Zinc and zinc alloy plating

Erik Galdames
Bach. of Eng.
E-46800 Xativa (Spain)
 Content
• Electroplating fundamentals
• Zinc plating
• Zinc plating coating properties
• Zinc plating hardware
• Zinc plating flow-chart
• Zinc plating process parameters
• Zinc plating process control
• Zinc alloy plating
• Zinc-nickel plating flow-chart
• Zinc-nickel process parameters
• Zinc-nickel process control
• Zinc and zinc-nickel plating performance
• Zinc and zinc alloy performance
 Electroplating. Fundamentals
• Faraday’s law:

m = electrodeposited mass (g): I = Current applied (A), t = time (s), M = Atomic weight (g) n =
interchanged electrons,
• Faraday’s law for thickness

e = electrodeposited thickness (µm) (g), j = current density (A/dm2), t = time (s), n =

interchanged electrons, d = element density (g/cm3).

• Theoretical performance. It is the expected performance according to Faraday’s law

expressed in percentage. Theoretical performance 100%
• Actual performance. It is the real performance taking into account physical constraints
(conductivity of the solution, heat losses, etc.) Actual performance < 100%
• Electrodeposition rate (µm/min.): Thickness of electrodeposited layer per unit of time
.
Electroplating. Fundamentals
 Electroplating. Fundamentals
FACTORS WITH AN INFLUENCE IN ELECTROPLATING
• Part geometry
• Position of anodes
• Position of cathodes
• Ratio cathode/anode
• Nature and surface condition of part
• Current density
• Agitation of electrolyte (bath)
• Temperature
• Concentration of metallic ions
• Concentration of hydrogen ions (pH)
• Additives (brighteners, surfactants, etc.)
 Electroplating. Fundamentals
 Current density
– The higher the current density, the higher the electrodeposited layer thickness
– Size of crystal formed is reduced, provided that current density is within limits
– If current density increases beyond practical limits, a more rugous film will be
electrodeposited
 Temperature
– Temperature generally favours electroplating processes. Less hydrogen is diffused on the
cathode (the part to be coated)
– If temperature and current density both increase, brighter deposits will be obtained
– If temperature increases and current density is not changed, the size of metallic crystals
will increase and consequently, rugosity of film will increase
– The higher the temperature, the higher the consumption of brighteners and other additives
in the bath
 Metallic concentration
– If the metal concentration is low, brighter deposits with fine crystals can be obtained. If
concentration is too low, layer thickness will be minimum
– If the metal concentration is too high, layers of higher roughness will be obtained
 Electroplating. Fundamentals
 Electroplated finishes are coatings of pure or allied metals by means of DC
 It is the reversed process produced in a battery. Electricity is generated by means
of ionic dissolution of metals in a battery
 In the case of electroplating processes metals are deposited from a ionic solution
by means of an electric current
 Electroplating processes follow Faraday’s law
– The quantity of an electrodeposited coating depends of the metal to be electrodeposited
(chemical equivalent)
– The higher the current, the higher the quantity of electrodeposited metal
– The larger the surface area to plate, the lower the quantity of electrodeposited metal
– The longer the electroplating process, the higher the quantity of electrodeposited metal
 Other factors
– The higher the conductivity of the bath, the higher the quantity of electrodeposited metal.
Type of electrolyte (acidic, alkaline)
– Temperature influences in the rate of metal electrodeposition
– Cleanliness of surface of the metal to be plated
– Content of impurities on the surface of the metal to be plated
 Zinc plating
 Electroplated zinc is widely used for coating steel parts for corrosion protection
 Zinc offers cathodic protection to steel due to a redox reaction. Zinc is rusted to
protect steel. As far as zinc is present, there will be cathodic protection against
corrosion
 If the zinc layer has cracks, steel will still be protected against corrosion
 This phenomenon does not occur with paints or with nickel and copper plating
where surface cracks or discontinuities allow corrosion to penetrate below the
surface and extend the corrosion under the coated surface and corrodes the base
mteal
 Zinc plating offers temporary corrosion protection
 Zinc also can be deposited in form of alloy with other metals such as nickel, iron,
cobalt and tin
 Zinc layers can be treated with chromic passivations and sealers, which increase
corrosion protection substantially (white and red rust). Zinc layers also allow further
lubrication, which changes the friction behaviour of metallic fasteners
 Nowadays, most of the passivation products do not contain Cr6+
 Zinc plating
 Zinc layers can be treated with chromic passivations and sealers, which increase corrosion
protection substantially (corrosion resistance to white and red rust). Lubrication with liquid or
solid lubricants is also possible. Lubrication changes the friction behaviour of the
electrodeposited surface completely, thus the properties of the coated part, especially in a
metallic threaded fastener
 Some years ago, it was common to see chromic formulations with Cr6+ for passivation
processes. Cr6+ is carcinogenic and has been prohibited for use in many industries. These
formulas were known as chromating or bichromating. Typical colours seen were:
– Yellow to bronze. Iridescent yellow
– Olive green
– Black
 Cr6+ was widely used by its corrosion protective properties, since it had self-healing effect, i.e.
sBadl scratches or superficial damage at microscopically level were self-repaired and corrosion
protection was maintained.
 Due to restrictions of use of Cr6+, the majority of passivation products are made of formulas
without Cr6+ (Cr6-free processes). They contain Cr3+ mainly. Typical colours:
– Transparent or clear, silver colour or bluish. Normally thin layer passivation
– Transparent iridescent with reddish, yellowish or bluish nuances. Known as thick layer passivation
– Yellow to bronze, iridescent yellow (not present in Europe)
– Black (not widely used)
 Cr3+ provides no self-healing effect and needs sealers or top-coats to increase corrosion
protection
 Zinc plating

