PDF PRESENTATION PRE-TREATMENTS OF METALS BEFORE PAINTING

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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


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BASICS ABOUT PRE-TREATMENT Properties of the Surface Residues at the Surface


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


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


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BASICS ABOUT PRE-TREATMENT Corrosion Filiform Corrosion on Aluminium

Scratch artificial damage starting point for corrosion

Corrosion Threads


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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 %)


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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


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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.


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AGENDA

1


2

Cleaning/Pickling

3


4


5

Summary

6



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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


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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


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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


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AGENDA

1


2

Cleaning/Pickling

3


4


5

Summary

6



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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


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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


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PHOSPHATING Crystalline Layer Phosphating Zinc Phosphating Thin Layer Phosphating:


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


Crystalline Structure of the Layer approx. 1,5 – 5,0 g/m²

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June 15th, 2014

AGENDA

1


2

Cleaning/Pickling

3


4


5

Summary

6



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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)


low application temperature (25-35 °C)

free of phosphates, nickel, nitrite, hydroxyl amine, hydroxyl ammonium sulfate

no sludge vs.: zinc phosphating: iron phosphating:


<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


Metal

Layer Formation

Metal

OH

HO

2 Cr3+ + 4 Zr4+ + 11 H2O

OH

OH

O


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


Metal


OH

Cr2O3* 4 ZrO2 + 22 H+

O

Cr

Metal

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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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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


ZetaCoat SurTec 609

DI-rinse

25-35 °C 0,5-3 min

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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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ALTERNATIVE PROCESSES Corrosion Protection VDA-621-415, cyclic Corrosion Test, 6 Cycles Polyester Powder Paint, Interpon D1036/Gloss(85), SGJ02G

Steel


Aluminium

EG

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HDG

June 15th, 2014

AGENDA

1


2

Cleaning/Pickling

3


4


5

Summary

6



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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


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Protection upgraded

Thank You.

AGENDA

1


2

Cleaning/Pickling

3


4


5

Summary

6



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SURTEC COMPANY PROFILE April 2014


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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


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Surtec

Highly Competent Chemicals for Surface Technologies

Success Factors High technical expertise Long-term customer relationships Individual solutions for our customers


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


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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


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


Electroplating

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Metal-Pretreatment

June 15th, 2014

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PDF PRESENTATION PRE-TREATMENTS OF METALS BEFORE PAINTING

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