“CHLORIDE ZINC FACTS”

FACT...Chloride Zinc is the most efficient zinc plating bath commercially

available.

FACT...Deposits from Chloride Zinc baths are brighter and more attractive than
those produced from any other zinc electrolyte.

FACT...Chloride Zinc electrolytes plate directly on cast iron, malleable steel and
carbo-nitrided steel.

FACT...Chloride Zinc solutions offer simplified waste treatment at substantially

lower costs than Cyanide Zinc.

FACT...One out of every two zinc platers has already made the switch to Chloride
Zinc.

FACT...MacDermid is the leader in Chloride Zinc plating with more types of

baths and more satisfied customers than any other supplier.
 TABLE OF CONTENTS

Page

I. Introduction 3

II. Available Products 4

III. Functions of Constituents 5

IV. Equipment Requirements 6

V. Acceptable Chemical Grades 9

VI. Bath Make-Up 10

VII. Analytical Procedures 11

VIII. Typical Process Cycles 17

IX. Solution Maintenance 18

X. Hull Cell Control 20

XI. Common Impurities 24

XII. Troubleshooting 27

2
I. Introduction

This manual has been designed to furnish the operator of a chloride zinc bath with
detailed information regarding the equipment, control, maintenance and general
practices of chloride zinc plating. “Chloride Zinc Facts” combines “state-of-the-art”
operating techniques with MacDermid’s years of experience in selling and servicing
chloride zincs to yield problem preventing suggestions and simplified solution
maintenance.

3
II. Products Available

A) Duzinc 019 LF Ammonia Free or Low Ammonia

B) Kenlevel Select, Select HT and Select Barrel Ammonia Free or Low Ammonia

C) Ultima 2000

D) Zincovet HT

4
III. Function of Constituents

Zinc Metal - Besides supplying the necessary ions for deposition of metal, the zinc
content has a significant affect on the throwing power and the bright plating range.
In general, the lower the zinc metal content, the better the throwing power. Low
zinc metal, however, can cause high current density (HCD) burning. Higher zinc
metal levels allow operation at higher current densities, however, throwing power
may be reduced. The metal is controlled by anode area and zinc chloride additions.

Total Chloride - The chloride in the bath supplies the conductivity. It also has
some affect on throwing power, though not as much as the zinc metal. Low chloride
will result in reduced conductivity (higher voltage required to maintain desired
current) and reduced throwing power. Higher total chloride improves throwing
power and conductivity, however, chloride levels too high can cause the Carrier
additive to “oil-out”. Care should be taken when adding chloride salts to avoid high
localized concentration of chloride which will cause “oil-out”. The chloride is
controlled by chemical additions.

Boric Acid/Ammonium Chloride - The boric acid (or ammonium chloride in a low
ammonia electrolyte) serves as a pH buffer, aids in leveling and extends the high
current density plating range. Low boric acid (or ammonium chloride) can cause
drastic pH fluctuation. The bath will require increased additions of hydrochloric acid
to maintain the desired pH. High Current Density burning may also result. This will
sometimes show up in barrel plating as white or gray barrel perforation marks on the
work. Boric acid concentrations over 37 g/l are not recommended. The boric acid
may salt out and create an insoluble film on the anodes causing them to polarize.
High ammonium chloride (over 30 g/l) in a low ammonia bath has no detrimental
affect. The concentrations are controlled by chemical additions.

pH - The pH of chloride zincs increase due to hydroxyl ion (OH -) generation during
plating. It is necessary to add hydrochloric (muriatic) acid to control the pH.
Potassium/Boric (ammonia free) baths should operate between pH 4.7 and 5.5.
Low and full ammonia baths are more tolerant and can operate in a pH range of 5.0
- 6.0. As the pH increases, the deposit becomes dull in the low current density
(recesses) areas, and throwing power is reduced. In barrel plating at higher pH
levels, the tendency for zinc from zinc delamination (flaking) is greater due to
passivation as the parts tumble. If the pH is allowed to fall below 4.5, the Carrier
additive may become completely insoluble and “oil-out”. Localized low pH must be
avoided. Hydrochloric acid should be diluted 1:1 with water and spread over the top
of the tank with good mixing.

See page 9 for acceptable grades of chemical additives.

5
IV. Equipment Requirements

Tanks - Steel tanks lined with rubber, polyethylene, polypropylene, PVC are
acceptable for chloride zinc plating.

All tanks must be thoroughly cleaned, leached and rinsed prior to solution make-up.
Leaching is accomplished with 5% by volume hydrochloric acid for a period of 24
hours. To this leach solution, add 0.1% by volume of the particular chloride zinc
wetter / carrier.

The leaching solution should also be passed through the filter and heat exchanger.
Plating barrels and racks should be passed through the leaching solution. After 24
hours, the tank is drained, rinsed well and the plating bath is made up per
instructions on page 10, “Bath Make-Up”.

