TARNISH AND CORROSION

CORROSION

o A 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.

Types of Corrosion

o Crevice corrosion - corrosion in narrow spaces caused by localized electrochemical

process and chemistry changes such as acidification and depletion of oxygen content.
E.g. Microleakage in dental restorations.
o Galvanic corrosion - corrosion on a less noble metal when electrochemically
dissimilar metals are in electrical contact in presence of corrosive liquid environment.
o Pitting corrosion - Sharply localised corrosion in base metals like iron, nickel and
chromium (which are naturally protected by a thin film of oxide) in the presence of
chlorides in the environment ,the film locally breaks down causing dissolving of the
metal underneath it in the form of pits.
o Stress corrosion –Degradation by the combined effects of mechanical stress and a
corrosive environment, usually in the form of cracking.

TARNISH

A process by which a metal surface is dulled in brightness or discoloured through the

formation of a chemical film, such as a sulphide and an oxide.

CONCENTRATION CELL

An electrochemical corrosion cell, in which the potential difference is associated with

the difference in the concentration of the solutions causing corrosion at different parts of
the metal surface.

Causes of Tarnish and Corrosion

o Formation of hard (calculus) and soft deposits (plaques and films composed of micro
organisms and mucin) on the surface of the restoration.
o Formation of thin films of oxides, sulphides and chlorides on a metal causing surface
discoloration.
o Corrosion results in surfaces under stress or with irregular impurities on the metal.

o Disintegration of a metal may occur through the action of moisture, atmosphere, acid
or alkaline solutions and certain chemicals.
o Tarnish that is formed in time can accumulate elements or compounds that chemically
attack the metallic surface. For e.g. and certain foods contain amounts of sulfur.
o Sulfides such as hydrogen and ammonium sulphides, corrode silver, copper and similar
metals present in dental alloys and amalgam.
o Water, oxygen and chloride ions present in saliva contribute to corrosion attack.

o Various acids such as phosphoric, lactic, acetic acids at proper concentration and pH
can produce corrosion.

Variables affecting corrosion

o Composition, physical state and surface condition of the metal

o Chemical components of the surrounding medium

o Temperature

o Movement or circulation of the medium in contact with the metal surface

o Nature and solubility of the corrosion products

TYPES OF CORROSION REACTION

1. CHEMICAL CORROSION

o Direct combination of metallic and non metallic elements. Also called dry corrosion As
it occurs in the absence of water or any other fluid electrolytes
o Eg.Oxidation

o Discoloration of silver by sulfur by formation of silver sulphides.

o It also corrodes the gold alloy that contains silver.

o Oxidation of alloy particles (silver-copper) in the dental amalgam. This prevents proper
amalgamation with mercury
o Modern low-copper amalgams have a powder component composed of 69.4% silver,
3.6% copper, 26.2% tin , and 0.8% Zinc .
o They have a liquid component of 42% to 45% mercury by weight.

o The principle steps of an oxidation reaction: Dissociative oxygen adsorption, metal and
oxygen ion diffusion through the growing oxide layer

2. ELECTROCHEMICAL CORROSION

o Also known as wet corrosion as it requires a fluid electrolyte or water.

o Requires a pathway for transport of electrons an electrical current.
 ELECTRO CHEMICAL CELL

o Applied in the oral cavity with two dissimilar fillings

o Possible reactions- reduction reactions

1. M + + e - M o

2. 2H + + 2e - H2

3. 2H 2 O + O 2 + 4e - 4(OH) -

o Metal ion may be removed to form metal atoms

o Hydrogen ions may be converted to hydrogen gas

o Hydroxyl ions may be formed

o The electrolyte provides the ions needed at the cathode to carry away the corrosion
products to anode.

Electromotive force series

o This is the classification for arrangement of the elements in the order of their
dissolution tendencies in water.
o Potential values are calculated with solutions containing one atomic weight, in grams,
of ions in 1000ml of water at 25 c.
o Metals with a more positive potential have a lower tendency to dissolve in aqueous
solutions.

GALVANIC CORROSION / DISSIMILAR METALS CORROSION

o An important type of electrochemical corrosion occurs when dissimilar metals are in

direct physical contact with each other. Hence the dental reference here is two dissimilar
restorations in the oral cavity. This metallic combination may produce Electro galvanism
or “Galvanic currents”. e.g. in AMALGAM GOLD fillings on opposite arches

Galvanic Shock

o A pain sensation caused by electric current generated by a contact between two

dissimilar metals forming a battery in the oral environment
o E.g. Amalgam filling opposing a gold inlay as both the restorations are wet in saliva, an
electrical couple exists, with a potential difference between the dissimilar restorations.
o When they come in contact, the potential is suddenly short circuited through the two
alloys resulting in a sharp pain.

STRESS CORROSION

o E.g. repeated removal and insertion of a partial denture will develop a severe stress
pattern of certain alloys especially at the grain boundaries. Combined with the oral
environment, the appliance develops stress corrosion resulting in fatigue and failure.
 CONCENTRATION CELL CORROSION

o Accumulation of food debris produces one type of electrolyte, normal saliva produces
another electrolyte. This difference in electrolyte causes an electrochemical corrosion of
the metal filling underneath the food debris.

PROTECTION AGAINST CORROSION

o Highly polished restorations

o A coat of noble metal over the base metal in dental casting(noble metals resist
corrosion because their EMF is positive)
o Paint application or coating with inorganic nonconductive coatings.

o Passivating metals-some metals form a thin protective layer when exposed to the
environment .E.g. chromium
o Electroplating with nickel followed by chromium for protective film. e.g. stainless steel

o As long as the film of chrome oxide is maintained, the stainless steel behaves like gold,
silver or platinum, or in other words, it has a passive behaviour. Stainless steel can also
develop active sites of corrosion if the protective film is destroyed by scratches, nicks,
stock deposits or contamination of steel by non-ferrous inclusions
o Chromium passivated metal will be corroded by chloride, hence patients on removable
dentures are instructed not to wash their appliances with household bleaches and
cleansers

CORROSION OF DENTAL RESTORATIONS

Affecting Factors

o Diet
o Drug

o Smoking

o Bacterial activity

o Oral hygiene and habits

Prevention of corrosion in dental restorations

o Addition of noble metals like gold, platinum and palladium in dental alloy
o Gold resist sulphide tarnish, palladium resists sulphide tarnishing with silver

o Base metals alloys such a s ni-cr,co-cr and ti are virtually resistant to sulphide
tarnish(Orthodontic wires) although they are susceptible to chloride corrosion
 Clinical considerations

o Application of varnish in the dentinal walls and on the surface of the filling to avoid
galvanism in amalgam restorations.
o Avoid giving amalgam restoration opposing gold filling because the mercury released
from the silver amalgam will weaken and discolour both the fillings and also gives a
metallic taste in the mouth.