Zn + transparent
passivation

Zn + transparent
iridescent passivation
 Zinc plating
 Surface preparation before coating mainly is:
– Chemical cleaning
– Rinse
– Acid pickling
– Rinse
– Anodic electrocleaning
– Rinse
– Acid activation (not used for acid zinc plating)
– Rinse
 Zinc plating has the following types of electrolyte
– Acid zinc plating
– Alkaline zinc plating
– Alkaline cyanide *
 Post-treatments
– Rinse
– Baking (for high tensile bolts > 10.9)
– Passivation (optional)
– Rinse
– Top-coats, sealers or lubrication (optional)
– *Not used anymore
 Zinc plating
 Acid zinc plating
 Widely used technology
 High plating efficiency > 90%
 Less quantity of H2 generated
 Faster electrodeposition
 Excellent covering power
 Poor throwing power
 Bright deposit, special for decoration purposes
 Less permeable to hydrogen effusion
 Poor thickness distribution
 Poor ductility
 Zinc plating
 Alkaline zinc plating
 Widely used technology
 Good plating efficiency > 60%
 More quantity of H2 generated
 Medium electrodepositing rate
 Less brighter deposit
 Good covering power
 Medium throwing power
 More permeable to hydrogen effusion
 Good thickness distribution
 Good ductility
 Zinc plating coating properties
 Layer thickness distribution
5 µm 20 µm 10 µm
5 µm

15 µm 8 µm

Long part The longer the part, the higher the Small part
differences in layer thickness between high
current /low current density areas

Recess areas are low current density

areas. Layer thickness is lower

Uneven coating layer thickness in low

current density areas wiith acid zinc plating.
Recess areas with poor layer thickness

Alkaline zinc plating Acid zinc plating

 Zinc plating technology
 Barrel zinc plating
 For small parts
 Bulk process
 Widely used and automated technology
 Good productivity
 Low labour cost
 Reproducible results
 Rack zinc plating
 For large parts
 Parts fixed on racks
 Widely used and almost totally automated technology
 Good productivity
 Higher labour cost if loading not automated
 Excellent appearance of coated parts
 Reproducible results, but effect of low/high current density
areas must be taken into consideration
Zinc plating hardware

