Chapter 7
Metal-Ceramic Alloys
I. Porcelain Supported by Metal
These alloys are frequently called porce-
lain-fuse-to-metal alloys or, simply, PFM
alloys. Metal-ceramic alloys is the pre-
ferred term that will be used in this chapter.
The porcelains that will be applied to these
alloys will be described in Chapter 8.
Porcelain has good and bad qualities as a
restorative material:
good: 1. Matches the color and translucence
of enamel
2. Well-tolerated by soft tissue
bad: 1. Difficult to form acceptable mar-
gins
2. Very brittle subject to fracture in
tension
The two bad characteristics can be over-
come by fusing the porcelain to a metal coping.
The metal supports the porcelain, increasing
its resistance to fracture. Secondly, the coping
is cast using lost-wax casting techniques,
which can produce a crown whose margins
closely fit the prepared tooth.
Metal-ceramic crowns and bridges make up
an increasing percentage of all crowns and
bridges placed by dentists. One reason for this
is that high speed handpieces make prepara-
tion of teeth for full crowns easier than in the
past. (Note: this is not conservative den-
tistry.) Consequently, fewer 3/4 crowns are
being placed. Also, the esthetics of metal-
ceramic crowns and bridges are highly accept-
able to patients.
II. Desirable Properties of Metal-ceramic
Alloys
High Melting Range
Alloys which will be covered by porcelain
must melt above the fusion temperature of
porcelain. Otherwise, the casting will distort
during the firing of the porcelain. It is recom-
mended that the fusing range of the alloy be
65-150oC above the fusion temperature of the
porcelain. Recall that alloys usually have a
melting range, rather than a melting point (a
single temperature at which melting occurs).
To increase the melting range of gold-based
alloys, high melting point metals such as plat-
inum and palladium are added to the alloy.
Nickel-based, cobalt-based and palladium-
based alloys have high melting ranges by
virtue of the melting temperatures of nickel,
cobalt and palladium, respectively.
Porcelains for veneering metal-ceramic
alloys typically fuse between 1000 and 1050oC.
All metal-ceramic alloys are designed to have
higher fusing temperature ranges than the
ADA gold casting alloys. This is so the alloy
will not flow at the fusion temperature of
porcelain. Because of this, investments that
will not break down at high temperature (e.g.,
phosphate-bonded investments) and heating
techniques that can achieve high temperatures
(e.g., gas-oxygen flames and induction melting)
are required.
Bonding to Porcelain
Dental porcelains are glass ceramics that
consist of crystalline filler particles (quartz,
alumina, or leucite) which are embedded in a
feldspathic glass matrix (see Chapter 8 for
more on this). This matrix extends throughout
the porcelain; it is present at the porcelain's
surface, but is not confined to the surface.
The process of bonding porcelain to
the metal coping. The dental technician
applies a slurry of porcelain particles and
water to the At high temperature, porcelain
particles (the frit) sinter together because this
glassy matrix partially melts. Particles that
1
 Metal-Ceramic Alloys
Oral Biomaterials - Chapter 7
are in contact with one another will be welded
together by the glassy silica matrix.
Oxides at the alloy surface. As a general
rule, silica glass will not bond to alloys unless
the alloy is covered with a metal oxide.
Oxide-free alloys will not bond to porcelain,
probably because the covalent bonding of the
glass is incompatible with the metallic bonding
of the alloy. Successful porcelain-metal bonds
can be formed if the alloy is covered with a
naturally occurring surface oxide (e.g., this
occurs in Ni-Cr alloys) or if a surface metal
oxide is produced by adding a small amount (1
%) of oxide former (e.g., Sn, In, or Fe) to the
alloy. At high temperature, the oxide former
diffuses to the alloy's surface, where it reacts
with oxygen in the atmosphere to produce the
surface metal oxide.
Bonding mechanisms. At the former
alloy surface, the feldspathic glass of the por-
celain matrix will be in nearly continuous con-
tact with the base metal oxide. Since the feld-
spathic glass is primarily an oxide of silicon, it
is chemically similar to the base metal oxide.
The oxides can diffuse (either by interdiffusion
of two viscous liquid oxides or by interdiffusion
of silicon and base metal atoms between two
solid oxides) into one another. The diffusion is
possible because the two oxides are chemically
similar and, therefore, are able to mutually
dissolve in one another. Note that normally
there will be little diffusion between an oxide-
free alloy surface and the silicate glass in den-
tal porcelain. Because the alloy exhibits
metallic bonding and the silicate glass cova-
lent bonding, metals and glasses exhibit little
mutual solubility.
For successful bonding, the bond must be
strong at both the metal/metal oxide interface
and the metal oxide/porcelain interface.
Selection of the proper oxide former ensures
that the metal oxide adheres to the underlying
alloy (not all will).
2
The bonding discussed in the preceding is
chemical, but it is believed that mechanical
interlocking also plays a role in the bonding
between some alloys and porcelains. At high
magnification, many porcelain-alloy interfaces
are found to be very irregular, perhaps, be-
cause of selective dissolution of some alloy
phases by the glassy porcelain. The irregular
interface may interlock the porcelain and the
metal.
Compatible Thermal Expansion With
Porcelain
The thermal expansion of the metal and
porcelain must be compatible. Bonds between
porcelain and metal formed at high tempera-
ture will break if the metal and porcelain
shrink at greatly different rates as they cool.
Ideally the rates of contraction of the metal
and porcelain should be equal or, also accept-
ably, the metal should contract at a slightly
higher rate than the porcelain. The latter con-
dition places the metal side of the joint in ten-
sion and the porcelain side in compression.
Since the porcelain is much stronger in com-
pression than in tension, this strengthens the
porcelain/metal joint. Reversing the thermal
contractions, so that the metal is placed in
tension and the porcelain in tension, is likely
to produce porcelain fracture or delamination.
No Discoloration
A metal-ceramic alloy should not discolor
the porcelain. Types III and IV ADA casting
alloys cannot be veneered with porcelain.
These gold casting alloys all contain copper,
which will react with porcelain to form blue or
blue-green reaction products at the porcelain-
metal interface. Gold-based alloys that con-
taining silver also discolor many porcelains.
Porcelain on these silver-containing alloys
takes on a very light green tint. Recently,
porcelains that resist such "greening" have
become available. These porcelains contain
 Metal-Ceramic Alloys
Oral Biomaterials - Chapter 7