Filtration - Continuous filtration is required for both rack and barrel plating. The
filter should be capable of circulating the total solution up to 1 - 2 times per hour. All
filter parts which contact the plating solution must be acid and chloride resistant, i.e.,
non-metallic. MacDermid has compiled a complete list of various filter
recommendations by their manufacturers for chloride zinc solutions. This is
available upon request to the Technical Service Department.

Heating - In installations where the solution temperature will fall below 21C, a
means of heating the solution is required. Coils should be fabricated of Teflon or
Titanium. Quartz immersion heaters are acceptable.

Cooling - Solution cooling may be required depending on the upper temperatures

limit of the electrolyte chose. Coils should be constructed of Teflon or titanium.
Titanium coil should be isolated from direct current. Solution circulation through a
refrigerated heat exchanger is the most effective method.

Anodes - Zinc ball, flat top, slab or oval anodes are acceptable. Anodes should be
pure zinc (99.99% zinc). Titanium baskets may be used, provided the applied
voltage does not exceed 9 volts or the basket may anodize and burn off. Baskets
must be kept full with all the zinc balls below solution level. Anode area must be
sufficient to keep the anode current density below (2.5 A/dm 2. Anode bags of
polypropelene are recommended for rack plating. Leach bags for 24 hours in a
solution of 1% by volume, hydrochloric acid with 0.1% by volume of the particular
chloride zinc wetter / carrier.

Agitation - Rack plating requires the use of cathode rod or air agitation. Rod
movement at 1 - 2 m/min produces effective agitation. The usual method for air
agitation is to use low pressure air from an air blower forced into the solution
through perforated pipes lying near the bottom of the tank.

Compressors must not be used, since these invariably contaminate the solution with
dirt and oil. Even using a blower, it is advisable to have an air filter in the inlet line.

6
Blower Size: 1.0 lt / sec for each 0.093 m 2 of tank surface area
0.07 kgs cm2 for each 450 mm of solution depth

Thus, for a tank 1820mm x 910mm, with a working depth of 910mm, the surface
area = 910mm x 1820mm’ = 1.65 m 2 ; so, a blower delivering 18 ltrs / sec at 0.14
kgs cm2 will be required.

Air Sparger Design

Pipe Size - Use small diameter 19 mm or 25 mm (preferred) PVC pipe either -

threaded or glued. This material is inert to most solutions.

Position - Lying on supports 75 mm to 150 mm off the bottom of the tank. This
should give you about 200 mm to 380 mm below the work. Do not install air pipes
directly beneath work, but offset to front sides of racks, or offset holes at a 30 to 45
degree angle from the vertical. Never install pipes where they will be close to the
anodes as this will cause particles to come out of anode bags and cause roughness
and sludging.

Inlets - Total cross-sectioned area of inlet pipes should equal or be slightly greater
than the total area of the perforated feeder pipes. Inlet pipes should join feeder
pipes every 2.4 m or less after any bends greater than 45.

Holes - The holes in feeder pipes are usually about 30 mm diameter, but may vary
from 12 mm to 60 mm. Spacing of holes varies from 25 mm to 125 mm apart,
smaller holes being closer together than larger ones. The total area of the holes
drilled must be somewhat less than the cross-sectioned area of the feeder pipes,
but not less than 165 mm since this would put too large a back pressure on the
pump.

The air agitation required in a chloride zinc bath should not be more than a roll in
the solution. Bubbling air like air agitated nickel baths will cause a high usage of
both primary and secondary brightener and excess foaming.

Solution agitation should be aided in all plating baths by placing the intake and
discharge of the filter at opposite ends of the tank with automatic machines, the
discharge should be counter-current to the work-flow.

Power Supply

Rack Plating 6 volt rectifier

Barrel Plating 12 volt rectifier

Rectifier ripple should not exceed 5%. The ammeter on the rectifier should be
checked for accuracy.

Bus Bar Protection - Cover bus bars with tape, clear vinyl, PVC pipe or plastisol

7
except at points of anode hook contact, to minimize corrosion and possible
contamination of solution.

Racks - Racks must be coated with suitable material such as Ohmax TM. Titanium or
Type 316 Stainless Steel tips are recommended.

Ventilation - Recommended with PVC or fiberglass ducts.

8
V. Acceptable Chemical Grades

The following chemical grades have been tested and approved for use with all
MacDermid chloride zinc solutions. Inferior grades must be avoided.

1. Zinc Chloride - 1) Mirro-MAC Chlorozinc Conc. 8350

2) Isobrite 408 or Zinc chloride solution C41851
3) Technical Grade Solid

2. Potassium Chloride - 1) U.S.P. Food Grade

2) 62.4% Standard Granular, Untreated
3) Standard 62
4) Chemical Grade
5) Industrial White Muriate, Untreated

3. Boric Acid - Technical Grade (Granular is preferred)

(Gran-Tech) Powdered, NF

4. Ammonium Chloride - Technical Grade, Untreated

5. Hydrochloric Acid - Technical Grade Water White

9
VI. Bath Make-Up

If a new liner or a liner that has previously been used for another electrolyte is
employed, be sure to follow leaching instructions given in Equipment Section
(Tanks).

