ACID COPPER Version: 16

Doc.-No.: 2099
DATA SHEET
IMDS-No.: 736943

Cupracid® 210
Bright copper plating solution

CONTENTS

Process Information ........................................................................................................................................... 2

Equipment .......................................................................................................................................................... 2
Make-Up ............................................................................................................................................................ 4
Working Parameters .......................................................................................................................................... 5
Maintenance ...................................................................................................................................................... 6
Effect of the Additives .................................................................................................................................... 7
Capability of Mixing the Additives.................................................................................................................. 7
Characteristics of the Additives during Electrolyte Cleaning ......................................................................... 8
Application Guidelines ....................................................................................................................................... 8
Anti-Pitting Additives ..................................................................................................................................... 9
Cupracid 530 Correction Solution ................................................................................................................. 9
Cupracid Antifoam .......................................................................................................................................10
Cupracid Promoter ......................................................................................................................................10
Cupracid Leveller Additive ...........................................................................................................................10
Cupracid Additive UN ..................................................................................................................................10
Copper Plating of Small Bulk Articles ..........................................................................................................11
SAP No. for Make - Up and Maintenance Products ........................................................................................11
Treatment of Waste Water...............................................................................................................................12
Analytical Instructions ......................................................................................................................................13
Determination of Copper by Titration ..........................................................................................................13
Determination of Sulfuric acid by Titration ..................................................................................................15
Determination of Chloride by Titration .........................................................................................................17
Determination of Make-Up Solution by Tensiometry...................................................................................19
Determination of Make Up Solution by CVS ...............................................................................................24
Determination of Part A by Photometry.......................................................................................................27
Determination of Part B by HPLC................................................................................................................29

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Bright copper plating solution Doc.-No.: 2099

Process Information

• Cupracid 210 is a decorative copper plating solution on a sulfuric acid and dye basis which is operated
at room temperature.

• Cupracid 210 is a robust, general-purpose electrolyte that produces good leveling and uniform
brightness. The copper deposit is low stressed and ductile.

• Cupracid 210 can be used for both metals as well as for plastics.

• Cupracid 210 is well-known for its simple bath maintenance.

Equipment

Filtration Continuous filtration required.

A filtration rate of 5 tank volumes per hour is recommended
to remove solids impurities. Filter area should be
2
10 – 20 cm per liter tank volume.

Tank Mild steel with hard rubber lining or PVC/Polyester-reinforced

material.

Exhaust Required.

Heating / Cooling Graphite, Titanium, PTFE, PVC or Polyethylene.

Mechanical agitation Recommended.

Additional use of cathode rod agitation is advantageous in
order to reach all parts of the rack by the air stream.

length of stroke double stroke/min

100 mm 20 – 25
60 mm 25 – 30

Cathode agitation should preferably be horizontal.

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Air agitation Required.

The volume of air required for this purpose is approx.
10 – 20 m3 per hour and meter cathode rod length.

The air agitation pipes are situated parallel to the cathode

rod, approx. 50 – 80 mm above the bottom of the tank.

Depending on the size of the tank, they are equipped with

holes with a diameter of about 3 mm drilled at intervals of
80 to 100 mm at an angle of 45° to the bottom of th e tank.
Each pipe has two rows of holes set opposite to each other
at intervals of 40 – 50 mm. It is advisable to install at least
two agitation pipes (internal diameter 20 – 40 mm) in the
bath.

The distance between the pipes should be 150 – 250 mm.

Suitable materials are PVC or polyethylene.

Anodes Special copper anodes with a phosphorus content of

0.03 – 0.06 %, like bar anodes or copper balls or clippings in
titanium anode baskets are required.

The anodes must be provided with bags made of special

acid-resistant, fully synthetic material (e.g. PP).

Anode bag frames with suitable bags made of special fully

synthetic material are applicable.