less sodium than the porcelains tra-

Ta ble 1
ditionally used on metal-ceramic ADA Classification of Metal-Ceramic Alloys
alloys.
Cla ssifica tio n Weig ht %
Sag Resistance
Hig h Noble Au + Pt g rou p > 90
A metal-ceramic alloy should
resist sag at high temperatures. Sag Mediu m Noble 90 > Au + Pt g rou p > 90
is distortion of the alloy under the
Low Noble Au + Pt g rou p
stress produced by its own weight,
which occurs at high temperature Base Metal Au + Pt g rou p = 0
during the fusing of the porcelain
onto the metal. If the sag resistance
(e.g., the metal's high temperature rigidi- Ta ble 2
ty) is inadequate, long span bridges can- Composition s of
not be placed on the casts from which Typical Metal-cera mic Alloy s of Ty pe
they were prepared.
Co mpo sitio n Oxi de
III. Classification of Metal-ceramic Ty pe (wt. %) Fo rmer
Alloys High Noble
The first metal-ceramic alloys intro- Au-Pd-Pt 75-98% Au Fe, Sn , In
duced during the 1960s were highly
noble gold-platinum-palladium alloys. Au-Pd 50-60% Au Sn, In
35-40% Pd
The cost of gold and other precious met-
als has lead to increased use of base met-
als in crown and bridge alloys. The Me diu m Noble
American Dental Association classifies Au-Pd-Ag 50-60% Au Sn, In
metal-ceramic alloys as shown in Table 25-30% Pd
1. Here "Pt group" means either plat- 10-15% Ag
inum or palladium. Pd-Cu 70-80% Pd Cu ?
5-15% Cu
As was the case for the ADA's classifi- Ga, Au
cation of bare-metal alloys (see Handout
No. 8), the classification in the Table is
Lo w Noble
not very useful for understanding the
properties of metal-ceramic alloys. Its Pd-Ag 50-65% Pd Sn or In
primary use is to classify the alloys 30-40% Ag
according to cost.
Ba se Meta l
In Table 2 and in Section IV and V to
follow, crown and bridge alloys for porce- Ni-Cr 70-85% Ni Cr, Be
9-20% Cr
lain application are classified according
to the principal elements found in each Co-Cr 65-70% Co Cr
alloy. Section IV deals with noble metal- 25-27% Cr
ceramic alloys and Section V with base
metal metal-ceramic alloys.

