Manual 8XX Titrando EN

NICKEL BRIGHT Version: 08
Doc.-No.: 2106
DATA SHEET
SAP-No.: 1681115
Supreme Plus IMDS-No.: 749088

Bright Nickel Process
CONTENTS
1. Process Information................................................................................................................................. 2
2. Equipment ............................................................................................................................................... 2
3. Make-Up .................................................................................................................................................. 4
4. Working Parameters ................................................................................................................................ 5
5. Maintenance ............................................................................................................................................ 5
General Data of Plating Solution ........................................................................................................ 5
Data of Additives of Plating Solution .................................................................................................. 6
Function and dosage of the Additives ................................................................................................ 6
6. Cleaning of the Plating Solution .............................................................................................................. 8
7. SAP No. for Make-Up and Maintenance Products .................................................................................. 8
8. Recommendations for Wastewater Treatment ........................................................................................ 9
9. Analytical Instructions ............................................................................................................................10
Determination of the Boric Acid Content by Titration .......................................................................10
Titrimetric Determination of Boric Acid with Glycerin Citrate Solution ("Mixed Solution")................12
Complexometric Determination of Nickel by Titration ......................................................................14
Determination of Chloride by Titration ..............................................................................................17
Determination of Copper by AA .......................................................................................................19
Determination of Nickel Carrier A-5 (2x) by UV/VIS Spectrometry ..................................................22
Determination of Nickel Additive SA-1 by Titration ..........................................................................24
Determination of Nickel Additive SA-1 by IC ....................................................................................26
Supreme Plus Brightener by HPLC-UV ...........................................................................................34
10. Document History ..................................................................................................................................38
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Bright Nickel Process Doc.-No.: 2106
1. Process Information
Supreme Plus is a bright nickel process which has been developed to produce excellent deposits over a
wide variety of suitably prepared substrates, such as steel, brass, copper and plastics. It can be used for
duplex or triplex nickel plating systems in the automotive industry.
Product Advantages
 Unsurpassed fast rates of brightening and leveling
 Ideal for high quality thin deposits on unpolished steel and tubular steel
 Used with air or mechanical agitation
 Process can be operated at lower metal concentration and lower temperatures without sacrificing
performance.
2. Equipment
Tanks Mild steel with hard rubber lining, PVC or PVC-Polyester

reinforced material.
Anodes Rolled pure nickel anodes, electrolytic nickel anodes, or

S-nickel rounds (INCO) in titanium anode baskets.
Anode bags required.
Anode bags Required; use of twin bags is recommended. Made of Dynel

or Polypropylene leached in a 10 % sulfuric acid solution
and then flushed with hot running water prior to use.
Heating Heaters: porcelain, hard glass, PTFE.

Heat exchanger: titanium, graphite.
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Mechanical agitation / Air agitation Required. Mechanical and / or air agitation.
stroke length double stroke/min

Horizontal 100 mm 20 – 25 (4 – 5 m/min)
Vertical 60 mm 25 – 30 (3 – 4 m/min)
The required amount of air is: 12 – 20 m3/h per meter of

cathode rod. Blowers are to be used in order to avoid
contamination of the electrolyte by oil or dirt in compressed
air. Additionally, use of cathode rod agitation is
advantageous in order to reach all parts of the rack by the air
stream.
Filtration Continuous filtration is recommended. The entire bath

volume should be filtered at least 4 – 6 times per hour with
5 µm filters. As a guide, it is suggested that the filter be
packed with 0.5 g of activated carbon per liter of solution per
40 production hours. It is further suggested that one-fifth of
this amount of carbon be added along with some filter aid per
eight production hours. When adding carbon to the filter, it
should be mixed with an equal volume of filter aid in order to
maintain a maximum rate of solution flow.
Filter aid Activated carbon; filter cellulose or diatomic earth
Exhaust Required.
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3. Make-Up
Make-Up of 100 l Liter kg