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Make-Up

Make-up of 100 l Cupracid 210 Liter kg

Water, deionized approx. 85.0 approx. 85.0
Copper(II)sulfate • 5 H2O* --- 22.0
Sulfuric acid (chem. pure, 96 % (w/w), d = 1.84 kg/l) 3.85 7.08
Sodium chloride (chem. pure) --- 0.016 (16.0 g)
Cupracid 210 Make-Up 1.0 1.0
Cupracid 210 A 0.05 0.05
Cupracid 210 B 0.05 0.05
* Fe: max. 0.1 % (w/w); Cl: max. 0.02 % (w/w)

IMPORTANT NOTE: In all work with Cupracid 210, make sure that all regulations on
operations with sulfuric acid solutions are carefully observed!

Make-Up Sequence

• The copper sulfate is dissolved in half the amount of required DI-water in an extra tank made of PVC,
polyethylene or stainless steel. To accelerate the dissolution of the copper sulfate the water should be
heated up to 50 – 60 °C.

• As soon as the copper salt is completely dissolved, 5 g/l powdered, activated carbon (low sulfur, low
iron; suitable activated carbon can be purchased from Atotech) is added and is allowed to react for
about 1 hour while stirring frequently and thoroughly. Afterwards agitation is turned off for 3 – 4 hours to
allow the activated carbon to settle to the bottom of the tank.

• The solution is filtered into the plating tank and filled with DI-water to nearly the required amount. The
filtration needs to be carried out very carefully as residues of activated carbon particles can cause matt
copper deposits. It is also necessary to clean thoroughly the filter afterwards to avoid later contamination
by residues of activated carbon if the filter is used for the continuous filtration of the bath.

• The sulfuric acid is added to the clear blue plating solution while stirring vigorously (Caution! Wear
safety goggles!). Make sure that the temperature does not exceed 60 °C.

• Allow the plating solution to cool down to about 25 °C. Add while stirring thoroughly sodium chloride
diluted in small amounts of water and add also Cupracid 210 Make-Up, Cupracid 210 A and
Cupracid 210 B required for the bath make-up. At higher solution temperatures the Cupracid 210
additives would decompose.

• After make-up it is absolutely necessary to dummy plate the electrolyte for 5 Ah/l to form the anode film.
Due to the film formation also an extra addition of Cupracid 210 A might be necessary after dummy
plating.

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Working Parameters

Metal content Approx. 56 g/l Cu

Bath density 1.17 g/cm3 at 20 °C

pH-value Less than 1; does not need to be monitored

Bath temperature 20 – 30 °C, preferably 21 – 27 °C.

If the temperature rises above 30 °C, the use of
Cupracid HT is recommended.

Filter aid Diatomaceous earth or filter cellulose

(A minor increase of additive consumption might occur for
usage of diatomaceous earth)

Voltage 1.0 – 4.0 V

with larger baths up to 6 V, depending on the current
density and the loading of the bath

Current density Cathodic: 3 A/dm2 (1.0 – 6.0 A/dm2)

Anodic: 0.5 – 2.5 A/dm2

To form the required anode film an anodic current density

greater than 0.5 A/dm2 is needed.

Current efficiency 100 % for cathode and anode

Rate of deposition 0.7 µm Cu at 3 A/dm²

The numbers in the following table have been rounded up and down respectively to the full minute:

Current density Layer thickness in µm

6 µm 9 µm 12 µm 24 µm 36 µm 48 µm
1.0 A/dm2 28 min 41 min 54 min 108 min --- ---
2.0 A/dm2 14 min 21 min 28 min 55 min 82 min 111 min
3.0 A/dm2 9 min 14 min 19 min 37 min 55 min 73 min
4.0 A/dm2 7 min 11 min 14 min 28 min 42 min 55 min
5.0 A/dm2 6 min 8 min 11 min 22 min 33 min 44 min
6.0 A/dm2 5 min 7 min 9 min 18 min 27 min 35 min

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Maintenance

On make-up (during operation) Operation limits

Copper 56 g/l (53 – 60 g/l) 50 – 65 g/l
Sulfuric acid 68 g/l (63 – 70 g/l) 60 – 75 g/l
Chloride ions 100 mg/l (80 – 130 mg/l) 70 – 150 mg/l

Suitable methods of analysis can be obtained from our "Analytical Instructions".

4.0 g/l of copper sulfate (CuSO4 • 5 H2O) increases the copper content by about 1 g/l.

