Advance coating materials based on polysilazanes
Transcript of Advance coating materials based on polysilazanes
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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]
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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
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Advance coating materials based on polysilazanes
CanVu
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
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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
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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.
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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
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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
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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
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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®
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Advance coating materials based on polysilazanes
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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
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Advance coating materials based on polysilazanes
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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
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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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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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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
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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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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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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
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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.