Group TechnologyNew Business Development
CanVu
Advanced coating materials based on polysilazane
Sol-Gel & Polymers Tours 2008
Dr Can Vu
Clariant Advanced Materials Group Technology
Email: [email protected]
Group TechnologyNew Business Development
Advance coating materials based on polysilazanes
CanVu
New Materials Technology
Polysilazanes: Si, N, H, C polymers , blockbuilders for advanced materials
Si N*R2
R1
R3*n
Organic Polysilazane
Si N*H
H
H*n
Inorganic Perhydropolysilazane
SiO2, α-Al203nanosuspensions10-50 nm30-50 % solidsaquasol/organosol
Group TechnologyNew Business Development
Advance coating materials based on polysilazanes
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Functional polysilazanes
� Various functional groups are incorporated in the polymer backbone
� Copolymers allow adjustment to desired end -product properties and curing conditions
� Products are commercially available at industrial scale
Group TechnologyNew Business Development
Advance coating materials based on polysilazanes
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Broad range of applicationsCoatings� Clear coatings� Anti-corrosion coatings� Gas barrier coatings� Easy-to-clean coatings� High temperature coatings
Polymer hybrids� Hybrid coatings� Engineering polymers
Ceramics� Ceramic fibers � Ceramic matrix composites
Group TechnologyNew Business Development
Advance coating materials based on polysilazanes
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Mechanism of adhesion
curing - NH3
substrate
NH-groups reactwith polar groups
of substrate
polysilazanes bondcovalently to
substrate
polysilazane layer
OH OH OHOHOHOH
SiN
Si
H
Si
N
SiN
SiN
Si
H
H
H
N
SiN
SiN
HH
H
HH
H
H
H
H
HH
HH
H
H H
H
H
H
H
OHOH
SiHH
NO
Si
NSi
N
SiH
H
N
SiN
SiH
H
H
H
H
HH
HH H
H
NO O
H
SiN
Si
H
HN
H
H
O
� excellent adhesion on most substrates like glass, polycarbonate,PMMA, PET, aluminium, steel, marble, varnishes, etc.
Group TechnologyNew Business Development
Advance coating materials based on polysilazanes
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Curing kinetics
T
Si
H
N
H
H+H2O
-NH3,-H2Si
O
OO
Si
OH
OHOH
-H2O
SiO2
SiO2
Si
CH3
H
N
H mSi
CH
CH3
NH
CH2
n
T
UV SiN hybrid polymer
Curing: room T, Thermal, Radiation
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Advance coating materials based on polysilazanes
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Application of PZane formulations
Wiping Roll coating
Spin coatingSpray coating Dip coating
� Low viscosity, high solids content allows various types of applications� Curing: room temperature to 200°C� Film thickness: from 0,3 to 50 µm
Group TechnologyNew Business Development
Advance coating materials based on polysilazanes
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Easy to Clean applications with Polysilazanes
� Transport: antigraffiti coatings
� Automotive: easy-to-clean rims
� Metal protection: anti-tarnish, anticorrosion
� Architecture: UV protection, self-cleaning
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Advance coating materials based on polysilazanes
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tutoProm®, graffiti removal
Graffiti ink completely removed
uncoated
tutoProm® coated
� interior lining samples of DB, partially coated with tutoProm®
� different „bad inks” were applied� poor wetting of graffiti inks on coated substrate� graffiti inks can be completely removed with graffiti cleaners� penetration of ink into uncoated substrate -> graffiti removal not
possible
Group TechnologyNew Business Development
Advance coating materials based on polysilazanes
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Anti-graffiti coating, tutoProm®
� tutoProm® is appoved by German railway (DB)
� fluorine-free anti-graffiti coating� based on organopolysilazane� cures at room temperature � coating thickness: ca. 3 µm� outstanding adhesion and stability � for interiour and exteriour application� prevents the penetration of graffiti
paints and inks into laquered surfaces� excellent performance demonstrated
after 10 months of application on ICE high speed train
Group TechnologyNew Business Development
Advance coating materials based on polysilazanes
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tutoProm®, weathering test
with tutoProm® without (reference) with tutoProm®
uncoated
coated
uncoated
coateduncoated
� weathering test results after ca. 3000 h (DIN 11341, xenon test)� no chalking when coated with tutoProm®
� good colour and gloss conservation of DB coating system with tutoProm®
Group TechnologyNew Business Development
Advance coating materials based on polysilazanes
CanVu
uv protection coatings,polysilazanes and nanoscaled metal oxides
uncoated
PHPS / nanoparticles
uv exposed unexposed
� uv protection of dyes for anodized aluminium� reduces fade out of alu dyes significantly� PHPS and nanoscaled metal oxide