1) Fill plating tank halfway with warm (45 - 60C) water.

2) Add required amount of boric acid and mix well to dissolve (Add ammonium
chloride if low ammonia bath is used).

3) Add required amount of potassium chloride and mix well to dissolve.

4) Add liquid zinc chloride and mix well.

5) Add water to bring solution volume close (leave 5%) to working level.

6) Using a reliable meter, check solution pH. Adjust to recommended level with
technical grade hydrochloric acid or potassium or sodium hydroxide (to raise pH).

7) Allow the solution to cool to 20 - 30C and add Carrier (wetter) component with
agitation.

8) Add brightener in required quantity. Mix well.

9) Bring solution to operating level with water.

10) Recheck pH and adjust, if needed.

11) The solution is now ready for use.

10
VII. Analytical Procedures (US calculations)

The following are the recommended procedures to analyze the electrolyte for zinc
metal, total chloride, boric acid and ammonium chloride.

1. Zinc Metal Procedure

Apparatus
2 ml pipette
25 ml graduated cylinder
50 ml burette
250 ml Erlenmeyer flask

Reagents
0.0575M EDTA - Dissolve 21.4 grams of EDTA (disodium dihydrate salt) in 500
ml distilled water. Transfer to a 1000 ml volumetric flask and dilute to the mark
with distilled water.

Buffer Solution - Dissolve 90.0 grams of sodium acetate (anhydrous) in 500 ml

distilled water. Add 15 ml of glacial acetic acid (A.R. Grade) and dilute in
volumetric flask to 1 liter with distilled water.

Indicator - Mix 0.10 gram of Xylenol-Orange (tetrasodium salt) with 100 grams
of sodium chloride.

Procedure

1) Pipette 5 ml of the plating bath into a 250 ml Erlenmeyer flask. Add 50 ml

D.I. water.

2) Add a pinch (approximately 1/4 gram) of the Xylenol-Orange indicator. Mix

and swirl to produce a violet color.

3) Add approximately 25 ml of buffer solution to produce a pH of approximately

5.5. Mix well to dissolve any precipitate.

4) Titrate immediately with 0.0575M EDTA to a yellow endpoint.

Calculation

ml EDTA x 0.75 - g/l Zinc Metal

(ml EDTA x 0.1 - oz/gal Zinc Metal)

11
2. Total Chloride Procedure

Apparatus
1 ml pipette
50 ml graduated cylinder
250 ml Erlenmeyer flask
100 ml graduated cylinder
50 ml burette

Reagents
0.1N Silver Nitrate - Dissolve 16.99 grams of silver nitrate in 500 ml distilled
water and dilute to 1000 ml in a volumetric flask.

Chromate Solution - Dissolve 10 grams of potassium or sodium chromate in 100

ml distilled water.

pH 5.5 Buffer Solution - Dissolve 150 grams sodium acetate (NaC 2H302 - 3H20)
in 600 ml D.I. H2o. Add 15 ml glacial acetic acid. Dilute to 1 liter with water.

Procedure

1) Pipette 1 ml sample into a 250 ml Erlenmeyer flask.

2) Add 50 ml distilled water.

3) Add 25 ml of pH 5.5 buffer solution.

4) Add 5 ml of sodium chromate indicator to produce a yellow color.

5) Titrate with 0.1N silver nitrate solution until permanent reddish-brown

coloration forms on the white silver chloride precipitate.

Calculation:

ml 0.1N AgNO3 x 3.58 = g/l Total Chloride

(ml 0.1N AgNO3 x 0.477 - oz/gal Total Chloride)

3) Boric Acid Procedure

Apparatus
5 ml pipette
250 ml Erlenmeyer flask

Reagents
0.1N Sodium Hydroxide(NaOH) - To 4.0 grams of A.R. Grade sodium hydroxide,

add sufficient deionized or distilled water to make 1 liter of solution. Standardize

12
 against a sulfuric acid of a known normality.

Mannitol - A.R. Grade

Bromcresol Purple Indicator Solution - Dissolve 0.1 gram of bromcresol purple

solid dye in 18 ml of 0.01N sodium hydroxide and dilute to 250 ml with
deionized or distilled water.

Procedure

1) Pipette 5 ml of plating solution into a 250 ml Erlenmeyer flask.

2) Add about 5 grams of Mannitol.

3) Add 3 to 5 drops of Bromcresol Purple Indicator.

4) Titrate with 0.1N NaOH. The color change is yellow to purple.

Calculation:

ml of 0.1N NaOH x 1.24 = g/l Boric Acid

(ml of 0.1N NaOH x .167 = oz/gal Boric Acid)

4) Ammonium Chloride Procedure

Apparatus
500 ml. Kjeldahl boiling flask
Condenser with jacket - 300 mm
Kjeldahl connecting bulb - spherical - 48 mm
Rubber stoppers* to fit condenser and boiling flask.
Plastic tubing
500 ml Erlenmeyer flask
Boiling beads or chips

* Need to have holes bored in them to fit the glass ends of connecting bulb.

