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ICDS12

International Conference DURABLE STRUCTURES: from construction to rehabilitation


LNEC Lisbon Portugal 31 May - 1 June 2012

DURABLE STRUCTURES

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LNEC Lisbon 31 May - 1June 2012

Organic-Inorganic Hybrid Coatings for Corrosion Protection of Steel


Substrates A Review
R. B. Figueiraa, E. V. Pereiraa, C. J. R. Silvab, M. M. Saltaa

Laboratrio Nacional de Engenharia Civil, Lisboa, Portuga


Centro de Qumica, Universidade do Minho, Braga, Portugal

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Corrosion Prevention Why Carbon Steel?


Used in large tonnages in construction industry.

By their nature of limited allowing content, usually less than 2%


of total weight, carbon steels are liable to very high corrosion rates
in aggressive solutions and atmospheres.
The traditional surface passivation treatment for steel is obtained
by conversion coating.

ICDS12
International Conference DURABLE STRUCTURES: from construction to rehabilitation
LNEC Lisbon Portugal 31 May - 1 June 2012

DURABLE STRUCTURES

Corrosion Prevention

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LNEC Lisbon 31 May - 1June 2012

2)

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Corrosion prevention technology uses one or more of the following


methods:
1) Allowing metals with elements that enrich the surface with a
corrosion-resistant component during the corrosion process;
Surface chemical conversion treatments
Chromating);
3) Addition of aqueous inhibitors,
which adsorb strongly on the
metal surface and prevent the
reaction with
the oxidizing
Metallic
4) Deposition
of protective
coatings.
substrate
agent;

(Phosphating

and

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Phosphate Conversion Coatings (phosphating)

ICDS12
International Conference DURABLE STRUCTURES: from construction to rehabilitation
LNEC Lisbon Portugal 31 May - 1 June 2012

DURABLE STRUCTURES

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LNEC Lisbon 31 May - 1June 2012

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Chromate Conversion Coatings (Chromating)

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Sol-Gel Tecnhology

The protection of metals with


coatings has been an active area
of materials science for many
years.
However,
over
the
decades, changing regulation
governing both environmental
issues
and
human
health
imposed an increasing of efforts
to the design of new corrosion
protective systems.

Optical and
Photonic

Chemical

Mechanical

Applications
of Sol-Gel
Method

Electronic
and
Magnetic

Biomedical

Thermal

ICDS12
International Conference DURABLE STRUCTURES: from construction to rehabilitation
LNEC Lisbon Portugal 31 May - 1 June 2012

DURABLE STRUCTURES

12

LNEC Lisbon 31 May - 1June 2012

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Sol-Gel Tecnhology

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Sol-Gel Technology Inorganic Coatings


Sol-gel oxide coatings (purely inorganic) disadvantages:

Highly porous with low mechanical integrity so annealing or sintering


at high temperatures is required in order to achieve a dense
microstructure.
Sintering at high temperatures might produce coatings with cracks
and/or delamination. Also limits application of sol-gel coatings on
temperature sensitive substrates and devices.

ICDS12
International Conference DURABLE STRUCTURES: from construction to rehabilitation
LNEC Lisbon Portugal 31 May - 1 June 2012

DURABLE STRUCTURES

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LNEC Lisbon 31 May - 1June 2012

Organic-Inorganic Hybrid (OIH) Materials

Why study and invest in this type of materials?

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i. Synergetic properties that can arise from the combination of organic


polymer and inorganic material;
ii. Wide application range;

iii. Could be easily obtained by sol-gel method;

iv. Large variety of available chemical precursors.

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Organic-Inorganic Hybrid (OIH) Materials


How to apply these materials on the surface of the
substrate?

Dipping

Spinning

ICDS12
International Conference DURABLE STRUCTURES: from construction to rehabilitation
LNEC Lisbon Portugal 31 May - 1 June 2012

DURABLE STRUCTURES

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LNEC Lisbon 31 May - 1June 2012

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Organic-Inorganic Hybrid (OIH) Materials

A systematic theory
and procedure of
how to evaluate the
coatings viability,
efficiency and
stability must be
implemented

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Organic-Inorganic Hybrid (OIH) Materials


Akid et al.[6] proved that the corrosion resistance of stainless steel (SS) could
be increased by a factor of 30 using Class I hybrid coatings prepared by the
dispersion of poly(methyl methacrylate), into zirconia sol.
Phase separation and subsequent
delamination caused long-term
failure of the film

Class II hybrids reduce the phase separation and delamination increasing


mechanical resistance. Thereby the research in this area headed to
organofunctional alkoxysilanes that have been extensively used in the last
decade.

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ICDS12
International Conference DURABLE STRUCTURES: from construction to rehabilitation
LNEC Lisbon Portugal 31 May - 1 June 2012

DURABLE STRUCTURES

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LNEC Lisbon 31 May - 1June 2012

Organic-Inorganic Hybrid (OIH) Materials


Authors

Precusors tested

Chou et al.
(2003)

Tetraethoxysilane (TEOS) and 3-methacryloxypropyltrimethoxysilane (MAPTS)

Results

Gunji et al.
(2004)

Methyltriethoxysilane (MTES) and tri-isopropoxy(methyl)silane

Castro et al.
(2005)

TEOS and MTES

Jianguo et al.
(2006)

TEOS and MAPTS

Wang and
Akid (2007)

AlCl36H2O, TEOS and MTES

Good corrosion resistance

Kannan et al.
(2010)

2-methacryloyloxyethyl-phosphate containing a
polymerizable methacrylate group and a
functional group with MAPTS

Coatings improved corrosion resistance

Uniform coatings, defect-free, excellent adhesion


and flexibility. Enhanced corrosion protection

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Coatings were thermally stable. The adhesion and


hardness increased with the heating time and
temperature.

Homogeneous and crack-free coatings

This system enhanced the erosion-corrosion


resistance

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FUTURE OIH SYSTEMS AND APPROACHES

Combined systems will be


developed in order to achieve
the best protection possible
against corrosion such as
metal-rich solgel coatings,
containing zinc or magnesium
particles or other inhibitor
particles, which combine the
barrier properties of solgel
layer and cathodic protection
of sacrificial particles

Weathering or
loading damage

Water and ions


transport through the
topcoat

Sol-gel topcoat

Self-healing
agents
migration

OIH Sol-gel with inhibitors and self-healing agents


Sol-gel coating
Oxide Layer

Corrosion
inhibitors
migration

Metallic substrate

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ICDS12
International Conference DURABLE STRUCTURES: from construction to rehabilitation
LNEC Lisbon Portugal 31 May - 1 June 2012

DURABLE STRUCTURES

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LNEC Lisbon 31 May - 1June 2012

FUTURE OIH SYSTEMS AND APPROACHES

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OIH gel materials synthesized


and found in the literature
demonstrated market viability
either due to unique properties
that
allow
new
end-use
applications
or
own
a
significantly
better
cost/performance
relation
comparatively with the available
materials in the marketplace.

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We are dedicated to maintain a Natural, Safe and


GREEN Environment

THANK YOU FOR YOUR ATTENTION

The authors thank to FCT for supporting this study: PhD scholarship SFRH/ BD/62601/2009.