Combining technology expertise with

market knowledge to help you develop

new materials with greater reliability
and improved performance.

Guide to Silane Solutions

from Dow Corning
Contents
3

Dow Corning – The Silane Technology Pioneer .......................................... 4

Your Continuing Resource for Innovation and Application Success ............ 5
The Basics of Silane Chemistry .................................................................... 6
The Concept of Coupling with Organofunctional Silanes .......................... 8
Silane Coupling Agents ............................................................................... 8
Why Silane Coupling Agents Are Used ....................................................... 8
The Silane Bond to the Inorganic Substrate ................................................ 9
The Silane Bond to the Polymer ................................................................ 10
How to Choose a Silane Coupling Agent ................................................... 10
Typical Silane Applications ........................................................................ 13
Silanes from Dow Corning........................................................................... 14
Fiberglass and Composites ....................................................................... 15
Mineral and Filler Treatment ...................................................................... 16
Paints, Inks and Coatings .......................................................................... 18
Primers.................................................................................................. 19
Zinc-Rich Primers ................................................................................. 20
Chromium Replacement ....................................................................... 20
Industrial Maintenance .......................................................................... 20
Automotive Clearcoats .......................................................................... 20
Architectural Coatings ........................................................................... 21
Typical Coating Benefits ....................................................................... 21
Pharmaceutical Manufacturing .................................................................. 22
Plastics and Rubber .................................................................................. 22
Rubber Compounding ........................................................................... 22
Polymer Manufacturing ......................................................................... 24
Plastics Compounding .......................................................................... 24
Adhesives and Sealants ............................................................................ 25
Adhesion Promoters ............................................................................. 25
Crosslinkers .......................................................................................... 26
Water Scavengers ................................................................................ 26
Coupling Agents .................................................................................... 26
Water Repellents and Surface Protection .................................................. 26
General Construction Applications ........................................................ 26
Other Surface Protection Applications .................................................. 27
Other Applications ..................................................................................... 27
The Surface and Interface Solutions Center –
A Valuable Resource for Customer Success ............................................. 28
More than Materials – Competitive Advantage .......................................... 28
Dow Corning – The Right Partner for You .................................................. 29
Visit Our Website ....................................................................................... 29
Dow Corning –
The Silane Technology Pioneer

ow Corning pioneered the development of organo-

silane technology more than 50 years ago to provide
new classes of materials – silicones and silanes – with special
physical and chemical properties. This research led to a new
industry based on the synergy of organic and silicon chemis-
tries. Silicones and silanes are now essential components in
many major applications; without them, many of the materials
we rely on today would not exist.

The value of silane coupling agents
was first discovered in the 1940s in
conjunction with the development of
fiberglass-reinforced polyester com-
posites. When initially fabricated,
these new composites were very
strong, but their strength declined
rapidly during aging. This weaken-
ing was caused by a loss of bond
strength between the glass and res-
in. In seeking a solution, research-
ers found that organofunctional
silanes – silicon chemicals that
contain both organic and inorganic
reactivity in the same molecule –
functioned as coupling agents in the
composites. A very small amount
of an organofunctional alkoxysilane
at the glass-resin interface not only
5
significantly increased initial com- building construction to sporting
posite strength; it also resulted in a goods, Dow Corning silanes are
dramatic retention of that strength an important component of today’s
over time. Subsequently, other ap- sophisticated technologies. They
plications for silane coupling agents enable new materials to be devel-
were discovered, including mineral oped with greater reliability and
and filler reinforcement; mineral improved performance.
dispersion; adhesion of paints, inks
With a full range of silane
and coatings; reinforcement and
product and application solutions,
crosslinking of plastics and rubber;
Dow Corning offers you technology
reinforcement and adhesion of seal-
leadership, reliable supply, world-
ants and adhesives; water repel-
class manufacturing and global
lents and surface protection.
reach. In addition to materials, we
offer supportive services and
Your Continuing solutions you may never have
Resource for imagined. Silane solutions.
Innovation and Distinctly Dow Corning.
Application Success
Dow Corning continues to pioneer
the development of innovative
technologies and applications for
organosilane and silicon-containing
materials through our global
research team and Surface and
Interface Solutions Center (SISC).
From automotive to marine to
aerospace, from electronics to
The Basics of Silane Chemistry

ilicon is in the same family of elements as carbon in

the periodic table. In their most stable state, silicon and
carbon will both conveniently bond to four other atoms; but
silicon-based chemicals exhibit significant physical and
chemical differences compared to analogous carbon-based
chemicals. Silicon is more electropositive than carbon, does
not form stable double bonds, and is capable of very special
and useful chemical reactions. Silicon-based chemicals
include several types of monomeric and polymeric materials.

Figure 1. Carbon vs. silicon chemistry.

Organic (Carbon-Based) Chemical

H (alkane hydrogen)

(methyl) CH3 � OCH3 (methyl ether)

CH2CH2CH2-NH2 (aminopropyl)

Silane (Silicon-Based) Chemical

H (hydride)

(methyl) CH3 �� OCH3 (methoxy)

CH2CH2CH2-NH2 (aminopropyl)

Monomeric silicon chemicals are
known as silanes. A silane structure
and an analogous carbon-based
structure are shown in Figure 1. The
four substituents have been chosen
to demonstrate differences and
similarities in physical and chemi-
cal properties between silicon- and
carbon-based chemicals. A silane
that contains at least one carbon-
silicon bond (CH3-Si-) structure is
known as an organosilane. The
carbon-silicon bond is very stable,
very non-polar and gives rise to low
surface energy, non-polar, hydro-
phobic effects. Similar effects can
be obtained from carbon-based
compounds, although these effects
are often enhanced with silanes.
The silicon hydride (–Si-H) structure
is very reactive. It reacts with water
to yield reactive silanol (-Si-OH)
species and, additionally, will add
across carbon-carbon double bonds
to form new carbon-silicon-based
materials. The methoxy group
on the carbon compound gives a
stable methyl ether, while its attach-
ment to silicon gives a very reactive
and hydrolyzable methoxysilyl
structure. The organofunctional
group, the aminopropyl substituent,
will act chemically the same in the
organosilicon compound as it does
in the carbon-based compound.
The distance of the amine, or
other organofunctional group, from
silicon will determine whether the
silicon atom affects the chemistry
of the organofunctional group. If the
organic spacer group is a propylene
linkage (e.g., -CH2CH2CH2-), then
the organic reactivity in the organo-
functional silane will be similar to or-
ganic analogs in carbon chemistry.
Certain reactive silanes, particularly
vinyl silanes (-Si-CH=CH2) and
silicon hydrides (-Si-H), are useful
reactive groups in silicon chemistry,
even though the reactive group is
attached directly to the silicon atom.
Attachment of chlorine, nitrogen,
methoxy, ethoxy or acetoxy directly
to silicon yields chlorosilanes, silyl-
amines (silazanes), alkoxysilanes
and acyloxysilanes, respectively,
that are very reactive and exhibit
unique inorganic reactivity. Such
molecules will react readily with
water, even moisture adsorbed on
7
a surface, to form silanols. These
silanols then can react with other
silanols to form a siloxane bond
(-Si-O-Si-), a very stable structure;
or in the presence of metal hydroxyl
groups on the surface of glass,
minerals or metals, silanols will form
very stable –Si-O-metal bonds to
the surface. This is the key chem-
istry that allows silanes to function
as valuable surface-treating and
coupling agents.
Chloro-, alkoxy-, and acetoxy-
silanes, and silazanes (-Si-NH-Si)
will react readily with an active
hydrogen on any organic chemical
(e.g., alcohol, carboxylic acid,
amine, phenol or thiol) via a proc-
ess called silylation.
R3Si-Cl + R'OH ‡
R3Si-OR' + HCl
Silylation is very useful in organic
synthesis to protect functional
groups while other chemical
manipulations are being performed.
The silylated organofunctional
group can be converted back to the
original functional group once the
chemical operation is completed.
Silylation is very important in the
manufacture of pharmaceutical
products.
The Concept of Coupling with
Organofunctional Silanes

Silane Coupling Agents

For a more detailed discussion of
this mechanism, read “A Silane
ilane coupling agents are silicon-based chemicals that
Primer: Chemistry and Applications
contain two types of reactivity – inorganic and organic of Alkoxy Silanes” by Gerald L.
– in the same molecule. A typical general structure is Witucki, Journal of Coatings
Technology, Volume 65, Number
(RO)3SiCH2CH2CH2-X,
822, July 1993, pages 57-60. A
where RO is a hydrolyzable group, such as methoxy, ethoxy, reprint of this article is posted in the
or acetoxy, and X is an organofunctional group, such as amino, Technical Library in the Fiberglass

methacryloxy, epoxy, etc. and Composites section of the

Dow Corning Silanes Solutions
A silane coupling agent will act at an interface between an website, www.dowcorning.com/
inorganic substrate (such as glass, metal or mineral) and an silanes.
organic material (such as an organic polymer, coating or
adhesive) to bond, or couple, the two dissimilar materials. Why Silane Coupling
A simplified picture of the coupling mechanism is shown in Agents Are Used
Figure 2. When organic polymers are re-
iforced with glass fibers or miner-
als, the interface, or interphase

Figure 2. The silane coupling mechanism. region, between the polymer and
the inorganic substrate is involved
in a complex interplay of physical
��������� �������
and chemical factors. These factors
���������� �� ������ are related to adhesion, physical
������� ��������
������ ��������

Figure 3. SEM of silica-filled epoxy resin.

