Dental Casting Alloys

Applications

All metal restoration

Removable Partial Denture (RPD)

Metal-ceramic or Porcelain-fused to metal restoration

Objectives
Understand the alloy classifications Know the roles of each element in dental casting alloys Know the requirements of porcelain-fused to metal (or metal-ceramic) alloys Understand the relation between the TCOE of PFM alloys and that of ceramics Recognize the importance of some properties of the alloys

History
1907 : Lost wax technique by Taggart 1932 - 1948 : Standardization of dental casting alloys 1950s -1960s : Development of porcelain-fusedto-metal (PFM) alloys
Found that adding Pd and Pt to gold (Au) would lower coefficient of thermal expansion sufficiently to ensure physical compatibility between the porcelain veneer and the metal substructure.

History
1970s : Placement of gold on the free market
Increased prices stimulates the search for alternative low gold and base metal alloys.

Terminology
Noble metals
Elements with good metallic surfaces that retain their luster in clean dry air Indicate the relative inertness of the element in relation to the standard EMF series Resist oxidation, tarnish and corrosion during heating casting and soldering
Platinum group (6 metals)
Platinum, Iridium, Osmium (atomic wt 190, density 22 g/cc) Palladium, Rhodium, Ruthenium (atomic wt 100, density 11-12 g/cc)

Gold (atomic wt 196, density 19.3 g/cc) (Silver?)

Terminology
Precious metals
Indicates how expensive a metal is based on supply and demand. **The descriptors precious and semiprecious should be avoided because they are imprecise terms.

Terminology
Gold content of a dental alloy
Karat, Carat (K)
Parts of pure gold per 24, e.g. 18K, 24K

Fineness
Parts of pure gold per 1,000
e.g. a 650 fine alloy has a gold content of 65%

Primarily used for gold solders

Pennyweight (dwt.)
1 dwt = 1.555 gm = 0.05 oz
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Classification
ADA Specification #5 Principal Elements

ADAs Classification

Descriptive Classification
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ANSI/ADA Specification #5
Referred to Gold-based alloys
Alloys can have any composition as long as they pass the tests for toxicity, tarnish, yield strength, and percent elongation.
Type I (soft) %Au & Pt 83 78 78 75 VHN 50-90 90-120 120-150 150-250 Restoration Inlay Inlay/onlay Onlay/Crown&B ridge Crown&Bridge/ RPD
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Strength

II (medium) III (hard) IV (extra-hard)

ADAs Classification (1984)

1. High noble (HN) 2. Noble (N) 3. (Predominantly) Base metal (PB)
Alloy Type High noble metal Noble metal Base metal Total Noble Metal Content Contains > 40 wt% Au and > 60% of the noble metal elements Contains > 25 wt% of the noble meal elements (Au, Pd, Pt) Contains < 25 wt% of the noble metal elements
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*No discrimination among alloys within a given category*

Principal Elements
When an alloy is identified according to the elements it contains, the components are listed in declining order of composition, with the largest constituent first followed by the second largest constituent.
e.g. Au-Ag-Pt (Au ~ 78%, Ag ~ 12%, Pt ~10%)

Exception: Certain elements that significantly affect physical properties or that represent potential biocompatibility concerns are often designated (regardless of their small amounts).
e.g. Au-Cu-Ag-Pd (Au ~40%, Cu ~7.5%, Ag ~47%, Pd~4%)
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Descriptive Classification
Normal-fusing alloys
Medium-gold Low-gold Silver-palladium Silver-indium

High-fusing alloys
(mostly for PFM) Gold-platinum-palladium Gold-palladium-silver Gold-palladium High-palladium Palladium-silver Base-metal
Cr/Co; Cr/Ni

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Alloy Type

Restoration Type

All-Metal Restorations

Metal-Ceramic and All-Metal Restorations

RPD

High Noble > 40 wt% Au and > 60% of the noble metal elements Noble > 25 wt% of the noble metal elements

