Electroless Deposition Processes and Applications

Chapter – V Non-electrolytic deposition
Chapter – V Non-electrolytic deposition
Jun 4, 2021 Chapter 5 1

Electro-less deposition
• Involves the oxidation of a soluble reducing agent which supports the cathodic deposition of metal on a catalytic surface
• This process uses only one electrode and no external source of electric current.
• Non-conductive surfaces (glass, ceramics, polymers, etc
 Excellent throwing power
 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:
• Metal ion + Reduction solution
Catalytic
surface
Metal solid + oxidation solution
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
• The deposits properties are difficult to control and the

deposit may be porous and poorly adherent.
• The rate of deposition declines with time and ceases

when the steel surface is completely covered with
copper.
• Hence, electroless deposition of metal is more

favourable. But, the surface needs to be catalytically
activated in order for the metal deposits to form.
Typically, What is in a Bath?
E.g., Electroless Ni-P
• Ions of the metal to be plated, e.g.
– Ni2+ (nickel ions) added as the chloride
• Complexant Other examples of reducing

– Acetate, succinate agents
• Formaldehyde
• Reducing agent • Hypophosphorus acid
– Hypophosphite ion = H2PO2- • Alkaline borohydrides
• Alkaline diboranes
• Additives
– Wetters, stabilisers, exhaltants, levellers, brightners, stress
modifiers…
The Electrochemical reactions
An open-circuit, redox process taking place

spontaneously on a single autocatalytic substrate.
Cathodic: Ni2+ + 2e- = Ni
Anodic: H2PO2- + H2O - 2e- = H2PO3- + 2H+
hypophosphite ion orthophosphite ion
Overall:Ni2+ + H2PO2- + H2O = Ni + H2PO3- + 2H+
Spontaneous reaction:Go =  48 kJ mol-1

Gibbs free energy change, Gcell
Gcell =  n F Ecell
Gcell > 0 , no spontaneous reaction

Gcell < 0 , spontaneous reaction
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
Typical thickness vs. time profiles
Deposit Electroplating
thickness
Electroless deposition
Immersion deposition (thin, porous deposits?)
0
0 Time
Properties of Electroless Deposition
• Must have an autocatalytic substrate

– To allow deposition to initiate and continue
• Constant deposition rate with time

– Typically 10-15 micron per hour
• Uniform deposit thickness

– Even on complex shapes
• Baths require good analytical control

– To maintain deposit thickness and composition
• Baths have a short lifetime

– Can be < 5 metal turnovers
– Spontaneous decomposition can occur – ‘bombing out’
Applications of Electro-less Deposition
 Printed circuits and resistors
 Temperature sensors
 Valves for fluid handling
 Moulds for plastic and glass
 Gears, crankshafts and hydraulic cylinders
 Magnetic tapes
 Coatings on aluminium (to enable this metal to be soldered)
 Corrosion-resistant coatings for components or structures
exposed to atmospheres or immersed in fresh or sea water
 Plating on plastics, e.g., car door handles and marine hardware
ELECTROLESS NICKEL PLATING
 ELECTROLESS NICKEL PLATING is used to deposit nickel without the
use of an electric current.
 The coating is deposited by an autocatalytic chemical reduction of
nickel ions by hypophosphite, aminoborane, or borohydride
compounds.
 Two other methods have been used commercially for plating nickel
without electric current, including immersion plating on steel from
solutions of nickel chloride and boric acid at 70 °C and decomposition
of nickel carbonyl vapor at 180 °C
 Immersion deposits, however, are poorly adherent and non-
protective, while the decomposition of nickel carbonyl is expensive
and hazardous. Accordingly, only electro-less nickel plating has gained
wide acceptance.
Cont’d
 Electro-less nickel plating has grown rapidly and now is an established industrial
process.
 Currently, hot acid hypophosphite-reduced baths are most frequently used to
plate steel and other metals, whereas warm alkaline hypophosphite baths are
used for plating plastics and non-metals.
 Borohydride-reduced baths are also used to plate iron and copper alloys
 Electroless nickel coatings are also frequently applied on aluminum to provide a
solderable surface and are used with molds and dies to improve lubricity and part
release.
 Because of these properties, electroless nickel coatings have found many
applications, including those in petroleum, chemicals, plastics, optics, printing,
mining, aerospace, nuclear, automotive, electronics, computers, textiles, paper,
and food machinery
Cont’d
Advantages
•Good resistance to corrosion and wear
•Excellent uniformity
•Solder-ability and braze-ability
•Low labour costs
Limitations
•Higher chemical cost than electroplating
• Poor welding characteristics due to contamination of nickel plate with nickel
phosphorus deposits
•Need to copper strike plate alloys containing significant amounts of lead, tin,
cadmium, and zinc before electro-less nickel can be applied
• Slower plating rate, as compared to electrolytic methods
17
Cont’d
Electro-less nickel solutions contain:
A source of nickel, usually nickel sulfate