The dry copper sulfate should be dissolved in warm (40 – 60 °C) DI-water and then treated with 10 mg
activated carbon per 1 g copper sulfate (for about 1 hour). Remember to filter before adding to avoid carrying
carbon into the plating bath.

0.57 ml/l sulfuric acid (chem. pure, 96 % (w/w), d = 1.84 g/cm3) increases the sulfuric acid content by
about 1 g/l. The sulfuric acid must be added while stirring thoroughly in order to avoid local overheating.

16.5 mg/l sodium chloride (chem. pure) increases the amount of chloride ions by about 10 mg/l.
Prior to addition, the sodium chloride must be diluted in a small amount of water.

Required for 10,000 Ah: 0.8 l (0.25 – 1.2 l) Cupracid 210 A

0.6 l (0.25 – 1.2 l) Cupracid 210 B
The consumption depends on the degree of brilliance and
leveling required. If bar anodes are used, consumption of
Cupracid 210 B can decrease.
0.5 l (0.4 – 0.8 l) Cupracid 210 Make-Up must be added in
some cases, e.g. for replenishment of drag-out and
evaporation losses.

If the number of Ampere hours is not 0.1 – 0.5 l (100 – 500 ml) Cupracid 210 A and
known, the following amounts should be 0.1 – 0.5 l (100 – 500 ml) Cupracid 210 B.
added to 1000 l electrolyte when the The addition should be done in steps of 100 ml additive per
degree of brilliance diminishes. 1000 l electrolyte.

To compensate drag-out losses, the The addition of copper(II)sulfate • 5 H2O serves as an

addition of Cupracid 210 Make-Up is indication for drag-out losses.
necessary. A dosage of 0.5 kg Cupracid 210 Make-Up is recommended
for the addition of 10 kg copper(II)sulfate • 5 H2O.

If the copper content of the solution For that procedure the salt will be dissolved in warm,
decreases below the standard during DI-water and the solution is then treated with activated
operation it must be replenished by carbon as described for „Make-Up“. After thorough filtration
adding copper(II)sulfate • 5 H2O. the solution can be added to the bath.

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Effect of the Additives

In order to achieve optimal leveling and brightness characteristics, Cupracid 210 A and Cupracid 210 B
must be present in the electrolyte in a certain prescribed proportion with respect to each other. Their mutual
proportion must be strictly observed, since the two substances have mutual influence on each other:
an excess of the one additive has the same effect as a lack of the other.

Lack of Cupracid 210 A or excess of Cupracid 210 B

Lack of Cupracid 210 A or excess of Cupracid 210 B can lead to low leveling, reduced brightness and
partly hazy deposits in medium to low current density areas. In this case gradually add
0.05 – 0.1 ml/l of Cupracid 210 A.

If frequent extra additions of Cupracid 210 A are required, the concentration of Cupracid 210 A as well as
Cupracid 210 B is to be determined via analysis. If necessary, reduce additions of Cupracid 210 B or
increase additions of Cupracid 210 A.

Lack of Cupracid 210 B or excess of Cupracid 210 A

A lack of Cupracid 210 B or an excess of Cupracid 210 A results in high current density burning.
Furthermore, a significant excess of Cupracid 210 A can cause roughness and pores.

If burns appear in high current density areas, Cupracid 210 B must be added in steps of 0.1 ml/l. In order to
prevent the formation of haze, small amounts of Cupracid 210 A must also be added simultaneously
(20 % based on the added amount of Cupracid 210 B).

Cupracid 210 A and Cupracid 210 B must be added separately to the plating solution while stirring
thoroughly.

The content of active Cupracid 210 Make-Up determined by tensiometry or CVS should usually be
between 3 – 13 ml/l in a Cupracid 210 electrolyte.

When high current density burning occurs, the concentration of inorganic constituents
(Cu, H2SO4, Cl-) should be analyzed prior to addition of the Cupracid 210 additives.

Capability of Mixing the Additives

Cupracid 210 Make-Up can be mixed in any and all proportions with Cupracid 210 B

Cupracid 210 A must never be mixed with Cupracid 210 B or Cupracid 210 Make-Up.

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Characteristics of the Additives during Electrolyte Cleaning

The following table shows how much of the additives will be removed when the electrolyte is cleaned by
several methods.

