Zinc-free anticorrosives: Challenges and latest · PDF fileField Rusting . Adhesion Accelerated ... • Stabilizing metal cations by chelating effect on iron’ Ion scavenger ......
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Zinc-free anticorrosives: Challenges and latest developments Lars Kirmaier, Heubach GmbH
Slide 2 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013 Heubach GmbH, Lars Kirmaier
Why change a winning team?
Driving force behind going zinc-free
What can we offer?
Orthophosphates, Polyphosphates, Silicas How about performance?
Modified acrylic dispersion with calcium phosphate
Solvent based alkyd system with calcium phosphate
Solvent based 2K PU with calcium aluminum
polyphosphate
Coil coating primer with polyphosphate synergists
Powder primer with calcium modified silica
Solvent-free UV primer with calcium modified silica Where are we going?
Agenda
Slide 3 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
Zinc phosphate- Labelling and classification
Slide 4 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
Zinc price development
Zinc Price 1992 - 2009 (Euro)
200920082007200220012000 2004200319991998199719961995199419931992 2005 200640,00 €
60,00 €
80,00 €
100,00 €
120,00 €
140,00 €
160,00 €
180,00 €
200,00 €
220,00 €
240,00 €
260,00 €
280,00 €
300,00 €
320,00 €
340,00 €
Slide 5 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
Alternatives to zinc- what do we have?
Slide 6 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
Requirements:
Modified non-zinc metal complex
Anodic inhibition and barrier properties
Universal applicability
Easy handling
Stability in a broad range of resins
Price stability (non LME metal like Zn)
The wish list
What’s the problem?
Zinc(II) compounds are amphoteric with a special solubility behaviour in acidic and basic environments that most of the alternate metals don’t show!
Slide 7 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
Zinc-free anticorrosive pigments:
Orthophosphates
Calcium phosphate
Mid-level performance and alternative to zinc phosphate
Polyphosphates:
Calcium aluminum polyphosphate silicate hydrate
Strontium aluminum polyphosphate hydrate
High-performance pigments, alternative to zinc and
chromate containing anticorrosives
Ion-exchanger:
Modified silica gel
High-performance pigment for demanding coating systems
Alternatives to zinc?
Slide 8 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
Corrosion protection with zinc-free orthophosphates
• Anodic passivation- phosphate layers • Precepetation of M(OH)x (barrier)
(M: Ca, Sr, Mg….)
Slide 9 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
Challenge: Long-term performance
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Start 0,5 1 1,5 2 2,5 3 3,5 4 4,5 5 5,5 6Time (weeks)
Perf
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zinc orthophosphates zinc-free orthophosphates
Slide 10 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
Formulating with zinc-free anticorrosives
• Is the PVC optimized, find the optimum CPVC/PVC!
• Morphology of extenders and fillers (platy, lammellar….)!
• Mind the Additive package (hydrophobic)!
• If you do not match the desired protective performance:
Make use of benefits of different pigments by combinations!
’ Synergy!
Slide 11 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013 Heubach GmbH, Lars Kirmaier
Zn-free water based industrial primer
Primer: Mod. acrylic dispersion DFT: 80 microns Substrate: CRS ST 1205 Application: Air Spray Drying: 14d RT/ 2h 50°C
Slide 12 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
Undercutting
Blistering
Field Rusting
Adhesion
Accelerated Weathering Tests
Slide 13 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
Control Zinc phosphate Calcium phosphate
144h salt spray test acc. to DIN EN ISO 9227/ ASTM B 117-11 on CRS
Zn-free water based industrial primer
Slide 14 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
Control Zinc phosphate Calcium phosphate
648h humidity test acc. to ISO 6270 / ASTM D 2247-02 on CRS
Zn-free water based industrial primer
Slide 15 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
• Deposition of polyphosphate films on the metal surface
• Stabilizing metal cations by chelating effect on iron’ Ion scavenger
• Dissociation back to orthophosphates, anodic passivation
• Precepetation of M(OH)x (barrier)
(M: Ca, Sr, Mg….)
