DEVICE CORROSION

Enumerate the electrical contact degradation and the types of mechanism involved in it.

Electrical contacts in electromechanical devices must maintain low contact loop resistance to avoid
power losses at the interfaces. Contamination and corrosion of exposed contact surfaces can occur
through outgassing of volatile species from surrounding materials. Modification of surface layers can
also occur through oxidation or segregation of contact alloy constituents. Low contact resistance values
are obtained by using bare metal surfaces, which are easily degraded by reaction with adsorbed species.

Clean electrical contacts are generally maintained by controlling the atmosphere in hermetically sealed
devices, a method that is not totally effective for extended life applications. Production processes
themselves often leave behind sources of contamination for the electrical contact surfaces, such as the
solder on the circuit board surface seen in the figure shown here. (reference)

Sulfur rich environments are common at industrial facilities such as petroleum and chemical plants,
refineries, paper and pulp recycling plants, sewer and wastewater plants. Such atmosphere produced by
various chemical technologies causes a serious corrosion problem for many metals used in electrical
apparatus.

An Electrical Connector is a device which bridges two or more points in an electric circuit without itself

having significant resistance. It usually insulates as well, isolating one part of a circuit from

another. Connectors take various forms, and range in size from those which serve power

distribution lines to the miniature variety of electronic circuits for signal transmission.

An Electrical Contact is the current-carrying part of a connector having an interface, usually solid-solid
between metals. Contacts may be primarily static or dynamic, depending on their function while
carrying current. Dynamic contacts include slip rings. Static contacts may be separable, like those of the
pin-in-socket connector, or permanent, like the solder contact, the evaporated film contact, and the
contacts in crimp and wire wrap connections.

Corrosion in electrical contacts: Corrosion is most concerned with the degradation of separable
contacts exposed to the atmosphere, in which closure is made by pressure. Hardware examples are
relay which switches current, and printed circuit board and mating connector.
Trends in Electronic Equipment that Affect Contacts

(a) Miniaturization: High contact pressures and large wipes on contact closure cannot as readily be
obtained with miniature as with larger connectors. Surfaces, therefore, must be maintained
film-free. The difficulty of obtaining clean surfaces, mainly because of air pollution, limits
connector miniaturization.
(b) Gaseous pollutants that attack metal surfaces
Tarnish—Tarnish films are relatively uniform. They can grow at low relative humidity by
mechanisms closely related to oxidation. Copper, silver, their alloys, and many other metals are
sulphided by H2S and its organic derivatives. Pollutants containing labile halogen also attack
these metals. Some metals form a surface layer of mixed oxide and sulphide. Even high carat
gold alloys containing copper or silver, such as the common contact alloy, 69% Au/25% Ag/6%
Pt, will
tarnish superficially at high sulfide concentrations.

Mechanisms of Degradation of Electric Contacts.

Contact Physics : When two metallic surfaces are placed in contact at a light normal load, they touch at
only a few small spots, or asperities. Load is concentrated on these spots, and plastic flow readily occurs.
As load is increased, more and more asperities come into contact, and the surfaces move together. The
true area of contact depends, therefore, on normal load and on the hardness of the metal. The real
contact area is only a fraction of the apparent contact area for most metals, except at very heavy loads.
If metallic surfaces are entirely covered by a non-conductive layer, such as an oxide or a sulphide tarnish
film, the area of metallic contact will be zero, provided the film is unbroken. If the film is not continuous,
or is punctured on making closure, load is borne by both film and metal.

Contact Chemistry : There are many types of environment induced contaminant films on contact
surfaces. Most are caused by air pollutants. Oxide films, however, are an exception, for they normally
form on base metals. Thus, easily oxidized hard metals, like chromium plate and molybdenum, are not
satisfactory for pressure contacts in low energy circuits at reasonable loads. In polluted environments,
contact surface films almost always are thicker and more detrimental than films formed in clean
atmospheres. Not only do oxides themselves grow more rapidly, but films form in polluted atmospheres
on certain metals which otherwise would be totally unaffected. The ancients considered silver to be as
noble as gold, because it remained bright and untarnished for long periods in the atmosphere, which
then was relatively sulfur-free. Palladium tarnishes only in SO2 containing outdoor atmospheres.