Reagents
Boric Acid Solution 40 grams per liter
NaOH pellets
0.5N HCL 41.7 mls. HCl per liter (standardize)
Methyl red/Bromcresol
Green Indicator Equal parts of methyl red solution and
bromcresol green solution mixed together

Methyl Red Solution Bromcresol Green Solution

0.10 g diluted to 100 ml. 0.10 gram dissolved in 20 ml.

with ethanol ethanol and then diluted to 100 ml. with water.
13
 Procedure

1) Set up equipment as per standard distillation (cold tap water through

condenser jacket).

2) In receiving flask (500 ml. Erlenmeyer), put 50 ml. boric acid solution plus 10
drops of methyl red/bromcresol green indicator.

3) Tube from condenser should extend below the surface of the boric acid
solution, but not touch the bottom of the flask.

4) In the boiling flask, pipette 10 ml. sample of bath. Add 150 mls. H 2O, a few
boiling beads and about 1 gram powdered pumice.

5) Quickly add 4 to 5 grams NaOH pellets to boiling flask and connect the bulb
to
the condenser.

6) Apply heat and gently boil the solution until 150 ml. of solution distills over into

receiving flask.

7) Carefully disconnect the bulb from the condenser (caution, very hot steam)
and then remove the source of heat.

8) Allow apparatus to cool somewhat, then rinse down the inside of condenser
with distilled H2O.

9) Titrate the contents of receiving flask with 0.5N HCl to a red endpoint.

10) Record mls. used.

Calculation:

(ml. HCl) x N HCl) x 53.4 = g/l Ammonium Chloride

10

(g/l x 7.5 = oz/gal Ammonium Chloride)

14
(Metric calculations)

5. Zinc Metal Procedure

Apparatus
2 ml pipette
25 ml graduated cylinder
50 ml burette
250 ml Erlenmeyer flask
Reagents
0.1M EDTA solution
0.880 Ammonia solution
Chloral Hydrate
Eriochrome or Solochrome Black T indicator

Procedure
1. Pipette 2 ml of the plating bath into a 250 ml Erlenmeyer
flask. Add 50 ml D.I. water.
2. Add 5 ml of 0.880 Ammonia solution.
3. Add 2 g of Chloral Hydrate.
4. Add a few specks of Eriochrome or Solochrome Black T
indicator. Mix to produce a violet colour.
5. Titrate immediately with 0.1M EDTA solution to a blue
endpoint.

Calculation
ml EDTA x 3.27 = g/l Zinc Metal

6. Total Chloride Procedure

Apparatus
1 ml pipette
50 ml graduated cylinder
250 ml Erlenmeyer flask
100 ml graduated cylinder
50 ml burette
Reagents
0.1N Silver Nitrate - Dissolve 16.99 grams of silver nitrate in
500 ml distilled water and dilute to 1000 ml in a volumetric
flask.
Chromate Solution - Dissolve 10 grams of potassium or
sodium chromate in 100 ml distilled water.

15
 Procedure
1. Pipette 1 ml sample into a 250 ml Erlenmeyer flask.
2. Add 50 ml distilled water
3. Add 5 ml of sodium chromate indicator to produce a
yellow color.
4. Titrate with 0.1N silver nitrate solution until permanent
reddish-brown coloration forms on the white silver
chloride precipitate.
Calculation:
ml 0.1N AgNO3 x 3.58 = g/l Total Chloride

7. Boric Acid Procedure

Apparatus
5 ml pipette
250 ml Erlenmeyer flask
Reagents
0.1N Sodium Hydroxide (NaOH) - To 4.0 grams of A.R.
Grade sodium hydroxide, add sufficient deionized or distilled
water to make 1 litre of solution. Standardize against a
sulfuric acid of a known normality.
Mannitol - A.R. Grade
Bromcresol Purple Indicator Solution - Dissolve 0.1 gram
of bromcresol purple solid dye in 18 ml of 0.01N sodium
hydroxide and dilute to 250 ml with deionized or distilled
water.
Procedure
1. Pipette 5 ml of plating solution into a 250 ml Erlenmeyer
flask.
2. Add about 5 grams of Mannitol.
3. Add 3 to 5 drops of Bromcresol Purple Indicator.
4. Titrate with 0.1N NaOH. The color change is yellow to
purple.
Calculation:

ml of 0.1N NaOH x 1.24 = g/l Boric Acid

16
VIII. Typical Process Cycle ( Barrel Plating)

1) Soak Clean

2) CWR

3) Electroclean

4) CWR

5)CWR

6) Acid Pickle

7) CWR

8) CWR

9) MacDermid Chloride Zinc Plate

10) CWR

11) CWR

12) Metex “IT”, 7.5 g/l, 27C, 20 sec.