 A reducing agent to supply electrons for the reduction of nickel
 Energy (heat)
 Complexing agents (chelators) to control the free nickel available
to the reaction
 Buffering agents to resist the pH changes caused by the
hydrogen generated during deposition
 Accelerators (exultants) to help increase the speed of the
reaction
 Inhibitors (stabilizers) to help control reduction
 Reaction by products
Electro-less copper plating
Electroless copper chemistry was first reported in the following

year by Narcus The first commercial applicability of electroless
copper was reported in the mid-1950s with the development of
plating solutions for plated-through-hole (PTH) printed wiring
boards.

Effect of solution temperature on the rate of
deposition

Effect of solution pH on deposition rate and deposit
phosphorus content

-cont’d-
Electroless copper plates much more slowly, and is a much more

expensive process, than electrolytic copper plating.
 offers advantages over electrolytic plating that make it the
method of choice in certain cases.
 Electroless copper plates uniformly over all surfaces, regardless
of size and shape, demonstrating 100% throwing power; and it may
be plated onto non-conductors, or on to conductive surfaces that do
not share electrical continuity.
 The ability to plate large racks of substrates simultaneously is also
an advantage in certain instances
-cont’d-
Typical electroless copper bath formulations will contain the following

ingredients:
•Copper salts
•Reducing agent (formaldehyde)
•Alkaline hydroxide
•Chelating agents (quadrol, EDTA, Rochelle salts, etc.)
• Stabilizers, brighteners, etc.

Typical process steps
1. Cleaning or cleaning/conditioning-3 to 5 min
2. Water rinse-30 sec to 2 min
3. Conditioning (optional)-3 to 5 min
5. Etch-2 to 3 min
7. Sulfuric acid, 10 to 15 percent by vol.-1 to 3 min
9. Activator pre-dip-1 to 2 rnin
10. Activator-4 to 7 min
11. Water rinse*-30 sec to 1 min
12. Post-activator-3 to 6 rnin
13. Water rinse’-2O sec to 1 min
14. Electroless copper-10 to 30 min

Choice of bath-Speed
Slow speed baths

Room temperature
1-2 millionths in./min (plating speed)
High speed bath
Room temperature-21 to 32' C
2-6 millionths in./min
High speed bath
Elevated temperature-36 to 60' C
2-6 millionths in./min

Temperature Vs rate of deposition

Chemical Parameters of Electro less Copper
 The chemical balance in any electroless copper formulation is

very important.
 The bath is designed to function most optimally when the
ratios of the ingredients to one another are close to the ratios
existent when the bath is initially made up.
 The main constituents to be monitored in any electroless
copper solution are copper metal, formaldehyde and
hydroxide (as sodium hydroxide, usually).
 Secondary to these main ingredients, but maybe requiring
periodic attention would be the chelating agent (or
complexor) and stabilizers

