Transfair Presentation 3 (pdf file 12MB)

Transcription

The IMF
welcomes you to
Transfair – Day 2
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IF YOU DISCOVER A FIRE:OPERATE THE NEAREST FIRE ALARM POINT.
ON HEARING THE FIRE ALARM:ALL PERSONNEL SHOULD EVACUATE THE BUILDING BY
THE NEAREST AVAILABLE FIRE EXIT AND ASSEMBLE AT
THE NEAREST ASSEMBLY POINT A, B OR C. (SEE MAP)
DO NOT STOP TO COLLECT PERSONAL BELONGINGS
DO NOT RE-ENTER THE BUILDING UNLESS
SPECIFICALLY INSTRUCTED TO DO SO BY THE
HERITAGE MOTOR CENTRE CONTROL/ DUTY OFFICER
FIRE ROUTINE
Keynote Address: Future trends in
the automotive sector
Alex Robinson; SMMT
An insight into the durability of
modern coatings
Peter Hope FIMF; LVH Coatings
Coffee and Networking
Open Forum
Chaired by Malcolm Griffiths FIMF
and Graham Armstrong FIMF
Further evolution in tri-valent
chromium passivation
Duncan Beckett; Coventya Ltd
Tin whisker growth from
electroplated finishes
Geoff Wilcox FIMF; Loughborough
University
A Future “Design Classic”
- Bright Chromium
Alan Gardner
What is a “Design Classic”?
• “Design Classics” are icons in the world of fashion and trend.
They are easy to recognise yet are so familiar they become
part of every day living. They often go unnoticed. They always
remain true to their original concepts
• They are more often noticed when they have unexpectedly
changed
• There endurance is due to qualities that cannot be easily
measured and they don’t become classics overnight
• We are aware of them even without knowing the influence
they have on our lives
MacDermid: all rights reserved
Evolution not Revolution …
• During their evolution, design classics tend to
retain the key features that make them
appealing…
– Note the Coca Cola logo remains consistent
Change Vs Evolution
• Iconic Endurance
– An iconic design can change, yet its intrinsic appeal can remain or
even grow
– We remain attracted to its values despite these changes
How far can Evolution go…
• Surprisingly…providing the original concept
and values are clearly reflected in the product,
company or service we embrace changes
Image or Name …
• Design Classics can be recognised equally
effectively by images, names or services:
• Coca Cola
• Mini
• Starbucks
– The iconic form is not critical, but its values are
Sustaining Values …
• How many here are truly Design Classics….
Why Bright Chromium is Iconic…
• Iconic Designs
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Recognised without need for description
Universally appreciated & valued
Sustains Core Values/Principals/Virtues
Not Diluted by Evolution
Multi Lingual
Imitations always compared to original
They endure through almost all changes
Bright Chromium…Appeal
• In France & Italy…almost 50% of the chromium
electroplate is consumed by Fashion and Cosmetics
Bright Chromium…Fashion
• A true Design Classic is always in demand
despite changes in fashion and trend…
Bright Chromium…Innovation
• A true Design Classic is always in demand
even at the leading edge of innovation…
Bright Chromium…Technology
• A true Design Classic always delivers…even
when designs and technologies change
Bright Chromium…Enduring Value
• A true Design Classic can continue to enhance
value through many design generations
Bright Chromium Technology
Bright Chromium Advances…
Hexavalent
Deposition Modes
Trivalent
Bright Chromium Advances…
• Latest generation trivalent chrome systems
deliver the same unique metallic style but with
added benefits:
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Choice of colours
Meet Environmental, HSE and Productivity needs
Experienced worldwide applicator base
Tough metallic films with high performance
Can’t be matched by paints
Bright Chromium…Options
Bright
Satin
Dark
• Colour evolutions open new markets and opportunities
Bright Trivalent Systems …
• TriMac
– TriMac trivalent chrome systems offer
colours plus high performance from
environmentally sound chemistry
– TriMacIII conventional chrome colour with
excellent performance
– TriMac RM a warm colour with maximum
“Russian Mud” corrosion performance
Darker Trivalent Systems…
• Twilite
– The first chrome to break from tradition,
Twilite has been adopted worldwide as a
new look stylish chrome
– Twilite a cool darker shade that brings a
subtle new look to metallic chrome, also
provides excellent performance in
“Russian mud”, CASS and NSS
Very Dark Trivalent Systems…
• Galaxy
– Galaxy is rapidly gaining a reputation
amongst designers as the new look dark
chrome
– Galaxy’s cool blue/gray shade works well
with modern fabrics and textures, it also
gives performance to match standard
chromium
Specified by General Motors (M24)
The Satin Revolution…
• M-Satin …
– Satin chrome has sparked new
opportunities in design studios. Stylish
options in satin chrome include systems
with highly consistent gloss and colour
– From the very light to dense and heavy,
satin continues to win over designers in all
application areas
– It has now started to appear on external
automotive parts
Bright Chromium and Performance…
• Trivalent Chromium is
solving the problem of
Russian Mud !!! A BIG
issue in some countries
during severe winters…
The Future…is Bright !!!
Chromium continues to be specified by major OEM’s:
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Automotive demand is at its highest for 20 years
Technology is improving to meet higher standards
Environmental pressures are driving technology
New finishes are attracting designers
Bright Chromium on plastics is preferred route
• These are hallmarks of a “Design Classic”
Bright Chromium…Automotive
100% of cars use Bright Chromium for plastic trim
2012
1 China Nationals
11,400,000
2 Toyota
9,500,000
3 VW
8,700,000
4 GM
7,200,000
5 Hyundai
7,000,000
6 Renault-Nissan
5,700,000
7 Ford
5,100,000
8 FIAT-Chrysler
4,250,000
9 Honda
4,000,000
10 PSA
2,950,000
11 Suzuki Global Total = +60m units per year
2,900,000
12 BMW
1,800,000
13 Daimler AG
1,750,000
BUT…Design Classics have Limits !!!