Au-Ag-Cu-Pd

Au-Pt-Pd Au-Ag-Cu-Pd Au-Pd-Ag (5-12 wt% Ag) Au-Pd-Ag (>12 wt% Ag) Au-Pd (no Ag)
Pd-Au (no Ag) Pd-Au-Ag Pd-Ag Pd-Cu Pd-Co Pd-Ga-Ag Pure Ti Ti-Al-V Ni-Cr-Mo-Be Ni-Cr-Mo Co-Cr-Mo Co-Cr-W

Ag-Pd-Au-Cu Ag-Pd

Ag-Pd-Au-Cu Ag-Pd

Base Metal < 25 wt% of the noble metal elements

Pure Ti Ti-Al-V Ni-Cr-Mo-Be Ni-Cr-Mo Co-Cr-Mo Co-Cr-W

Fundamental Properties of Noble Metals

Gold (Au) Platinum (Pt) Palladium (Pd) Silver (Ag) Minor alloying elements

Gold (Au)
Soft, (most) malleable and ductile Relatively low strength Tarnish resistant in air and water at any temp. Attacked by only a few of the most powerful oxidizing agents Insoluble in sulfuric, nitric, or hydrochloric acids Soluble in a combination of nitric and sulfuric acids (aqu a-regia) Small amounts of impurities (ie. lead, mercury, base met als) have a pronounced and usually detrimental effect on its properties.
Fusion temp = 1063C Density = 19.3 g/cm3 Thermal coef. of exp. = 14.2x10-6/C MOE = 80 GPa

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Platinum (Pt)
Tough, malleable and ductile Very high cost (usually replaced by Pd in most modern alloys) High corrosion resistance Higher melting temp than porcelain
Fusion temp = 1755C Density = 21.37 g/cm3 Thermal coef. of exp. = 8.9x10-6/C MOE = 147 GPa

>Au >Au <Au >Au

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Palladium (Pd)
Not used in the pure state dentistry Has replaced Pt in dental casting alloys Decreased cost v.s. Pt Helps prevent corrosion of silver in the oral environmen t Absorbs H2 gas when heated improperly
Fusion temp = 1555C Density = 11.4 g/cm3 Thermal coef. of exp. = 11.1x10-6/C MOE = 112 GPa

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Silver (Ag)
Noble? Malleable and ductile Best known conductor of heat and electricity Harder than gold Unaltered in clean dry air, however, combines with sulfur, chlorine and phosp horus resulting in severe t arnish in the oral environ ment
Occludes large quantities of O2 in molten state O2 gas will evolve during solidification resulting in pits and porosities.
Fusion temp = 960.5C Density = 10.4 g/cm3 Thermal coef. of exp. = 19.7x10-6/C MOE = 120 GPa

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Minor Alloying Elements

Iridium (Ir) - grain refining Ruthenium (Ru) - grain refining

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 Grain refining
The addition of as little as 50 ppm (0.005%) of Ir and Ru results in a 100x increase in the no. of gr ains per unit volume. Increases the alloys tensile strength and %elongation by >30% Increases tarnish resistance, slightly increases yield strength Does not appreciable affect hardness

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Alloys for All-Metal Restoration

High-noble and Noble Metal Alloys
Au-Ag-Cu-Pd Ag-Pd Metal Ceramic Alloys

Base Metal Alloys

Au-Ag-Cu-Pd Alloys
Primarily ternary alloys of Au, Ag and Cu, with minor amounts of Pt, Pd and Zn. Approx. >90% of the total alloy content is Au, Ag and Pd

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Au-Ag-Cu-Pd: Composition
Gold (Au)
Tarnish and corrosion resistance
Tarnish is an inverse function of gold content.

Silver (Ag)
Helps control the color of the alloy, neutralizing the red color imparted by Cu Promotes ductility
Au/Cu alloys (75% Au) break apart at grain boundaries during heat treatment if no Ag is present.

