4 Questions on Platers Minds
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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