Noooooo !!!
Thank You…
For more information about our world of
“Fashion Finishes”
see our web site
www.macdermid.com/industrial
www.macdermid.com/autotype
Overview of UK Automotive Industry
Alex Robinson, Supply Chain Development Manager
THE SOCIETY OF MOTOR MANUFACTURERS AND TRADERS LIMITED
SMMT, the ‘S’ symbol and the ‘Driving the motor
industry’ brandline are trademarks of SMMT Ltd
What is the SMMT?
Established in 1902, SMMT supports the interests of UK automotive.
One of the largest and most influential trade bodies in the UK, SMMT is a member
organisation that represents nearly 600 automotive companies.
Promoting the interests of industry at home and abroad, SMMT acts as the voice for UK
automotive promoting a united position to government, stakeholders and the media.
SMMT provides members with:
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A representative forum to engage with UK governments and EU institutions.
Automotive data and market intelligence.
Data analysis services.
Practical technical advice.
International and national exhibition opportunities
SOCIETY OF MOTOR MANUFACTURERS AND TRADERS LIMITED
PAGE 37
THE UK AUTOMOTIVE SECTOR
• UK automotive sector makes 1.6 million cars and commercial
vehicles and over 2.5 million engines annually
• Automotive is vital to the UK economy
– Around £55 billion turnover
– £12 billion value added
– Over 730,000 jobs dependent on automotive
– More than 11% of total UK exports
– Invests £1.3 billion each year R&D
• UK is home to 7 volume car manufacturers, 8 premium &
specialise vehicle manufacturers, 8 commercial vehicle, 10
bus & coach, over 100 niche vehicle manufacturers and
around 2350 component manufacturers
PAGE 38
Vehicle plant locations and output in 2012
Engine plant locations and output in 2012
UK vehicle production in 2012
‘Export-led growth and Green Economy potential’
• UK car manufacturing broke all-time export records in 2012, with volumes sent overseas exceeding 1.2
million, up 8% on last year.
• Total vehicle output increased 8% last year to 1.58 million units, the highest level since 2008.
• Car output rose 9% in 2012 to 1.46 million units, ending the year with a 6% rise in December.
Total
Export
1,600,000
1,500,000
UK car manufacturing
1,400,000
1,300,000
1,200,000
1,100,000
1,000,000
900,000
800,000
700,000
600,000
2007
2008
2009
2010
2011
2012
Car manufacturing, 2007-2012, total and export volumes
PAGE 41
State of the market 1970-2016
UK automotive manufacturing
2,500,000
2016 target
1972 peak
2,000,000
2.0m +
1.92m
1,500,000
1,000,000
Manufacturing
output: 1970-2011
500,000
Manufacturing
forecast: 2012-2016
0
1970
1980
1990
2000
2010
PAGE 42
Current state of the market
£6.5bn investment
Toyota: £100m
New hatchback
Honda: £267m
Civic and CR-V
models
Nissan: £250m
New Infiniti
Vauxhall: £125m
Ellesmere Port
MINI: £250m
Production triangle
Jaguar Land Rover:
£500m
New engine plant
• 14,000 direct new jobs; thousands more in supply chain
PAGE 43
Current state of the market – supply chain
Rosti McKechnie:
new jobs by 200
2017
Brose:
£15m expansion
GKN: £12m
expansion
Unipres: £41m
Investment and
350 new jobs
Cab Auto: 66
new jobs
NSK Bearings:
£27m expansion
Nifco: £30m
expansion
Calsonic Kansei:
£15.3m expansion
PAGE 44
Opportunities for UK based suppliers
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At a headline level, the opportunity is
estimated to be at least £3 billion-worth
of tier 1 parts sales per annum, at
current vehicle output rates
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The estimate only includes
opportunities regarded as viable by
respondents, does not include planned
output growth, and has not been
factored to account for vehicle makers
outside the survey.
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This is however not necessarily an
immediate requirement, but should
emerge as contracts come up for
renegotiation or renewal
Calsonic Kansei:
£15.3m expansion
PAGE 45
How SMMT is supporting the UK supply chain
Industry events
• SMMT International Automotive Summit
• SMMT Open Forum
Exporting
• International trade shows
• International trade missions
Business development
• Automotive Supplier Finder (ASF) database
• SMMT Meet the Buyer events
Government funding
• Regional Growth Fund
• Advanced Manufacturing Supply Chain Initiative
PAGE 46
Automotive Supplier Finder (ASF)
• Free profile, free to search
• Company profile with
categories, contacts, quality
standards and capabilities
• Browse by company name,
category and brand name
• Send Requests for
Quotation/Information
New look, easier to use site launching soon
www.autosupplierfinder.com
PAGE 47
Meet the Buyer events
Through the Automotive Supplier Finder and
‘Meet the Buyer’ networking events, we aim
to promote and encourage sourcing from
local suppliers within the UK.
‘By invitation only’ Meet the Buyer
networking events are organised by using
the ASF to search for suitable suppliers.
Our latest event in May 2013 was the biggest
yet, with over 400 delegates registered to
attend, nearly 60 purchasing personnel
representing over 25 OEM and Tier 1 buying
organisations and over 360 one to one
appointments facilitated on the day at our
venue in Cranmore Park, West Midlands.
PAGE 48
In conclusion
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SMMT is one of the UK’s largest trade
bodies in the UK, representing around
600 companies in the UK.
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SMMT acts as the voice for the UK’s
automotive industry, providing
members with a forum to discuss and
debate the issues affecting industry
and representation to UK and EC
governments.
