Electroplating/

Electrodeposition

Wei Yan

ABC’s of Electrochemistry

03/22/2012
 OUTLINE

• Introduction

• Electroplating Setup

• Importance of Electrodeposition

• Electrochemistry Fundamentals

• Factors affecting the Electrodeposits

• University
Ohio Conclusions
- Avionics Engineering Center 2
 Introduction
Definition
Electroplating? Electrodeposition? Electrolytic deposition?

• Electroplating is often also called "electrodeposition,” a short version of

“electrolytic deposition,” and the two terms are used interchangeably.

• It’s a process using electrical current to reduce cations of a desired

material from a solution and to coat the material as a thin film onto a
conductive substrate surface.

Reference:
http://electrochem.cwru.edu/encycl/art-e01-electroplat.htm

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 Electroplating Setup
Electrolytic Cell
1. Is the core part of the
electroplating.
2. Cathode: the object to
be plated
3. Anode: (1)dissolvable
anode (2) inert
anode
4. Electrolyte/plating
bath
Reference: http://electrochem.cwru.edu/encycl/art-e01-electroplat.htm
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 Table =The metals can be plated

Part of Periodic Table. Metals inside the frame

can be electrodeposited from aqueous solutions
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 Importance of Electrodeposition
Applications
• 1. Decoration: Coating a more expensive metal onto a base metal
surface in order to improve the appearance. Such as jewelry,
furniture fitting
• 2. Protection: Corrosion-resistant coatings such as chromium
plating of automobile parts
• 3. Electroforming: Manufacture of sieves, screens, dry shaver
heads and dies.
• 4. Enhancement: coatings with improved electrical and thermal
conductivity, reflectivity etc.
In CEER,
Electrodeposition of Metals in Catalyst Synthesis

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 Electrochemistry Fundamentals
A typical electroplating setup for plating copper one mistake?

Anode Cathode

Anode Cathode

Reference: http://chem1.eng.wayne.edu/~yhuang/Papers/Book_Plating_ECHP

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 Electrochemistry Fundamentals

Anode and Cathode

• Cathode:

Cathode Reduction reaction

• Anode:

Anode Oxidation reaction

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 Electrochemistry Fundamentals
Faraday’s Laws of Electrolysis
According to the Faraday’s first law and second law of
electrolysis, the amount of material deposited on an
electrode is proportional to the amount of electricity used.

m is the number of moles of the metals

reduced by charge Q;
F is Faraday constant
Mw is the atomic weight

W is the weight of deposit

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 Electrochemistry Fundamentals

Current Efficiency, and Current Distribution

• Current efficiency = 100 * WAct/WTheo
Wact is the weight of metal deposited or dissolved
WTheo is the corresponding weight to be expected from Faraday’s
laws if there is no side reaction.

Cathode efficiency

Anode efficiency

Current distribution

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 Electrochemistry Fundamentals
Overpotential and overvoltage
• Overpotential is the difference in the electrode potential of
an electrode between its equilibrium potential and its
operating potential when a current is flowing.
• It represents the extra energy needed to force the
electrode reaction to proceed at a required rate.

• A slow reaction will require a larger overpotential for a given

current density than a fast reaction.

Reference : http://chem1.eng.wayne.edu/~yhuang/Papers/Book_Plating_ECHP

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 Electrochemistry Fundamentals
Overpotential and overvoltage
• Overvoltage is the difference between cell voltage and the
open circuit voltage (OCP) when a current is flowing.
• It represents the extra energy needed to force the cell
reaction to proceed at a required rate.

• The overvoltage is the sum of the overpotentials of the two

electrodes of the cell and the ohmic loss of the cell.
Unfortunately, the terms overvoltage and overpotential are
sometimes used interchangeably.
.

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 Electrochemistry Fundamentals

How to determine the potential of deposition

Fig. Typical voltammogram for a single-metal deposition

Reference: http://electrochem.cwru.edu/encycl/art-e01-electroplat.htm

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 Electrochemistry Fundamentals

• How to determine the potential of deposition for two metals

codeposition ?
Key point- the onset of the reduction peaks in CV
(1) If the two reduction peaks of metals are not separated, both
of metals can be reduced when operating potential is more
negative than the onset potential.
(2) If the two reduction peaks of metals are clearly separated,
both of metals can be reduced (codeposition) at a more
negative potential than onset potential of the less noble
metal

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 Electrochemistry Fundamentals

How to determine the potential of deposition

E < -0.75 V, cathodic deposition

-0.75V <E< -0.3V double layer

response

E > -0.3V anodic dissolution

Fig. CV for Ni-Co codeposition in the plating bath containing 0.06M NiCl2 and
0.06M CoCl2 at 25C.
Reference: Chi-chang Hu and Allen Bai, J.Electrochem.Soc. 149(615) 2002

