them with SiH groups carried by
functional oligomers such as described above (4). A few
polymers can be bonded to this functional oligomer (4),
as follows [4]:
where  represents the remaining valences of the silicon
atom in intermediate (4).
The addition occurs mainly on the terminal carbon
(b–addition) and is catalysed by Pt or Rh metal
complexes, preferably organometallic compounds to
enhance their compatibility with the medium. The
following mechanism has been proposed (oxidative
addition of the SiH on the Pt, H transfer on the
double bond in the b–position, and reductive
elimination of the product):
where to simplify, other Pt ligands and other Si
substituents are omitted.
There is no by-product with this reaction: moulded
pieces made with a product using this cure mechanism
are very accurate (no shrinkage). However, handling
these 2-part products (polymer and Pt catalyst in one
component, SiH oligomer in the other) requires some
precautions: the Pt in the complex is easily bonded to
electron-donating substances like amine or organosul-
phur compounds to form stable complexes with these
poisons, rendering the catalyst inactive. Caution needs
also to be taken as the reaction of SiH intermediate with
water may lead to highly exothermic process, liberating
explosive hydrogen gas.
3.3. Crosslinking with radicals
Efficient cross-linking with radicals is only achieved
when some vinyl groups are present on the polymer
chains. The following mechanism has been proposed for
the cross-linking made by radicals, which can be
generated from organic peroxide [6]:
Rd þ CH2 ¼ CH2Si 
-R2CH2 2CH2Si 
RCH2 2CHd 2Si  þCH3 2Si 
-RCH2 2CH2 2Si  þ  Si2CHd2
 SiCH2d þ CH2 ¼ CH2Si 
-  Si2CH2 2CH2 2CHd 2Si 
 Si2CH2 2CH2 2CHd 2Si  þ  Si2CH3
-  Si2CH2 2CH2 2CH2 2Si  þ  Si2CHd2
2  Si2CHd2 -  Si2CH2 2CH2 2Si 
where  represents 2 methyl groups and the rest of the
polymer chain.This reaction is used for high consistency
silicone rubbers (HCR) like the ones used in extrusion or
injection moulding and which are cross-linked at
elevated temperatures: the peroxide is added before
use. During cure, some precautions are needed to avoid
the formation of voids by the peroxide’s volatile
residues; post-cure may also be necessary to remove
these volatiles, which can act as depolymerisation
catalysts at high temperatures.
4. Properties of silicones
The position of the silicon element in the periodic
table, led to a belief of the existence of analogue
 F. de Buyl / International Journal of Adhesion & Adhesives 21 (2001) 411–422 415

compounds analogous to carbon. Most of these

analogue compounds do not exist or behave very
differently. There are few similarities between SiaX
bonds in silicones and CaX bonds [2,4]:

()
Element (X) Bond length (A Ionic character (%)
SiaX CaX SiaX CaX
Si 2.34 1.88 F 12
C 1.88 1.54 12 F
H 1.47 1.07 2 4
O 1.63 1.42 50 22

Between any given element and Si, bond lengths are

longer than for C with this element. The lower
electronegativity of Si (1.8) vs. C (2.5) leads to a very
polarised SiaO bond, highly ionic and with a large
bond energy, 452 kJ/mole (108 kcal/mol). The SiaC
bond has a bond energy of 7318 kJ/mole (76 kcal/mol),
slightly lower than a CaC bond while the SiaSi bond
is weak, 193 kJ/mole (46.4 kcal/mole). These values
partially explain the stability of silicones: the SiaO
bond is highly resistant to homolytic scission; on the
other hand, heterolytic scissions are easy, as demon-
strated by the re-equilibration reactions occurring
during polymerisations catalysed by acids or bases.
Another example of the difference between analogues
is the tetravalent diphenyldisilanol, (C6H5)2Si(OH)2,
which is stable while its carbon equivalent, a gem-diol,
will dehydrate. The SiaH bond is weakly polarised, but
here in the direction of a hydride, and is more reactive
than the CaH bond. Overall, there are few similarities
between a silicone polymer and a hydrocarbon polymer.