Alex Robinson, Supply Chain Development Manager, SMMT [email protected]
Any questions?
PAGE 49
Peter Hope FIMF - Technical Director,
LVH Coatings Ltd.
Institute of Materials Finishing
TransFair Conference, June 2013
o
For decoration and protection (it looks good and
solid and stays looking good – and stays solid!).
• 75% of new car buyers state that colour is
important
when choosing a vehicle.
• Significant effect on residual (second hand) value.
A crazy way of showing how many automotive colours are available.
This is better organised!
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Underlying driver is DESIGN which determines
function, performance and appearance
specifications.
Overriding constraint is REGULATION which
restricts what chemicals and processes can be
used.
Paint FORMULATION requires working with other
industry specialists who create effective and
compliant raw materials and processes.
Specified targets are met and refined through
TESTING.
restriction
hydrolytic
Polymers photolytic
dynamic
REGULATION
innovation
colour fastness
Pigments photocatalysis
anti-corrosion
durability
weathering
Stabilisers
UV absorber
+
HALS
mechanical
FORMULATION
TOP COAT PAINTS
Mappa Mundi
for this
presentation
TESTING
PRIMER PAINTS
Electrochemistry
Metallurgy
Corrosion
resistance
Metal
Pretreatment
Substrates
Structure/function
Adhesion
Plastic
DESIGN
Surface
chemistry
Polymer/resin
chemistry
appearance
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The traditional workhorse structural material for
cars is mild steel with its combination of strength,
formability and low cost.
However it is very prone to corrosion problems –
especially in salty environments.
Paint provides a protective barrier against corrosive
environments.
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A significant milestone in the automotive industry
was the introduction of electrophoretically applied
primer paints in the 1960s (aka E-coat , Electrocoat
etc.).
This technique went some way to solving the
problems of the “inside out” corrosion of box
sections/sills etc.
The paint on this car stops rust.
It must be
Electrophoretic!
1960s American cars were first to have electrophoretic paint
as an anti-corrosion primer.
Historically, corrosion has been a serious problem.
E-coat layer: Anodic resin systems included modified alkyd,
epoxy ester, polybutadiene etc. Anti-corrosive pigments
(typically based on Pb and Cr6) as standard.
Phosphate layer:
Zn type typically with
Cr6 ‘seal’.
Mild steel substrate.
“Stone chip” penetration of the coating down to the substrate.
[Anodic E-coat]
sharp, penetrating object
[Anodic E-coat]
[Anodic E-coat]
Phosphate and metal exposed to the elements.
[Anodic E-coat]
Ingress of water + salt (source of chloride ions)
NaCl
This challenge is investigated by various Accelerated Corrosion Tests. Many test
Protocols have been developed to try and simulate real life conditions. Historically, the
Continuous neutral salt spray test (ASTM B117) was the benchmark, but more emphasis
is now placed on cyclic tests that have been proven to provide better service life
prediction.
[Anodic E-coat]
Complex galvanic reactions at the metal/phosphate interface result in
generation of strongly acid and alkaline domains.
NaCl
HCl
+
-
NaOH
The presence of sodium hydroxide around the paint/phosphate
Interface is catastrophic.
[Anodic E-coat]
Formation of undercut corrosion. Anodic/acid conditions dissolve and
Oxidise the metal. Rust accumulates at the metal surface and spreads
under the paint.
NaCl
+
-
NaOH simultaneously:
• Dissolves the phosphate.
• Hydrolyses any ester linkages in the resin
(alkyds, epoxy esters and acrylics).
• Tries to re-solubilise the (anodic) resins via their high acid value
Paint spalling off a
corrosion patch at the
edge of a wheel arch.
A good example of bad corrosion
protection.
- most probably perforation from the
inside.
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Intrinsically high acid value/alkali-soluble for
aqueous dispersion.
Resins frequently based on esters and so prone to
alkaline hydrolysis.
Anodic deposition process is oxidative to the
substrate – unsuitable for steel.
Requires input from the POLYMER/RESIN chemists.
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Low amine value/acid soluble functionality
utilised for cross-linking, so resolubilisation is denied.
Not hydrolysable.
Cathodic deposition process has no
deleterious effect on basis steel
[Cathodic E-coat]
Cathodic E-coat process
uses different resin chemistry
NaCl
HCl
+
-
NaOH
The cathodic E-coat is not hydrolysed or re-solubilised and so inhibits
Dissolution of the phosphate and spread of corrosion. The production of
Magnetite (Fe3O4 – black iron oxide) under predominantly reducing
(cathodic) conditions tends to “choke off” corrosion leaving a characteristic
“scab” effect.
-
NaOH
+
HCl
But, anodic activity is concentrated in the underlying steel, mining out the
metal and potentially resulting in perforation. This can come in from the
outside - per the stone-chip illustration – or come out from the inside of
box-sections etc.
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Although far better than anodic E-coats, regulatory
forces mitigated success by demanding removal of
Pb and Cr6 based anti-corrosive pigments.
Adding Ni to Zn/Mn phosphate systems (“tricationics”) compensates to a degree by altering the
galvanic environment to favour “choke-off” thereby
reducing “scab” size.
The ‘ultimate’ solution comes from
electrochemistry – using the galvanic character of
zinc metal to provide cathodic protection for the
steel.
[Cathodic E-coat]
By pre-coating the steel with zinc, anodes and cathodes are now in the
right places for preventing corrosion.
Cathodic protection of steel by zinc
E-coat
Zinc
Steel
-
NaCl
+
Steel pre-plated with a zinc-iron alloy is typical because of its suitability
for welding.
Phosphating maximises paint adhesion.
