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Universal Dental Gold

Alloys in New
Metal-Ceramic Systems

Jef M. van der Zel*, PhD,MSc


**Director Quality Assurance Elephant Dental B.V.

Porcelain-fused-to-metal (PFM) crowns and bridges represent the majority of


lab-fabricated prostheses. Where aesthetics and biocompatability are
desired irrespective of cost, the choice is a high-noble, rich-yellow ceramic
alloy. Unfortunately platinum and palladium, which are normally added to
alloys for strength, also reduce the rich yellow colour so that a gold content in
excess of 84% is usually required in ceramic alloys in order to approach the
highly desired “yellow” colour. The most common high-noble PFM crown
fabricated in Canada contains roughly 51% gold content and presents as
“steel” in colour or “white” as defined by the industry. The dental industry has
long searched for a more aesthetic solution.

Since 1990, the Carrara System (1) has offered one. Using a low-firing temperature veneering
ceramic and gold alloys with a lower platinum and palladium content, a deep and rich yellow colour
results. What makes these alloys “universal” is the fact that they can be used for ceramic as well as
full gold restorations as well as inlays and full arch bridges. All applications result in a rich yellow,
high-lustre finish. Aesthetic matches for mixed restorations in the same quadrant (ie PFM and full gold
crowns) are simplified. Galvanic reactions to alloys of different compositions are reduced or
eliminated. Dentists and patients see what they expect to see in “gold” restorations. Alloy and
porcelain inventory in dental laboratories is simplified as the porcelain used for PFMs is also suitable
for feldspathic veneers/inlays and pressable single-unit applications. A review of the development of
alloys over the past 50 years is discussed along with the evolution of the universal alloys.

Introduction

The dental laboratory industry is constantly exposed to a plethora of alloys produced by a number of
manufacturers. It is not uncommon for a lab to use 6 or more dental alloys for different applications.
Inventory accumulates despite the best of intentions, and 6 buttons constantly tie up hundreds of
dollars.

The dentist is frequently just as confused with the choice of alloys. A 51% PFM alloy appears
indistinguishable from a non-precious crown except for the “Identalloy” sticker along with it. A 62%
gold content full gold crown is a nice yellow colour compared with a 62% gold content porcelain-fused
-to-metal (PFM) alloy that is “white” in colour. When a “yellow” PFM option is offered to the dentist by
the lab, it is often frequently requested thereafter. The aesthetics of a yellow-coloured gold in PFM
restorations is highly sought and appreciated by many dentists although the high cost with high gold
content sometimes curtails the desire.

The quest for a rich-yellow, reasonably priced, ceramic alloy has been the focus of many a metalurgist
for decades. This desire is also connected with the wish to avoid firing porcelain on metal in the
posterior chewing surfaces of the mouth, because of the high hardness of porcelain with respect to the
opposing natural teeth. A distinction has therefore always been made between crown & bridge alloys
derived from carat gold for casting all-metal restorations (full-gold crowns: FGC) and alloys used for
veneering with porcelain or PFM.

TABLE 1. Crown & bridge alloys [Non-Ceramic; FGC].

Year of Commercial Company Composition in wt-% Melting Properties after


o
Market Registered Interval, C Hardening Treatment
Intro- Trade Name
Duction of the Alloy Vickers Yield
Hardness Strenght,
Au Ag Pd Pt Cu Zn Rest , HV MPa

1955 Degulor M DeguDent 70.0 13.5 2.0 4.4 8.8 1.2 Ir 900- 970 235 620
1977 Degulor NFIV DeguDent 71.0 10.0 2.0 12.9 0.0 4.0 Ir 1000-1100 230 590
1961 Maingold OG Heraeus 70.0 13.4 1.0 7.5 7.6 0.5 Ir 930- 990 295 730
1978 Apollo 4 Elephant 70.0 13.4 2.0 4.5 9.0 1.0 Sn,Ir 900- 975 240 650
1988 Apollo 4CF Elephant 68.0 21.4 6.0 1.0 0.0 3.4 Sn,Ir 1000-1070 250 630

