Dental Amalgam

Kraig S. Vandewalle, Col, USAF, DC

Official Disclaimer
The opinions expressed in this presentation are
those of the author and do not necessarily
reflect the official position of the US Air Force or
the Department of Defense (DOD)
Devices or materials appearing in this
presentation are used as examples of currently
available products/technologies and do not
imply an endorsement by the author and/or the
USAF/DOD

Overview

History
Basic composition
Basic setting reactions
Classifications
Manufacturing
Variables in amalgam
performance
Click here for briefing on dental amalgam (PDF)

History
1833

Crawcour brothers introduce

amalgam to US

powdered silver coins mixed with mercury

expanded on setting

1895

G.V. Black develops formula

for modern amalgam alloy

67% silver, 27% tin, 5% copper, 1% zinc

overcame expansion problems

History
1960s
conventional low-copper lathe-cut alloys
smaller particles

first generation high-copper alloys

Dispersalloy (Caulk)
admixture of spherical Ag-Cu
eutectic particles with
conventional lathe-cut
eliminated gamma-2 phase

Mahler, J Dent Res 1997

History
1970s

first single composition spherical

Tytin (Kerr)
ternary system (silver/tin/copper)

1980s

alloys similar to Dispersalloy and Tytin

1990s

mercury-free alloys

Mahler, J Dent Res 1997

Amalgam
An alloy of mercury with another metal.

Why Amalgam?
Inexpensive
Ease of use
Proven track record
>100 years

Familiarity
Resin-free
less allergies than composite
Click here for Talking Paper on Amalgam Safety (PDF)

Constituents in Amalgam
Basic
Silver
Tin
Copper
Mercury

Other
Zinc
Indium
Palladium

Basic Constituents
Silver (Ag)
increases strength
increases expansion

Tin (Sn)
decreases expansion
decreased strength
increases setting time

Phillips Science of Dental Materials 2003

Basic Constituents
Copper (Cu)
ties up tin
reducing gamma-2 formation

increases strength
reduces tarnish and corrosion
reduces creep
reduces marginal deterioration

Phillips Science of Dental Materials 2003

Basic Constituents
Mercury (Hg)
activates reaction
only pure metal that is liquid
at room temperature
spherical alloys
require less mercury
smaller surface area easier to wet
40 to 45% Hg

Click here for ADA Mercury

Hygiene Recommendations

admixed alloys
require more mercury
lathe-cut particles more difficult to wet
45 to 50% Hg

Phillips Science of Dental Materials 2003

Other Constituents
Zinc (Zn)
used in manufacturing

decreases oxidation of other elements

sacrificial anode

provides better clinical performance

less marginal breakdown

Osborne JW Am J Dent 1992

causes delayed expansion with low Cu alloys

if contaminated with moisture during condensation

Phillips RW JADA 1954

H2O + Zn ZnO + H2
Phillips Science of Dental Materials 2003

Other Constituents
Indium (In)
decreases surface tension
reduces amount of mercury necessary
reduces emitted mercury vapor

reduces creep and marginal breakdown

increases strength
must be used in admixed alloys
example
Indisperse (Indisperse Distributing Company)
5% indium

Powell, J Dent Res 1989

Other Constituents
Palladium (Pd)
reduced corrosion
greater luster
example
Valiant PhD (Ivoclar Vivadent)
0.5% palladium

Mahler, J Dent Res 1990

Basic Composition
A silver-mercury matrix containing filler particles of
silver-tin
Filler (bricks)

Ag3Sn called gamma

can be in various shapes

irregular (lathe-cut), spherical,

or a combination

Matrix

Ag2Hg3 called gamma 1

cement

Sn8Hg called gamma 2

voids

Phillips Science of Dental Materials 2003

Basic Setting Reactions

Conventional low-copper alloys
Admixed high-copper alloys
Single composition high-copper alloys

Conventional Low-Copper Alloys

Dissolution and precipitation
Hg dissolves Ag and Sn
from alloy
Intermetallic compounds
formed

Ag-Sn Alloy
Hg

Hg

Ag Ag
Ag
Sn
Sn
Ag-Sn
Ag-Sn
Alloy
Alloy
Mercury
(Hg)
Sn

Ag3Sn + Hg Ag3Sn + Ag2Hg3 + Sn8Hg

Phillips Science of Dental Materials 2003

Conventional Low-Copper Alloys

Gamma ( ) = Ag3Sn

unreacted alloy
strongest phase and
corrodes the least
forms 30% of volume
of set amalgam

Hg
Ag-Sn Alloy
Hg
Hg
Ag
Ag-Sn
Alloy

Sn
Sn

Ag

Ag

Sn

Mercury

Ag-Sn
Alloy

Ag3Sn + Hg Ag3Sn + Ag2Hg3 + Sn8Hg

Phillips Science of Dental Materials 2003

Conventional Low-Copper Alloys

Gamma 1 ( 1) = Ag2Hg3

matrix for unreacted alloy

and 2nd strongest phase
10 micron grains
binding gamma ( )
60% of volume

Ag-Sn Alloy

1
Ag-Sn
Alloy

Ag-Sn
Alloy

Ag3Sn + Hg Ag3Sn + Ag2Hg3 + Sn8Hg

Phillips Science of Dental Materials 2003

Conventional Low-Copper Alloys

Gamma 2 ( 2) = Sn8Hg

weakest and softest phase

corrodes fast, voids form
corrosion yields Hg which
reacts with more gamma ( )
10% of volume
volume decreases with time
due to corrosion

