NiClipse. Zinc Alloy Plating NiClipse

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1 Zinc Alloy Plating Systems NiClipse NiClipse is an acid zinc/nickel plating process that offers exceptional corrosion resistance, along with bright deposits, exceptional distribution and covering power. With low stress and high ductility, this process is suitable for either rack or barrel plating. NiClipse deposits easily accept clear, yellow or black chromate conversion coatings. v 1,000+ hours to red rust in salt spray v Controllable nickel alloy for both the 6-8% and 12-15% Range v Can be run with or without ammonium chloride v Bright and ductile zinc nickel deposits v Low temperature application v Suitable for rack and barrel v Can be run with single or dual rectification v Patent Pending Pavco Inc John Crosland Jr. Dr. Charlotte, NC Phone Fax Toll Free

2 Pavco NiClipse Page 2 Operating Parameters using potassium chloride & boric acid Zinc: Nickel: 12-15% Nickel alloy 12-15% Nickel alloy Range oz/gal (19-38 g/l) oz/gal ( g/l) 2-4 oz/gal (15-30 g/l) oz/gal (11-19 g/l) Optimum 3.5 oz/gal (26 g/l) 4.0 oz/gal (30 g/l) 3 oz/gal (22.5 g/l) 1.7 oz/gal (13 g/l) Potassium chloride: Total chloride: Boric acid: oz/gal g/l oz/gal g/l oz/gal (26-34 g/l) 25 oz/gal. 188 g/l 4 oz/gal (26 g/l) NiClipse Starter: 3-6% 4 % NiClipse Brightener: % 0.02 % Temperature: F (25-35 C) 34 oz/gal 260 g/l 80 F (27 C) ph: Cathode Current Density (Rack): ASF ( ASD) 15 ASF (1.6 ASD) Cathode Current Density (Barrel): amps/ft amps/dm 2 5 amps/ft amps/dm 2 Operating Parameters using ammonium chloride Zinc: 12-15% Nickel alloy Nickel: 12-15% Nickel alloy Ammonium chloride: Total chloride: Range oz/gal (19-38 g/l) oz/gal ( g/l) 2-4 oz/gal (15-30 g/l) oz/gal (11-19 g/l) oz/gal g/l oz/gal g/l NiClipse Starter: 3-6% 4 % Optimum 3.5 oz/gal (26 g/l) 4.0 oz/gal (30 g/l) 3 oz/gal (22.5 g/l) 1.7 oz/gal (13 g/l) 25 oz/gal 188 g/l 25 oz/gal. 188 g/l NiClipse Brightener: % 0.02 % Temperature: F (25-35 C) 80 F (27 C) ph: Cathode Current Density (Rack): ASF ( ASD) 15 ASF (1.6 ASD) Cathode Current Density (Barrel): amps/ft amps/dm 2 5 amps/ft amps/dm 2

3 Pavco NiClipse Page 3 Operating Parameters using potassium & ammonium chloride Zinc: 12-15% Nickel alloy Nickel: 12-15% Nickel alloy Ammonium chloride: Total chloride: Potassium chloride: Range oz/gal (19-38 g/l) oz/gal ( g/l) 2-4 oz/gal (15-30 g/l) oz/gal (11-19 g/l) 7-9 oz/gal g/l oz/gal g/l oz/gal g/l Optimum 3.5 oz/gal (26 g/l) 4.0 oz/gal (30 g/l) 3 oz/gal (22.5 g/l) 1.7 oz/gal (13 g/l) 8 oz/gal 60 g/l 25 oz/gal. 188 g/l NiClipse Starter: 3-6% 4 % NiClipse Brightener: % 0.02 % Temperature: F (25-35 C) 23 oz/gal 173 g/l 80 F (27 C) ph: Cathode Current Density (Rack): ASF ( ASD) 15 ASF (1.6 ASD) Cathode Current Density (Barrel): amps/ft amps/dm 2 5 amps/ft amps/dm 2 Equipment Tank: Anodes: Anode Baskets: Anode Bags: Anode S-Hooks: Anode Bars: Filtration: Rectifier: Temperature: Control: Ventilation: A polypropylene, PVC, or Koroseal lined tank is required. Anodes should be a mix of treated zinc slab anodes with nickel anodes. Zinc balls are NOT recommended and will cause failures Napped, laundered polypropylene or double cotton that has been leached. Avoid bags if possible by increasing filtration. Bags are not recommended for barrel applications. Titanium S-hooks Use copper anode bars, preferably shielded with plastic. Use a 5-10 micron cartridge or plate filter. Filtration speed should be a minimum of 1 tank turnover per hour. Up to 12 volts Consistent temperature is necessary in order to maintain a constant alloy in the deposit. Automatic temperature control is mandatory. Separate titanium heat exchangers are recommended for both cooling and heating. Recommended. Comply with all local regulations

