TARNISH AND CORROSION

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Contents
 Introduction to Tarnish and Corrosion
 Causes of Tarnish and Corrosion
 Classification of Corrosion
 Effects & Protection Against Corrosion
 Conclusion

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 Definitions
Tarnish: surface discoloration on a metal or as a slight loss
or alteration of the surface finish or luster.

Corrosion: the actual detoriation of a metal by reaction with

the environment.

*GPT- 8
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 Introduction

Metals are used in dentistry in various forms, such as

metallic restorative materials in the mouth or as various
instruments to be used in the oral cavity or as numerous
tools and equipment associated with clinical and
laboratory work.
All metals used in dentistry undergo tarnish or
corrosion, the percentage of corrosion varying from
metal to metal.

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The mouth is moist, warm, salty, acidic, and
is continually subjected to fluctuations in temperature.
The food and liquid that we take have a wide range
of pH.
All these environmental factors contribute to
the degradation of the metals used in the oral cavity.

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However in the dental practice, a limited amount of
corrosion around the margins of dental amalgam
restorations may be beneficial, since the corrosion
products tend to seal the margin gap and inhibit the
ingress of oral fluids and bacteria.

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Tarn
ish

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The outermost surface layer of many semi-reactive metals
such as copper, brass, silver, and aluminum undergo a
chemical reaction forming a thin layer known as tarnish.
This is a surface phenomenon that is self limiting unlike
rust.
It is mainly caused by chemicals in the air, such as sulfur
dioxide.
Tarnish is manifested as a dull gray or black film or coat
over the metal surface.

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The formation of tarnish is a protective phenomenon
that involves the reaction of only the top few layers of
metal. The layer of tarnish then seals and protects the
underlying layers. This layer of tarnished metal is called
PATINA.

The formation of patina is necessary in applications

such as copper roofing, and outdoor copper, bronze, and
brass statues and fittings.

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 Causes of Tarnish

In the oral environment, tarnish occurs due to the

formation of soft deposits (plaque and mucin) and hard
deposits (calculus) on the surface of the restoration.

Stain or discoloration arises from pigment producing

bacteria, drugs containing chemicals such as iron or
mercury, and adsorbed food debris.

Formation of thin films such as oxides, sulfides,

or chlorides may cause surface discoloration

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Corrosio
n

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Corrosion is a chemical or electrochemical process
wherein a metal is attacked by natural agents, resulting
in its partial or complete dissolution or deterioration.
Eg. Rust, the most familiar example of corrosion.

It differs from tarnish in that it is not merely a surface

deposit but an actual deterioration ofthe metal due to a
reaction with its environment.

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Corrosion in the oral environment is either by chemical or
electrochemical process through which a metal is attacked
by natural agents, such as air and water, resulting in partial
or complete dissolution, deterioration, or weakening
of any solid substance.

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 Causes of Corrosion

Tarnish is often the forerunner of corrosion.

 Water, oxygen, and chlorine ions present in saliva
contribute to corrosion attack.
Various acidic solutions such as phosphoric, acetic, and
lactic acids often present in the oral cavity at proper
concentrations and pH can promote corrosion.
Examples:
Eggs: contain high amounts of sulfur,
Ions such as oxygen and chlorine corrode amalgam.

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 Classification of Corrosion

Electrochemical/Wet
Chemical/Dry corrosion
corrosion

Concentration
Galvanic corrosion Stress corrosion cell/crevice
corrosion

-By Fontana and Jones

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 Non aqueous (dry) or Chemical corrosion:

In chemical corrosion, there is a direct reaction between

the metallic and nonmetallic elements to yield a
chemical compound through processes such as oxidation,
halogenation, or sulfurization in the absence of water or
another fluid electrolyte.

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 Aqueous (wet) or Electrolytic corrosion

Electrochemical corrosion occurs in the presence of a

fluid electrolyte such as water. Hence, it is also known as
wet corrosion.
Only this type of corrosion occurs in the oral cavity
where the electrolyte is the saliva.