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 Metal-Ceramic Alloys
Oral Biomaterials - Chapter 7
IV. Noble Metal-ceramic Alloys
High Gold (Gold-Platinum-Palladium)
Alloys
These contain between 75 and 98% gold.
Because of their high density (18 to 19 g/cc)
and high precious metal content, these are the
most expensive metal-ceramic alloys per den-
tal unit (e.g., per coping or pontic). Most of
these alloys are yellow-gold. This color is par-
ticularly pleasing under porcelain. The high
noble metal content of these alloys makes
them very resistant to tarnish and corrosion.
The platinum and palladium in these alloys
push their melting temperatures well above
the fusion temperature of porcelain. These
alloys contain iron (in the older alloys), tin, or
indium to produce the oxide film which is
apparently prerequisite to bonding between
the metal and porcelain.
Most of these alloys are more ductile, softer,
and weaker than other metal-ceramic alloys.
Consequently, these alloys are easier to grind,
polish and burnish than other metal-ceramic
alloys.
Negative factors associated with these
alloys include their cost, lack of rigidity (low
elastic modulus) and lack of sag resistance.
The cost for the alloys alone (not including the
dental technician's labor) is about $50 per pon-
tic or $28 per coping. If a long-span bridge is
not rigid, flexing of the bridge can cause the
bond between the metal and the porcelain to
fail or the porcelain itself to fracture. As men-
tioned above, sag of a long-span bridge can
cause it not to fit over the prepared teeth.
Gold-Palladium-Silver Alloys
These alloys contain between 50 and 60%
gold and between 20 and 30% palladium.
Again, tin and indium are added to promote
bonding. The lower gold content and lower
density (13 to 14 g/cc, because there is less of
the dense gold) of these alloys decreases the
4
cost per dental unit. They are corrosion resist-
ant and can be ground, polished and bur-
nished. These alloys are slightly more rigid
and sag less than High Gold metal-ceramic
alloys. The main advantage of these alloys is
that they are gold-like alloys that cost only
60% as much as the High Gold alloys. Their
main disadvantage is that, under some condi-
tions, the silver in these alloys can cause the
porcelain to discolor.
Gold-Palladium Alloys
These are similar to Au-Pd-Ag metal-ceram-
ic alloys, except that the silver has been re-
moved to prevent greening of the porcelain.
They contain 40-59-0% gold and 3-40% palladi-
um. The elimination of silver reduces the
thermal expansion of these alloys. The reduc-
tion leads to a thermal expansion incompati-
bility with some high thermal expansion
porcelains. Alloy manufacturers readily admit
this incompatibility and list incompatible
porcelains for their alloy.
These silver-free alloys have largely sup-
planted the Au-Pd-Ag alloys in the U.S. mar-
ket. Like the Au-Pd-Ag alloys, they are 60% of
the cost of the High Gold alloys.
Palladium-Silver Alloys
These alloys contain no gold. Typical for-
mulations would include 50 to 65% palladium,
30 to 40% silver, and 4 to 10% base metals (tin
or indium). The low density of these alloys (10
to 11 g/cm) and the absence of gold makes
these the least expensive of the precious metal
alloys. They are only 14% of the cost of the
High Gold alloys. These alloys have the high-
est sag resistance of the precious metal-
ceramic alloys.
Unless special procedures are followed,
these alloys will tint most porcelains green.
Recent studies show that silver from the alloy
can diffuse through the porcelain to the metal
surface. This explains why the greenish tint is