Without Silane With Silane


strength, coefficient of expansion,
concentration gradients and reten-
tion of product properties. A very
destructive force affecting adhe-
sion is migration of water to the
hydrophilic surface of the inorganic
reinforcement. Water attacks the
interface, destroying the bond
between the polymer and reinforce-
ment, but a “true” coupling agent
creates a water-resistant bond at
the interface between the inor-
ganic and organic materials. Silane
coupling agents have the unique
chemical and physical properties
not only to enhance bond strength
but also, more importantly, to
prevent de-bonding at the interface
during composite aging and use.
The coupling agent provides a
stable bond between two otherwise
poorly bonding surfaces. Figure 3
shows (via an SEM of the fracture
surface) the difference in adhesion
between a silica-filled epoxy resin
Figure 4. Hydrolysis of alkoxysilanes.
���������� RSi(OCH3) 3
H2 O
������������ RSi(OH) 3
R R
HO-Si-O-Si-O-Si-OH
O O
H H
9
with silane vs. without silane. With The Silane Bond
silane, the epoxy coating on the to the Inorganic
silica particles is apparent; without
Substrate
silane, clean silica particles can be
seen in the epoxy matrix. Silane coupling agents that contain
three inorganic reactive groups on
In composites, a substantial
silicon (usually methoxy, ethoxy or
increase in flexural strength is
acetoxy) will bond well to the metal
possible through the use of the
hydroxyl groups on most inorganic
right silane coupling agent. Silane
substrates, especially if the sub-
coupling agents also increase the
strate contains silicon, aluminum or
bond strength of coatings and
a heavy metal in its structure. The
adhesives as well as their resistance
alkoxy groups on silicon hydrolyze
to humidity and other adverse
to silanols, either through the
environmental conditions.
addition of water or from residual
Other benefits silane coupling water on the inorganic surface.
agents can provide include: Then the silanols coordinate with
metal hydroxyl groups on the
• Better wetting of inorganic
inorganic surface to form an oxane
substrates
bond and eliminate water. See
• Lower viscosities during Figures 4 and 5.
compounding
• Smoother surfaces of
composites
• Less catalyst inhibition of
thermoset composites
• Clearer reinforced plastics
Figure 5. Bonding to an inorganic surface.
� � �
CH3OH �� �� � �� � �� ��
�������� � � �
�������
� � � � � �
� � � ���������
H2 O
R ���
� � �
���� �� �� � �� � �� ��
O ���������
� � � ���������
H
 Silane molecules also react with
each other to give a multimolecular
structure of bound silane coupling
agent on the surface. More than
one layer, or monolayer equiva-
lents, of silane is usually applied to
the surface. This results in a tight
siloxane network close to the inor-
ganic surface that becomes more
diffuse away from the surface.
The Silane Bond to
the Polymer
The bond to the organic polymer is
complex. The reactivity of a ther-
moset polymer should be matched
to the reactivity of the silane. For
Figure 6. The inter-penetrating network (IPN) bonding mechanism.
���������� ��������
���������������� ����������
�����������
�����������
Silica
�����������
�����������
�������������� �������
example, an epoxysilane or amino-
silane will bond to an epoxy resin;
an aminosilane will bond to a
phenolic resin; and a methacrylate
silane will bond through styrene
crosslinking to an unsaturated
polyester resin. With thermoplastic
polymers, bonding through a silane
coupling agent can be explained by
inter-diffusion and inter-penetrating
network (IPN) formation in the
interphase region. See Figure 6.
To optimize IPN formation, it is
important that the silane and the
resin be compatible. One method
is to match the chemical character-
istics of the two materials. This will
help improve the chances of form-
ing a good composite with optimum
properties. Even with thermoset
polymers, where reactivity plays an
important role, chemical structure
matching will enhance the physical
properties of the composite.
How to Choose a
Silane Coupling Agent
All silane coupling agents with three
OR groups on silicon should bond
equally well with an inorganic sub-
strate. A variety of organofunctional
alkoxysilanes is available. See
Figures 7 and 8.
 11

Matching the organofunctional Figure 7. Silane coupling agent variations – basic structure.
group on silicon with the resin poly-
mer type to be bonded will dictate Basic Structure R
R = alkyl, aryl, or
which silane coupling agent should Si
organofunctional group
be used in a particular application. R'O OR'
OR' = methoxy, ethoxy,
The organic group on the silane can or acetoxy OR'
be either a reactive organic group NH2
OEt
(i.e., an organofunctional group), Z-6030
H2C CH3 Z-6011
OEt
EtO Si Z-6911
or it can be a non-reactive organic H2 MeO
C C EtO
MeO
group. The groups can be hydro- H2
Si O O
C SH Si
phobic or hydrophilic, with varying H2
EtO
OMe
OEt
thermal stability characteristics.
The solubility parameters of the O
CH2
groups will vary, depending on the MeO
CH O EtO
organic structure; this will influence, MeO
Si EtO
Si
Z-6341
to some extent, the interpenetration MeO Z-6040
OMe Si
OMe
the polymer network will have into Z-6300 MeO OEt

the siloxane network of the surface

treatment. Table 1 lists some of the
characteristics for common organic Figure 8. Silane coupling agent variations – alternative “Bis” structure.
substituents attached to silicon.
Alternative “Bis” Structure
The choice of silane should involve
matching chemical reactivity, R'O OR'
solubility characteristics, structural R
R'O Si Si OR'
characteristics and, possibly, the
R'O OR'
thermal stability of the organosilane
with the same parameters in the OEt
polymer structure. OMe
MeO H2 H2 H2 H2 OMe Si
H2 H2 OEt
C EtO CH2 OEt
C C Si C C
Si C C H2C S C Si
MeO C N H2 EtO C S H2
H2 H OMe H2
OMe OEt
Z-6920
Z-6670

Table 1. Characteristics of Various Organic Substituents on Silanes

Organosilanes R-Si(OMe)3
R Characteristics of “R”
Me Hydrophobic, Organophilic
Ph Hydrophobic, Organophilic, Thermal Stability
i-Bu Hydrophobic, Organophilic
Octyl Hydrophobic, Organophilic
-NH(CH2) 3NH2 Hydrophilic, Organoreactive
Epoxy Hydrophilic, Organoreactive
Methacryl Hydrophobic, Organoreactive
Table 2. Non-Organoreactive Alkoxysilanes A list of alkyl and aryl, non-organo-

Dow Corning® Organic Alkoxy reactive alkoxysilanes is provided

brand Silane Group Group Chemical Name in Table 2. Those silanes give
Z-6697 - Ethoxy TetraEthoxysilane modified characteristics to inorganic
Z-6070 Methyl Methoxy Methyltrimethoxysilane surfaces, including hydrophobic-
Z-6366 Methyl Methoxy Methyltrimethoxysilane (HP) ity, organic compatibility and lower
Z-6370 Methyl Ethoxy Methyltriethoxysilane surface energy.

More Hydrophobic
Z-6383 Methyl Ethoxy Methyltriethoxysilane (HP)
Based on experience and histori-
Z-6194 Methyl Methoxy Dimethyldimethoxysilane
cal applications of silanes, a list of
Z-6265 Propyl Methoxy Propyltrimethoxysilane
silane coupling agents and recom-
Z-6535 Propyl Ethoxy Propyltriethoxysilane
Z-2306 i-Butyl Methoxy Isobutyltrimethoxysilane mendations for evaluation with
Z-6403 i-Butyl Ethoxy Isobutyltriethoxysilane various polymer types is provided in
Z-6124 Phenyl Methoxy Phenyltrimethoxysilane Table 3. A correlation can be seen
Z-6341 n-Octyl Ethoxy n-Octyltriethoxysilane between the chemistry and struc-
tural characteristics of the silane
coupling agent and the chemistry
and structural characteristics of the

Table 3. Silane Coupling Agent Recommendations for Various Polymers – polymer.

