New Developments in Surface Finishing

New Developments in Surface Finishing Dr. Klaus Wojczykowski, CTO COVENTYA Group 2016 Beyond the Surface

Beyond the Surface www.coventya.com

Content

Drivers for Innovation in Surface Finishing REACH Increased Quality and Performance Requirements New Applications

Innovation Management from a Process Supplier’s View Technology Monitoring and Benchmarking Strategic R&D Project Selection and Management

Innovation Pipeline Current R&D Focus at COVENTYA (PROTECTIVE) Radical Innovations in Other Fields

New Developments – 2016


Drivers for Innovation: REACH SVHC


Last Update: December 17th, 2015 Now 168 Substances Member States propose new Additions Proposal needs Dossier for Justification

SVHC ANNEX XIV or XVII


Drivers for Innovation: REACH SVHC



Drivers for Innovation: Performance


Quality requirements were partly defined by warranty durations given by car manufacturers (liability mostly limited to functional aspects for longer durations) A big amount of new vehicle registrations are commercial through OEM’s leasing company Re-sell value of car after lease ends becomes an important factor

http://www.sternpartner.de

http://audi100.net

„10 Years warranty against corrosion perforation“

„Young Stars – As Mercedes as on the first day“


Drivers for Innovation: New Applications


www.energy.siemens.com

www.sglgroup.com

New materials and components with new requirements come from major trends in the energy and mobility sector but also from changes in demographics and consumer behaviour…

www.rp-online.de


Drivers for Innovation



Content






25%

75%F&E

others

Investment in R&D Investment in Personnel and CAPEX in the COVENTYA Group

Employees by department

The R&D group expanded by 500% since the year 2000.

Sales/Service 50%

Manufacturing 20%

R&D 6%

Administration 24%

Investment in different areas



Areas of Research COVENTYA drives Innovation in all areas of our business…

ALUMINIUM DECORATIVE ORGANIC COATINGS PRECIOUS METALS WATERCARE

DATA STORAGE

FUNCTIONAL POP

PROTECTIVE



Strategic R&D Project Selection and Management Initiation of R&D projects follows a clear process with mandatory input of

product management and sales During the run of a project its value to the company is constantly monitored and benchmarked



The “House of Quality”



Example: A new Black Top-Coat

How does it correllate? e.g. more black less corrosion resistance

What does the customer want? e.g. „black“

How does the competition perform?

How to measure? e.g. L-value

What‘s the target? e.g. L < 20 using

BYK Colorimeter XY



Example: A new Black Top-Coat

The targets, probabilities and competitive environment is well defined at the very beginning of the development per the best available knowledge

The progress can be constantly benchmarked during the development

Whenever new approaches are taken (e.g. basic formulation changes) the potential consequences on the outcome can be forseen



Content






Corrosion Protection

Barrier Cathodic

Concept Challenge

Development Potential

• Lower Potential than base material (Zn, ZnX, Al)

• Isolate the base material from corrosive media (Nickel, Lacquer)

• Layer thickness • Protect the sacrifical

layer against corrosion

• Pore free • Crevice corrosion

• Lower corrosion rate by increased potential of the deposit

• Primer and Top-Coats for good adhesion and durable coatings



Cathodic Corrosion Protection Known Components and their Properties

Diffusion layer with base material (hot dip galvanizing, sheradizing)

- Alloy components for a lower corrosion rate (Sn, Ni, Fe) or better self passivation (Mg, Al, Mn) - Dispersion Coating

- Thick, compact conversion coating - Incorporation of inhibitors (SiO2, Co, V, Zr

etc.) - „Sealing“/Increase of layer weight by Post-Dip

- Temporary isolation, Protect the passivate against dehydratation, Control surface properites like the coefficient of friction

Passiviate Post-Dip

Sealer/ Top-Coat

Zinc (+X)

Base Material



“Morphological Box” *

*F. Zwicky

Application for problems of non-reducible complexity - Definition of main- and secondary goals - List all essential parameters and properties - Combination of properties to generate a new product

Sacrificial Coating Barrier Coating Distribution of corrosion current

Conversion Coating Dip-Spin Coating Monolayer

Self Passivation Inhibitor Intrinsically noble layer

Batch Coating Continuous Coating Coating of single Pieces

Permanent Protection of Base Material

Permanent Protection of entire Part

Permanent Protection of Entire Part with changed

Aspect

CMR-Metal containing CMR-Metal free Metal free

…

Example of a morphological box for an innovative corrosion protection system



Concepts of Innovation

*Clayton M. Christensen, Harvard Business School „disruptive“ Innovation „sustaining“ Innovation

The S-Curve Concept

Limit of old Technology

Limit of new Technology

Status Today

Status Today Technological Potential

Performance of the Technology

Cumulated R&D Investment



COVENTYA’S PLAN FOR INNOVATIVE CORROSION PROTECTION

Improved Performance of Established Processes (e.g. ZnNi, Co-free Passivates) through sustaining Innovation with parallel Development of Novel Processes using Harmless and Sustainable Materials (disruptive Innovation)



COVENTYA’S PLAN FOR INNOVATIVE CORROSION PROTECTION

2015 2016 2017 2018

Duktile Alkaline ZnNi

„Drop“-free Cr(III) Post-Dip

Improved Flow Silicate Sealer

Complete Replacement of Cobalt in Passivates

High Performance (Boric-Free) Acid ZnNi

Alloy to Replace ZnNi

Development Introduction Fully Implemented

PROTECTIVE (Zn & Zn Alloys)

2015 2016 2017 2018

Curable Top Coat Range for electroplated Fasteners

Rheology modified Zinc Flake Process

ORGANIC COATINGS

2015 2016 2017 2018

Cr(III) Conversion Processes for 7xxx Aluminium-Alloys

REACH adapted Cleaning and Sealing processes

ALUMINIUM



Alkaline ZnNi for Bendable Parts PERFORMA 288 produces ZnNi deposits with high corrosion protection after bending or crimping due to a specific crystal structure.

