DENTAL AMALGAM:

COMPOSITION, STRUCTURE,
PROPERTIES AND
CONTROVERSY
Dr Ian MacAskill, BEng, MASc, DDS
 INTRODUCTION
• Amalgam: is an alloy of mercury and one or more other metals

• Dental amalgam alloy: is an alloy that contains solid metals of

silver, tin, copper and some times zinc and palladium.

• Dental amalgam: is produced by mixing liquid mercury with

solid particles of an alloy containing predominantly silver, tin, and
copper:
 ADVANTAGES
• Dental amalgam restorations are
inexpensive and reasonably easy to
insert. Not overly technique sensitive.

• Proven track record (>100 years)

• Maintain anatomical form and have

reasonably adequate resistance to
fracture.

• Can be used in stress-bearing areas,

and have a relatively long service life

Courtesy J. Martin Anderson, University of Washington Department of Restorative Dentistry, Seattle, WA

DISADVANTAGES
 HISTORY
• Prior to 1900: Many compositions were tried but few were
successful when placed in the oral environment

• Around 1900: Scienti c testing was applied to the problem, which

led to a composition of silver and tin in the form of Ag3Sn with small
amounts of copper and occasionally Zn added:

• Propensity for fracture at the edge or margin of the amalgam restoration

next to tooth structure, commonly called marginal fracture.

• Fractures were considered to be exacerbated by the presence of the tin-

mercury phase (Sn7-8Hg), γ2, which results when Ag3Sn reacts with mercury
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 HISTORY
• 1960s:

• First generation high-copper

alloys: - Dispersalloy (Caulk) -
Admixture of spherical Ag-Cu eutectic
particles with conventional lathe-cut
Ag3Sn particles in a ratio of 1:2

• Rationale was to enhance the strength

but the unexpected elimination of the
γ2 phase provided signi cant bene t.

• Extent of marginal fracture was either

eliminated or reduced signi cantly in
restorations made from Dispersalloy
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 HISTORY
• 1970s:

• First unicompositional spherical

alloy.

• Tytin (Kerr)- γ2 phase eliminated

by combining a signi cant amount
of Cu3Sn together with Ag3Sn.

• 1980’s and 90’s

• Further unicomposition alloy

development.
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 ALLOY POWDER
COMPOSITION
• Basic Constituents:

• Silver
(Ag), Tin (Sn), Copper (Cu),
Mercury (Hg)

• Other:

• Zinc (Zn), Palladium (Pd)

• ANSI/ADA (American National Standards Institute/American
Dental Association) speci cation No. 1 (ISO 24234) for amalgam
alloy:

• Shall consist primarily of silver, tin, and copper.

• ISO 1559 (Dental Materials: Alloys for Dental Amalgam).

Current limits (in wt.%):

- Silver: 40 (min).

- Tin: 32 (max).

- Copper: 30 (max).

- Zinc: 2 (max).

- Mercury: 3 (max)
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 ALLOY POWDER COMPOSITION

• Silver (Ag)
• Advantage: increasing strength, promoting setting when mixed with
mercury (increasing the setting time), reducing the ow and resisting the
tarnish and corrosion.

• Disadvantage: High degree of setting expansion.

• Tin (Sn)
• Advantage: Aids in amalgamation process because it has great af nity to
mercury and decrease expansion within practical limit.

• Disadvantage: Decreased strength, prolonged setting time, decreased

corrosion resistance and increased ow of amalgam.
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 ALLOY POWDER COMPOSITION

• Copper (Cu): Ties up Tin (Sn) to reduce γ2 formation

• Advantage:

• Increases strength and hardness.

• Reduces tarnish and corrosion.

• Reduces creep.

• Reducing marginal deterioration.

• Decreases ow of amalgam.

• Disadvantage: Increased setting expansion.

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 ALLOY POWDER COMPOSITION
• Zinc (Zn): presence is not essential.
• Advantages: Prevents oxidation during alloy ingot manufacture.

• Disadvantages: May give rise to delayed or secondary expansion if

contaminated with moisture during condensation.