4 Pavco NiClipse Page 4 Anode Preparation Zinc and nickel anodes are recommended for the NiClipse system. The zinc anodes need to be treated before use. In a side tank mix the following: Maintenance of the Solution NiClipse Brightener: Zn Ni lbs/gal (60 g/l) nickel sulfate or nickel chloride lbs/gal (250 g/l) ammonium chloride. 3. Add water to 90% volume and mix well. 4. Lower ph to 5.5 with hydrochloric acid 5. Immerse zinc anodes in solution until gassing stops. 6. Anodes should be coated with a dark grey film. 7. Typical treatment times are 24 hours at 70 F (21 C); 3 hours at 120 F (49 C). 1 gal./ 10,000-20,000 A-hr 1 liter / A-hr by analysis by analysis Bath Make Up 1,000 Gallons (3785 l) using potassium chloride & boric acid (12-15% Nickel Alloy) 1. Prepare a lined tank by leaching it with 5% hydrochloric acid for a period of hours. 2. Rinse the tank clean with water. 3. Fill the lined tank with 600 gallons (2271L) of water. 4. Add 457 pounds (208 kilograms) of anhydrous zinc chloride and mix well. For liquid zinc chloride, use 48 gallons (183 L) of 62.5% liquid zinc chloride 5. Add 759 pounds (345 kilograms) of nickel chloride (hexahydrate) and mix well. For liquid nickel chloride, use 127 gallons (479L) 6. Add 250 pounds (100 kilograms) of boric acid and mix well. 7. Add 2125 pounds (966 kilograms) of potassium chloride and mix well. 8. Hang treated zinc anodes in the bath. 9. Add 40 gallons (150 l) of NiClipse Starter and gallons (1-2 l) of NiClipse Brightener. Mix well. 10. Adjust the ph to 5.3 with hydrochloric acid. 11. Add water to the final working level, mix thoroughly, and analyze the bath. Make adjustments if necessary. vliquid zinc chloride at 62.5% contains 9.45 #/gal of zinc chloride. vliquid nickel chloride contains 6#/gal of nickel chloride

5 Pavco NiClipse Page 5 Bath Make Up 1,000 Gallons (3785 l) using ammonium chloride (12-15% Nickel Alloy) 1. Prepare a lined tank by leaching it with 5% hydrochloric acid for a period of hours. 2. Rinse the tank clean with water. 3. Fill the lined tank with 600 gallons (2271L) of water. 4. Add 457 pounds (208 kilograms) of anhydrous zinc chloride and mix well. For liquid zinc chloride, use 48 gallons (183 L) of 62.5% liquid zinc chloride 5. Add 759 pounds (345 kilograms) of nickel chloride (hexahydrate) and mix well. For liquid nickel chloride, use 127 gallons (479L) 6. Add 1563 pounds (710 kilograms) of ammonium chloride and mix well. 7. Hang treated zinc anodes in the bath. 8. Add 40 gallons (150 l) of NiClipse Starter and 0.1 gallons (380 ml) of NiClipse Brightener. Mix well. 9. Adjust the ph to 5.3 (if necessary) with hydrochloric acid. 10. Add water to the final working level, mix thoroughly, and analyze the bath. Make adjustments if necessary. Bath Make Up 1,000 Gallons (3785 l) using potassium & ammonium chloride (12-15% Nickel Alloy) 1. Prepare a lined tank by leaching it with 5% hydrochloric acid for a period of hours. 2. Rinse the tank clean with water. 3. Fill the lined tank with 600 gallons (2271L) of water. 4. Add 457 pounds (208 kilograms) of anhydrous zinc chloride and mix well. For liquid zinc chloride, use 48 gallons (183 L) of 62.5% liquid zinc chloride 5. Add 759 pounds (345 kilograms) of nickel chloride (hexahydrate) and mix well. For liquid nickel chloride, use 127 gallons (479L) 6. Add 500 pounds (227 kilograms) of ammonium chloride and mix well. 7. Add 1438 pounds (653 kilograms) pounds of potassium chloride and mix well 8. Hang treated zinc anodes in the bath. 9. Add 40 gallons (150 l) of NiClipse Starter and 0.1 gallons (380 ml) of NiClipse Brightener. Mix well. 10. Adjust the ph to 5.3 (if necessary) with hydrochloric acid. 11. Add water to the final working level, mix thoroughly, and analyze the bath. Make adjustments if necessary.

