Dental Amalgam

Course Date: 11/05 Reviewed/Updated: 10/10 Expiration Date: 10/13

Objectives
Review dental amalgam and its role in dentistry. Provide general information on types of amalgam, amalgam characteristics and handling properties, and alloy selection.

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

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 mercury-free alloys

1990s

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

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

For additional info please see the 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 voids

Sn8Hg called gamma 2

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
Ag3Sn + Hg
Ag-Sn Alloy Hg Sn Hg

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

Ag3Sn + Ag2Hg3 + Sn8Hg

1 2
Phillips Science of Dental Materials 2003

Conventional Low-Copper Alloys

Gamma ( ) = Ag3Sn

Hg

unreacted alloy strongest phase and corrodes the least forms 30% of volume of set amalgam Ag3Sn + Hg

Ag-Sn Alloy
Hg Hg Ag Sn Ag Sn Ag

Ag-Sn Alloy

Sn

Ag-Sn Alloy

Mercury

Ag3Sn + Ag2Hg3 + Sn8Hg

1 2
Phillips Science of Dental Materials 2003

Conventional Low-Copper Alloys

Gamma 1 ( 1) = Ag2Hg3

Ag-Sn Alloy

matrix for unreacted alloy and 2nd strongest phase 10 micron grains binding gamma ( ) 60% of volume Ag3Sn + Hg

1
Ag-Sn Alloy Ag-Sn Alloy

Ag3Sn + Ag2Hg3 + Sn8Hg

1 2
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

1 2
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

Hg Ag Ag-Sn Alloy

Ag Ag Sn Sn

Hg
Ag

Both Ag and Sn enter Hg from Ag3Sn particles

Ag3Sn + Ag-Cu + Hg

Ag-Sn Alloy

Mercury

Ag3Sn + Ag-Cu + Ag2Hg3 + Cu6Sn5

1
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

1
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

1
Phillips Science of Dental Materials 2003

Single Composition High-Copper Alloys

Gamma sphere ( ) (Ag3Sn) with epsilon coating ( ) (Cu3Sn) Ag and Sn dissolve in Hg
Ag-Sn Alloy
Ag Sn Sn

Ag
Ag-Sn Alloy Ag-Sn Alloy

Mercury (Hg)

Ag3Sn + Cu3Sn + Hg

Ag3Sn + Cu3Sn + Ag2Hg3 + Cu6Sn5

1
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

1
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 at expense of Ag

Now contain 9 to 30% Cu

Phillips Science of Dental Materials 2003

Particle Shape
Lathe cut

Spherical

low Cu

low Cu

New True Dentalloy ANA 2000

Cavex SF

high Cu

high Cu

Tytin, Valiant

Admixture

high Cu

Dispersalloy, Valiant PhD

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 Tytin (Kerr) Valiant (Ivoclar Vivadent)

Examples

 Composition

Admixture: Lathe-cut + Spherical Eutectic (ALE)

2/3 conventional lathe cut (3% Cu) 1/3 high Cu spherical eutectic (28% Cu) overall 12% Cu, 1% Zn no gamma 2 within two years

Initial reaction produces gamma 2

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 Valiant PhD (Ivoclar Vivadent)

Example

Manufacturing Process
Lathe-cut alloys

Ag & Sn melted together alloy is cooled

phases solidify

heat treated

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)

ratty edges or margins that catch are a result of mercuroscopic expansion of the material, leading to a small unsupported ledge of amalgam that is broken off during function. It is not recurrent caries. Most amalgam restorations placed in this country are replacements of older amalgamsthe rationale? Recurrent caries at the margin. ( usually an incorrect diagnosis) Isnt there a less invasive, better method than replacement? Why not place a sealant at the margin?