Corrosion Protection with zinc-free Polyphosphates
↔
Slide 16 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
Special modification of SAPP, for application like coil coating etc.
Altered solubility behavior due to the basic reacting metal oxides compared to amphoteric zinc
Strontium aluminum polyphosphate hydrate
SRPP
Strontium aluminum polyphosphate hydrate
SAPP
I: Modified polyphosphate hydrates
II: Modified polyphosphate silicate hydrates
Altered solubility behavior due to the calcium which is not chemically amphoteric as compared to zinc, in combination with the fixed active components
Calcium aluminum polyphosphate silicate hydrate
CAPP
Corrosion Protection with zinc-free Polyphosphates
Slide 17 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013 Heubach GmbH, Lars Kirmaier
Zn-free solvent based industrial primer
Primer: 2K-Polyurethane DFT: 60 microns Substrate: HDG Application: Air Spray Drying: 5 weeks RT/ 2h 50°C
Slide 18 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
1406h salt spray test acc. to DIN EN ISO 9227/ ASTM B 117-11 on HDG
Control Calcium phosphate CAPP
Zinc-free polyphosphates versus orthophosphates
Slide 19 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013 Heubach GmbH, Lars Kirmaier
Zn-free water based industrial primer
Primer: Epoxy ester DFT: 40 microns Substrate: CRS ST 1205 Application: Air Spray Drying: 2 weeks RT/ 2h 50°C
Slide 20 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
552h salt spray test acc. to DIN EN ISO 9227/ ASTM B 117-11 on CRS
Control Mod. Zinc phosphate CAPP
Zinc-free polyphosphates versus zinc orthophosphates
Slide 21 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
Synergy may be defined as two or more agents working together to produce a result not obtainable by any of the agents independently.
1+1=3
Using synergies- Let‘s work together
Higher efficiency in
anodic and cathodic areas
Slide 22 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013 Heubach GmbH, Lars Kirmaier
Using zinc-free synergies in Coil Coating primers
Primer: High molecular polyester (primer) Top Coat: Polyester DFT: Primer: 6-8 microns, Topcoat: 20-24 microns Substrate: Zincalume, pre-treated Cr-free HDG, pre-treated Cr-free Application: Doctor blade PCM: 232°C/450°F for primer and topcoat
Slide 23 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
T-Bend AS/NZS 2728:2007
Slide 24 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013 Heubach GmbH, Lars Kirmaier
1120h salt spray test acc. to DIN EN ISO 9227/ ASTM B 117-11 on zincalume
Using zinc-free synergies in Coil Coating primers
Slide 25 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
Strontium chromate SRPP/CAPP 1:1
1120h salt spray test acc. to DIN EN ISO 9227/ ASTM B 117-11 on zincalume
Using zinc-free synergies in Coil Coating primers
Slide 26 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
T-Bend ECCA –T8 [1996]
1t bend
3t bend
Vertical scribe
Horizontal scribe
Slide 27 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013 Heubach GmbH, Lars Kirmaier
2000h salt spray test acc. to DIN EN ISO 9227/ ASTM B 117-11 on HDG
Using zinc-free synergies in Coil Coating primers
Slide 28 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
Strontium chromate SRPP/CAPP 4:1
2000h salt spray test acc. to DIN EN ISO 9227/ ASTM B 117-11 on HDG
Using zinc-free synergies in Coil Coating primers
Slide 29 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
Strontium chromate SRPP/CAPP 4:1
2000h salt spray test acc. to DIN EN ISO 9227/ ASTM B 117-11 on HDG
Using zinc-free synergies in Coil Coating primers
Slide 30 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
Modified silica pigments
• Formation of a passive layer (barrier)
• Adsorption of corrosion stimulators
Slide 31 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013 Heubach GmbH, Lars Kirmaier