Product 5 g/l Activated 5 g/l Carbon 1 ml/l H2O2 30 % 100 mg/l

carbon + 2 g/l KMnO4 NaPS*
Cupracid 210 A completely completely almost completely slightly
Cupracid 210 B insignificant completely partly slightly
Cupracid 210 Make-Up partly completely not at all not at all
Cupracid Wetting Agent Plus almost completely completely not at all not at all
Cupracid Super Wet 42 almost completely completely not at all not at all
* NaPS = Sodium persulfate (Na2S2O8)

Application Guidelines

In order to maintain the quality of the deposition, we recommend to carry out the following:
The components of the bath should be analyzed regularly, in order to avoid high fluctuations in
concentration. For the same reason, it is recommended to run periodically Hull Cell tests.

If new titanium baskets and anode bags (made of polypropylene) are used, the following must be
observed:
The anode baskets are to be cleaned by means of hot degreasing, to avoid contamination of the electrolyte
by oil and metal cuttings.
Anode bags are cleaned first in a hot sodium carbonate solution (1.5 % (w/w)) to remove the impregnation
followed by a neutralization in a 1 % (v/v) sulfuric acid solution.

Evaporation losses must be replenished with DI water.

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Anti-Pitting Additives

Adverse construction of the air agitation equipment or porous filter systems, among other things, can cause
small air bubbles, which are distributed in the electrolyte.

These air bubbles adhere preferably at the bottom of the parts and partially disturb the deposition of copper
so that pores are formed. Cupracid Wetting Agent Plus or Cupracid Super Wet 42 can be used as soon
as those air pores occur.

However Cupracid Super Wet 42 should not be added to solutions with temperatures higher than 30 °C as
the active component could precipitate due to the cloud point of the wetting agent.
Cupracid Super Wet 42 reduces the foam formation on the electrolyte.

The Cupracid Wetting Agent Plus is a foam producing product. The use of Cupracid Wetting Agent Plus
in combination with the Cupracid 530 Correction Solution proved beneficial.

Cupracid Wetting Agent Plus or Cupracid Super Wet 42 should be added in accordance with the
respective data sheets.

Cupracid 530 Correction Solution

Cupracid 530 Correction Solution is used to improve the brightness throwing power in acid copper plating
solutions.

When used in conjunction with Cupracid Wetting Agent Plus, Cupracid 530 Correction Solution also
prevents the formation of pores.

Under certain circumstances, depending on air injection and the shape of the parts, it is possible that small
air bubbles get stuck on the surface causing air pores in the copper deposits.

In that case add Cupracid 530 Correction Solution and Cupracid Wetting Agent Plus to the plating
solution.

Cupracid 530 Correction Solution and Cupracid Wetting Agent Plus should be added in accordance with
the respective data sheets.

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Cupracid Antifoam

If the foam formation of the Cupracid 210 plating electrolyte is too strong, once Cupracid Antifoam can be
added as a foam reducer.

Afterwards it should be checked if the added amounts of Cupracid 210 Make-up or Cupracid Wetting
Agent Plus were too high. If necessary the addition of Cupracid 210 Make-up needs to be reduced
accordingly.

If the Cupracid Antifoam concentration in the plating bath is too high, the efficiency of Cupracid anti-pitting
additives will be reduced.
Cupracid Antifoam should be added in accordance with its data sheet.

Cupracid Promoter

Cupracid Promoter can be used to stabilize the Cupracid 210 process and the consumption of the organic
additives. Cupracid Promoter has no negative influence on the processing of the Cupracid 210.
Cupracid Promoter can be analyzed.

Cupracid Leveller Additive

Cupracid Leveller Additive is used to improve the leveling effect and the brightness in the medium to high
current density range of Cupracid 210 plating solutions. Cupracid Leveller Additive can be used if an
addition of 0.2 ml/l Cupracid 210 A has not any improving effect.

To avoid “burning” at high current density areas a sufficient high content of Cupracid 210 B is important.
Alternatively, the dosage of Cupracid 210 A can be reduced by up to 20 %.

Cupracid Leveller Additive should be added in accordance with its data sheet.

Cupracid Additive UN

The Cupracid Additive UN is used as special brightener in acid dips before the Cupracid 210 process but
can also be directly added to the Cupracid 210 electrolyte.