FRETTING CORROSION : Fretting corrosion refers to corrosion damage at the asperities of contact
surfaces. This damage is induced under load and in the presence of repeated relative surface motion, as
induced for example by vibration. ... Contact surfaces exposed to vibration during transportation are
exposed to the risk of fretting corrosion. Fretting corrosion is the degradation mechanism of surface
material. Fretting corrosion occurs when there is a relative movement between electrical contacts with
surfaces of ignoble metal. The small wear particles oxidize and areas of oxides become larger and thicker
on the contact surface. The phenomenon of fretting corrosion is also a familiar factor in connection with
mechanical bearings. However, the effects of fretting on electrical contacts are different from the effects
on bearings. Since the basic function of electrical contacts is electrical conduction and oxides are
electrically resistant, with a small amount of oxides being already sufficient to lead to failures of
electrical contacts.
Factors influencing fretting corrosion.

(a) Displacement amplitude is a measurement of distance of the movement of a particle

from its equilibrium position in a medium as it transmits a second wave.

(b) Both external forces(vibrations) and local differences in thermal expansion can cause the relative
movement between the electrical contacts. Electrical contacts must often be used in places with
vibration. Avoiding fretting corrosion is therefore extremely challenging in electronic devices with
pluggable electrical connections.

Causes and Development of fretting corrosion : Fretting corrosion is mainly fretting oxidation of the
zone of contact of electrical contacts. The causes of fretting corrosion are wear debris and oxides, which
form a thick insulting layer in the zone of contact of the mating surfaces. It is presumed that fretting is
concerned with slip amplitudes not greater than 125 μm. Since this movement is of limited amplitude, it
is ineffective in flushing away the wear debris and accumulating oxides in the zone of contact of the
mating surfaces. Metals should be regarded as the main cause for the rapid increase of contact
resistance because of their high specific electrical resistance.

Stage-wise process of fretting corrosion’ : Fretting process can be a one-stage process for ignoble
metals such as tin and nickel or a two-stage process for noble metals such as gold, palladium and silver.

Fretting wear : Relative motions between electrical contacts lead to wear of the coatings. The causes of

coating wear can be a result of different thermal expansions on both sides of electrical contacts,

mating of contacts or mechanical vibration.

Fretting wear and Fretting corrosion :Fretting corrosion and fretting wear are two different phenomena.
Based on the weamechanisms, fretting wear can be adhesive wear or/and abrasive wear. A differentiate
investigation of the two phenomena is important so as to understand the fretting process. This is
especially true for electrical contacts with a plating of noble metal. Since noble metals do not oxidize,
fretting wear alone would not impair the electrical conduction. For plating with noble metals, the
development of fretting corrosion can be largely influenced by the wear of the final coating.

Wear Patterns of electrical contacts : Three wear patterns can possibly develop. Wear pattern I—total
wear out of the final coating. Wear pattern II—partial wear out of the final coating and contact surface
not totally covered with oxide. Wear pattern III-- partial wear out of the final coating, contact surface
not totally covered with oxide, and noble metal at the bottom of the wear crater is covered with debris
of oxide.

Corrosion and FRET wear - Methods of Protection.

✔ Noble metals as final coating materials,

✔ design which reduces the wipe caused by external forces and thermal expansion,

✔ lubricants that prevent the zone of contact from exposure to the atmosphere and therefore

from the fretting oxidation,

Write notes on (a) Anodic corrosion (b) Electrolytic metal migration (c) Atmospheric corrosion

(d) Pore & Creep.

Anodic corrosion : Presence of low levels of hydrogen sulphide could create severe problems in
electronics. The most susceptible material to H2S in the electronic system is silver due to the formation
of silver sulphide crystals. Silver-palladium thick film gets damaged due to its exposure to H2S. The
problem is well known in environments even with low concentrations of H2S (under 50ppb), which is
below the detection limit of H2S by smell.

Electrolytic Metal Migration (ECM) : Electrolytic migration is a typical form of corrosion found on
electronic systems. In an electronic system, electrolytic migration occurs due to the presence of a
potential gradient between two conductors connected by a thin layer of solution. For example two
solder points on a PCB connected by a thin layer of liquid water. The metal ions dissolve from the
positive electrode (anode) and migrate towards the oppositely charged negative electrode (cathode)
and deposit there. In humid environment with chlorides, aluminium dissolves and forms hydroxide (or
hydroxy chlorides) instead of migrating to the cathode regions. On the other hand metals like Cu, Ag, Sn,
Pb etc. migrate upon dissolution and deposit at the cathode. Due to electrolytic migration, dendrites
grow from cathode to anode filling the gap finally leading to electric short and system failure. Similar
behavior could be observed for the corrosion of copper connecting lines on an IC chip.

