METALLURGY

Dr.Weboko I.F BDS(UoN),

MScD Endodontics(UE)
• Cast metals used to
Onlays
construct many
types of metallic Implant
prostheses Inlays
abutments
• Used as frameworks
for metal-ceramic &
metal-resin
prostheses Partial & Pd
full crowns frameworks

posts Bridges
 Implant abutments
Onlays

PFM bridge Inlays

https://www.intechopen.com/books
• Understanding the structure &
properties of cast metals is essential to
ensure the optimal quality and
performance of metallic-based
prostheses and restorations
• Also helps diagnose clinical
failures of cast restorations
Why study the science of physical
metallurgy?
Cast metal technology
Heat Casting
treatment processes

Physical &
Mechanical
properties

Effects of
Deformation
composition
 Key terms
• Alloy— A crystalline solid with metallic properties,
composed of 2 or more chemical elements at least 1 of
which is a metal and all of which are mutually soluble in
the molten state
• Alloy system— All possible alloyed combinations of 2 or
more elements at least 1 of which is a metal
• Binary metal alloy— An alloy that contains 2 chemical
elements at least 1 of which is a metal
• Coring— A microstructure in which a composition
gradient exists between the center and the surface of
cast dendrites, grains, or particles
• Dendritic microstructure— A cast alloy structure of
highly elongated crystals with a branched morphology
• Equiaxed grain microstructure— A cast alloy
microstructure with crystal (grain) dimensions that
are similar along all crystal axes
• Grain— A single crystal in the microstructure of a
metal
• Grain boundary— Interface between adjacent grains
in a polycrystalline metal
• Dental alloys are polycrystalline solids consisting of
many individual grains (crystals) separated by grain
boundaries
• Homogeneous nucleation— Formation
of nuclei that occur at random
locations within a supercooled molten
metal in a clean, inert container
• Metal— An element or alloy whose
atoms readily lose electrons to form
+vely charged ions
• A metallic material composed of 1 or
more chemical elements that is
opaque, ductile, malleable, good
conductor of electricity, heat and
lustrous
• Heterogeneous nucleation— Formation of solid nuclei
on the mold walls or on particles within a solidifying
molten metal
• Microstructure— Structural features of a metal,
including grains, grain boundaries, phases, and defects
eg. porosity, revealed by microscopic imaging of the
chemically or electrolytically etched surface of a flat,
polished specimen
• Nucleus— A stable cluster of atoms in a new phase
that forms within a parent matrix phase during the
solidification of a microstructure
• Phase— A homogeneous, physically distinct, and
mechanically separable portion of a metal
microstructure
• Phase diagram (constitution diagram)— A graph of
equilibrium phases and solubility limits for an alloy
system as a function of composition and temperature
• Solid solution (metallic)— A solid crystalline phase
containing 2 or more elements at least 1 of which is a
metal and whose atoms share the same crystal lattice
• Quaternary alloy— An alloy that contains 4 elements at
least 1 of which is a metal
• Tarnish— Superficial discoloration or dulling of a metal
surface
• Often caused by a reaction with oxygen or sulfur
• Ternary alloy— alloy that contains 3 elements at least 1 of
which is a metal
Dental casting alloys are associated with the
following groups
Dental
amalgams

At least 40wt% Au Hg, Ag, Sn, Cu

˂ 25 wt% of
& 60wt% noble
noble metals
metals
Pre
High
noble dominantly
alloys Base metal
alloys

• Pd- main noble metal

• Total noble metal content at least
25wt% Noble
metal
• May contain Au, Ag, Cu, Ga, In, Ptalloys
& Sn
Predominantly base metal alloys

Ni-Cr Fe-C-Cr Ti-Al-V

Co-Cr CPTi
 Metallic bonding
• Metals conduct heat and electricity
• This is associated with the mobility of its free valence
electrons
• Since the outer valence electrons can be removed easily
from metal atoms, the nuclei containing the balance of
the bound electrons form +vely charged ionic cores
• In addition to covalent and ionic bonds, atoms in solid
metals are held together primarily by metallic bonds
• Because the cloud of electrons is shared among many
atoms, metallic bonds are nondirectional
• Metallic bonding is also responsible for luster of polished
metals and ability to undergo permanent deformation
(ductility & malleability)
• These characteristics are not typical of ceramics and
polymers, whose atoms & molecules are bonded by
covalent and ionic mechanisms
• Pure metals can be identified by their specific melting and
boiling points and by their basic physical & chemical
properties
• Pure metals have limited uses in dental and engineering
applications, because they are too soft and some may
corrode excessively
• To optimize properties, most metals used are either
mixtures of 2 or more metals or mixtures of 1 or more
metals and nonmetals
• These alloys are prepared by fusion of the elements
above their melting points
• Eg. a small amount of C is added to Fe to form steel
• A certain amount of Cr is added to Fe, C, and other
elements to form SS
• SS is highly resistant to corrosion
• Cr provides corrosion resistance by forming Cr2O3 that
prevents diffusion of O2 or other corroding elements
• Pure gold is highly resistant to corrosion but copper is
added to gold for many dental alloys to increase
strength and resistance to permanent deformation
Physical properties of alloy forming elements
 Classification of alloys

