A Sustainable Approach to
Crystallinity and Corrosion of
Electroless Nickel Plating
400µ" and 455µ“
September 7 2009
Overview
 What is sustainability?
 History of Regulatory Impact on Surface Finishing
 Examples of sustainability in surface finishing
 What is driving innovation in the EN plating tank?
 The Next Generation of EN
 Development objectives/challenges
 Reduced Ion Technology Performance Characteristics
Process/Deposit
Benefits of Reduced Ion Technology
 A look to the future
 What is sustainability?
 It’s a long term mindset where ecology and economy merge into one and humans
live within the limits of available resources. Where all actions taken are
considered for their effect on the environment and the well being of future
generations.
Sustainability in Surface Finishing
 Surface finishing by its very nature, is a sustainable process
Surface treatment extends useful of
life of many components in a wide
variety of applications
Annual cost of corrosion worldwide is
3% global GDP (1)
Applying a very thin film on relatively
inexpensive and readily available
material vs the use of exotic alloys is
a sustainable practice
Surface finishing allows the use of
lighter materials that improve fuel
efficiency and reduce carbon
footprints
(1)"Now is the Time," a paper presented by George F. Hays, PE, Director
General, World Corrosion Organization.
Sustainability in Surface Finishing
• Relevant Aspects of Sustainability
Overall concept of surface finishing is sustainable
Environmentally responsible
Stewards of the environment or just complying?
Consumption responsible
Consumer responsible
History of Environmental Regulations
that impacted surface finishing
Clean Air Act-1970
Clean Water Act-1972
RCRA-1976
TSCA-1976
LRTAP-1979
Superfund-1980
CWA 413/433-1985
Montreal Protocol-1989
NESHAP 1995
ELV-2000
MPM-2002
WEEE-2003
Stockholm convention-2004
ROHS-2006
REACH-2007
CWA 413/433 Review-2015
CAA Air Toxics Update-2015
Impacted Elements, Compounds and
Substances
 Environmental Regulations have banned or restricted the use of:
Cyanide
Solvents
CFC’s
Cr+6
Lead
Cadmium
PFOS
Borates
EDTA
Ammonia
Cobalt
Phosphates
Sustainability in Surface Finishing
 Examples of eco-innovations
Replacement of Halogenated Solvents with Alkaline Cleaners
Low phosphate/phosphate free cleaners
Removal of CN from Zn plating processes
Cr+6 substitutes
Fume suppressants in chrome plating
Pb and Cd replacement in EN (RoHS and ELV)
PFOS and PFC free
Borate free
EDTA free
Ammonia free
Cobalt free
Reduced surface tension
Electrodialysis for EN and acids
Water re-use and recovery
Zero discharge
History of Commercial EN
1st Generation ~ 1950
Kanigen - 7-9% P, difficult to operate, general
purpose EN
2nd Generation ~ 1970 - 1980
High corrosion resistance high phosphorus EN
developed by commercial pioneering companies
like Elnic and Allied Kelite
3rd Generation ~ 1980 - 2000
Wide expansion of processes, including
composites, low phosphorus, ternary alloys. Many
suppliers contributed
4th Generation ~ 2000 - present
Lead and cadmium free
5th Generation ~ 2012+
Eco-optimized EN
Reduced Ion Technology
Low temperature EN
History of “EN”novation Drivers
1970-1980 Performance based
Improved corrosion protection
Simplified operation
Longer solution life, faster plating speeds, brighter deposits
1990-2000 Need to meet specific applications
Improved solderability
Increased thermomagnetic stability
Higher “as plated” hardness
Increased lubricitiy
2000 to today Eco-responsibility and compliance
 ELV,WEEE,ROHS led to cadmium/lead free systems
Waste minimization –Steady state EN, extended bath life
Future Drivers for “EN”novation
Reduced Environmental Impact
 Waste minimization
 Overall reduction of waste to treat or dispose of
 Simplification of treatment





Reduction in use of strong complexors
Reduction of nickel in waste stream
Reduction of nickel in air emissions
Lower energy consumption
Reduced Carbon footprint
 Improved workplaces
 Nickel allergies
 Air Emissions – Inhalation