Nickel Sulfate (NiSO4  6 H2O) --- 25.00
Nickel Chloride (NiCl2  6 H2O) --- 6.00
Boric Acid --- 4.00
Nickel Carrier A-5 (2x) 2.0 2.2
Nickel Additive SA-1 0.30 0.35
Supreme Plus Brightener 0.04 0.04
Supreme Plus Leveller (if required) 0.20 0.20
Wetting Agent NP-A 0.20 0.20
(for air agitation)
Wetting Agent Ni M 0.15 0.15
(for mechanical agitation)
The solution should be made up in a storage tank which has been thoroughly cleaned. The plating tank and
all associated plumbing, including pumps, spargers, heaters, filters, racks, etc., should be cleaned. All dirt,
grease etc. should be wiped off and the tank sides and bottom scrubbed with a wetting agent and hot water
and thoroughly rinsed. The lining of the tank, filters, etc. should be leached with a 0.2 – 0.5 % (v/v) of sulfuric
acid heated to 60 °C, containing 1 l of Wetting Agent NP-A or Wetting Agent Ni M per 1000 liter of acid.
Leaching should continue overnight.
 Fill the off-line tank about two thirds full with distilled or deionized water, heat to 70 – 100 °C.
 Dissolve the boric acid, nickel sulfate and nickel chloride in the hot water while stirring well.
 Raise the pH to approx. 5.2 (measured electrometrically) by adding nickel carbonate or
4 % (42 g/l) sodium hydroxide solution, with vigorous stirring.
 Add 4 g/l of Atotech activated powdered carbon and stir for 30 – 60 minutes. Turn off agitation and
allow carbon to settle to bottom of the tank for 3 – 4 hours or preferably overnight.
 Pump the solution above the carbon through a filter into the clean plating tank. (Take care that the
temperature of the solution during filtration stays above 50 °C to prevent precipitation of boric acid).
 Clean and repack the filter with filter aid material then add a mixture of filter aid and activated carbon
(0.15 g per liter of solution).
 Fill the tank to nearly the final volume with DI-water. Check and, if necessary, adjust the operating
temperature.
 Adjust the pH to 4.0 with a 10 % (v/v) solution of sulfuric acid.
 Electrolyze the solution with dummy cathodes at 0.54 Ah/l for about 12 hours or until recesses in the
corrugated cathodes are light in colour. Use of agitation and filtration during this period is beneficial.
 Readjust the pH, if necessary.
 Add the required amounts of
Nickel Carrier A-5 (2x),
Nickel Additive SA-1,
Supreme Plus Brightener,
Supreme Plus Leveller,
Wetting Agent NP-A or Wetting Agent Ni M and circulate for 20 minutes to assure thorough mixing.
 The electrolyte is now ready for use.
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4. Working Parameters
Temperature 55 °C (50 – 60 °C)
pH Electrometrically: 4.4 (4.0 – 4.6)

Lyphan(R)-Paper (Range 3.9 – 6.0) : 4.6 (4.2 – 4.8)
Density 1.19 g/cm3 at 20 °C
2 2
Current Density cathodic: 3.0 A/dm (1.0 – 6.0 A/dm )
2
anodic: less than 3.0 A/dm
Ratio Anode : Cathode 1 : 1 to 2 :1
Current efficiency 94 – 96 %
Deposition rate Approx. 1 µm Ni in 1.7 min at 3 A/dm²
Bath Voltage 4 – 12 V
5. Maintenance
General Data of Plating Solution
Nominal values On make-up During operation

Nickel 70 g/l 55 – 80 g/l
Chloride ions 18 g/l 10 – 25 g/l
Boric acid 40 g/l 35 – 50 g/l
Additions of 10 g/l each of the following salts will change the inorganic bath values as follows:
Salt Nickel Chloride ions Boric Acid

10 g/l Nickel Sulfate (NiSO4  6 H2O) 2.2 g/l --- ---
10 g/l Nickel Chloride (NiCl2  6 H2O) 2.5 g/l 3.0 g/l ---
10 g/l Boric acid (H3BO3) --- --- 10.0 g/l
The pH can be adjusted with sulfuric acid (diluted to 10 % (v/v)) or – if there is a lack of chloride ions – with
hydrochloric acid (diluted at a ratio of 1 : 1).
Evaporation losses must be replenished by adding distilled or deionized water.
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Data of Additives of Plating Solution
Nominal values On make-up During operation

Nickel Additive SA-1 3.0 ml/l 2.5 – 5.0 ml/l
Nickel Carrier A-5 (2x) 20 ml/l 15 – 25 ml/l
Supreme Plus Brightener 0.4 ml/l 0.3 – 4.0 ml/l
Supreme Plus Leveller (if required) 2.0 ml/l 0 – 3.0 ml/l
Wetting Agent NP-A (for air agitation) 2.0 ml/l 1.0 – 5.0 ml/l
Wetting Agent Ni M (for mechanical agitation) 1.5 ml/l 1.0 – 2.0 ml/l
Function and dosage of the Additives
Consumption for 10,000 Ampere hours Liter kg

Nickel Additive SA-1 0.8 (0.7 – 1.0) 0.9 (0.8 – 1.2)
Nickel Carrier A-5 (2x) 0.5 (0 – 1.5) 0.8 (0 – 1.6)
Supreme Plus Brightener 0.8 – 1.5* (0.6 – 2.0*) 0.8 – 1.6* (0.6 – 2.1*)
Supreme Plus Leveller (if required**) 0.6 (0 – 0.8) 0.6 (0 – 0.8)
Wetting Agent NP-A (for air agitation) 0.2 (0.2 – 0.3) 0.2 (0.2 – 0.3)
Wetting Agent Ni M (for mechanical agitation) 0.2 (0.15 – 0.3) 0.2 (0.15 – 0.3)
* Higher concentration of Supreme Plus Brightener is required if no Supreme Plus Leveller is used.
** For higher levelling Supreme Plus Leveller can be used
Supreme Plus Brightener

With the Supreme Plus Brightener bright and leveled nickel layers can be deposited over a wide current
density range.
Lack of Supreme Plus Brightener results in reduced brightness and leveling.