Silicones displays the unusual combination of an
inorganic chain similar to silicates and often associated
with high surface energy but with side methyl groups
that are, on the contrary, very organic and often
associated with low surface energy [10]. The SiaO
bonds are strongly polarised and without protection
should lead to strong intermolecular interactions [4]: yet,
the methyl groups, only weakly interacting with each
other’s, shield the main chain. This is made easier by the
absence of side-groups at the O atom, and therefore high
flexibility of the siloxane chain. The resulting open
structure is the basic reason for the lower barrier to
rotation around the SiaO bond, of about 2.5 kJ/mol,
approximately equal to RT at room temperature,
compared with barriers of about 17 kJ/mol in alkanes
[11]. Thus the polydimethylsiloxane chain can adopt
many conformations.
The inequality of the Si (ySi D701) and O (yO D371)
valence angles means that, distinct from carbon and
carbon-oxygen chains, the all-trans chain of polydi-
methylsiloxane is not an extended chain. It shows a
Fig. 1. Helical conformation of polydimethylsiloxane backbone.
closed polygon after about eleven repeating units (22
chain bonds), which results in a flat helical chain
conformation [10] (Fig. 1). Thus the ease with which
silicones may adopt many conformations is confirmed
by monolayer absorption studies on water: two struc-
tures have been proposed, an open one where the
SiaOaSi bonds are oriented towards the aqueous
phase, and a more compact one where the chain adopts
the helical structure The important point is the low
energy difference between these two structures, demon-
strating once again the flexibility of the siloxane chain
[7].
Despite a very polar chain, silicones can be compared
to paraffin, with a low critical surface tension of wetting.
The surface activity of silicones is displayed in many
circumstances [7,10]:
* The polydimethysiloxanes have a low surface tension
(20.4 mN/m) and are capable of wetting most
surfaces. With the methyl groups pointing to the
outside, this gives very hydrophobic films and a
surface with good release properties, particularly if
the film is cured after application. Silicone surface
tension is also in the most promising range consid-
ered for biocompatible elastomers (20–30 mN/m).
Silicone sealants based on PDMS polymer show
416 F. de Buyl / International Journal of Adhesion & Adhesives 21 (2001) 411–422
similar surface characteristics, however some differ-
ence between various curing chemistry may be
exploited to the benefits of specific customer require-
ments [12].
* Silicones have a critical surface tension of wetting
(24 mN/m) higher than their own surface tension: this
means that silicones are capable of wetting them-
selves; this will promote good film formation and
good surface covering.
* Silicone organic copolymers can be prepared with
surfactant properties, with the silicone as the hydro-
phobic part, e.g. in silicone glycols copolymers.
The low intermolecular interactions in silicones has
other consequences [10]:
* Glass transition temperatures are very low, e.g. 146 K
for a polydimethylsiloxane compared to 200 K for
polyisobutylene, the analogue hydrocarbon.
* The presence of a high free volume compared to
hydrocarbons explains the high solubility and high
diffusion coefficient of gas into silicones: silicones
have a high permeability to oxygen (Table 1),
nitrogen or water vapour, even if water is not capable
of wetting a silicone surface; as expected, silicone
compressibility is also high.
* In silicone, the activation energy to the viscous
movement is very low, and the silicones viscosity is
less dependent on temperature compared to hydro-
carbon polymers; moreover, chain entanglements are
involved at higher temperature and contribute to
limit the viscosity reduction [4].
The presence of groups others than methyl along the
chain leads to a reduction of the polymer’s thermal
stability, but with this substitution, some of the above
properties can be modified:
* A small percentage of phenyl groups along the chain
perturb sufficiently to affect crystallisation and allow
the polymer to remain flexible at very low tempera-
tures; the phenyl groups also increase the refractive
index.