Cathodic corrosion: Some metals used for electronic systems are soluble in acidic and alkaline
environments over a wide range of potentials and pH. In a micro-galvanic cell, at the cathode oxygen
reduction takes place, which produce OH ions. Production of OH ions at the cathode surface shifts the
pH to alkaline values causing the metals like aluminum to dissolve. The ―pop corning effect‖ is due to
the ingression of moisture during the soldering process causing de-bonding and cracking.

Galvanic corrosion: This type of corrosion is attributed to the use of materials with widely varied
electrochemical properties. For connectors and switches, the corrosion products formed by the galvanic
corrosion induce high resistance in the circuit.

Atmospheric corrosion: "Damp atmospheric corrosion" occurs above a critical relative humidity in the
presence of traces of gaseous (or solid) pollutants. A film, usually quite heterogeneous, grows rapidly on
many metals at these conditions. Nickel, lead, and tin are quickly coated in SO2 polluted atmospheres
above 70% relative humidity with sulfates, oxysulphates, and oxides. If water can condense on the
contact surface at least part of the time, "wet atmospheric corrosion" may occur. This is common with
contacts exposed out-of-doors, and is associated with dewing. The palladium-SO2 reaction probably is
one of wet corrosion. In addition to sulphur and halogen containing gaseous .pollutants, it is likely that
contact metals are degraded by oxidizing agents, such as ozone and the oxides of nitrogen, and by NH3
atmospheres.

Pore & Creep Corrosion: To prevent tarnishing of connectors and contacts, a noble metal (e.g., gold) is
plated on the contact surface. Since the coverage is never complete, the substrate material can corrode
at the imperfections. If the substrate is copper or silver, and it is exposed to a sulfur- or chloride
containing environment, corrosion products can creep out from the pores and over the gold plating,
forming a layer with high contact resistance.
(a) Pore Corrosion- Pore corrosion in thin porous plating results in the formation of galvanic cell
formed in the presence of thin water layer containing ionizable gas. The corrosion products are
transported from the reactive base or substrate metal through the hole in the plating to the contact
surface. This type of corrosion is usually associated with a synergistic effect between chlorides, oxides
and sulphates and it is evidenced appearance of pores which are defects in a coating which expose the
underlying metal underplate or underplate and substrate.

(b) Creep Corrosion Creep corrosion can occur when a reactive substrate metal like silver on copper is
next located to and in physical contact with a noble alloy inlay of plating. The substrate metal corrosion
products creep over the noble metal surface. Creep can also be initiated from the pores in thin gold
plating. This corrosion process is usually associated with copper sulphide and silver sulphide corrosion
films.

Discuss about the following factors causing corrosion. (i) Demand for miniaturization (ii)

Multiplicity of materials (iii) Airborne contaminants (iv) Gas contaminants.

The demand for miniaturization: The trend toward miniaturization of technology has led to the
development of small personal electronic devices such as pagers, cellular phones, etc. Miniaturization is
the process of reducing the size and distance between the components. Overall size of electronic
equipment has also been decreasing presently at a faster rate. The size of the ICs has been decreased by
a factor of 10 over the last couple of years, which means that the spacing between the IC components is
~ 200 nm. The reduction in size and distance between components makes the system more susceptible
to corrosion problems. To generate a fault in the conducting path of such constructions, a material loss
of the order of picograms (10-12) is sufficient. Therefore, even a small environmental impact can cause
huge damages if the components are not well protected.

Multiplicity of materials used: Multiplicity of materials used simultaneously with several other factors
are highly conducive for electronic corrosion. As the materials used are many and designs are
complicated, The components undergo significant corrosion problems are Integrated Circuits (ICs),
Printed Circuit Board (PCB), Switches, Magnetic Recording Media (Hard disc), Packaging and shielding
parts,Connectors,etc.

Airborne Contaminants: One of the most common reasons for electronic failure is environmental
contaminants and conditions. The list of contaminants includes fine and coarse particles of such species
as chlorides, sulfates, sodium, ammonium, potassium, magnesium, and calcium. The single most
important environmental condition affecting the impact of particulate matter and gases (such as sulfur
dioxide and nitrogen oxides) is relative humidity. Coarse particles (2.5 to 15 microns) are typically
formed as a result of human activity or originate from soil. Fine particles (0.1 to 2.5microns) come from
the combustion of fossil fuels and, at times, from volcanic and geological activity. In electronic devices,
coarse particles may cause malfunctions by interrupting electrical contact between mating pairs of
contacts on connectors or relays. They typically require higher relative humidity conditions than the fine
particles. According to the ISA – Instrument Systems and Automation Society standard, there are four
classes of industrial atmospheres with respect to copper reactivity.

Explain the IC and PCB corrosion occurs due to process and service-related residues.