Excess of Supreme Plus Brightener could cause skip plating in LCD areas and the nickel deposit could
become brittle.
In most installations, Supreme Plus Brightener is sufficient to maintain the required brightness, leveling and
metal throw. However, in some installations, depending on current density, drag-out losses etc., small
supplemental additions of the other additives e.g. Supreme Plus Leveller may be required to balance the
bath or optimum performance.
For the maintenance of Supreme Plus Brightener an automatic dosing based on Amperehours is
recommended.
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Supreme Plus Leveller

Supreme Plus Leveller can be added on make-up of a new bath or on conversion of any existing bath.
Supreme Plus Leveller can be used in addition to Supreme Plus Brightener in order to increase the
leveling of the bath when electroplating badly polished or unpolished work and in situations where the
maximum rate of leveling is required. Supreme Plus Leveller must be used in conjunction with Supreme
Plus Brightener – it is NOT a replacement for Supreme Plus Brightener.
A typical addition of Supreme Plus Leveller is 0.25 – 2.0 ml/l depending on leveling required. Generally
Supreme Plus Leveller is added as and when required although it can be added on a continuous basis to
tailor make the process to meet specific needs.
Excess of Supreme Plus Leveller could cause skip plating in LCD areas.
Nickel Carrier A-5 (2x)

Nickel Carrier A-5 (2x) is important for the ductility and reduces the inner stress of the nickel layer.
Nickel Carrier A-5 (2x) is needed for maximum brightness and ductility. Nickel Carrier A-5 (2x) is depleted
very slowly by electrolysis and is removed only slightly by continuous filtration through a carbon pack.
Nickel Additive SA-1

Nickel Additive SA-1 is added to provide maximum rates of brightness and leveling. It also diminishes the
tendency of liberated hydrogen to form gas pits. A too low Nickel Additive SA-1 concentration may result in
reduced luster and leveling of plated parts.
Nickel Additive SA-1 is lost mainly by electrolysis. Average amounts of activated carbon (2.4 – 6.0 g/l) will
not substantially reduce the concentration of Nickel Additive SA-1.
Wetting Agents NP-A and Ni M

Wetting Agent NP-A is a wetting agent for air agitated solutions. It should be maintained at a level to give a
surface tension of 40 – 45 dynes/cm.
Wetting Agent Ni M should only be used when the solution is operated with mechanical agitation.
Both wetting agents are removed by batch treatments with activated carbon and to some extent when
operating with a carbon packed filter.
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6. Cleaning of the Plating Solution
In order to reduce the content of metallic impurities, a continuous or periodic electro cleaning with
0.05 – 0.3 A/dm2 (the area of the cathode should be as large as possible) is recommended. Agitation
improves the cleaning effect.
In order to reduce the content of organic impurities (break down products and drag in) batch treatment with
activated carbon is recommended at certain intervals.
To increase the intervals between batch carbon treatments, continuous treatment with granulated activated
carbon (approx. 4 g per 100 l of electrolyte) as media on a filter or in activated carbon cartridges is
recommended. The consumption of wetting agent is slightly increased.
7. SAP No. for Make-Up and Maintenance Products
PRODUCT SAP No.

NICKEL CARRIER A-5 (2X) 1455013
NICKEL ADDITIVE SA-1 1455369
SUPREME PLUS BRIGHTENER 1667138
SUPREME PLUS LEVELLER 1667140
WETTING AGENT NI-M 1421676
WETTING AGENT NP-A 1667582
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8. Recommendations for Wastewater Treatment
Rinse water
Nickel can be precipitated by adjusting the rinse water pH to between 9.5 – 10. The filtered solution can
subsequently be sent to final neutralization.
Concentrates
The following options are possible when concentrated Nickel solutions must be treated.
When nickel is to be recycled, it is generally necessary to treat these nickel solutions separately from other
solutions.
The following recycling methods are typical, although others can be recommended:
 Electrowinning of nickel using an appropriated electrolytic cell.
 Treatment of nickel concentrate, or of a precipitated nickel sludge, by a specialized recycling company.
If these methods cannot be used, the nickel concentrate together with the complexing agent free
wastewaters can be treated by adjusting the pH to between 9.5 – 10. For better precipitation the
concentrates must be diluted in a ratio of 1 : 10 before sending to the wastewater treatment plant.
For better flocculation we recommend to add a flocculant (e.g. a polyacrylamide/anionic with a mol mass of
4 – 6 million). The solution is then stirred and the precipitation is allowed to settle for better filtration.
Concentrate regeneration
The available bath regeneration system using membrane anodes and adsorber type Nikotect can be
recommended. Please see the respective special data sheet for details.
Membrane anodes:
This system avoids an increasing of the Ni-content in the bath due to different current efficiencies at the
electrodes.
Adsorber:
The adsorber system using a special resin eliminates organic contaminations from the Ni-electrolyte.
This recommendation for the treatment of wastewater is in accordance with the Regulation
on requirements for the discharge of wastewater into water (Allgemeine
Abwasserverordnung, AbwV) and was issued on the basis of the limits provided in Annex
40 of the AbwV "Metal Handling and Metal Processing".
Be sure to observe all local regulations concerning the limiting values of pollutants
including the general regulations on dangerous materials!
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9. Analytical Instructions
Version: 04
Determination of the Boric Acid Content by Titration
Doc.-No.: EXT-0352-TIT-04
Principle:
Acid-Base Titration
Reagents required*:
 Sodium Hydroxide volumetric solution 0.1 M