In dentistry, the first modern gold alloys used to cast all-metal crowns and bridges were derived from
jewelry carat gold alloys using the lost-wax casting technique introduced by Taggart in 1935 (Table 1).
The application was successful, as these alloys have been used extensively for “full-gold” crowns,
bridges, inlays and telescopic work for decades. In most of Canada, the trend has been to use a
“crown and bridge” alloy containing 60-62% gold. An appreciable and distinguishable difference in
colour exists between “crown and bridge” alloys having more than a 10% difference in gold content
and the cost per crown is relatively minimal in comparison. Many other alloy manufacturers have
since followed suit by developing “crown and bridge” alloys with similar and varying compositions. The
application of these rich-yellow 70% gold alloys to veneering porcelain was less than ideal due to the
fact that the high copper content often resulted in greening of porcelain margins and the low solidus
temperatures made them susceptible to slumping during porcelain firing. In addition, the thermal
expansion coefficients (CTE) were on average 2.0 µm/m.K too high for the porcelains on the market at
that time.
The copper free versions had all the characteristics to become precursors for the universal gold alloys
developed later, however the paradigm that zinc in porcelain-veneering alloys should be low or absent
due to its potential to cause bubbling in porcelain made them less than desirable choices.

TABLE 2. Gold-platinum alloys for porcelain veneering.

Year of Commercial Company Composition in wt-% Thermal Melting Properties after


Market Registered expansion Interval, Porcelain Firing Cycle
o
Intro- Trade Name Coefficient, C
Duction of the Alloy µm/m.K Vickers Yield
(25-500oC) Hardness Strenght,
Au Ag Pd Pt Zn In Rh Rest , HV MPa

1967 Degudent U DeguDent 77.3 1.2 8.9 9.8 0.0 1.5 0.0 Sn,Cu,Ir 13.8 1150-1260 210 580
1970 Herador H Heraeus 78.5 0.0 7.8 10.0 0.0 3.5 0.0 Ir 14.1 1145-1255 220 600
1977 Orion UX Elephant 77.0 1.5 9.2 9.6 0.0 1.5 0.0 Fe,Cu,Ir 13.8 1040-1130 225 520

1995 BioGoldPlus Elephant 86.0 0.0 0.0 10.5 1.5 0.2 1.5 Ta,Mn 14.3 1040-1115 220 550
1995 BioOcclus 4 DeguDent 85.8 0.0 0.0 11.0 0.2 1.7 0.7 Ta 14.4 1050-1130 205 500
1995 BioHerador N Heraeus 86.2 0.0 0.0 11.5 1.5 0.0 0.0 Ru,Ta 14.3 1050-1130 205 500

In the 60’s and 70’s, alloys were developed with as high a gold content as possible, but with palladium
and platinum to add strength for longer span bridges. While these alloys were high-noble in their
content and their efforts, more than a 7% palladium makes all ceramic gold alloys “white” in colour. As
a consequence, they were expensive yet non-gold in colour. They were, neverthless, a good match
for the high fusing (900-950oC) porcelains available at the time.

In 1995, five years after the introduction of the ideal universal gold alloys (to be discussed shortly), a
new generation of high-gold alloys was developed for the high-fusing porcelains (Table 2; latter 3
alloys). The gold content of these alloys was high enough to keep them a rich yellow colour even with
the addition of platinum for strength. Palladium is noticably absent from these newer alloys, as
numerous reports over the past 12 years have shown sensitivity in some patients to this component
(5,6). Palladium toxicity has resulted in Switzerland banning its use. Similarly, the German Health
Ministry has been warning dentists since 1993 not to use palladium or copper-containing alloys. These
new high-gold, yellow alloys have gained some market share, however they have not been able to
regain the market shift which has already taken place to the universal gold alloys. This is primarily
because the universal alloys allow one alloy to work for both “crown and bridge” as well as porcelain
fused-to-metal restorations. The universal alloys also offer the same rich yellow colour but contain only
75% gold content rather the the 84%+ gold of these newer alloys. Esthetics can be maximized and
costs minimized (due to lower gold content) with the universal alloys.

Low-melting, high-expansion porcelains

The introduction of universal gold alloys was driven by the development of low-melting, high-
expansion veneering porcelains. The melting point or firing temperature of these porcelains had to be
50oC, and preferably 100oC lower than the solidus temperature of the gold alloys, for maintaining the
form stability of the metal frame during the firing cycles of the veneering ceramic (2,3).