Deposit Properties
Plating Rate and Deposit Thickness-plating rate is a key characteristic
of an electroless copper plating bath. Plating rate and useful range of
deposit thickness dictate the specific applicability of a formulation.
Plating baths are typically categorized as low build, high (heavy) build, or
full build
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.
High (heavy) build deposits 2 to 3 μm in about 20 min and typically

operates at elevated temperature (35 to 55 °C), but room-temperature
formulations are also available. These baths are usually based on EDTA.
-cont’d-
 Full build typically deposits 25 μm or more of copper over a

more prolonged plating cycle of up to 15 h. The typical
temperature of operation is 55 to 80 °C.
 A fundamental requirement in developing this type of bath has
been the achievement and maintenance of deposit
characteristics such as
 High ductility and tensile strength,
 Fine grain structure,
 Low intrinsic stress, and so on throughout the thick deposit.
 The most critical deposit characteristics are ductility and tensile
strength, particularly at the elevated temperatures (260 to 288
°C,) employed in the printed wiring board assembly processes

-cont’d-
Purity, Density, and Electrical Properties-Typical acid-copper

electrolytic baths produce films of 99.9% purity, 8.92 g/cm3
density, and 1.72 μΩ· cm volume resistivity (at 20 °C) whereas
the printed wiring board industry standard for full-build
electroless copper is 99.2% purity (min), 8.8 ±0.1 g/cm3 density,
and 1.90 μΩ· cm (at 20 °C) resistivity (max).
Grain Structure. Because electroless copper deposition is
initiated on the randomly distributed catalyst particles on the
substrate, initial grain structure is largely determined by that
surface morphology.
Bath formulation is of course a strongly determining factor as
well, and it will control the grain structure as the deposit
thickness increases.

-cont’d-
Tensile Strength and Ductility-

Advances in electroless copper formulations, particularly for full-
build applications in printed wiring board applications, have
centered on achieving deposit mechanical properties,
specifically tensile strength and ductility, that ensure the needed
film reliability
Tensile strength of up to 490 MPa and elongation of up to 15%
can now be achieved ,although these properties are not
achieved from the same formulation.

Applications
Printed Wiring Boards (PWBs)-
-made by a subtractive process using base material, typically
epoxy-glass laminate, clad with electrolytic copper foil.
-substrate is drilled, after which electroless copper is plated
through the holes (and incidentally over the foil surface).
-electrolytic copper buildup and surface copper imaging (using dry
film) take place; the order of these processes defines the
fabrication process as either panel plating or pattern plating
Decorative Plating-on-Plastic (POP)
Functional POP (Electromagnetic Interference Shielding)
Hybrid and Advanced Applications-
 Molded Interconnect Devices
 Composite Connectors
 Multichip Modules
 Silicon Devices
Electro-less deposition of gold
 In recent years, an unconventional technique, electro-less
deposition, has become increasingly attractive, particularly in
the electronics industry where the use of nonconductive
substrates and the miniaturization of the circuitry presents
difficulties in using conventional techniques
 By definition, electroless deposition is the controlled
autocatalytic reduction of a dissolved metal by a dissolved
reducing agent at an interface. This process requires a
reducing agent to provide the electrons for the reduction of
the metal ion to the metal to be deposited on the metal
substrate.
 Electroless copper and electroless nickel are widely used
There is a growing interest in the electroless plating of gold
and, to some extent, other precious metals such as palladium
and silver.

Properties of Electro-less Gold Films
 Depending on bath chemistry, the color of electroless gold films varies
from pale yellow to dark brown; the surface texture can be matte,
semibright, or reflective.
 The purity of electroless gold deposits is 99.9% or better. This results in
a soft gold film of less than 90 Knoop hardness, suitable for soldering
and bonding.
 The density of the deposited metal is about 19.3 g/cm3.
 The grain structure, as observed by scanning electron microscopy
exhibits a relatively tight distribution of fine particles. The porosity of
such gold films depends on the thickness, but above 1.5 μm the deposit
is generally pore-free.
SEM micrograph of an electro-less gold film deposit

obtained using a cyanide-base system with potassium
boro-hydride as the reducing agent.
Deposit thickness, 1.5 μm. 5000×