13) CWR

14) Appropriate MACromate chromate

15) CWR

16) CWR

17) Dry

17
IX. Solution Maintenance

Zinc Metal - The required zinc metal content in the plating bath should be
maintained by adjusting the anode area. In most installations, anode area
should be adjusted to yield a maximum anode current density of 2.5 A/dm 2. Too
much anode area can cause an increase in zinc metal content in the plating bath
and an increase in brightener consumption. Low anode area can cause
coverage problems and the plating bath will require additions of zinc chloride
which increase operating costs.

Metex ChloroZinc Concentrate/Isobrite 460 or an approved grade of Zinc

Chloride can also be used to add zinc metal.

Zinc Chloride (ZnCl2) contains 48% zinc metal and 52% chloride ion by weight.
To raise the zinc metal content of a plating bath 7.5 g/l, add 15.6 g/l of dry zinc
chloride. This addition will raise the total chloride level in the plating bath by 8.1
g/l.

Total Chloride - The chloride derived from the salt additions are as follows:

Potassium Chloride (KCl) contains 48% by weight chloride ion. To increase the
total chloride level by 7.5 g/l, add 15.6 g/l of potassium chloride.

Ammonium Chloride (NH4Cl) contains 66% chloride ion by weight. An addition of

11.3 g/l of ammonium chloride will increase the total chloride level by 7.5 g/l.

Example 1 - A 5000 lt potassium chloride bath has a total chloride content of 105
g/l. We desire to raise the total chloride to 120. This requires an addition of 155
kgs of potassium chloride, calculated as follows:

(15 g/l increase) x (2.1 g required to raise Cl- 1 g/l) = 31 g/l of KCl
required

(31 g/l ) x 5000 ltrs = 155 kgs.

Chloride salts are readily soluble. The salts should be added to the tank slowly
with good mixing, to avoid localized high total chloride which can cause the
chloride zinc additives to oil out. With horizontal barrel machines, the chloride
salts may be added into the barrel and placed into the tank.

Proportional Additions

Potassium Chloride/Boric Acid Bath - Since the chloride and boric acid are
consumed mainly by drag-out, proportional additions allow the operator to
maintain the correct electrolyte content with less analytical work. For each 100
18
kgs of potassium chloride added, 15 kgs of boric acid should be added along
with a certain volume of Carrier (wetter) as given in the particular technical data
sheet. The chloride content should be analyzed daily and the boric acid and zinc
metal twice weekly.

Potassium/Low Ammonium Bath - For each 100 kgs of potassium chloride

added, add 15 kgs of ammonium chloride and the required Carrier. This will
maintain the ammonium chloride level at 30 g/l. The ammonium chloride content
should be tested weekly.
NOTE: Although Carrier additions are made proportionally with chloride salts,
they should not be made at the same time or in the same location. This is to
avoid “oil out” caused by localized high chloride. It is best to wait 30 minutes
after the chloride salts have been added and spread the Carrier slowly over the
tank.

pH - The pH should be checked twice each shift with a reliable meter and
adjusted as needed.

Brightener Additions - All of MacDermid’s chloride zinc brighteners are water

soluble and may be added directly to the plating bath without dilution. Automatic
ampere-hour feeders are recommended to maintain the brightness at a
consistent level. The Hull Cell is the best method to test the brightener level
(see pg. 18).

Carrier (Wetter) Maintenance - The chloride zinc carrier or wetter is controlled

partially by replenishing, proportionally with chloride salts. Hull Cells can serve
as an indication of wetter level (see pg. 18). MacDermid Inc. can analyze for the
wetter in their laboratories. In most installations, a wetter analysis every 2 to 3
months is sufficient.

19
X. Hull Cell Control

Test Parameters:

Current: 2 Amps (Rack)

1 Amp (Barrel)
Agitation: Air, Hull Cell Agitator or glass rod
Temperature: At temperature of plating solution
Time: 5 minutes
Post Dip: Metex IT,

1) Prior to running a Hull Cell, the bath chemistry should be analyzed and recorded.

2) A panel with the bath chemistry unchanged is then run and maintained.
This is known as the “as is” panel.

3) A new sample is added to the Hull Cell and the chemistry adjusted to the
recommended parameters. Adjustments are made to a 267 ml. Hull Cell as
follows:

a) To raise the zinc metal 1.0 g/l - add 0.5 ml Mirro MAC Chloro Zinc
Conc. This will also raise the total chloride approximately 1.0 g/l.
b) To raise the total chloride 1.0 g/l - add Potassium Chloride – 0.6 g.
or Ammonium Chloride – 0.4 g.
c) To raise the boric acid/ammonium chloride 1.0 g/l - add 0.3 g of
boric acid/ammonium chloride.

The pH should be adjusted to the recommended range and second panel

run.

4) If the Hull Cell panels display dullness in the low to mid current density range,
a brightener addition of 0.05% by volume (0.15 ml) should be added to the
Hull Cell and a third panel run.