usually most striking where the porcelain is
thin. Here diffusing silver atoms rapidly
reaches the surface. More research is needed
on mechanism of greening. As was mentioned
earlier, there are now porcelains on the mar-
ket that resist greening.
It is also possible to prevent greening by
painting a layer of colloidal gold on the alloy.
After firing, a thin layer of gold forms on the
surface of the casting. This gold layer reduces
the concentration of silver available to diffuse
into the porcelain. Other manufacturers rec-
ommend a ceramic conditioner. Such condi-
tioners are also fired onto the alloy beneath
the porcelain. They are thought to act as a
barrier to silver diffusion. The colloidal gold
and ceramic conditioners share the disadvan-
tage that both require an additional firing
cycle.
Porcelain furnaces that have been used to
fire porcelain on Ag-Pd alloys become contami-
nated with silver. Subsequently, even silver-
free alloys fired in these furnaces will have
green-tinted porcelain. Fortunately, this can
be prevented by placing a graphite block near
the alloy being fired. The graphite produces a
local reducing atmosphere near the alloy.
Palladium-Copper Alloys
In the early 1980s, alloys with 70 to 80%
palladium and up to 15% copper were intro-
duced. Some of these alloys also contain tiny
amounts of gold and up to 8% gallium. Recall
that copper in gold-containing alloys turns
porcelains blue or blue-green. Copper in Pd-
Cu does not discolor dental porcelains. Their
principal advantage is that unlike the Pd-Ag
alloys, they do not turn porcelain green.
V. Base Metal Alloys (Nickel-Chromium
Alloys)
Over 95% of the base metal alloys are nick-
el-chromium alloys. Most contain between 70
and 85% nickel and between 9 and 20%
Metal-Ceramic Alloys
Oral Biomaterials - Chapter 7
chromium. The remaining 5% of the available
base metal alloys are iron-chromium and
cobalt-chromium, both of which contain 12 to
15% chromium. Beryllium is added to many of
these alloys to improve their castability and to
control surface oxide thickness (see below).
Advantages
Because these alloys do not contain precious
elements, they are very much cheaper than
other metal-ceramic alloys. Other advantages
of nickel-chromium alloys include their high
resistance to sag and their high rigidity (high
elastic modulus).
Disadvantages
The nickel-chromium alloys are very hard
and strong. As a result, grinding and polish-
ing are difficult. In addition, casting proce-
dures for these alloys (see section IV) are often
not as refined as for noble metal alloys.
Consequently, some experimentation may be
required in order to consistently obtain suc-
cessful castings.
Bonding to Porcelain
Indium, tin, or iron must be added to noble
alloys to produce a chemical bond between
metal and porcelain. Without these additional
elements, alloys of gold, platinum and palladi-
um would not form the transitional oxides that
are necessary for bonding.
Role of chromium. There is no need to
add oxide-forming elements to nickel-chromi-
um alloys. Chromium in these alloys oxidizes
very readily (much more readily than nickel),
forming chromium oxide (Cr2O3). In the
mouth, this chromium oxide protects the alloy
from further chemical attack. The alloy sur-
face resists tarnish because of this protection.
Unfortunately, at the high temperatures
where porcelain is fired, the chromium oxide
can grow too thick. Such a thick oxide may be
brittle and, as a result, porcelain may not
adhere to such surfaces. In addition, thick
5
 Metal-Ceramic Alloys
Oral Biomaterials - Chapter 7