Matching Organoreactivity to Polymer Type
Dow Corning®
brand Silane Organic Reactivity Application (suitable polymers)
Acrylic, Nylon, Epoxy, Phenolics, PVC, Urethanes,
Z-6011 Amino Melamines, Nitrile Rubber
Acrylic, Nylon, Epoxy, Phenolics, PVC,
Z-6020 Amino Melamines, Urethanes, Nitrile Rubber
Z-6028 Benzylamino Epoxies for PCBs, Polyolefins, All Polymer Types
Z-6030 Methacrylate Unsaturated Polyesters, Acrylics, EVA, Polyolefin
Z-6032 Vinyl-benzyl-amino Epoxies for PCBs, Polyolefins, All Polymer Types
Z-6040 Epoxy Epoxy, PBT, Urethanes, Acrylics, Polysulfides
Z-6076 Chloropropyl Urethanes, Epoxy, Nylon, Phenolics, Polyolefins
Acrylic, Nylon, Epoxy, Phenolics, PVC,
Z-6094 Amino Melamines, Urethanes, Nitrile Rubber
Z-6106 Epoxy/Melamine Epoxy, Urethane, Phenolic, PEEK, Polyester
Z-6128 Benzylamino Epoxies for PCBs, Polyolefins, All Polymer Types
Acrylic, Nylon, Epoxy, Phenolics, PVC,
Melamines, Urethanes, Nitrile Rubber (especially
Z-6137 Amino suited for water-based systems)
Z-6224 Vinyl-benzyl-amino Epoxies for PCBs, Polyolefins, All Polymer Types
Graft to Polyethylene for Moisture Crosslinking,
Z-6300 Vinyl EPDM Rubber, SBR, Polyolefin
Z-6376 Chloropropyl Urethanes, Epoxy, Nylon, Phenolics, Polyolefins
Graft to Polyethylene for Moisture Crosslinking,
Z-6518 Vinyl EPDM Rubber, SBR, Polyolefin
Z-6675 Ureido Asphaltic Binders, Nylon, Phenolics; Urethane
Z-6910 Mercapto Organic Rubber
Z-6920 Disulfido Organic Rubber
Z-6940 Tetrasulfido Organic Rubber

Typical Silane
Applications
Coupling Agent: Organofunctional
alkoxysilanes are used to couple
organic polymers to inorganic ma-
terials. Typical of this application
are reinforcements, such as
fiberglass and mineral fillers,
incorporated into plastics and
rubbers. They are used with both
thermoset and thermoplastic
systems. Mineral fillers, such as
silica, talc, mica, wollastonite,
clay and others, are either pre-
treated with silane or treated in situ
during the compounding process.
By applying an organofunctional
silane to the hydrophilic, non-
organoreactive filler, the surfaces
are converted to reactive and
organophilic. Fiberglass applica-
tions include auto bodies, boats,
shower stalls, printed circuit boards,
satellite dishes, plastic pipes and
vessels, and many others. Mineral-
filled systems include reinforced
polypropylene, silica-filled molding
compounds, silicon-carbide grinding
wheels, aggregate-filled polymer
concrete, sand-filled foundry resins
and clay-filled EPDM wire and
cable. Also included are clay- and
silica-filled rubber for automobile
tires, shoe soles, mechanical goods
and many other applications.
Adhesion Promoter: Silane cou-
pling agents are effective adhesion
promoters when used as integral
additives or primers for paints, inks,
coatings, adhesives and sealants.
As integral additives, they must
migrate to the interface between the
adhered product and the substrate
to be effective. As a primer, the
silane coupling agent is applied to
the inorganic substrate before the
product to be adhered is applied.
In this case, the silane is in the
optimum position (in the interphase
region), where it can be most
effective as an adhesion promoter.
By using the right silane coupling
agent, a poorly adhering paint, ink,
coating, adhesive or sealant can
be converted to a material that
often will maintain adhesion even if
subjected to severe environmental
conditions.
Hydrophobing and Dispersing
Agent: Alkoxysilanes with hydro-
phobic organic groups attached
to silicon will impart that same
hydrophobic character to a hydro-
philic inorganic surface. They are
used as durable hydrophobing
agents in construction, bridge
and deck applications. They are
also used to hydrophobe inorganic
powders to make them free-
flowing and dispersible in organic
polymers and liquids.
Crosslinking Agent: Organo-
functional alkoxysilanes can react
with organic polymers to attach
the trialkoxysilyl group onto the
polymer backbone. The silane is
13
then available to react with moisture
to crosslink the silane into a stable,
three-dimensional siloxane struc-
ture. Such a mechanism can be
used to crosslink plastics, especially
polyethylene, and other organic res-
ins, such as acrylics and urethanes,
to impart durability, water resistance
and heat resistance to paints, coat-
ings and adhesives.
Moisture Scavenger: The three
alkoxy groups on silanes will hydro-
lyze in the presence of moisture to
convert water molecules to alcohol
molecules. Organotrialkoxysilanes
are often used in sealants and other
moisture-sensitive formulations as
water scavengers.
Polypropylene Catalyst “Donor”:
Organoalkoxysilanes are added to
Ziegler-Natta catalyzed polymer-
ization of propylene to control the
stereochemistry of the resultant
polypropylene. The donors are
usually mono- or di-organo silanes
with corresponding tri- or di-alkoxy
substitution on silicon. By using
specific organosilanes, the tacticity
(and hence the properties) of the
polypropylene is controlled.
Silicate Stabilizer: A siliconate
derivative of a phosphonate-
functional trialkoxysilane functions
as a silicate stabilizer to prevent
agglomeration and precipitation of
silicates during use. The predomi-
nant application is in engine coolant
formulations to stabilize the silicate
corrosion inhibitors.
Silanes from Dow Corning

ow Corning is the industry leader in supplying silane and

intermediate product solutions; this is one of our com-
pany’s core businesses. Our silanes business unit encompasses the
following product groups:

• Chlorosilanes
• Organofunctional silanes
• Specialty silanes
• Alkylsilanes

Methylchlorosilanes are the basic building blocks of all of our silicon-

based materials. They are used in basic synthesis of silanes and
siloxanes, as protecting agents for intermediates in pharmaceutical
synthesis, and as precursors in the manufacture of silicon-carbide
coatings. Chlorosilanes are essential raw materials in the electronics
and telecommunications industries and for the production of optical
fibers, silicon wafers and chips, as well as the starting materials for
fumed silica.

Alkylsilanes, specialty silanes and organofunctional silanes have

alkyl, aryl or organofunctional groups attached to silicon and have
methoxy, ethoxy or acetoxy groups attached to silicon to allow them
to function in the manner described in this brochure.

Lists of silanes commercially available from Dow Corning can be

found at www.dowcorning.com/silanes. Data sheets for these products
can be viewed and downloaded from the website. We have many
other silicon-based materials that may be of value to you as well.
Information about these products can be obtained by contacting
Dow Corning Customer Support either by e-mail or telephone.

Fiberglass and
Composites
Silane coupling agents are a critical
component of fiberglass-reinforced
polymers. The glass is very hydro-
philic and attracts water to the
interface. Without silane treatment
on the surface, the bond between
the glass fiber and the resin would
weaken and eventually fail. Silane
coupling agents are used on
fiberglass for general-purpose
reinforced plastic applications, such
as automotive, marine, sporting
goods and building construction,
as well as for high-performance
applications in printed circuit
boards and aerospace composites.
Dow Corning® brand silanes figure
prominently in the trend toward
increasingly more-durable, higher-
strength plastic composites.
The chemical structure of the organic
group in a silane coupling agent has
a great effect on its performance
in a composite, as measured by
improvement of strength proper-
ties under wet and dry conditions.
A wet-aging test, usually in boiling
water, will show differences in the
effectiveness of various silanes.
The effect of the organic structure
of the coupling agent on improving
the flexural strength of a glass-
reinforced, unsaturated polyester
composite is shown in Figure 9.
The vinylbenzyl-functional silane
coupling agent (Dow Corning®
Z-6032 Silane, in this case) yields
greater improvement in the flexural
Figure 9. Effect of silane coupling agents on the strength
of glass-reinforced epoxy.
700
600
500
Flexural Strength, MPa
400
300
200
100
0
Dry Strength
strength of a glass-reinforced
epoxy system than does the epoxy-
functional silane coupling agent
(Dow Corning Z-6040 Silane). ®
More significantly, the retention of
strength after aging for 72 hours in
boiling water is better with either
silane than if no silane coupling
agent is used; but Z-6032 Silane
provides better retention of flexural
strength. These are the types of
effects generally expected from the
use of silane coupling agents.
Fiberglass for general-purpose
applications is treated with a dilute
aqueous sizing bath consisting of a
combination of ingredients (organic
film formers, lubricants, antistats
and a silane coupling agent). The
silane must be soluble in the
aqueous bath at levels of 0.2 to 1
percent. Normally, if a water bath
is acidified with acetic acid to a pH
of 4, even hydrophobic silanes will
dissolve in the bath at low con-
centrations and give the stability
needed to treat the fiberglass.
Certain silanes, such as aminosi-
lanes, are more hydrophilic and will
15
None
Z-6040 (Epoxy)
Z-6032 (Vinyl-
benzylamino)
Wet Strength, 72-hour water boil
dissolve at high concentrations in
water even without pH adjustment.
The size is applied to the fiberglass
at the glass fiber manufacturing
plant immediately after the glass
fibers are extruded and bundled
into glass fiber rovings.
Fiberglass for high-performance
electronics, such as printed circuit
boards, is processed differently.
The glass fiber is treated with a
starch size at the glass manufactur-
ing plant, after which a “fiberglass
weaver” weaves the fiber into glass
cloth. The weaver then burns off
the starch size at high temperature,
producing “heat-cleaned” glass
cloth. This clean cloth is then
passed through a bath containing
0.2 to 0.5 percent silane coupling
agent. Usually, no other significant
sizing chemical is in the bath. The
glass cloth is dried, inspected for
flaws and supplied to a fabricator
who makes epoxy, or other polymer,
prepregs and laminates for printed
 Figure 10. Thermal stability of silanes at 300ºC (572ºF), TGA. functional silanes, can provide
benefits. The improvement in
Stability of RSiO3/2 in Air thermal stability of a fiberglass-
��� polyimide composite is shown in
�� R - On Silicon
Table 4.
��
HCl
% R Remaining

