Evolution of

Inorganic/Organic
Hybrid Systems for the
Protective Coatings Industry

By Neil Wheat, Ameron BV, Geldermalsen, The Netherlands

he chemistry
low VOC content means that they pro- marine, offshore, and onshore facilities.
and performance
vide reductions in solvent emissions to Research and development in the area
of inorganic/
comply with VOC legislation world- of polysiloxane coatings chemistry has
organic hybrid
wide, a significant advantage over other led to the development of more types
of polysiloxane hybrids. This article discoatings are well lower solids, high weather-resistant
cusses how these inorganic/organic
documented in
coatings, such as acrylics and fluohybrids continue to be developed. Their
publications,
ropolymers.
performance characteristics and potenpapers, and
Since their introduction, these types
tial uses in protective coating systems
patents from the coatings industry and of coatings, generally referred to as
are detailed.
other scientific establishments. This polysiloxanes, have been used on
area of research has been one of the numerous major projects worldwide for
Performance of
most rapidly expanding withPolysiloxanes
in the coatings industry over
In protective coating systems,
recent years. The introduction
the use of a single, high-build
of hybrid coatings in the mid
polysiloxane topcoat to replace
1990s provided the first new
the traditional two-coat epoxy
generic type of protective
intermediate/polyurethane
coating for over 25 years,
over either an inorganic zinc
since the introduction of
silicate or an epoxy zinc-rich
polyurethanes. The perforprimer has been proven both in
mance properties (e.g., weaththe laboratory (Table 1) and in
ering resistance) and non-isothe field.
cyanate curing mechanisms of
In addition to the extensive
hybrids have made them costlaboratory testing, major field
effective and safer alternaprojects around the world have
tives to polyurethane topDevelopment continues on siloxane hybrids, expanding their versatility.
been undertaken with these
coats. Their high solids and
Photos courtesy of Ameron International

30

JPCL / August 2005 / PCE

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Table 1: Comparison of a Two-Coat Zinc-Rich Epoxy Polysiloxane System

and a Three-Coat Zinc-Rich Epoxy/Polyurethane System
Test Description
3,000 Hours Testing
Salt spray (ISO 7253)
Scribe blistering (ASTM D1654/A)
Blistering/Rusting
Cyclic (ISO 20340 Procedure A)
Scribe blistering (ASTM D1654/A)
Blistering/Rusting
Cyclic (ASTM D5894)
Scribe blistering (ASTM D1654/A)
Blistering/Rusting

Epoxy Zinc/Epoxy Siloxane

@ 75/125 m

Epoxy Zinc/HB Epoxy/PU

@ 75/200/50 m

2mm
None/Ri0

2.5mm
None/Ri0

4mm
None/Ri0

5mm
None/Ri0

2.5mm
None/Ri0

2.5mm
None/Ri0

Present Polysiloxane
Coatings Technology

Table 2: General Properties of Typical Examples

of Commercially Available Siloxane Hybrids
Test Description
Drying Times (ASTM D1640)
Touch at 21 C
Touch at 4 C
Through at 21 C
Through at 4 C
Pendulum Hardness (in seconds,
per ASTM D4366)
@ 7 days
@ 14 days
@ 21 days
@ 35 days
Corrosion Resistance 3,000 hours
(125 m over 75m epoxy zinc rich)
Salt spray (ISO 7253)
Creep
Blistering/rusting
Prohesion (ASTM G85)
Creep
Blistering/rusting
Cleveland Humidity (ASTM D2247)
Creep
Blistering/rusting

Epoxy Siloxane

Acrylic Siloxane

1 hr
4 hrs
3 hrs
16 hrs

4 hrs
8 hrs
10 hrs
24 hrs

78
101
103
110

33
57
60
71

0.5mm
0/Ri0

0.5mm blisters 3 (S5)

Blisters 2 (S2)/Ri0

1mm
0/Ri0

3mm
0/Ri0

0mm
Blisters 4 (S2)/Ri0

0mm
Blisters 4 (S4)/Ri0

two-coat systems, with currently up to

10 years of exposure in some of the
most severe environments.
Two-coat systems do, of course, have
limitations. Experience has shown that
when applying a two-coat system, care
is needed to ensure that adequate film
thickness is achieved, particularly at
edges. Stripe coating is a good practice
with any protective coating system;
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insufficient in providing all the properties required from a protective coating.