chromium oxide layers are dark green or gray.
This color may show through the porcelain,
producing a poor color match with natural
teeth.
To reduce the thickness of the chromium
oxide, small amounts of elements that oxidize
more readily than chromium are added to the
alloy. These form thin surface oxides, which
act as a barrier between oxygen and chromi-
um, thereby, decreasing the amount of chromi-
um oxide and chromium, thereby, decreasing
the amount of chromium oxide that forms.
Therefore, the elements aluminum, molybde-
num and beryllium are added to some nickel-
chromium alloys to reduce the thickness of the
chromium oxides. Beryllium is the most effec-
tive of these elements for this purpose. Other
manufacturers suggest that the thickness of
the oxide be reduced by sandblasting the
oxide.
Aside from minimizing the thickness of
chromium oxides, there is no general rule for
achieving bonding between nickel-chromium
alloys and porcelain. In some alloys, interme-
diary oxides, which affect the transition from
the alloy (metallic structure) to the porcelain
(glassy structure), are apparently formed. For
a particular alloy, these transition oxides may
include one or more of the following: chromi-
um oxide (Cr2O3), nickel oxide (NiO), berylli-
um oxide (BeO), and complex nickel-chromium
oxides.
Mechanical retention of porcelain.
Other nickel-chromium alloys appear to relay
wholly or, at least partially, on mechanical
bonding to achieve adhesion between porcelain
and metal. Many alloy manufacturers achieve
bonding through trial and error experimenta-
tion. It is important that dental laboratories
follow the alloy manufacturer's procedures
exactly. Procedures that may or may not be
used include preoxidation treatments, which
produce an oxide before porcelain is applied,
and sandblasting, which may increase
mechanical bonding by roughening the surface
of the alloy.
Biocompatibility
Nickel dust. The nickel and beryllium in
nickel-chromium alloys are potentially haz-
ardous. Long-term exposure to nickel dust has
lead to cancers of the lung and nasal passages.
However, such long-term exposure has been
observed only in the nickel industry where the
quantity and persistence of the exposure
would be expected to be much greater than
that encountered in dental laboratories.
Nickel allergies. A substantial percentage
of patients are allergic to nickel. Such aller-
gies are sometimes missed by dentists. In
some patients, nickel allergy manifests itself
as swollen and reddened soft tissues in the
mouth. In other patients, there is no evidence
of intraoral reaction. Instead, nickel alloys
can produce dermatitis at sites distant from
the prosthesis (e.g., inside the elbow or in the
arm pit). In the U.S., up to 12% of women
tested and a growing percentage of men are
allergic to nickel. Before nickel-chromium
crowns and bridges are placed, patients should
be asked if they have experienced rashes when
wearing nickel plated jewelry.
Beryllium. Beryllium, which is added in
small quantities to some nickel-chromium
alloys, is a hazard to laboratory personnel who
can breathe in the dust during grinding or the
fumes during casting. Exposure to very small
quantities of beryllium can produce contact
dermatitis, ulcers, corneal burns, and respira-
tory diseases. Symptoms of acute berylliosis
may include pulmonary dysfunction, conges-
tive heart failure, and spleen and liver
enlargement.
Fortunately, berylliosis has yet to be docu-
mented in a dental setting. Nevertheless,
avoidance of grinding dust (proper masks) and