PERFORMA 288 more (330) slip planes

Standard alk. ZnNi more (600) planes

600 330

X-Ray Diffraction shows the preferred crystalline orientation of the ZnNi γ-Phase

Standard alk. ZnNi

PERFORMA 288

The Bending Test shows less damage of the coating and better corrosion protection



024681012

0

5

10

15

20

%Ni µm

High Performance Acid ZnNi

γ-Phasen ZnNi

PERFORMA 560 BF gives superior aspect and corrosion protection through a burn free deposit with a very homogeneous alloy distribution.

Standard Acid ZnNi

2A, 5 min

PERFORMA 560 with new Additive System

Simple bath control with only 3 fully analyzable organic additives

Simple air agitation possible due to low foaming

PERFORMA 560 FINIDIP 129 FINIGARD 200A

After 25 cycles GMW14872-10



Improved Flow Silicate Sealer FINIGARD 503 is an inorganic sealer

for high heat and chemical resistance.

Dedicated organic functionalization gives a crack-free amorphous film. Dynamic Surface Tension

FINIGARD 503 Std. Silicate Sealer

Small amounts of a harmless solvent lead to superior film formation properties compared to competitive products, little residue at edges and corners and completely covered iridescence.

SiOx

x SiOx

SiOx y

z



Overview of known Zn alloys:

Alloy as ZnNi Replacement

ZnCo ZnNi ZnCr ZnSn ZnMn ZnFe

+

- Good corrosion resistance

- Easy passivation (esp. black)

- Excellent corrosion resistance

- Established processes

- Might be an interesting alternative

- Very good corrosion resistance

- Good ductility and solderability


- Self-passivating property


- Easy passivation (esp. black)

- Alloys with high Fe content are potentially interesting

-

CMR!! - Price - Waste water

treatment - Nickel is potentially

CMR

- Chrome is also a candidate to be potentially replaced

- Price (!!) - Availability of Sn - Passivation - Aspect

- Passivation (esp. black)

- Aspect of corrosion products

- Bath maintenance

- Bath maintenance - Alloys with high Fe

content are not well researched



Experiments regarding the ideal alloy composition:

* Adaniya et al., Zinc-Iron alloy electroplating on strip steel , Nippon Kokan KK, 1975

The Phase Diagram* shows a ZnFe Γ-phase like in ZnNi alloys. In ZnNi this is the phase with the highest corrosion resistance.

COVENTYA found a bath composition and plating parameters that allow to plate ZnFe alloys in a wide range of Fe contents.




X-Ray Diffraction at different Fe-contents

Fe

without

without

∆T

∆T

Fe

With and without baking



Fe

Fe

without

without

∆T

∆T

X-Ray Diffraction at different Fe-contents With and without baking



It was shown, that a pure Γ-phase is only present at 30% Fe. The full phase equilibrium only takes place at baking temperatures

higher then in the typical hydrogen relief bake.

Which composition is really preferred for the layer properties and also without baking??

X-Ray Diffraction at different Fe-contents



9,3 % 15 % 19,6 %

19,4 %

22,2 %

24,8 %

25 % 26,7 %

28,1 %

31

Crystallite morphology at different Fe contents



Chronopotentiometry j= 10 mA/cm² in NaCl 50 g/L

earlier Layer Dissolution later

less

nob

le

P

oten

tial

no

ble

[V] [min]

Electrochemical Properties

The alloy with 13% Fe shows, like ZnNi, a delayed layer dissolution with steps.



Finidip 128 CF + Finigard 150

Corrosion Test

NSST

The alloy with 13% Fe shows the best aspect and the best corrosion resistance.


Beyond the Surface www.coventya.com 34

Zinc ZnFe 13% ZnNi 15%

1200h NSST

Comparison of zinc processes With cobalt-free passivation and top-coat



ZnFe with 13% Fe is an interesting alternative for ZnNi The alloy and its protective properties are known for at least three

decades and it can be deposited from known ZnFe electrolytes with slight modifications.

Structure, aspect and passivate acceptance are comparable with current zinc processes.

It has to be confirmed in the industrial test for which application the process is suitable regarding layer properties like ductility as well as bath maintenance.




Curable Top Coat Range for electroplated Fasteners

In comparison to classical “Sealers” in electroplating, a new generation of top-coats will apply paint technology to get to the next level of performance

In return, the new processes will offer longer un-changed optical appearance and even higher resistance to red corrosion



REACH adapted Cleaning and Sealing processes (Aluminium)

Example: Cleaner for Aluminium: Borate, EDTA, NTA and Silicate-free

after before



Radical Innovations in Other Fields Cr(VI)-free etch for POP pre-treatment



Radical Innovations in Other Fields

R&D Roadmap: Corrosion Protection

Cr(III) Hard Chrome

Results from „IRT M2P“ Project (France) Up to 200 µm can be plated

No adhesion failure ASM 2460



„The future is already here, it is just not evenly distributed“

William Gibson

Thank You for your Attention!


New Developments in Surface Finishing

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