Among the environmental Factors which accelerate Device Corrosion, a significant factor is the
residues found on the PCBs and ICs.

Process Related Residues: Process related residues are the contamination on the surface due to the
remains of the chemicals used for the manufacturing process. This could be the leftover of original
chemicals or decomposed fractions of a compound formed during the production cycle. These are the
fluxing agents, etching medium, plating bath residues, or additives from the polymeric materials.
Although the solder fluxes are designed to give (especially the no-clean variety) essentially no residue
after the soldering process, depending on the temperature cycles and applications, small amount of
original compound or decomposed products could remain on the surface.

In practice, tiny fractions of these chemicals are enough to accelerate the corrosion process. The
effect of no-clean flux on electrolytic migration found that fluxes like RF800 and TN/4A are problem free
for PCBs or hybrid circuits, while SL65 and LP-11AC varieties are only suitable for PCBs. Use of SL65 and
LP-11AC for hybrid circuit applications resulted in Ag dendrites due to electrolytic migration.

Service-related residues: The service related residues are the residues introduced during exposure to
service environments. They can be aggressive ions like chlorides, SO2(g), NO2(g), or other types of
chemically aggressive ions. Presence of such substances trigger corrosion to a large extent under humid
conditions. The dust particle is another issue, which can act as a moisture trapping agent. Formation of
water layer is easy on a dusted surface compared to the clean one. Therefore, corrosion is possible even
at relatively low humidity such as 50-70%.

Water layer or a tiny water drop-let sitting on the surface of a PCB can generate micro galvanic
cell by electrically connecting the two metallic parts. Within the micro-galvanic cell, cathodic reaction
takes place on the noble electrode (eg. graphite, gold, silver, copper or negatively charged part under
applied potential), while the anodic reaction occurs on the active electrode by metal dissolution.
However, due to the large ohmic drop experienced in the thin film solution, anodic reaction often takes
place on a close by cathodic part. It is important to notice that the electrical charge is transported by
electrons in the metallic material and by ions in the liquid. The transfer of charge from metal surface
(electronic conductor) to solution (ionic conductor) interface occurs by an electrochemical reaction
namely oxidation or reduction.

From the mechanistic viewpoint, corrosion of electronics is similar to the atmospheric corrosion.
Under humid conditions, the condensed water layer at the surface of a PCB generates conducting path
(electrolyte) for corrosion. It is like a tiny corrosion cell with adjacent components on a PCB acting as
electrodes. The cathode reaction will be the reduction of oxygen by the diffusion of oxygen from the
atmosphere through the thin layer of water to the electrode surface. And the anodic reaction is the
dissolution of metal subjected to corrosion.

Cathodic reaction: O2 + 2H2O + 4e- −> 4OH-

Anodic reaction: 2Me −> 2Me++ + 4e-

One problem with atmospheric corrosion is that the conditions can change with time. This could
be due to a change in the weather, local environment, conditions related to the equipment etc.
Therefore, in general the rate of corrosion is determined by the following factors: (i) Wet/dry cycle – the
time of which the surface is wet or dry, (ii) Composition of the moisture, (iii) Temperature.
Elucidate the causes, influencing factors and control measures of fretting corrosion.

Fretting corrosion is the degradation mechanism of surface material. Fretting corrosion occurs when
there is a relative movement between electrical contacts with surfaces of ignoble metal. The small wear
particles oxidize and areas of oxides become larger and thicker on the contact surface. The phenomenon
of fretting corrosion is also a familiar factor in connection with mechanical bearings. However, the
effects of fretting on electrical contacts are different from the effects on bearings. Since the basic
function of electrical contacts is electrical conduction and oxides are electrically resistant, with a small
amount of oxides being already sufficient to lead to failures of electrical contacts.

Causes and Development of fretting corrosion

Fretting corrosion is mainly fretting oxidation of the zone of contact of electrical contacts. The
causes of fretting corrosion are wear debris and oxides, which form a thick insulting layer in the zone of
contact of the mating surfaces. It is presumed that fretting is concerned with slip amplitudes not greater
than 125 μm. Since this movement is of limited amplitude, it is ineffective in flushing away the wear
debris and accumulating oxides in the zone of contact of the mating surfaces. Metals should be regarded
as the main cause for the rapid increase of contact resistance because of their high specific electrical
resistance.

Corrosion and FRET wear - Methods of Protection

There are a variety of basic approaches to the solutions of the problems caused by fretting wear and
fretting corrosion.