Zinc plating line on barrel

Zinc plating hardware

Zinc plating barrel

Zinc plating hardware

Zinc plating line on rack

 Zinc plating hardware

ELECTROCLEANING

ACID ACTIVATION
ACID PICKLING

ZINC PLATING
ZINC PLATING

ZINC PLATING

ZINC PLATING

ZINC PLATING

ZINC PLATING

ZINC PLATING

ZINC PLATING
CLEANING

RINSE

RINSE
RINSE

RINSE

RINSE

RINSE

RINSE

RINSE
Typical lay-out of a conventional
ACID ACTIVATION

HOT AIR DRYING

zinc plating line on barrel.

COLD DRYING
PASSIVATION
Design may vary and may

TOP-COAT

SPINNING
include other additional baths or
RINSE

RINSE

RINSE

RINSE

RINSE

RINSE

RINSE
plating stations to increase
production (up to 20 plating
stations)
Hydrogen embrittlement relief is
done just after plating.
Passivation is applied after
hydrogen embrittlement relief

HYDROGEN EMBRITLEMENT RELIEF OVEN

Lay-out of a zinc plating line

 Zinc plating hardware

Ancillary tank
Plating
for zinc anode Reservoir
station
dissolution

Rectifier

Every plating station has its own

rectifier. An ancillary tank is
used for all stations to provide
the necessary amount of Zn
ions. A filter is used to filtrate
the plating solution

Lay-out of a zinc plating line

 Zinc plating flow-chart
CLEANING 2-STEP RINSE

RINSE YES
Hydrogen
embrittlement DRYING
relief?
ACID PICKLING
NO
BAKING

2-STEP RINSE ACID ACTIVATION

COOL DOWN

ELECTROCLEANING PASSIVATION

2-STEP RINSE 2-STEP RINSE

ACID ACTIVATION COLD DRYING

RINSE TOP-COAT

ZINC PLATING DRYING

 Zinc plating process parameters
Agent Temperature Process parameters Description

Cleaning Alkaline soak cleaner 50 to 60ºC Removal of soils (oil, grease, machining residues)

Acid cleaning HCl or H2SO4 with acid RT or 35ºC HCl = 10-25% Removal of rust
inhibitor H2SO4 = 10 – 15%

Electrocleaning Alkaline soak cleaner 60ºC to 70ºC NaOH: 50 to 100 g/L Cleaning l of soils not removed by previous steps
applied under current Current dens..: 5 to 10 A/dm2 (e.g. fingerprints,

Acid activation HCl RT 5% Activation of the surface prior to coating

Zinc plating Zn 20º to 28ºC Zn: 7 to 10 g/L Plating

NaOH NaOH: 110 to 120 g/L
(alkaline non-
Carriers Current density: 1 to 2 A/dm2
cyanide) Brightener Voltage: 5 to 10 V
t = 50 to 60 min.
Carriers and brightener acc. to
formulator

Baking -- 200ºC to 220ºC > 4 h (1 h max. within Removal of hydrogen introduced by acid pickling
electroplating and baking) and electroplating itself. Applicable to high-
strength fasteners P.C. ≥ 10.9 and 1000 N/mm 2

Acid activation HNO3 RT 1% Previous step to passivation

Passivation Cr containing acidic RT or Conc. depending on formulator Increase of corrosion protection (white rust
solutions 35ºC to 60ºC pH 1,3 to 2,5 prevention), colour (silver, silver iridescent, black,
yellow

Top-coat Organic and mineral based Mainly RT, up to 50ºC Depending on formulator Enhancement of corrosion protection of metallic
alkaline solution pH slightly alkaline coatings. Integrated solid lubrication (optional)