The CTE (thermal expansion coefficient from 25oC to 500oC) of these new porcelains should be at
least 0.5 µm/m.K lower than that of the gold alloys. This allows the alloy-porcelain combination to cool
down without crack formation of the porcelain due to the faster contracting, highly conductive alloy.
However when the porcelain has a CTE that is more than 2.0 µm/m.K higher than that of the alloy,
then the faster contracting/cooling will lead to bending forces in the metal and chipping in the outside
layer of the porcelain. A slow cooling process would be required to avoid this potential problem.

To accomodate the porcelain veneering of alloys with a CTE range between 15.8 and 17.0 µm/m.K, a
strict and tedious temperature-change control is therefore normally required. In the Carrara porcelain
developed by Elephant in NV, such control is acheived by a mixing a specific porcelain composition in
which leucite (the expansion controlling crystalline compond) is in equilibrium with its surrounding
glass matrix. This was ingeniously solved by using principally three functionally different glass frits:
1. a high expansion leucite-forming frit
2. a complementary glass frit in equilibrium with the glass matrix of the first frit
3. a low melting glass frit that acts neutral towards the other two frits
The firing temperature of the Carrara porcelain is 840-860oC and the CTE is 14.7 µm/m.K after normal
cooling and 15.3 µm/m.K after slow cooling of the porcelain.

Experience has shown that a low stress combination is possible when the difference in thermal
expansion between the alloy and the porcelain up to the softening point, [“the mismatch”] = ∆αT, is
between 0.6-1.7 µm/m.K. This makes a low stress combination with Carrara porcelain possible after
normal cooling with alloys with a CTE as low as 15.8 µm/m.K (∆αT: 1.1 µm/m.K, normal cooling) and
after slow cooling with alloys up to 17.0 µm/m.K(∆αT: 1.7 µm/m.K, slow cooling).
The Universal Alloys: Low-melting, high-expansion gold alloys

The first Carrara alloys and Carrara porcelain that appreared on the market were developed by
Elephant, NL in 1990. These alloys had relatively high CTE’s of up to 17,0 µm/m.K. These alloys were
approaching the ideal, because they could offer a yellow colour at 50% gold content and be used with
a low-fusing porcelain. Such an achievement traditionally required nearly 86% gold content with
palladium/platinum added for strength in regular fusing-porcelains. The combination of alloy and
porcelain however was not yet perfected.

In the process of development, Elephant, NL was purchased by Degussa. Further developments


continued and the ultimate success was acheived in 1993, when the ceramic veneering alloy
Degunorm® (4) that was developed in a joint venture between Degussa AG (now: DeguDent GmbH)
and Ducera GmbH (now: Degudent), who developed Degunorm and repectively a compatible low-
melting ceramic Duceragold (790oC) with the integral technical expertise of Elephant. Because of the
low firing temperature of the ceramic the new alloy was based on Degulor®M, a crown and bridge alloy
already developed in the fifties (Table 1), by essentially halving the copper content to bring down the
copper oxide surface layer formation. The metal-ceramic system was marketed under the name
“Golden Gate System”, and grew to become the most significant metal-ceramic systems on the dental
market during the last decade. Elephant introduced its own “Carrara system” with Carrara PdF alloy
as a parallel to the “GoldenGate” system, and it has been very well received in Europe.

The addition of rhodium,and/or iridium gives these alloys a fine grained structure.Tantalum when
added in amounts up to 1 wt.-% increases the resistance against sagging and the strength of the alloy.
Among zinc, indium and tin, the preferable hardening element is zinc because of its light oxide and
because it leads rapidly to a proper hardening.