 Indicator solution (0.04 % solution of bromocresol purple in alcohol)
 Karion F liquid 1 l = 1.29 kg (manufacturer: E. Merck AG, Darmstadt) or mannitol (solid)
Be sure to observe all local regulations concerning the permitted limits for
pollutants, including the general regulations for hazardous materials!
Procedure:
 2.0 ml** sample solution are pipetted into a 300 ml Erlenmeyer flask and mixed with
 10 ml of DI water and
 1 ml of indicator solution.
The resulting solution is then neutralized drop by drop with
 0.1 M sodium hydroxide volumetric solution until the solution turns purple. (Neutralization is not
necessary if the solution turns purple after the addition of the indicator solution.)
 50 ml of Karion F liquid or equivalent 5 g of mannitol are then added to it and mixed up well, which
turns the solution golden yellow. Titration is now performed with
 0.1 N sodium hydroxide volumetric solution until the color changes to purple.
Alternative: The Titration can be conducted as a turning point titration using a

titroprocessor equipped with a pH electrode to determine the endpoint.
Multiplying the number of ml 0.1 N sodium hydroxide volumetric solution*** used by 3.092 produces the
content of boric acid in the solution in g/l.
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Example:
For the titration of 2.0 ml of the sample solution 11.0 ml of 0.1 M sodium hydroxide volumetric solution was
used.
Calculation:
11.0  3.092 = 34.0 g/l boric acid
Quality assurance: For maintenance, calibration of measuring devices and the use of
standards and reference materials please refer to the corresponding guidelines.
* 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.
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Version: 02
Titrimetric Determination of Boric Acid
with Glycerin Citrate Solution ("Mixed Solution") Doc.-No.: EXT-0478-TIT-02
*
Reagents required :
 "Mixed solution": 60 g of sodium citrate are dissolved in distilled water, and then add 600 ml glycerin to
it. Dissolve 2 g phenolphthalein in the minimum amount of warm alcohol (denaturated with benzol) and
add this to the citrate-glycerin solution. Make-Up to 1 l with distilled water. (If the mixture turns red after
the addition of phenolphthalein - as a result of alkali in the glycerin - it can be neutralized by means of
careful addition of 0.1 N sulphuric acid until the red discoloration just disappears.)
 Sodium Hydroxide volumetric solution 0.1 N
Procedure:

**
1.0 ml nickel bath are mixed in a 300 ml Erlenmeyer flask with
 100 ml distilled water and
 25 ml "mixed solution". This is then titrated with
 0.1 N sodium hydroxide volumetric solution until the pale green colour of the solution changes to a
definite red or violet. Since the solution is viscous, it must be well stirred continuously as otherwise the
red colour forms on every drop of caustic soda solution added and only disappears when the solution is
well stirred.
***
Multiplying the number of ml 0.1 N caustic soda volumetric solution used by 6.184 produces the boric acid
content of the bath in g/l.
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Example:
6.2 ml of 0.1 N sodium hydroxide volumetric solution were used for the titration of 1 ml nickel bath.
Calculation:
6.2 x 6.184 = 38.3 g/l boric acid

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Version: 04
Complexometric Determination of Nickel by Titration
Doc.-No.: A0000364-04
Principle: Complexometric titration
Reagents for manual titration:
 0.1M Na2-EDTA volumetric standard

 25 % Ammonia solution
 Murexide indicator triturate (1 : 100 with sodium chloride)
Reagents for titroprocessor:
 0.1M Na2-EDTA volumetric standard

 0.1M Copper diamin-EDTA solution (e.g.: Merck 1052170500)
 Buffer-solution pH 10 (54 g ammonium chloride dissolved in 200 ml DI-water mixed with 350 ml of
ammonia 25 % and made up to 1000 ml with DI-water.)
Please follow the general regulations for hazardous materials in the Safety data
sheets!
The analytical procedure is to be followed exactly.
pollutants.
Equipment required:
 usual laboratory equipment

 Titroprocessor with Cu-ISE and Ag/AgCl refrence, e.g. Metrohm 904 Titrando with Metrohm Cu-ISE
(Order No. 6.0502.140) and LL ISE Reference electrode (Order No. 6.0507.100) with Electrolyte
solution c(KCL)=3 M (only if a titroprocessor is used for the determination)
The above listed equipment is only valid when this method was created. For purchase of new
analytical equipment the recommend equipment list has to be followed:
https://10.187.127.52/Communication/html/scientific_services_chemical_services_analytics.php
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Operating Parameters (for Titroprocessor only)
Modus: Dynamic Titration U
Titrationspeed: Optimal
Stop EP: 1
EP crit.: 20
Procedure:
Manual titration:
 1.0 ml** of the sample is transferred into a suitable vessel and mixed with
 80 ml deionized water,
 10 ml 25 % ammonia solution and
 2 spatula tips of indicator triturate.
 Titrate with 0.1M Na2-EDTA volumetric standard to a deep purple endpoint. At the end of the titration
the EDTA volumetric solution should be added carefully, because of a slight delay of color change.
Potentiometric indication
 1.0 ml** of the sample is transferred into a suitable vessel. Add