Avoids European: December 2010 rule CLP 00/ATP 01
Toxic: danger of serious damage to health by prolonged exposure through
inhalation
Cost Reduction
EN Development Objectives to Meet
Future Demands
 Develop EN technology
with at least a 33%
reduction in nickel
concentration without
sacrificing either :
 Intrinsic deposit characteristics
 Process performance
 Reduce process cost by
minimum of 5%
EN Development Challenges
 Earlier industry attempts to reduce nickel metal simply
involved using less nickel.
 Other components were never adjusted
 Over 50 years of commercial R&D work was centered on 6 g/l technology
 Required to optimize complexor type and concentration
Formulate chemistry to accommodate less nickel
maintain critical operating parameters within normal specifications (e.g.
operating temperature and pH)
 Critical stabilizer/additive selection and concentration
 Selection of additives (e.g. stabilizers, brighteners, etc.) to maintain or
enhance deposit characteristics while not sacrificing operating performance
EN Testing Matrix
Process Performance
Deposit Performance
• Lower nickel must not reduce plating
speed
• Corrosion and hardness
performance must be maintained or
increased
Reduced production not an option
• Adjusted complexing agent and
additives must not negatively impact
stability
Increased equipment plate out would be
unacceptable
• New chemistry must maintain or
extend current expected bath life
Waste reduction and cost are technology
drivers
Lower cost and increased productivity mean
nothing if quality requirements aren't met
• Deposit tensile stress over the life of
the bath must not vary considerably
from 6 g/l counterpart
• Surface roughness and appearance
must be maintained or enhanced
• No negative impact on deposit
staining
EN Testing Matrix
 Tested the following criteria
Plating rate vs bath age (by weight
gain and XRF)
Stability (Boiling test)
Brightness (Gloss measurements)
Specific gravity/staining
Nickel drag out
Neutral slat spray
Morphology
Reduced Ion MPEN
Plating Speed
Temp
190 ± 2oF
pH
4.9±0.2
loading
0.7 ft2/gal
Reduced Ion MPEN
Stability
~8% increase in solution stability
pH
4.9±0.2
volume
200 mL
Reduced Ion MPEN
Specific Gravity
 Difference of 0.026
g/cc at 5 mto’s
 Comparable to rinsing
in beer vs pure water
 108 lbs less of “stuff” in
a 500 gallon EN tank
 Consider the impact of
this on drag out and
staining
Reduced Ion MPEN
Nickel drag out*
PPM
*Method: 5 panels plated consecutively with 5 sec dwell time over EN bath after plating followed by rinsing
into beaker with deionized water. “Rinse water” collected and brought to standard volume in a volumetric
flask and analyzed via AA spectrophotometer
• Reduction of ~50% Ni concentration in rinse water
Reduced Ion
Impact on deposit staining
(0.2 mils barrel plated EN on 1010 mild steel stamping)
*Surface tension reduced from 50 to 32 dynes/cm
Reduced Ion
Impact on Deposit Morphology
(High Phosphorus EN, 0 metal turnovers, SEM 500X)
0.5 mil deposit
3.0 mil deposit
Reduced Ion
Conventional
Reduced Ion MPEN
Deposit Brightness
5G MPEN
500
480
470
460
450
440
Standard MPEN
490
RI MPEN
Gloss meter Readings (GU 60)
Standard MPEN
430
420
410
400
0
0.5
1
1.5
2
2.5
3
4
5
6
7
8
Metal Turnovers
Improved consistency of brightness over bath life vs conventional 6 g/L MPEN
Reduced Ion MPEN
Neutral Salt Spray
Rating System: A: 0 rust spots, B: 1-5 spots,
C: 6-10 spots, D: 11-20 spots
24 hrs
48 hrs
72 hrs
96 hrs
RI MPEN 100 Hrs
RI MPEN
0 MTO
A
A
B
B
0 MTO
A
A
A
A
7 MTO
A
A
B
B
7 MTO
A
A
A
A
0 MTO
7 MTO
Standard MPEN
0 MTO
A
A
A
B
0 MTO
A
B
B
B
7 MTO
A
A
A
B
7 MTO
A
A
B
B
Temp
190 ± 2oF
pH
4.9±0.2
Bath loading
0.7 ft2/gal
Thickness
1.0 mil / 25 µm
substrate
Steel Q-panel
Standard MPEN 100 Hrs
0 MTO
7 MTO
Benefits of Reduced Ion EN Technology
 ECO-benefits
 Reduced Ni metal in rinse water by 50%
 Longer solution life reduces bath make-up and associated treatment
 Safer work environment