* Trifluoropropyl groups along the chain will change
significantly the solubility parameter of the polymer,
which enables copolymers of PDMS with methyl,-
trifluoropropyl siloxane blocks to be used for
Table 1
Permeability coefficient to oxygen
107 P O2 (cm2 s@1 bar)
PDMS 605
Poly methyl phenyl siloxane 25
Poly tetrafluoroethylene 4.2
Polyethylene 0.4
Nylon 6 0.04
preparing elastomers with little swelling in alkane or
aromatic solvents.
5. Applications to silicones adhesives and sealants
The main property of a sealant is that of sealing a
joint between various building components or materials.
Sealing is actually taken to understand the provision of
a barrier against specific environmental influences
whichFdepending on the application envisagedFmay
include humidity, driving rain, still or pressurized water,
draughts, sand, dust, etc. [13]. The sealing properties are
basically achieved when the sealant adheres to the
adjoining based materials and is also able to absorb
movements of the joint without tearing away form the
substrate, or without tearing apart itself.
In order to ensure a long life expectancy of a building
joint seal, a sound knowledge of the chemistry and
physical properties of the selected sealant is required.
Among the main three types of sealants that can be
found on the marketFhardening, plastic, elasticFsili-
cone sealant are particularly appreciated for their elastic
behaviour. The ability of silicone sealant to absorb
movements is therefore typically the highest compare to
other families of sealant, which means that silicone
sealants can afford 25–30% joint movement as ex-
pressed as the percentage of initial joint width.
Regardless of whether they are formulated as one or
two components systems, the chemistry of elastic sealant
is characterized by the fact that a flexible polymer
component is ‘‘cross-linked’’ to form a three-dimen-
sional structure. This network has elastic properties that
can be determined by macroscopic measurements, like
tensile strength versus elongation strain plots according
to standard test method used in the building industry
[18] (Fig. 2).
The reactive polymer contained in the sealant
corresponds to a spiral bedspring which has loops
attached to its ends. The cross-linking agent corresponds
to punctiform fixing device with three arms, which is
able to anchor three end loops of the spiral bedsprings at
one point. As cross-linking is progressing further, a
three-dimensional network is building-up, and we may
easily imagine that such a structure can be elongated
and compressed in all three dimensions and has a high
degree of elastic restoring capacity.
Plasticizers are typically added to silicone sealant
compositions in order to adjust rheology of the paste,
and make easier for the polymer chains to slide over
when the cured material is elongated or compressed in
his real-life joint configuration. The effect of adding
non-reactive plasticiser, which is typically 100–
1000 mPa s viscosity trimethylsilyl-terminated PDMS,
is actually reducing the modulus and hardness of the
sealant.
 F. de Buyl / International Journal of Adhesion & Adhesives 21 (2001) 411–422
Fig. 2. (a) Tensile strength versus percentage strain for Tensile-
Adhesive joint between anodised aluminium and glass for a typical
low modulus neutral cure (condensation) sealant. Joint dimension are
12  12  50 mm3 size. Speed of testing in tensile mode is 5 mm s@1. (b)
Same specimen maintained at 100% extension for 24 h. Elastic
recovery is >95% for typical silicone sealant.
Overall, a silicone sealant formulation may contain up
to 10 components as described in Table 2.
The speed of cure of so-called one-component-room-
temperature-vulcanisation (1-RTV) depends naturally
on the moisture level in the ambient air, i.e. typically
these sealants cure more slowly when there is little
moisture in the atmosphere than when the percentage
relative humidity is high. However, it is surprising to
note the number of queries received by sealant
manufacturers during autumn and winter months,
which indicates that many applicators of 1-RTV
sealants are not as familiar with this phenomenon or
the dependency of curing properties on temperature and
relative humidity as it is commonly assumed.
The number of different possible types of cure systems
that silicone sealants can offer is far higher than with
any other raw material base. In theory, this makes
possible to develop the ‘‘ideal’’ silicone sealant for
almost every sort of application.