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It is now common to protect the E-coat with a
dedicated anti-chip primer prior to application of the
top-coat system.
Interiors of box sections are injected with wax.
Vulnerable underbody surfaces are coated with thick
anti-chip compounds.
The likelihood of stone chip penetration to the basis
steel is negligible.
But if the coating system is penetrated, galvanised
steel + cathodic epoxy E-coat will provide best
resistance to corrosion.
Last but not least – DESIGNERS have learned to design
car bodies that are easy to paint!
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Primer layer resin requires immunity to hydrolysis
and permeability by water, and high resistance to
oxidation.
Galvanic and electrochemical challenges drive pretreatment processes.
Test methods must reflect the full range of
challenges. Various cyclic tests demonstrate good
correlation with real conditions.
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Compared to steel, aluminium is generally less
susceptible to corrosion. Regulation-compliant
anti-corrosion pretreatment processes are readily
available and effective.
Plastics do not have comparable corrosion issues,
but the physical properties of the paint system
must be compatible with those of the basis plastic
because the plastic/paint ‘composite’ will behave
as a single material.
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Epoxy resins make very good anti-corrosion
primers but they have no resistance to sunlight
(UV).
Top coats should resist the ravages of the vehicles’
working environment to allow the primer coat to do
its job – and still look good when the replacement
engine is getting old!
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Developing and manufacturing colourants (dyes &
pigments) tends to be a specialised branch of Big
Chemistry.
The interaction of pigments and paint resins in
respect of “weathering” can be unpredictable and
so TESTING is absolutely essential.
Various accelerated techniques are available, but
hard experience has shown that real life testing –
e.g. Florida exposure for a number of years – is
necessary for any sensible conclusions about
service life.
Bench-top Xenon Arc test apparatus.
- Incorporates “solar spectrum” light source + water spray
(to simulate “real” weather conditions).
Typical weathering test panel.
Masked/unexposed
area for reference
Exposed area
displaying
fade/colour change
A classic case of colour fade – this is what happens in real life.
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“Colour” is only what “visible light” is not absorbed
by the pigment.
What is the rest of the electromagnetic spectrum
doing to the pigment?
UV causes chemical changes
which can be accelerated by the heating effects of visible and Infrared.
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Polymer resistance to hydrolysis, photolysis and
photo-oxidation.
Colourants/extenders resistant to colour change
and without photocatalytic effects on polymer.
TESTING methods must encompass global
variations in climate challenge.
The dragon eats its own tail:
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>50% world’s population are urban dwellers
Highest concentration of vehicles is in cities
The most likely place for a car to be ‘out in the open’ is on a road in
or near a city
(combustion) vehicles add energy and chemistry to the urban atmosphere
Sunlight is energetic enough by itself to damage paints.
In combination with moisture and airborne chemicals
(man-made or natural) it becomes highly aggressive –
especially at elevated temperatures.
• Higher urban temperatures + PHOTOCHEMICAL effects destroy paints
Satellite picture of Boston USA – visible light
Satellite picture of Boston USA – Infra Red
hotter
cooler
Urban Heat Island Effect
Ozone + NOx + hydrocarbons
= photochemical smog
3oC – 5oC higher air temperatures in urban areas.
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Direct photolysis of polymers and colourants by energetic
(UV) photons.
◦ Some pigments can act as photocatalysts (notably titanium
dioxide).
◦ Colours change or fade and pigments are released by
polymer breakdown (chalking).
Indirect photochemical effects.
◦ Oxidative erosion by ozone created within the microclimate on the paint surface.
◦ Acid etching and hydrolysis by nitric and sulphuric acids
derived from NOx and SO2.
All the above accelerated by temperature.
◦ Colour shade can exacerbate: ‘Black’ paint can be up to 30C
hotter than ‘white’ paint in sunny daylight conditions.
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Polymer and pigment chemists develop materials
that are resistant (and of course compliant with
REGULATION). Relevant TESTING is essential.
UV absorbers coupled with free radical scavengers
(HALS) mitigate photonic effects.
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Making polymers ‘resistant’ themselves to UV
means they become non-absorbing and so do not
offer any protection to pigmentation – or the
underlying primer.
UV Absorbers are added that soak up the UV and
dissipate it at a ‘safe’ energy level.
HALS mop up any free radicals initiated by photons
that have evaded the UV Absorbers.
The UV Absorber/HALS combination package is the
norm for UV protection.
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Traditional ‘hard colour’ car body finishes were
classical pigmented resin paint systems.
‘Metallic’ finishes based on aluminium flake
pigments required an extra clear resin top-coat to
protect the pigments from corrosion.
This ‘clear over base’ concept has become the
norm.
A standard clear top-coat system possessing all of
the durability essentials can be applied over any
colour effect base coat.
Corrosion and weathering problems eliminated!
– what about the car wash?
We rely on the brush designers to select materials that will not damage
the paintwork.
But what can be done with the paint to prevent scratching in general?
‘Permanent’ visible scratching results from multiple
fractures or tearing within the indentation of
the scored paint film.
This is principally governed by properties of the
polymer/resin system including:
• Hardness
Plastic
• Elastic modulus
deformation
• Cohesive strength
Fracture
deformation
stylus-generated scratch
enlarged cross-section
Even ‘polishing out’ a thermoplastic paint
may not repair the fractures.
The only option is abrasive removal with
a consequent reduction in thickness.
Polymer engineering can provide the capability
to deform without fracture – and then to regain
the original form via thermoplasticity upon
suitable polishing action, or spontaneously via
viscoelastic recovery.
The latter phenomenon is accelerated by the
warming effect of solar (IR) radiation..
warming effect of solar (IR) radiation…
The surface recovers its original unscratched form.
warming effect of solar (IR) radiation…..
