Protection upgraded
Pre-Treatments of Metals before Painting Phosphatings and Energy-Efficient Alternatives Peter Volk Fachforum parts2clean June 25th, 2014
AGENDA
1
Basics about Pretreatment
2
Cleaning/Pickling
3
Conversion Treatment: Phosphating
4
Conversion Treatment: Alternative Processes
5
Summary
6
Annex - SurTec Fields of Application
SurTec International GmbH
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June 15th, 2014
BASICS ABOUT PRE-TREATMENT
SurTec International GmbH
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June 15th, 2014
BASICS ABOUT PRE-TREATMENT Properties of the Surface Residues at the Surface
SurTec International GmbH
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June 15th, 2014
BASICS ABOUT PRE-TREATMENT Properties of the Surface Scheme of the Aluminium Surface
SurTec International GmbH
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June 15th, 2014
BASICS ABOUT PRE-TREATMENT Properties of the Surface Insufficient Removal of Oxides or Deformed Layers Aluminium
SurTec International GmbH
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June 15th, 2014
BASICS ABOUT PRE-TREATMENT Corrosion Filiform Corrosion on Aluminium
Scratch artificial damage starting point for corrosion
Corrosion Threads
SurTec International GmbH
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June 15th, 2014
BASICS ABOUT PRE-TREATMENT Corrosion Filiform Corrosion on Steel
SurTec International GmbH
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June 15th, 2014
BASICS ABOUT PRE-TREATMENT Corrosion Filiform Thread
„Head“ Cl-, H+, Mex+, O2
The „Head“ contains corrosive salts The „Thread“ contains corrosion products and oxides „Thread“ MexOy, Me(OH)z
Filiform corrosion proceeds: in direction of the structure of the material (creases, scratches) Filiform threads do not cross thickness of paint has no influence the head is „supplied“ with O2 and H2O through the thread
Filiform corrosion occurs: defect in the paint „activation“ with salt rel. humidity: 80 % (40-90 %)
SurTec International GmbH
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June 15th, 2014
BASICS ABOUT PRE-TREATMENT Purpose of the Pre-Treatment Defined State of the Surface = cleaning, removing oxides, free of salts, inert conversion coating
Adhesion of the coating (paint) = Surface Tension Part > Surface Tension Coating
σc ≤ σs
σp = Surface Tension of Coating σs = Surface Tension of Part
Typically demanded: σs = 38-40 mN/m the coating can wet the surface and spread
Aim: corrosion protection minimise corrosion between coating and part minimise Filiform corrosion
SurTec International GmbH
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June 15th, 2014
BASICS ABOUT PRE-TREATMENT Possibilities of Pre-Treatment Mechanical Pre-Treatment Cleaning - Blasting, Grinding, Brushing – Cleaning
Chemical Pre-Treatments Cleaning Cleaning/Conversion Treatment (e.g. Iron Phosphating) Cleaning – Conversion Treatment (e.g. Zinc Phosphating) Cleaning – Pickling – Conversion Treatment Cleaning – Pickling – Conversion Treatment - Passivation
Conversion Layer = Transformation of the surface A conversion layer is defined as non-metallic, mostly inorganic, very thin layer on a metal surface, that usually is produced by chemical reaction of the metal in a water based process solution.