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 Electrochemistry Fundamentals
How to determine the potential of deposition

E < -1.00V Fe and Ni

codeposition

-1.00V <E< -0.6 V Ni only

deposition

Fig. CV for Ni-Fe codeposition in the plating bath containing 0.06M NiCl2 and
0.06M FeCl2 at 25C.
Reference: Chi-chang Hu and Allen Bai, J.Electrochem.Soc. 149(615) 2002

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 Factors affecting the Electrodeposits

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 Factors affecting the Electrodeposits

• Surface Preparation

• Physical & chemical nature of substrate surface

• Deposition temperature

• Deposition current / deposition potential

• Bath composition

• Power supply current waveform

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 Factors affecting the Electrodeposits
Surface Preparation
“ one can make a poor coating perform with excellent
pretreatment, but one cannot make an excellent coating
perform with poor pretreatment”

Three basic steps:

1. Surface cleaning – chemical way and mechanical way
2. Surface Modification
3. Rinsing

Reference: http://electrochem.cwru.edu/encycl/art-e01-electroplat.htm

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 Factors affecting the Electrodeposits
Deposition current
Current density of deposition can make an influence on

(1) Current efficiency

(2) Thickness of deposit

(3) Structure of deposit

(4) Composition of deposit

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 Factors affecting the Electrodeposits
Deposition current- Example

Reference: M.J.Rahman, S.R.Sen. J. Mechanical. Engineering. 40(1) 2009

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 Factors affecting the Electrodeposits
Bath composition and additives
• Ingredients of a Plating Bath
(1) Metal salt solution-To provide a source of the metal or metals being
deposited.
(2) Various Additives

• The purposes of Additives:

1.To form complexes with ions of the depositing metal
2. To provide conductivity.
3. To stabilize the solution e.g. against hydrolysis.
4. To act as a buffer to stabilize the pH.
5. To modify or regulate the physical form of the deposit.

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 Factors affecting the Electrodeposits
Bath composition and additives- Example

without boric acid with boric acid

Apart from a buffer, boric acid can inhibit zinc deposition

and promote nickel discharge
Reference: M.J.Rahman, S.R.Sen. J. Mechanical. Engineering. 40(1) 2009
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 Factors affecting the Electrodeposits
Power supply current waveform
• Types of current : (1) Direct current plating (2) Pulse plating

In dc-plating, constant current is used, and the rate of arrival of metal ions
depends on their diffusion coefficient (electrode-to-part spacing and agitation).

• The pulse current (PC) and pulse-reverse current (PRC) are used to get the
deposit with reduced porosity, and finer grains , and to minimize the use of
additives and , contamination, etc.

• The morphology of some metal and alloy deposits were found to be superior to the
dc-plated deposits.

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 Factors affecting the Electrodeposits
Power supply current waveform
• Characteristics of Pulse Currents (PC)

• PC, where all the pulses are in one

direction (with no polarity)

Each pulse consists of an ON-time (TON)

during which potential /current is applied,
and an OFF-time (TOFF) during which
zero current is applied

Reference: M.S. Chandrasekar, M. Pushpavanam. Electrochim Acta 53 (2008)

3313–3322

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 Factors affecting the Electrodeposits
Power supply current waveform
• Characteristics of PRC
• PRC, where anodic and cathodic pulses
are mixed.
• To characterize a train of pulse-reverse
current waveform, key parameters need
to be known.
(1) The cathodic peak pulse current
density (Ic); The cathodic pulse length
(Tc)
(2) The anodic current density (IAA); The
anodic pulse time (TAA)
(3) IA = (Ic x Tc + IAA TAA) / (Tc + TAA)
Reference: M.S. Chandrasekar, M.
average current density
Pushpavanam. Electrochim Acta 53 (2008)
3313–3322 (4) T is the cycle time

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 Electrochemistry Fundamentals

E < -1.00V Fe and Ni

codeposition

-1.00V <E< -0.6 V Ni only

deposition

Fig. CV for Ni-Fe codeposition in the plating bath containing 0.06M NiCl2 and
0.06M FeCl2 at 25C.
Reference: Chi-chang Hu and Allen Bai, J.Electrochem.Soc. 149(615) 2002

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 Conclusions

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 Conclusions

1. “Electroplating/ Electrodeposition: historically old,

technologically advanced” D.Gabe said.

2. The purpose of electroplating is to produce a qualified coating

with the desirable attributes. Each kind of coating needs a
special electroplating process with a given application.

3. It is easy to get the coatings of metals, but it is not easy to get

the coatings with good quality. Key points are those factors
affecting the electrodeposits, which is crucial for the final
deposits.

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Questions?