6 Pavco NiClipse Page 6 NiClipse Operating Tips v CRITICAL: Successful operation of this process requires the ability to determine the nickel composition of your deposit. You must have X-Ray Fluorescence analytical capability and it needs to be set up for analysis of zinc nickel thickness and composition. Standards for zinc nickel alloy and composition are required v Consistent temperature control is critical. Alloy composition will fluctuate with temperature. You need to be able to keep the temperature within +/- 1 or 2 degrees. There must be separate coils for both heating and cooling. If alloy composition is incorrect, check and adjust chemistry first. v Brightness is obtained as a synergy of the Pavco additives and the alloy composition. It also cannot be achieved below 10% Nickel composition. When optimizing brightener concentrations, always first adjust nickel composition to within 10-14% nickel in the deposit v Alloy composition will fluctuate with agitation. High agitation suppresses nickel deposition. To obtain uniform alloy and brightness in rack operation, you must have uniform agitation v Due to the high chloride levels in the bath, it is recommended that the solution be continuously agitated and temperature must be maintained above 68F (20C) at all times. This will prevent crystallization of salts in the tank blocking the air sparge. If crystallization does occur, turn air off and temporarily raise temperature to 110F to aid in clearing air lines. v Operation at lower temperature (78-82F/25-28C) provides optimal LCD performance in both rack and barrel applications. Some applications with no LCD areas may allow for higher temperature operation, (100F) but in general, lower temperatures allow for the greatest plating range. High temperature operation can lead to dark LCD deposits v Coating of anodes with nickel conditioning solution is critical to preventing zinc growth. Coating can degrade during plating. Poorly coated anodes will gas substantially when not in use. Some gassing is normal when the rectifier is off. If anodes continue to gas after 8 hrs of downtime, they need to be removed and recoated. If zinc growth is not an issue, anode recoating will be less frequent. Higher temperature operation will accelerate zinc anode dissolution.

7 Pavco NiClipse Page 7 Troubleshooting Chart Problem Cause Possible Solution Low Nickel alloy Low nickel Add nickel anodes Add liquid nickel chloride Low temperature Raise temperature Excessive agitation Reduce air High Zinc Increase number of nickel anodes Dull Deposit Low Nickel alloy (<10%) Adjust to above 10% Nickel Dark Low current density High Nickel Reduce nickel anoding High temperature Reduce temperature and raise nickel to maintain alloy Low Niclipse Starter Add 1% increments Niclipse Starter Burning/blistering Low boric acid or ammonium Analyze and adjust chloride Low temperature Adjust temperature to the recommended range Low zinc level Increase zinc High ph Reduce ph to 5.3 High iron Check for iron and treat with % hydrogen peroxide Excessive plating current Reduce current Poor throw High temperature Reduce temperature Low chloride Raise chloride Poor anoding Correct anoding Excessive agitation Reduce agitation Poor preparation Check preparation Electrical problems Check connections Zinc metal growth High temperature Lower temperature Anodes poorly conditioned Pull anodes and retreat. If excessive, pull anodes when not in use. Non-uniform alloy Low Niclipse Starter Add 1% increments of Niclipse Starter Non-uniform agitation Check and clean air sparge. Redesign sparge if needed Inconsistent alloy Poor temperature control Check cooling system and ensure sufficient solution agitation

8 Pavco NiClipse Page 8 Analysis Procedures Zinc Analysis: Reagents 1. Methylthymol Blue indicator M EDTA solution 3. ph 10 Buffer solution To make this solution: a. Add mls of ammonium hydroxide to a 1 liter volumetric flask b. Add 70 g of ammonium chloride to the flask c. Bring to volume with de-ionized water and mix well 4. 1M KCN solution To make this solution: a. Add 65 g of potassium cyanide to a 1 liter volumetric flask b. Bring to volume with de-ionized water and mix well 5. 8% formaldehyde Procedure 1. Pipette a 2 ml sample of the bath into a 250 ml Erlenmeyer flask 2. Add 100 mls of de - ionized water 3. Add 10 mls of KCN solution, 10 mls of buffer solution, and 15 mls of 8% formaldehyde 4. Add ~ 0.1g of methylthymol blue and titrate with 0.1M EDTA solution to a light blue endpoint Calculations Zn g/l = [(ml of EDTA)(M of EDTA)(65.4 g/mol)]/(mls of sample) Zn oz/gal= (Zn g/l)(0.13) Boric acid: Equipment 150 ml beaker 5 ml pipette Reagents De-ionized water Dilute sulfuric acid 1N sodium hydroxide Mannitol Procedure Note: Make sure all the boric acid is in solution before proceeding with this analysis. Heat the bath to put all the boric acid in solution. 1. Pipette a 5 ml bath sample into a 150ml beaker and add 20ml of D.I. water. Add a tefloncoated magnetic stir bar and mix solution on stir plate throughout procedure. 2. Using a ph meter, adjust ph of solution to , using either sodium hydroxide or sulfuric acid. Record final ph. 3. Add 2g mannitol. (Excess mannitol is necessary at all times.) 4. Slowly titrate the solution with 1N sodium hydroxide until original ph is reached. Calculation oz/gal H 3 BO 3 = [ _ml (NaOH) x N (NaOH) x g/mol H 3 BO 3 ] [ ml sample x 7.5 (g/l)/(oz/gal)]