SurTec International GmbH
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June 15th, 2014
AGENDA
1
Basics about Pretreatment
2
Cleaning/Pickling
3
Conversion Treatment: Phosphating
4
Conversion Treatment: Alternative Processes
5
Summary
6
Annex - SurTec Fields of Application
SurTec International GmbH
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June 15th, 2014
CLEANING Mechanism Cleaning – removing loosely bound pollutants
vegetable, animal and mineral oils metal soaps corrosion inhibitors pigments residues of a mechanical treatment
Schematic:
hydrophobic particles (coal, soot) hydrophilic particles (oxides) builder chips fat, wax, oil, lubricant surfactant
SurTec International GmbH
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June 15th, 2014
CLEANING
Poor Cleaning Result: release agents, oils, silicones, pigments remain on the surface coatings cannot wet the surface and have poor adhesion Wettability of the Surface indicates the Quality of the Cleaning
water Hill GmbH
SurTec International GmbH
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June 15th, 2014
PICKLING Mechanism Pickling – Chemical Attack of the Surface Removing: scales from casting or rolling oxides corrosion products grates mechanically deformed layers
Me2+ + 3 H2O
MeO + 2 H3O+
Oxides and Boundary Layers may act like a Separating Agent
Magnesium Pickling SurTec 486
Alloy: MgAl4RE4Mn
SurTec International GmbH
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June 15th, 2014
AGENDA
1
Basics about Pretreatment
2
Cleaning/Pickling
3
Conversion Treatment: Phosphating
4
Conversion Treatment: Alternative Processes
5
Summary
6
Annex - SurTec Fields of Application
SurTec International GmbH
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June 15th, 2014
PHOSPHATING General Differences Amorphous Layer Phosphating (Iron Phosphating): water based solution of phosphate anions solution contains no metal cations taking part in the layer formation only cations coming from the base material take part
Crystalline Layer Phosphating: water based solution of phosphate anions and metal cations the cations of the solution take part in the film formation additionally, cations from the base material can take part main processes: zinc phosphating, manganese phosphating, zinc calcium phosphating
SurTec International GmbH
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June 15th, 2014
PHOSPHATING Amorphous Layer Phosphating (Iron Phosphating) Properties
low cost
cleans and phosphates in one step
spray and immersion application
easy processing Cleaning
Cleaning/ Phosphating
rinse
rinse
DI-rinse
Phosphating
rinse
rinse
DI-rinse
Typical Process Sequences
thin coating
suitable for steel
with fluorides suitable for zinc and good cleaning for aluminium
much less sludge compared to zinc phosphating
automatic dosing possible (pH-value)
amorphous (non-crystalline) structure approx. 0,3–0,8 g/m²
SurTec International GmbH
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June 15th, 2014
PHOSPHATING Crystalline Layer Phosphating Zinc Phosphating Thin Layer Phosphating:
spray and immersion application
excellent corrosion protection
good adhesion of coatings
suitable for Fe- und Zn-materials
with fluoride suitable for aluminium
short application time
Comparison to Iron Phosphating
more difficult to handle
formation of sludge
SurTec International GmbH
Crystalline Structure of the Layer approx. 1,5 – 5,0 g/m²
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June 15th, 2014
AGENDA
1
Basics about Pretreatment
2
Cleaning/Pickling
3
Conversion Treatment: Phosphating
4
Conversion Treatment: Alternative Processes
5
Summary
6
Annex - SurTec Fields of Application
SurTec International GmbH
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June 15th, 2014
ALTERNATIVE PROCESSES General Properties Phosphating
iron phosphating (Fe, Zn)
zinc phosphatierug (Fe, Zn, Al)
„New Technologies“
multi-metal (Fe, Zn, Al)
spray and immersion application
low application temperature (25-35 °C)
free of phosphates, nickel, nitrite, hydroxyl amine, hydroxyl ammonium sulfate
no sludge vs.: zinc phosphating: iron phosphating:
SurTec International GmbH
<0,1 g/m² 3-6 g/m² 0,5 g/m²
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June 15th, 2014
ALTERNATIVE PROCESSES ZetaCoat Real Conversion Coating The surface is attacked chemically and transformed into stable Cr(III)/Zr(IV)-oxides. Due to the slight attack by acids, the oxides are thoroughly linked to the metal. The layer is thin (approx. 20-40 nm) and coherent.