Creep
Slow deformation of amalgam placed under a constant load

load less than that necessary to produce fracture slow strain rates produces plastic deformation
allows gamma-1 grains to slide

Gamma 2 dramatically affects creep rate

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

Dentist-Controlled Variables
Manipulation

trituration condensation burnishing polishing

Trituration
Mixing time
refer to manufacturer recommendations

Overtrituration

hot mix

sticks to capsule

decreases working / setting time slight increase in setting contraction grainy, crumbly mix
Phillips Science of Dental Materials 2003

Undertrituration

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 less leakage

Ben-Amar, Dent Mater 1987

Combined

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

Alloy Selection
Handling characteristics Mechanical and physical properties Clinical performance

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)
Amalgam Type Low Copper1 1 hr 145 7 days 343 2.0 60

% Creep

Tensile Strength (24 hrs) (MPa)

Admixture2
Single Composition3
1Fine

137
262

431
510

0.4
0.13

48
64

Cut, Caulk Caulk 3Tytin, Kerr

2Dispersalloy,

Phillips Science of Dental Materials 2003

Survey of Practice Types

Civilian General Dentists

32%

Amalgam Free

Amalgam Users

68%

Haj-Ali, Gen Dent 2005

Amalgam use 2007

63.4% still use amalgam, 36.6 do not The dentists who still use amalgam are more satisfied with it as a material in 2007 than they were in 2000.

From ADA Council on Scientific Affairs, 2010

Amalgam Debate/Update It never ends

In June 2008, Consumers for Dental Choice required the FDA to withdraw claims of dental amalgams safety from its website and issue an advisory that clearly indicates that " Dental amalgams contain mercury, which may have neurotoxic effects on the nervous systems of developing children and fetuses. In July 2009, FDA classified dental amalgam as a class 2 medical device with moderate risk, even though recent extensive studies touted its safety. In December 2010, this issue will be debated again!

Frequency of Posterior Materials

by Practice Type
3% 7% 39%

Amalgam Users
51%

Amalgam

Direct Composite

Indirect Composite

Other

12% 8%

3%

Amalgam Free

Haj-Ali, Gen Dent 2005

77%

Profile of Amalgam Users

Civilian Practitioners
Do you use amalgam in your practice?
22%

Do you place fewer amalgams than 5 years ago?

12%

No Yes

No Yes

78%

88%

DPR 2005

Review of Clinical Studies

(Failure Rates in Posterior Permanent Teeth)
% Annual Failure

8 6 4 2 0

Amalgam

Direct Comp

Comp Inlays

Ceramic CAD/CAM Inlays Inlays

Gold Inlays & Onlays

GI

Longitudinal

Cross-Sectional
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

GI

Am al ga Di m re ct Co Co mp m po m Co er m p Ce In la ra ys m ic In la CA ys D/ CA M Ca st G ol d

Tu nn el

Manhart, Oper Dent 2004

AR T

Bottom Line (and editorial)

Amalgam is time-tested and has a record of incredible clinical success. However, it is not pretty, and there is exposure to mercury, but it is miniscule and will not put anyone at risk. Dental offices produce a significant amount of bound mercuric waste that has the potential for toxicity to the environment. Amalgam separators should take care of that issue, but there will still be consumer groups that argue the issue. Amalgam is the easiest, least expensive and least technique sensitive direct filling material we have. Dentists not getting good isolation or whose skill is below proficient should use amalgam in posterior direct restorations.

Editorial (cont.)
Dentists with excellent technique, isolation, and an appropriate matrix system should give the patient the option for either a composite restoration or amalgam after discussing the risks, benefits, and alternatives to treatment. Every case is different, and the provider must be able to articulate the rationale behind his/her recommendations. If there is a material that is obviously easier, better, and faster than amalgam we will finally see amalgam disappear.

References
Powers JM. Amalgam. In: Powers JM and Sakaguchi RL, eds. Craigs Restorative Dental Materials, 12th ed. Philadelphia: Elsevier, 2006: 236-259. Marshall SJ, Marshall GW, and Anusavice KJ. Dental Amalgams. In: Anusavice KJ, ed. Phillips Science of Dental Materials, 11th ed. St. Louis: Saunders, 2003: 495-540.