Dental Amalgam

DENTAL AMALGAM

Where is it?

Elemental Mercury
Un-ionized mercury High vapor pressure
significant to dentistry

Absorption
readily from lungs poorly from GI and skin
< 0.1% not toxic when swallowed
Clarkson Crit Rev Clin Lab Sci 1987

Mercury Vapor
Accounts for most occupational and home exposures
mercury spills
thermometers fluorescent light bulbs

Significant toxicity when inhaled

80% absorbed by lungs

Acute toxicity is rare

Hursh Arch Environ Health 1976

Inorganic Mercury
Highly toxic as inorganic salts Hg2+ mercuric ion
mercuric oxide
swallowed batteries by children

mercuric sulfide
red tattoos

Hg1+ mercurous ion

mercurous chloride
laxatives teething powder
Wands Am J Med 1974 Litovitz Pediatrics 1992

Organic Mercury
Alkyl
methyl - most toxic form
95% absorbed in gut responsible for several mass poisonings
Minamata Bay, Japan - 1950 inorganic mercury dumped in bay methylated by aquatic organisms concentrates up food chain

ethyl preservative
Thimerosal
anti-microbial in pharmaceuticals

Aryl highly toxic

antifungal on seeds
Renzoni Environ Res 1998

Mercury Monitoring
Exhalation
difficult to perform reliably

Urine
best method for chronic exposure
symptoms 300 g/L normal < 25 g/L

Goldfranks Toxicologic Emergencies 1990

Mercury Monitoring
Blood
normal < 6 g/L reflects recent exposure
3-day half-life

reliable measurement of methylmercury exposure

Hair
not a reliable method
WHO Environmental Health Criteria

Dental Occupational Exposure

Higher mercury level found in providers with poor mercury hygiene
screening of dentists
2% had elevated urinary mercury levels
avg. 36 g/L

evidence of adverse preclinical effects

Echeverria Neurotoxicol Teratol 1995

Comparison of Toxic Effects

Amalgam
Systemic Toxicity - acute - chronic Allergic Reactions Anaphylaxis Cytotoxicity Mutagenicity or Carcinogenicity Lichenoid reactions
None Not verified Rare None Not verified Rare, but many components have allergic potential Isolated cases Slight to high Certain components mutagenic in vitro Yes None Not verified Extremely rare

Composite

Glass Ionomers

None so far Low None Yes

None so far Slight to high Slight mutagenicity None

WHO 1997

AMALGAM TERMINOLOGY
AMALGAM = an alloy containing Hg as the major ingredient. DENTAL AMALGAM = an alloy of Hg with Ag-Sn. DENTAL AMALGAM ALLOY = a Ag-Sn alloy (to be mixed with Hg).

ALLOY PRODUCTION
Melting / Casting / Comminution IRREGULAR Particles Cast ingots --> filed into powder Irregular particles = lathe cut = filings Polycrystalline particles Homogenized by HT to remove coring Annealing HT to relieve cold work in filings Melting / Spray Atomization SPHERICAL PARTICLES Hot alloy sprayed into cold air Particles spherodize and solidify Spheres are acid-washed Generally spheres are HT

Hg / Alloy RATIOS

50:50 42:58

ALLOY MANIPULATION
Manual Trituration Procedures: Alloy + Hg mortar + pestle manual mixing

Mechanical Trituration Procedures: Powdered alloy + Hg capsule + pestle Pelleted alloy + Hg capsule + pestle

amalgamator amalgamator

Powdered alloy + Hg

pre-capsulated

amalgamator

Dispersion Hardening
A crack will dead end or terminate on a sphere that is dispersed in the matrix, preventing a fatal crack of the material

Propagation of a dental amalgam crack

 Conventional amalgam mixed small spheres of the eutectic of AgCu in the powder, the phase The eutectic was used for the low melting point.

To incorporate dispersion hardening into dental amalgams:

Final composition of the dispersion strengthened amalgam (admixed alloy)

Before adding spheres After adding spheres

Ag Sn Cu Zn

71 % 26 % 2% 1%

69.7 % 17.7 % 12 % 0.9%

Sphere size ranged from 20-60m diameter

Dispersion Hardened Amalgam

Clinical experience showed that the amalgam performed well and showed little corrosion. The amalgam contained no 2 phase The spheres were disappearing from the amalgam

Setting Reaction
Sn7Hg + Ag3Cu 2 Sn5Cu6 + Ag3Hg 1

The 2 phase is converted to the and the 1 phase The Cu is the active metal in the conversion This reaction is slow, taking months to go to completion Cu could be added to the alloy
The Cu must replace the Ag not the Sn

The addition of spheres for dispersion hardening does not produce the intended result

High Cu single composition alloys

The development of making spheres of eutectics produced the technology of making spheres of ternary alloys, producing all-spherical alloys Most high copper alloys are spherical single composition alloys Particle sizes are below 30 m for most of these compositions

Single composition all-spherical alloys

The advantages of the all spherical particles is that Close dense packing can be achieved Less Hg is required ( 40 - 45 % by wt ) The amalgam sets faster (more surface area of the particles)

CLASSIFICATION
Copper content = low copper, high copper Particle size (and shape) = irregular, spherical Number of particle types = 1 or 2 Zinc content = Zn-containing, Zn-free

Application of system of nomenclature

Alloy Name: New True Dentalloy Velvalloy Dispersalloy Tytin Copper Content: Low Low High High Particle Shape: Irregular Irregular Both Spherical Number of Particles: 1 Particle 1 Particle 2 Particles 1 Particle Zinc Content: No No Yes No