MeOx + 2x H+ Me + n H+
Chemical Attack Me OH OH O
Men+ +x H2O Men+ + 0,5n H2 ↑
OH
OH OH OH OH OH OH
O
OH
O
OH OH OH OH OH OH OH OH OH OH
OH OH OH OH OH OH OH OH OH OH OH OH OH OH OH OH OH OH OH OH OH OH OH OH
Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me
Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me
Metal
Layer Formation
Metal
OH
HO
2 Cr3+ + 4 Zr4+ + 11 H2O
OH
OH
O
Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me
O
Zr
Cr
OH OH OH OH OH OH OH OH OH OH OH OH OH OH OH OH OH OH OH OH OH OH OH OH
O
O
O
O
OH O
Zr Zr O
OH
OH OH
Cr O O
O
HO
O
O O
O
Zr
O
O
Zr
Cr
O
O
Zr
O
O O
O
O
OH OH
O
Zr
OH HO O OH OH OH O OH O O O Zr Cr Zr O O Cr
Zr
Zr O
HO
Zr
Zr O
O
O OH
Cr
Zr O
O
O
Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me
Metal
SurTec International GmbH
OH
Cr2O3* 4 ZrO2 + 22 H+
O
Cr
Metal
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June 15th, 2014
ALTERNATIVE PROCESSES SEM-Analysis of the treated surface
Non-treated Deposited Zr-/Cr(III)-oxides
Treated in SurTec 609 ZetaCoat SurTec International GmbH
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June 15th, 2014
ALTERNATIVE PROCESSES ZetaCoat Simplification of the Process Phosphating
Cleaning SurTec 168/086
rinsing
Activiating SurTec 610 V
rinsing
rinsing <350 µS
Phosphating SurTec 618 SurTec 618 LT
rinsing
Passivating SurTec 580
DI-rinse
ZetaCoat
Cleaning SurTec 168/086 40-60 °C 1-3 min
SurTec International GmbH
ZetaCoat SurTec 609
DI-rinse
25-35 °C 0,5-3 min
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June 15th, 2014
ALTERNATIVE PROCESSES Waste Management Increasing Salt Concentration in the Active Bath: increasing need of rinsing water increasing amount of sludge during the waste water treatment more complex waste water treatment and higher consumption of chemicals
Comparison of the processes
(concentration in the bath [ppm]):
Iron-Phosphat.
Zinc-Phosphat.
SurTec 609 ZetaCoat
phosphate
2000-10000
5000-20000
-
zinc
-
1000-10000
-
manganese
-
20-1000
-
nickel
-
50-1000
-
fluoride
100-500
100-500
< 500
chromium(III)
-
Sum
< 10500
< 100
< 32500
< 600
Up to 50-times less sludge during waste treatment of SurTec 609 ZetaCoat. SurTec International GmbH
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June 15th, 2014
ALTERNATIVE PROCESSES Corrosion Protection VDA-621-415, cyclic Corrosion Test, 6 Cycles Polyester Powder Paint, Interpon D1036/Gloss(85), SGJ02G
Steel
SurTec International GmbH
Aluminium
EG
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HDG
June 15th, 2014
AGENDA
1
Basics about Pretreatment
2
Cleaning/Pickling
3
Conversion Treatment: Phosphating
4
Conversion Treatment: Alternative Processes
5
Summary
6
Annex - SurTec Fields of Application
SurTec International GmbH
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June 15th, 2014
SUMMARY Pre-treatment of Metal Surfaces In order to obtain good adhesion and corrosion protection, a pre-treatment is essential
removal of contaminants (oils, fats, particles)
removal of sorption layers, oxides, deformed layers
achieving a stable and uniform state of the surface having a high surface tension
conversion layers partially provide a temporary corrosion protection (until the coating has been applied)
improving the adhesion of successively applied coatings
minimising corrosion between metal und coating/paint
So-called “New Technologies” increasingly compete with Phosphatings
the new technologies run free of Ni, Mn, PO4, NO2, HAS/HA
they produce virtually no sludge
they show similar performance as the phosphatings
SurTec International GmbH
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June 15th, 2014
Protection upgraded
Thank You.