3 principle Dominant
Use Major elements Nobility
elements phase
• C&B • Au based • High noble • Au-Pd-Ag • Single
• Metal ceramic • Pd based • Noble • Pd-Ag-Sn • Eutectic
• Post & core • Ag based • Predominantly • Ni-Cr-Be • Peritectic
• Implants • Ni based base metal • Co-Cr-Mo • Intermetallic
 Effects of alloy elements on
properties of high noble and noble
metal alloys
• Pure gold lacks sufficient strength and stiffness for any
dental application except as direct filling gold (also
known as gold foil)
• Gold is inert, extremely malleable, provides tarnish &
corrosion resistance, excellent ductility, minimal
abrasiveness
• Au is useful to raise the thermal expansion coefficient
(TEC) of Pd alloys
• Whereas, Pd is used to lower the TEC of Au-based PFM
alloys
• Palladium whitens gold alloys markedly
• It raises the melting range, elastic modulus, strength,
hardness of Au alloys as well as lowers their density
• Gallium is used in Pd-based PFM alloys to strengthens
and decreases their melting range
• Platinum used in yellow-gold PFM alloys to increase
melting range, hardness, strength & elastic modulus and
decreases their TEC
• Pt affect the properties of gold alloys to a lesser extent
compared with Pd
• Silver is added to Au-Ag-Cu alloys to offset the reddish
hue contributed by Cu
• In Pd-based PFM alloys, Ag is used to raise the TEC
• It decreases the melting range of both Pd & Au alloys
and improves the flow of alloys & solders
• Copper strengthens and reddens Au-Ag-Cu C&B alloys
• It’s added to Pd-based PFM alloys to increase their TECs
• Cobalt alternative to Cu in Pd-based PFM alloys
• However, like Cu, it also forms dark-colored oxides
• Zinc is added to C&B alloys as an oxygen scavenger,
thereby reducing gas porosity in castings
• For PFM alloys, zinc can be added also to strengthen
and harden the alloys and/or to increase the TEC and
decreases the melting range
• Indium is used in some Au-Ag-Cu casting alloys to
improve their castability
• In Au-& Pd-based alloys, it strengthens and hardens
them, increases their TECs, and decreases their melting
temperature range
• Also contributes to formation of a bonding oxide in PFM
alloys
• Tin also contributes in formation of a bonding oxide and it
strengthens and hardens Au- and Pd-based PFM alloys
• It also decreases the melting range of Au-based and Pd-
based alloys and increases their TECs
• Iron is used to strengthen Au-Pt alloys for PFM application
• Like Sn and In, it also forms a bonding oxide
• Iridium (Ir), rhenium (Re), and ruthenium (Ru)] are used
as grain refinement agents to restrict growth of grains
during solidification
Solidification and microstructure of
cast dental alloy

A time-temperature
Temp cooling curve for a
pure metal, illustrating
supercooling

Time
 Nucleus formation
• Solidification begins with the formation of embryos in
the molten metal—i.e., small clusters of atoms that form
nuclei of crystallization
• At temperatures above the fusion temperature (Tf),
these embryos will also form spontaneously in the
molten metal
• The surface free energy (FS) of an embryo is greater
than its internal energy
• The volume free energy contribution (FV) is the
difference between the free energies of the solid and
liquid states
Solidification process from the
viewpoint of thermodynamics

Free energy of formation of a

nucleus as a function of its
radius
FV is the volume free energy
of the embryo
FS is the free surface energy
R is the resultant free energy
• For an embryo of radius (ro), the overall free
energy (R) decreases upon the addition of another
atom and continues to decrease as the embryo
grows
• Embryos with radii smaller than ro are unstable and
spontaneously form and disappear in the liquid
metal
• Whereas embryos with radii larger than ro become
stable nuclei and continue to grow during
solidification
• The process of nucleus formation in the bulk liquid
metal is called homogeneous nucleation, since it
occurs in the absence of a surface that would
promote heterogeneous nucleation
• Imperfections in the mold walls, particles of dust,
and other impurities in the molten metal can
produce heterogeneous nucleation of crystals
Liquid-to-solid transformation of cast
metals