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 Process of Electrochemical Corrosion

The electrochemical cell is made up of three main

components: an anode, a cathode, and an electrolyte.
The anode is the surface or sites on a surface where positive
ions are formed.

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ANODE: undergoes an oxidation reaction with the
production of free electrons. Thus, the metal
surface corrodes due to loss of electrons.
M0 → M+ + e -

CATHODE: The free electrons that are released by the

anode are taken up by the cathode or the cathodic
sites, where a reduction reaction occurs.
M+ + e- → M0

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Electrolyte is the medium that carries the ions away from
the anode, and these ions are then taken up by the cathode.
It also carries away the corrosion products formed at
the anode.
The pathway of transfer of electrons from the anode to the
cathode forms the external circuits that serve as a conduction
path.

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 Electromotive Series of Metals

All metals have a tendency to give away

electrons; only their degree of tendency differs.
The electromotive series of metals arranges them in
order of dissolution tendencies in water and
classifies metals by their equilibrium values of
electrode potential.

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 Galvanic Corrosion/ Electrogalvanism

This type of electrochemical corrosion occurs when two or

more dissimilar metals are in direct physical contact with
each other, e.g. two adjacent or opposing restorations made
of different alloys. Here, saliva acts as
an electrolyte.

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Galvanic corrosion occurs due to the galvanic
coupling of dissimilar metals involved.
Less corrosion-resistant metals become anode and
usually corrode.

Schoonover and Souder reported that gold

restorations were corroded by mercury released from
amalgam fillings because of an electrochemical
reaction.

Fusayama et al. observed that silver-colored stains

formed on the surface of gold inlays that had got into
contact with fresh amalgam mix or fillings.

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 Galvanic Shock
A pain sensation caused by electric current
generated by a contact between two dissimilar
metal forming a galvanic cell in oral environment.
Patient may also experience pain by touching the
tine of a silver fork to a gold foil or inlay
restoration.

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Galvanic Corrosion cause:
 weakening of both the alloys
 discoloration of both the restorations,
 and presence of a metallic taste in the
mouth.

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 Stress Corrosion
A metal which has been stressed by cold working,
becomes more reactive at the site of maximum stress. If
stressed and unstressed metals are in contact in an
electrolyte, the stressed metal will become the anode of a
galvanic cell and will corrode.

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Stress corrosion most likely to occur during fatigue
or cyclic loading in the oral environment.
Eg. Repeated removal and insertion of a partial
denture will develop a severe stress pattern in the
appliance causes stress corrosion resulting in
fatigue and failure.

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Concentration cell corrosion/ Crevice corrosion

This type of corrosion occurs when a liquid corrosive or an

electrolyte is trapped in narrow gaps between metals or
between metals and nonmetals.

A homogeneous metal or alloy can undergo electrolytic

corrosion when there is a difference in electrolyte
concentration across the specimen.

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Example; a metallic restoration which is partly covered
by food debris will differ from that of saliva, and this can
contribute to the corrosion of the restoration.

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Crevices are unavoidable with surgical implants
where a screw or plate contacts the bone. The local flux
of ions is drastically enhanced at crevice sites and
tissue impregnation follows.

The contact region of a screw or implant material can

form the crevice. In the small space the liquid and
oxygen exchanges are severely limited, and surface in
the crevice undergoes active corrosion and cause
further deterioration.

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 EFFECTS OF CORROSION

Nobel Metal: Nobel metals resist corrosion because

their electromotive force is positive when compared to
any other metal used in the oral environment.

To protect an alloy from corrosion, alloys used in

dentistry should have at least half the components as
noble metals (gold, palladium, and platinum) – Lang et al

Gold, resist sulfide tarnishing.

 Palladium is found to be effective in resistance of
silver
alloys to sulfide tarnishing.