Cupracid Additive UN can be used either to prevent or decrease any impairment of the brightness caused
by pores or pitting.

Cupracid Additive UN should be added in accordance with its data sheet.

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Copper Plating of Small Bulk Articles

Cupracid 210 is also suitable for the copper plating of small bulk articles in a barrel. The make-up
specifications and the maintenance instructions are exactly the same as for rack plating.

Current density Approx. 1.0 A/dm2 (referred to the total surface area of the
articles in the barrel)

Voltage 6.0 – 10.0 V

SAP No. for Make - Up and Maintenance Products

PRODUCT SAP No.

CUPRACID 210 A 395962
CUPRACID 210 B 395970
CUPRACID 210 MAKE-UP 395418
CUPRACID WETTING AGENT PLUS 1668575
CUPRACID SUPER WET 42 1668965
CUPRACID PROMOTER 1681313
CUPRACID 530 CORRECTION SOLUTION 32979
CUPRACID ANTIFOAM 1558246
CUPRACID LEVELLER ADDITIVE 1667509
CUPRACID ADDITIVE UN 1672338

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Treatment of Waste Water

Rinse water

Copper can be precipitated by adjusting the rinse water pH to between 8.5 - 9.5. The filtered solution can
subsequently be sent to final neutralization.

Concentrates

The following options are possible when concentrated copper solutions must be treated.

When copper is to be recycled, it is generally necessary to treat these copper solutions separately from other
solutions.

The following recycling methods are typical, although others can be recommended:
• Electrowinning of copper using an appropriated electrolytic cell.
• Treatment of copper concentrate, or of a precipitated copper sludge, by a specialized recycling
company.

If these methods cannot be used, the copper concentrate together with the complexing agent free
wastewaters can be treated by adjusting the pH to between 8.5 – 9.5. 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.

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

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Analytical Instructions
Version: 03
Determination of Copper by Titration
Doc.-No.: EXT-0410-TIT-03

Principle: Complexometric Titration

Reagents required*:

• Ammonia solution 5 M; (5 N); (375 ml/l Ammonia solution 25 %); density 0.91 g/cm3)
• Indicator PAN (0.1% in alcohol)
• EDTA volumetric solution 0.1 M (EDTA = disodium salt of ethylenediamine tetraacetic acid)

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

Procedure:

• 1.0 ml** of the sample is placed into a 500 ml volumetric flask and dilute with 100 ml DI water.
• Carefully add 5 M of ammonia solution until the colour of the solution turns dark-blue (pH-value of 9.5 –
10.0 is reached).
• If the copper bath contains a substantial amount of iron, which can be recognized by the precipitated
iron hydroxide, a fresh sample must be taken and the iron hydroxide held in solution by adding
• about 3.0 g of sodium potassium tartrate (Seignette salt), before addition of 5 M ammonia solution.
• After addition of few drops of indicator solution titrate with
• 0.1 M EDTA volumetric solution, until the colour of the solution changes from dark blue to green

The number of ml of 0.1 M EDTA volumetric solution*** used - multiplied with 6.354 – gives
the content of copper in g/l.

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Example:

During titration of 1.0 ml bath, 8.4 ml of 0.1 M EDTA volumetric solution was used.

Calculation:

8.4 x 6.354 = 53.4 g/l copper.

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
Determination of Sulfuric acid by Titration
Doc.-No.: EXT-0411-TIT-02

Principle: Acid-Base Titration

Reagents required*:

• Methyl orange indicator solution 0.1 %

• Sodium Hydroxide volumetric solution 0.1 M; (0.1 N); (4 g/l NaOH)

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

Procedure:

• 1.0 ml** of the sample are placed into a 250 ml volumetric flask and diluted with 100 ml of DI water.
• Add 5 drops of methyl orange indicator solution and titrate against
• 0.1 M sodium hydroxide volumetric solution until the color of the solution changes from red to yellow.

• Alternatively a titration processor with a pH electrode can be used (titration to the first point of
equivalence)
***
The number of ml of 0.1 M sodium hydroxide volumetric solution used - multiplied with 4.9 - gives the
content of sulfuric acid in g/l.