Basically, all 1-RTV and 2-RTV silicone sealants and/
or adhesives can be divided into three classes: acid,
neutral and alkaline, depending on the chemical by-
product that is released during the curing process of the
417
sealant (see Table 2). Of all these cure systems, 1-RTV
acetoxy, or acetic acid system is without any doubt the
most widely used. Despite the fact that use of acetoxy
sealant is restricted because the corrosion phenomenon
it causes to certain metals and its reaction with alkaline
surfaces, it does offer excellent adhesion to glass and
ceramic surfaces and has therefore become an important
adhesive in the glass and sanitary industries [14].
To provide a solution to the above mentioned
incompatibility issue of acetoxy sealant in a large
number of applications, neutral cure systems have been
developed since the beginning of the 1970’s. In the
neutral family of silicone sealant, we may find basically
the oxime, which are based on cross-linking agents that
liberate methyl-ethylketoxime upon cure, and the
alkoxy, which are based on all sorts of cross-linking
agents that liberate methanol, ethanol, and possibly iso-
propanol. Alkoxy and oxime cure systems are now
available in either transparent (silica filled composition
only) or non-transparent/solid colour (silica and/or
chalk filled composition containing appropriate pig-
ment) versions. Their chemical neutrality enables these
systems to offer a wide range of adhesive bonding
capabilities to metals (copper, brass, zinc, galvanized
steel, aluminium), including polyester powder coated
metals, and all sorts of brick, concrete masonry, and
marbles. A primer might be required for some difficult
metals and in applications where we expect the
assemblage being exposed to severe weathering condi-
tions.
5.1. Thermal ageing resistance
Silicones are used in numerous applications requiring
high temperature resistance [4,7]. During thermogravi-
metry and in absence of impurities, the polydimethylsi-
loxane degradation only starts at around 4001C. Yet the
term thermal stability must be used with caution, as it’s
meaning is largely dependent on the application
considered and often implies many different properties:
depolymerisation, oxidation or fire resistance. Applica-
tions are diffusion pump fluids, heat transfer fluids,
elastomers for oven seals or for electrical cable insula-
tion. In case of fire, a silicone elastomer insulating an
electrical cable will decompose to give insulating silica
rather than electrically conducting carbon as produced
by the combustion of an elastomer formulated with
hydrocarbon polymer.
Depending on their formulation and cure chemistry,
commercial silicone sealants can be exposed to max-
imum service temperature of 120–1801C. Silicones can
be however degraded, particularly at elevated tempera-
tures, by substances capable of acting as depolymerisa-
tion catalysts, such as metals salts, fillers, and cure by-
product that show acid or basic character [4,17].
418 F. de Buyl / International Journal of Adhesion & Adhesives 21 (2001) 411–422

Table 2
Typical components in a silicone sealant formulationa

Component Typical chemical Function

Polymer Hydroxyl BSiOH, Binder required to form the elastomeric network

Vinyl BSiaCH2 ¼ CH2
Plasticizer Trimethylsilyl- BSi(CH3)3 Adjustment of mechanical properties such as hardness, visco-elasticity,
rheology.
Paraffin oil of high boiling point. Organic plasticizers (diluents) may reduce formulation cost as well as
providing some special ease-of-use properties.
Reinforcing fillers (active) Fumed silica (SiO2); precipitated calcium Thixotropic reinforcers (non-slump), adjustment of mechanical prop-
carbonate (CaCO3) carbon black erties (cohesion); provide toughness to the elastomer as opposed to
brittle materials.
Non-reinforcing fillers Ground calcium Carbonate (CaCO3) Reduce formulation cost, adjust rheology and mechanical properties.
(passive)
Cross-linkers Acetoxy BSi(OC(O)CH3)3 Cross-linking of the polymeric component; privide network structure.