��
��
��
��
��
��
�� � ��
�
� � � �
circuit boards. This application
requires excellent coupling agent
technology to provide the flaw-free
benefits required. Dow Corning
Z-6032 Silane, and variations on
this product, have been developed
to provide the necessary quality
and performance for printed circuit
boards.
Depositing the silane as a silse-
quioxane (organosilicon with three
oxygen atoms shared with other
silicon atoms) on a surface and
measuring the weight loss by
thermal gravimetric analysis (TGA)
Table 4. Thermal Stability of Mixed Silanes – Phenyl + Amino,
S-Glass/Polyimide Laminates
Properties of
Laminates, MPa
(CH2)3NHCH2CH2NHCH2
-NH3
-NH3
-CH2CH2CH2O-
-CH2CH2CH2NH-
-(CH2)3NHCH2CH2NH2
���
� � �� �� �� �� ���
Hours at 300°C (572°F)
can determine the thermal stability
of the silane. Results of isothermal
TGA at 300ºC (572ºF) for several
silanes are shown in Figure 10.
The diaminosilane (Dow Corning®
Z-6020 Silane) exhibited very poor
thermal stability. As expected,
the phenyl silane (Dow Corning®
Z-6124 Silane) showed excellent
thermal stability. Surprisingly,
the complex vinylbenzyl silane
(Z-6032), based on Z-6020,
showed very good thermal stability.
These data suggest that for high-
temperature applications, Z-6032,
or blends of Z-6124 with other
Coupling Agents on Glass
9:1 Blend, Aminosilane Alone,
Silane A and C Silane B
-CH=CH2 Some of the benefits imparted to
fiberglass-reinforced plastics by
Dow Corning silanes include:
• Improved mechanical strength
of the composites
• Improved electrical properties
• Improved resistance to
moisture attack at the interface
• Improved wet-out of the
glass fiber
• Improved fiber strand integrity,
protection and handling
• Improved resistance to hot
solder during fabrication
• Improved performance in
cycling tests from hot to cold
extremes
Table 3 on page 12 suggests
silanes for evaluation with vari-
ous fiberglass-reinforced polymer
systems. Product data sheets are
available at www.dowcorning.
com/silanes.
Mineral and Filler
Treatment
Mineral fillers have become increas-

Flexural Strength, initial 544 476 ingly important additives and modifi-
ers for organic polymers. The metal
1000 hr @ 260°C (500°F) 409 258
hydroxyl groups on the surface of
2000 hr @ 260°C (500°F) 306 134
minerals are usually hydrophilic and
Silane A: Z-6124 Ph-Si(OCH3)3
Silane B: Z-6011 H2N(CH2)3Si(OCH2CH3) incompatible with organic polymers.
Silane C: Z-6020 H2N(CH2)3NH(CH2)2Si(OCH3)3 Alkoxysilanes are a natural fit to
treat the surface of the mineral to

make it more compatible and dis-
persible in the polymer, or even to
make the filler a reinforcing additive.
In addition to plastics applications,
the use of silane-modified minerals
in organic rubber, especially tires,
has become increasingly important.
Minerals with silicon and aluminum
hydroxyl groups on their surfaces
are generally very receptive to
bonding with alkoxysilanes. The
treatment of a mineral surface by
an organosilane is depicted in
Figure 11. Silica (both fumed and
precipitated), glass beads, quartz,
sand, talc, mica, clay and wollaston-
ite have all effectively used silane
coupling agents in filled polymer
systems. Other metal hydroxyl
groups, such as magnesium
hydroxide, iron oxide, copper oxide,
and tin oxide, may be reactive to a
lesser extent, but often benefit from
silane treatment. Traditionally,
silane coupling agents give poor
bonding to carbon black, graphite
and calcium carbonate.
Silane treatment can improve proc-
essing, performance and durability
of mineral-modified products by:
• Improving adhesion between
the mineral and the polymer
• Improving wet-out of the
mineral by the polymer
Flexural Strength, MPa
• Improving dispersion of the
mineral in the polymer
• Improving electrical properties
• Increasing mechanical
properties
• Reducing the viscosity of
the filler/polymer mix
17
An example of the benefit of silane Z-6030 Silane (methacrylate) re-
treatment of a silica filler used in an duced viscosity by only 10 percent.
unsaturated polyester resin com-
Similarly, the ability of silane
posite is shown in Figure 12. As is
coupling agents to impart improved
generally the case, the silane treat-
electrical properties is shown in
ment results in higher initial strength
Table 5 on page 18. An epoxy resin
and better retention of strength after
was cured with and without quartz
humidity aging. The silane also can
filler as the reinforcement. Without
reduce the viscosity of the uncured
filler, the epoxy resin showed good
resin/filler mixture, to allow easier
electrical properties, dielectric
processing, with different silanes
constant and dissipation factor,
giving different effects. In this case
even after aging for 72 hours in boil-
Dow Corning Z-6032 Silane (vinyl-
ing water. However, once quartz
benzyl-amine) reduced viscosity
filler was added, the hydrophilic
by 65 percent while Dow Corning
Figure 11. Filler surface treatment.
���������
��� + �� ��� ��
��������� Inorganic Surface
Surface Is Hydrophilic
�
� � Converted to
� �� Organoreactive
�� �� Surface
� � �
� � � + ���
Mineral, Metal, Glass
Figure 12. Viscosity and coupling effect – polyester
castings with 50% silica.
�������������������
��� No Silane – 24,500 Pa•s
Z-6030 (Methacrylate) – 22,000 Pa•s
Z-6032 (ViBz Amine) – 8,700 Pa•s
���
���
��
�
��� �����������������
�������������������������������
Table 5. Ability of Silane Coupling Agents to Impart Electrical Properties
Dielectric Constant
System1 Initial
Unfilled Resin 3.44
Quartz, no Silane 3.39
Quartz, Z-6040 3.40
Quartz, Z-6011 3.46
1
Z-6040 = Epoxysilane; Z-6011 = Aminosilane
2
72-hour water boil
surface of the quartz led to severe
loss of electrical properties during
the water boil test. With either
epoxy-silane (Dow Corning
Z-6040 Silane) or aminosilane
(Dow Corning Z-6011 Silane), the
quartz-filled composite exhibited
improved retention of electrical
properties.
Minerals are treated with either
neat silane or a solution of silane in
water and/or alcohol. With a neat
silane, the adsorbed water on the
filler surface is often sufficient to
hydrolyze the alkoxysilane and
simultaneously bond the silane
to the filler surface. It is important
that the filler be coated uniformly
through the use of intensive mixing,
such as with a Henschel mixer.
Commercial processes are continu-
ous, often in a heated chamber,
followed by further heat treatment to
remove byproducts of alcohol and
water and to complete the bonding
of the silane to the surface.
The loading level of silane on the
filler surface is a function of the
surface area of the filler. While it
was thought that one monolayer of
Dissipation Factor
Water Boil2 Initial Water Boil2
3.43 0.007 0.005
14.60 0.017 0.305
3.44 0.016 0.024
3.47 0.013 0.023
silane should be sufficient, experi-
mentation has shown that several
layers of silane give optimal results.
For example, typical fillers with
average particle sizes of 1 to 5
microns often give best results
when treated with about 1 percent
silane. The optimal level of silane
treatment should be determined
experimentally.
The choice of which silane to use
in a particular application is deter-
mined by the nature of the benefit
that is to be derived from the silane.
All alkoxysilanes will bond to a
receptive filler or mineral surface.
If the silane treatment is designed
to provide surface hydrophobicity,
then a silane with a hydropho-
bic group, such as butyl, octyl,
fluorocarbon or phenyl, should be
chosen. If the silane treatment is
designed to provide compatibility
of the mineral in a polymer matrix,
then the nature of the organic group
on the silane should be similar
to the chemical structure of the
polymer (i.e., an octyl or longer-
chain alkyl group will help provide
compatibility and dispersibility of the
mineral in a polyolefin matrix). If the
silane treatment is to bond a filler to
a polymer matrix, then an organo-
reactive silane should be chosen
that would bond chemically to reac-
tive sites present in the polymer.
A list of some mineral/filler applica-
tions is shown in Table 6.
Table 3 on page 12 suggests
silanes for evaluation with
various filled polymer systems.
Product data sheets are available
at www.dowcorning.com/silanes.
Paints, Inks and
Coatings
Tightening volatile organic com-
pound (VOC) regulations in the
coatings industry, along with
demand for improved physical prop-
erties and extended performance
life, have spurred interest in silane
technology. The unique capability
of silanes to create covalent bonds
between inorganic and organic
compounds, and the inherent
stability of the siloxane (Si-O-Si)
bond, make this technology a key
component in high-performance
paints and coatings. These proper-
ties lie at the heart of the ability of
these materials to withstand physi-
cal, chemical, environmental and
thermal degradation.
Silane monomers, in the form of
organofunctional alkoxysilanes,
are utilized widely in coatings as
adhesion promoters, pigment treat-
ments and crosslinkers. Inorganic
alkoxy functionality coupled with a
wide range of organofunctional
 19

