PDF PRESENTATION PRE-TREATMENTS OF METALS BEFORE PAINTING

Download 15 Jun 2014 ... cleaning, removing oxides, free of salts, inert conversion coating. Adhesion of ... water based solution of phosphate anion...

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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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BASICS ABOUT PRE-TREATMENT Properties of the Surface Scheme of the Aluminium Surface

SurTec International GmbH

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BASICS ABOUT PRE-TREATMENT Properties of the Surface Insufficient Removal of Oxides or Deformed Layers Aluminium

SurTec International GmbH

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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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BASICS ABOUT PRE-TREATMENT Corrosion Filiform Corrosion on Steel

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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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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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