 10 ml of 0.1 M Copper(NH4)2-EDTA solution and
 20 ml of buffer pH 10. Wait 5 minutes and add
 70 ml DI-water before titrating with 0.1M Na2-EDTA volumetric standard to the first endpoint.
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Evaluation:
The consumption of 0.1M Na2-EDTA volumetric standard in ml***, multiplied by 5.871 gives the content of
Nickel in g/l.
Example:
The titration of 1.0 ml sample consumed 8.50 ml 0.1M Na2-EDTA volumetric standard.
8.5 x 5.871 = 49.9 g/l Nickel

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Version: 06
Determination of Chloride by Titration Doc.-No.: A0000480-06
Reagents required*:
 Potassium chromate indicator solution (saturated)

 Silver nitrate volumetric solution 0.1 M
Procedure:
 2.0 ml of the nickel bath are mixed in a 300 ml Erlenmeyer flask with
 100 ml of DI water and, after the addition of a few drops of saturated potassium chromate indicator
solution, titrated with
 0.1 M silver nitrate volumetric solution. The titration process is complete when the initially white
precipitate turns brownish.
Alternative: The Titration can be conducted as a turning point titration using a

titroprocessor equipped with an Ag/AgCl electrode to determine the endpoint.
The consumption of 0.1 M silver nitrate volumetric solution*** in ml – multiplied by 1.77 – gives the total
chloride content of the bath in g/l.
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Example:
7.6 ml of 0.1 M silver nitrate volumetric solution were used for the titration of 2.0 ml nickel bath.
Calculation:
7.6 x 1.77 = 13.5 g/l Chloride

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Version: 01
Determination of Copper by AA
Doc.-No.: EXT-1016-AA-01
Principle:
The sample containing copper is diffused and after atomizing in a compression air/acetylene-flame of the
flame-atomic absorption spectrometer, the absorption is measured at a wavelength of 324.7 nm. The
determination is carried out through external calibration by using corresponding standard solution.
Reagent required*:
 HNO3 conc. 65 %
 Copper standard solution: 1000 mg/l
 DI-water
Equipment:
 Atomic Absorption Spectrometer with control and evaluation unit (e.g. Perkin Elmer, Varian)
 Burner: Air/Acetylene one-slit burner head
 Hollow cathode lamp: Copper
Standards:
SIPS-autocalibration with 5 mg/l Multi IV-standard solution, 5-point calibration up to 5 mg/l for Cu.
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Operating conditions:
Varian AA 280FS
Lamp current 7 mA Gas mixture Compression 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 324.7 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.
Procedure:
 1.0 ml** and 2.0 ml of the sample is placed into a 20 ml volumetric flask. Add
 1 ml of nitric acid conc. Then fill the volumetric flask up to the mark with DI water. The well-mixed
solution is now measured at a wavelength of 324.7 nm (optimum must be adjusted) and an oxidizing,
strong blue flame against the standard solution.
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!
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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 copper concentration C Cu [mg/l] for
the diluted sample must be multiplied with the dilution factor. The determined copper content must be within
the calibration curve, otherwise choose another dilution.
CCu [mg/l]  dilution factor = mg/l of Cu in the sample.
Example:
0.5 mg/l  10 = 5.0 mg/l of copper

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Version: 01
Determination of Nickel Carrier A-5 (2x) by UV/VIS
Spectrometry Doc.-No.: EXT-1299-UV-01
Principle:
At 269 nm the Nickel Carrier A-5 (2x) shows an extinction maximum that is used for the quantitative
determination.
Reagents required*:
 DI-water
 Nickel Carrier A-5 (2x), reference material
sheets!
pollutants.
Equipment:
 UV/VIS Spectral photometer (e.g. Perkin Elmer Lambda 2S)

 Quartz glass cuvette (pathlength: 1 cm)
 Usual lab equipment
Operating parameter UV/VIS spectrometer:
Method UV-VIS Curve Linear

Wavelength 269 nm Ordmode Single wave
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Procedure:
Standard preparation:
 Exactly 2.0 ml** of the Nickel Carrier A-5 (2x) reference material is pipetted into a 100 ml measuring
flask and filled up to the mark with DI-water (concentration: 20 ml/l Nickel Carrier A-5 (2x))
Standard and sample measurement:
 The standard and the sample is diluted in a ratio of 1 : 40 each.