If the panel displays high current density burning or striations, an addition of

0.5% (1.5ml) of Carrier should be added and a third panel run.

NOTE: As a safety measure, initially add one half the proportional Hull Cell add to
the plating tank.

The next page illustrates more Hull Cell panel interpretations.

20
Hull Cell Interpretation

NORMAL

Current: 2A, Time: 5 min., Temperature: 80F, Agitation: Air,

Post Dip: 7.5 g/l Metex IT

Panel A: Panel E:

Dull L.C.D. Mid C.D. Feathering

Panel B: Panel F:

H.C.D. Burn Black after bright dip

Panel C: Panel G:

XX
X
X X
X

H.C.D. Striations Dark L.C.

Panel D: Panel H:

L.C.D. Skip-Plate H.C.D. Blistering

21
I. Causes of Hull Cell problems (on previous page)

Panel A

Demonstrates dullness in low to middle current density range. May be caused

by:

1. Low brightener
2. Low total chloride
3. High pH

Panel B

Demonstrates burning (powdery deposit) in the high current density area.

1. Low boric acid (or ammonium chloride in low ammonia bath)

2. Low Carrier
3. High pH
4. Low zinc metal

Panel C

Demonstrates striations (gas streaks) in HCD area.

1. Low boric acid

2. Low Carrier

Panel D

Demonstrates skip plate (no plate) in extreme LCD area.

1. Metal contamination (Chrome)

2. Brightener overload
3. High pH

Panel E

Demonstrates feathering (cloudy streaks) in mid to high current density range:

1. Low Carrier

Panel F

Panel turns black after bright dipping.

1. Metal contamination (copper)

2. Brightener overload

22
Panel G

Demonstrates dark or black deposit in LCD area.

1. Metal contamination (cadmium, iron)

2. Brightener overload
3. Low total chloride

Panel H

Blistering or brittle deposit in high current density area.

1. Low Carrier
2. Low boric acid or ammonium chloride
3. High pH
4. High brightener

23
XI. Common Impurities and Treatments

Metallic Impurities

IMPURITY SOURCE TOLERABLE EFFECT TREATMENT

LIMIT

Aluminum 50 ppm Rough Deposit Filter low

micron size

Copper Bus bars 10-15 ppm Darkening of LCD dummy

deposit after bright (under 1.0 asd)
dip

Cadmium Impure or 5-10 ppm Dark plate LCD dummy

mixed anodes Zinc dust treat
1#/400 ltrs

Iron Dissolution 80 ppm Dark spots 30% hydrogen

(Barrel) peroxide
8 mls/100 ltrs

Lead Soldered parts 5 ppm Skip plating LCD dummy

Zinc dust treat
1#/400 ltrs

Chromium Cr+3 Chromates 20 ppm Rough deposit Filter out

insoluble
compound

Cr+6 Chromates 5 ppm Dull deposit Sodium

Skip plate hydrosulfite
Peroxide treat

Oils, Grease Drag-in Dull plate

Blistering deposit
Lack of brightener
response

24
Iron Contamination

IRON will be introduced into the plating bath from dissolution of steel parts. The
majority of the iron is removed by continuous filtration. The iron which remains in the
ferrous state must be oxidized and precipitated by treatment with hydrogen peroxide
(30%) at the rate of 8 mls/100 ltrs. of plating solution. This may be done while the bath
is operating. The optimum solution pH for treatment is 5.5 for boric systems 6.0 for
ammonium systems.

The peroxide should be diluted 5:1 with water and spread evenly over the top of the
tank. It is best to peroxide treat at the end of the work shift. Care should be taken to
minimize iron contamination. Other recommendations are:

1. Rake the bottom of the tank with a magnet to remove fallen parts, after each shift.

2. Keep the filter clean and operating at all times.

3. Do not allow work to stay in the plating bath with the current off.

Iron levels may be checked by atomic absorption or more practically by placing 3-5
drops of 30% hydrogen peroxide into a beaker of the plating solution and stir. The
presence of a brown, murky precipitate indicates iron is present and treatment is
required.

Carbon Treatment

Carbon Pack Filtration - Carbon filtration will remove most common organic impurities
effectively in chloride zinc solutions. Carbon filtration is recommended as a preventive
measure every 4 or 5 filter “break downs”. Simply pack the filter to the recommended
capacity with of mixture of 1:1 filter media and activated carbon.

Massive Treatment - If a plating bath became heavily contaminated with organic

impurities like oil, grease or extraordinarily high levels of brightener, a massive carbon
treatment may be required. The plating bath must be transferred to a liquid storage
tank. 0.5 kg of activated carbon per 100 ltrs of plating solution is then added to the
solution. The solution is next agitated with a propeller type mixer or by an air sparger
for 3-5 hours. The agitation is stopped and filter powder is sprinkled over the top of the
tank to form a blanket 20 mm high.

The solution is left to stand overnight. In the morning, the plating solution is filtered
back into the plating tank. Care must be taken to avoid allowing the filter intake to pick
up the settled carbon or clogging will occur quickly.