Table 6. Mineral/Filler Applications

Fillers Comments
Kaolin Clay Reinforced Nylon, Wire and Cable (EPDM)
Talc Stiffness, Abrasion Resistance – Polypropylene (auto)
Mica Stiffness – Polypropylene (auto)
Silica Reinforced Rubber, Epoxy PCBs
Wollastonite Reinforced Plastics, Coatings
Glass Fiber/Beads Reinforced Plastics
Aluminum Trihydrate Flame Retardance
Magnesium Hydroxide Flame Retardance
Crystobalite Abrasion Resistance – Plastics
Titanium Dioxide Colorant, Filler – Plastics

groups allows for covalent bonding
between organic polymers and
inorganic surfaces (e.g., pigments,
fillers, and glass and metal sub-
strates). The same coupling agent
mechanisms described earlier
allow for bonding between organic
polymers and inorganic surfaces. All
alkoxysilanes will bond essentially
identically to inorganic surfaces, but
the organofunctionality of the silane
must be matched with the chemistry
of the organic polymer in the paint,
ink or coating to obtain optimum
performance from the silane.
The use of silanes in coatings can
provide improvements in adhesion;
resistance to moisture, chemicals,
ultraviolet (UV) rays and abrasion;
and improved dispersion of fillers.
Alkoxysilane monomers (which are
not silicones, per se) are completely
miscible with many organic resins.
In fact, silanes are reasonably
strong polar solvents. Polymeriza-
tion of the silanes into silicone
resins and fluids impacts the
compatibility and performance of
the resulting polymer.
Silanes are also used as interme-
diates to produce silicates and
siliconates via reaction with metal
hydroxide (e.g., sodium or potas-
sium hydroxide). These materials
are used in protective finishes,
such as zinc-rich primers, masonry
treatments for water repellency, or
compounded directly into concrete
coatings for improved physical
properties and water repellency.
Silicates are derived primarily from
tetra-alkoxysilanes. In contrast, sili-
conates are produced via reactions
of mono- or di-organo (e.g., methyl
or other alkyl moieties) alkoxy-
silanes, which allow a broader
range of performance properties,
such as water repellency and
substrate penetration.
Primers
Silanes provide crucial functionality
in the primer segment of the coat-
ings industry. Alkoxysilanes have
broad utility in formulating primers
for a variety of metal and siliceous
substrates. Especially attractive to
the formulator is the wide range of
organo-reactive and non-reactive
moieties attached to the silicon
atom, which allows formulas to
be tailored to specific application
performance requirements. Widely
known as adhesion promoters,
alkoxysilane primers also offer
controlled hydrophobicity, excellent
UV and thermal stability, surface
activity, chemical resistance and
corrosion protection.
The silane coupling agent must act
at the interface between the sealant
or adhesive and the substrate. It
is chosen by matching its organic
functionality to the organic moiety
in the coating that is to be bonded.
Table 3 on page 12 suggests
silanes for evaluation based on the
nature of the organic moiety in the
coating. Often, mixtures of silanes
are used as adhesion promoters to
provide enhanced hydrophobicity,
thermal stability or crosslinking at
the bonding site.
Using a silane as a primer ensures
that the silane will be at the substrate-
polymer interface where it can
enhance adhesion. Silane primers
are often dilute solutions of silanes,
0.5 to 5 percent, in an alcohol or
water/alcohol solvent. They are
wiped or sprayed on the substrate
followed by solvent evaporation.
Zinc-Rich Primers
As early as 1962, partial hydroly-
zates of alkoxysilanes (e.g., tetra-
ethoxysilane), or alkali silicates,
combined with zinc metal powder
were found to provide galvanic
protection of ferrous substrates
beyond that imparted by organic
resin-based zinc primers. Initially,
1 employee health and safety.
this technology was limited by its
inherently short pot and shelf life.
Later, the stability and overall per-
formance of the primer was greatly
improved by trans-esterifying the
silicate with organic polyols (e.g.,
ethylene glycol or glycerol). This
2
innovation is one of the most widely
cited silicon-based inventions
(34 citations). These materials,
based on partial hydrolyzates of
tetra-ethoxy silane, are available
as either one- or two-part systems
and have been the dominant
galvanic primer used in the paint
industry. They are characterized
by tolerance to high humidity
and low-temperature application.
Solvent-based primers are best
suited for on-site application under
difficult weather conditions.
Chromium Replacement
State-of-the-art metal surface prep-
arations for adhesive bonding con-
sist mainly of anodization or etching
processes employing strong acids.
Many of these surface preparations
also contain hexavalent chromium.
Surface treatment is followed by the
application of a corrosion-inhibiting
adhesive primer that typically con-
tains high levels of volatile organic
compounds (VOCs) and additional
hexavalent chromium. Alternatives
to chromium compounds are being
sought due to new regulations, the
increased cost of hazardous waste
disposal and the increased aware-
ness of the costs associated with
In 1983, a primer composed of an
acrylic copolymer, an epoxy resin,
a silica sol and a trialkoxysilane
compound was developed. The
primer provided superior paint-
ability, degreaser resistance and
corrosion resistance after painting.3
Twelve years later, a wash primer,
without the acrylic copolymer or the
epoxy resin, was developed that
provided similar benefits.4 Metal
was pretreated with an alkaline
solution containing at least one
of a dissolved inorganic silicate,
a dissolved inorganic aluminate,
an organofunctional silane, and a
crosslinking agent containing
trialkoxysilyl groups. The metal
was then dried to completely cure
the functional silane, resulting in
an insoluble primer layer bonded
tightly to the metal substrate.
Industrial Maintenance
Combining the cure profiles and
barrier properties of organic resins
with the thermal and UV stability of
silanes, formulators have created
high-performance coatings with
excellent resistance to corrosion
and chemical attack as well as
thermal and UV degradation. A
blend consisting of an epoxy resin,
an epoxy resin curing agent, an
organofunctional alkoxysilane and
a catalyst for condensation poly-
merization of a silane compound
can provide high heat resistance
and excellent mechanical strength.5
Similarly, epoxy resins can be
reacted with hydrolyzed alkyl and
phenyl alkoxysilanes to produce
copolymers with improved water
and moisture resistance.6,7 Utilizing
the functional groups available from
silane monomers, resin formulators
have created organofunctional (e.g.,
epoxy and amine) silicone resins
for epoxy resin modification.8,9
Automotive Clearcoats
Color-plus-clear coating systems
involving the application of a colored
or pigmented base coat to a sub-
strate followed by application of
a clear topcoat have become the
standard as OEM finishes for
automobiles. Color-plus-clear
systems have outstanding appear-
ance properties (such as gloss and
distinctness of image) due, in large
part, to the clear coat. These clear
coatings are, however, subject to
damage from environmental
elements, such as acid rain, UV
degradation, high relative humidity
and temperatures, stone chipping
and abrasive scratching of the
coating surface.