• Palladium (Pd): Improves the corrosion resistance and the

mechanical properties.
CLASSIFICATION OF DENTAL
AMALGAM ALLOYS

• Particulate shape of alloys (lathe cut, spherical, admixed)

• Particulate size (Coarse vs Fine)

• Zn Content (Zn containing (>0.01%) and Zn free(<0.01%)

• Cu Content (High Cu (>6%) and low Cu (<6%))

• Number of alloying elements (Binary, tertiary, quaternary)

• Equilibrium phase diagram for silver (Ag) and tin (Sn)
LATHE CUT AMALGAM ALLOY
SPHERICAL AMALGAM ALLOY
PARTICULATE SHAPE

•A - Lathe cut

•B - Spherical

•C - Admixed
• Mercury (Hg): Activates reaction

• Only pure metal that is liquid at room temperature.

• Spherical Alloys: require less Hg (40-45%), smaller surface

area, easier to wet

• Admixed Alloys: require more Hg (45-50%), irregular surface

of late cute particles are more dif cult to wet.
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AMALGAMATION PROCESS
Low Copper alloys - Pre 1960’s

• Intimate mixing of Amalgam Alloy

and liquid Hg.

• Remove surface oxide layers on alloy

particles.

• Diffusion of Hg into the alloy

particles.

• Intermetallic compounds are formed.

AMALGAMATION PROCESS
• Low Copper alloys:

• γ1 = Ag2Hg3

• 2nd strongest phase.

• 54 to 56% of volume γ1.

• 27 to 35% of volume γ.

Ag3Sn + Hg ⇒ Ag3Sn + Ag2Hg3 + Sn7-8Hg

γ γ γ1 γ2
AMALGAMATION PROCESS
• Low Copper alloys:

• γ2 = Sn7-8Hg

• Weakest and softest phase,

except for voids

• Corrodes fast, voids form, corrosion

yields Hg which reacts with more γ.

• 11to 13% by volume. Volume

decreases with time due to corrosion.
Ag3Sn + Hg ⇒ Ag3Sn + Ag2Hg3 + Sn7-8Hg
γ γ γ1 γ2
 ADMIXED HIGH-COPPER ALLOYS
• Spherical Ag-Cu Eutectic
Alloy

• Both Agand Sn enter Hg

from Ag3Sn particles.

• Fully set mix has no

γ2

Ag3Sn + Ag-Cu + Hg ⇒ Ag3Sn + Ag-Cu + Ag2Hg3 + Cu6Sn5

γ γ γ1 η′
 UNICOMPOSITIONAL HIGH-COPPER ALLOYS
• γ sphere (Ag3Sn) with ε coating (Cu3Sn)

• Ag and Sn dissolve in Hg.

• γ1 (Ag2Hg3) crystals grow binding

together partially-dissolved γ alloy particles
(Ag3Sn).

• ε (Cu3Sn) develops crystals on surface of γ

particle (Ag3Sn) in the form of η′ (Cu6Sn5).

• Prevents γ2 formation.

Ag3Sn + Cu3Sn + Hg ⇒ Ag3Sn + Cu3Sn + Ag2Hg3 + Cu6Sn5

γ ε γ ε γ1 η′
 PHYSICAL AND
MECHANICAL PROPERTIES
• ANSI/ADA speci cation No. 1 (ISO 24234) for
amalgam alloy:

• The minimum allowable compressive strength is 80MPa for 1h

after setting and 300MPa for 24h after setting.

• The dimensional change between 5 min. and 24 h must fall

within the range of −15 to +20 μm/cm.

• The maximum allowable creep is 1%

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 PHYSICAL AND
MECHANICAL PROPERTIES
 PHYSICAL AND
MECHANICAL PROPERTIES
• Compressive Strength:

• Amalgam is strongest in compression and much weaker in

tension and shear.

• Forrapid application of stress either in tension or in

compression, a dental amalgam does not exhibit signi cant
deformation or elongation and, as a result, functions as a brittle
material: Fracture.

• Thecompressive strengths at 15 minutes for the high-copper

unicompositional alloys are signi cantly higher than for the
other alloys. What is the clinical signi cance?
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 PHYSICAL AND
MECHANICAL PROPERTIES
• Dimensional Change
• Most high-copper amalgams mixed with mechanical amalgamators usually
have negative dimensional changes (ie. undergo a net contraction):

• Initial contraction after a short time (the rst 20 min.) is associated with
the solution of the alloy particles in Hg.

