Metallurgy

Why do we use alloys?

Changes to improve strength allowed by pure metals
Change the grain size through cooling
Work hardening
o Take the metal beyond its yield point so that it shows some plastic deformity and lengthens
o When lengthened again, a higher force is required to cause the same plastic deformity
Changes to pure metals are limited so we create alloys
5 reasons to alloy
Strength
Corrosion resistance reduced or more predictable corrosion
o Capacity to form stable oxides (oxide layer) to which porcelain can be fused
o Add material to make is less corrosion resistant (eg. add metals to steel to form stainless
steel)
o Use an already corrosion resistant material but add other materials for strength without
compromising corrosion resistance (eg. gold alloys)
Castability can flow and pour into investment better
o Change melting range, lower surface temperature and wettability (more detail achieved)
Elastic memory/super elastic behaviour
o eg. Nickel and titanium used in endodontics and orthodontics
Decrease the melting point less shrinkage occurs on setting
Examples used in dentistry
Pure metals: titanium used for implants still has residual oxygen, carbon and nitrogen that are not
removed in refining process
Alloys:
o Alloys of gold noble alloys with copper, silver, palladium and platinum
o Iron with chrome and nickel stainless steel
o Cobalt with chrome and nickel for frameworks of partial dentures
o Nickel with other metals for base metal alloys used in copings and post/cores in crown and
bridge
o Nickel with titanium for pseudo-elastic alloys used for orthodontic wires and flexible
endodontic files
Alloys are formed by fusion of metals above their melting points

Features of alloys
Alloy: combination of 2 or more metals which are generally mutually soluble in the molten state
Most alloys solidify over a range of temperatures
o Solidification temperature range is typical for the system
Sag: deformation of a metal or alloy that occurs at high temperatures (eg. during porcelain firing)
o Should be similar to ceramic so that they fuse together well
Substitution alloys: 1 atom (solute) substitutes for another on the metals lattice (solvent)
o Solvent: material whose lattice persists OR the metal which consists of >50% in a solid
solution where the lattice persists throughout complete composition range
o Different sizes of atoms in the lattice leads to distortion and increases the strength of the
metal
o Random organization of solute atoms causes increase in energy of system and allows the
atoms to diffuse more readily
Classification of substitution alloys
o Infinite solubility (complete solid solution): atoms of 2 metals are randomly positioned on
sites of a common space lattice

Completely homogenous mixture only 1 phase present

Phase: physically distinct homogenous and mechanically separable portions of a
system
Eg. palladium and gold
o Limited solubility: atoms of 2 metals are mixed but 1 metal will eventually be saturated in
the other
Intermediate phases are formed where there is not complete solubility
Contain regions with islands of metal A in a sea of metal B and regions of islands
of metal A in a sea of metal B (ie. regions where A has dissolved in B and regions
where B has dissolved in A)
Eg. gold and copper
Interstitial alloys: much smaller atoms (eg. carbon or nitrogen) get positioned between solvent atoms
in normal lattice positions
Polycrystalline alloys (limited substitution and interstitial): never reach true equilibrium
o Rigid crystalline structure inhibits necessary level of diffusion
o Finite cooling rate allows for structure unstable at high temperatures to be apparently stable
at ambient room temperature
o Energy of grain boundaries is not relieved as long grain boundaries exist

Conditions for solubility of metals

Favourable size structure
o Ideal: <15% difference in atomic size
Same valency
o Metal of higher valence is more soluble in the metal of lower valence
Chemical affinity (reactivity)
o High chemical affinity leads to increased tendency to form inter-metallic compounds
Lattice type
o Only metals with the same lattice type can form complete series of solid solutions

Structure of metals
Face centred cubic crystals: atoms situated at the corners of the cube with others positioned in the middle of
the faces of cube most alloys used in dentistry
Slip is more difficult in substitution alloys with FCC crystals = increased strength, proportional limit,
hardness, decreased ductility solid solution hardening
o Greater the disparity between atoms, the greater the effect
Body centred cubic crystals: atoms situated at the corners of the cube with others positioned at the centre of
each cube alloys containing iron
Formation of crystals
Occurs with cooling by diffusion of atoms from molten metal to the site of nucleation which are areas
of more ordered atoms
o Sites of nucleation can be increased with introduction of grain refiners (eg. iridium particles)
that lower local free energy
o Grain refiners have higher melting point so remain solid and act as the site of nucleation
More ordered atoms occur close to the mould surface or around impurities
Crystals formed irregularly with lattice discontinuities and imperfections are constantly formed and
repaired
Size of crystals is determined by collision between 2 growing crystals that collide and stop growing
Grain: single crystal of metal seen in the metals microstructure (homogenous crystals of a single
orientation)
o Grains have different internal energies