The repeating silicon-oxygen structure
of the polysiloxane molecule provides
the backbone of the superior weatherability of polysiloxanes. However,
organic modification of the polysiloxane
is necessary to achieve a balance of
properties, such as film formation, corrosion resistance, and adhesion. A level
of organic modification of around 20
50% has been identified to optimize the
required properties.

Aliphatic epoxy-modified polysiloxane

coatings have been commercially available since the mid 1990s. More than 5
million square metres (54 million sq ft)
have been coated in Europe alone.
More recently, acrylic-modified polysiloxanes have been introduced.
Comparisons of both of these coating
types and their performance characteristics have been carried out in detail. It
can be concluded that both these
hybrids have their relative merits.
Generally, the epoxy siloxane shows
higher solids, lower VOC, and faster
cure and hardness development. The
acrylic siloxanes generally show
improved UV resistance. Corrosion
resistance of the epoxy siloxane tends
to be better in higher humidity (Table 2).

New Inorganic/Organic Hybrids

particular attention to stripe coating is

required for a two-coat system.
However, even with the increased
attention needed during application,
the advantages of applying two coats
instead of three coats and obtaining
improved durability and performance
can significantly reduce both applica tion and life cycle costs.
Polysiloxane binders themselves are
JPCL /

August 2005

PCE

The versatility of siloxane chemistry

allows the formation of
inorganic/organic hybrids with a wide
range of organic polymers. The original
aliphatic epoxies and later acrylic
siloxanes provide excellent performance as protective coatings. In addition, combinations with vinyls, aceto
acetates, fluoropolymer, elastomeric
epoxy, and phenol binder systems have
also been developed. Self-curing siloxane hybrids also show potential. These
new hybrids not only improve the current polysiloxane coatings but also
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Table 3: Comparison of Properties of Single-Pack Acrylic Siloxane Hybrids

Test Description
Volume Solids (ISO 3233)
VOC (EPA Method 24)
Viscosity (Krebs Units)
QUV-B Weathering
Gloss retention
500 hours
1,000 hours
1,500 hours
2,000 hours
2,500 hours

First Generation One-Pack

Acrylic Siloxane
55%
384 g/l
80 ku

Second-Generation One-Pack
Acrylic Siloxane
80%
262 g/l
79 ku

89%
85%
69%
48%
35%

89%
89%
85%
75%
59%

Table 4: Comparison of ASTM C-589 Compressive Strength

after Seven Days Chemical Immersion

Chemical
None
Acetic acid
Xylene
NH4OH 28%
NaOH 50%
Conc. HCl
Methanol
NAOCl 5%

Aromatic Amine-Cured Epoxy Elastomeric Epoxy Siloxane

Compressive
Compressive
Strength psi
% Retained
% Retained
Strength psi
10,950
10,875
10,220
93.3
97.1
10,555
10,750
98.2
98.9
10,715
10,400
95.0
95.6
10,875
10,150
92.7
98.7
10,735
11,150
101.8
97.6
10,610
6,450
58.9
98.7
10,735
11,750
107.3
98.8
10,745

provide potential to expand their use

in areas such as tank linings; adhesives;
flooring; architectural systems; laminates; and single-pack high solids, highbuild maintenance coatings.

Fluorinated Epoxy
Siloxane Hybrids
Coatings formulated with fluorinated
epoxy siloxane hybrids may provide
high durability. The use of fluoropolymers for highly weather-resistant coatings is well known; but such products
tend to have relatively low solids and
high VOC levels. Fluorination of the
epoxy siloxane hybrid provides the
UV resistance of the fluoropolymer
together with the high solids and low
VOC of the epoxy siloxane. Results of
accelerated testing provide between
20-50% improvement in weatherability
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have been investigated with positive

results.