9 Pavco NiClipse Page 9 Analysis Procedures Cont d Nickel Analysis: Reagents 1. Concentrated ammonium hydroxide M EDTA solution 3. Murexide indicator : 1 part murexide, 200 parts sodium chloride Procedure 1. Pipette a 1 ml sample of the bath into a 250 ml Erlenmeyer flask 2. Add ~ 100 mls of de-ionized water 3. Add ~10 mls of concentrated ammonium hydroxide 4. Add ~ 0.5 g of Murexide indicator and mix the solution thoroughly 5. Titrate with 0.1M EDTA to a violet - blue end point 6. Record the volume of EDTA solution used Calculations Ni g/l = [(ml of EDTA)(M of EDTA)/ (mls of sample) - (Zn g/l)/ (65.4 g/mol)] (58.7) Ni oz/gal= (Ni g/l)(0.13) Total Chloride Analysis: Equipment ml Erlenmeyer flask 2. 1 ml pipette Reagents 1. De-Ionized water 2. Dextrin/Calcium carbonate buffer (mixed 1to1 by weight) 3. Dichlorofluorescein indicator N silver nitrate solution Procedure 1. Pipette a 1 ml sample of the bath into a 250 ml Erlenmeyer flask. 2. Add approx. 50 mls of de-ionized water 3. Add one scoop - approx. 2 grams of buffer 4. Add 0.5 ml of dichlorofluorescein indicator 5. Swirl the flask to mix thoroughly 6. Titrate the solution with N silver nitrate until the color changes from yellow to pink 7. Record the titration Calculation Total chlorides in oz/gal = (mls silver nitrate) x (0.724) Zn metal X = oz/gal chloride in zinc chloride = A Ni metal X = oz/gal chloride in nickel chloride = B Ammonium chloride in oz/gal = [total chloride - (A+B)] X 1.51 Ammonium Chloride Analysis: A procedure is available utilizing an ammonium ion selective electrode. Consult your Pavco representative.

10 Pavco NiClipse Page 10 Waste Treatment Dispose of the concentrates or solutions thereof according to local waste treatment regulations. Safety Handling Pavco mandates that the following safety equipment be used when handling chemicals in an electroplating environment: safety glasses, face shield, plastic or rubber apron, rubber gloves and safety shoes. Chemicals should only be handled by trained and experienced personnel. Storage Store Pavco products in a clean, well ventilated room which temperature remains above 45º F (7º C). Pavco products should remain in their original container with the lid or cap tightened. Drum pumps or pails must be clean prior to dispensing Pavco products to prevent contamination. If NiClipse Starter or NiClipse Brightener freeze during shipment or storage, warm the product and mix it well before use. Emergency Procedures Refer to the MSDS for detailed emergency procedures Eye Contact Seek immediate medical attention. Flush the eyes with water for 15 m minutes. Skin Contact Remove all contaminated clothing. Wash the skin with soap and water. Seek medical attention Inhalation Remove the person to an area with fresh air. Seek medical attention if necessary Ingestion Seek immediate medical attention Spill Dike the area to contain the spill. Refer to the MSDS for clean-up. Notify the proper authorities if required. *Note: Refer to the MSDS for detailed emergency procedures Product Description & Shipping NiClipse Starter (ZN 5000) is a transparent dark brown liquid with a specific gravity between 1 and 1.1 and a ph greater than 4 NiClipse Brightener (ZN 1010) is a transparent dark blue liquid with a specific gravity between 1 and 1.1 and a ph of less than 6 Revision Date: 9/3/2010 Revision Number 7 WARRANTY AND DISCLAIMER Technical information and recommendations contained herein are believed to be reliable, however, the accuracy or completeness thereof is not guaranteed. No statement or recommendation shall constitute a representation unless set forth in an agreement in writing by the seller and manufacturer. NO WARRANTY OR MERCHANTABILITY OR WARRANTY OF FITNESS FOR A PARTICULAR PURPOSE IS MADE. The following warranty is made in lieu of any other warranties, express, implied, or statutory. Products are warranted to be free from defects on material and workmanship at the time sold. The sole obligation of the seller and manufacturer under this warranty shall be to replace any product defective at the time sold. Under no circumstances shall the manufacturer or seller be liable for any loss, damage, expense, direct or consequential, arising out of the use of or inability to use the product. Materials shall not be returned to the seller or manufacturer without express written permission. No information or suggestions given by us shall be deemed to be a recommendation to use any product in conflict with any existing patent rights.