Process Description
Deposition of gold without an external source Immersion plating process is the

of current can occur by a simple displacement displacement reaction between a less noble
reaction between two metals: metal (nickel) and a more noble metal (gold)
in an immersion gold bath:
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
-cont’d-
Thickness of gold as a function of time Thickness of gold as a function of time for an

for an immersion electroless gold autocatalytic electroless gold plating bath.
plating bath Theoretical curve at optimum conditions

Compositions and operating conditions for cyanide-base
electroless gold plating baths
 Potassium gold cyanide, KAu(CN)2, and

 potassium chloroaurate, KAuCl4--there is a growing interest in
using sodium gold sulfite in the formulation of cyanide-free
systems.
 Different reducing agents can also be used, and their activity
influences both the rate of deposition and the stability of the
bath.
 Other components of electroless gold baths include some
chelating agents, stabilizers, buffers, accelerators, and wetting
agents.

Process Variables and Parameters.
1. Gold Concentration. As the gold concentration decreases, the rate of
deposition also decreases. In order to keep the rate of deposition
constant, periodic addition of gold should be made in the form of a
gold salt. Replenishment can be made based on analysis data and/or
close monitoring of the quantity of metal deposited on the substrate.
2. Reducing Agent. The concentration of the reducing agent is almost as
critical as the concentration of gold. The decrease in the reducing
agent concentration is not only a function of the reduction of gold, but
also is affected by possible degradation reactions, such as those that
occur with sodium borohydride. The concentration level should be
frequently analyzed and adjusted.
.

Cont’d
3.Stabilizers. Free cyanide seems to have a beneficial effect on the
stability of most cyanide-base electroless gold baths. However, excess
amounts will overstabilize the bath and inhibit the deposition of gold
4.Contaminants. Organic and inorganic contaminants can have very

deleterious effects on electroless gold baths.
For example, trace amounts of nickel ions are sufficient to cause a rapid
decomposition of the boro-hydride bath.
Because of the effects of nickel, the use of an immersion gold coating of

about 0.25 μm over a nickel substrate is often recommended prior to
electroless gold deposition.

-cont’d-
5.Temperature. All electroless gold baths are temperature-

dependent. In general, the higher the temperature, the faster the
speed of deposition. An adverse effect of high temperature is bath
decomposition. High temperatures also cause rapid consumption of
reducing agents, creating the need for frequent replenishment.
6.Agitation. The rate of deposition of gold as well as the uniformity

of the gold film will be influenced by the agitation. Both the solution
and the workpiece can be moved to ensure good uniformity.
Agitation is also required to prevent localized heating and possible

decomposition of the solution.

-cont’d-
7.The effect of pH is particularly important when plating on pH-sensitive

substrates. For example, degradation of polyimide substrates will occur in
very alkaline baths. Alumina-ceramic substrates are also incompatible with
highly alkaline systems, and they should be treated in electroless gold baths
operating at neutral pH (such as sulfite gold baths, which have a pH of 8.0).
8.Surface preparation is a key issue in any deposition process. Cleaning

and activation of the gold substrate are necessary prior to plating in order
to prevent contamination and to enhance adhesion. When plating gold
directly over nickel or copper, the removal of the oxide layer is essential for
achieving excellent adherence of the gold film. In this respect, a flash of
nickel may be beneficial.
9.Processing Equipment. Because of their sensitivity to high
temperature and to contamination, electroless gold baths
should be run in carefully controlled equipment.
For operating very small units (3 gal or less), pyrex jars or

jacketed beakers are practical. For larger units, polypropylene
tanks or Teflon-coated stainless steel tanks are recommended.