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Example:

During titration of 1.0 ml of the bath, 11.9 ml of 0.1 M sodium hydroxide volumetric solution was used.

Calculation:

11.9 x 4.9 = 58.3 g/l sulfuric 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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Revision: 02
Determination of Chloride by Titration
Doc.-No.: EXT-0412-TIT-02

Principle:

Potentiometric Titration

Reagents required*

• Hydrochloric acid 0.1 M; (0.1 N); (8.3 ml/l HCl, density 1.19 g/cm3)
• Silver nitrate volumetric solution 0.01 M; (0.01 N) (produced by topping up 100.0 ml of 0.1 M silver
nitrate volumetric solution in a 1000 ml volumetric flask)

Measuring apparatus Titroprocessor or voltmeter with a millivolt scale

Indicator electrode Ag/AgCl Electrode with silver chloride coating

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

Coating of the silver electrode

The silver electrode (silver wire 2 mm) is thoroughly degreased and connected to the positive pole of a
direct-current generator. A platinum electrode (platinum coil, positive pole for electroanalytical metal
deposition) is connected to the negative pole. The electrodes are now immersed to a depth of about 5 - 6 cm
in 0.1 M hydrochloric acid and electrolysed while stirring continuously for about 1 - 2 hours, at 1 - 2 mA. After
this period of time the silver electrode should have a uniform brown appearance.

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Procedure

• 50.0 ml** copper bath are placed into a 150 ml beaker and mixed with
• 50 ml of fully demineralized water.
• The solution is titrated with 0.01 M silver nitrate volumetric solution until the first turning point (potential
jump)

Note: The Titration can be conducted only a turning point titration using a
titroprocessor / voltmeter equipped with a Ag/AgCl electrode to determine the
endpoint. No visual indication is possible.

***
The ml of 0.01 M silver nitrate volumetric solution used - multiplied with 7.09 – gives the content of chloride
ions in mg/l.

Example:

Titration of 50.0 ml sample consumed 10.75 ml of 0.01 M silver nitrate standard solution.

Calculation

10.75 x 7.09 = 76 mg/l chloride

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
Determination of Make-Up Solution by Tensiometry Doc.-No.: EXT-0421-PHY-02

Principle:

The surface tension will be measured by tensiometry and after external calibration the content of active
Make-Up Solution is determined.

Reagents required*:

• DI water
• Methanol p.a.
• Standard 2.5ml/L, 5.0 ml/L, 7.5ml/L, 10.0ml/L Make-Up Solution

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

Equipment required:

• Oasis MCX Vac Rac Cartridges (Messrs. Waters)

• Cartridge system with vacuum pump (Messrs. Vaccubrand)
• Round bottom flask 100 ml
• Rotary evaporator (Messrs. Buechi / Swiss)
• Temperature control unit
• Tensiometer SITA online t60
• Capillary TYP2 (black)

Working Parameters Tensiometry:

Rotation evaporator

Vacuum 250 mbar

Piston rotation 250 U/min

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Tensiometer

Average of measured value 50

Lifetime of bubbles 20.0 s

Frequency 0.500 Hz

Tolerance ±5%

Note: Temperature of the sample must be kept at 20 °C

Conditioning of the Cartridges

• The Oasis MCX cartridges will be conditioned with 1 ml of DI-water and methanol each.

Sample Preparation:

• 2.0** ml of sample are pipetted into the cartridge and diluted with
• about 8 ml of water and mixed thoroughly. Then rinse the cartridge again with
• about 1 ml DI-water. Now the cartridge will be eluted with
• 4.0 ml methanol in a 100 ml round bottom flask. The eluted sample will then be evaporated with a rotary
evaporator and taken up with
• 20.0 ml DI-water.

Note: It is absolutely necessary that the residue is free of methanol.