Grain boundaries
Areas of discontinuity where 2 grains join
Features of grain boundaries
o Areas of high energy slip less likely to occur strongest parts
AIM: increase in number of grain boundaries to increase strength of alloy
o Areas where most impurities gather
o Areas most readily attacked by chemicals

Controlling properties of metals

Pure metals
Crystal size
Degree of super-cooling (actual temperature that metal is cooled to) rate of cooling (rate of removal
of heat)
o Control the number of nuclei forming and rate of growth
o Fast rate of cooling (quenching) = more nuclei and smaller crystal size
Nuclei collide more often creating more sites of nucleation while inhibiting the
growth of other crystals
Smaller grains = increased surface area of crystals for the same volume = increased number of grain
boundaries = increased strength and higher internal energy
Larger grains = less surface area of crystals for the same volume = more relaxed and soft structure
Crystal shape
Equiaxed grain structure desirable crystals are in a random
orientation with approximately equal shape and size
properties are more even
o Equilibrium structure
Radial/columnar grain structure directional grains present
and occur due to removal of heat in a particular direction only
properties are unidirectional
Grain structures and boundaries
Grain boundaries act as barriers to movement of dislocations
Smaller grain structures = increased concentration of grain boundaries = increased concentration of
inhibited dislocations = increase in strength and proportional limit
Work-hardening
Place forces on a metal so that it passes the yield point (eg. bending a wire)
Increases the strength and creates a permanent set/residual strain in the wire
o If you try to re-bend the wire, it will cause the neighbouring part to bend to as the bent part
is stronger than the original

Alloys
Cold working: turning as cast into wrought
As cast structure: molten material is solidified with equal properties in all directions
o Created after quenching or cooling
o Eg. inlays, crowns, bridges
Wrought structure: cast structure is cold-worked (shaped after setting) so that it gains unidirectional
properties
o Keep thinning it out one portion at a time as going too thin in one go is more likely to pass its
ultimate tensile strength
o May need to do it while it is hot as some stages and cold at the last stage
o Has higher potential energy input but considered stable (to a certain energy level)
o Eg. wires (strong lengthwise but flexible across)
Perfect wrought crystal whiskers can have tensile strength up to 10 000 times stronger than the as
cast version
o as cast lattice has imperfections due to crystals being irregular
Lattice sites left vacant, different sizes, some atoms deposited interstitially
Act as point or line defects to form dislocations
Annealing: turning wrought back to as cast
Process by which control of the strain hardening effects can be achieved
Involves heating of a cold-worked structure
Usually not desirable for dentistry
3 stages
o Recovery
Heat cold-worked metal to a certain temperature (1/3 melting point) so that
atomic structure is not changed
Relief of internal stresses and relaxation of metal occurs
Tensile strength decreases, ductility increases
Ideal stage when annealing materials used in dentistry (eg. soldering/welding wires)
o Re-crystallization
Further heating gives the wrought metal just enough energy to leave the stable
zone and returns to the more stable as cast structure
Complete loss of strain hardening
Nucleation of new grains
New crystals appear first from most strained areas
New grains and grain boundaries are formed
Tensile strength increases, ductility decreases
Equilibrium (equiaxied) structure formed by the end of this stage
Called equilibrium but it is impossible to achieve this as there is a limited
ability for atoms to move through the crystal lattice
o Grain growth
Continued heating causes grains to grow bigger at the expense of the smaller grains
(fusion of small grains)
Tries to become closer to a true equilibrium single grained metal with no
impurities, grain boundaries etc
Features of annealing
o Temperature of annealing depends on:
Melting point of the metal (1/3-1/2 the melting point) heat/energy =
temperature x time
Degree of cold working the metal has been subject to
o Presence of vacancies in structure permits ready transport of the atoms through the solid
Diffusion process depends on activation energy
Higher temperatures = higher rates of diffusion
o Excessive annealing can lead to increased grain size (only for wrought metals where large
grain sizes possible)
o It is impossible to consider effect of annealing that occurs during soldering and welding
wrought denture retainer wires and orthodontic wires and heating of dental instruments

Wire structures should only be recovery heat treated

Take note of sensitization of stainless steels during annealing
Austentitic stainless steels: 18% chrome, 8% nickel
Grain structure: equal spacing of atoms with a minimum of 12% chrome for strength
Passivating layer present in a thin, even layer to prevent rusting
When heated:
Chrome has more affinity for carbon
Chrome carbon moves towards grain boundaries making these areas more
brittle and subject to fractures
Grains with <12% chrome are more susceptible to rusting
Leads to loss of passivating layer of chrome oxide and a decrease in
corrosion resistance and mechanical properties

Infinite solubility alloys (complete solid solutions)