Ag-Sn Alloy

Ag-Sn
Alloy

Ag-Sn
Alloy

Ag3Sn + Hg Ag3Sn + Ag2Hg3 + Sn8Hg

Phillips Science of Dental Materials 2003

Admixed High-Copper Alloys

Ag enters Hg from Ag-Cu spherical eutectic
particles

Ag-Cu Alloy

eutectic

an alloy in which the elements are completely soluble in

liquid solution but separate into distinct areas upon
solidification

Both Ag and Sn enter Hg from Ag3Sn particles

Hg

Ag Ag
Ag

Ag-Sn
Alloy

Sn

Hg
Ag

Sn

Mercury

Ag-Sn
Alloy

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

Phillips Science of Dental Materials 2003

Admixed High-Copper Alloys

Sn diffuses to surface of
Ag-Cu particles

Ag-Cu Alloy

reacts with Cu to form

(eta) Cu6Sn5 ()

around unconsumed
Ag-Cu particles

Ag-Sn
Alloy

Ag-Sn
Alloy

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

Phillips Science of Dental Materials 2003

Admixed High-Copper Alloys

Gamma 1 ( 1) (Ag2Hg3)
surrounds () eta phase
(Cu6Sn5) and gamma ( )
alloy particles (Ag3Sn)

Ag-Cu Alloy

Ag-Sn
Alloy

Ag-Sn
Alloy

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

Phillips Science of Dental Materials 2003

Single Composition
High-Copper Alloys
Gamma sphere ( ) (Ag3Sn)
Ag-Sn Alloy

with epsilon coating ( )

Ag
(Cu3Sn)
Sn
Sn
Ag
Ag-Sn Alloy
Ag and Sn dissolve in Hg
Ag-Sn Alloy
Mercury (Hg)

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

Phillips Science of Dental Materials 2003

Single Composition
High-Copper Alloys
Gamma 1 ( 1) (Ag2Hg3) crystals
grow binding together partiallydissolved gamma ( ) alloy
particles (Ag3Sn)

Epsilon ( ) (Cu3Sn) develops

crystals on surface of
gamma particle (Ag3Sn)
in the form of eta () (Cu6Sn5)

Ag-Sn Alloy

Ag-Sn Alloy
Ag-Sn Alloy

reduces creep
prevents gamma-2 formation

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

Phillips Science of Dental Materials 2003

Classifications
Based on copper content
Based on particle shape
Based on method of adding
copper

Copper Content
Low-copper alloys
4 to 6% Cu

High-copper alloys
thought that 6% Cu was maximum amount

due to fear of excessive corrosion and expansion

Now contain 9 to 30% Cu

at expense of Ag

Phillips Science of Dental Materials 2003

Particle Shape
Lathe cut

low Cu

New True
Dentalloy

high Cu

ANA 2000

Admixture

high Cu

Dispersalloy, Valiant PhD

Spherical

low Cu

Cavex SF

high Cu

Tytin, Valiant

Method of Adding Copper

Single Composition Lathe-Cut (SCL)

Single Composition Spherical (SCS)
Admixture: Lathe-cut + Spherical Eutectic (ALE)
Admixture: Lathe-cut + Single Composition
Spherical (ALSCS)

Single Composition Lathe-Cut

(SCL)
More Hg needed than spherical alloys
High condensation force needed due to
lathe cut
20% Cu
Example

ANA 2000 (Nordiska Dental)

Single Composition Spherical

(SCS)
Spherical particles wet easier with Hg
less Hg needed (42%)

Less condensation force, larger condenser

Gamma particles as 20 micron spheres

with epsilon layer on surface

Examples

Tytin (Kerr)
Valiant (Ivoclar Vivadent)

Admixture:
Lathe-cut + Spherical Eutectic
(ALE)

Composition

2/3 conventional lathe cut (3% Cu)

1/3 high Cu spherical eutectic (28% Cu)
overall 12% Cu, 1% Zn

Initial reaction produces gamma 2

no gamma 2 within two years

Example

Dispersalloy (Caulk)

Admixture:
Lathe-cut + Single Composition
Spherical (ALSCS)
High Cu in both lathe-cut and spherical
components
19% Cu

Epsilon layer forms on both components

0.5% palladium added

reinforce grain boundaries on gamma 1

Example

Valiant PhD (Ivoclar Vivadent)

Manufacturing Process
Lathe-cut alloys

Ag & Sn melted together

alloy is cooled

heat treated

phases solidify
400 C for 8 hours

ground, then milled to 25 - 50 microns

heat treated to release stresses of grinding
Phillips Science of Dental Materials 2003

