NOBLE METAL ALLOYS

INTRODUCTION
For casting of dental restorations, it is necessary to combine various metals to produce alloys with adequate properties, for dental applications. These alloys are produced largely from gold combined with other noble metals and certain base metals to produce properties most acceptable for their intended dental applications such as inlays, onlays, bridges, removable cast restorations etc. The noble metals are those elements with a good metallic surfaces that retain their surfaces in dry air. The 6 metals of the platinum group are platinum, palladium, iridium, rhodium, osmium, ruthenium, and along with gold, are called noble metals. The history of dental casting alloys has been influenced by three major factors: 1 The technologic changes of dental prosthesis. ! "etallurgic advancements. # $rice changes of the noble metals since 1%6&. Taggart's presentation to the (ew )or* odontological group in 1%+, on the fabrication of cast inlay restorations often has been ac*nowledged as the first reported application of the lost wa- technique in dentistry. The inlay technique described by .aggart was an instant success.

 /t soon led to the casting of comple- inlays such as onlays, crowns, fi-ed partial dentures and removable partial denture framewor*s. 0ecause pure gold did not have the physical properties required or these dental restorations, e-isting jewellery alloys were quic*ly adopted. These gold alloys were further strengthened with copper, silver, or platinum. /n 1%#!, the dental materials group at the (ational 0ureau of 1tandards surveyed, the alloys being used and roughly classified them as: Type / 2 1oft345(36+ to %+. Type // 2 "edium 45( of %+ to 1!+. Type /// 2 5ard 45( of 1!+ to 16+. Type /4 2 7-tra 5ard 45( 16+. 0y 1%8&, the composition of dental noble metal alloys for cast metal restorations had become rather diverse. 9ith these formulations, the tarnishing tendency of the original alloys apparently had disappeared. /t is now *nown that in gold alloys, palladium is added to counter act the tarnish potential of silver. 0y 1%,&, the price of gold was climbing so rapidly that attention focused on the noble metal alloys 2 to reduce the precious metal content, yet retain the advantages of the noble metals for dental use.

Desirable properties of casting alloys

:ast metals used in dental laboratories must e-hibit the following properties: 1 /t should be biocompatible. ! 7asy to melt. # 7asy to carry out casting, bra;ing <soldering and polishing. 8 =ittle solidification shrin*age. 6 "inimal reactivity with the mold material. 6 >ood wear resistance. , 5igh strength and sag resistance <metal ceramic alloys . & 7-cellent tarnish and corrosion resistance.

Classification of Dental Casting Alloys

?ccording to ?@? specification (o.6, the castings alloys can be classified as: 1 Type / <1oft small inlays, easily burnished and for restorations subject to very slight stress such as inlays. ! Type // <"edium /nlays subject to moderate stress including onlays, thic* A crowns, thin cast bac*ings, abutments, pontics and full crowns. # Type /// <5ard /nlays subject to high stress including thin A crowns, thin cast bac*ings, abutments, pontics, full crowns denture bases and short span fi-ed partial dentures.

8 Type /4 <7-tra hard /nlays subjected to very high stresses including denture base bars and clasps, partial dentures, framewor*s and long3 span fi-ed dentures, full crowns are often made for this type high stresses such as endodontic posts B core. The development of modern direct tooth coloured filling materials has almost eliminated the use of type /3 // alloys. Types / and // alloys are often refined to as C/nlay alloys. Types /// and /4 are generally called C:rown B bridgeD alloys. /n 1%&8, the ?@? proposed a simple classification for dental casting alloys: Alloy Type 1 5igh noble metal. ! (oble metal. Total Noble Metal Content :ontains 8+wtE?uF6+wtE of noble metal elements <?uF/1FGsF$dFHhFHu . :ontains !6wtE of the noble metal elements.

# $redominantly base metal. :ontains I!6wtE of the noble metal elements. According to Marzouk Type / Type // 1 :lass / 2 >old and platinum group based alloys Type /// Type /4 ! :lass // =ow gold alloys <gold content I6+E . # :lass /// (on3gold palladium based alloys. 8 :lass /4 (ic*el3chromium based alloys.