• An expansion occurs due to the reaction of Hg with Ag and Sn and the

formation of intermetallic compounds.

• Contraction leaves marginal gap. Initial leakage (post-

operative sensitivity). Reduced with corrosion over time
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 EFFECTS OF MOISTURE
CONTAMINATION
• Results in excessive expansion

• Withzinc-containing amalgam, the moisture and zinc react

which liberate hydrogen gas which leads to delayed expansion

• Protrusion of the restoration leads to:

• Secondary caries at overhang

• Corrosion

• loss of strength
 DENTIST CONTROLLED
VARIABLES
• Manipulation

• Trituration

• Condensation

• Burnishing

• Polishing
• A, Alloypowder and mercury. B, Undertriturated amalgam is
dry and crumbly. C, Properly triturated amalgam has a satin-
like appearance. D, Overtriturated amalgam appears too wet.
 DENTIST CONTROLLED
VARIABLES
• Condensation

• Lathe cut alloys

• Small condensers / high forces

• Spherical alloys

• larger condensers, less sensitive to amounts of force

• Admixed alloys

• Intermediate
1.5mm ø 1.0mm ø

1N/mm2 = 1MPa, therefore require 10N/mm2

1.5mm diameter =1.76mm2 1.0mm diameter = 0.78mm2

= 17.6N = 7.8N
= 1.8Kg = 0.8Kg
2.5mm ø 3.65mm ø

1N/mm2 = 1MPa, therefore require 10N/mm2

2.5mm diameter =4.9mm2 3.65mm diameter = 10.5mm2

= 49N =105N
= 5Kg = 10.7Kg
Endodontic Plugger
 DENTIST CONTROLLED
VARIABLES
• Burnishing

• Pre-carve

• Removes excess mercury and

improves marginal adaptation

• Post-carve

• Improves smoothness

• Combined

• less leakage
 DENTIST CONTROLLED
VARIABLES
• Polishing

•8 min

• for those alloys which exhibit

high initial strength polishing
can be completed 8-10min
after trituration.

• 24 hour

• for those alloys which have low

initial strength, polishing should
be delay for 24 hours.
 “The non-gamma 2 admix alloy
unsurpassed by any other with its
high strength, high polishability
and superior handling qualities.
The alloy to mercury varies
between 46.2% to 49.5% by
weight mercury. The compressive
strength of Permite at 24 hours is
500 MPa, and the dimensional
change during hardening is
+0.04%”
• Carryingon the Valiant tradition in a phase-dispersed
formulation, Valiant Ph.D. has one of the lowest mercury
content of any dispersed phase system and a high copper
content that eliminates the Gamma II compound completely.

• Palladium enriched to build early strength, Valiant Ph.D. resists

corrosion, tarnishing and marginal deterioration. Plus, its new
particle size results in smoother carving, faster wetting, faster
setting and a denser amalgam mass. Valiant Ph.D. is also
available in extended working time formulas: Valiant Ph.D.
XT
219MPa
521MPa
 CDA POSITION ON
DENTAL AMALGAM
• Current scienti c evidence on the use of dental amalgam
supports that amalgam is an effective and safe lling material
that provides a long-lasting solution for a broad range of
clinical situations.

• Dentalamalgam delivers bene ts over other lling materials

with respect to ease of use and longevity, especially in patients
with a high risk of tooth decay.

• https://www.cda-adc.ca/_ les/position_statements/amalgam.pdf

• http://www.ada.org/en/about-the-ada/ada-positions-policies-
and-statements/statement-on-dental-amalgam
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THE MINAMATA CONVENTION
AND DENTAL AMALGAM
• The Convention’s provisions for dental amalgam—a mercury-
added product containing 50% mercury—make it highly
relevant to the dental profession.

• Dental amalgam is the only mercury-added product subject to a

phase-down. All other uses of mercury in products addressed in
the Convention are subject to a ban or phase-out (ban to take
effect at a later date). The Convention does, however, set out
nine provisions for its use.

• Theexpected result for dental amalgam is a reduction in

demand through increased efforts: at prevention, to use
alternative materials where clinically indicated
and to research improved alternative materials