Advantages of electro-less deposition of gold
· Uniform, thin gold films can be deposited over electrically isolated

tracks and bonding pads.
· Gold can be uniformly deposited on complex shaped and hollow
articles, provided there is adequate agitation of the solution and/or the
articles to be coated.
· Gold can be deposited on non-conducting substrates such as glass,
ceramics, polymeric materials, etc., provided the substrate is activated.
· Gold films resulting from electro-less deposition are 99.9% pure;
therefore, they have excellent electrical, soldering, and bonding
properties

Limitations
 The electroless gold deposition rate is generally slow. The

typical rate is 2 to 3 μm/h, compared to 10 or more μm/h for
electroplating baths.
 The chemistry of electroless gold baths is complex; the baths
require tight control because they are very sensitive to
operating conditions as well as to organic and inorganic
contaminants.
 Consequently, they have a shorter lifetime and are more
expensive to operate than conventional baths.

Applications
 Electroless gold finds its application primarily in the electronics industry, where
it is used for the metallization of conductors and insulators in printed circuit
boards .
 Appropriate to use electroless gold on electrically isolated tracks and bonding
pads that require uniform gold films, which are difficult to achieve by
electrolytic gold deposition.
 To achieve good ohmic contacts on III-V semiconductor materials such as
n-GaAs, InP, etc.
 Fabrication of multilayer ceramic packages to improve their brazing, soldering,
and wire bonding properties.
 For uniformly plating hollow articles that cannot be successfully plated by
electrolytic deposition because their shape results in bad electric field
distribution.
-cont’d-
Environmental Considerations. Spent electro-less gold baths should be

treated both for environmental reasons and for gold recovery. All major suppliers
of plating chemicals offer waste treatment guidelines that should be followed by
their customers, particularly those operating the cyanide systems.
Health and Safety Considerations. All electro-less gold baths contain

chemicals that can be harmful to the user's health if not handled safely. The use
of protective goggles, gloves, and lab coats is strongly recommended. The plating
solutions should not be swallowed. They should be stored in cool and well-
ventilated rooms and used under well ventilated hoods.
The Material Safety Data Sheets provided by the manufacturer should be read
carefully before using any plating products.

5.5 Electro-less Alloy Deposition
METALLIC NONELECTROLYTIC ALLOY COATINGS produced from aqueous
solutions are commercially used in several industries, including electronics,
aerospace, medical, oil and gas production, chemical processing, and
automotive.

-cont’d-
 Nonelectrolytic coating systems use two types of reactions to deposit
metal onto a part: electroless and displacement.
 The electroless or autocatalytic process uses reducing agents to
convert the metal from its metal salt. Displacement reactions use
oxidation and reduction of the base metal to deposit a thin coating of
metal.
 The advantage of using non-electrolytic alloy coating systems over
electrolytic is the uniformity of deposit in alloy composition and
thickness, the ability to perform bulk processing, and the ability to
produce unique catalytic coatings. These coatings are produced from
aqueous chemical processes by conventional aqueous pre-treatment
procedures
Electroless (Autocatalytic) Alloy Coatings
 Electrolessly produced metallic alloy coatings use a reducing agent to
cause the metal salts to be reduced onto an oxide-free part surface.
This reduction reaction proceeds until the part is removed from the
process.
 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 electroless process can be complex and involve several

simultaneous reactions producing hydrogen and electrical charge at
the interface. Through experience and good operating techniques
the plating operation can produce a uniform alloy with specific phase
structures and compositions.

Electro-less dispersion alloy coatings
 Electroless dispersion alloy coatings use the conventional electroless
reduction reaction process with a suspension of particles to produce a
deposit with unique macroproperties. These particles fall into two categories:
lubricants or hard load bearing particles.
 The soft particles contain powders of polytetrafluoroethylene (PTFE),
fluorinated carbons (CFx), and fluoride salts, whereas hard particles consist of
carbides, ceramics, insoluble powders, and diamonds.
 Dispersion coatings contain particles in the concentration range of 5 to 30%,
depending on the particle and wear system. These alloy coatings are used in
applications in which significant wear is present or repair and service are
difficult.
Displacement (immersion) alloy coatings
 Displacement (immersion) alloy coatings use the corrosion (oxidation)