Typical process parameters of zinc plating on barrel. They can be

different according to the needs of the plater
 Zinc plating process control
 Characteristics to be checked
 Concentration of cleaner, temperature, filtration and oil skimming
 Concentration of acid pickling bath, pollutants such as Zn and Fe. Inhibitor performance
> 90%
 Anodic electrocleaning must be used for fasteners. Temperature
 Concentration of Zn, NaOH of zinc plating bath
 Temperature of zinc plating bath
 Current density. Current and voltage of rectifiers
 Plating time
 Hull cell to control additives (carriers, brighteners)
 Automated dosing of chemicals
 Filtration of the zinc plating bath
 Ratio cathode/anode
 Alkaline vs. acid electrolyte for hydrogen embrittlement avoidance
 Hydrogen embrittlement relief for high-strength fasteners mandatory (P.C. >10.9 bolts
and parts with Rm ≥ 1000 N/mm2
 Concentration of passivation, pH, pollutants (mainly Zn, Fe), temperature
 Efficiency of rinsing operations. Concentration of pollutants. Use of flow-meters
 Zinc alloy plating
 Zinc allows its electrodeposition as an alloy with other
metals such as cobalt, nickel, iron and tin
 The most widely used are zinc-iron, zinc-nickel and also tin-
zinc.
 Zinc-iron. It consists of an alloy of zinc and iron with a content of
Fe of 0,3 to 0,8% approximately. It allows Cr3-free black
passivation and also transparent passivation, though black
passivation is widely used. Medium corrosion protection. This
finish is not longer preferred
 Zinc-nickel. It consists of an alloy of zinc and nickel with a 12%
to 15% Ni content. Excellent corrosion protection even on high
temperature conditions (vehicle compartment applications). It
allow Cr3-free transparent and black passivations. Good base for
e-coat paints. High temperature resistance. High ductility after
bending and crimping operations
 Tin-zinc. It consists of an alloy of zinc and tin (Sn 70% Zn 30%).
Excellent corrosion protection. Very good weldability and
electrical conductivity
 Zinc-Nickel plating flow-chart
CLEANING 2-STEP RINSE

RINSE YES
Hydrogen
embrittlement DRYING
relief?
ACID PICKLING
NO BAKING

2-STEP RINSE
COOL DOWN

ELECTROCLEANING PASSIVATION

2-STEP RINSE 2-STEP RINSE

ACID ACTIVATION COLD DRYING

RINSE TOP-COAT

ZINC-NICKEL PLATING DRYING

 Zinc-Nickel plating process parameters
Agent Temperature Process parameters Description

Cleaning Alkaline soak cleaner 50 to 60ºC Removal of soils (oil, grease, machining
residues)
Acid cleaning HCl or H2SO4 with RT or 35ºC HCl = 10-25% Removal of rust
acid inhibitor H2SO4 = 10 – 15%
Electrocleaning Alkaline soak cleaner 60ºC to 70ºC NaOH: 50 to 100 g/L Cleaning l of soils not removed by previous
applied under current c.d.: 5 to 10 A/dm2 steps (e.g. fingerprints,

Acid activation HCl RT 5% Activation of the surface prior to coating

Zinc-Nickel Zn 20º to 28ºC Zn: 8 to 11 g/L Plating

plating NaOH Ni: 1,9 to 2,3
(alkaline) Carriers NaOH: 110 to 130 g/L
Brightener c.d.: 1 to 2 A/dm2
t = 120 to 160 min.

Baking -- 200ºC to 220ºC > 4 h (1 h max. within Removal of hydrogen introduced by acid
electroplating and baking) pickling and electroplating itself. Applicable to
high-strength fasteners P.C. ≥ 10.9 and 1000
N/mm2

Passivation Cr containing acidic RT or Conc. depending on Increase of corrosion protection (white rust
solutions 35ºC to 60ºC formulator prevention), colour (silver, silver iridescent,
pH 1,3 to 2,5, depending black, yellow
on type of passivation

Top-coat Organic and mineral Mainly RT, up to Depending on formulator Enhancement of corrosion protection of
based alkaline solution 50ºC pH slightly alkaline metallic coatings. Integrated solid lubrication
(optional)