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Measurement with the Tensiometer:

• Measurement is carried out with the software SITA Online. First calibrate the tensiometer with DI water.
• The measurement cannot be started until the water value matches the value of 72.74 mN/m given in the
table.
• The samples cooled down to about 20 °C are then pl aced into thoroughly cleaned and dry
• 20 ml beakers and measured at the tensiometer.
• It must be assured that the samples have all the same temperature when measuring.
• The 2.5, 5.0, 7.5 and 10.0 ml/L standards, which was prepared the same way as the sample, must be
measured to set up the calibration curve (quadratic). After that the capillary is immersed into a water
vessel and for
• 10 s the “clean”-function at the tensiometer is started. Subsequently the capillary is carefully dried with
a piece of cloth.
• 50 measurements will be carried out. From the measured values the average will be generated, not
taking into account the lowest and the highest result.
• From the mean value of the measured surface tension the content of active Make-Up Solution can be
determined via calibration.
• Samples with measuring values of > 63.3 mN/m must be diluted in a ratio of 1:1 and measured again.
After each measurement “clean” must be carried out for 10 s.
• A double determination must always be carried out (sample preparation included). Measuring values,
which are outside the calibration, must be diluted in such a manner, that the measuring value is within
the calibration. The measuring desk must be chosen in a manner, that possibly sparse concussions
have an influence on the result. The glass vessels must be very clean and must not contain rinsing
agent residues.

• A new calibration curve must be set up when exchanging the capillary or

after longer idle times.

Surface tension of DI-water

19 °C 72.9 mN/m
20 °C 72.74 mN/m
21 °C 72.59 mN/m
22 °C 72.44 mN/m
23 °C 72.28 mN/m

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Calculation:

Example:

Standard 2.5ml/L : 68.3 mN/m

Standard 5.0ml/L : 65.0 mN/m
Standard 7.5ml/L : 63.2 mN/m
Standard 10.0ml/L : 62.1 mN/m

Make Up Solution 210

74
72,5
72
Surface Tension mN/m

70

68 68,3

66
65
64
63,2
62 62,1
y = 0,088x2 - 1,916x + 72,5
60 R2 = 0,9996
0 2 4 6 8 10 12
Content in ml/l

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Calculation is carried out in accordance with quadratic calibration

 
 1.916 - 1.916 2 − 4 × 0 . 088 × ( H 2 O − measuring value ) 
 value  × Dilution Factor = ml/l Make Up Solution
 
 2 × 0.088 
 

Measuring value Sample: 65.1 mN/m

Dilution: 1:1

 
 1.916 - 1.916 2 − 4 × 0 . 088 × ( 72 . 5 − 65 . 1 ) 
  × 2 = 10.0 ml/l Make Up Solution

 2 × 0.088 

 

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.

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Version: 02
Determination of Make Up Solution by CVS Doc.-No.: EXT-0445-CVS-02

Reagents required*:

• Copper Basic Electrolyte: 220 g/l CuSO4 x 5 H2O

60 g/l H2SO4
120 mg/l NaCl
• DI-water
• Sulfuric acid 2.5 M

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

Equipment required

• CVS unit QP 4000 (e.g. ECI Multiline or equivalent model)

• QPMS 4 measuring booth (e.g. ECI Multiline or equivalent model)
• Dosing unit Microlab 900 (e.g. ECI Multiline or equivalent model)
• A piston pipette (e.g. Eppendorf) is used when the dosing is carried out manually.
• Reference electrode: Ag/AgCl
• Electrolyte key: H2SO4, 2.5 M
• Backing electrode: copper
• Working electrode
• Electrolyte volume: 80.0 ml
• Electrolyte temperature: RT (22° C)

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CVS Parameter

Scan rate 100 mV/s

Negative limit -0.225 V

Positive limit 1.575 V

Integration limit 0.375 V

Contamination potential 1.075 V

Chloride potential 1.475 V

Rotation rate 2500 rpm

Standard concentration 10 ml/l

Addition volume 0.15 – 0.25 ml/l

End point 0.6

Stop point 0.58

Procedure

• A freshly made up bath is used as standard solution, which contains 10.0 ml/l Make Up Solution

Sample Solution

The bath sample is measured directly without any further sample preparation by CVS. If the concentrations
of Make Up Solution is < 5 ml/l the concentration must be increased by adding Make Up Solution.