6 :astable moldable ceramics. Other Classifications: 1. )ellow golds )ellow coloured >old content J 6+E !. =ow gold K economy gold. Lsually yellow coloured. 0ut with gold content 6+E #. 9hite >olds 9hite coloured >old content J 6+E CLASSI!ICATION O! ALLOYS !OR ALL"METAL RESTORATION# METAL CERAMIC RESTORATIONS# AND !RAME$OR%S !OR REMO&ABLE 'ARTIAL DENTRUES
Alloy Type 1 5igh (oble All"Metal ?u3?g3:u3$d "etal3:eramic alloys ?g3$d3:u ?g3$d "etal3:eramic alloys Metal"Cera(ic ?u3$t3$d ?u3$d3?g <631!wtE?g ?u3$d3?g <J1!wtE?g ?u3$d <Mn ?g $d3?u <Mo ?g $d3?u3?g $d3?u $d3:u $d3:o $d3>a3?g Re(o)able 'artial Dent*re ?u3?g3:u3$d

! (oble

?g3$d3?u3:u ?g3$d

Note : The principle reasons that alloys for all3metal restorations cannot be used for metal3ceramic restorations are that: 1 the alloys may not form thin, stable o-ide layers to promote bonding to porcelain, ! their melting range may be too low to resist sag deformation or melting at porcelain firing temperatures their thermal contraction co3efficients may not be close rough to those of commercial porcelains. /ngredients of noble metal alloys : The most important element in dental gold alloys are gold, copper, silver, platinum metals and ;inc . 6

Gold 1 >old is primarily responsible for @eformability <ductility Han*s lowest in strength. :haracteristic yellow colour with a strong metallic luster. @ensity <sp.gravity 1%.#gKcm#. Tarnish resistance. Fusion temperature 2 1+6#N:. (ot soluble in sulphuric, nitric or hydrochloric acids. =owest density necessitates more force in centrifugal casting to compensate for lower wtKvol. 5owever, lower density will allow more restorations per unit wt which can be economical to some e-tent lowest density necessitates more force in centrifugal castings to compensate for the lower wtKvol. 5igh density enables case of castings. ?lloys for dental use should be atleast 16O resistance. ! Platinum : "ay be added to: 1. 1trengthen the alloy. !. Haise the fusion point <1,66 . #. /mport rigidity, nobility, hardness. 8. 9hiten the alloy. 6. 1p gravity !1.#, 6. ?lso malleable and ductile. /ts coefficient of e-p is close to that of porcelain to prevent buc*ling of the metal or fracture of porcelain during changes in temperature.

# Palladium 1erves the same functions but is much less e-pensive than platinum. Disadvantages 2 $alladium hydrogen gas because gold containing palladium may be more porous when cast 1$.>r 11.8 melting point 2 1666N:. 4) ridium! "uthenium and "hodium Trace amounts of these metals are added as C>rain HefinersD "elting point %6+, 6N: below the melting point and both gold and copper as little as +.++6E is sufficient to refine the grain si;e. >rain refiners produce smaller grains. Fine grained alloys have smaller grains compared to coarse3grained alloys which relatively larger grains. Fine3grained alloys are generally more stronger and more ductile than coarse grained alloys. ndium 2 can also act as a savenger for the alloy during cast procedure. :an also serve to increase the tarnish and corrosion. 6 #ilver also contributes to hardness and strength of the alloy. ?lthough it mimics gold in its deformability effect, it adversely affect the mobility. /n other words it lowers tarnish resistance. 3 tarnish on silver. 3 copper. 1ilver serves to balance the red colour given by Food containing sulphur compounds cause severe

?dding small amounts of palladium to silver containing alloys prevents the rapid corrosion of such alloys in the oral environment. ?lso occludes appreciable quantities of G! in the molten state. $orosities or rough casting surface can be prevented by adding 631+E :u.

6 Co$$er : :ontributes strength and hardness, but decreases the mobility of the alloy, i.e. it decreases the tarnish and corrosion resistance because the ma-imum content should not e-ceed 16E. 1 >ives the alloy and reddish appearance. ! =owers, the fusion temperature. %inc : <$resent only in low percentages, around +.6E acts as a deo-idi;er and reduces the o-ygen content. <0ecause G! released during solidification results in porosity . &arat and 'ineness Oarat is the traditional unit e-pressing gold content in an alloy. Oarat refers to the parts of pure3gold in !8 parts of an alloy. 3 3 $ure gold is !8 *arat. !!O gold is an alloy containing !! parts pure gold in and ! parts of other metals. Fineness Fineness is the percentage of gold multiplied by 1+ because a !8 *arat alloy would have a fineness of 1++ - 1+, or 1+++ and a 1!3*arat alloy would be 6++ fine <6++f .