6

casting fumes (adequate venting) seems pru-
dent. There is no evidence that beryllium in
crowns and bridges is harmful to the patient.
VI. Techniques for Metal-Ceramic Alloys
Investing
Because of their higher fusion tempera-
tures, metal-ceramic alloys undergo more ther-
mal contraction on cooling than do gold and
silver-palladium casting alloys. Consequently,
investments for metal-ceramic alloys must be
expanded more than investments for gold and
silver-palladium casting alloys. Also because
of the higher melting range of metal-ceramic
alloys, gypsum-bonded investments cannot be
used. Instead, phosphate-bonded investments
are used.
These investments are heated to tempera-
tures between 700oC and 950oC. (A specific
temperature will be recommended by the alloy
gold
manufacturer). There are two reasons for
using these high temperatures: (1) the high
copper
temperatures increase the thermal expansion
of the investment, and (2) the high tempera-
tures are necessary so that alloy will remain
fluid when in contact with the walls of the
mold. Fluidity is a problem because of the
high fusion temperatures of metal- ceramic
alloys; they quickly become viscous at lower
disorderedViscous liquid
temperatures. ordered
alloy may have
difficulty flowing into fine chambers of the
mold cavity.
Casting
Metal-ceramic alloys are usually cast with a
gas-oxygen torch or with an induction casting
machine. The melting characteristics of all
the metal-ceramic alloys except the nickel-
chromium alloys are fairly similar to those of
gold and silver-palladium casting alloys. That
is, the alloys will pool into single circular glob-
ules. Most nickel-chromium alloys, on the
other hand, do not coalesce into circular glob-
ules. The relatively thick oxide scale on the
Metal-Ceramic Alloys
Oral Biomaterials - Chapter 7
alloys tends to restrict the alloy ingots to their
original shapes. The correct casting tempera-
ture is recognized by noting when the ingots
begin to "slump".
K = c
, (4)
o
If heating is continued in an effort to pro-
duce spherical globules, an overheated liquid
alloy will be cast. Such a liquid alloy will
attack the surfaces of the mold and the result-
ing casting will have a rough surface. In addi-
tion, overheating the alloy can cause low melt-
ing point elements in the alloy to evaporate.
Loss of such elements can affect bonding of
porcelain to the alloy. The oxide scale can
also cause one to under heat the melt. The
oxide scale may be lowing white-hot, but the
alloy below may be considerably cooler.
Because under heated alloy is relatively vis-
cous, castings are likely to be incomplete.
Another property specific to palladium-sil-
ver alloys and nickel-chromium alloys is their
low density. To achieve sufficient casting
pressures, arms of centrifugal casting
machines may need to be wound one or two
more extra turns. the extra spring tension
will produce higher rotational velocities and,
consequently, will increase the casting pres-
sure.
Cleaning Castings
Metal-ceramic alloys should not be pickled.
Acids may selectively dissolve base metals
which are important in achieving bonding to
porcelain. Generally, it is recommended that
the alloys be cleaned by sandblasting. Sand-
blasting may also be necessary for freeing the
castings from phosphate-bonded investments.
This is particularly true for nickel-chromium
alloys, most of which form surface oxides
which interact with the investment.
a
= 1+ 2 ,
Objectives
VII. Behavioral
max (5)
b
From a list of choices, you will be able to
select:
7
 Metal-Ceramic Alloys
Oral Biomaterials - Chapter 7

13. the reason why metal-ceramic alloys

should not begin to melt at too low a tem-
1. the effect of the relative thermal contrac-
perature.
tion of metal and porcelain on the bonding
of metal to porcelain. 14. elements that are typically included in
gold-based metal-ceramic alloys in order to
2. the purpose of adding iron, tin and indium
raise the alloy's melting range.
to noble metal-ceramic alloys.
15. correct statements about the relative ease
3. the effect of copper in metal-ceramic alloys
of grinding Ni-Cr and Co-Cr metal- ceram-
on the color of porcelain.
ic alloys as compared to other metal-
4. the effect of silver in metal-ceramic alloys ceramic alloys.
on the color of many dental porcelains;
16. correct statements about why the high
ways of preventing porcelain greening due
elastic modulus of Ni-Cr is an advantage
to silver in the alloy.
when making crowns or fixed partial den-
5. the recommended fusion temperatures of tures.
metal-ceramic alloys.
You will be able to select the correct defini-
6. two reasons for adding beryllium to Ni-Cr tion or description of the following terms, or,
alloys. given the definition or description, select the
correct term.
7. potential hazards to laboratory personnel
and to patients associated with Ni and Be metal-ceramic alloy
in Ni-Cr alloys.
PFM alloy
8. two reasons why investments for metal-
sag resistance
ceramic alloys are heated to higher tem-
peratures than investments for gold and
silver-palladium casting alloys.

9. the difference between the appearance of

liquid gold alloys that are ready to cast
and of liquid nickel-chromium alloys that
are ready to cast.

10. the recommendations for pickling and

cleaning metal-ceramic alloys and the
rationale for these recommendations.

11. correct statements about the influence of

beryllium, aluminum, and molybdenum on
the formation of chromium oxide on nick-
el-chromium alloys.

12. a correct definition of sag resistance and

the relative resistances of High Gold, Pd-
Ag, and Ni-Cr metal-ceramic alloys.