Typical process parameters of zinc-nickel plating on barrel. They

can be different according to the needs of the plater
 Zinc-nickel plating process control
 Characteristics to be checked
 Concentration of cleaner, temperature, filtration and oil skimming
 Concentration of acid pickling bath, pollutants such as Zn and Fe. Inhibitor performance > 90%
 Anodic electrocleaning must be used for fasteners. Temperature
 Concentration of Zn, Ni, NaOH of zinc-nickel plating bath. Use of AAS (Atomic Absorption
Sprectroscopy) for analysis of metal content
 Temperature of zinc-nickel plating bath(use of heat exchangers)
 Current density. Current and voltage of rectifiers
 Plating time
 Hull cell to control additives (carriers, brighteners)
 Automated dosing of chemicals
 Filtration of the plating bath
 Ratio cathode/anode
 Turnover (recycling of bath to maintain homogeneous concentration)
 Removal of carbonates (chiller or membrane technology)
 Alkaline vs. acid electrolyte for hydrogen embrittlement avoidance. Acid electrolyte for parts made of
cast iron and high-carbon steel
 Hydrogen embrittlement relief for high-strength fasteners mandatory (P.C. >10.9 bolts and parts with
Rm ≥ 1000 N/mm2
 Concentration of passivation, pH, pollutants (mainly Zn, Fe), temperature
 Efficiency of rinsing operations. Concentration of pollutants. Use of flow-meters
 Zinc and zinc-nickel plating performance

Zn Zn Zn ZnNi ZnNi ZnNi

Coating Zn+transp. Zn+passiv. Zn+thick layer ZnNi+transp. ZnNi+transp. ZnNi+black

passivation transp.+sealer passivation passivation passivation passivation
Layer thickness 8 µm 8 µm 8 µm 8 µm 8 µm 8 µm

NSS WR 24 120 h 72 h 96 h 120 h 96 h

NSS RR 144 h 240 h 144 h 720 h 720 h 720 h

Colour Silver Silver Iridescent yellow Silver Silver Black

Cr6+ No No No No No No

Hydrogen Yes Yes Yes Fair Fair Fair

embrittlement
risk
Temp. Resistance 80ºC 100ºC 80ºC 150ºC 150ºC 150ºC

Multi-tightening NO Conditional No No Conditional No

Sealing No Yes No No Yes Yes

Cost + ++ + ++++ ++++ ++++

 Zinc and zinc alloy properties
Properties of zinc and zinc alloy coatings Alkaline zinc Alkaline zinc nickel Alkaline zinc-iron

Properties Appearance Good Good Good

Weldability Fair Fair Fair
Wear resistance Fair Good Fair
Ductility Fair Fair Fair
Corrosion protection White rust Fair Excellent Excellent
(as plated) Red rust Fair Excellent Good

Corrosion resistance White rust Low Good Low

(after thermal Red rust Low Good Low
conditioning)

Corrosion resistance White rust Fair Good Fair

(after bending) Red rust Fair Good Fair
Characteristics of Distrib. (min./max) Good Excellent Good
electrolyte Plating efficiency Fair Low Fair
Covering power Fair Fair Fair
Bath control Good Fair Fair
Analysis and X-ray fluorescence Good Good Good
measurement Magnetic induction Good Bad Fair
techniques Coulometric Good Good Good
Alloy content % Good --
(X-ray fluorescence)
--
 Summary
 Electroplated zinc provides cathodic protection to steel parts. It
provide medium term corrosion protection
 Zinc can also be electrodeposited as an alloy to provide better
corrosion protection
 Zinc-nickel and tin-zinc can provide excellent corrosion protection
compared to pure zinc
 Zinc-nickel is widely used in the automotive industry
 Tin-zinc is used in welding applications and where conductivity is
important. It is used in aerospace industry
 Zn, ZnNi, SnZn provide good electrical conductivity
 Good (pure and tin-zinc) to fair weldability (zinc-nickel)
 Zn, ZnNi provide uniform coating distribution except on large parts
(high-current density areas)
 Risk of hydrogen embrittlement on high-strengh fasteners (≥ 10.9
bolts or parts with tensile strength > 1000 N/mm2). Necessary to
apply hydrogen embrittlement relief processes