 Ag-Cu


RECENT ADVANCES IN
AMALGAM

 Hg 
 Ag-Sn
 CONTENTS
• INTRODUCTION
• CLASSIFICATION
• COMPOSITION
• SETTING REACTION
• INDICATION
• CONTRAINDICATION
• ADVANTAGES
• LIMITATION
• RECENT ADVANCES
• -BONDED AMALGAM
• -GALLIUM ALLOY
• -INDIUM ALLOY
• -FLUORIDE CONTAINING
• -SELENIUM ALLOY
• - Hg FREE DIRECT FILLING SILVER ALLOY
• -PREAMALGAMATED ALLOY
• CONCLUSION
 INTRODUCTION
Amalgam is one of the oldest of all
materials used for restoring the carious
lesion. It has been used more than any other
materials in restorative dentistry. Thus on
the basis of frequency of use, one might say
that dental amalgam is the most important
restorative material used by the dentist.
• “Amalgam” derived from Greek word
“Emolient” which means paste.

 Amalgam is an alloy of 2 or more metals in

which one of the constituents is essentially Hg.

 Dental amalgam is an alloy of Hg, Ag, Cu &

Sn which may contain Zn, Pd & other elements
to improve handling characteristics & clinical
performance. (Kenneth. J. Anusavice)
 • CLASSIFICATION
• I. Based on No. of alloyed materials
 Binary : Ag – Sn
 Ternary : Ag – Sn – Cu
 Quarternary : Ag-Sn-Cu-In
II. Based on Cu content
 High Cu (6-30%)
 Low Cu (Less than 6%)
• III. Based on Zn content

 Zn free (less than 0.01%)

 Zn containing (0.01% or more)

IV. Based on Powder Particle size

 Microcut
 Fine cut
 Coarse cut
v. Based on composition .
 Unicomposition (Same chemical composition)
 Admixed (spherical eutectic high Cu + lathe
cut low Cu) .

VI. Based on shape of powdered particles .

 Spherical.
 Lathe cut .
 Spheroidal.
VII. Based on addition of noble metals
 Palladium
 Gold
 Platinum
 Indium
VIII. Based on generation
1st Generation – 3 parts Ag +1 part Sn
(Peritectic)
2nd Generation–3 parts Ag+1 part Sn+Cu +
1% Zn
3rd Generation – blending spherical Ag-Cu
(Eutectic) to original powder

• 4th Generation – Alloy Cu to Ag & Sn upto

29% ternary alloy

• 5th Generation - Ag + Cu + Sn + In

• 6th Generation – Alloy Pd (10%), Ag (62%) &

Cu(25%) to 1st, 2nd, 3rd generation
 LOW COPPER ALLOY
• Silver: 63-70%
Tin :26-28%
• Copper : 2- 5%
Zinc : 0-2%
1.SILVER
• Constitutes 2/3rd of amalgam alloy
• Increases strength
• Increases expansion
• Decreases creep and flow
Increases resistance to tarnish and corrosion

2. TIN
• Decreases setting expansion
• Decreases Strength
• Decrease tarnish resistance
• Increases setting time
• 3. COPPER
• Decreases brittleness

• Increases hardness

• Increases setting expansion

• 4. ZINC
• Scavenger

• Increases plasticity

• Decreases tarnish & corrosion

• Prevents oxidation of alloy during

manufacture .
5. PALLADIUM

Increases hardness

Whitens alloy

• 6. MERCURY
• Sometimes present in alloy powder in

range of 2 – 3% - PRE AMALGAMATED

ALLOY
 SETTING REACTIONS

LOW COPPER
On trituration Sn & Ag dissolve into Hg .
Hg has limited solubility for Ag 0.035 wt% & 0.06
wt% for Sn .
Solubility of Ag < Sn Therefore, 1 ppt.
When solubility exceeds, crystals of 2 binary metallic
compounds ppt. into Hg .
These are body centered cubic Ag2Hg3 (1) &
hexagonal Sn7Hg ( 2) .
Alloy particles ( β +  )+ Hg - 1 + 2 + unconsumed
alloy.
• After trituration - alloy powder coexists
with liquid Hg - plastic consistency of
mix .
• Remaining Hg dissolves alloy particles (Ag-
Sn) covered with newly formed 1 crystals
- Reaction rate decreases  alloy
hardens .
• Hg insufficient to completely consume alloy
 unconsumed particles present in set
amalgam .
• Low Cu amalgam  unconsumed particles
embedded in 1 & 2 phases .
• Dominating phase in well condensed low copper amalgam is  1

(54 % - 56%) ; unreacted alloy (27%-35%) &  2 (11% - 13%) .

• More the unconsumed alloy , more strong the amalgam .

• Weakest phase   2  least stable in corrosive environment

•  phase strengthens amalgam when bound to matrix .