TABLE 3. Universal gold alloys for veneering with low-melting porcelain

Year of Commercial Company Composition in wt-% Thermal Melting Properties after


Market Registered Expansion Interval, Porcelain Firing Cycle
o
Intro- Trade Name of Coefficient C
duction the Alloy µm/m.K Vickers Yield
(25-500oC) Hardness, Strenght,
Au Ag Pd Pt Cu Zn In Rh Rest HV MPa

1990 Carrara H Elephant 75.0 15.4 7.0 0.5 0.0 2.0 0.0 0.0 Ta,Ir 16.4 1000-1065 220 580
1990 Carrara R Elephant 50.0 36.7 9.9 1.0 0.0 1.8 0.0 0.0 Ir, Sn 17.0 1050-1100 230 550
1992 Carrara PdF Elephant 75.0 9.3 0.0 9.0 0.0 2.0 0.0 1.5 Ta,Ir 15.8 1000-1070 220 550
1993 Degunorm DeguDent 73.8 9.2 0.0 9.0 4.4 0.0 0.0 0.0 Ir 16.7 900- 990 200 500
1993 Mainbond KF Heraeus 74.0 11.2 6.0 4.0 0.0 1.0 2.0 0.0 Mn,Ir 16.6 960-1070 230 600
1998 Cera R plus Elephant 58.0 27.5 9.0 2.0 0.0 3.0 1.0 0.0 Ir 16.8 1000-1050 220 510
2001 Cera F Elephant 58.0 27.3 7.0 3.0 0.0 2.3 0.2 0.0 Ta, Ru 16.3 1005-1065 240 685

These alloys with more than 70 percent gold show a rich yellow gold color. Those in the 58% gold
content range were still “yellow” in colour. The initial Carrara Alloys showed a high CTE. To later
acommodate Carrara PdF in the Carrara System the thermal expansion coefficient of the new Carrara
Vincent porcelain was increased by 0.3 µm/m.K, to give it a closer match (∆αT ) with Carara PdF of 1.1
µm/m.K., which is regarded as ideal for obtaining a low-stress, low defect combination.

Since their introduction in the 90’s, this new generation of universal low-melting, high expansion gold
alloys has quickly gained market share, starting in Germany. These universal alloys have continued to
steadily replace the traditional gold-platinum alloys (Fig. 1). This marketshare trend is due to a
combination of reasons. The first was the aesthetics of the universal alloys. The second was the
properties of the hydrothermal porcelain applied to these alloys. The third was the ability of both the
universal alloys and the porcelain to be used in multiple applications.

The first universal alloys contained 75 wt-% gold and up to 9 wt-% platinum or palladium. They
provided a metal-ceramic system in which a gold alloy with rich yellow colour is fired to a carefully
matched dental porcelain. The tailored match requires compatible coefficients of thermal expansion
(CTE), and compatible melting or softening points of metal and porcelain. The major concerns during
initial development were with thermal stability during firing, the thermal expansion coefficient of the
alloy against the porcelain (compatibility) and the yellow color.
Since the development of a 75% rich-yellow universal alloy (Carrara PdF), Elephant has engineered
other alloys with lower gold contents to suit requests and still be compatible with hydrothermal
porcelain. Two alloys have been developed in the range of 50-60 wt-% gold and still offer a “yellow”
rather than “rich-yellow” colour. A silver/palladium alloy (Cera E) was also developed with almost no
gold (0.1%). This range of alloy offers the dental laboratory flexibility for use of the same porcelain for
multiple purposes (high-noble to maryland bridges) and use of the same alloy (Carrara PdF) for
multiple indications.

Thermal compatibility

A specific difference in the CTE (∆αT) is an important parameter in predicting metal-ceramic


compatibility. In general, the alloy must have a higher CTE (thermal expansion coefficient), measured
between room temperatuure (25oC) and the glass transformation temperature of the porcelain (500oC).
As high silver content is added to gold reduced alloys as a cost saving measure, this raises the CTE.
In order to bring their CTE’s more in line with the expansion of the high gold universal alloys, silver
content can be lowered by increasing the gold content (e.g. Cera R plus) and further still with the
addition of tantalum (e.g. Cera F).

Metal-ceramic bond

A good bond between the alloy and ceramic is a pre-requisite for a durable dental restoration. The
most recognized and standardized test available for evaluatiing this bond is a shear-bending test (H.
Schwickerath-test) which meets ISO/DIS 9693 (1999) Metal-ceramic dental restorative systems. Data
was obtained on the porcelain/alloy bond strength with 3 different porcelains (Table 4.). The
measurements were made on specimens directly after firing and after storaged for 30 days in a 0.1 M
Lactic Acid/0.1 M NaCl-solution with pH 2.3. A 1.0 mm thick layer of porcelain was applied and fired
on the central part of alloy strips of 0.5 mm thickness. Although the bond strength of the Carrara
combination decreases with 16% after storing in a corrosive solution according to ISO/DIS 10271, it is
still above the value of 25 Mpa requirement of ISO/DIS 9693 (1999).