 The solutions are transferred into a quartz glass cuvette. The absorbency at 269 nm versus a DI-water
blank is read off.
Calculation:
Ext .sample
Content Nickel Carrier A-5 (2x) in ml/l =  20
Ext .s tan dard
Example:
0.621
 20  18.1 ml/l Nickel Carrier A-5 (2x)
0.685

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Version: 03
Determination of Nickel Additive SA-1 by Titration
Doc.-No.: A0001050-03
Principle: Redox titration
Please take care: The results from the determination of the content of the Nickel
Additive SA-1 via ion chromatography may differ from the titration results. This
causes in the higher selectivity and sensitivity of the IC method. It is recommended
to determine the content of the Nickel Additive SA-1 via ion chromatography.
Reagents required*:
 0.05M Bromide/Bromate solution (Titrisol ampoule for 1000 ml, Merck: 1.09905.0001)
 0.1M Sodium thiosulfate volumetric standard
 30 % Potassium iodide solution in DI-Water
 1 % Starch solution
 conc. Hydrochloric acid
 Charcoal activated
sheets!
pollutants.
Equipment required:
 usual laboratory equipment

 vacuum filtration system is recommended
The aforesaid listed equipment is only valid when this method has been created.
For purchase of new analytical equipment the recommend equipment list has to be followed:
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Procedure:
 Mix 200 ml sample with 15 g charcoal in a suitable beaker, stir for 15 min and filter afterwards.
 50.0** ml filtrate are transferred into an iodine flask.
 Add 20.0** ml 0.05M Bromide/Bromate solution and 20 ml conc. Hydrochloric acid.
 Cover the flask and leave it in the dark for 20 min.
 Add 5 ml 30 % potassium iodide solution and 2 ml 1 % starch solution.
 Titrate with 0.1M sodium thiosulfate volumetric standard until the color changes from dark blue to bright
green.
Evaluation:
The consumption of 0.1M sodium thiosulfate volumetric standard in ml*** subtracted from the amount of
0.05M Bromide/Bromate solution used, multiplied by 0.616, gives the amount of Nickel Additive SA-1
in ml/l.
Example:
During titration of 50.0 ml nickel bath, 15.6 ml 0.1 M sodium thiosulfate standard solution*** was used.
(20.0 – 15.6) x 0.616 = 2.7 ml/l Nickel Additive SA-1

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Version: 02
Determination of Nickel Additive SA-1 by IC
Doc.-No.: A0002265-02
Principle:
Ion Chromatography (IC) with conductivity detection
Please take care: The results from the determination of the content of the Nickel
Additive SA-1 via Ion chromatography may differ from the titration results. This
causes in the higher selectivity and sensitivity of the IC method. It is recommended
to determine the content of the Nickel Additive SA-1 via Ion chromatography.
Reagents required:
 Nickel Additive SA-1, reference material

 Sodium hydroxide solution 50 %w/w p.a.
 Bromine CAS-Number: 7726-95-6.
Alternatively: if nor bromine is available in your country, please follow the instructions as described in
the appendix.
 Sodium metabisulfite Na2S2O5 p.a. CAS-number: 7681-57-4
 De-ionized water Millipore quality, degassed for eluent preparation*
*Water for analysis (Merck, P/N 1.16754.5000) proved to be a good alternative for Millipore water.
sheets!
pollutants.
Equipment required:
 Ion chromatograph Thermo/Dionex DX 500, ICS 3000, ICS 5000 or equivalent

 Single use syringes and syringe filters (Ø 0.45 µm)
 Standard laboratory equipment
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Operating Parameters:
Operation mode: gradient

Eluent A: de-ionized water
B: 50 mM NaOH (5.24 ml NaOH 50 %ww / 2 l degassed H2O)
Anion trap Dionex IonPac ATC-3, 9 mm x 24 mm
Flow rate: 1.5 ml/min
Gradient:
Time (min) %A %B c NaOH
in mM
0.0 99 1 0.5
2.0 99 1 0.5
8.0 40 60 30
8.1 0 100 50
11.0 0 100 50
11.1 99 1 20
15.0 99 1 0.5
Injection volume: 25 µl, full loop

Guard column: Dionex IonPac AG11-HC, 4 mm x 50 mm
Analytical column: Dionex IonPac AS11-HC, 4 mm x 250 mm
Runtime: 15.0 min (including re-equilibration time)
Suppressor: ASRS 300 4 mm, 186 mA external water mode
Pressure: approx. 1990 psi
Detection: suppressed conductivity
The aforesaid listed equipment is only valid when this method has been created.
For purchase of new analytical equipment the recommend equipment list has to be followed:
Procedure:
Reagent Solutions
Bromine solution, 1 % v/v: 1 ml Bromine is pipetted into a 100 ml volumetric flask and filled up to the
calibration mark with de-ionized water. The mixture has to be well shaken until the most bromine is diluted
(it is a saturated solution, so it could be possible that some bromine remains without dissolving)
Sodium metabisulfite solution, 10 % w/w: approx. 10 g sodium metabisulfite are weighed into a 100 ml
volumetric flask and filled up to the calibration mark with de-ionized water.
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Stock Solution 1.0 ml/l Nickel Additive SA-1
100 µl Nickel Additive SA-1 are pipetted into a 100 ml volumetric flask and filled up to the calibration mark
with de-ionized water.
Standard Solutions
Standard solutions with 10.0 µl/l, 20.0 µl/l and 40.0 µl/l SA1 have to be prepared out of the stock solutions
following the same procedure as with the sample (see below).
Standard and Sample Preparation
The sample has to be diluted in a way that the measured peak areas are within the calibration curve, e.g.
1 : 250 or 1 : 200.
- Corresponding to concentrations of 10.0 µl/l, 20.0 µl/l and 40.0 µl/l Nickel Additive SA-1 1.0 ml,
2.0 ml and 4.0 ml of the SA-1 stock solution are pipetted into three 100 ml volumetric flask and
filled with approx. 50 ml de-ionized water
- Corresponding to a 1 : 250 and a 1 : 200 dilution 0.4 ml and 0.5 ml sample are pipetted into two
100 ml volumetric flask and filled with approx. 50 ml de-ionized water
- Approx. 150 µl bromine solution are added to each flask and for a few minutes softly shaken. After
this the solutions should be slightly yellowish. Add more bromine solution in 50 µl steps if this is not
the case.
- Approx. 150 µl sodium metabisulfite solution are added and softly shaken until the yellowing
disappear
- Approx. 50 µl 50 % NaOH are slowly added to the sample solution and softly shaken
- The solutions are filled up to the calibration mark with de-ionized water
- The prepared sample solutions are filtrated using a single use syringe filter. Discard the first
2 – 3 ml
The standard and sample solutions are analyzed directly after preparation.
Evaluation:
Retention time SA-1: approx. 7.0 min.
The content of Nickel Additive SA-1 is evaluated via external calibration.
Content analyte mg/l = content mg/l  dilution factor

