Chapter - V Non-Electrolytic Deposition
Chapter - V Non-Electrolytic Deposition
Allow plating on articles of very complex shapes and plating through holes.
• The solution needs to contain a reducing agent so that the reaction can proceed:
Catalytic
surface
Metal solid + oxidation solution
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Types of Metal Deposition
• Electroless deposition
– E.g., nickel deposits. open-circuit using a
reducing agent
• Electroplating
– E,g, nickel deposited at cathode using external
d.c. power supply
• Immersion deposition
– E.g., steel nail in copper sulfate, open-circuit,
displaces copper metal from solution onto nail
Immersion deposition
• A displacement reaction occurs on the surface of the anode.
• The work piece (anode) dissolves to metal ions. Metal ions
in solution deposits at the cathode, in the absence of an
external power source.
• This is a spontaneous reaction, driven by the electrode
potential of the reaction.
Cu2+ + 2e Cu
anode cathode
E = + 0.337 V vs. SHE
Fe2+
Fe2+ + 2e Fe Cu2+
Fe Cu
E = 0.440 V vs. SHE
Cu
Overall reaction
Cu2+ + Fe Fe2+ + Cu Ecell = Ecathode Eanode = 0.737 V
Limitation of immersion deposition
Gcell = n F Ecell
n = number of electrons
F= Faradays constant, 96485 C
mol-1
Ecell = Ecathode Eanode
Although the term electro-less deposition broadly describes all
processes of metal and alloy deposition without an external
source of electrical current, it should be noted that this term is
commonly used the for autocatalytic deposition process.
The term electro-less deposition is used only for the
autocatalytic deposition processes. The development of electro-
less deposition is mainly connected with Ni or Cu deposition.
However, other electro-lessly depositable metals and/or alloys
such as Ag, Au, Co, Sn, AuSn, NiWP, etc. have also been studied
because of their important applications
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Typical thickness vs. time profiles
Deposit Electroplating
thickness
Electroless deposition
0
0 Time
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Properties of Electroless Deposition
17
Cont’d
•Alkaline hydroxide
Low build deposits about 0.5 μm (or less) in about 20 min and typically
operates at ambient temperature.
These deposits are typically fine-grain and exhibit good deposit integrity.
They are suitable for applications such as subtractive printed wiring
board.
To achieve thicker gold deposits, the use of a true electro-less gold bath is required. Such
baths are based on a reducing agent that provides the electrons necessary for the
reduction of gold ions absorbed on a gold substrate. The catalytic effect of metallic gold
promotes the process. This deposition reaction is called an autocatalytic process
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-cont’d-
For example, trace amounts of nickel ions are sufficient to cause a rapid
decomposition of the boro-hydride bath.
The Material Safety Data Sheets provided by the manufacturer should be read
carefully before using any plating products.
During the reaction, metal and reducing agents are depleted and
require replacement to continue the processing. The process is called
electroless because no external electrical power is applied. The term
autocatalytic is the technical term for the process.
The tumbling of part on part and glass bead on part creates kinetic
energy that serves to cold weld the spheroidal metal particles to the
substrate.
The diameters of the most commonly used glass beads are
nominally 5 mm, 1.5 mm , 0.7 mm, and 0.25 mm. The ratio of glass
beads to parts is about 1.5:1 by weight, but varies depending on the
part mass and geometry and on the coating thickness required
(greater thicknesses sometimes require a higher ratio of beads to
parts and the use of larger beads).
The barrels rotate at a surface speed of 43 to 75 m/min and at a tilt
angle of about 30° from horizontal
Glass beads are constantly reused and recycled through a glass bead
recovery and pumping system, which is part of the standard
mechanical plating equipment package
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Process Steps
The mechanical plating process requires a series of chemical
additions. The quantity depends on the total area of part surface.
The total area must be determined prior to each cycle.
All of the plating steps are performed in the same barrel, normally
without rinsing or stopping the rotation. The only exception is
removal of heavy oil or scale; these contaminants should be removed
before parts enter the plating barrel.
The first process steps include a series of chemical and metal
additions designed to mildly acid clean and activate the substrate and
then to apply a thin, uniform copper strike. The copper strike
provides a clean, galvanically receptive part surface.
The next step involves adding an "accelerator" or "promoter" agent,
which creates a chemical environment that controls the rate of
deposition and subsequent bonding of the plating metals.
A defoaming agent is used during the process to control foaming and
to prevent any associated loss of plating solution.
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-cont’d-
The plating metal is added as a dry, fine powder or a water slurry
containing the powder. Platers add metal in a series of steps and in
amounts proportional to the coating thickness desired.
Commercial plating thicknesses of 5 to 12.5 μm usually require two to
three additions of metal, while greater thicknesses or "galvanized"
coatings can demand eight or more.
Typical sequence of operations for mechanical plating:
1. Alkaline or acid pre-clean (if necessary)
2. Prepare surface
3. Copper strike
4. Add accelerator/promoter
5. Add plating metal