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+eat Treat(ent of ,ol- Alloys

>old alloys can be significantly hardened if the alloy contains a sufficient amount of copper <at least & wtKcopper . 5eat treatment is a process of healing a metal to improve its properties. ?n alloy can be subjected to 2 5ardening heat treatment also Cage hardeningD, softening heat treatment also referred to as Csolution heat treatmentD.

.Softening +eat Treat(ent

:asting is placed in an electric furnace for 1+ minutes at a temperature of ,++N: <1!%!NF and then quenched in water. @uring this period, all intermediate phases are presumably changed to a disordered solid solution and the rapid quenching prevents ordering from occurring during cooling. 1oftening heat treatment reduces 3 Tensile strength 3 $roportional limit 3 5ardness but improves 2 @uctility. 1oftening heat treatment is indicated for, structure that are to be ground, shaped or otherwise cold wor*ed. 5ardening heat treatment 2 can be accomplished in many ways. Gne of the most practical hardening treatments is by Csoa*ingD or aging the casting at

a specific temperature for a definite time usually 163#+ minutes before it is water quenched. The aging temperature on the alloy composition but is generally between !++N: <8++NF and 86+N: <&8+NF . ?ge hardening improves3 1trength <yield . 3 $roportional limit. 3 5ardness. ?ge hardening is indicated for metallic partial dentures, saddle bridges and other similar structures. For small structures such as inlays, a hardening heat treatment is not usually employed. /deally before the alloy is given an age3 hardening heat treatment, it should be subjected, 1 to a softening heat treatment for ! reasons: to reline all strain hardening, if it is present, ! to start the hardening treatment with the alloy as a disordered solid solution.

Casting S/rin0age
"ost metals and alloys including gold and the noble metal alloys shrin* when they change from the liquid to the solid state. The shrin*age occurs in # stages: 1 The thermal contraction of the liquid metal between the temperature to which it is heated and the liquidus temperature. ! The contraction of the metal from liquid to solid shape.

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# The thermal contraction of the solid metal that occurs down to room temperature. The values for casting shrin*age differ for the various alloys presumably because of difference in their composition. /t has been shown that platinum, palladium and copper all are effective in reducing the casting shrin*age of an alloy. The following table shows the linear solidification shrin*age of casting alloys: ?lloy Type /, gold base Type //, gold base Type ///, gold base 0ase metals <(i3:r3"o30e3:o3:r3"o 1.66 1.#, 1.8! !.#

Co(position of Tra-itional I to I& alloys

Type / // /// /4 A* &#E ,, ,6 6% C* 6 , % 1+ Ag 1+ 18 11 1!.6 'l +.6 1 #.6 #.6 Sn# In# !e# 1n# ,a 0alance 0alance 0alance 0alance

Sil)er"'alla-i*( Alloys
These alloys are white in colour.

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 "ain component is silver, but small amounts of palladium <attract !6E is also present <$alladium added to provide mobility and tarnish resistance . :opper may or may not be present and a small amount of gold. :opper3free silver3palladium alloys may contain ,+3,!E silver and !6E palladium and may have physical properties of type /// gold alloys. Gther silver3based alloys might contain roughly 6+E silver, !6E palladium and as much as 16E or more of copper. These alloys have properties triangular to Type /4 gold alloy. Disadvantages : >reater potential for tarnish and corrosion.

+ig/ Noble Alloys for Metal"Cera(ic Restoration

The original metal3ceramic alloys contained &6E gold and were much too soft for stress3bearing restorations such as fi-ed partial dentures. There was no evidence of a chemical bond between these alloys and dentinal porcelain. Therefore mechanical retention and undercuts were used to prevent detachment of the ceramic veneer. Lsing the C1tress bond testD, it was found that the bond strength of the porcelain to this type of alloy was less than the cohesive strength of the porcelain itself. 1o, stress was concentrated at $orcelain3metal interface. 0y adding less than 1E of o-ide3forming elements such as iron, indium and tin to this high3gold content alloy, the porcelain metal bond strength was improved.

1!