The bath must now be adjusted with brightener additives. Normally, half of the original
charge of brightener is required along with 0.25-0.75% by volume carrier. Exact
requirements should be determined by Hull Cell analysis.

25
Zinc Dust Treatment

A chloride zinc solution may be treated for metallic contamination with zinc dust in most
cases without pumping the solution out of the plating bath. Simply sprinkle zinc dust
0.5 kg per 4000 ltrs) over the top of the plating bath with vigorous air agitation. Metallic
contaminants will be displaced onto the zinc powder and be removed by the filter. The
plating tank should be allowed to filter for 2-3 hours and then the filter media should be
changed to remove the zinc dust so the contaminants are not redissolved. If high
levels of metallic impurities are present, it is advisable to pump the plating bath into a
storage tank for treatment. Agitate the zinc dust in the tank for 30 minutes. Allow zinc
to settle and filter solution over to the plating tank. A second treatment in the plating
tank may be required .

Electrolytic Purification

Electrolytic purification (dummying) is carried out using corrugated stainless steel

panels as cathodes at low current densities (0.1 – 0.3 amps dm 2). If corrugated panels
are not available, scrap work will suffice. In barrel baths, one or two barrels may be
loaded with work and used in place of panels. Dummying to remove metallics is done
in 6-12 hour intervals (overnight). Brightener additions may be required after
dummying.

26
XII. Troubleshooting Chart

The following is a list of problems that have been cited in chloride zinc solutions. The
problems may be evident using either Hull Cell evaluation or on the final plated parts.

CONDITION POSSIBLE CAUSE CORRECTIVE MEASURE

1. Dullness in low current Brightener too low Add to Hull Cell in 0.05%
density volume increments

High pH Adjust pH electrometrically to

recommended range

Total chloride too low Analyze and adjust to

recommended range
2. Burning in high current Current density too high Increase workload (area) or
density reduce current

Zinc metal too low Analyze and adjust

accordingly

High pH Adjust pH electrometrically to

recommended range

Poor agitation Check for dead spots with the

air agitation

Low boric acid/ammonium Analyze and adjust. Maintain

chloride boric acid/ammonium chloride
by proportional adds with
potassium chloride salts and
analysis

Low carrier Use Hull Cell to determine

addition required add in 0.5%
increments

Anode to cathode distance to Increase by removing anode

small (<150 mm) too close to work
3. High consumption of Salt additions are being made Add in different areas
brightener and poor throw in same area as brightener
in low current density area (localized salt out)
or overall dullness
Low total chloride Analyze and adjust

Brightener not mixed in bath Mix plating solution or install

air agitation

Low boric acid/ammonium Increase boric

chloride acid/ammonium chloride to
recommended range

27
4. Streaking or pitting in high High brightener Dummy - Reduce additions of
current density area brightener

Too high current density Reduce current

High total chloride Reduce chloride

Low boric acid/ammonium Increase boric

chloride acid/ammonium chloride
additions
Low Carrier
Add in 0.5% increments to
Hull Cell
Low pH
Increase to 5.0 (minimum)
5. Work turns black after Copper, lead or cadmium Zinc dust treat. 0.075 gm/l.
bright dip or blue bright contamination Check anodes for purity.
chromate Check barrel danglers for
exposed copper
6. Yellow or white streaks High plating current density Reduce current
after blue bright (near burning)
chromates

High brightener Dummy - Reduce additions

High chloride Reduce total chloride to 127-

135 gm/l

Foaming Reduce air agitation to a roll.

Place filter discharge below
solution level. Use approved
defoamer.

Contamination in chromate Dump chromate

Poor rinsing prior to chromate Improve rinsing. Use a bright

dip prior to chromating

7. Poor adhesion of yellow Too high plating current Reduce current

28
 chromate density

Brightener imbalance in bath Correct by Hull Cell analysis

High chloride Reduce chloride to 127-135

gm/l

High temperature in chromate Reduce temperature below

32oC

Too long immersion in Reduce time and/or chromate

chromate or too high concentration
chromate concentration

Poor rinsing and activating Improve rinsing. Use a bright

after zinc dip prior to chromate

Improper chromate Select a chromate more

suitable for use with chloride
zinc

8. Barrel hole burning (white High current in a barrel (over Reduce current
or gray spots) 1.0 amp/dm2

Anode to cathode distance Reposition anode bars

<150mm

Flat parts against barrel walls Add breakers to the barrel

load

Too many parts in barrel Reduce load size

Slow barrel rotation speed Increase rotation speed

Imbalance in bath chemistry Adjust bath chemistry

and brightener

Barrel perforations to small or Examine barrel perforations

peened holes

Low boric acid/ammonium Analyze and adjust

chloride concentration

9. Burning of parts, on the Anodes or anode baskets too Shorten anodes

29
 side or bottom of the long
racks
Too many anodes extending Remove or reposition anodes
beyond the racks