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Measurement

• Conditioning with copper basic electrolyte for 30 cycles (until the loading amount is constant).
• Calibration of the system with standard solution.
• Analysis of the bath sample with a content of 5 – 15 ml/l Make Up Solution.
• Between the single determinations the electrode system must be conditioned again with the copper
basic electrolyte (approx. 5 – 10 cycles).
• If the concentration of Make Up Solution is significantly higher than 15 ml/l, the addition volume must be
decreased correspondingly.
• If the content of Make Up Solution in the sample to be determined is lower than 5 ml/l the analytical
results must be very erroneous. In this case we recommend to increase the concentration by adding a
known amount of Make Up Solution.
• To this e.g. exactly 1.0 ml/l Make Up Solution is placed into a 100 ml measuring flask and is filled up to
the mark with the sample to be determined (corresponds to an addition of 10.0 ml/l Make Up Solution
which must be subtracted from the analytical result).

Evaluation

The evaluation is carried out automatically with the software through dilution titration.
• The analytical result is given directly in ml/l Make Up Solution.

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.

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Version: 02
Determination of Part A by Photometry Doc.-No.: EXT-0422-UV-02

Principle:

The content of Part A can be photometrically determined at a wavelength of 560 nm. Since the extinction to
be measured depends on both the concentration of Part A, as well as on the content of copper, analysis for
determination of the copper content is also necessary (for example: by complexometric titration according to
our Analytical Instructions for acid copper baths).

Reagents* and Equipment required:

• UV/VIS spectrometer
• Quartz-, glass- or plastic cuvettes (layer thickness 1 cm)

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

Procedure:

A photometer is used to measure the extinction of the sample to be analyzed. The analysis is performed
directly, against water (to provide the blank value), in 1-cm cuvettes, at a wavelength of 560 nm.

Calculation:

E - (Cu x 0.00424) = g/l of Part A

0.29

E = the extinction measured for the sample

Cu = the copper concentration of the sample in g/l

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Example:

Extinction: 0.332
Copper: 53.3 g/l

0.332 - (53.3 • 0.00424)

= 0.37 g/l of Part A
0.29

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.

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Version: 02
Determination of Part B by HPLC Doc.-No.: EXT-0423-LC-02

Principle: RP-HPLC with UV-Detection

Reagents required*:

• Part B, reference material

• Acetonitril, HPLC-quality
• DI-water (Millipore-quality)
• (NH4)2SO4, analytical grade

Please follow the general regulations for hazardous materials in the Material safety
data sheets!
The analytical procedure is to be followed exactly.
Be sure to observe all local regulations concerning the permitted limits for
pollutants.

Equipment and Working Parameters

Type WATERS 510 or equivalent type

Mobile phase 95% Millipore Water +20 mmol (NH4)2SO4 + 5% Acetonitrile

Flow Rate 0.8 ml/min

Injection System

Type WATERS WISP 712 B or normal injection valve

Injection volume 50 µl

Running time 10 min

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Pre Column

Material HYPERSIL ODS (Thermo or similar)

Granulation 5 µm

Length 10 mm

Diameter 4.6 mm

Column

Material HYPERSIL ODS (Thermo or similar)

Granulation 5 µm

Length 25 cm

Diameter 4.6 mm

Detector

Detection UV-Detector

Type WATERS 481 LAMBDA MAX or equivalent type

Wave length 198 nm

Range 1

Response 0.1

Retention time

Time Approx. 5.7 min

Product Part B

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Preparation of Standards

The standards are prepared by dilution of the Part B Additive with Millipore Water.
Following standard concentration are used for calibration:
0.1 ml/L, 0.25 ml/L and 0.5 ml/L Part B

Preparation of Samples

The sample is being diluted with Millipore Water in a ratio of 1:10

Evaluation:

An evaluation software is used for peak integration.

All peaks are being evaluated by Peak Area.
The calibration curve is established (linear through zero).
The amount of ml/L Part B will be given directly by the software.

The peak area of the sample has to be within the calibrated range.
If necessary a different sample dilution has to be chosen!

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Standard chromatogram Part B: 0.1 ml/L

0,010

Part B - 6,016
0,000

-0,010

-0,020
AU

-0,030

-0,040

-0,050

-0,060

-0,070

-0,080
0,50 1,00 1,50 2,00 2,50 3,00 3,50 4,00 4,50 5,00 5,50 6,00 6,50 7,00 7,50 8,00
Minutes

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.

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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