Alkoxy BSi(OR)3
Oxime BSi(ON ¼ CRR0 )3
Amine BSi(NHR)3
Specific additives Catalysts: organo-Sn, -Ti, -Pt, -Zn, -Rh Acceleration/retardation of the curing process;
Adhesion Promoter: XaCH2CH2- Enhance the adhesive bonding properties against substrates;
CH2aSi(OR)3
Water scavenger Prolonging shelf life.
Pigments Offering wide range of colours.
Rheology additive Adjust ease-of-use characteristics and features.
Biocides Provide fungus growth resistance, e.g. sealing of sanitary devices and
equipments.
a
Note typically: R and R0 =CH3, C2H5. X=organic functional group like amino, mercapto, vinyl, epoxy, methacryloxy, etc.

5.2. Chemical ageing and weathering resistance
Silicones sealants are used in the building industry as
sealing or coating materials for their outstanding
durability and resistance to a variety of weathering
conditions [14–16]. This behaviour is a direct result of
the unusual organic/inorganic hybrid nature of their
siloxane polymer backbone, which provides the low
reactivity of the various bonds towards polluted air or
water, the hydrophobic character limiting their contact
with many aqueous solutions and allows their use in the
presence of many chemical compounds, and their
transparency to UV radiation. Other properties make
them suitable as building sealants: silicones are easy to
pigment as they are transparent at visible wavelengths;
and the low chain-to-chain interaction results in
elastomers with very low modulus, which reduces
permanent join stresses and increases longevity of
assemblages. Using copolymers can reduce swelling of
elastomers in common solvents.
The role of the various composition ingredients in the
durability of a sealant, and in particular the durability of
its adhesive bonding properties during service-life in real
aging conditions has been discussed recently [17].
Fundamental questions have also been recently raised
e.g. ‘Whether the pressure on formulators to reduce
formulation cost is compatible with durability?’ and
‘What criteria should a sealant specifier use to select a
durable sealant for any particular application?’
For instance, most of the siloxane polymers and
plasticizers used in commercial silicone sealants are of
the same chemical nature, i.e. have a PDMS backbone.
Therefore, differences in the durability of 100% silicone
sealants are essentially due to differences in their cure
chemistry (catalyst and cross-linker), these differences
being typically noticeable after prolonged periods of
weathering [17].
Due to the low glass transition and melting tempera-
tures of PDMS polymer, 100% silicone sealant do not
substantially stiffen at lower service temperature.
Typically, their Young’s modulus is maintained within
a 725% range over a temperature range of @40–
+801C.
Actually, exposure of silicone sealants to water or
high humidity at moderate temperature conditions
initially results in a completion of their cure process
accompanied by an overall improvement in their
physical properties, e.g. increase in tensile strength,
elongation at break and adhesion against substrates.
This is illustrated by the effect of pre-conditioning
tensile-adhesive joint specimens used for testing adher-
ence properties of sealants according to building
industry standards (cf Fig. 3) [18].
5.3. Adhesive properties
Sealants are designed for use in adhesive joints that
undergo significant dimensional changes during their
 F. de Buyl / International Journal of Adhesion & Adhesives 21 (2001) 411–422
Fig. 3. Typical 4-sided structural glazing design.
service life. Understanding physics of cure of 1-RTV
issued from the various silicone sealants curing chem-
istry, as well as the long-term performance of sealant
joints is therefore critical to the sealant developer and
specifier [14,19]. For a rapid overview of what are
important aspects of the science of adhesion, the reader
may refer to reasonably recent publication on the
subject, which compares theories and adhesives systems
for their respective peculiarities [20].
An important aspect that readily needs to be well
understood is the phenomenon of gradients that occurs
across a deep section of any joint design, which is
directly linked to the curing process triggered by the
moisture entrance from the outer layer down to the
inner regions of the joint. The installation of such a
gradient has direct consequences on ultimate adhesive
strength between the sealant and the substrates.