Manufacturing Process
Spherical alloys

alloy is melted
atomized

spheres form as particles cool

sizes range from 5 - 40 microns

variety improves condensability

Phillips Science of Dental Materials 2003

Material-Related Variables

Dimensional change
Strength
Corrosion
Creep

Dimensional Change
Most high-copper amalgams undergo a
net contraction
Contraction leaves marginal gap
initial leakage
post-operative sensitivity

reduced with corrosion over time

Phillips Science of Dental Materials 2003

Dimensional Change
Net contraction
type of alloy
spherical alloys have more
contraction
less mercury

condensation technique
greater condensation = higher contraction

trituration time
overtrituration causes higher contraction

Phillips Science of Dental Materials 2003

Strength
Develops slowly
1 hr: 40 to 60% of maximum
24 hrs: 90% of maximum

Spherical alloys strengthen faster

require less mercury

Higher compressive vs. tensile strength

Weak in thin sections
unsupported edges fracture
Phillips Science of Dental Materials 2003

Corrosion
Reduces strength
Seals margins

low copper

6 months

SnO2, SnCl
gamma-2 phase

high copper

6 - 24 months
SnO2 , SnCl, CuCl
eta-phase (Cu6Sn5)
Sutow, J Dent Res 1991

Creep
Slow deformation of amalgam placed under
a constant load

load less than that necessary to produce

fracture

Gamma 2 dramatically affects creep rate

slow strain rates produces plastic deformation

allows gamma-1 grains to slide

Correlates with marginal breakdown

Phillips Science of Dental Materials 2003

Creep
High-copper amalgams have creep resistance
prevention of gamma-2 phase
requires >12% Cu total

single composition spherical

eta (Cu6Sn5) embedded in gamma-1 grains

interlock

admixture

eta (Cu6Sn5) around Ag-Cu particles

improves bonding to gamma 1

Click here for table of creep values

Dentist-Controlled Variables
Manipulation

trituration
condensation
burnishing
polishing

Trituration
Mixing time
refer to manufacturer
recommendations
Click here for details

Overtrituration

hot mix

sticks to capsule

decreases working / setting time

slight increase in setting contraction

Undertrituration

grainy, crumbly mix

Phillips Science of Dental Materials 2003

Condensation
Forces
lathe-cut alloys
small condensers
high force

spherical alloys
large condensers
less sensitive to amount of force
vertical / lateral with vibratory motion

admixture alloys
intermediate handling between lathe-cut and spherical

Burnishing
Pre-carve
removes excess mercury

improves margin adaptation

Post-carve

improves smoothness

Combined

less leakage
Ben-Amar, Dent Mater 1987

Early Finishing
After initial set

prophy cup with pumice

provides initial smoothness to restorations
recommended for spherical amalgams

Polishing

Increased smoothness
Decreased plaque retention
Decreased corrosion
Clinically effective?
no improvement in marginal integrity
Mayhew, Oper Dent 1986
Collins, J Dent 1992
Click here for abstract

Alloy Selection
Handling characteristics
Mechanical and physical
properties
Clinical performance

Click here for more details

Handling Characteristics
Spherical
advantages
easier to condense
around pins

hardens rapidly
smoother polish

disadvantages
difficult to achieve tight contacts
higher tendency for overhangs

Phillips Science of Dental Materials 2003

Handling Characteristics
Admixed
advantages
easy to achieve tight contacts
good polish

disadvantages
hardens slowly
lower early strength

Amalgam Properties
Compressive
Strength (MPa)

% Creep

Tensile Strength
(24 hrs) (MPa)

Amalgam Type

1 hr

7 days

Low Copper1

145

343

2.0

60

Admixture2

137

431

0.4

48

Single
Composition3

262

510

0.13

64

Fine Cut, Caulk

2
Dispersalloy, Caulk
3
Tytin, Kerr

Phillips Science of Dental Materials 2003

Survey of Practice Types

Civilian General Dentists

32%

Amalgam
Free

Amalgam
Users

68%

Haj-Ali, Gen Dent 2005

Frequency of Posterior Materials

by Practice Type
3%

7%
39%

Amalgam Users
51%
Amalgam Direct Composite Indirect Composite Other
12%

3%

8%

Amalgam Free

Haj-Ali, Gen Dent 2005

77%

Profile of Amalgam Users

Civilian Practitioners
Do you use amalgam in
your practice?

Do you place fewer amalgams

than 5 years ago?

22%

No

No
Yes

Yes

78%

DPR 2005

Review of Clinical Studies

(Failure Rates in Posterior Permanent Teeth)
% Annual Failure

8
6
4
2
0

Am a lg a m

D ire c t
C omp

Comp
In la y s

L o n g itu d in a l

C e ra m ic
In la y s

C AD /C AM
In la y s

Go ld
In la y s &
O n la y s

GI

C ro s s -S e c tio n a l
Hickel, J Adhes Dent 2001

Review of Clinical Studies

(Failure Rates in Posterior Permanent Teeth)
% Annual Failure

15
Standard Deviation

10
Longitudinal and Cross-Sectional Data

5
0

Manhart, Oper Dent 2004

Click here for abstract

Acknowledgements
Dr. David Charlton
Dr. Charles Hermesch
Col Salvador Flores