TABLE 4. Metal-ceramic bond strength of three universal alloy-porcelain systems

Alloy Company Veneering ceramic Company Bond Strength, MPa


Directly after After 30 days
firing immersion
Carrara PdF Elephant Carrara Vincent 840oC Elephant 55.60 ± 4.8 46.81 ± 5.5
Degunorm DeguDent Duceragold 800oC DeguDent 45.76 N.D.
Maingold KF Heraeus Omega 800oC Vita / Vident 35 N.D.

Conclusion

The quest for a rich-yellow Universal Gold alloy for almost all lab-fabricated indications has been met
and has been available for the past 15 years. Advances in alloy engineering and in the development
of unique porcelain systems have resulted in a highly compatible match. Clinically-proven success,
unparalleled aesthetics, and a superior alloy/ceramic bonding interface were only some of the benefits
resulting from the development of these unique alloys.

Alloy market shares in those countries where these alloys have been effectively marketed clearly
demonstrates both an industry acceptance and a clinical success. Universal Gold Alloys have the
benefit of 1) reducing alloy inventory in labs, 2) offering simplicity in choice and results for both
dentists and dental labs, 3) offering outstanding aesthetics, 4) providing a superior porcelain/alloy
bonding over regular feldspathic porcelain/alloy interfaces, 5) depending upon alloy selection -
providing patients with more biocompatible alloy composition, 6) meeting and exceeding ISO and CE
requirements and testing and 7) offering a more economical choice for dentists who wish rich-yellow
PFM restorations (costs for traditional 84-88% gold content PFM alloys >75% gold content Universal
alloy:Carrara PdF).
The patient also clearly benefits by 1) potentially having only one colour of alloy in the mouth as
universal alloys can be used for all indications, 2) having the rich yellow colour expected in a gold PFM
restoration, 3) veneering of hydrothermal porcelain on these alloys. In the latter, hydrothermal
porcelains offer a) a homogenous and smooth structure which provides low abrasion and a resistance
to plaque build-up, b) a Vicker’s hardness similar to natural teeth for comparable wear rates, and c)
the ability to self-seal in the mouth for crack resistance and intra-oral polishability.

We can expect that the Universal alloys will continue to penetrate markets where traditional alloys
have the majority market share. Dentist and lab advantages will result in the transition. The universal
alloys have already established their rightfull place in the dental market. In the last 15 years, they have
also shown to be the most significant development in dental metal-ceramics since its start five
decades ago.

References

1. A Dental Porcelain, a Method of Producing a Dental Restoration, a Dental Alloy, J.M. van der Zel, Elephant
Dental B.V., Pr.D. 10 September 1990, Eur Pat 475,528, Gold Bull., 1992, 25, 4:126.
2. J.M. Van der Zel, Materialkundliche Aspekte des Carrara Metall-und-Keramik-Systems, Dental Labor,
1991, 39, 9:1199-1202.
3. J.M. Van der Zel, Carrara: nach 5 Jahren unter die Lupe genommen, Dental Labor, 1996, 44, 6: 973-981.
4. Edelmetalltaschenburg, ed. Degussa, 2. Auflage, Hüthig-Verlag, Heidelberg, 1995, p.521.
5. Aberer, W., Holub H., Strohal, R., and Slavicek, R. Palladium in dental alloys –the dermatologist’s
responsibility to warn? Contact Dermatitis, 1993 Mar; 28(3):163-165.
6. B. Windham. Adverse Health Effects of Palladium.
http://www.geocities.com/HotSprings/Spa/2021/palladium.html. Information and 16 references.

FIGURE 1. Relative market shares in volume of universal gold alloys, gold-platinum ceramic
alloys and gold crown & bridge alloys in Germany.

100%
90%
80%
70% Universal Gold
60% Alloys
50% Gold-Platinum
40% Ceramic Alloys
30%
20% Gold Crown &
Bridge Alloys
10%
0%
1990

1992

1995

2000

2003