•  > 1 >  2 .
The original Gamma Phase (Ag3Sn) - which has not been
completely dissolved in mercury. Strongest phase and it
could occupy maximum available space in the volume of
restoration.

The Gamma -1 Phase (Ag2Hg3) – is the noblest phase and

most resistant to tarnish and corrosion.

The Gamma -2 Phase (Sn7-8Hg) – it is least resistant to

tarnish and corrosion. More prone to corrosion and creep

The Mercury Phase – unreacted residual mercury will be

present within the amalgam mass. Weakest phase and when
exceeds a certain volume limit, there will be drastic drop in
the strength of the amalgam.
 The Voids (Pores) Phase- occurs on the process of
building amalgam restoration. Traps air bubbles or
voids lead to corrosion and early failure of
restoration.

 The Trace Element Phase – in which copper and zinc

might be found, only in trace amounts in the final
product.

The Inter Phase – applies to the inter phases

between gamma, gamma -1 and gamma -2. In the final
restoration, the more continuous they are and close
together, the better is the bonding.
• High copper alloys: It is the material of choice

because of their improved mechanical properties,

corrosion characteristics and better marginal

integrity, as compared to low – copper alloys . As

silver-copper particles acts as strong fillers

strengthening the amalgam matrix

• There are 2 basic types :

1. Admixed alloys
• Single composition

• COMPOSITION OF ADMIX ALLOYS

• Silver-69 %
• Copper-13 %
• Tin-17 %
• Zinc-1 %
• Admixed alloys:

• In 1963, Innes and Youdelis added spherical –

copper eutectic alloys which contained about 79%

wt of silver and 28% of copper particle to lathe cut

low copper amalgam alloys, which was the major

change in the composition of alloys since GV Black’s

work on amalgam.
• These admixed alloys consists of 30-50wt%
of spherical high copper powder.The copper
content ranges from 9-20%.

• The silver - copper alloy consists of mixture

of two phases, a silver rich and copper rich.
When mercury reacts with an admixed alloys
there are two simultaneous mechanisms taking
place.
• The silver enters the mercury from the copper silver alloy particle and both silver

and tin enter the mercury from Ag-Sn. And will form  1 and  2 phase,leaving

some unreacted silver tin particles .The  2 phase will react with Ag-Cu alloy

particles and react to form a new phase called Eta phase () (Cu+Sn) The gamma

1 phase also forms simultaneously surrounds both the eta-covered Ag-Cu alloy

particle and the AgSn alloy particles

• Alloy particles (+ ) + Ag-Cu eutectic + Hg  1 +  + unconsumed alloy of both types of

particles
• Single composition alloys:

• These alloys are called so, because each particle of

their alloy powder has the same chemical

composition,unlike admixed alloy powders. Therefore,

they are called single – composition or

unicompositional alloys.
• The spherical alloy particles are 5 to 40 um in size.

• Composition:

• Silver 40-60%

• Tin 22-30%

• Copper 13-30%

• Zinc 0-4%

• AgSnCu + Hg Cu6Sn5 +Ag2Hg3 +AgSnCu

 INDICATION FOR USE OF AMALGAM

In Class I, Class II, Class V, and Class III on distal of

cuspids
Cemental caries
Short life expectancy of tooth
Preventive procedure
Core build-up
Age of the patient
Galvanism
Complex restoration
Retrograde filling
Economic
 CONTRAINDICATION

ANTERIOR TEETH :Occasionally a class III

amalgam restoration may be done if isolation
problem exist. In rare situations,classV amalgam
restoration is indicated in anterior areas where
esthetics is not important.
Small to moderate defect in posterior should
be restored with composite as preparation for
amalgam is larger.
 ADVANTAGES
Ease of use
High compressive strength
Execellant wear resistance
Favorable long term clinical research
results

Lower cost than for composite

restoration
 DISADVANTAGES

Noninsulating
Nonesthetics
Less conservative
Weakens tooth structure
More technique sensitive
More difficult tooth preparation
Initial marginal leakage
 Limitations of Dental Amalgam

The shortcomings of dental amalgam are;

Poor esthetics
Mercury toxicity

High thermal conductivity

Galvanic effects
Lack of adhesion

Secondary caries

Marginal integrity
• RECENT ADVANCES IN DENTAL
AMALGAM:

 BONDED AMALGAM
 GALLIUM ALLOYS
 INDIUM ALLOYS
 FLUORIDE CONTAINING AMALGAM
 SELENIUM CONTAINING AMALGAM
 Hg FREE DIRECT FILLING SILVER ALLOYS
 PREMALGAMATED ALLOYS
 BONDED AMALGAM RESTORATION:

Adhesive systems designed to bond

amalgam to enamel and dentin . They
have been introduced in an effort to
compensate for the "disadvantages
particularly marginal microleakage and
need for additional retentive devices.
 ADVANTAGES
The advantages of adhesive amalgam restoration over
non-adhesive treatment alternatives are