</ron also increases the proportional limit, and strength of the alloy . 0ecause this 1E addition of base metals to the gold, palladium and platinum alloy produced a slight o-ide film on the surface of the substructure to achieve a porcelain3metal bond strength level that surpassed the cohesive strength of the porcelain itself. This new type of alloy, with small amounts of base metals added became the standard for the metal3ceramic restoration. /n spite of vastly different composition, these alloys share at least three common features: 1 They have the potential to bond to dental porcelain. ! They possess coefficients of thermal contraction compatible with those of dental porcelains. # Their solidus temperature is sufficiently high to permit the application of low3fusing porcelains. The coefficient of thermal e-pansion tends to have a reciprocal relationship with the melting point of alloys. The higher the melting temperature of a metal, the lower its :T7. The high noble alloys for metal3ceramic restorations are: () Gold)$latinum)$alladium allo*s: >old content ranges upto &&E. 4arying amounts of palladium, platinum and small amounts of 0 metals. :olour 2 yellow

1#

Disadvantages : 1usceptible to sag deformation and F$@ should be restricted to #3unit spans, amount cantilever or crowns. +) Gold)$alladium)silver allo*s: >old content ranges between #%E 3 ,,E gold. $alladium 2 #6E. 1ilver 2 less than !!E. 1ilver increases the thermal contraction coefficient. Disadvantages : 1ilver present in this alloy can discolour same porcelains. ,) Gold)Palladium allo*s >old content ranges for 88E to 66E $alladium #6E to 86E. These alloys have remained popular despite of their relatively high cost. Disadvantage : The lac* of silver results in freedom from silver distry. The lac* of silver results in a decreased coefficient thermal content because these alloys must be used only with porcelains that have low :T contraction to avoid the development of initial circumferential tensile stresses in deny cooling point of 333333333.

Noble Alloys for Metal"Cera(ic Resins

?ccording to ?@? classification of 1%&8, noble alloys must contain at least !6wtE of the noble metals but do not necessarily contain any gold. (oble palladium3based alloys after a compromise between the high3noble gold alloys and predominantly base metal alloys.

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 ?lso, the price K ounce of a palladium alloy is generally one half to one third that of a gold alloy. @ensity is midway between that of base metal and high noble alloys. $alladium3based alloys have a wor*ability angular to gold and scrap value. () Palladium)silver allo*s: These alloys were introduced widely in the late 1%,+s <to overcome some disadvantages of early 0.". alloys e.g. : castability, porcelain bonding and wor*ability problems . /n the recent years the popularity of these alloys has declined because of the disadvantages with these alloys is it discolours porcelain during firing. This discolour, is usually a greenish3yellow discolor and is popularity termed as C>reeningD. >reening occurs mainly because of the presence of silver 1ilver vapor escapes for the surface of these alloys during firing of the porcelain. @iffuses as ionic silver into the porcelain. Finally reduced to colloidal metallic silver in the surface layer of porcelain. (ot all porcelains are susceptible to silver discolour because some do not contain the necessary elements to reduce the ionic silver. To eliminate the greening problem, palladium alloys with no silver were developed.

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 These alloys contain ,6E to %+E palladium. 1ome of these high palladium alloys develop a layer of dar* o-ide on their surface during cooling from the degassing cycle. This o-ide layer has proven difficult to mar* by the opaque porcelain. Gther high palladium alloys such as the $d3>a3?g3?u type do not seem to be plaqued. This alloy type was introduced to the L.1. mar*et in 1%,8 as the 1 st free noble metal available for metal ceramic restorations. Com$osition : $alladium 2 6#E to 61E. 1ilver 2 !&E to 8+E. 1mall amounts of tin F indium or both are added to promote o-ide formation for adequate bonding of porcelain. /n some alloys, the formation of an internal o-ide layer rather than an e-t. o-ide layer has been reported. /ncreasing the silver content tends to a lower the metal range and raises the contraction coefficient of an alloy. 0ecause of the high silver content, silver discolouration effect is most severe for these alloys. 5owever, gold metal conditioners or ceramic coating agents may minimi;e this effect.

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 The low specific gravity of these alloys <1+E to 11E combined with their low intrinsic cost ma*es these alloys attractive as economical alternatives to the gold3based alloys.