The ‘scratch’ can virtually ‘disappear’ as the
‘damage’ is repaired.
But this ‘scratch resistant’ resin system must
retain all of the other essential performance
and resistance properties!
Further improvements in scratch resistance
are being gained via nanocomposite technology.
A typical automotive paint layer system for metal
substrates.
Clear coat – first line of defence with resistance
to chemicals, scratches, UV/weathering etc.
Effect pigment layer – metallic and pearlescent
effects now generally use treated mica in place
ofaluminium flakes.
Base colour layer – fundamental to both hard
colours and ‘effects’.
Base coat primer
Chip resistant primer/surfacer
E-coat
Metal treatment – e.g. zinc galvanising +
Phosphate (for steel).
Basis metal.
Not to scale!
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Inter-coat adhesion
Thermal shock
Stone/gravel chip
Bee droppings
Fluid resistance (fuels, brake fluid, antifreeze etc.)
(Interior) Personal care products (sun-screen, insect
repellent)
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The evolution of modern high durability
paint systems requires a multi-disciplinary
approach by the formulator.
Input from many areas of materials science
and technology is required to meet the
demands of designers within regulatory
constraints.
The provision in the automobile sector of
long term anti-corrosion warranties testifies
to the success of this approach.
Finish guaranteed - any questions?

Please visit the exhibition
Don’t forget the “Land Rover” Experience
Have a look at the Heritage Museum

Please be back for 11.00am!
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Recent Developments in
Trivalent Chrome Passivation
12th June 2013
Introduction
• Corrosion protection systems based on zinc and zinc
alloys are seen as state of the art in many industries
•
•
•
•
Automotive manufacturing
Mechanical engineering
Fittings
Fasteners
• However, ever-growing demands of environmental, labour
and consumer protection require continuous improvement
of the processes and chemistry used
12.06.2013- 110
Passivation on Zinc
Structure of Layer
Sealer
Passivate
Zinc Layer
Steel substrate
All aspects of the coating system must meet the
new environmental regulations
12.06.2013- 111
Present Status of Passivation
• Cr (VI)-free passivation
• Systems with high performance usually contain cobalt
• Original requirements:
• High concentrations
• High temperatures
• Today:
• Low concentration
• Low temperature
• Nearly all colours are available and all alloys can be coated
• By using the correct passivation it is possible to obtain
extremely high levels of corrosion protection
12.06.2013- 112
Different Finishes with Trivalent Systems
Decorative
Blue
Technical
Blue
Transparent/
Yellow
irridescent
Black
Irridescent
Zn
12.06.2013- 113
Zn
Zn
Zn-Ni
Zn-Ni / Zn-Fe
Zn
Zn-Fe
Zn
Zn-Ni / Zn-Fe
12.06.2013- 114
ZnNi passivated
and sealed
ZnNi
passivated
ZnNi
ZnFe passivated
And sealed
ZnFe
passivated
Zn passivated
and Sealer
Zn
passivated
Zn
Rack
Barrel
Rack
Barrel
Rack
Barrel
Rack
Barrel
Rack
Barrel
Rack
Barrel
Rack
Barrel
Rack
Barrel
h NSST
Tested to VDA- 233-101
Corrosion Resistance
800
700
600
500
400
WR
300
RR
200
100
0
Function of Cobalt
• Cobalt was introduced in the 1980‘s into trivalent
chromium passivates
• Initially this was to offer an improved blue passivate
• However it was also found to give the following
advantages
Improved Corrosion
Resistance
Improved Performance
after
Heat Treatment
More Consistent
Appearance
• For these reasons Cobalt is commonly used in most
trivalent passivates
12.06.2013- 115
However - Europe and REACh
(Registration Authorization and Restriction of Chemicals)
Began in 2007
Continues to expand the number of chemicals classified as Carcinogenic,
Mutagenic or Reprotoxic (CMR)
Substances of Very High Concern (SVHC) are evaluated for authorization
ECHA (European Chemicals Agency) evaluates & recommends for
authorization
Among those recommended by the ECHA are the following Cobalt salts:
Cobalt dinitrate
Cobalt dichloride
Cobalt sulfate
Cobalt carbonate
Cobalt diacetate
This is the final step and Parliament is expected to vote them onto Annex XIV
Sunset date for Cobalt salts expected to be February 2017
REACh Annex XIV – Timeline
Source: NASF TAC Quarterly Report February, 2012
expected 04/2016 –
06/2016
Commentphase „Public
consultation“
(60 days)
RAC and SEAC
create
comments (9 or
12 month)
03/2016
Public phase
for comments
(6 month)
Socioeconomic
analysis of
the use. Data
and
information
may be
introduced
(stakeholders,
ZVO)!
expected 01/2015 – 12/2015
12/2014
Time axis Cobalt(II)-Salts
Decision of
the
Commission
whether and
how an
inclusion in
Annex XVII
done
(3 month)
Search For Sustitutes
• Due to REACh an alternative is required
• Possible substitutes for cobalt must meet a
number of requirements
• Suitable solubility
• Economic availability
• Safety regarding toxicology and environmental
sustainability
• Technically manageable
• The list of requirements makes the
selection of appropriate elements a
challenge for the formulators
12.06.2013- 119
Cobalt Substitutes
• The search for replacement metals which meet all these
requirements has proved to be extremely difficult
• New Research has focused on using non metallics and
nano particles based on silica
• Some success has been found using these materials as
a replacement
Cobalt free Nanoparticle Passivates
Oberflächenanalyse Lanthane TR 175
Nanoparticle-containing passivation
Low Cr (III) concentration
Built-SiO2 particles
High layer thickness
Cr2O3, SiO2 and ZnO-based film
Atomkonzentration [%]
100,00
80,00
C
60,00
O
Si
40,00
Cr
Zn
20,00
0,00
0,00
5,00
10,00
15,00
20,00
25,00
Sputterzeit [min]
P/B calculated for different elements in an
Auger composition profile
SEM image of a passivation of the third
generation of zinc (C)
Thickness ~ 400 nm
12.06.2013- 121
Element Mass percentage in the
film
C
9
O
45
Si
32
Cr
6
Zn
8
Cobalt Free Nano Particle Passivate
Characteristics
Chromium(VI)-free.