It has been shown that the depth of cure (z) of a
silicone sealant with butanone ketoxime reactive groups,
and some moisture curing isocyanate adhesives is given
by the following equation [21,22]:
z ¼ ð2VPptÞ1=2 :
Here V is the volume of sealant that reacts with 1 mole
of water, P the permeability coefficient for water across
the cured sealant, p the vapour pressure of water and t
the time. The assumptions that underlie the above
equation are that the chemical reactions involved in cure
are much faster than the permeation of water in the
cured layer, and that the reactive groups are immobile.
Any water that passes through this cured layer quickly
reacts with uncured sealant, and thus the barrier is
thickened. There is thus a distinct barrier between cured
and uncured sealant.
In a recent study [23,24], sealant that is essentially
ethoxy-terminated PDMS with a non-reactive PDMS
and a mixture of reactive substances (organosilanes and
organotitanate), which perform as cross-linking and
419
coupling agents, has been studied. The depths of cure (z)
at static humidity’s and temperatures have been
measured. Plots of cure depth (z) against the square
root of time are initially linear, and later deviate from
this line. The point at which this deviation begins is
termed the kink, and beyond the kink the slope of the
line becomes increasingly positive. The kink separates
what we called the outer and inner regions of cure. The
time at which the kink occurs increases with tub depth.
These observations have prompted the authors to
measure swelling of the cured sealants from various
depths in toluene, and to study adhesion to aluminium
and glass in the two regions.
Mean joint strengths with standard deviations and
modes of failure are shown in Table 3. These show that
joints taken from the outer regions are stronger than
those taken from the inner regions.
Conclusions from all experiments are actually con-
sistent with the diffusion of organosilanes species to the
outer region during cure. Initially these are uniformly
distributed through the samples. The cure process
involves indeed water diffusing into the sealant from
the outer face, to reach reactive groups in the PDMS,
silanes and titanates. However once they are consumed
there will be a flux of organosilanes molecules in the
opposite direction to replace them, as well as volatiles
by-products. This flux meets the water molecules and
reacts with them. The effect of this is that the rate of cure
can be reduced whence zoð2VPptÞ1=2 , which is what we
have observed with most sealant and in most curing
conditions. Eventually the concentration of silanes and
titanates towards the bottom of the tubs is diminished,
and this gives rise to the increase in the gradient of the
plots of z against t1=2 . There will be overall more cross-
linking and coupling species reacted in the outer region
and therefore an increase of the strengths of lap joints by
increasing both the cohesion of the sealant and the
strength of the interface with the substrate. Hence
420 F. de Buyl / International Journal of Adhesion & Adhesives 21 (2001) 411–422
Table 3
Testing of single lap joints against aluminium and glass for 1-RTV Alkoxy cure silicone sealanta
T1C rel. hum. (%) Joint strengths (N) with mode of failure
Aluminium–aluminium
Inner region
5 100 196736C*
25 75.4 167752I
35 100 115713I+C
a
Failure modes are shown by the following codes: C=100% cohesive failure, C*=dominantly cohesive failure. I=100% interfacial failure,
I*=dominantly interfacial failure, I+C=mixed failure.
increases in strengths in the outer region are recorded in
Table 3 for some joints that failed cohesively, and for
others where failure was interfacial.
The interpretation of the swelling behaviour is less
straightforward, and this is because the number of cross-
link sites in the PDMS, namely the SiaOR end groups,
is constant, and will not be increased by further amounts
of organosilanes and organotitanates in the system.
What seems possible is that with increasing amounts of
these, increasingly longer chains from the polymerised
silanes and titanates link the end groups in PDMS, or
interpenetrating networks are formed of PDMS and the
cross-linking agents. If the former is the case the reduced
swelling in toluene in the outer region will be due to the
tri-dimensional polysiloxane ‘‘resin’’ being less compa-
tible than linear PDMS backbone with toluene. How-
ever both of these views are consistent with the diffusion
of cross-linking and coupling species into the outer
region.