Current too high Lower current

Imbalance in bath chemistry Adjust bath chemistry

or brightener
10. Low plating rate and poor Low Carrier Add in 0.5% increments
covering power (low
efficiency) Low brightener Add in 0.05% increments

Low chloride Raise total chloride Check

drag-in/drag-out rate

Low current Raise current - Check anodes

for polarization

Low metal Increase metal to

recommended range adjust
anode area

Low temperature Raise temperature to

recommended range

Titanium basket polarized Use slab anodes Reduce

voltage to 9.5

Error in area calculation Check area calculation

11. No plate in low current Metallic contamination (lead) a) Electrolyze at low current
density range density for 12 hours

b) Zinc dust treat

Low Carrier Add in 0.5% increments

High pH Check and adjust to range

Hexavalent chromium Treat with hydrogen peroxide

contamination

High brightener Electrolyze and reduce adds

12. Blistering or flaking High brightener Reduce adds and electrolyze
deposit
High pH Check and adjust to range

Low carrier Use a Hull Cell to determine

correct addition required.
Add in 0.5% volume
increments

30
12. Blistering or flaking Low zinc metal Adjust to recommended
deposit (contd.) range

High boric acid Analyze and adjust

High total chloride Allow to drop or reduce by

dilution

Poor cleaning or acid Adjust cleaner concentration

activation prior to zinc plate temp., current density or cycle
time. Use 50% muriatic acid
with a compatible inhibitor
additive

Low temperature Increase to recommended

range.

Over-pickled work Reduce time in pickle or dilute

acid concentration

Oil or grease in plating tank Remove by skimming. Use

carbon pack or massive batch
treat if necessary

Leaded steel Use 4 oz/gal fluoride salts in

acid pickle prior to plating

Iron contamination Peroxide treat and filter

Current too high in plating Adjust to give proper current

bath density

Lead contamination a) Electrolyze at LCD

b) Zinc dust treat
13. White cloud in mid to Low brightener Determine addition required
high current density by Hull Cell test
range
Low carrier Use Hull Cell to determine
required addition (May require
1% or more)

Excessive air agitation Adjust air to a gentle roll, turn

air off overnights/weekends

Excessive air agitation in one Adjust air sparger

end of the plating tank
14. Poor throwing power Low total chloride Analyze and adjust

High pH Check and adjust to

recommended range

14. Poor throwing power High zinc metal Analyze and allow to fall to
31
 cont’d. recommended range.
Reduce anode area if
necessary

High temperature Cool bath to recommended

temperature range

Iron contamination Peroxide treat

Low boric acid/ammonium Analyze and adjust

chloride

15. Roughness Insolubles Filter, check anode bags

High current density area Increase load or reduce

current

Low anode area Maintain minimum 1:1 anode

to cathode ratio. Check
anode purity

Iron contamination Peroxide treat and filter.

Check flow rate on filter

High pH Adjust to recommended

range
16. Brittle deposit especially High brightener Reduce adds, electrolyze
in high and mid current
density range Low Carrier Add to Hull Cell in 0.5%
volume increments to
determine required addition

Low temperature Increase to recommended

range

High pH Lower to recommended range

17. Cloudy, turbid solution High brightener, low Carrier Add Carrier in 0.5%
increments in a Hull Cell to
determine required addition

Filtration problem Check filtration system

High chloride Reduce total chloride to

recommended range

Temperature too high Cool to recommended

temperature range

32
17. Cloudy, turbid solution High pH Lower as required
cont’d.
Tin contamination (75-100 Filter and electrolyze at low
ppm) current density

18. Dark barrel perforation Iron contamination Precipitate with hydrogen

marks on work or black peroxide
spots on parts

33
Hull Cell Troubleshooting Chart
(267 ml Cell)

CONDITION POSSIBLE CAUSE CORRECTIVE MEASURE

1. Dull deposit at 0.1 – 2.0 Low brightener Add brightener in 0.15 ml
amps / dm2 increments

High pH Adjust to range

Low chloride Analyze and adjust to

range

2. Dark band in deposit at Low carrier Add carrier in 1.5 ml

2 – 3 amps / dm2 increments

Low brightener Add brightener in 0.15 ml

increments

High pH Adjust to range

Low chloride Analyze and adjust to

range
3. Bright brittle deposit High brightener Add carrier in 1.5 ml
over 4 amps / dm2 increments

Low carrier Add carrier in 1.5 ml

increments

High chloride Analyze and adjust to

range

4. Soft, spongy or burnt Low carrier Add carrier in 1.5 ml

deposit over 5 amps / increments
dm2
Low zinc metal Analyze and adjust to
range

Low boric acid/ammonium Analyze and adjust to

chloride range

High pH Adjust to range

5. Thin deposit (0.1 –3.0 Low brightener Add brightener in 0.15 ml

34
 amps / dm2) increments

6. No deposit (0.1 – 5.0 High brightener Add carrier in 1.5 ml

amps / dm2 ) increments

High pH Adjust to recommended

range

35