Zinc-free powder primer
Primer: Carboxylated polyester powder DFT: 100 microns Substrate: CRS ST 1205 Application: Korona Baking: 20 mins at 180°C
Slide 32 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
2520h salt spray test acc. to DIN EN ISO 9227/ ASTM B 117-11 on steel
Control Mod. zinc phosphate CTF
Zinc-free powder primer
Slide 33 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
Zinc-free UV primer
Primer: 100% Epoxy-Acrylate DFT: 30 microns Substrate: CRS ST 1205, HDG UV lamp: Mercury lamp 120W/cm Application: Roller Coater
Slide 34 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
480h salt spray test acc. to DIN EN ISO 9227/ ASTM B 117-11 on CRS
Control Zinc phosphate Mod. Zinc
phosphate
CTF
Zinc-free UV primer
Slide 35 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
1200h salt spray test acc. to DIN EN ISO 9227/ ASTM B 117-11 on HDG
Control Zinc phosphate Mod. Zinc
phosphate
CTF
Zinc-free UV primer
Slide 36 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
• Replacing zinc in anticorrosive pigments while
maintaining long-term performance is a challenge but
possible
• Using synergies by pigment combinations helps to
improve the overall performance (2-way synergy)
Novel multiphase pigments with mixed
inhibitive effect (1-way synergy)
New organic surface functionalizion
Ion-scavenging, complexation, coupling
Conclusions so far and new approaches
NEW!
Slide 37 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013 Heubach GmbH, Lars Kirmaier
Zinc-free synergistic pigment
Primer: Water based acrylic dispersion DFT: 70 microns Substrate: CRS ST 1205 Application: Air spray Drying: 21d RT/ 2h 50°C
Slide 38 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
240h salt spray test acc. to DIN EN ISO 9227/ ASTM B 117-11 on CRS
Zinc-free synergistic pigment
Control Calcium phosphate Zinc-free synergistic pigment
Mod. zinc phosphate
Slide 39 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
552h salt spray test acc. to ISO 6270 / ASTM D 2247-02 on CRS
Zinc-free synergistic pigment
Control Calcium phosphate Zinc-free synergistic pigment
Mod. zinc phosphate
Slide 40 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013 Heubach GmbH, Lars Kirmaier
Zinc-free surface functionalized pigment
Primer: Solvent based short-oil alkyd DFT: 70 microns Substrate: CRS ST 1205 Application: Air spray Drying: 21d RT/ 2h 50°C
Slide 41 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
Control Ca base pigment Functionalized Ca pigment
Zinc-free surface functionalized pigment
Slide 42 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
408h salt spray test acc. to ISO 6270 / ASTM D 2247-02 on CRS
Zinc-free Mg base pigment
Functionalized Mg pigment
Note: Surface modification has to be well matched to the base pigment!
No improvement!
Zinc-free surface functionalized pigment
Slide 43 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013 Heubach GmbH, Lars Kirmaier
Primer: Solvent based short-oil alkyd DFT: 50 microns Substrate: CRS ST 1205 Application: Air spray Drying: 21d RT/ 2h 50°C
Organophilized pigment
Slide 44 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
504h salt spray test acc. to ISO 6270 / ASTM D 2247-02 on CRS
Control Calcium phosphate Zinc phosphate molybdate
Organophilized zinc-free pigment
Organophilized pigment
Slide 45 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
504h salt spray test acc. to ISO 6270 / ASTM D 2247-02 on CRS
Control Calcium phosphate Zinc phosphate molybdate
Organophilized zinc-free pigment
Organophilized pigment
Slide 46 / 46 European Coatings CONFERENCE „Protective coatings“, 12. – 13. September 2013
Future targets:
Learn more about synergistic effects
Enhance universal applicability
Find the multi-tool of corrosion protection
Conclusions so far
Klicker / pixelio.de
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