5.4. Structural adhesives
The need of architect and designers for perfectly
smooth glazed facade where the architectural fusion of
the building skeleton with the facade could be reached
appears as early as in the twenties and became a reality
only after silicone sealant had been developed in the
fifties and the structural glazing techniques being made
technically possible in the sixties. Structural Glazing is
the method of bonding glass, ceramic, metal, stone or
composite panels to the frame of a building utilising the
strong and long-term adhesive benefits of silicones
(Fig. 3). This technique provides the architects with
limitless design possibilities, the concept of totally glazed
facade, while ensuring full performances to the building
owner as silicone sealant not only improve the air and
weather tightness of the structure but also support the
panels and increase the rigidity of the facade while
providing a flexible rubber anchorage that absorbs
differential movements between dissimilar materials
from thermal or even seismic loading or bomb-blasting
[25].
Glass–glass
Outer region Inner region Outer region
283720C 255741C 339747C
292718C* 232768I* 344754I
257739C* 272723C 304724C
In Structural Glazing, the silicone adhesive plays a
triple role. It resists the constraints imposed by the effect
of the wind on the glass elements combined with a
permanent load in case of unsupported system, roof
glazing or sloped glazing. In addition, it withstands the
imposed movement created by the differential thermal
dilatation between the glazing element and the internal
structure. Essential is therefore to use a sealant material
with best viscoelastic properties and not a rigid adhesive
as the material should resist to both a load and a
movement without creating stresses at the glass interface
or failing cohesively. Owing to its excellent adhesion to
glass, its thermal stability, its elasticity, and its resistance
to UV radiation and ozone, silicone proved to be
extraordinarily suitable for the composition of such
sealant. The explanation lies in the fundamental
chemical properties of this type of material, which are
in fact close to the glass structure.
Basically, Structural Glazing technology using sili-
cone sealants has been proven answering the best to the
technical requirements these sorts of architectures
impose: mechanical resistance and stability, safety in
normal conditions of use and in case of fire, respect of
hygiene, health and environments aspects, protection
against noise, and needs to reduce energy consumption
and retain heat in the buildings. This later argument is
reinforced by the commitment given at the Kyoto
conference by the European Union regarding Carbon
Dioxide emissions, which has literally catalysed new
developments in the area of glass and facade in
architecture. From passive, facade systems are becoming
reactive: to save energy is not anymore the only
objective but also to supply energy to the building.
5.5. Release properties
Transfer paper for self-adhesive labels is obtained
with silicone paper coatings [10]. Silicones are applied as
liquid before curing them, usually via an addition
reaction to give film coated paper; self-adhesive labels
can be applied to this paper without risk of permanent
bonding: the adhesive surface tension (30–40 mN/m)
does not allow enough wetting of the silicone, and this
 F. de Buyl / International Journal of Adhesion & Adhesives 21 (2001) 411–422
reduces the actual contact surface and the adhesion
work; this will allow easy removal of the label from the
silicone coated paper.
Similarly, a silicone elastomer can be used to prepare
a mould from an original object like a sculpture, which
is covered with a 2-part elastomer. The low surface
tension of the silicone will allow a perfect wetting of the
original surface and will give, after cure, a perfect
negative. Plaster or a thermosetting resin (polyester,
epoxy, y) can be cast in this mould to give a copy that
has all the details of the original master; the low surface
energy of the silicone will allow an easy demoulding of
this copy.
5.6. Safety and impact on the environment
Most siloxanes have a very low level of toxicity; this
explains the use of silicone fluids as ingredients in many
cosmetic products and of silicone elastomers as materi-
als in biomedical applications [4].
Silicone elastomers are currently used in many
approved class II or class III medical devices as defined
by the EEC Medical Device Directive, e.g. as electrical
insulation on pacemaker leads or as pacemaker coating,
as tubing in cardiopulmonary bypass sets or in hydro-
cephalic shunts because of the excellent biocompatibility
of the PDMS polymers: again the low reactivity of all
the bonds present in dimethylsiloxane, their insolubility
in aqueous media and the low surface energy of the
resulting elastomers are all contributing factors. Sili-
cones are also used in pharmaceutical formulations as
excipient or drug carrier, e.g. fluids in dermatological
sprays or elastomers in inserts because of the high
permeability of a silicone elastomer and the high but
controlled drug diffusivity that is made possible; silicone
are also used as active, e.g. fluids used in many
deflatulant pharmaceutical compositions because of
their low surface tension and defoaming performances.