'alla-i*("copper Alloys
This alloy type is comparable in cost to the $d3?g alloys because alloys of this type are recent introductions to the dental mar*et, little clinical information is available on their long3term clinical success. @isadvantages because of their low melting range of appro- 11,+N: to 11%+N:, these alloys are susceptible to creep deformation <1ag at elevated firing temperatures. Thus, one should e-ercise caution in using these alloys for long3span fi-ed partial dentures with relatively small connectors. Com$osition: $alladium 2 ,8E and &+E. :opper 2 %E to 16E. 1ome may contain as little as !E gold 2 this small amount of gold serves no useful purpose. $orcelain discolouration due to copper is possible but does not appear to be a major problem. There has also been some concern recently over the potential cytoto-ic effect of copper released intra3orally from certain $d3:u alloys. Gne should also be aware of the potential effect on aesthetics of the dar* brown or blac* o-ide formed during o-idation and subsequent firing cycles.

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 :are should be ta*en by the technician to mas* the o-ide completely with opaque porcelain and to eliminate the unaesthetic dar* bond that develops at metal3porcelain junctions. /t is also important that technician ensure that a brown rather than a blac* o-ide is formed on the metal surface during o-idation treatment otherwise, poor adherence to porcelain may result. 1ome of these alloys are technique sensitive with respect to casting. /n some instances the molten alloy should have a thin o-ide firm appearing on its surface at the casting temperature. 1ome instructions specify that heating be maintained for an additional , seconds beyond the point at which a rolling motion of the alloys is observed. 0ecause of the lac* of a specifically defined melt appearance, there may be a tendency to overheat the alloy to eliminate this film. This error would cause significant changes in the properties of the alloy and a decrease in metal3porcelain bond strength. Lnderheating of the molten alloy is also possible because of the difficulty in judging the proper melt appearance this could result in incomplete castings or rounded margins. 0ecause alloys have a poor potential burnishing, e-cept when the marginal areas are relatively thin.

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 ?lthough thermal incompatibility is not considered to be a major distortion of ultrathin metal copings <+.1mm has been occasionally reported. The e-act cause of this effect is not *nown. /t could be : 3 3 0ecause of metal3porcelain incompatibility stresses. 5igh creep rate of these alloys at temperatures near the glass transitions temperature of porcelain. 3 Hela-ation of elastic stresses due to solidification, grinding and sandblasting. This distortion of single unit K multiple unit castings could be overcome by using thic*er copings K connectors or changing the band of porcelain or by using a different metal3ceramic system with more acceptable overall properties.

'alla-i*("Cobalt Alloys
This alloy group is comparable in cost to $d3?g and $d3:u alloys. They are often advertised as gold3free, nic*el3free, beryllium free and silver free alloys. =i*e many noble metals, these alloys have a fine grain si;e to minimi;e hot tearing during the solidification process. This $d3:u group is the most sag resistant of all noble metal alloys. Com$osition : 3 3 $alladium 2 ,&E to &&E. :obalt 2 8E to 1+wtE.

1%

 Gne commercial alloy contains &E gallium. ?n e-ample of typical properties of a $d3:u alloy is as follows: 5ardness 2 !6+@$5. )ield strength 2 6&6 "$a. 7longation 2 !+E. "odulus of elasticity &6.! >$a ?lthough these alloys are silver free, discoloration of porcelain can still result because of the presence of cobalt. 0ut this is not a significant problem. Failure of the technician to completely mas* out the dar* metal o-ide colour with opaque porcelain is a more common cause of unacceptable aesthetic results. (o metal casting agents are required to mas* the o-ide colour or to promote adherence to porcelain. =i*e the $d3?g and $d3:u alloys the $d3:o alloys generally tends to have a relatively high thermal contraction coefficient. 5ence would be more compatible with high e-pansion porcelains.

'alla-i*(",alli*("Sil)er an- 'alla-i*(",alli*("Sil)er",ol- alloys

These alloys are the most recent of the noble metals. This groups of alloys was introduced because they tend to have a slightly lighter coloured o-ide than the $d3:u or $d3:o alloys. The silver content is relatively low <63&wtE and is inadequate to cause porcelain greening.

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 1ince they have a low coefficient of thermal contraction they would be more compatible with lower e-pansion porcelains <e.g. vita porcelains .

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Concl*sion
(umerous types of casting alloys have been used for the restoration of teeth while gold3based alloys have played the major role for many years their dominance has been challenged now by base metal system. The main reason is that base metals are less e-pensive as compared to gold alloys. Lnfortunately these substitutes have been less than ideal in numerous way and one of greatest questions about them is their biological compatibility. 5owever, further investigation need to be conducted to evaluate their biocompatibility. 5owever, the performance of any restoration is related to multiple factors for e-: the design of the appliance, the s*ill and accuracy with which it has been fabricated and the properties of the materials used.

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