It is a treatment option for extensively carious

posterior teeth, with a lower cost than either cast metal
restoration or metal-ceramic crowns.
It allows use of amalgam in teeth with low gingivo-
occlusal height which is not possible in conventional
amalgam, amalgam with pins, inlays, onlays, complete cast
crown restoration.
 It permits more conservative cavity preparations, as it
does not require additional retention in form of groove, pins
etc.
It reduces marginal leakage to minimal.
It reinforces the tooth structure weakened by caries and
cavity preparation, which is not with pin amalgam.
It reduces incidence of post-operative sensitivity
commonly observed with amalgam restorations.
It reduces incidence of marginal fracture and recurrent
caries.
It can be done in single sitting.
It allows for amalgam repairs.
AMALGAM BONDING AGENTS:
Some bonding agents which are able to bond amalgam to
tooth structure are:
Amalgam bond plus
All Bond 2 and AU Bond Liner F
Panavia Ex .
Chemical composition
Amalgam bond plus:
Activator/Conditioner: 10% citric acid, 3% ferric
chloride.
Wetting agent: HEMA (Hydroxyethyl methacrylate).
Catalyst: TBB(Tri-N-Butyl-Borane oxide).
Base: 4META(4-Methacryloxyethyl trimellitate
anhydride).

INDICATIONS
•Auxiliary retention, reinforcement of remaining tooth
structure and improvement of marginal seal.
•Extensively carious posterior teeth.
•Teeth with low gingivo occlusal height.
 ADVANTAGES
It increases the fracture resistance of restored
teeth.
It blocks bacterial microleakage at the enamel
margins and ensures long-term success against
recurrent caries.

It improves the retention with no need for undercuts

allowing conservative preparations.

It provides a seal at the margins and reduces

postoperative sensitivity.

Allows biological sealing of pulpo-dentin complex.

 MECHANISM OF BONDING
First the dentin and enamel are treated with an acid
conditioner i.e. 10% citric acid, 3% ferric chloride for 10
seconds. This causes the removal of smear layer and
partial demineralization of dentin with removal of only
apatite mineral and preserving the integrity of dentinal
protein molecules.

These open pores are now penetrable by 4

META/MMA-TBB monomer. Monomer penetration can be
improved by treating the surface with application of
HEMA. This will enhance the diffusion of monomer into
the dentin and around the exposed collagen.
To enable the polymerization in situ, accomplished
by unique initiator, tri-n-butyl borane (TBB) in
conjunction with O2 and H2O available from dentinal
tubules.

Once polymerized, the resin formed not only

entangles and envelops collagen but also
encapsulates hydroxyapatite crystals, creating the
acid-resistant, insoluble transitional zone, hybrid
layer. The width of hybrid layer in 5 m and is
sandwiched between cured resin and dentin.
LIMITATIONS OF BONDED AMALGAM

Time consuming and may be technique sensitive due to

bonding agents used.
Requires practitioner to adapt to new technique.
Increases cost of amalgam restorations.
 GALLIUM ALLOYS
Recent controversy surrounding mercury has
renewed interest in developing a mercury free
restorative material with physical properties
comparable to dental amalgam.
Puttkammer suggested the use of gallium in
dental restoration in 1928. However, attempts
to develop satisfactory gallium restorative
materials were unsuccessful until Smith and
others in 1956, showed that improved Pd-Ga and
Ag-Ga materials has physical and mechanical
properties that were similar to or even better
than those of silver amalgam.
 Composition
Alloy:
Liquid:
Silver (Ag) 60% Gallium (Ga) 62%
Tin (Sn) 25% Iridium (Ir) 25%
Copper (Cu) 13% Tin (Sn) 25%
Palladium (Pd) 20%

Reaction

The alloy and liquid are mixed as usual. The structure of gallium
alloy resembles that of amalgam. The reaction between AgSn
particles and liquid Gallium involves the formation of AgGa phase
and a pure tin phase.
AgSn + Ga  AgGa + Sn.

After mixing, the alloy tends to adhere to the walls of capsule, thus
difficult to handle. Moreover, by adding few drops of alcohol, the
problem of sticking can be minimized.
ADVANTAGES OF GALLIUM BASED ALLOYS
Rapid solidification.
Good marginal seal by expanding on
solidification.
Heat resistant.
The compressive and tensile strength
increases with time comparable with silver
amalgam
Creep value are as low as 0.09%
It sets early so polishing can be carried out
the same day
LIMITATIONS
After mixing the alloy tends to adhere to the capsule.
The setting expansion of 0.39% for the gallium alloy
suggests there may be a problem if the material is used to
restore large cavities, especially where weakened cusps
may be prone to fracture as the setting material expands.
Poor handling characteristics of gallium alloy may make
its use in the clinical situation extremely difficult.
The product suffers from some limitations especially
excessive corrosion and decreased workability (Navarro et
al, 1996).
Hg free direct filling silver alloys