The most common PDMS polymers, e.g. PDMS with
viscosities between 10 and 100,000 cP, have a very low
acute toxicity via the main routes of administration [26];
orally they are not absorbed but excreted unchanged
and they are not absorbed through the skin; repeated
oral, dermal or inhalation dosage showed no significant
adverse effects to various species; in-vitro studies
showed no indication of mutagenic potential. This
explains why PDMS polymers have been widely used
in application involving humane exposure.
Recent work has clarified the fate of silicone in the
environment [27]. In the environment, there is no
evidence suggesting a negative impact. The most widely
used, the PDMS, are nearly insoluble in water and
absent from the water cycle. Because of their extremely
low solubility in water and low surface tension, these
polymers will accumulate in the sludge of wastewater
treatment plant or be strongly absorbed by particulate
421
material in sediments. Upon disposal of the sludge, e.g.
by land amendment, these polymers can be chemically
degraded, in example by clay containing soils, to lower
molecular weight species, mainly siloxanols binding to
soils or volatilised and oxidised in the atmosphere.
Furthermore, studies have shown that volatile silicone
oligomers like polydimethylcyclosiloxanes and short
chain linear oligomers of low molecular weight do not
contribute in the lower atmosphere to the formation of
ozone and these volatile silicone oligomers have been
granted an exemption from the volatile organic com-
pounds (VOC) regulations by the EPA in the USA; in
the higher atmosphere, volatile silicones oligomers are
quickly photochemically degraded and do not deplete
the ozone layer neither contribute significantly to global
warming [28].
Other silicone products, e.g. elastomers, are disposed
by landfill or incineration, their combustion leading to
amorphous silica, CO2 and H2O.
6. Conclusions
PDMS are formed from compounds that are largely
available: quartz and methanol, and if necessary, the
latter can be produced from wood distillation [10]. Often
referred to as silicones, they are used in many applica-
tions because of their stability, low surface tension and
lack of toxicity. Methyl group substitution or introduc-
tion of tri- or tetra-functional siloxane units leads to a
wide range of structures. Polymers are easily cross-
linked at room or elevated temperature to elastomers,
without loosing the above properties. These factors
explain the commercial success of silicones and should
support their future development.
100% silicone sealants show excellent resistance to the
combined effect of the key weathering factors: water,
heat and ultraviolet light. The actual response to this
environmental challenge depends on the particular cure
chemistry and the ingredients formulation of the silicone
sealanty as well as on the creativity of the formulators.
To address the questionFwhat criteria should a
sealant specifier use in the selection of a sealant product
in order to have confidence in its performances and
durability in its use?Fwe may reasonably consider few
key performances parameters:
* Mechanical performance criteria, e.g. elasticity,
modulus and movement capability.
* Adhesion to specific substrates, with primer if
necessary.
* Aesthetic changes: discoloration, surface cracking or
staining.
We assume the sealant specifier has made the
appropriate choice as far as concerned the chemistry
422 F. de Buyl / International Journal of Adhesion & Adhesives 21 (2001) 411–422
of sealant and its compatibility for the applications
considered.
Maybe further more importantly, successful specifiers
will ensure having good relationship with reputable
sealant suppliers who can provide technical consultation
and up-to-date documentation during project planning.
Field experience and case histories remain the most
valuable source of inspiration when designing the
adequate sealant and application procedure for a new
project. Predictive laboratory tests are helpful, but the
correlation with the real-life situation is always based on
numerous assumptions that are not systematically
verified.
Acknowledgements
The author would like to thank particularly Prof.
John Comyn and Dr. Bhukhan Parbhoo for suggesting
publishing this review, and help reviewing the manu-
script.
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