Single-Pack, High-Solids
Acrylic Siloxane Hybrids
Acrylics have been the resin of choice
for weatherability in the protective
coatings market for a number of years.
Combining an acrylic with siloxane can
improve weathering while increasing
solids and reducing VOC content. Both
single-pack and two-pack acrylic silox anes have been commercially available
over the past two to three years.
Self-curing polysiloxanes offer
advantages over two-pack materials.
Single-component materials lend themselves to easier application without the
usual need for mixing, restrictions in
application time due to pot-life, and
waste because of unused, catalysed
material. These properties make selfcuring polysiloxanes ideal for use in
maintenance situations, particularly for
brush and roller application in difficult
access areas. A medium-solids, highVOC, self-curing acrylic siloxane mate rial has been commercially available in
the past two years. Further development of this technology has
resulted in the formulation of
a higher solids material with a
much reduced VOC and volume solids of 80% (Table 3).
Significant improvement in
weathering resistance over
the lower-solids, acrylic siloxane materials has been measured.

High weathering resistance, a property of the original polysiloxane, is even higher in the new generation hybrids.

over the aliphatic epoxy polysiloxane,

even better than the acrylic siloxane
materials. This improvement is
achieved with no compromise on the
corrosion resistance afforded by epoxy
siloxane material. The level of improvement depends on the type of fluorinated species used to modify the epoxy
siloxanes. A number of modifications
JPCL / August 2005 / PCE

Chemical-Resistant
Elastomeric Epoxy
Siloxane Hybrid

Elastomeric epoxy siloxane hybrids

exhibit excellent chemical resistance to
acids, alkalis and solvents, together
with excellent mechanical properties.
They show potential as alternatives to
MDA and aromatic amine-containing
epoxy coatings that are generally used
where overall chemical resistance is
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of siloxane hybrid coatings for application at the thicknesses typical for twopack polyurethane topcoats. These new
hybrids can be applied at dry film thicknesses of 4075 microns with excellent
weathering, low solvent content, and no
harmful isocyanates. Such polysiloxanes may find practical use in other
market segments such as original equipment manufacturing but they will also
have great potential as cost-effective
replacements for polyurethane topcoats
in the protective coatings industry.

Conclusion
Fig. 1: Comparative QUV-B Data of Pigmented Fluorinated Epoxy Siloxane Hybrids

Inorganic/organic siloxane hybrid

coatings are the first new generic coating type to be introduced to the protective coatings industry since
polyurethanes more than 25 years ago.
Since commercialization in the 1990s,
their use has grown rapidly and their
performance has been proven. The
potential for the development of further siloxane hybrids is vast; new products continue to evolve. These new
hybrids show improvements over the
currently available materials and provide potential for use in exposures for
which polysiloxane coatings were previously restricted.

Fig. 2: Comparative QUV Data of First-Generation and Second-Generation Single-Pack Acrylic Siloxanes

desired. Elastomer modification is

brought about by the introduction of
carboxyl-terminated butadiene-acrylonitrile (CTBN). In combination with
standard epoxy resins, this modification normally has a tendency to
reduce chemical resistance. However,
in combination with epoxy siloxane,
this reduction does not occur (Table 4).
The curing agent is formed by the
blending of aminosilane and aliphatic
amine. These formulations provide not
only outstanding chemical resistance
but also excellent resistance to thermal
cycling and cracking at ultra-high film
thicknesses in excess of 700 microns.
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The coatings provide solutions for

chemical processing, secondary containment, and other environments
where a high level of chemical resistance is required.

Thin-Film Siloxane Hybrids

The commercially available polysiloxane coatings are currently high-build
products with typical dry film thicknesses of 100150 microns per coat.
This build provides the basis for their
use in replacing the traditional
epoxy/polyurethane intermediate/topcoat system. However, recent developments have led now to the formulation
JPCL / August 2005 / PCE

Neil Wheat has over 20 years of experience in the field of protective coatings. In
1998, he was appointed UK laboratory
manager for Ameron BV and subsequently
was made the head of the companys
product maintenance and development
laboratories in The Netherlands and the
UK. He is now technical director of
Ameron BV Performance Coatings and
Finishes Group.
Mr. Wheat, a member of the Royal
Society of Chemistry, has a formal education in applied chemistry from North
Nottinghamshire College and Sheffield
Hallam University. He is an active member
of the British Coatings Federation High
Performance Coatings Group and CEPEs
Protective Coatings and Marine Technical
Committees.
33