Typically, a harder, more highly
crosslinked film may exhibit im-
proved scratch resistance; however,
high crosslink density embrittles the
film, making it much more suscep-
tible to chipping and/or thermal
cracking. A softer, less-crosslinked
film, while not prone to chipping
or thermal cracking, is susceptible
to scratching, water spotting and
acid etch. Clear coats in color-plus-
clear systems have demonstrated
improved scratch resistance with
the inclusion of surface-reactive,
inorganic microparticles, such
as silane coupling agent treated
colloidal silica.10
Architectural Coatings
Changes in building practices,
including concrete facades on multi-
floor buildings and shifts in the eco-
nomics of material and labor costs,
have contributed to the trend toward
silane-modified architectural paints.
By using a reactive organic group
on a trialkoxysilane to react into a
latex polymer backbone, the latex
polymer has the ability to crosslink
via a moisture crosslinking mecha-
nism once the coating is applied.
A primary concern for water-based
formulations is the stability of
alkoxysilanes in an aqueous envi-
ronment. Alkoxysilane adhesion
promoters (also known as coupling
agents) do react with water. For
silanes to provide the intended
benefits of adhesion or crosslinking,
the hydrolysis reaction is a neces-
sary and desired process step.
Modifying the silane, via transesteri-
fication, from methoxy functionality
to longer alkoxy groups (e.g.,
isopropoxy) can slow, but not
prevent, hydrolysis. Attaching an
alkoxy chain length sufficient to
eliminate hydrolysis would essen-
tially deactivate the silane. By
formulating to conpensate for the
inevitable hydrolysis and subsequent
condensation of alkoxysilanes,
coating formulators can still utilize
this technology to improve the
performance of many water-based
coatings.
Many coatings fail because water is
absorbed by or penetrates the film,
ultimately reaching the coating-
substrate interface. Alkoxysilanes
are well known for improving the
adhesion of coatings to metal or
siliceous substrates by forming
covalent bonds via dual organic-
inorganic reactivity. This is one of
several mechanisms by which
alkoxysilanes provide benefit. In
addition to chemical bonding, si-
lanes improve the hydrolytic stability
and integrity of the film. Including
alkoxysilanes in coating formula-
tions can create a more tightly
crosslinked, hydrophobic film that is
much less susceptible to moisture
attack. Significant benefit can be
achieved by adding 0.5 percent
silane (based on system solids) to
acrylic latex-based coatings.
Treatment of mineral pigments and
fillers (e.g., silica, titanium dioxide,
etc.) with alkoxysilanes is well
known in the coatings industry.
While pigment or filler suppliers
often treat fillers with silanes,
similar benefits can be observed
by incorporating the alkoxysilane
21
directly into a water-based coating
formulation. The presence of water
at typically high pH levels results
in hydrolysis of the silane and
condensation around the solid
particles. The net effect is better
integration of the inorganic particle
into the binder matrix, improved
dispersion and physical properties.
Successful incorporation of silanes
into water-based formulations
requires good dispersion of the
silane prior to complete hydrolysis
and condensation. Adequate mix-
ing is essential. Along with good
mixing, pre-diluting the silane into
a coalescing solvent or plasticizer
before adding it to the latex will
minimize condensation of the silane
monomers (and potential gel forma-
tion) and encourage interaction with
the other components of the coating
formulation.
Typical Coating Benefits
Silanes can impart several benefits
to coatings, including:
• Abrasion resistance
• Adhesion
• Better flow
• Crosslinking to improve thermal
stability and durability
• Pigment and filler dispersion
• UV resistance
• Water and chemical resistance
A list of Dow Corning® silanes for
use in paints, inks and coatings
is available at www.dowcorning.
com/silanes.
Pharmaceutical
Manufacturing
The pharmaceutical industry relies
heavily on silane chemistry in the
synthesis of antibiotics, drugs and
medicines. Through a process
called silylation, the chemistry of
silanes allows them to be used as
protecting groups that permit chemi-
cal procedures to be performed,
while retaining the desired organic
functionalities necessary in the
pharmaceutical molecular structure.
Silylation is the displacement of
an active hydrogen in an organic
molecule by a silyl (R3Si) group.
The active hydrogen is usually -OH
(alcohol, carboxylic acid, phenol),
-NH (amine, amide, urea) or -SH
(thiol). The silylating agent is often
a trimethylsilylhalide, dimethylsilyldi-
halide or a trimethylsilyl nitrogen-
functional compound. However,
often larger, bulkier groups (e.g.,
tert-butyl) are on the silylating
agent to control the chemistry of the
reaction. Newer silylating agents
will cleave esters and ethers. A
mixture of silylating agents may be
used, such as trimethylchlorosilane
plus hexamethyldisilazane. This
blend is more reactive than either
reagent alone. The byproducts
combine to form neutral ammonium
chloride, e.g., in the following
reaction where the -Si(CH3)3 group
replaces the active hydrogen in the
R-OH molecule.
R-OH + (CH3)3SiNHSi(CH3)3
+ (CH3)3 SiCl ‡ 3 RO-Si(CH3)3
+ NH4Cl
The unique chemical properties of
silanes allow them to replace one
or more active hydrogens during
chemical synthesis to protect these
groups, while subsequently allowing
other chemistries to be performed
on the molecules without destroy-
ing or altering the protected organic
functionalities. After the desired
chemical procedures are carried
out in other parts of the molecules,
the silane protective group can be
removed to regenerate the original
organic functionality.
Silanes have been used for many
years in the production of antibiotics,
such as penicillin and cephalosporin-
type medications. Tertiary-
butyldimethylchlorosilane is used
in anti-cholesterol drug production
as a “super-protector” during the
manufacturing process. Other
silanes, such as chloromethylsi-
lydimethylchlorosilanes, have been
used in direct chemical synthesis
of herbicides where the silicon atom
becomes a chemical part of the
final product.
As the global market for biologi-
cal and pharmaceutical products
increases, due to population growth
and increasing demand for health-
care, manufacturers will rely on
silanes as they develop the next
generation of medicinal therapies.
A list of Dow Corning® brand silylat-
ing agents for use in pharmaceuti-
cal manufacturing is available at
www.dowcorning.com/silanes.
Plastics and Rubber
The unique properties of silanes are
used to enhance performance and
improve processes in the plastics
and rubber industries. Silanes
function as coupling and dispers-
ing agents for fillers in rubber and
plastics formulations, as polymer-
ization modifiers in the synthesis of
polypropylene, and as crosslinking
agents for polyethylene homopoly-
mers and copolymers.
Rubber Compounding
A major use for silanes has devel-
oped in the organic rubber industry
as a result of the benefits that can
be obtained from the use of
inorganic filler in place of carbon
black in the reinforcement of rubber.
Silica and other inorganic filler
reinforcements for rubber provide
unique physical properties and
performance properties versus
carbon black reinforcement; how-
ever, silane coupling agents are
necessary for the non-black
reinforcing fillers to be effective.
Silanes are the key to providing a
method of effectively bonding the
inorganic fillers to organic elasto-
mers. Silane-coupled, mineral-filled
rubber products are used for auto-
motive and off-road tires, shoe soles,
belts, hoses and mechanical goods.
The mechanism is similar to that
described earlier under “Mineral
and Filler Treatment.” Methoxy- or
ethoxy-silanes will bond tenaciously
to the silica or clay surface; then the
organic portion of an organofunc-
tional silane will bond to the rubber
polymer. See Figure 13.
 23

Figure 13. Bonding organic rubber to silica with sulfur silanes. completed. This can be done with
�������������������������������� silane coupling agents that have
������������������������������ triethoxysilyl groups at both ends of
EtO
a polysulfido (tetrasulfide, disulfide
OEt
Si OEt
or mixture thereof) organic group.
OEt OEt s See Figure 14.
Si O Si Sx Si O Si S
O OEt O OEt s
Si OH Si OH
s
These coupling agents are supplied
OEt O OEt
O
Si O Si Si O Si as neat liquids or as blends with a
O O O Sx
Silica O Sx
Silica s carrier such as carbon black. See
Si O Si Si O Si Rubber
O O O O Table 7. Even though silica can be
Si O Si Sx Si O Si S
O OEt O OEt used as the only filler, rubber tires
Si O Si O s
s
incorporate small levels of carbon
EtO Si
EtO OEt s black to give consumers the uniform
The silane can react in the black color they expect. Without
sulfur vulcanization carbon black in the rubber com-
pound, it is possible to make tires
Figure 14. Structure of sulfidosilanes used in rubber compounds.
in a variety of colors.
EtO H2 H2 OEt A specific example of this applica-
C Sx C tion is the silica/silane technology
Si C C C C Si used in “green” tires to impart:
H2 H2 H2 H2
EtO OEt OEt OEt • Increased abrasion resistance
• Reduced rolling resistance
x ranges from 2 to 10 and improved fuel economy
These are termed S2, S3, etc., monomers of tires
Bis-TriEthoxy Silyl Propyl Polysulfide - TESPX
• Better grip on wet and snow/
ice surfaces
The silane is usually added during and react over the filler surface
Silica-reinforced tires are known
the compounding process to treat and still be able to react with the
as “green” tires because they pro-
the filler in situ. It must have the elastomer at a rate that allows
vide improved fuel economy while
proper rate of reactivity to spread processing of the rubber to be