Cobalt-free.
Pale iridescence aspect
High corrosion resistance
Mechanical shock resistance properties
Based on nanotechnology
12.06.2013- 122
The solution contains
Cr(III)-salts
organic compounds
Colloidal nano-particles
Special elements to improve corrosion resistance
To be applied on
Alkaline zinc although not all systems work identically
Can be used on zinc nickel
12.06.2013- 123
Corrosion resistance according to ISO 9227 standard, with 10 µm of alkaline Zinc,
parts treated in the passivate using optimum conditions
Thermal shock 24 hrs 120oC
SALT SPRAY TEST RESULTS
Rack application
Barrel application
First WR points (hours)
without thermal
shock
with thermal
shock
without thermal
shock
with thermal
shock
Passivate / HNO3 (0,5% )
> 240 h
> 240 h
> 200 h
> 200 h
Passivate / Prepassivation
> 300 h
> 300 h
> 240 h
> 240 h
Note: there is a strongly positive influence when using
the pre-passivate treatment on the corrosion resistance
12.06.2013- 124
• Silica containing passivates show similar self-healing properties to
mechanical damage when compared to Cr(VI) chromates
12.06.2013- 125
Cobalt free Nanoparticle Passivates
Corrosion protection of the nanoparticle-containing passivation
As Plated
After 288h NSS
After heat treatment for 24h/120oC
Barrel Plated at a customer
12.06.2013- 126
High Build Clear Cobalt Free
Appearance on different Substrates
Alkaline Zn/Ni
•
•
Uniform blue aspect
Similar appearance to Cobalt
systems
12.06.2013- 127
Alkaline Zn
•
•
Irridescent appearance
Similar to traditional “thick
film” passivates
Corrosion Protection (Zn/Ni)
• Screws and plates were treated in CF passivate with and without thermal
shock (24 h/120oC).
Salt spray test
Rack
Barrel
Rack
Barrel
% white rust after
300 hours
% white rust after
600 hours
% white rust after
300 hours
% white rust after
600 hours
Without thermal shock
With thermal shock
Passivate in Laboratory
0%
0%
0%
0%
Passivate at Customer
0%
0%
0%
0%
• There is only a white haze after 600 hours SST with or without thermal
shock.
• The corrosion resistance is excellent.
12.06.2013- 128
Chromium content in layer
Rack
Barrel
Chromium layer weight
Cr in mg/dm²
Passivate in Laboratory
0.9
0.7
Passivate at Customer
0.9
0.8
12.06.2013- 129
Cobalt Free Options
Cobalt free Passivates
Substrate
Type
NSS (hrs w/c) Notes
Zinc
Deep Blue
24 - 48
Single additive
Zinc
Blue
72 - 96
Single additive RT
Zinc
Clear/Irridescent
96 - 168
Single additive RT
Zinc/Zinc alloys
Clear/Irridescent
120 - 168
Self healing RT 2 additive
Zinc Nickel (12 - 15% Ni) Silver/Blue
120 - 168
Single additive
Zinc/Zinc alloys
144 - 288
High performance
120
Excellent appearance
Blue/irridescent
Zinc Nickel (12 - 15% Ni) Black
12.06.2013- 130
Effect of Heat Treatment
(Tested with and without Cobalt)
• Test procedure (Carried out in Coventya)
•
•
Samples were plated with 8-12 microns alkaline zinc then
passivated (rack and barrel)
Working parameters (plating and passivate) by TDS
• Three schemes
•
•
•
24h aging/annealing at RT
24 h/120oC and 8 h/210oC
Cool (max. 24 hours)
• Corrosion Test to DIN EN ISO 9227
(3 rack and 5 barrel parts were tested for each option)
12.06.2013- 131
Effect of Temperature
Passivate A CF
Slight purple
colouration of the
part after heat
treatment
Passivate A CF
After 480 h
Testing to
DIN EN ISO 9227
24h / 120oC
12.06.2013- 132
8h / 210oC
Effect Temperature
Passivate A
Slight Purple
coloration of
the part after
heat
treatment
Passivate A
After 480 h
Testing to
DIN EN ISO 9227
12.06.2013- 133
Effect Temperature
Passivate A
CF
Slight purple
colouration of
the part after
heat treatment
Passivate A CF
After 480 h
Testing to
DIN EN ISO 9227
12.06.2013- 134
Effect Temperature
Passivate B CF
Slight yellow
colouration of the
part after heat
treatment
Passivate B CF
After 240 h
Testing to
DIN EN ISO 9227
12.06.2013- 135
Effect Temperature
Passivate B
Slight yellow
colouration of the
part after heat
treatment
Passivate B
After 240 h
Testing to
DIN EN ISO 9227
12.06.2013- 136
Effect Temperature
Passivate C
Very slight yellow
colouration after heat
treatment
Passivate C
After 336 h
Testing to
DIN EN ISO 9227
12.06.2013- 137
Effect Temperature
Passivate D CF
Slight yellow
colouration after heat
treatment
Passivate D CF
After 336 h
Testing to
DIN EN ISO 9227
12.06.2013- 138
Effect Temperature
Passivate E CF
Very slight violet
discolouration after
heat treatment
Passivate E CF
After 168 h
Testing to
DIN EN ISO 9227
12.06.2013- 139
Effect Temperature
Passivate E
Very slight purple
colouration after
heat treatment
Passivate E
After 168 h
Testing to
DIN EN ISO 9227
12.06.2013- 140
Effect Temperature
Passivate F CF
Slight yellowing of