of the base material to produce a galvanic (reduction) reaction
producing a thin alloy coating.
 This process is self-limiting and will stop when the oxidation reaction
of the base metal stops. Generally these coatings are very thin and
contain elements of the base material. These coatings are used
primarily in electronic applications.
 Immersion alloy deposition processes are easy to control and require
little metal replacement because of the very thin deposits produced.
 Displacement tin-lead solder processes are the exception, producing
thicker deposits requiring more frequent additions.
Types of Electro-less Alloy Plating Systems
1.Nickel-Phosphorus. Electroless nickel-phosphorus is the most
common nonelectrolytic alloy coating system. Electroless nickel has
been used since the early 1950s and continues to show the most growth
and development.
-used for control of wear and corrosion. An important property is the
amorphous structure in the as-plated condition and the ability to heat
treat the deposit by precipitation hardening to produce a crystalline
structure
2.Nickel-Boron. Another family of nonelectrolytic alloy coatings uses
boron-based reducing agents. These are classified by boron alloy
content.
-low-boron coatings are used in electronic applications as a
replacement for gold. The higher-boron coatings are used to provide a
hard surface to prevent galling in iron and nickel wear applications.

-cont’d-
3.Hypophosphite-reduced Cobalt alloy Coatings-Non-electrolytically
produced cobalt alloy coatings have been used in a limited number of
magnetic and wear applications. These coatings are produced from
sodium hypophosphite based solutions at a slightly alkaline pH range at
elevated temperatures.
4.Boron-reduced cobalt alloy coatings -are produced by a reduction
reaction of sodium boro-hydride or DMAB (Dimethylamine borane)
reducing agents. The deposits are harder and have higher melting points
than those alloyed with phosphorus. These coatings have not been
commercially available. They could be used in wear applications where
service at higher temperatures is required.
5.Ternary alloy coatings are used to provide higher performance in
specific properties over conventional electroless coating systems. By
incorporating a third element in significant or trace levels, the basic
structure and physical properties of the coating can be altered

MECHANICAL PLATING
 Method for coating ferrous metals, copper alloys, lead, stainless steel, and
certain types of castings.
 The process applies a malleable, metallic, corrosion-resistant coating of zinc,
cadmium, tin, copper, or aluminum; combinations of metals can be applied
as codeposits or as "sandwich" layered deposits.
 Mechanical plating has been used internationally for over 40 years and is
referred to by a variety of names, including peen plating, impact plating, and
mechanical galvanizing.
 Mechanical plating often can solve engineering, economic, and pollution-
related plating problems. It offers a straightforward alternative method for
achieving desired mechanical and galvanic properties with an extremely low
risk of hydrogen embrittlement
54
-cont’d-
Mechanical plating is accomplished at room

temperature, without the electrical charge
passing through the plating medium that is
necessary with electroplating or electro-
coating.
The metallic coating is produced by tumbling
the parts in a mixture of glass beads, metallic
dust or powder, "promoter" or "accelerator"
chemicals, and water.
The glass beads provide impacting and
hammering energy, which serves to pound the
metallic particles against the surfaces of the
parts.
The result is a tight, adherent metallic coating
produced by "cold welding" fine, powdered Cost comparison of mechanical
plating and electroplating.
metallic particles to the surfaces of parts.
Approximate costs shown are for
chemicals only and do not include
labor or overhead
Special advantages of the mechanical plating
Recent improvements in deposit quality, cost-effectiveness, and ease of

application have induced many finishing engineers to investigate and adopt
mechanical plating for certain applications. Special advantages of the
mechanical plating and galvanizing process are that it:
 Greatly reduces part susceptibility to hydrogen embrittlement
 Can be used to deposit a wide variety of metals in a broad range of coating

thicknesses
Consumes comparatively low amounts of energy
 Does not require the use of toxic chemicals
 Simplifies waste treatment
Provides greater uniformity of coatings (when used for galvanizing)

Hydrogen embrittlement
 The need to prevent hydrogen embrittlement was one of the major reasons for
the creation and use of mechanical plating.
 A critical concern in electroplating and other coating processes used on ferrous
parts is the embrittling effects of hydrogen absorbed by the part.
 The current used in electroplating acts to enhance the possibility of hydrogen
embrittlement—both because most electroplating generates hydrogen at the
cathode and because the negative charge acts to pull hydrogen into the part.
 Hydrogen embrittlement can cause sudden development of breaks or cracks in
highly stressed areas, with subsequent total rupture of the part or the assembly.
 The risk increases for parts that have high hardness from cold working or heat
treating, especially those made of high-carbon steels.