Problem: is completely homogenous so may not have an oxide layer to allow us to bond it using adhesives to
tooth/gold crowns/ceramics
Phase equilibrium diagram
Pure metals have a particular melting temperature
Alloys have a temperature range over which solidification will occur
Each particular alloy composition in a system will have a slightly different temperature range for
solidification
o Melting ranges for entire system of alloys collected and compared to create PHASE
EQUILIBRIUM DIAGRAM
Liquidus (TL): temperature above which all of an alloy is a liquid
Solidus (TS): temperature below which all of an alloy is a solid
Line is drawn across the points at the temperature where all of the alloy is a solid solidus
Between liquidus and solidus: alloy is a combination of solid and liquid
In pure metals: solidus and liquidus is at the same point

Coring
Example: cooling of 40% metal A, 60% metal B alloy
Cooling until it reaches TL
o At this point: all of the 60% alloy will be liquid BUT 82% alloy will be at TS so it is solid

Problem:
o Within an alloy (even if it is complete solid solution), the overall composition may be 60%
metal B BUT throughout the grain the composition changes
o May be some regions in the grain that are 82% and start to form solids at this temperature
(nuclei/dendrites)
o If cooling continues to temperatures between TL and TS, then more nuclei will form of
different compositions (eg. 74%) until cooling reaches TS where the remaining 60% alloy
solidifies
o Cooling melt becomes richer in metal A so alloys have decreased ductility
o Effectively creates different alloys in the one structure so more likely to corrode and create
passivating layer
Solution:
o Hold the melt at a temperature just above TS
o Atoms gain more energy and are able to diffuse down the concentration gradient
(concentrations of different alloy compositions)
o Nucleation and crystal growth still occur but due to diffusion a homogenized mixture is
obtained less likely to corrode
o Similar to heat-treating wrought metals but nucleation and crystal growth occurs at a greater
extent than wrought metals

Limited solubility alloys (eutectic alloys)

Phase equilibrium diagram
Has solvus lines that indicate the solubility of a metal in a component phase at different
temperatures in the solid state
Eutectic composition = lowest temperature at which an alloy of the system is essentially liquid
There is no solidification range for eutectic composition
At a particular temperature there exists:
o x% liquid contained in solid of y%
o solid surrounding the 2 with z% composition
Features
Strength and hardness is usually greater than the constituent materials but have decreased tarnish
resistance
Properties of alloys do not change linearly with composition
Coring will occur
Most of the alloys used in dentistry

Ag-Cu system
-

Binary eutectic alloy made up of 2 metals that have limited solubility

Eutectic reaction: liquid solid solution + solid solution
Classic eutectic: consists of phase fields since there is limited solubility
o Phase fields form when heating past the melting point where some material does not mix
well with other areas
o Hyper-eutectic alloys in Ag-Cu system will have a microstructure of Cu rich phase grains
surrounded by Ag rich phase
o Hypo-eutectic alloys will have Ag rich phase surrounded by Cu rich phase
Benefits of eutectic system
o Resistant to corrosion
o Precipitation hardening distortions in overall lattice from different phases give it hardness
and strength
o Oxide layer can be created for bonding

Phase equilibrium diagram for a classic eutectic material

Cooling from T1 at TL first solid forming Ag rich phase (98% Ag, 2% Cu)
Final solid formed while cooling from T1 with alloy composition 95% Ag, 5% Cu
Dendrites formed have initial layer of 98% Ag phase and outermost layer 95% Ag phase
Remains constant until T2 reached on the SOLVUS line
phase is super saturated with respect to copper and further cooling causes copper to be less soluble
in phase
Copper rich phase formed

Au-Cu system
-

Extensively used in dentistry (usually 75% Au)

Alloy with extended solubility
o Above a certain temperature (before melting point), the 2 metals display infinite solubility
even in the solid state (Au-Cu system: >420C)
o Partial solubility at low temperatures due to dissimilarities in size
Insoluble as temperature decreases giving intermediate phases as a result of solid state reaction

Phase equilibrium diagram for an extended solubility alloy

Formation of Type III and Type IV gold casting alloys to achieve desirable properties
o Slow cooling from T2 results in solid state reaction
o Ordering of substitutional disordered solution to form a super lattice
Long range ordering
o aka. Age hardening
Time dependent precipitation of Au-Cu phase
Time taken depends on rate of atomic diffusion for the alloy system
Time and temperatures are different for particular alloys
o Slow cooling to temperatures below 420C (T2)
o Preferential movement of Cu atoms to replace Au face centred cubic crystals at sites in
centre of the face
Atoms are smaller so distortion of the lattice occurs
No over distortion to each individual unit but OVERALL distortion of the alloy
Super lattice formed
Strengthening of the alloy system
o Solution heat treating: soaking the alloy at high temperature to produce the solid solution