Table 7. Sulfidosilanes for Rubber

EtO H2 H2 OEt
C Sx C
Si C C C C Si
H2 H2 H2 H2
EtO OEt OEt OEt
Dow Corning® brand Silane Features Average Value of X
Z-6920 Liquid TESPD 2.20
Z-6925 Solid TESPD, 50% on Carbon Black 2.20
Z-6940 Liquid TESPT 3.75
Z-6945 Solid TESPT, 50% on Carbon Black 3.75
maintaining or improving other tire
properties (as listed above). They
also use a mineral-derived filler
rather than one derived from a
fossil fuel (natural gas or oil). This
is currently the largest market for
silane coupling agents.
The use of vinyl silanes as a cou-
pling agent in kaolin clay reinforced
EPDM wire and cable coatings is
another important rubber applica-
tion. The vinyl silane improves the
electrical properties of the rein-
forced rubber so a stringent power-
factor electrical test can be passed,
but only when optimum silane
coupling agent technology is used.
In addition to silanes, Dow Corning
is a major supplier of silicone
rubber. Silicone rubber is made
from silicone polymers compounded
with non-black fillers, usually
fumed or precipitated silica.
These compounds require silanes
and functional silicone fluids.
Silanol-functional silicone fluids and
vinyl-functional silanes are available
for silicone rubber compounding.
A list of Dow Corning silanes for
rubber compounding is available
at www.dowcorning.com/silanes.
Information about our silicone
rubber materials is available at
www.dowcorning.com/rubber.
Polymer Manufacturing
Selected silanes, known as “exter-
nal donors,” or electron donors, are
used in conjunction with Ziegler-
Natta catalysts in the manufacture
of polypropylene. Ziegler-Natta
catalysts are organometallic
compounds. Organoal-koxysilanes
can chemically coordinate with the
organometallic catalyst to modify
the course of the polymerization.
Specific variations in the tacticity of
the propylene polymer are possible
by optimizing the use of a silane
donor in the process. Different
silane donors with differing organo-
alkoxy structures are used depend-
ing on the exact nature of the
catalyst and the type of polypropyl-
ene being manufactured. Organic
substituents, such as cyclohexyl,
cyclopentyl, methyl, isobutyl and
phenyl, are some of the organic
groups attached to silicon. The
alkoxy groups are either methoxy
or ethoxy with one, two, or three
alkoxy groups on the silane
molecule. Three of the more
common silane donors are Donor C,
cyclohexylmethyldimethoxysilane
(Dow Corning® Z-6187 Silane);
Donor D, dicypentyldimethoxysilane
(Dow Corning® Z-6228 Silane);
and di-isobutyldimethoxysilane
(Dow Corning® Z-6275 Silane).
Reactive silicone polymers have
also been used to produce ther-
moplastic vulcanizates (TPVs).
TPVs are prepared by chemically
crosslinking a rubbery phase in
a thermoplastic matrix. TPVs are
produced by dynamic vulcanization,
and silane chemistry allows new
and unique crosslinking chemistries
to be used in the manufacturing
process.
A list of Dow Corning silanes for
polymer manufacturing is available
at www.dowcorning.com/silanes.
Plastics Compounding
Vinyl silanes have been used
commercially since the 1970s to
crosslink polyethylene homopolymer
and its copolymers. Vinyltrimeth-
oxysilane and vinyltriethoxysilane
are the most common silanes used
in the process. In an extruder in the
presence of peroxide and heat, the
vinyl group will graft to the polyeth-
ylene backbone, yielding a silane-
modified polyethylene that contains
pendant trialkoxysilyl functionality.
The grafted polyethylene can then
be immediately crosslinked in the
presence of a tin catalyst, moisture
and heat to create a silane-
crosslinked product. Diagrams of
the grafting of vinyltrimethoxysilane
(VTMOS) to polyethylene and the
moisture crosslinking process are
shown in Figures 15 and 16. The
ease of processing and the simple
equipment required make this the
preferred method of producing
crosslinked ethylene polymers and
copolymers. The process also
allows crosslinking to be delayed
until after the grafted product is
transformed into its final product
configuration. Using the same
silanes, it is also possible to copoly-
merize the vinyl silane with ethylene
monomer to make trialkoxysilyl-
functionalized polyethylene. This
then can be crosslinked in the same
manner as the graft version.
Silane-crosslinked polyethylene is
used for electrical wire and cable
insulation and jacketing where ease
of processing, increased tempera-
ture resistance, abrasion resistance,
stress-crack resistance, improved
low-temperature properties and
 25

retention of electrical properties are Figure 15. Grafting of VTMOS to polyethylene – Sioplas® process.
needed. Other applications for this
technology include:

• Cold- and hot-water pipe

where resistance to long- OMe
term pressure at elevated
ROOR OMe

temperatures is essential + Si
OMe Heat
Si
OMe
• Natural gas pipe with good OMe
OMe
resistance to stress cracking VTMS
Silane-Grafted
• Foam for insulation and Polyethylene
packaging with greater
resiliency and heat resistance
Polyethylene
• Other product and process
types, such as film, blow-
molded articles, sheeting Figure 16. Crosslinking of polyethylene in the presence of moisture
and thermoforming – Sioplas® process.
A list of Dow Corning silanes for
plastics compounding is available
at www.dowcorning.com/silanes.
Si OMe
Additional information is available at MeO
Si OMe
www.dowcorning.com/plastics. MeO
MeO �����
O
MeO ����������
Adhesives and MeO
Si OMe
Sealants MeO
Si OMe

Silanes are widely used to improve

the adhesion of a broad range of
sealants and adhesives to inorganic
substrates, such as metals, glass
and stone. Sealants are based on
filled, curable elastomers and have
the dual purpose of preventing
passage of water, air and chemicals
through the zone where applied; in
some cases they also serve as an
adhesive. Their usefulness in the
aircraft, automotive and construc-
tion industries depends upon their
ability to form durable bonds to
metal, glass, ceramic and other
surfaces – bonds that will withstand
exposure to heat, ultraviolet radia-
tion, humidity and water.
DBTDL = Dibutyltindilaurate
Adhesion Promoters
A silane coupling agent will function
at the interface between the seal-
ant or adhesive and the substrate
to act as an adhesion promoter.
An organofunctional silane uses
a mechanism similar to that
described earlier for bonding an
inorganic substrate and a sealant or
adhesive polymer. The silane
coupling agent is chosen by
matching its organic functionality
to the polymer to optimize bonding.
Table 3 on page 12 sugests silanes
to evaluate for various polymer
systems.
Often, mixtures of silanes are used
as adhesion promoters to provide
enhanced hydrophobicity, thermal
stability or crosslinking at the
bonding site.
The silanes can be blended into
an adhesive formulation or used
as primers on substrates. When
added to the adhesive formulation,
the silane must be free enough to
migrate to the interphase region
between the adhesive/sealant and
the surface of attachment. The
structure and reactivity of the silane
will affect the ability of the silane
to migrate. Usually more than one
silane is evaluated for an applica-
tion to empirically choose the best
performing silane.
The most effective way to promote
adhesion is to apply the silane as a
primer to the surface, followed by
application of the adhesive/sealant.
In this way, the silane will be on the
surface and therefore at the inter-
face where it can enhance adhesion
between the polymer and the sub-
strate. Silane primers are usually
dilute solutions of 0.5 to 5 percent
silane in alcohol or water/alcohol
solvent. They are wiped or sprayed
on the substrate, after which the
solvent is allowed to evaporate.
When added to sealants or adhe-
sives or used as primers on
substrates, an improvement in
adhesion is often realized with the
bond showing greater resistance
to moisture attack at the interface.
This can result in:
• Increased initial adhesion
• An adhesive bond with
longer life
• Greater temperature
resistance
• Greater chemical resistance
Crosslinkers
Silanes can be used to crosslink
polymers such as acrylates, poly-
ethers, polyurethanes and polyes-
ters. The organofunctional portion
of the silane can react, and bond to,
the polymer backbone in a sealant
or adhesive. The alkoxysilyl group
on the silane should not crosslink
prematurely in order to be available
to provide crosslinking once the
sealant or adhesive is applied in its
intended application.
A silane-crosslinked sealant or
adhesive can show enhanced prop-
erties, such as:
• Tear resistance
• Elongation at break
• Abrasion resistance
• Thermal stability
• Moisture resistance
Water Scavengers
The ability of alkoxysilanes to react
very rapidly with water makes them
useful in sealant and adhesive
formulations to capture excess
moisture. A very common moisture
scavenger is vinyltrimethoxysilane.
The presence of the vinyl group at-
tached to silicon increases the rate
of reaction of the methoxysilane
with water to give efficient elimina-
tion of water. Methanol is formed
as a byproduct, and the vinyl silane
crosslinks into an inactive species
in the formulation. Other silanes,
such as methyltrimethoxysilane, are
also used as water scavengers.
Silane water scavengers in a formu-
lation can:
• Prevent premature cure
during compounding
• Enhance uniform curing
• Improve in-package stability
Coupling Agents
Silane coupling agents are used to
increase adhesion between fillers
and the polymer matrix in sealants
and adhesives. The mechanism
and mode of action was described
earlier under “Mineral and Filler
Treatment.”
The silane coupling agent treatment
on the filler can provide:
• Better bonding of the pigment
or filler to the resin
• Improved mixing
• Increased matrix strength
• Reduced viscosity of the
uncured sealant or adhesive
A list of Dow Corning® silanes for
use in formulating sealants and
adhesives is available at
www.dowcorning.com/silanes.
Water Repellents and
Surface Protection
General Construction
Applications
Silanes can be chosen to impart
hydrophobic (water repellent) and/
or oleophobic (oil and stain repel-
lent) characteristics to surfaces.
Silanes with alkyl groups (such

