Palnilux®
Palladium-Nickel Plating Process / Version: 04
Doc.-No.:3106

Contents

1.Process Information

2.Equipment and Working Parameters

3.Make-Up

4.Replenishment

5.Maintenance

6.SAP No. for Make - Up and Maintenance Products

7.General Safety Precautions

8.Recommendations for Wastewater Treatment

9.Analytical Instructions

Determination of Palladium by Titration

Determination of Nickel by AA

Determination of Pd Replenisher Salt A by Titration

  1. Process Information

Palnilux is an ammonium-based palladium-nickel process designed to provide fully bright, ductile, 80/20 w/w Pd/ Ni deposits with highest corrosion resistance properties for all decorative and technical applications.

  1. Equipment and Working Parameters

Tanks / PVC, polyethylene, polypropylene, PVC / polyester reinforced material.
Cathode / electrolyte agitation / Required, 1 - 2 m/min, freely adjustable
Fume extraction / Required
Filtration / Required
Solution temperature / 20 - 35 °C; preferably 30 °C
Anodes / Graphite anodes. Titanium anode/cathode bars are also strongly recommend. Contact to the anode bar should be made well above the solution surface, using plastic screws.
Solution density / 1.06 g/cm3 at 20 °C
pH (by pH meter) / Optimum: 8.7 (range 8.0 - 9.0)
Typical voltage across the tank / 2 - 4 V
Current density / Optimum: 1.0 A/dm² (range 0.5 - 1.5 A/dm²)
Metal concentration / At optimum: 6.0 g/l Pd, 9.0 g/l Ni
Note: for special applications, both metals may be increased to 10 g/l.
Rate of deposition / Under optimum conditions: 1 µm in 4.5 min at a current density of 1 A/dm², equivalent to 26 - 28 mg/Amin for an 80/20 Pd/ Ni alloy.
  1. Make-Up

Make-Up of 100 l / Liter / kg
Deionised or distilled water / 23.9
PalniluxMake-up Solution / 75.0 / 80.0
Palnilux Replenishment SolutionPart 1 / 1.0 / 1.1
Palnilux Wetting Agent / 0.1 / 0.1

Procedure:

  • Add the water to the pre-cleaned and rinsed tank.
  • In the following order, with good mixing between additions add the Palnilux Make-up Solution,Palnilux Replenishment SolutionPart 1 and Palnilux Wetting Agent Palnilux.
  • Dilute to final volume if necessary, mix well and measure and adjust pH to optimum (8.5) using either dilute ammonia solution (25 %v/v) or hydrochloric acid (50 %v/v).
  • Switch on filtration and heating and allow the solution to attain 30 °C.
  • The electrolyte is ready to use.

Note: If new anode and anode bags are to be used, it is preferable to add 1 ml/l Palnilux Brightener.

Care must be taken to ensure anodes and bags are well cleaned and rinsed prior to use.

  1. Replenishment

For routine replenishment of the Palnilux electrolyte, the following products should be added, according to deposit weight or Ampere minute throughput:

Based on deposit weight: For every 100 g of 80/ 20 w/w Pd/ Ni alloy deposited, please add the following:

Palnilux Replenishment Solution Part 1 / 0.780 l (0.880 kg)
Palnilux Replenishment Solution Part 2 / 0.250 l (0.311 kg)
Palnilux Brightener / 0.250 l (0.298 kg)

Based onAmpere minute throughput: For every 100Amins throughput, please add the following:

Palnilux Replenishment Solution Part 1 / 21.1 ml (23.4 g)
Palnilux Replenishment Solution Part 2 / 7.0 ml (8.1 g)
Palnilux Brightener / 7.0 ml (8.3 g)

pH control: It is strongly recommended to regularly monitor and control the electrolyte pH using a suitable, buffered pH meter. Adjustments to the electrolyte may be carried out using either ammonia solution (25 %v/v), or by adding gaseous ammonia under the solution surface.

Note: In situations where pores or spots are observed on the deposit surface an addition of 1 ml/l of Palnilux Wetting Agent to the electrolyte may prove beneficial.

  1. Maintenance

For corrective action, based on analysis:

To raise the palladium by 1 g/l add 10ml (11g) of Palnilux Replenishment Solution Part 1 per litre of electrolyte volume.