Reduction in nickel emissions-must confirm both experimentally and in the field
Less nickel reduces exposure for those allergic to nickel
 Improved bath stability

Reduced plate out on equipment requires less work with hazardous stripping chemicals

Longer strip solution life and less generation of waste
 ECO-nomical benefits
Savings for the initial tank/bath make up of 5-10% due to reduced nickel
Less nickel to treat/more creative options for treatment
Unique complexor system simplifies waste treatment of spent solution
RI users that haul spent EN away report ability to reduce waste volume by
30% when evaporating
Reduced Ion EN Technology in the real world
• Since its limited release in 2012 there have been nearly 200
large reduced Ion EN baths made up and operated in several
respected EN platers in North America and Europe
In France, it was required to avoid a placard with this
phrase:
R48/23 phrase: toxic danger of serious damage to health by
prolonged exposure through inhalation
Process/Deposit Performance
Slightly longer bath life
Brighter MPEN deposit
Smoother HPEN deposit
Reduced staining
Less nickel in waste stream
No impact on speed provided bath maintained above 80% activity
Approximate 5-10% cost savings realized
Reduced waste volume for those that evaporate/haul
Future Eco-barriers
Water
 Water will be the most prized
commodity in the future.
 By 2050, without a dramatic shift in global
management of water resources more than
½ of the world’s grain production and
population (4.8 B people) will be
unsustainable. (1)
 45% of projected global GDP ($78 trillion)
will be under stress (1)
 Expect tighter discharge limits in the future
and the potential for required
recycling/reuse and zero discharge
scenarios
http://growingblue.com/water-in-2050/
Future Eco-barriers
Workplace Safety
 Emphasis on safe work
environments will expand
 Targeted source reductions never
cease

2015 review of water soluble nickel
compounds

EPA will continue to restrict emissions
and Europe’s standards often will move
West

Maine's attempt to place soluble nickel in
top 49 toxic metal list
Future Eco-barriers
Climate Change
 Truth lies somewhere between
practical science and exploitation of
diverse political agendas
 Safe bet is to focus on a long term,
sustainable view
 Reducing our demand and associated use
of fossil fuels cant be a bad thing?
 Pursue surface finishing technology that
operates in parallel to this thinking.


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Reduced operating temperatures on all
process tanks
Improved insulating methods
Plating process friendly foam blankets
Air free agitation
Reduced chilling demands
Future Eco-barriers
Consumer Impact
 Our industry is being driven, more than ever, by consumer decisions
 Global expansion of consumer based economies
 Consumers make highly informed decisions and have numerous choices

Cost, features, color, finish, material, content safety
 Consumers have integrated eco-conscious criteria in their decision making process

Dolphin safe tuna, product carbon footprint, conflict free diamonds
 Consumer product companies and everyone in the supply line must:
 align their objectives
 react quickly
 recognize that successful surface finishing companies exploit these
opportunities
A look to the not so distant future
 Chrome free etchants for POP
 High performance and economical
alternatives to cadmium for aerospace
and electronics
 Chrome free passivates for zinc and zinc
alloy
 Viable alternatives to Cr+6 hard chrome
 Consumer safe decorative and precious
metal technology
Closing Remarks
 Suppliers and applicators share responsibility
to overcome current and future barriers
 Commitment to continuous investment in R&D
 Partnering with Universities
 Supporting industry groups both financially and with
active participation
 Aligning with suppliers that share this long term,
sustainable view
 Forward thinking companies don't wait for
regulations to force their actions.
 Innovative companies see barriers as
opportunities; to elevate technology and their
organization
 Long term, successful companies will need to
embrace the triple bottom line of People,
Planet, Profit
Acknowledgment
 Ambrose Schaffer who co-developed this latest generation of EN
technology, conducted the lab trials and provided the bulk of the
technical data herein
 Christian Richter for his invaluable input on the various regulations that
appear as a barrier but often act as a ladder for our industry
Thank you