Crystallinity and Corrosion of 400µ" and 455µ“

September 7 2009

A Sustainable Approach to Electroless Nickel Plating

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 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.

Surface finishing by its very nature, is a sustainable process

Sustainability in Surface Finishing

• Relevant Aspects of SustainabilityOverall concept of surface finishing is sustainable

Environmentally responsibleStewards of the environment or just complying?

Consumption responsible

Consumer responsible

History of Environmental Regulations that impacted surface finishing

Clean Water Act-1972

Clean Air Act-1970

RCRA-1976

TSCA-1976

LRTAP-1979

Superfund-1980

CWA 413/433-1985

Montreal Protocol-1989

NESHAP 1995

ELV-2000

MPM-2002

Stockholm convention-2004

WEEE-2003

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-innovationsReplacement 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 EN1st Generation ~ 1950

Kanigen - 7-9% P, difficult to operate, general purpose EN

2nd Generation ~ 1970 - 1980High corrosion resistance high phosphorus EN developed by commercial pioneering companies like Elnic and Allied Kelite

3rd Generation ~ 1980 - 2000Wide expansion of processes, including composites, low phosphorus, ternary alloys. Many suppliers contributed

4th Generation ~ 2000 - presentLead and cadmium free

5th Generation ~ 2012+Eco-optimized EN

Reduced Ion Technology

Low temperature EN

History of “EN”novation Drivers

1970-1980 Performance basedImproved corrosion protection Simplified operationLonger solution life, faster plating speeds, brighter deposits

1990-2000 Need to meet specific applicationsImproved solderabilityIncreased thermomagnetic stabilityHigher “as plated” hardnessIncreased lubricitiy

2000 to today Eco-responsibility and compliance ELV,WEEE,ROHS led to cadmium/lead free systemsWaste 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 01Toxic: 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 nickelmaintain 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• Lower nickel must not reduce plating

speedReduced 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

Deposit Performance• Corrosion and hardness

performance must be maintained or increased

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 criteriaPlating 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 MPENPlating Speed

Temp 190 ± 2oF

pH 4.9±0.2

loading 0.7 ft2/gal

Reduced Ion MPENStability

~8% increase in solution stability

pH 4.9±0.2

volume 200 mL

Reduced Ion MPENSpecific 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 MPENNickel drag out*

• Reduction of ~50% Ni concentration in rinse water

*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

PPM

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

Reduced Ion Impact on Deposit Morphology(High Phosphorus EN, 0 metal turnovers, SEM 500X)

0.5 mil deposit

Conventional

3.0 mil deposit

400

410

420

430

440

450

460

470

480

490

500

0 0.5 1 1.5 2 2.5 3 4 5 6 7 8

Standard MPEN 5G MPEN

Glo

ss m

ete

r R

ea

din

gs (

GU

60)

Metal Turnovers

Improved consistency of brightness over bath life vs conventional 6 g/L MPEN

Reduced Ion MPENDeposit Brightness

Sta

nd

ard

MP

EN

RI M

PE

N

24 hrs 48 hrs 72 hrs 96 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

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

RI MPEN 100 Hrs

Standard MPEN 100 Hrs

Rating System: A: 0 rust spots, B: 1-5 spots, C: 6-10 spots, D: 11-20 spots

0 MTO

0 MTO

7 MTO

7 MTO

Temp 190 ± 2oF

pH 4.9±0.2

Bath loading 0.7 ft2/gal

Thickness 1.0 mil / 25 µm

substrate Steel Q-panel

Reduced Ion MPENNeutral Salt Spray

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 benefitsSavings 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 PerformanceSlightly 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-barriersWater

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

• (1) International Food Policy Research Institute (IFPRI)

http://growingblue.com/water-in-2050/

Future Eco-barriersWorkplace 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-barriersClimate 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.

Reduced operating temperatures on all process tanks

Improved insulating methods Plating process friendly foam blankets Air free agitation Reduced chilling demands

Future Eco-barriersConsumer 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

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

A look to the not so distant future

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