as butyl and octyl) and aromatic
groups (such as phenyl) and even
some organofunctional groups
(such as chloropropyl and metha-
crylate) are hydrophobic. Similarly,
silanes containing fluoroalkyl
groups are oleophobic (oil repel-
lent). Alkoxysilyl groups attached to
these silanes allow them to actually
penetrate, cure in and even bond to
many inorganic substrates. These
unique properties allow for versatile
and durable formulating solutions
for protection against harmful water-
and oil-borne elements.
Dow Corning brand water and stain
repellent materials can be used in
solvent- or water-based systems
to provide the formulating flexibility
needed to meet VOC and ease-
of-use requirements. These silane-
based water and stain repellents
are available for use in formulations
that penetrate a broad range of
substrates, including:
• Poured-in-place or pre-cast
concrete
• Concrete block
• Sandstone/granite
• Brick/tile/grout
• Wood
• Gypsum/perlite
• Limestone/marble
Silane-based water repellents from
Dow Corning create an envelope
of protection that extends the life
of substrates for years in challeng-
ing environments. Potntial benefits
include:
• Excellent water repellency
• Long-term durability
• UV stability
• Depth of penetration
• Water vapor permeability
• High dilution capability and
stability
• Clear, uniform, neutral
appearance
Benefits of protection include:
• Reduced efflorescence
• Reduced freeze-thaw damage
• Chloride ion resistance to
deter corrosion of reinforcing
steel in concrete structures
• Preservation of aesthetics
Other Surface Protection
Applications
Dow Corning also manufactures a
range of silicates and siliconates
for use in formulating pore-blocking
sealers and consolidators. These
silicates and siliconates are alkali
metal salts of hydrophobic silane
oligomers and adhere tenaciously
to inorganic substrates and surfac-
es in much the same way as simple
alkoxysilanes do. Applications for
these materials fall into two groups:
sealers and consolidators.
Sealers fall into two sub-groups:
• Pore blockers provide little
penetration and, instead, form
a resin barrier on the concrete’s
surface. Pore blockers are
27
further distinguished by their
ability to partially or fully fill the
surface pores, a capability not
shared by hydrophobing agents.
• Hydrophobing agents, on
the other hand, penetrate the
material deeply. They allow the
concrete to breathe and do not
interfere with concrete cure.
Consolidators can extend the life
of stone and concrete because they
penetrate and cure in and through
these materials to help bind them
together. They are used in a
variety of restoration and flooring
applications.
A list of Dow Corning® silanes for
water repellents and surface protec-
tion is available at www.dowcorning.
com/silanes. Additional information
is available at www.dowcorning.
com/construction.
Other Applications
The possible applications for
silanes are certainly not limited to
those provided in this brochure.
Silanes bring performance-
enhancing and problem-solving
benefits to a wide array of specialty
applications. Whether your
application is typical or unique,
Dow Corning can provide the silane
solution and technical support you
require, either through the proven
resources of our Application
Engineering Technical Service
department or through the innova-
tion expertise of our Surface and
Interface Solutions Center.
The Surface and Interface Solutions Center –
A Valuable Resource for Customer Success

ow Corning’s Surface and Interface Solutions Center

(SISC) in Seneffe, Belgium, is pioneering the devel-
opment of next-generation technologies and applications for
organosilane and silicon-containing chemicals.

The SISC designs innovative molecules, composites, proc-

esses, and surface interface and interphase technologies,
including material science for filler reinforcement, crosslinking
and adhesion. The center serves the needs of customers in
multiple markets, including plastics, rubber, adhesives, seal-
ants, coatings, textiles and electronics.

Because it is located in Europe, the SISC complements our

other silanes technology facilities in Midland, Michigan, USA,
and Chiba, Japan, and expands our ability to provide you with
advanced application and development support, worldwide.

More than Materials – Competitive Advantage

The scientists and engineers at the SISC are linked to
Dow Corning’s global network of technology experts and to
external sources of expertise. Because the center combines
technology expertise with market knowledge, it enables us
to identify previously unimagined opportunities to meet new
and emerging customer needs.

The SISC can provide you with novel materials that open
the doors to new markets and applications. We can help you
achieve a competitive advantage in other ways as well, by
engineering solutions tailor-made to help you achieve your
specific business goals and objectives. Whether you are
looking for innovation support, performance improvement,
increased productivity or business growth, the SISC can help.
More information on the SISC is available at www.dowcorning.
com/silanes/siscmain.asp.
Dow Corning –
The Right Partner for You
29

ore than 50 years ago, Dow Corning pioneered

the development of organosilane technology.
Today, we are recognized in the industry for our innovations,
technical achievements and competence in silicon technology.
Our exclusive focus on silicon-based chemistry guarantees
state-of-the-art material, manufacturing and expertise. We
have world-class facilities to study, handle and produce
these materials.

We have made significant investments to support the silanes

market. These investments will enable us to further grow our
silanes product line and identify new opportunities to provide
you with performance-enhancing solutions.

We invite your inquiries. We are anxious to discuss your

opportunities, to assist you in optimizing your current applica-
tions, and to counsel you in the use of silane solutions in the
development of emerging technologies. Our goal is to help
you use the best silane technology to satisfy the needs of your
customers, and thereby maximize your business potential.

Visit Our Website

Visit our website, www.dowcorning.com/silanes, and explore
the silanes and other silicon-based technologies we have to
offer. There you will find links to technical papers, data sheets,
product and technology brochures, and other information that
can assist you in finding solutions to your needs.

Dow Corning is pleased to offer you “Silane Solutions.”

Footnote References
1
S.L. Lapata and W.R. Keithler; Carboline Company; U.S. Patent 3,056,684, October 2, 1962.
2
G.D. McCleod; G.D. McCleod & Sons Inc.; U.S. Patent 3,917,648, November 4, 1975.
3
T. Hara; M. Ogawa; M. Yamashita; Y. Tajiri; Nippon Kokan Kabushiki Kaisha; U.S. Patent
4,407,899, October 4, 1983.
4
Wim J. van Ooij; Ashok Sabata; Armco, Inc.; U.S. Patent 5,433,976, July 18, 1995.
5
Y. Murata, et al.; Shell Oil Company; U.S. Patent 6,005,060 – “Epoxy Resin Composition and
Cured Composite Product,” December 21, 1999.
6
R. Mikami; Toray Silicone Co. Ltd.; U.S. Patent 4,283,513 – “Siloxane-Modified Epoxy Resin
Composition,” August 11, 1981.
7
R. Mikami; Toray Silicone Co. Ltd.; U.S. Patent 4,287,326 – “Siloxane-Modified Epoxy Resin
Composition,” August 11, 1981.
8
G. Decker, et al.; Dow Corning Corp., Toray Industries; U.S. Patent 5,135,993 – “High Modulus
Silicones as Toughening Agents for Epoxy Resins,” August 4, 1992.
9
G. Witucki, et al.; Dow Corning Corp.; U.S. Patent 5,280,098 – “Epoxy-functional Silicone
Resin,” January 18, 1994.
10
Donald H. Campbell; Janice E. Echols; Walter H. Ohrbom; BASF Corporation; U.S. Patent
5,853,809, December 29, 1998.

Additional References
1. E.P. Plueddemann; Silane Coupling Agents, 2nd ed., Plenum Press, NY, 1991.
2. M.K. Chaudhury; T.M. Gentle; E.P. Plueddemann; J. Adhes. Sci. Technol., 1(1), 29-38, 1987.
3. Y.K. Lee and J.D. Craig; The Electrochem. Soc. 159th Mtg., Paper 141, Minneapolis, 1981.
4. E.P. Plueddemann; H.A. Clark; L.E. Nelson; K.R. Hoffmann; Mod. Plast., 39, 136, 1962.
5. L.H. Lee; Adhesion Sci. & Technol., Vol. 9B, 647, Plenum, NY, 1975.
6. E.P. Plueddemann; Proc. Am. Soc. for Composites 1st Tech. Conf., Technomic Publ. Co.,
264-279, 1985.
7. P.G. Pape; J. Vinyl Additive Technol., 6(1), 49-52, 2000.
8. B. Thomas and M. Bowery; “Crosslinked Polyethylene Insulations Using the Sioplas
Technology,” Wire J., May, 1977.
9. P.G. Pape and E.P. Plueddemann; “History of Silane Coupling Agents in Polymer
Composites,” History of Polymer Composites, VNU Science Press, 105-139, 1987.
10. P.G. Pape and E.P. Plueddemann; “Methods of Improving the Performance of Silane
Coupling Agents,” Silanes and Other Coupling Agents, K.L. Mittal, ed., VSP, Utrecht, 1992.
11. E.P. Plueddemann and P.G. Pape; “The Use of Mixed Silane Coupling Agents,” SPI
Reinforced Plastics Technical Conference, Session 17-F, 1-4, 1985.
12. C.A. Roth; “Silylation Chemistry,” Ind. Eng. Chem. Prod. Res. Develop, 11, 134, 1972.
13. N.C. Angelotti and P.G. Pape; “Analytical Methods for Identification of Silanes and Silicones
in Plastics,” Soc. Plastics Engineers RETEC, Atlantic City, NJ, 187-196, 1996.
Contact
Dow Corning

How to Contact Us
Dow Corning has sales offices,
manufacturing sites, and science
and technology laboratories around
the globe. Telephone numbers of
locations near you are available
on the World Wide Web at
www.dowcorning.com, or by
calling one of our primary locations
listed below.

Your Global Connection

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