To raise the nickel by 1 g/l add 12.2ml (15g) of Palnilux Replenishment Solution Part 2 per litre of electrolyte volume.

The density of the electrolyte will be adjusted with Pd Replenisher Salt A.

To increase the density of 0.005 g/cm³ are 25 g/l Pd Replenisher Salt A needed.

Afterwards should the pH checked and adjusted.

Losses by evaporation are adjusted with DI water.

  1. SAP No. for Make - Up and Maintenance Products

PRODUCT / SAP No.
PALNILUX MAKE-UP SOLUTION / 729418
PALNILUX REPLENISHMENT SOLUTION PART 1 / 729376
PALNILUX REPLENISHMENT SOLUTION PART 2 / 729392
PALNILUX WETTING AGENT / 729350
PALNILUX BRIGHTENER / 729434
PD REPLENISHER SALT A / 1680023
  1. General Safety Precautions

Avoid direct contact with this material. Do not inhale associated mist or vapors. Wash contaminated clothing before reuse. Refer to Material Safety Data Sheet (MSDS) for specific precautions before handling this material and for first aid recommendations. As applicable, keep exposure below the limits recommended by the appropriate regional regulatory agencies.

For further information on product safety refer to the corresponding MSDS. The MSDS is enclosed at the first delivery of a product. Otherwise a MSDS for a product is available on request from the appropriate regional Atotech office. /
  1. Recommendations for Wastewater Treatment

This productcontains complexing agents and therefore cannot be sent to the general circulation of rinse water. The wastewater generated by this product must therefore be treated separately.

Rinse water

Rinse water can be sent into the treatment plant for an organosulfide treatment (min. dilution 1 : 15), or it can be placed over a selective ion exchanger (e.g. Lewatit TP214 H+ Messrs. Lanxess) with a concentration of maximum 130 mg Pd/l followed by a Ni precipitation as described below.

The ion exchanger resin, loaded with Pd, can then be sent to a special separation company for recovery of the palladium.

If no recovery system exists on the drag-out rinse after using Palniluxthe rinse water has to be treated using e.g. Sediganth C at a pH of 6 – 8 to precipitate heavy metals.

Indication of complete precipitation can be obtained potentiometrically. The amount of Sediganth C (approx. 800 ml per gram atom heavy metal) has to be determined by a prior test (as described below.) After a reaction time of about 30 min., providing thorough agitation a small amount of flocculant will be added and then the solution will be filtered via a special filter press. Then adjust the pH to 6.5 – 9. The filtrate must be sent to the final neutralization process, bypassing the waste water treatment plant.

To determine the required amount of precipitation agent

  • 0.1 ml precipitation agent Sediganth C is added to
  • 100 ml of rinse water sample at a pH of 6 – 8 while continuously stirred.
  • After a reaction time (while the solution is stirred) of 5 min., the solution to be treated has to be clear and colorless.
  • When another 0.1 ml precipitation agent Sediganth C is added no further clouding should appear.

The resulting ml of precipitation agent Sediganth C for 100 ml rinse water sample gives the amount of precipitation agent in liter for 100 l rinse water to be treated.

Bath concentrates

Concentrates can be sent to a special company for recovery or be treated by a suitable method of electrolysis or reduction. Otherwise, bath concentrates must be diluted in a ratio of at least 1 : 3 before being processed in the wastewater treatment plant.. This treatment is carried out as described above.

IMPORTANT NOTE: Be sure to observe all local regulations concerning the limit values of pollutants including the general regulations on dangerous materials!

  1. Analytical Instructions

Determination of Palladium by Titration / Version: 01
Doc.-No.: EXT-0609-TIT-01

Principle:Redox titration

Reagents required*:

  • Ammonia solution 5 N (375 ml/l ammonia conc., density = 0.9)
  • Potassium silver cyanide 54 %
  • Potassium iodide solution 1 M (166 g/l KJ)
  • Silver nitrate volumetric solution 0.1 M
  • Potassium cyanide volumetric solution 0.1 M (6.512 g/l KCN) (The factor of this solution must be adjusted prior to use).