Optical microscopic image of a polished

and etched palladium-based alloy with a
dendritic as-cast microstructure

SEM image of the fracture surface of a

cast base metal alloy for RPD
frameworks, showing the pattern of
crack propagation in the dendritic
microstructure
SEM image of a polished and etched
high-palladium alloy with an equiaxed
fine-grain as-cast microstructure
The white-appearing particles are
ruthenium-rich and arise from the use of
ruthenium as a grain-refining element
Stages in the formation of
metallic grains during the
solidification of a molten
metal
 Grain refinement and grain size

• N metal casting alloys for dental prostheses generally

have equiaxed fine-grain microstructures
• They contain small amounts of iridium (ir), ruthenium
(ru), or rhenium (re) as grain-refining elements
• The grain size of HN and N metal casting alloys controls
the yield strength of engineering alloys
• Fine grain sizes are promoted by rapid solidification that
occurs during casting (the time is inadequate for large
crystal growth)
• The compositional uniformity and corrosion resistance of
a cast dental alloy is superior for a fine grain size
• Because there is less opportunity for microsegregation
• Base metal and titanium-based casting alloys have
dendritic as-cast microstructures
• Dendritic microstructures form during the freezing of pure
metals by thermal supercooling
• During such processes, crystals are nucleated along the
investment walls and dendrites grow perpendicular to the
walls toward the center of the mold cavity
• Most dental casting alloys solidify from a liquid to a
liquid-plus-solid phase at a lower temperature i.e., the
liquidus temperature, and then to a solid phase at the
solidus temperature
• The liquidus temperature is the lowest temperature at
which all components of an alloy can be in a liquid state
• In a specific temperature range, the solid and liquid
phases coexist in equilibrium rather than at a single
temperature, as in a pure metal
• Concentration of each element can be expressed as a
weight % (wt%) or atomic % (at%)
• Eg. AuCu3 phase, has 51 wt% Au and 49 wt% Cu, but
on an atomic basis, has 25 at% Au and 75 at% Cu
• Usually, the properties of an alloy relate more directly to
the atomic percentage rather than the weight
percentage of each element
 Solid solutions
• Majority of noble metal casting alloys for dental
restorations are based on solid solutions
• Eg. when Pd-Ag alloy system is solidified, the Ag atoms
are distributed randomly in the FCC structure of pure
pd, forming a solid solution
• Because the Ag atoms become integrated into the
crystal structure of pd, no microstructural features can
be mechanically separated into two or more phases
(only 1 solid phase is present)
• However, Ag atoms may not be randomly located in the
pd crystal structure when a dental casting is cooled
rapidly and the atom species may be segregated
• To produce a homogeneous structure, heat treatment
at elevated temperatures for sufficiently long times
promotes solid-state diffusion that ensures the
uniform distribution of pd and Ag atoms
 Solutes and solvents
• When 2 metals are mutually soluble in the solid state, the
solvent is that metal whose crystal structure is retained
over the composition range of interest
• In Pd-Ag alloys, the 2 metals are completely soluble in all
proportions and the same type of crystal structure occurs
throughout the alloy system
• In such a case, the solvent is defined as the metal whose
atoms occupy the majority of the total number of
positions in the crystal structure
 Principal arrangements for binary
solid solutions
• Substitutional solid solution- solute metal atoms occupy
positions in the crystal structure that are normally
occupied by the solvent atoms in the pure metal
• Eg. Pd-Ag alloy in which Pd is the solvent metal, Ag
atoms replace the Pd atoms randomly in the crystals
• Interstitial solid solution-solute atoms are present in
random positions (interstices) between the atoms in the
crystal structure of the solvent metal
• Requires that solute atoms be much smaller in diameter
than solvent atoms
 Conditions for solid solubility
• For 2 or more species
Atom size
to be mutually soluble
difference
in solid solution,
several conditions
must be satisfied Cryst
Valen al
ce struct
ure

Potential to order
solvent atom
Equilibrium-phase diagrams

Identify phases
present in an alloy
system for different
compositions and
temperatures
Equilibrium-phase
diagram for the Pd-Ag
system showing %s by
weight
Coring and homogenization heat
treatment

• Under rapid solidification conditions, the alloy has a

cored structure
• The core consists of dendrites and the matrix is the
portion of the microstructure between the dendrites
• A homogenization heat treatment, which promotes
atomic diffusion, can eliminate as-cast compositional
difference and produce equiaxed grains
A, Copper-silver alloy (1%) as cast
B, The same cast alloy after homogenization heat
treatment
Color range of Au-Ag-Cu
alloys
Thank you