alu dye nanoscaled uv absorber
aluminium
PHPS coating
Al2O3 through anodization process
Group TechnologyNew Business Development
Advance coating materials based on polysilazanes
CanVu
Brake dust barrier coatings
reference80°C / 2 h
reference160°C / 2 h
organopolysilazane160°C / 2 h
� simulation of brake dust impact on clear coated rims � reference: conventional rim coating system� brake dust was mixed with water and applied on sample,
exposed at 80°C and 160°C � attack of brake dust on rims is prevented
Group TechnologyNew Business Development
Advance coating materials based on polysilazanes
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Metal protection
� anti-tarnish
� anti corrosion
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Advance coating materials based on polysilazanes
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Anti-tarnish coatings, AgTive®
� anti-tarnish coatings for silver, copper, brass and bronze
� barrier effect of AgTive® coating prevents silver from tarnishing, even in H2S atmosphere
� based on inorganic polysilazanes or organopolysilazanes
Silver, after H2S exposure
uncoated
coated
uncoated
coated
Copper, 14 days of outdoor weathering
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Advance coating materials based on polysilazanes
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Corrosion protection coatings
uncoated organopolysilazane hybrid system
chromated aluminium panels after CASS test, 240 h
� excellent adhesion on different aluminium alloys� CASS test passed (240 h), DIN 50021, with
- organopolysilazanes- organopolysilazanes combined with silica nanoparticles- hybrid systems
� coating thickness between 8 – 10 microns
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Advance coating materials based on polysilazanes
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Automotive applications
� easy-to-clean RIMS
� gas manifold, heat exchanger
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Advance coating materials based on polysilazanes
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Ceraset High temperature coatings
Heat exchanger coated with Ceraset HTT Engine Manifold coated with Pigmented Ceraset HTT
Features:•No delamination•Excellent resistance to thermal oxydation•Excellent resistance to corrosive atmospheres•Efficient thermal barrier, •High efficiency engines, energy saving
Group TechnologyNew Business Development
Advance coating materials based on polysilazanes
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Heat resistant Coatings on various Metals
� Conversion of polysilazanes to ceramics at high temperature providesgood
protection against oxidation and corrosion
� Adhesion is excellent e.g. on mild steel even after several cycles of heating
to 1000°C and immersion into cold water
� Can be used for coating heat exchangers, engine manifolds, exhaustpipes etc.
Brass coupon, half coated
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Advance coating materials based on polysilazanes
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Polymer Hybrid Composites with
Polysilazane
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Advance coating materials based on polysilazanes
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Hybrid polymers with polysilazanes
Example: reactivity of PZanes with isocyanate and epoxy groups
Si N NR
O
H
Si NH
RNCOOCN
O
RO
R
O ON N
SiSi
++
� SiH and NH are reactive groups � Genuine hybrid polymers can be made� Exceptional properties expected: mechanical strength, resistance to
chemicals, to temperature and excellent adhesion on various substrates
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Advance coating materials based on polysilazanes
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Products: PZane-Isocyanate Composites
Si N SiR
HH2N
HN
R
HHn
HRN N C OCO+
N SiHN
R
HHn
HSiR
HH2N N
RN
CO
CO
Ceraset VL20 / HDI trmer/fiber glass
� Exceptional Strength� Extreme Durability� Non-Burning � No Smoke Generation� Cost Effective (High Fill Loading)� Uses include products for transportation components, sporting goods, civil
infrastructure components, ship components, marine structures, chemical process components, etc.
Composite PU2K system with VL20/ IPDI
Composite PU1K system with VL20/ blocked HMDI
Group TechnologyNew Business Development
Advance coating materials based on polysilazanes
CanVu
Conclusions
� Polysilazanes are a new class of inorganic polymers produced at industrial scale by Clariant
� Large scope of applications:Protection coatings, Hybrid coatings, composites PMC, ceramics
CMC
� Advanced properties: very good resistance to thermal, chemical, mechanical,
environmental aggression.
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