Contributes burnishability, ductility, and ability to heat harden the alloy

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Au-Ag-Cu-Pd: Composition
Platinum (Pt)
Very expensive ingredient Contributes strength Whitens the alloy Increases the fusion temperature

Palladium (Pd)
Like Pt but more effective and less expensive than Pt Alloying metal of choice v.s. Pt

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Au-Ag-Cu-Pd: Composition
Copper (Cu) ***
Principle hardener in gold alloys Conc. >12% of Au amount alloy can be heat treated Conc. >18% decrease the melting temp of the alloy

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Au-Ag-Cu-Pd: Composition
Copper (Cu) ***
When alloyed with Ag, Cu increases the alloys hardness and decreases melting temp. Cu imparts a reddish color to the metal and contributes most to the corrosion of gold alloys. Ag/Cu ratio is important to tarnish resistance (but not as important as the Ag/Pd ratio). Cu is not found in PFM alloys due to its tendency to discolor the porcelain.

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Au-Ag-Cu-Pd: Composition
Zinc (Zn)
O2 scavenger 1-2% helps to counteract the absorption of O2 by silver. Increases the castability, decreases porosities, and increases the hardness and brittleness of the alloy

Indium (In), Tin (Sn), Iron (Fe)

Hardens the alloy
(Provides oxides for ceramic bonding in PFM alloys)

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Au-Ag-Cu-Pd: Composition
Iridium (Ir), Ruthenium (Ru), Rhenium (Rh)
Grain refining Gallium (Ga)
Added to high Pd alloys or non-silver Au/Pd metal ceramic alloys to compensate for a decrease in the TCOE caused by the elimination of the Ag. (Also provides oxides for ceramic bonding)

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Au-Ag-Cu-Pd: Composition
Alloy Type

Main Elements High noble (Au base) High noble (Au base) High noble (Au base) Noble (Au base) High noble (Au base)

Cu/ Au

Au 83 77 75 46 56

Cu 6 7 9 8 14

Ag 10 14 11 39 25

Pd 0.5 1 3.5 6 4

Sn, In, Fe, Zn, Ga

I II III III IV

7% 9%
12% 17%

Balance Balance Balance Balance Balance

25%

Copper: Conc. >12% of Au amount alloy can be heat treated Conc. >18% decrease the melting temp of the alloy

Types I and II gold cant be heat treated and have a higher melting temp v.s. Types III and IV.
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Heat Treatment
Cu/Au system is the basis for heat treatment
Cu:Au ratio > 12:88 the alloy is heat treatable.

100%Au

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Heat Treatment
Above 424C solid solution
Quenching from above 424C will result in a softer, more ductile alloy with decreased strength solid solution
424C

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Heat Treatment
Below 424C ordered crystal lattice
Alloy has increased strength, hardness and decreased ductility. The amount of transformation is time and temperature dependent and the process is reversible.

424C

Ordered crystal lattice

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Softening Heat Treatment (Solution Heat Treatment)

Heat alloy to 700C for 10 min. then quench.
Decreased tensile strength, proportional limit and hardness Increases ductility and %elongation MOE not significantly altered.

700C 424C

Indicated prior to adjusting, burnishing and polishing

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Hardening Heat Treatment (Age Hardening)

Heat alloy to 450C for 2 min., cool slowly to 250C over 30 mins then quench. Or Heat to 350C for 10 15 min. and quench
Increases strength, proportional limit and hardness Decreases ductility and %elongation
424C

Indicated for RPD frameworks and long span FPDs

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Silver-Palladium Alloys (Ag-Pd)

Ag:Pd ratio approx 3:1 (60-70% Ag, 25% Pd) to render silver tarnish resistant in the oral cavity. Both Ag and Pd absorb gases during heating, casting is very technique sensitive. Pd-Ag alloys (for PFM restorations)
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Ag-Pd: Composition
Alloy Type

Main Elements Noble (Ag base) Noble (Ag base)

Cu/ Au

Au

Cu

Ag 70

Pd 25 25

Sn, In, Fe, Zn, Ga

III IV

Balance Balance

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14

45

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Alloys for PFM or Metal Ceramic Restoration

Au-Pt-Pd Au-Pd-Ag Au-Pd Pd-Ag High Pd

No Copper!