the deposit after
heat treatment
Passivate F CF
After 264 h
Testing to
DIN EN ISO 9227
12.06.2013- 141
Passivation Summary
Corrosion Results to w/c
Rack
Barrel
No HT
24h/ 120°C
8h/ 210°C
No HT
24h/ 120°C
8h/ 210°C
Passivata A
> 480 h
< 480 h
< 216 h
> 480 h
> 480 h
< 480 h
Passivate A CF
> 480 h
< 480 h
< 456 h
< 480 h
> 480 h
< 120 h
Passivate B
> 240 h
> 240 h
> 240 h
> 240 h
> 240 h
> 240 h
Passivate B CF
< 192 h
< 24h
< 24h
< 144 h
< 24 h
< 24 h
Passivate C
> 336 h
> 336 h
> 336 h
> 336 h
> 336 h
> 336 h
Passivate D CF
> 336 h
< 144 h
> 336 h
> 336 h
> 336 h
> 336 h
Passivate E
> 168 h
< 48 h
< 48 h
< 168 h
< 48 h
< 48 h
Passivate E CF
> 168 h
< 48 h
< 48 h
< 168 h
< 48 h
< 48 h
12.06.2013- 142
Conclusions
• Not all passivates are yet suitable to be formulated
Cobalt Free on zinc
• It is possible to obtain excellent results using cobalt free
processes
•
•
Rack and barrel
Resistant to heat treatment
• Lower performance systems are more dependant on
cobalt
• Black passivates are not yet available but expected to
be so within 12 months
•
Presently in customer Beta tests
Zinc Nickel Cobalt Free Process
• Cobalt-free passivations for ZnNi alloy layers are already
in widespread industrial use
•
The nickel in the alloy assists the passivate formation in a
similar way to cobalt
• The inherently high corrosion resistance of the alloy to
white corrosion helps in meeting the requirements
• Black passivation for ZnNi
•
•
Low Cr content of about 2.5 g/L
Operated at 25oC
12.06.2013- 144
Cobalt Free Process
Corrosion of cobalt-free black passivated ZnNi layers
As Plated
12.06.2013- 145
After 720 hrs NSS
Cobalt Free Passivates Conclusion
• Co-free passivates generally allow customers to obtain the
same results that they can achieve with their Cobalt containing
products
• The transition from Co containing to Co-free alternatives can be
simple.
• All products are designed to operate with similar parameters
(concentration, pH, time, temperature, etc.)
• Many of the Co-free passivate options have been in use for
years!
• Many of the Co-free passivate options are already approved by
automotive OEM’s
• There are still some areas where more work is required
• Lower level blue/irridescent passivates on zinc
• Black passivates on zinc
12.06.2013- 146
Tin Whisker Growth from Electroplated
Finishes Used in Electronics
G.D.Wilcox, M.A.Ashworth, R.L.Higginson, R.J.Heath and C.Liu
Department of Materials
Loughborough University,
Leicestershire, LE11 3TU.
UK
148
Tin Whisker Growth from Electroplated
Finishes Used in Electronics
G.D.Wilcox, M.A.Ashworth, R.L.Higginson, R.J.Heath and C.Liu
Loughborough University,
Leicestershire, LE11 3TU.
UK
149
Presentation Contents
 Introduction – what are tin (and zinc)
whiskers?
 An historical perspective on tin whisker
investigations and current theories
 Zinc whisker formation
 The WHISKERMIT research programme at
Loughborough University.
150
What is a Metal Whisker ?
J-C.Hsleh, C-C.Hu & T-C.Lee J.Electrochem.Soc 155, D675 (2008)
•
•
It’s not a dendrite formed during
electrodeposition !
It’s a spontaneous (probably) single crystal
metallic eruption from the metal surface after
electrodeposition.
2 μm
151
Introduction to Whiskers
•
•
•
“Hair-like” crystal structures that grow from
surfaces coated by pure tin (or Zn or Cd) finishes
Typically single crystals
Large variations in shapes and sizes
- filaments (typically, 1-5m diameter
and <1mm in length)
- nodules
- odd-shaped eruptions (OSE)
Filaments
•
•
•
•
•
Spontaneous growth in common service
Incubation period before growth
Growth mechanism is still not fully
elucidated
No useful models for predicting whisker
growth
Whiskers are not the same as dendrites
Nodule
152
Odd-shaped
eruptions
Electrical Shorting Phenomena
Electroplated Tin
coating
Short circuiting
substrate
Part A
Fig.1 - Two mutually-isolated parts of
one electrical circuit
153
Part B
Issues Helping the Occurrence of Tin Whiskers
• Miniaturisation in
electronics – whiskers
can bridge components
and tracks
• Lower voltages –
whiskers can sustain
currents
• Environmental
legislation – EU RoHS
directive, pure tin often
the first finish to replace
Sn-Pb
C.Minter, DMSMS Conf., Charlotte, USA,
10-13th July 2006.
154
Metal Whisker Failures
155
Whiskers from an Historical Perspective
S.C.Britton, ‘Spontaneous growth of
whiskers on tin coatings: 20 years of
observation’, Transactions of the Institute
of Metal Finishing, 52, 95-102, 1974.
www.airforce.forces.gc.ca/.../liberator-eng.asp
Cadmium electroplated leaves in
capacitors in Consolidated Liberator
aircraft radios. Whisker growth resulted in
shorting between plates.