Mechanical Plating Equipment
 Mechanical plating is accomplished in mild steel or stainless steel
variable-speed tumbling barrels. process takes place at low (1 to 2)
pH, the barrels must be lined with an inert, abrasion-resistant
protective coating such asneoprene, polypropylene, polybutylene,
or urethane.
 The lining is usually applied at a thickness of 19 to 25 mm; thicker
linings may be used in high wear areas such as the inner base of the
barrel.
 Typical tumbling barrels have capacities of 0.04 to 1.13 m3, where
capacity is the total available working volume, which is typically
about 25 to 35% of the total volume.
-cont’d-
 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 plating beads -functions
 Assist cleaning and oxide removal through a mildly abrasive
scrubbing action
 Facilitate mixing and displacement of the chemicals
 Consolidate the metallic coating
 Protect and separate parts from one another, thereby preventing

edge damage
 Help push the plating metal into corners, recesses, and blind areas
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
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.
-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

-cont’d-
 The plating cycle is carried out at temperatures between 15 and 32 °C.
 A pH between 1 and 2 is required at all times to ensure proper
adhesion and a high plating efficiency.
 These temperature and pH conditions facilitate mechanical bonding
("cold welding"). The process has an efficiency of about 92%; that is,
approximately 92% of the plating metal added is actually plated on the
parts.
 The mechanical plating process usually takes about 45 min. At the
conclusion of the cycle, the slurry of glass beads, coated parts, and
water discharges into a vibrating surge hopper under the plating barrel.
 The capacity of this hopper should be large enough to accept the entire
load, thereby freeing the barrel to begin plating the next load.
 The slurry dumps onto a vibrating screen or magnetic separator. Water
sprays are used to wash and remove glass beads from the parts.

Specific Characteristics, Advantages, and Limitations
 Because of the dust or powder form in which metals are deposited,
the surfaces of mechanical coatings will have matte to medium-
bright luster. It is possible to achieve very smooth surfaces, but the
mirror like surfaces typical of electroplated parts cannot be
obtained.
 For this reason, mechanical plating finishes are considered to be
functional rather than decorative.
 Parts with holes and recesses that are difficult to electroplate to the
desired thickness usually can be properly plated via mechanical
plating.
 Parts with hole diameters as small as 0.78 mm even where the
depth of the hole is greater than the diameter--frequently can be
plated successfully.
 Mechanical plating is often more economical and more flexible for
parts that require special racking or special anode configurations to
electroplate recessed areas.
-cont’d-
 Powder metallurgy parts can be coated by mechanical plating

without prior sealing of their surfaces.
 Because mechanical plating solutions are generally chemically
consumed, little excess is available to be entrapped in the pores of
the substrate.
 The initial galvanically deposited copper strike will permeate such
pores, and the metal powder will fill and bridge them.
 the potential for hydrogen embrittlement is extremely low, any
pores in the part should not accumulate significant amounts of
hydrogen.

Quality Control
To ensure the quality of the mechanically plated parts, the operator must pay
constant attention to the coating adhesion, weight and thickness, consolidation,
uniformity, and general appearance and brightness.
The main causes of non-uniform appearance include:
Use of glass media in poor condition
Insufficient cleanliness of parts prior to plating
Insufficient burnishing time at the end of the plating cycle
Wet parts kept in surge hopper too long
Conductivity of water too high
Zinc added to cycle too quickly or in incorrect amounts.
Applicable Specifications. ASTM B 635, B 695, and B 696 are standard
specifications for mechanical plating.
Waste Treatment
Before choosing a wastewater treatment system for mechanical plating,
engineering and analytical data must be gathered. The preliminary work
should determine:
Treatment options for the metals in solution
Present and future flow rates, and batch collection volume

requirements
Water conservation possibilities
What is required to meet discharge limits
Availability and type of treatment chemicals
How sludge will be dewatered, dried, and disposed