AGENDA
1
Basics about Pretreatment
2
Cleaning/Pickling
3
Conversion Treatment: Phosphating
4
Conversion Treatment: Alternative Processes
5
Summary
6
Annex - SurTec Fields of Application
SurTec International GmbH
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June 15th, 2014
Protection upgraded
SURTEC COMPANY PROFILE April 2014
SurTec International GmbH
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Experts for Surface Technology and Electroplating
surtec
1993
2005
Foundation in Germany (MBO)
1975-1987 Acquisition of 2 small cleaner suppliers, setup of an ample program for parts cleaning and pretreatment
Foundation of SurTec in Poland, Scandinavia, Croatia, Romania, Slovakia, PR China and Benelux
2002 Foundation of the Holding SurTec International
1999/2000 New building in Zwingenberg, Germany; foundation of SurTec in China, Brazil and USA
1994-98 Foundation of SurTec in
1974 Switzerland, Korea, Unilever buys Kemia Serbia, Bosnia, Austria (metal cleaning, and Czech Republic aircraft industry) SurTec International GmbH
Electroplating
1988 Business unit OFT with SurTec brand gets started
Industrial Parts Cleaning
1989 Unilever buys Elektro-Brite, start of the plating business
R&D-Centre in Brazil
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Metal-Pretreatment
Development of the SurTec Group
2014 Acquisition of SurTec MMC, Japan
2010 SurTec becomes a business unit of Freudenberg Chemical Specialities, Munich
2009 Start of business unit Metal Pre-Treatment; foundation of SurTec Asia Pacific, Vietnam and Russia
2006-2008 Foundation of SurTec in India, South Africa, Slovenia, France, Japan and Mexico, Middle East; new building in China
June 15th, 2014
Vision And mission Vision
We are the preferred supplier of chemical specialties for surface treatment. We are unique in delivering solutions for Industrial Parts Cleaning, Metal Pre-treatment and Electroplating.
Mission
Our commitment is to develop and manufacture high quality chemical specialties and processes to meet our customers requirements. We sell directly on a worldwide basis and provide excellent technical consulting and services. Our products and processes ensure superior economy based on price/performance evaluations and minimal effect on the environment. People
Motivated and committed employees
SurTec is a leading player in chemicals for surface treatment processes
Environmentally superior product/process characteristics
Aprrox. 360 people
Customers
Turnover 2013: EUR 60m
Superior efficiency and performance
More than 800 products and formulations
Products & Services Broad product portfolio and dedicated services
SurTec International GmbH
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June 15th, 2014
Surtec
Highly Competent Chemicals for Surface Technologies
Success Factors High technical expertise Long-term customer relationships Individual solutions for our customers
SurTec International GmbH
Global Presence
SurTec – A Powerful Brand
SurTec has an effective international network in terms of
Products of highest possible quality and performance
Research & Development
Production
Sales
Service
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Superior economy, based in price/performance evaluations
Minimal effect to the environment
June 15th, 2014
SurTec
Fields of Application
Industrial Parts Cleaning (IPC)
Electroplating (ELP)
Metal Pre-treatment (MPT)
Final Cleaning
Functional Plating
Pre-treatment of Lightmetals
Interoperational Cleaning
Decorative Plating
Pre-treatment of Femetals
MRO Cleaning
Plating on Plastic
Stainless Steel
Temporary Corrosion Protection
Special Plating
Hot Dip Galvanizing
SurTec International GmbH
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June 15th, 2014
SURTEC Affiliates and Partners Americas
SurTec do Brasil, Brazil SurTec, Inc., USA SurTec Mexico Steel Quimica, Argentina Alianza Limitada, Chile GMP Productos Quimicos, Columbia
EMEA
SurTec Deutschland SurTec France SurTec Ges.m.b.H., Austria SurTec Scandinavia SurTec Benelux SurTec Polska, Poland OOO SurTec, Russia SurTec Split, Croatia SurTec SK, Slovakia SurTec ČR, Czechia SurTec Čačak, Serbia SurTec Adria, Slovenia SurTec Romania ST Ibérica, Portugal SurTec Schachen, Switzerland SurTec Eurosjaj, Bosnia/Herzegovina
SurTec Egypt SurTec South Africa SurTec Middle East
SurTec International GmbH
Italtecno, Italy Coquinesa, Spain DEDE, Turkey - 37 -
Asia/Pacific SurTec Hangzhou, China YST Surface Technology, China SurTec Chemicals, India SurTec Vietnam SurTec MMC, Japan SurTec Korea, South Korea SurTec M.E., Pakistan SurTec Taiwan Cahaya Chandra Cemerlang, Indonesia Morimura, Japan MS Chem, Malaysia Electrochemical, Thailand
Australia
Consolidated Alloys
June 15th, 2014
surtec
Selective Customers
Industrial Parts Cleaning
SurTec International GmbH
Electroplating
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Metal-Pretreatment
June 15th, 2014
Protection upgraded
Thank You.
SurTec International GmbH
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