Reported in H.L.Cobb, ‘Cadmium Whiskers’. Monthly
Rev. Am. Electroplaters Soc., 33 (28), 28-30, Jan
1946.
• Electrodeposited tin coatings on brass
should be applied over an undercoat of
nickel or copper
• Refrain from using bright tin
•Tin electroplated coatings should be at
least 8 μm if not flow melted
• Heat treat tin coatings after electroplating
• Avoid corrosion in storage and service
environment
• Hot dipped or flow melted coatings less
problematic for whiskers
• Sn-Pb coatings of over 8 μm are safer
• Avoid local pressure
• Immunity from whiskers from Sn(65%)-Ni
alloy
• Thick layers of resin effective as
insulating barrier
• Removal
156of whiskers by vacuum system
Whisker growth on
intermetallic phases in
Sn-3.8Ag-0.7Cu1.0Ce/Er/Y solder joints.
– Yaowu Shi and Hu Hao,
The Beijing University of
Technology
The Driving Force for Whisker Growth
 The driving force for the spontaneous growth of whiskers is
generally accepted as resulting from the formation of
compressive stress in the coating. The compressive stress may
be generated by:
 Intermetallic formation (Cu6Sn5)
 CTE mismatch, e.g. Sn plated onto Alloy 42
 Residual electroplating stress in deposit
 Externally applied mechanical stress
157
Examples of Zinc Whisker Growth
 Studies of zinc whisker formation and growth from
bright zinc electrodeposits; Sugiarto, Christie and Richards
– Trans. Inst. Met. Fin 62, 92 (1984)
 Zinc whisker growth on rotary switches; Downs and
Francis –– Met. Fin. 23 (1994)
 Zinc whisker growth on hot-dip galvanised coatings;
Lahtinen and Gustafsson –– J. Appl. Surf. Fin. 2, 15 (2007).
 Effect of heat treatment on promoting zinc whisker
growth from bright zinc electrodeposited coatings;
Chapaneri et al – Trans. Inst. Met Fin 87, 159 (2009)
158
Zinc Whiskers on Hot Dipped Galvanised Coatings
Hot dipped galvanised coated pipe reported to be ~15 to
20 years old and kept in warehouse storage.
Sample provided by R. Lahtinen (VTT, Finland)
Received by J. Brusse/QSS Group Inc. Sept. 2005
[email protected]
159
Zinc Whiskers – Raised Flooring in Computer Rooms
Wood fibre core with zinc electroplated
steel sheet on sides and reverse
Top and side view of floor tile
Jay Brusse and Michael Sampson, IT Pro, Nov/Dec 2004, pps 43-47.
160
Zinc Whiskers from Zn-Ni – Effect of Stress
Filamentary whisker growing from a Zn-Ni alloy
electrodeposit
Whisker growing in the vicinity of a surface
depression from the Zn-Ni alloy electrodeposits
Annealed at 150°C for 72 hrs
161
Coatings vs. Whiskers
Zinc whisker growing through a trivalent
chromium conversion coating
Micrograph of acid zinc deposit with hexavalent
chromium passivation film (heat treated at 150°C
for 24h)
162
The WHISKERMIT Approach
Whisker
Mitigation
Modification of
the
Electroplating
Process
Development of
Conformal
Coatings
Plating process variables
Bath constituents
Pulse plating
Co-deposition of nanoparticles
Coatings to retard whisker growth
Optimisation of coating formulation
163
Effect of Electroplating Parameters on Whisker
Growth
Low current density
 Optimisation of the tin electroplating
process to improve the resistance of the
deposit to whisker growth
 Current density, deposit thickness
20µm
 Substrate material
 Characterisation of deposit structures
and correlation with whisker growth rates
 Use of accelerated temperature and
humidity to accelerate whisker growth
20µm
High current density
164
Pulse Plating as a Potential Whisker Mitigation
Strategy?
 Why pulse plating?
Direct current
 Potential to manipulate the grain structure and
orientation of the tin deposit to promote improved
whisker resistance
 Only a few studies looking at the effect of pulse plating
100m
on whisker formation
- Suggest improved resistance to whisker formation
Pulse plating
- Control of residual stresses
 Evaluate effect of duty cycle and pulse frequency on
100m
whisker growth
165
Conformal Coatings to Mitigate Whisker Growth
 Polymer conformal coatings may be used to mitigate whisker growth
 Evaluate the ability of different coating materials to prevent whisker
growth and subsequent penetration of the coating
 Develop new coating materials based on an understanding of structure /
property relationships
166
Effect of Co-deposited Particles on Whisker
Formation
 Co-deposited particulates may alter residual electroplating
stress and influence the orientation of the deposit
 Preparation and characterisation of composite deposits
 Evaluate the effect of co-deposited particles on whisker
growth using deposition conditions known to promote rapid
whisker growth
1m
1m
167
Co-investigators and Industrial Supporters
 Chris Stuttle, Roger Mortimer, Jing Wang, Han Jiang,
Keming Chen, Andrew Ebbage, Darrell Bunyan and
Liang Wu
 Companies supporting the WHISKERMIT research
programme:
Rolls Royce, Aero-Engine Controls, Gen3
Systems, MBDA, MacDermid, NPL and Park Air
Systems Ltd.
 Innovative Electronics Manufacturing Research
Centre (IeMRC) and the EPSPC (UK) for funding.
168
Any Questions ?
C.Minter, DMSMS conf., Charlotte, USA, 10-13th July 2006.
169

Please visit the exhibition
Don’t forget the “Land Rover” Experience
Have a look at the Heritage Museum

Please be back for 2.00pm!



Transfair Presentation 3 (pdf file 12MB)

Transcription

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