-cont’d-
 Removal of heavy metals from mechanical plating effluent is

accomplished by precipitating metal hydroxides. This is done
routinely as long as the metal ions in the effluent are not complexed
and the pH is high enough to ensure optimum precipitation.
 Chromium presents a special problem when present as a chromate
(hexavalent state). Hexavalent chromium must first be reduced to
the trivalent state before standard precipitation can proceed. Sodium
metabisulfite or ferrous sulfate added at a pH of about 2 will reduce
the hexavalent chromium and allow the resultant trivalent chromium
to be combined with other wastes for regular precipitation.

Electroless Deposition Processes and Applications

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Electroless Deposition Processes and Applications

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Chapter – V Non-electrolytic deposition

Chapter – V Non-electrolytic deposition

Jun 4, 2021 Chapter 5 1

 Excellent throwing power

• Metal ion + Reduction solution

• The deposits properties are difficult to control and the

• The rate of deposition declines with time and ceases

• Hence, electroless deposition of metal is more

• Complexant Other examples of reducing

An open-circuit, redox process taking place

Cathodic: Ni2+ + 2e- = Ni

Anodic: H2PO2- + H2O - 2e- = H2PO3- + 2H+

hypophosphite ion orthophosphite ion

Overall:Ni2+ + H2PO2- + H2O = Ni + H2PO3- + 2H+

Spontaneous reaction:Go =  48 kJ mol-1

Gcell > 0 , no spontaneous reaction

Immersion deposition (thin, porous deposits?)

• Must have an autocatalytic substrate

• Constant deposition rate with time

• Uniform deposit thickness

• Baths require good analytical control

• Baths have a short lifetime

Electro-less nickel solutions contain:

A source of nickel, usually nickel sulfate

Electroless copper chemistry was first reported in the following

Jun 4, 2021 Chapter 5 19

Jun 4, 2021 Chapter 5 20

Jun 4, 2021 Chapter 5 21

Electroless copper plates much more slowly, and is a much more

Typical electroless copper bath formulations will contain the following

•Reducing agent (formaldehyde)

•Chelating agents (quadrol, EDTA, Rochelle salts, etc.)

• Stabilizers, brighteners, etc.

Jun 4, 2021 Chapter 5 23

Jun 4, 2021 Chapter 5 24

Slow speed baths

Jun 4, 2021 Chapter 5 25

Jun 4, 2021 Chapter 5 26

 The chemical balance in any electroless copper formulation is

Jun 4, 2021 Chapter 5 27

High (heavy) build deposits 2 to 3 μm in about 20 min and typically

 Full build typically deposits 25 μm or more of copper over a

Jun 4, 2021 Chapter 5 29

Purity, Density, and Electrical Properties-Typical acid-copper

Jun 4, 2021 Chapter 5 30

Tensile Strength and Ductility-

Jun 4, 2021 Chapter 5 31

Jun 4, 2021 Chapter 5 33

SEM micrograph of an electro-less gold film deposit

Deposit thickness, 1.5 μm. 5000×

Deposition of gold without an external source Immersion plating process is the

Thickness of gold as a function of time Thickness of gold as a function of time for an

Jun 4, 2021 Chapter 5 36

 Potassium gold cyanide, KAu(CN)2, and

Jun 4, 2021 Chapter 5 37

Jun 4, 2021 Chapter 5 38

4.Contaminants. Organic and inorganic contaminants can have very

Because of the effects of nickel, the use of an immersion gold coating of

Jun 4, 2021 Chapter 5 39

5.Temperature. All electroless gold baths are temperature-

6.Agitation. The rate of deposition of gold as well as the uniformity

Agitation is also required to prevent localized heating and possible