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Base Metal Alloys: Generally, base metal alloys are
very resistant to tarnishing.

Much of the corrosion resistance of the base metal

alloys is due to the development of a thin, tough,
adherent layer of oxide.
This layer prevents the penetration of corrosive ions
into the underlying metal and reduces
electrochemical behavior to a passive state.

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Base metals, such as stainless steels, nickel-
chromium alloys, and cobalt-chromium alloys,
are virtually immune to sulfide tarnishing, but
these alloys are susceptible to chlorides.

Silver Points/Cones contains Cu & Ni cause

corrosion when get in contact with periradicular
tissue and cause cytotoxicity.

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Titanium and its alloys are superior in their resistance
to chloride attack, compared with the other dental base
metal alloys, as titanium forms a relatively stable
oxide layer, and this is the basis for the corrosion–
resistance property and biocompatibility.

Lucas and Lemons have reported that the formation

of oxide film on titanium provides corrosion-
resistance under static conditions.

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Stainless Steel: The corrosion resistance of stainless
steel is attributed to the presence of chromium in
the alloy.
Approximately, 11% chromium is needed to
produce corrosion resistance in pure iron.

Chromium resists corrosion well because of the

formation of a strongly adherent coating of oxide
on the surface, which prevents further reaction
with the metal below the surface. The formation
of such an oxide layer is called passivation.

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 Corrosion of Amalgam
Low copper amalgam has much lower resistance to
tarnish and corrosion as compared to high copper
amalgam due to the formation of γ₂-phase, which
has least resistance to corrosion.

It has been found that phosphate buffer solutions

inhibit the corrosion process; hence, it can be
said that saliva may provide some protection to
dental amalgam from corrosion.

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Amalgam restorations are subject to tarnish
and corrosion in the oral environment.
It has been suggested that the corrosion process
although detrimental in some respects may also
have beneficial effects.

Wagner has credited the corrosion process with sealing

of leaky margins and mechanical anchoring of the
restoration to cavity walls by deposition of corrosion
products.

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Tissue discoloration: During placement of
amalgam in cavity, some spillage tends to occur in
the surrounding tissues. If not removed carefully,
these remnants may corrode and lead to mucosal
tissue discoloration known as amalgam tattoo or
focal argyria.

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 Protection Against Corrosion

Passivation: This is the method by which certain

metals develop a thin, adherent, highly protective film
when they react with the environment. Such metals
are known as passive metals.
e.g: Thin coatings of electrolytic zirconium oxide
(ZrO2) deposited on cobalt-chromium alloys
reduce chromium-release levels in artificial saliva,
as compared to uncoated cobalt-chromium alloys.

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Electroplating: Electroplating is the application of
electrolytic cells in which a thin layer of metal is deposited
onto an electrically conductive surface.

The process used in electroplating is called

electrodeposition.
Boris Jacobi a Russian scientist developed
electroplating.
 Reasons for electroplating
• corrosion resistance.
• to improve the appearance and value of the items.
• to increase the thickness of an item.

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Increasing noble metal content: Since noble metals
have higher electromotive potential (positive) when
compared to any of the other metals used in the oral
environment, they can be added to alloys to reduce
corrosion.

 Polishing restorations

 Avoiding dissimilar metal restorations

 Maintenance of oral hygiene

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 Conclusion

Though corrosion is almost always undesirable, there

are some instances where it is beneficial such as around
the margins of dental amalgam restorations as it seals
the marginal gap.
It is difficult to prevent corrosion completely in oral
cavity. Hence the selection of restorative material and
good oral hygiene helps in minimizing corrosion
process.

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 Reference
s
Phillips Science Of Dental Material 10th & 11th Edition

Restorative Dental Materials – Craig 13th Edition

Schoonover, I.C. And SOUDER, W.: Corrosion Of

Dental Alloys, JADA 28:1278-1291, 1941.

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