analyte
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Example:
Content SA1 ml/l = 10.82 µl/l  250  0.001ml/µl  2.70 ml/l Nickel Additive SA-1
Document of Analysis:
Fig. 1: Example chromatogram of a sample solution diluted 1 : 200
CD_1
900
µS
800
600
1 – SA-1 - 6,990
400
200
0
min
-100
0,0 2,0 4,0 6,0 8,0 10,0 12,0 14,0 15,0
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Fig. 2: Example chromatogram of a sample solution diluted 1 : 200 (zoomed detail)
CD_1
48,1
µS
40,0
30,0
20,0
10,0
1 – SA-1 - 6,990
0,0
min
-5,2
6,13 6,50 7,00 7,50 8,00 8,50 9,00 9,26

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Appendix 1: Laboratory Production of Bromine
Principle:
Potassium bromide (KBr) reacts with manganese (IV) dioxide (MnO 2) and sulfuric acid (H2SO4) to produce
bromine (Br2) and other by products, according to the following chemical formula:
2 KBr + MnO2 + 2 H2SO4 = Br2 + K2SO4 + MnSO4 + 2 H2O
The reaction takes place in a boiling solution.

With the help of a distillation apparatus the produced gaseous bromine is liquefied by cooling and transferred
to a flask containing water. In this way bromine is dilute in water. This bromine-water solution is then used
during preparation of the standards and sample for the determination of the nickel additive SA-1.
Reagents required:
 Potassium Bromide KBr CAS-Number: 7758-02-3

 Magnesium Dioxide MNO2 CAS-Number: 1313-13-9
 Sulfuric Acid 98 % CAS-Number: 7664-93-9
 DI-Water
Equipment:
 Two 50 ml round-bottom flasks with ground glass joint

 Metal clips
 Distillation apparatus with short condenser
 PVC tubes
 Heating device: burner or heating oil bath
 Boiling chips
Procedure:
- Approx. 1000 mg KBr, 250 mg MnO2 and some boiling chips are transferred in a round-bottom flask
(boiling flask).
- 1 ml H2SO4 98 % is carefully transferred to 20 ml de-ionized water and mixed.
- 10 ml of the prepared H2SO4 solution are added to the KBr / MnO2 containing flask.
- 10 ml de-ionized water are transferred to the receiving flask.
- Set up the distillation apparatus (see Fig. 1).
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Fig.1: Set up of the distillation apparatus for the production of bromine. Start of the reaction.
 All components of the distillation apparatus must be stabilized with the help of support stands and
clamps.
 Glass connections must be secured with metal clips.
 The condenser has to be connected to a source of running water in order to cool the produced bromine
(use for this purpose rubber or plastic tubes).
 The whole process including preparation of the chemicals and waste disposal has to take place
extremely careful, inside an exhaust hood and by wearing the personal protective equipment!
 It is an opening with a PVC tube between condenser and receiving flask in order to release pressure in
the apparatus: the system must NOT be completely sealed! Use for this purpose a PVC tube to lead
some gaseous bromine into the exhaust.
 The reaction is concluded when no more bromine development is observed. The content of the
receiving flask (bromine-water solution) has to be carefully transferred to a brown glass bottle or used
immediately for the preparation of the standards or sample
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Fig.2: Set up of the distillation apparatus for the production of bromine during the reaction.
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Version: 01
Supreme Plus Brightener by HPLC-UV Doc.-No.: A0002026-01
Principle: High Performance Liquid Chromatography (HPLC) with UV detection
Reagents required*:
 Supreme Plus Brightener, 1000 ml/l, certified reference

 De-ionized water (Millipore quality)
 Phosphoric acid H3PO4 85 %, analytical grade
 Acetonitrile, chromatography grade
Equipment required:
HPLC-System with diode array detector (DAD) or variable wavelength detector (VWD)
e.g. Waters Alliance 2695 with Waters 2996 or Waters 2487
Standard laboratory equipment
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Operating Parameters:
Operation Mode gradient