Firing
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some important

Requirements

Must have the potential to bond to dental porcelain

need oxide-forming elements (small amount of base metals)

Posses coefficient of thermal contraction compatible with those of dental porcelains Sufficiently high solidus temp (fusing temp) to permit the application of low-fusing porcela ins
>100C than the firing temp of the ceramic
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Ceramic-Metal Bond
Typically, TCOE of porcelain = 13.0 to 14.0 x 10-6/C and the metals = 13.5 to 14.5 x 10-6/C . The difference of 0.5 x 10-6/C causes the metal to contract slightly more than does the ceramic during cooling after firing t he porcelain. This condition puts the ceramic under slight residual compression, which makes it less sensitive to applied tensile f orces.

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Gold-Platinum-Palladium Alloys (Au-Pt-Pd)

Composition
Au (84-86%); Pt (4-10%); Pd (5-7%); Ag (0-5%); Fe, In, Sn (2-3%) (high noble)

Advantages
Excellent bonding to porcelain Reproduces fine margins and occlusal detail Easily finished and polished Corrosion resistant and non-toxic Adequate yield strength and MOE (most cases)

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 Disadvantages
low sag and creep resistance not strong enough for long span FPDs High cost

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Gold-Palladium-Silver Alloys (Au-Pd-Ag)

Composition
Au (45-52%); Pd (26-31%); Ag (6-16%); In, Sn (5-7%) (high noble)

Advantages
Higher melting range Better sag and creep resistance Higher yield strength and MOE for long span FPDs Good castability Easily finished and polished Non-toxic and lower cost v.s. Au-Pt-Pd alloys

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 Disadvantages
Ag may cause greening of porcelain. White color may show through tissues as gray and may not be as acceptable as gold collars. High Pd content may increase the risk of H2 gas absorption during casting, and bonding of porcela in may be affected by oxidizing procedures.

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Gold-Palladium Alloys (Au-Pd)

Composition
Au (45-52%); Pd (38-45%); In (8.5%); Ga (1.5%) (high noble)

Advantages
same as for Au-Pd-Ag alloys with the addition of potentially better porcelain color due to lack of Ag

Disadvantages
same as for Au-Pd-Ag alloys with the exception of porcelain greening
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Palladium-Silver Alloys (Pd-Ag)

Composition
Pd (53-88%); Ag (30-37%); In (4-7%); Sn (4-7%) (noble)

Advantages
High yield strength and MOE Better sag and creep resistance Non-toxic and low cost

Disadvantages
Castability < gold alloys High Ag porcelain greening, bonding High Pd gas absorption and poor color
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High Palladium Alloys

Composition
Pd (74-88%); Cu (10-15%); Ga (9%); Au (0-2%); Co (4-5%); In (0-5%) (noble)

Advantages
High yield strength and sag and creep resistance Non-toxic, low cost Castability = gold alloys (easy) Excellent porcelain color
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 Disadvantages
Porcelain bond strength may be variable. High Pd content H2 gas absoption, poor solderability Cant be used with carbon investments or crucibles
Carbon or Silicon contamination will cause brittle castings which may crack or tear at grain boundaries u nder stress.

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Palladium in PFM Alloys

Hardens the alloy Whitens the alloy Increases the alloys casting temp. Increases the alloys MOE Renders silver tarnish resistant Decreases the alloys density Decreases the alloys thermal coef. of exp.