Rx and MICROSTRUCTURE
Ag Sn Cu Zn Hg Primary reactant Creates solubility, fluidity Reacts with Sn Alloy processing aid Reactant with Ag (and Sn)

Irregular Alloy

Spherical Alloy

SETTING REACTIONS
Low-Copper Dental Amalgam: I/S-Alloy Ag-Sn Ag3Sn + Hg + Hg + Hg + Hg Residual Alloy Ag-Sn Ag3Sn + 1 + + Matrix-1 + Matrix-2 + Ag-Hg + Sn-Hg + Ag2Hg3 + Sn7-8Hg
2

1-Particle High-Copper Dental Amalgam: S-Alloy + Hg Residual Alloy Ag3Sn/Cu+ Hg Ag3Sn/Cu + Hg + 1 + I-Alloy S-Alloy Alloy + Hg Residual Alloy + Hg ( Ag3Sn) + + Hg Residual Alloy + Hg Alloy (Ag-Cu) + Matrix-1 + Matrix-2 + Ag2Hg3 + CuSn + Cu3Sn + + Matrix-1 + Matrix-2 + ( 2) + Matrix-1 + Matrix-2 + 1 + +

2-Particle High-Copper Dental Amalgam:

1

Rx and MICROSTRUCTURE

+ Hg

+ 1

+ 2

Penetrating Corrosion

Rx and MICROSTRUCTURE
+ Hg + spheres
69 Ag 18 Sn 12 Cu 1 Zn DISPERSALLOY

+ 1

+ +

PHASE DIAGRAMS

Ag3Sn + Hg >>> Ag2Hg3 = 1 (26Ag-74Hg)

1 Ag

Hg

Overview of Manipulation
TIME Onset of MIXING Placement and Condensation Onset of WORKING Carving Burnishing Polishing

Onset of SETTING

End of SETTING

24 hours

Selection / Proportioning / Amalgamation / Manipulation / Polishing

Amalgamators

SPEED TIME ENERGY = Speed x Time

Excess Hg-rich matrix eliminated by condensation.

Ag-Hg crystal reaction products

Residual alloy

Unset amalgam

Setting amalgam

DIMENSIONAL CHANGES
Dimensional changes on setting: CONTRACTION during alloy dissolution EXPANSION during impingement of reaction product crystals (EXPANSION if side reactions due to H2O contamination)
EXP (+)

ADA = 20 m

TIME

CONT (--)

Dimensional changes on depend on reaction variables: Particle size, Hg/alloy ratio, trituration time, condensation, ...

AMALGAM PROPERTIES
A. Introduction: 1. Specifications for Amalgam Properties a. ADA / ANSI and ISO b. Determination of safety and efficacy 2. Clinical Performance a. Longevity = 20-25 yrs ideally, 8-12 yrs practically b. Modes of failure = caries, marginal fracture, bulk B. Properties: 1. 2. 3. 4. Physical Mechanical Chemical Biological
UNITED STATES ADA ANSI WORLD

FDI ISO

Physical Properties
1. 2. 3. 4. 5. Thermal conductivity = [High] Electrical conductivity = [High] Coefficient of thermal expansion = 25 ppm/C Radiopacity = [>2 mm Aluminum] Color = [Lustrous, shiny, white]

Mechanical Properties
Compressive Strength (psi) 15-min 1-hr 24-hr LOW COPPER: Velvalloy Spheralloy HIGH COPPER: Optalloy II Dispersalloy Indiloy Sybraloy Tytin 5,400 17,400 56,200 5,800 18,500 56,900 9,100 6,200 4,600 23,800 10,200 23,800 22,400 26,300 50,000 40,800 55,900 59,900 64,500 72,700 79,100 Tensile Strength (psi) 15-min 1-hr 24-hr 625 450 1,000 575 450 2,190 990 1,900 1,550 2,350 1,750 2,400 4,700 4,000 9,000 8,800 7,250 6,990 6,500 6,600 9,300

Mechanical Properties
TYTIN (Kerr Dental Mfg) = tie up the tin High-Copper, Spherical, 1 Particle, Zn-free 42% Hg mixed with alloy Fast-setting High early strength

Fracture Surface Polished Surface

Chemical Properties
CHEMICAL CORROSION:
(b)

AgS
(a)

Sn-O-Cl Sn-O
Clean Surface, High O2 Potential (CATHODIC) Plaque Buildup, Low O2 Potential (ANODIC) Plaque Buildup

(a)

(b)

ELECTROCHEMICAL CORROSION: Galvanic corrosion Local galvanic corrosion (structure selective) Crevice corrosion (concentration cell) Stress corrosion

Biological Properties
Mercury Toxicity: OSHA maximum TLV = 50 g/m3 (vapor) per 40 hr work week. Transient intraoral release (<35 g/m3). Mercury Hypersensitivity: Low level allergic reaction. Estimated to be < 1 / 100,000,000 Amalgam Tatoo: Can occur during amalgam removal if no rubber dam. Embedded amalgam particles corrode and locally discolor gum. No known adverse reactions.

Clinical Performance
Reasons for Failure: Low-copper amalgam marginal fracture and secondary caries. High-copper amalgam marginal fracture and bulk fracture.
Penetrating Corrosion Superficial Corrosion Corrosion Products

Internal corrosion

Corrosion at margins

Sn-O-Cl and Sn-O

Jorgensen theory of mercuroscopic expansion (and marginal fracture)

Clinical Evaluation
Hi-Cu Mahler scale: Low-Cu

Hi-Cu, +Zn Hi-Cu, no Zn Low-Cu, +Zn Low-Cu, no Zn