Outline Curriculum (5 lectures)

Each lecture  45 minutes

• Lecture 1: An introduction in electrochemical coating

• Lecture 2: Electrodeposition of coating
• Lecture 3: Anodizing of valve metal
• Lecture 4: Electroless deposition of coating
• Lecture 5: Revision in electrochemical coating
 Lecture 2 of 5

Electrodeposition of Coating
 Electrochemical Surface Engineering

• An electro-chemical reaction
• Cathode: Metals/alloys coatings
• Anode: Soluble or insoluble
• Conductive solution: ionic species
• Transfer of electrons
 An example of electroplating of copper
Power
Supply e-

Copper Steel
Anode Cathode

Main reaction
Cu2+ + 2e-  Cu
Other possible electrochemical reactions
At the cathode
Electrodeposition of copper Cu2+ + 2e-  Cu
Hydrogen evolution 2H+ + 2e-  H2

At the anode
Soluble anode
Dissolution of copper Cu  2e-  Cu2+
Insoluble anode
Oxygen evolution H2O  2e-  2H+ + 0.5 O2

Overall reaction
Cu2+ + H2O  Cu + 2H+ + 0.5 O2
Definition: Electron transfer reactions

• Oxidizing agent + n e- = Reducing agent

• Oxidizing agents get reduced

• Reducing agents get oxidized

• Oxidation is a loss of electrons (OIL)

OILRIG
• Reduction is a gain of electrons (RIG)
Typical steps in the electroplating of metals

1. Cleaning with organic solvent or aqueous

alkaline; to remove dirt or grease.
2. Is the surface is covered by oxides as a result of
corrosion, clean with acid.
3. Rinse with water to neutralise the surface.
4. Electroplate metals under controlled condition.
5. Rinse with water and dry.
6. Additional step: heat treatment in air or vacuum
environment
 What is the Job of the Bath?
• Provides an electrolyte
– to conduct electricity, ionically
• Provides a source of the metal to be plated
– as dissolved metal salts leading to metal ions
• Allows the anode reaction to take place
– usually metal dissolution or oxygen evolution
• Wets the cathode work-piece
– allowing good adhesion to take place
• Helps to stabilise temperature
– acts as a heating/cooling bath
 Typically, What is in a Bath?
e.g., Watts Nickel
• Ions of the metal to be plated, e.g.
– Ni2+ (nickel ions) added mostly as the sulphate

• Conductive electrolyte
– NiSO4, boric acid, NiCl2

• Nickel anode dissolution promoter

– NiCl2 provides chloride ions

• pH buffer stops cathode getting too alkaline

– Boric acid (H3BO3)

• Additives
– Wetters, levellers, brighteners, stress modifiers..
 Current efficiency
• pH changes accompany electrode reactions wherever H+ or OH- ions are
involved.

• In acid, hydrogen evolution occurs on the surface of cathode. This

will result in a localised increase in pH near the surface of the electrode.
2H+ + 2e-  H2
• In acid, oxygen evolution occurs on the surface of anode.
This will result in a drop of pH near the surface of the electrode.

H2O  2e-  2H+ + 0.5 O2

• pH buffer stops the cathode getting too alkaline. H+
– Boric acid (H3BO3) H2
Cathode
OH
H2O  H+ + OH
 Current efficiency
• Is the ratio between the actual amount of metal
deposit, Ma to that calculated theoretically from
Faradays Law, Mt.

Ma
Current efficiency   100%
Mt
 Parameters that may influence the
quality of electrodeposits
• Current density (low to high current)
• The nature of anions/cations in the solution
• Bath composition, temperature, fluid flow
• Type of current waveform
• the presence of impurities
• physical and chemical nature of the
substrate surface
An example of Current vs. Potential Curve
for electroplating of metal
Typical Recipe and Conditions
Watts Nickel
Component Concentration/g L-1
Nickel sulphate 330
Nickel chloride 45
Boric acid 40
Additives various
Temperature 60 oC
pH 4
Current density 2-10 A dm-2
 Faraday’s Laws of Electrolysis
Amount of material = amount of electrical energy

q [C]
n [mol] 
zF [C mol1 ]

n = amount of material
q = electrical charge
z = number of electrons
F = Faraday constant
Faraday’s Laws of Electrolysis:
Expanded Relationship
q
n n = amount of material
w = mass of material
zF
M = molar mass of material
I = current
w It t = time

M zF z = number of electrons
F = Faraday constant
 Current, Current density, Surface area

I
j
A
j = current density [mA cm-2]
I = current [A]
A = surface area of the electrode [cm2]
jelectroplate = electroplating current density (metal electroplate)
jcorrosion = corrosion current density (metal corrosion/dissolution)
 Faraday’s Laws of Electrolysis:
Average thickness

M .I .t w = weight (mass) of metal

w M = molar mass of metal
z .F I = current
t = time
M .I .t z = number of electrons
x
 .A.z .F
F = Faraday constant
x = thickness of plating
Faraday’s Laws of Electrolysis:
Average deposit thickness
M .I .t
x
 .A.z .F
The thickness of plate depends on:
- the current (I)
- the time for which it passes (t)
- the exposed area of the work-piece (A)
- a constant (M/AzF)
which depends on the metal and the bath
 Faraday’s Laws of Electrolysis:
Question - Nickel Plating
Nickel is plated from a Watts bath at
a current density of 3 A dm-2.

The current efficiency is 96%.

The molar mass of nickel is 58.71 g mol-1.
The density of nickel is 8.90 g cm-3.
The Faraday constant is 96 485 C mol-1.

What will be the averaged plating thickness

in 1 hour?
 Faraday’s Laws of Electrolysis:
Answer - Nickel Plating
Assume that the reaction is:

Ni2+ + 2e- = Ni

So, two electrons are involved for every Ni atom,

and z = 2

The current density used in plating nickel is

96% of the total current, i.e., 0.96 x 3 A dm-2.
 Faraday’s Laws of Electrolysis:
Answer - Nickel Plating
The average deposit thickness is given by:

M .I .t
x
 .A.z .F
1
(58.71 g mol )(0.96 x 3 A)(3600 s)
x 3 2 1
(8.90 g cm )(100 cm )( 2)(96485 C mol )

x  3.54 x10 cm  35.4 x10 cm  35m

3 4
 Summary
• Electrodeposition is a versatile coating technique.

• There is a high degree of control over deposit thickness.

• Many metals can be electroplated from aqueous baths.

• So can some alloys, conductive polymers and composites.

• Rates of electroplating can be expressed via Faraday’s

Laws of electrolysis.

Thank you for your attention!