Eluent A: 1000 ml Millipore-H2O + 1.0 ml H3PO4
B: Acetonitrile
Gradient
Time Flow %A %B Curve
min mL/min
1 1.00 100.0 0.0
2 1.70 1.00 100.0 0.0 6
3 1.71 1.50 0.0 100.0 6
4 5.00 1.50 0.0 100.0 6
5 5.10 1.00 100.0 0.0 6
6 10.0 1.00 100.0 0.0 6
Analytical Column Waters Atlantis T3, 4.6 x 100 mm, 3 µm

Temperature room temperature
Runtime 10 min, including re-equilibration time
Injection volume 10 µl
Detection 260 nm
Standard Preparation:
The Supreme Plus Brightener concentrate is diluted 1 : 1000 with eluent A (1000 ml Millipore-H2O + 1.0 ml
H3PO4) resulting in a content of 1 ml/l*.
This solution is diluted 1 : 25, 1 : 10 and 1 : 5 with eluent A (1000 ml Millipore-H2O + 1.0 ml H3PO4), resulting
in the following concentrations: 0.04 ml/l, 0.1 ml/l and 0.2 ml/l*
* The correct values have to be calculated out of the real content in the certified reference.
Sample Preparation:
The sample is diluted with eluent A (1000 ml Millipore-H2O + 1.0 ml H3PO4) in a way, that the measured peak
areas are within the calibration curve, e.g. 1 : 10 and 1 : 5.
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Evaluation:
The content of the brightener is evaluated by linear external calibration through the origin.
Retention time Supreme Plus Brightener: approx. 1.6 min
Calculation:
ContentBrightener ml/l= content Brightener ml/l dilutionfactor
Statistics:
Reproducibility RSD < 5.0 %

LOD Brightener : 0.02 ml/l in the bath *
LOQ Brightener : 0.06 ml/l in the bath *
* Based on a sample dilution of 1 : 2.5
Documents of Analysis
Fig. 1: Chromatogram of a sample solution at 260 nm, diluted 1 : 10.
0,140
0,130
0,120
0,110
0,100
0,090
0,080
0,070
AU
0,060
0,050
0,040
Brightener - 1,616
0,030
0,020
1,526
1,733
0,010
0,000
0,00 1,00 2,00 3,00 4,00 5,00 6,00 7,00 8,00 9,00
Minutes
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Fig. 2: Chromatogram of a sample solution at 260 nm, diluted 1 : 10, zoomed detail.
0,028
0,026
0,024
0,022
Brightener - 1,616
0,020
0,018
0,016
0,014
AU
0,012
0,010
0,008
0,006
1,526
0,004
0,002
0,000
1,30 1,35 1,40 1,45 1,50 1,55 1,60 1,65 1,70 1,75 1,80 1,85 1,90 1,95
Minutes

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

06 30.June.2014 AI added A0002265-01; AI update
A0001050-03
07 04.Jan.2016 AI update A0000364-04
08 11.Jan.2017 AI update A0002265-02
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17.01.2017 BTT DECO

Manual 8XX Titrando EN

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NICKEL BRIGHT Version: 08

Supreme Plus IMDS-No.: 749088

Released on: Released by:

17.01.2017 BTT DECO

 Unsurpassed fast rates of brightening and leveling

 Used with air or mechanical agitation

Tanks Mild steel with hard rubber lining, PVC or PVC-Polyester

Anodes Rolled pure nickel anodes, electrolytic nickel anodes, or

Anode bags Required; use of twin bags is recommended. Made of Dynel

Heating Heaters: porcelain, hard glass, PTFE.

Released on: Released by:

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Mechanical agitation / Air agitation Required. Mechanical and / or air agitation.

stroke length double stroke/min

The required amount of air is: 12 – 20 m3/h per meter of

Filtration Continuous filtration is recommended. The entire bath

Filter aid Activated carbon; filter cellulose or diatomic earth

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Make-Up of 100 l Liter kg

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Temperature 55 °C (50 – 60 °C)

pH Electrometrically: 4.4 (4.0 – 4.6)

Density 1.19 g/cm3 at 20 °C

Ratio Anode : Cathode 1 : 1 to 2 :1

Deposition rate Approx. 1 µm Ni in 1.7 min at 3 A/dm²

Nominal values On make-up During operation

Salt Nickel Chloride ions Boric Acid

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Data of Additives of Plating Solution

Nominal values On make-up During operation

Function and dosage of the Additives

Consumption for 10,000 Ampere hours Liter kg

Supreme Plus Brightener

Lack of Supreme Plus Brightener results in reduced brightness and leveling.

Released on: Released by:

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Supreme Plus Leveller

Nickel Carrier A-5 (2x)

Nickel Additive SA-1

Wetting Agents NP-A and Ni M

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6. Cleaning of the Plating Solution

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

PRODUCT SAP No.

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8. Recommendations for Wastewater Treatment

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 Sodium Hydroxide volumetric solution 0.1 M

Alternative: The Titration can be conducted as a turning point titration using a

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11.0  3.092 = 34.0 g/l boric acid

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

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 Sodium Hydroxide volumetric solution 0.1 N