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Minor Elements in PFM Alloys

In, Sn, Fe, Ga - provide metallic oxides for porcelain bonding, and harden the alloy. Ga - increases the thermal coef. of exp. to compensate for decreased or absence of Ag .

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Heat Treatment
PFM alloys can be heat tx however clinical condition is dependant on ceramic applicatio n.

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Base Metal Alloys

Ni-Cr, Co-Cr Pure Ti, Ti alloy

Co-Cr and Ni-Cr alloys

Co-Cr Ni-Cr

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Composition
Chromium (11-20%)
responsible for tarnish and corrosion resistance due to its passivity passivation if >30% difficult to cast and brittle

Cobalt or Nickel (65-78%)

Co and Ni are pretty much interchangeable. Ni alloys have decreased strength, hardness, MOE, fusion temps and increased ductility and % elongation v.s. Co alloys.
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Composition
Minor alloying elements
control the majority of the physical properties Carbon (0.1-0.5%)
increases strength, hardness, and brittleness. increased by 0.2% alloy too hard and brittle for dental use decreased by 0.2% decreases yield strength and UTS to unacceptable levels.

Molybdenum (3-6%)
increases strength, hardness, and %elongation
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Composition
Aluminum (4-5%)
forms a Ni3Al in NiCr alloys which contributes to precipitation hardening resulting in increased tensile and yield strength.

Beryllium (0.5-2%)
decreases the fusion temp by approx 100C increases fluidity during casting allows for electrolytic etching (with resin bond prosthesis)

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Composition
Manganese (5%) and Silicone (0.5%)
increases fluidity and castability of the molten alloy + Boron deoxidizers (essential in Ni containing alloys)

Iron and Copper

increase hardness

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Heat Treatment
Most desirable properties are in the as cast condition. (= no need for heat tx)

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Titanium and Titanium Alloys

Forms a very stable oxide layer Commercially pure titanium (cp Ti) is used for dental implants, surface coatings, and crowns, partial and complete dentures, and orthodontic wires. Ti-6Al-4V is the most widely used.
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Cast Titanium
Problems
High melting point (~ 1700C) Chemical reactivity
Reacts with gaseous elements easily, esp. at high temp (>600C)

Need a well-controlled vacuum in processing The technology required makes casting Ti so expensive.
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Considerations on Properties

Melting Range
The solidus-liquidus range should be narrow to avoid having the alloy in a molten state for extended times during casting.
To decrease oxides and contamination

Liquidus temp determines the burnout temp, type of investment, and type of heat-source.
Burnout temp liquidus temp 500C Burnout temp >700C, cannot use gypsum-bonded investment
Liquidus temp: Base-metal 1400-1500C vs. cast gold Type I-IV 8001050C

Liquidus temp < 1100C gas-air torch, >1100C gas-oxygen torch or electrical induction

Solidus temp is important to soldering and formation of ordered phases.

Limit heating to 50C below the solidus temp.

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Density
Alloys with high densities will generally accelerate into the mold during casting faster and tend to form complete castings more easily.
Base-metal 7-8 g/cc vs. High Noble 13-18 g/cc

Alloys with lower density lighter

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Yield Strength
Can be increased with treatment and changing the compositions

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Hardness
Is a good indicator of the ability of an alloy to resist local permanent deformation under occlusal load Gives some indication of the difficulty in polishing the alloy Most noble casting alloys < enamel (343 Kg/mm2) and < base-metal alloys
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Elongation/Fatigue
Important property for RPD alloys For crown and bridge applications, a low value of elongation for an alloy is not a big concern.
However, the elongation will indicate if the alloy can be burnished.

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Biocompatibility
Noble alloys related to elemental release from the alloys (i.e., from the corrosion process). Base-metal alloys
Be from contact dermatitis to severe chemical pheumonitis Ni sensitivity
5-10 times higher for females 5%-8% of females

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End of Dental Casting Alloys

Noble Casting Alloys

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Properties of Elements in Dental Casting Alloys

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Inlay, onlay

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