 Mercury free direct filling alloy based

on mercury coated Ag-Sn particles that
can be self welded by compaction to create
a restoration.
If alloy particle size are chosen judiciously
chosen to pack together well,it is possible
to minimize the mercury required for
mixing to the 15%-25% range.
 FLUORIDE RELEASING AMALGAM
• A fluoride-releasing dental amalgam composition for a
tooth restoration comprising mixture of a dental amalgam
alloy material and a glass particulate powder component of
a fluoride-containing, fluoride-leachable acid-etchable
glass ionomer cement.

• wherein the amalgam alloy material comprises:

40-70% Silver 26-30% Tin 2-30% Copper 0-2% Zinc
• glass particulate powder comprises:
• 41.9-35.2% SiO2
• 28.6-20.1% Al2O3
• 1.6-2.4% AlF3.
• 15.7-20.1% CaF2
• 9.3-3.6% NaF
• 3.8-12.0% AlPO4.
• The present invention relates to a composition
comprised of a novel dental amalgam
restorative material that releases fluoride
through the judicious incorporation of an acid-
leachable glass component which has been
preferably sintered with elemental silver.
• The silver contained in the glass becomes
incorporated into the set amalgam matrix
(gamma 1), thus chemically bonding the particle
to the restoration surface. Upon exposure to an
acid environment, the acid leachable glass
particle at the restoration surface will elute
small amounts of fluoride, which provides a
cariostatic effect on surrounding tooth
structure
ADVANTAGES
• The capability to reduce the possibility of
secondary decay approximate to a
restoration as a result of fluoride release.
• Provides a cariostatic effect on
surrounding tooth structure.
• An additional advantage to this system is
that the fluoride content of the glass
particles can be recharged with the use of
a fluoride-containing dentrifice, or with
periodic applications of topical fluoride
• A Study of in vivo Fluoride Uptake by Dental
Tissues from Fluoride-containing Silver Amalgams
Teeth to be extracted for orthodontic reasons
were filled in vivo with regular and fine-cut silver
amalgams containing 1%o and 5% SnF2. The teeth
were extracted after 15 or 30 d, and the in vivo
fluoride release and uptake by the dental tissues
were studied using an electron microprobe analysis
technique. The obtained results show that the use
of SnF2 silver amalgams can be of potential value
for minimizing caries adjacent to dental
restorations.

• J Dent Res 60(2):105-108 February 1981

 Selenium-containing amalgam
• Selenium-containing amalgam alloys for
dental restoration comprising of a
copper alloy powder containing no less
than 50% by weight of copper and 0.01-
5% by weight of selenium, mixed with
50-99.9% by weight of a silver-tin-
copper amalgam alloy powder.
• The amalgams have their mechanical properties
affected by the functions of various γ 2 , ε and
η phases formed therein. When selenium is
present, however, its part reacts with silver to
yield a SeHg phase in addition to the said
various phases found in the conventional
amalgams. That SeHg phase forms just after
triturating alloy and mercury, and has an
influence on both a lowering of the plasticity of
an amalgam slurry, which contributes to
increasing the initial compressive strength, and
improvements in the mechanical properties of
the set amalgam, such as its final compressive
strength or flow.
Indium containing alloy & binary mercury – Indium
liquid alloy
 Powell et al in 1989
 Pure indium powder admixed into
dispersed phase high Cu alloy .
 Decrease in mercury evaporation
 As the amount of indium increased from 0
to 14%  decrease in Hg vapour .

 Commercially available in name of

‘Indisperse’
• Pre Amalgamated Alloys:

• In this, the surface of alloy particles

has been introduced to mercury by
manufacturer for rapid amalgamation
after trituration to make pre-
compacted pellets.
• Pre amalgamated alloy contain upto 35%
mercury and may be indirectly
responsible for reducing total mercury
content to less than 40%.
 CONCLUSION
Dental amalgam has been used in dentistry for over
150 years. From the conventional composition of dental
amalgam which was proposed by Dr. G.V.Black to the new
generation adhesive, amalgam has come a long way with
the advent of adhesive materials, which actually bonds
amalgam to the tooth structure, the protocol for
placement of amalgam restoration has changed.
There are certain advantages inherent with amalgam
such as technique insensitive, excellent wear resistance,
less time consuming, less expensive which are not
present in the newer materials, these factors will
continue to make amalgam the material of choice for
many more years to come.
REFERENCE:-

Phillips Science of dental materials,

Anusavice; 11th edition
Textbook of operative dentistry; Vimal K
Sikri
Sturdevant’s Art and science of operative
dentistry, Theodore M Robertson; 5th edition