✔ Noble metals as final coating materials,

✔ design which reduces the wipe caused by external forces and thermal expansion,
✔ lubricants that prevent the zone of contact from exposure to the atmosphere and therefore
from the fretting oxidation.

These are widely used measures to enhance the resistance to fretting corrosion.

Gold Plating: Many standard and custom electrical contacts are comprised of conductive metals, such as
nickel, copper, cadmium, and other various alloys. Although these materials are capable, they can and
do degrade over time due to oxidation, corrosion, erosion, and heat. For this reason, many
manufacturers apply a thin layer of gold plating with a nickel undercoating to protect their contacts and
improve their capabilities. Gold has various physical and chemical properties that make it ideal for
electronic applications. 

1. Better corrosion protection: Gold boasts an incredible resistance to oxidation, which produces
corrosion; this makes it ideal for contacts exposed to corrosive environments or agents.
2. Improved electrical conductivity: Corrosive environments and agents degrade metals commonly
used in contacts, thus interfering with their conductivity. Gold doesn’t break down under these
conditions and protects the contacts from corrosion and rust.
3. Increased durability: Gold provides considerable protection from regular wear and tear like
fretting, which is erosion caused by repeated rubbing and friction; this can considerably prolong
a contact’s lifespan.
 4. Ease of application: An electrical contact requires just a very thin layer of plating—any excess
coating will negatively inhibit its efficiency. Gold is an incredibly malleable metal, making it very
simple to apply the proper amount of plating for each unique application.
5. Excellent heat resistance: Gold’s properties make it a valid form of protection for contacts
routinely exposed to high temperatures (>125°C/257°F).

The amount of gold used for electrically conductive surface is determined by the area and the thickness
of gold plating. The basic idea of selective gold plating is that gold is plated at and around the electrical
contact areas and not on the whole surface of electronic components. In this way the area of gold
plating can be reduced to the minimum. Depending on the contact operating conditions and contact
functions the thickness of gold plating varies from 0.1 to 5 μm.

Different ways to minimize the consumption of gold for electrically conductive surface and to improve
the performance of gold plating are:

1. Increasing the hardness by means of: Optimized proportion of alloy elements and Hard

nanoparticles.

2. Improved wear resistance and wear pattern of coatings;

3. Improved surface perfection with thin coatings by employing SAM (self-assembled

monolayer).

The high degree of hardness of hard gold is achieved by alloying elements such as cobalt, iron

or nickel. However, the effect of alloying elements is limited by the electroplating process and

other surface properties, such as ductility and cracking, which are also important for the final

coatings.

PTFE(Poly Tetra Fluoro Ethylene) Instead of alloying elements, nanoscale particles mostly metal oxides
can be used for the modification of gold plating. The reason for using nanoscale particles is based on the
fact that the hardness of pure gold is about 70 HV and the hardness of hard gold is about 170 HV (10
N/mm2). The hardness of nanoscale particles of metal oxides ranges from 700 to 2300 HV (10 N/mm2).
PTFE reduces the friction between contacts. These can provide an additional lifetime improvement.
However, PTFE is basically an isolator therefore only nanoparticles of PTFE can be used for electrical
contacts, in order to alleviate increase of contact resistance.

Passivation

Another means of corrosion protection of electrically conductive surfaces is the passivation of

surface. Passivation is the change process of metal surface, which creates the resistance to
environmental media. Metal surfaces can be passivated either by their own gastight oxide layer or
through the assembly of a non-reactive layer such as self-organization of nanoparticles, monolayers,
SAM (self-assembled monolayer).
Besides the resistance to corrosion there are two very important requirements for electrically
conductive surfaces:

1. The passivation layer should not increase or destabilize the electrical resistance markedly;

2. For many applications the passivation layer must resist the operating temperature which is the sum of
resistive heating and ambient temperature.

How the following factors helps to control corrosion? (i) Improvement of gold coating (ii)

Utilization of PTFE and PFPE as lubricants.

Improvement of Gold Plating to Control Corrosion: Different ways to minimize the consumption of gold
for electrically conductive surface and to improve the performance of gold plating are:

1. Increasing the hardness by means of: Optimized proportion of alloy elements and Hard

nanoparticles.

2. Improved wear resistance and wear pattern of coatings;

3. Improved surface perfection with thin coatings by employing SAM (self-assembled

monolayer).

The high degree of hardness of hard gold is achieved by alloying elements such as cobalt, iron

or nickel. However, the effect of alloying elements is limited by the electroplating process and

other surface properties, such as ductility and cracking, which are also important for the final

coatings.

Utilization of PTFE and PFPE as Lubricants to Prevent Corrosion: