4 Questions Questions: (On(On Platers’Platers’ Minds)Minds) 1. What is the current status of zinc alloys as cadmium replacements?
2. What is the status of hexavalent chromium replacements?
3. IsIs nickelnickel platingplating inin trouble?trouble?
4. What role is nanotechnology playing in By: Frank Altmayer, CEF, President, electroplating? Scientific Control Labs, Inc. Technical Director, AESF
Galvanic Series (V) Questions: 0 = - E (SO4 ) Galvanic Series, E (Cl ) Mg --2.37 Mg --2.37 Mg --2.37 1.What is the current status of AI --1.66 AI --1.66 AI --1.66 zinc alloys as cadmium Zn --0.76 Zn --0.76 Zn --0.76 0.320.32 Fe --0.44} Cd --0.54 Cd --0.54 replacements? 0.100.10 replacements? Cd --0.40 Fe --0.44} ZnNi --0.50 0.060.06 Co --0.29 Co --0.29 Fe --0.44} Ni -0.25 Co -0.29 2.2. What is the current status of hexavalent chromate Ni --0.25 Ni -0.25 Co -0.29 replacements?replacements? Sn --0.14 Sn --0.14 Ni --0.25 H 0.00 H 0.00 Sn --0.14 3.3. IsIs nickelnickel platingplating inin trouble?trouble? Cu +0.34 Cu +0.34 H 0.00 Au +1.68 Au +1.68 Cu +0.34 4.4. What role is nanotechnology playing in electroplating? Au +1.68
Zinc-Nickel Zinc-Cobalt Processes · 5--15% Ni · Excellent salt spray · Alloy = 0.2--0.6% cobalt. performance · Deposit is bright/level · Alkaline or acidic solutions Chromating solutions · Good Kesternich performance will require modification · Zinc--cobalt is better · Rack or barrel plated · Chromate performance · Lower cost enhanced by heating · Co is not regulated (yet) · Favorable galvanic couple with · No high--temperaturetemperature-- aluminum resistantresistant chromateschromates · Good formability & weldability
1 SaltSalt SpraySpray Comparison,Comparison, JohnJohn StropkeStropke,, BattelleBattelleInstituteInstitute andand GlenGlen H.H. Graham,Graham, CEF,CEF, TinkerTinker AFBAFB (Proceedings(Proceedings ofof 31st31st Aerospace/AirlineAerospace/Airline PlatingPlating &&MetalMetal Tin-Zinc Alloy Plating FinishingFinishing Forum,Forum, AprilApril 25,25, 1995)1995) Coating Panel Hrs To WR Hrs To RR ·· Alloy is 25--30% Zinc Cadmium11 Scribed 504504 >1000>1000 ·· Cyanide or Acidic Solutions Cadmium11 Not Scribed 672672 >1000>1000 Available Cadmium22 Scribed 168168 >1000>1000 Cadmium22 Not Scribed 672672 >1000>1000 ·· High Corrosion resistance ZincZinc--Nickel33 Scribed 168168 336336 (especially(especially inin sulfursulfur Zinc-Nickel33 Not Scribed 168 336 atmosphere) Zinc-Nickel Not Scribed 168 336 ZincZinc--Nickel44 Scribed >1000>1000 >1000>1000 TinTin--zinc,zinc, asas PlatedPlated andand ·· Excellent solderability ZincZinc--Nickel44 Not Scribed >1000>1000 >1000>1000 chromatedchromated ·· Good frictional properties ZincZinc--TinTin44 Scribed 168168 >1000>1000 4 ·· Excellent ductility ZincZinc--TinTin4 Not Scribed 672672 >1000>1000 ZincZinc--Cobalt 33 Scribed 168168 504504 · Soft (subject to damage) · Soft (subject to damage) ZincZinc--Cobalt 33 Not Scribed 168168 336336 ·· Dull, matte finish ZincZinc--Cobalt 44 Scribed 168168 504504 ·· Excellent couple with Al ZincZinc--Cobalt 44 Not Scribed 336336 672672 1=chromated,1=chromated, 2=not2=not chromatedchromated 3=acid3=acid solutionsolution 4=alkaline4=alkaline solutionsolution
Fatigue Resistance Comparison HSC Comparison
Coating Avg. FLC* (0.1 s r**) Avg. FLC* (0.43 s r) Coating #--Tests Time (Hrs.) To Failure/Pass Unplated 242,456242,456 ------None 2 (2) >200, (2-Pass) Cadmium11 760.038760.038 40,45240,452 None 2 (2) >200, (2-Pass) 11 Cadmium22 730,733730,733 runrun--outout Cadmium 6 (1)(1) 183183 (Fail),(Fail), (5)(5) >200,>200, (5(5--Pass) ZincZinc--Nickel33 15,26215,262 5,4385,438 Cadmium22 3 (3)(3) 213,213, 213,213, 213213 (3(3--Pass) 3 ZincZinc--Nickel 3 39,81939,819 39,81939,819 Zinc--Nickel 33 3 (3)(3) 0.5,0.5, 0.4,0.4, 0.50.5 (3(3--Fail) ZincZinc--Nickel44 9,9419,941 11,91111,911 Zinc--Nickel 33** 3 (3)(3) 240,240, 240,240, 240240 (3(3--Pass) ZincZinc--Nickel44 runrun--outout 42,31142,311 Zinc-Nickel 44 6 (1) 141 (Fail), (5) >200 (5-Pass) ZincZinc--TinTin44 7,6207,620 nono datadata Zinc-Nickel 6 (1) 141 (Fail), (5) >200 (5-Pass) 44 ZincZinc--Cobalt 33 7,4597,459 nono datadata Zinc--Tin 3 (3)(3) 0,0, 0,0, 0.20.2 (3(3--Fail) ZincZinc--Cobalt 44 22,52122,521 nono datadata Zinc--Cobalt33 3 (3)(3) 0.8,0.8, 5.7,5.7, 4.44.4 (3(3--Fail) Zinc--Cobalt44 3 (3)(3) 4.5,4.5, 4.5,4.5, 8.38.3 (3(3--Fail) *Fatigue*Fatigue LifeLife CycleCycle **stress**stress ratioratio ** AlternateAlternate SolutionSolution SupplierSupplier 1=chromated,1=chromated, 2=not2=not chromatedchromated 3=acid3=acid solutionsolution 4=alkaline4=alkaline solutionsolution 1=chromated,1=chromated, 2=not2=not chromatedchromated 3=acid3=acid solutionsolution 4=alkaline4=alkaline solutionsolution
Adhesion of Cadmium Substitutes Breaking Torque ToTo PlasticallyPlastically DeformedDeformed SteelSteel SubstrateSubstrate of Cadmium Substitutes Proceedings, Sur/Fin '92- Atlanta, Mark Ingle, James Ault, "Corrosion Control Performance Proceedings, Sur/Fin '92- Atlanta, Mark Ingle, James Ault, "Corrosion Control Performance After 12 months in Marine Atmosphere Best EvaluationEvaluation ofof EnvironmentallyEnvironmentally AcceptableAcceptable AlternativesAlternatives forfor CadmiuCadmiumm Plating")Plating") Worst coat coat coat coat - - - - Zinc Zinc Zinc Zinc - - - - Nickel Nickel Nickel Nickel - - - - Ceramic Ceramic Ceramic Ceramic Cadmium Tin Cadmium Tin Cadmium - Tin Cadmium - Tin - - Zinc (alk) Zinc (alk) Emulsion Zinc (alk) Emulsion Zinc (alk) Emulsion Emulsion Zinc Zinc Zinc Zinc Epoxy E Epoxy E Epoxy E Epoxy E Inorganic Zinc IVD Aluminum Metal Inorganic Zinc IVD Aluminum Metal Inorganic Zinc IVD Aluminum Metal Inorganic Zinc IVD Aluminum Metal Zinc (chloride) Zinc (chloride) Zinc (chloride) Zinc (chloride) IVD Al + Topcoat Titanium Nitride IVD Al + Topcoat Titanium Nitride IVD Al + Topcoat Titanium Nitride IVD Al + Topcoat Titanium Nitride Electrolytic Nickel Electrolytic Nickel Electroless Nickel Electrolytic Nickel Electroless Nickel Electrolytic Nickel Electroless Nickel Electroless Nickel
2 Questions: Background History & Issue •• The European Parliament & the Council of 1.1. What is the current status of zinc alloys as cadmium European Union signed the End--of--Life vehicle replacements?replacements? (ELV)(ELV) directivedirective onon 9/18/009/18/00
2. What is the current status of •• Directive 2000/53/EC,, AnnexAnnex II,II, limitslimits Hexavalent Chromium to 2.0 grams per vehicle for hexavalent chromate corrosion protection purpose only; 00.0 gram for replacements? any other application in a motor vehicle •• ImplementationImplementation (Cr(Cr+6+6)) --January 2003, now 3.3. IsIs nickelnickel platingplating inin trouble?trouble? delayed to July, 2007
4.4. What role is nanotechnology playing in electroplating? •• The Directive covers 4 heavy metals-- Hexavalent Chromium,, Lead,Lead, Mercury,Mercury, andand CadmiumCadmium
Details of ELV Directive 2000/53/EC (from End--of--Life vehicle (ELV) Directive -- European Union) 2000/53/EC
•• Objective is the prevention of waste from vehicles and •• Re--use & recovery @ 85% minimum by 1/1/2006 for all also the reuse, recycle, & recovery of end--of life vehicles & ELVs (presently(presently 70%)70%) components •• Re--use & recovery increased to 95% by 1/1/2015 •• Vintage & historic vehicles are exempted
• Components, materials, as well as spare & replacement • Components, materials, as well as spare & replacement •• The OEMs must publish information to prospective parts are also covered buyers & in their literature
•• Automotive component manufacturers to provide •• Member States already have all laws, regulations & appropriate information to treatment facilities, concerning administrative provisions to comply with the Directive dismantling, & reuse
Why is this so important? Cost Factor
•• Estimated cost increase in NA 10%--30%?
•• OEMs may not accept any • Several Reasons – componentscomponents withwith CrCr+6+6 afterafter • Several Reasons – 07/200707/2007 (for(for 2003MY)2003MY) •• Raw material cost ~ 10% to 30% higher •• Concentration of Cr+3+3 @ 10--12% Vs 2--4% •• Heated bath Vs ambient, Shorter bath life •• Currently an average vehiclevehicle == 44 toto 88 gramsgrams ofof Cr+6+6 (some(some >> 10g)10g) •• InitialInitial studystudy indicatingindicating costcost factorfactor @@ 1.0--1.7
•• NOT anan Option;Option; MUSTMUST •• Volume, selection of coating,, asas wellwell asas supplier’s complycomply toto meetmeet capability could be some of the major determining customer’scustomer’s requirementsrequirements factors for higher cost & stay in business factors for higher cost
3 Technical Issues Where Is It?
•• Hexavalent Chromium is found in the corrosion •• Chromium exists in four valence states: preventive and conversion coatings on numerous •• Cr°° key steel and aluminum automotive components • Cr++³ • Cr ³ (usually(usually asas chromatechromate films)films) •• Cr+2+2 •• Cr+6+6 •• Metal parts (such as fasteners, levers, fuel/brake •• Trivalent and Hexavalent Chromium: lines,lines, alloyalloy wheels,wheels, etc.)etc.) •• corrosioncorrosion protectionprotection coatingscoatings andand applicationapplication •• processprocess intermediatesintermediates •• sometimessometimes changeschanges statesstates (Cr(Cr+3+3 toto CrCr+6+6)) duringduring thethe • Polymer pigments applicationapplication processprocess • Polymer pigments •• Hexavalent is self healing trivalent is not •• Pre--painting and anodizing sealing chromate rinse •• Neither Cr 00 nor Cr 33 are legislated in the European Union Directive at present •• Phosphates (acidulated rinse)
Test Methods for Cr+6 Choice of Alternatives ~9 test methods available, DELPHI Procedure •• Two Major Alternatives – Summary: Trivalent Chromate 22 •• 50 cm minimum sample •• Commercially available globally, many •• Chromatedparts must be >24hrs. and <30 suppliers offer proven technology days old •• Enhanced corrosion protection with a sealer or a topcoat; several color finishes •• 5--7 minutes extraction in boiling water a topcoat; several color finishes •• Black may be hard to produce • Remove part(s), filter water if cloudy • Remove part(s), filter water if cloudy Chrome--Free Substitutes •• Acidify with sulfuric acid •• Limited universal availability •• Add diphenylcarbizide solution •• Application limited to spray or spin & spray in •• Measure color at 540nm most cases ( Geomet,, PlusPlus Sealers)Sealers) •• Mostly silver or gray (black finish limited) +6+6 •• Repeat extraction to confirm all Cr +3+3 removedremoved •• Cost may be higher than Cr
Questions: IsIs NickelNickel PlatingPlating InIn Trouble?Trouble?
1. What is the current status of zinc alloys •• Sweden/Denmark Lead Ban On Nickel In as cadmium replacements? Jewelry •• <0.05%<0.05% NiNi inin anyany jewelryjewelry alloyalloy 2. What is the current status of hexavalent • Denmark/Germany chromate replacements? • Denmark/Germany •• <0.5<0.5mmg/cmg/cm22/week/week releaserelease toto artificialartificial perspirationperspiration
•• EEC793/93 Existing Substances 3. IsIs nickelnickel platingplating inin Regulation trouble? – Data Collection (completed) – Priority Setting (completed) 4.4. What role is nanotechnology playing in electroplating? – Risk Assessment (completed) – Risk Reduction (draft completed, not released)
4 European Regulations Affected IsIs NickelNickel PlatingPlating InIn Trouble?Trouble? •• Directive 76/769/EEC Restrictions on marketing/use of dangerous substances •• California, IARC & •• Euro Coinage • Consumer protection, food contact materials NTP have linked • Consumer protection, food contact materials NTP have linked •• Directive 98/83/EC water quality standards some nickel •• Directive 90/385/EEC implantable medical devices compounds to •• Directive 88/378/EEC toy safety cancer •• Directive 89/106/EEC construction products •• Directive 96/61/EC pollution prevention & control •• Directive 76/464/EEC aquatic environments •• TERA (Toxicology •• Directive 2000/60/EC water policy Excellence for Risk •• Directive 80/68/EEC groundwater protection Assessment) Finds •• Directive 98/24/EC protection of workers • Directive 2000/76/EC incineration of waste “insufficient data” • Directive 2000/76/EC incineration of waste •• Directive 91/689/EEC No. 259/93 hazardous waste
IsIs NickelNickel PlatingPlating InIn Trouble?Trouble? Questions:
Substitutes: 1. What is the current status of zinc alloys Substitutes: as cadmium replacements? •• Cu--Zn--Sn (Trade Name: Alballoy) Name: Alballoy) 2. What is the current status of hexavalent – 55--60%Cu, 20--30%Sn, chromate replacements? 10--20%Zn – Bright 3. IsIs nickelnickel platingplating inin trouble?trouble? – Solderable – Hardness > nickel – Solution is hard to 4.What role is nanotechnology control playing in electroplating? – Cyanide process
Nano-technology & Electroplating Nano-technology & Electroplating Micro-electrodeposition MEMS* Nickel Plating Prof. George Whitesides Harvard University MEM: Tel: 617-495-9430 Nano--scalescale componentscomponents producedproduced byby E-mail: [email protected] combinationcombination ofof lithographylithography andand electroplatingelectroplating Electrochemical System, Inc. Provides electroplating system for R&D purpose in Applications: Provides electroplating system for R&D purpose in Pressure Transducers MEMs field. Also provides electroplating service Medical monitors Trusses,Trusses, 11--100100 mm m MEM, Pure such as special bath, plating, etc.. Airbag sensors Nickel Contact: Bio-terror sensors Bio-terror sensors IgorIgor KadiyaKadiya oror XiaoyiXiaoyi GuGu Miniature power supplies Miniature power supplies 240 King Blvd. Newark, NJ Heat exchangers 240 King Blvd. Newark, NJ Aircraft components 07102 (973)242(973)242--8988, (201)670--8397 Fax: (201)670(201)670--0620, (201)997--7213 Via E--mail: Market: $5b+ [email protected] or [email protected] *Micro*Micro--electroelectro--mechanical systems
5 US Pat 6,455,233 MEMS Process Details
Structures of micro--miniature dimensions are A conductive plating base or seed formedformed byby scanningscanning aa nearlynearly parallelparallel beambeam ofof highhigh layerlayer overover siliconsilicon (sputtered(sputtered nickel)nickel) andand aa meansmeans toto patternpattern thethe electroelectro-- energy light ions across the surface of a resist depositdeposit (photolithography)(photolithography) areare material such as PMMA in a predetermined pattern. needed.needed.
The resulting chemical changes in the exposed Adhesion Promotion: resistresist materialmaterial allowsallows aa chemicalchemical developerdeveloper toto Application of sputtered Ti or Cr, oror rougheningroughening ofof SiSi removeremove thethe exposedexposed materialmaterial whilewhile leavingleaving thethe unexposed material substantially unaffected. Typically,Typically, thethe electrodepositelectrodeposit isis unexposed material substantially unaffected. patternedpatterned byby anan additiveadditive processprocess (selective(selective deposition)deposition) insteadinstead ofof aa By simultaneously scanning the beam and subtractivesubtractive processprocess (etching).(etching). orienting the resist layer in a controlled manner, Solution:Solution: NickelNickel Sulfate,Sulfate, 200200 g/L,g/L, resistresist structuresstructures ofof threethree dimensionaldimensional complexitycomplexity Nickel Chloride 5 g/L, Boric Acid 25 g/L,g/L, SaccharinSaccharin 33 g/L,g/L, pHpH 4,4, 2323°°C, can be micro--machined. 0.735mA/cm0.735mA/cm22,, 50%50% dutyduty (pulse)(pulse)
MEMS Features (According to JPL): The End
· 10 to 1,000 times reduction in size, weight, and power consumption over conventional technology
· Matched or better performance · New function and capability not realizable with traditional technology Thank You! · Significant improvement in operation endurance (shock, vibration, and temperaturetemperature cycling)cycling)
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