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TARNISH AND CORROSION

Dr LAKSHMI RAVI M.D.S


Asst Professor
Dept of Orthodontics
St.G.D.C
CORROSION
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
 Crevice corrosion - corrosion in narrow spaces caused by
localized electrochemical process and chemistry changes such
as acidification and depletion of oxygen content.
Eg. Microleakage in dental restorations.

 Galvanic corrosion - corrosion on a less noble metal when


electrochemically dissimilar metals are in electrical contact in
presence of corrosive liquid environment.
 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.

 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 discolored through the formation of a chemical
film,such as a sulfide 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.
CONCENTRATION CELL
Causes of Tarnish and Corrosion
 Formation of hard(calculus) and soft deposits(plaques and films
composed of micro organisms and mucin) on the surface of the
restoration.

 Formation of thin films of oxides, sulfides and chlorides on a


metal causing surface discoloration.

 Corrosion results in surfaces under stress or with irregular


impurities on the metal.

 Disintegration of a metal may occur through the action of


moisture, atmosphere, acid or alkaline solutions and certain
chemicals.
ELECTRON MICROSCOPIC PICTURE OF CORROSION

SALT OF THE METAL


 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.

 Sulfides such an hydrogen and ammonium sulfides, corrode


silver, copper and similar metals present in dental alloys and
amalgam.

 Water ,oxygen and chloride ions present in saliva contribute


to corrosion attack.

 Various acids such as phosphoric, lactic, acetic acids at


proper concentration and pH can produce corrosion.
SCANNING ELECTRON MICROSCOPE PICTURE OF METAL WITH CORROSION

PIC. COURTESY PAX CAM


Variables affecting corrosion
 Composition, physical state and surface condition of
the metal
 Chemical components of the surrounding medium
 Temperature
 Temperature fluctuations
 Movement or circulation of the medium in contact
with the metal surface
 Nature and solubility of the corrosion products
Corrosion of steel under a droplet of water
TYPES OF CORROSION REACTION
1.CHEMICAL CORROSION
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
Eg.Oxidation
- Discoloration of silver by sulfur by formation of silver
sulfides.
- It also corrodes the gold alloy that contain silver.

- oxidation of alloy particles (siver-copper)in the dental


amalgam.This prevents proper amalgamation with mercury

Modern low-copper amalgams have a powder component composed of


69.4% silver, 3.6% copper, 26.2% tin, and 0.8% Zinc.
They have a liquid component of 42% to 45% mercury by weight.
 The principle steps of an oxidation reaction:
Dissociative oxygen adsorption, metal and
oxygen ion diffusion through the growing
oxide layer
2.ELECTROCHEMICAL CORROSION
Also known as wet corrosion as it requires a fluid electrolyte or
water.
Requires a pathway for transport of electrons an electrical
current.

English chemists John Daniell (left)


and Michael Faraday (right), both
credited to be founders of
electrochemistry as known today.
ELECTRO CHEMICAL CELL
APPLIED IN THE ORAL CAVITY WITH TWO DISIMILIAR
FILLINGS

Ammeter

Amalgam Anode ……………………………….. Gold alloy cathode


+ ion ………………………………. - ION
……………………………….
……………………………….
………………………………..
………………………………
Saliva electrolyte
POSSIBLE REACTIONS- REDUCTION REACTIONS

1. M+ + e- Mo
2. 2H+ + 2e- H2
3. 2H2O + O2 + 4e- 4(OH)-

 Metal ion may be removed to form metal atoms

 Hydrogen ions may be converted to hydrogen gas

 Hydroxyl ions may be formed

 The electrolyte provides the ions needed at the cathode to


carry away the corrosion products to anode.
Electromotive force series
 This classification for arrangement of the elements
in the order of their dissolution tendencies in water.
 Potential values are calculated with solutions
containing one atomic weight ,in grams, of ions in
1000ml of water at 25 c.
 Metals with a more positive potential have a lower
tendency to dissolve in aqueous solutions.
Galvanic corrosion / Dissimilar metals corrosion
 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”.

AMALGAM
GOLD
Galvanic Shock
 A pain sensation caused by electric current generated by a
contact between two dissimilar metals forming a battery in
the oral environment

GOLD FILLING

S A L I V A
AMALGAM FILLING ENAMEL
DENTINE
PULP
Eg. 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.
When they come in contact, the potential is
suddenly short circuited through the two alloys

resulting in a sharp pain.


Stress corrosion
 Eg.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
 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
 Highly polished restorations

 A coat of noble metal over the base metal in dental


casting(noble metals resist corrosion because their EMF is
positive)

 Paint application or coating with inorganic nonconductive


coatings.

 Passivating metals-some metals form a thin protective layer


when exposed to the environment .Eg,chromium

 Electroplating with nickel followed by chromium for


protective film.eg.stainless steel
•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 behavior. 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

•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
 Diet

 Drug

 Smoking

 Bacterial activity

 Oral hygiene and habits


Prevention of corrosion in dental
restorations
 Addition of noble metals like gold, platinum
and palladium in dental alloy
 Gold resist sulfide tarnish, palladium resists
sulfide tarnishing with silver
 Base metals alloys such a s ni-cr,co-cr and ti
are virtually resistant to sulfide
tarnish(Orthodontic wires) although they are
susceptible to chloride corrosion
Clinical considerations
 Application of varnish in the dentinal walls and on the
surface of the filling to avoid galvanism in amalgam
restorations.
 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.

MERCURY

SEPAGE OF MECURY FROM AN AMALGAM FILLING


ELECTRON MICROSCOPE PICTURE
Luigi Galvani -1737 - 1798
 Galvani was born, educated and taught anatomy
in Bologna. The Italian physiologist made
one of the early discoveries that advanced the
study of electricity. His work with frogs led to
his discovery in 1781 of galvanic or voltaic electricity.

 Galvani found he could make the muscles of a dead


frog twitch when he touched them with different
metals or the current from a nearby static electric generator.
But he incorrectly thought fluid in the frog's body was the
source of the electricity. This discovery soon led to another
by Allesandro Volta, who invented the electric cell or early
battery.
Alessandro Volta - 1745 - 1827
 Count Alessandro Volta was born in Como, Italy,
into a noble family, Count Volta was a physicist and pioneer
in the study of electricity. "Volt," named after Count Volta.

 Inventor of the Battery. Around 1800, he invented a wet battery called a


Voltaic Pile.

 The Voltaic Pile consisted of discs of copper and zinc separated by discs of
paper or cardboard (soaked in salt water). Attached to the top and bottom
of this "Pile" was a copper wire. When Volta closed the circuit, electricity
flowed through the pile.

Volta's battery was later refined by other scientists, and the French
emperor, Napoleon, made Volta a "Count" for his discovery.