Be sure to observe all local regulations concerning the permitted limits for pollutants, including the general regulations for hazardous materials! /

Determination of the amount of 0.1 M potassium cyanide volumetric solution:

  • 20.0 ml** of the 0.1 M potassium cyanide solution will be diluted with 70 ml of DI water and after addition of
  • 5.0 ml of 1 M potassium iodide solution and
  • 5.0 ml of 5 M ammonia solution the solution will be titrated with
  • 0.1 M silver nitrate volumetric solution until the precipitate formed on entry of the drops into the titrated solution does not dissolve anymore after swirling the flask a few times and causes a permanent turbidity of the solution.

The amount of ml of 0.1 M silver nitrate volumetric solution used divided by 10, gives the amount of 0.1 M potassium cyanide volumetric solution.

Procedure:

  • 2.0 ml of the electrolyte will be placed into a flask and diluted with 100 ml of DI water. After addition of
  • 1 g potassium silver cyanide the solution will be shaken or stirred for 10 min. Then add
  • 5.0 ml of 1 M potassium iodide solution and
  • 50.0 ml of 0.1 M potassium cyanide volumetric solution.
  • Now titrate with 0.1 M silver nitrate volumetric solution until the precipitate formed on entry of the drops into the titrated solution does not dissolve anymore after swirling the flask a few times and causes a permanent turbidity of the solution.

The number of ml of 0.1 M silver nitrate volumetric solution used must be multiplied by 2 and subtracted from the 50.0 ml of 0.1 M potassium cyanide volumetric solution. During this procedure both factors of the volumetric solutions have to be taken into consideration***.
The resulting consumption of 0.1 M potassium cyanide volumetric solution – multiplied by 1.33 – gives the total metal content, calculated as palladium. From this value the nickel content multiplied by 1.81 must be subtracted.

Example:

During titration of 2.0 ml bath with a nickel content of 8.5 g/l, 16.8 ml of 0.1 M silver nitrate volumetric solution was used.

Calculation:

50.0 ml 0.1 M potassium cyanide volumetric solution

- (16.8 x 2) = 33.6 ml 0.1 M silver nitrate volumetric solution

= 16.4 ml 0.1 M potassium cyanide volumetric solution

16.4 x 1.33 = 21.8 g/l total metal content calculated as Pd

21.8 – (8.5 x 1.81) = 6.4 g/l palladium

*Unless otherwise stated, these are always analytical grade substances.

**Volumes given exact to a decimal point must be measured with a volumetric pipette.

***For the purpose of calculation, the factor of the standard solution is assumed to be 1.000 and is therefore not taken into account in the examples.

Determination of Nickel by AA / Version: 01
Doc.-No.: EXT-0188-AA-01

Reagents required*:

  • Nitric acid conc. (65 % w/w, d = 1.39 g/cm³)
  • 30% H2O2
  • Nickel standard solution: 1000 mg/L

Be sure to observe all local regulations concerning the limiting values of pollutants including the general regulations on hazardous materials! /

Standards:

2 mg/l Ni:1.0 ml of nickel standard solution and 5 ml of 5 M nitric acid are to be pipetted into a 500 ml flask then filled up to the mark with DI water and mixed thoroughly.

4 mg/l Ni:1.0 ml of nickel standard solution and 5 ml of 5 M nitric acid are to be pipetted in to a 250 ml flask then filled up to the mark with DI water and mixed thoroughly.

Operating conditions:

Perkin Elmer 2100/4100

Lamp current / 30 mA / Gas mixture / air/acetylene
Calibration / Peak height / Fuel flow / 1.8 l/min
Integration time / 1.0 s / Oxidant flow / 7.5 l/min
Replicates / 3 / Wavelength / 232.0 nm
Background correction / D2-lamp / Slit / 0.2 nm

Varian AA 280FS

Lamp current / 7 mA / Gas mixture / air/acetylene
Calibration / New-Rational / Fuel flow / 2.0 l/min
Integration time / 5.0 s / Oxidant flow / 13.5 l/min
Replicates / 3 / Wavelength / 232.0 nm
Background correction / ON / Slit / 0.2 nm
Delay / 30 sec / Measurement Time / 10 sec
Please consult the instruction manual provided by the manufacturer of the AAS system, for information on the individual parameters such as the flame, the slit width, the integration period, etc. /

Preparation of the sample:

  • 1.0 ml** of the sample is placed into a 100 ml volumetric flask.
  • Add 10 ml of nitric acid conc, 1 ml 30% H2O2 and shortly boil the solution. AVOID ANY BOILING RETARDATION!
  • Then fill the volumetric flask up to the mark with DI water.
  • The digested solution is diluted 1:20 with DI water
  • The well-mixed solution is now measured at a wavelength of 232.0 nm

Determination with the F-AAS:

For calibration 2.0 mg/l S1 and 4.0 mg/l S2 Ni are used as standard. Nullification is carried out with DI water prior to measurement.

For the operational range please refer to the Datasheet and chose dilution accordingly!
If the sample absorbance is out of the calibrated range another dilution has to be chosen! /

Calculation:

The determination of the content in the diluted sample is carried out automatically through the PC-software via the external calibration, which was carried out before. The determined palladium concentration CNi [mg/l] for the diluted sample must be multiplied with the dilution factor. The determined palladium content must be within the calibration curve, otherwise choose another dilution.

After 10 measurements a control sample has to be measured! If the deviation is >5% the system has to be re-calibrated! /

CPd [mg/l]  dilution factor = mg/L of Ni in the sample.

Example:

Dilution: 1.0 ml sample to 100 ml and subsequent dilution 1:20 (dilution factor = 2000); Nickel concentration measured by AAS: 2.3 mg/l.

Calculation:

2.3 mg/l  2000 = 4.6 g/l of Nickel

*Unless otherwise stated, these are always analytical grade substances.

**Volumes given exact to a decimal point must be measured with a volumetric pipette.

Determination of Pd Replenisher Salt A by Titration / Version: 01
Doc.-No.: EXT-0681-TIT-01

Principle:Potentiometric precipitation titration

Reagents required*:

  • Silver nitrate volumetric solution 0.1 M
  • Phosphoric acid 2 M (135 ml/l H3PO4 85 %)
  • DI-water

Be sure to observe all local regulations concerning the permitted limits for pollutants, including the general regulations for hazardous materials! /

Equipment

  • Titro processor (e.g. Metrohm)
  • Standard laboratory equipment

Parameter Titro processor

Combined metal electrode (Ag):Metrohm, No.: 6.0418.100 (OC)

Delay:10 s

Drift:100 mV/min

Measurement point density:4

Dosimat rate:max.

Max. volume:20 ml

Procedure

  • 0.5 ml** of the sample is submitted into a titration beaker.
  • 2 ml of 2 M phosphoric acid is added. (The precipitation formed at the beginning must solve again.) Then
  • approx. 70 ml of DI-water is added to this solution.
  • Subsequently titration is carried out until final point at the titro processor with a combined metal electrode (Ag) with AgCl-coating and 0.1 M silver nitrate-volumetric solution.

Calculation

Content of Pd Replenisher salt A (g/l) = consumption*** [ml AgNO3] x 10.7 – content of Palladium (g/l)

Example:

Palladium content= 10.0 g/l

Consumption= 4.8 ml of 0.1 M silver nitrate volumetric solution

4.8 ml x 10.7 – 10 g/l = 41.4 g/l of Pd Replenisher salt A

*Unless otherwise stated, these are always analytical grade substances.

**Volumes given exact to a decimal point must be measured with a volumetric pipette.

***For the purpose of calculation, the factor of the standard solution is assumed to be 1.000 and is therefore not taken into account in the examples.

This sheet shall serve for your information. The content of the sheet is based on our best knowledge. We do not undertake any duty to advise. The contents of the sheet shall not be considered as an agreement on condition and quality of the goods delivered.
The decision to use our products for its production purposes is the responsibility of our customer. We can accept liability only for the quality of our products at delivery. If difficulties arise in the application of our products, we propose that you contact our technical service department. / Atotech Deutschland GmbH
P.O. Box: 21 07 80
10507 Berlin, Germany
Erasmusstraße 20
10553 Berlin, Germany
phone +49 (0) 30 349 85 0
fax +49 (0) 30 349 85 777
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Released on: / Released by:
09.05.2011 / BTT FEC