CHAPTER 10 – PHASE DIAGRAMS

10.1 INTRODUCTION
 There is a strong correlation between microstructure and mechanical properties of alloy systems
o The development of microstructure of alloy system is related to the characteristics of the
phase diagram
 Phase diagrams also provide valuable information about melting, casting, crystallization, and
other phenomena
 Component = pure metals and/or compounds of which an alloy is composed
o Can further specify to solute and solvent
 System
o May refer to a specific body of material under consideration (ex. a ladle of molten steel),
or
o May relate to the series of possible alloys consisting of the same components but
without regard to alloy composition (ex. the iron-carbon system)
 Solid solution – consists of atoms of at least two different types
o The solute atoms occupy either substitutional or interstitial positions in the solvent
lattice
o The crystal structure of the solvent is maintained**

10.2 SOLUBILITY LIMIT

 Solubility limit = the maximum concentration of solute atoms that may dissolve in the solvent to
form a solid solution
o Exists many alloy systems at specific temperatures
 The addition of solute in excess of this solubility limit results in the formation of another solid
solution or compound —> this will have a distinctly different composition
 Solubility limit depends on temperature**
o Ex. max solubility of sugar in water at 20ºC is 65 wt%

10.3 PHASES
 Phase = a homogenous portion of a system that has uniform physical and chemical
characteristics
o Every pure material is a phase
o Every solid, liquid, and gaseous solution is a phase (ex. sugar-water syrup)
 If more than one phase is present in a given solution, each will have its own distinct properties
o A boundary separating the phases will exist, across which there will be a discont. and
abrupt change in physical and/or chemical characteristics
 Note: not necessarily differences in both physical and chemical characteristics
(ex. water and ice existing together – physically different, but chemically
identical)
 When a substance can exist in two or more polymorphic forms (ex. having both FCC and BCC
structures), each of these structures is a separate phase
o Physical characteristics differ, thus different phases
 Homogenous system = a single-phase system (ex. solid solution)
 o Material will have a uniform texture
 Heterogenous system (mixture) = systems composed of two or more phases
o Most metallic alloys are heterogenous*
o When examining the material, different phases may be distinguished by their
appearance (following polishing and etching)

10.4 MICROSTRUCTURE
 Physical properties and, importantly, the mechanical behaviour of a material often depends on
microstructure
 In metal alloys, microstructure is characterized by how many phases present, their proportions,
and the manner in which they are arranged
 Microstructure of an alloy depends on:
o The alloying element(s) present & their concentrations
o The heat treatment of the alloy

10.5 PHASE EQUILIBRIA

 Free energy is a fn of the internal energy of a system (enthalpy) and the randomness/disorder of
atoms or molecules (entropy)
 A system is at equilibrium if its free energy is at a minimum under some specified combination
of temp, pressure, and composition
o The characteristics of the system do not change with time —> persist indefinitely
o The system is stable
 A change in temp, pressure, composition for a system in equilibrium will cause an increase in the
free energy and/or a possible spontaneous change to another state (which would have lover free
energy)
 Phase equilibrium = equilibrium as it applies to systems in which more than one phase may exist
o In many metallurgic systems of interest, phase equilibrium will involve only solid phases
—> state of the system is reflecting in the characteristics of the microstructure
 Metastable = a state or microstructure that is nonequilibrium but persists for long periods of
time because the rate of approach to equilibrium is extremely slow
o A state that may persist indefinitely, experiencing only extremely slight and almost
imperceptible changes as time progresses
o Often the case in solid systems —> equilibrium is never reached because time required
is so long
10.19 THE IRON-IRON CARBIDE PHASE DIAGRAM

 Iron carbide = Fe3C

 Ferrite (α-iron) – stable form of iron at room temperature; has BCC crystal structure
 Austenite (gamma-iron) – transformation of iron at 912ºC; has FCC crystal structure
o This austenite persists until 1394ºC, where it reverts back to a BCC phase, delta-ferrite
 Iron melts (no longer solid) at 1538ºC
 Cementite – intermediate compound iron carbide (Fe3C) formed at 6.7 wt% C
o Represents vertical line in phase diagram
 Carbon is an interstitial impurity atom and forms a solid solution with each of the alpha- and
delta-ferrites as well as with austenite
 In alpha-ferrite, only small concentrations of carbon are soluble (max solubility of 0.022 wt% C at
727ºC)
o BCC crystal structure of α-ferrite —> shape and size of interstitial sites makes it hard to
accommodate C atoms
o α-ferrite is relatively soft
 Austenite iron, when alloyed with carbon alone, is not stable below 727ºC
o Max solubility of C in austenite is 2.14 wt%, occurs at 1147ºC
 Solubility higher in FCC due to octahedral interstitial sites larger than BCC
tetrahedral sites
  Cementite forms when solubility limit of carbon in α-ferrite is exceeded below 727ºC (then you
get α + Fe3C)
o Cementite also coexists with gamma phase between 727ºC and 1147ºC
o Mechanically, cementite is very hard and brittle
 When present as a phase in some steels, strength of steel is greatly enhanced**
 Cementite is metastable —> remains as a compound indefinitely at room temp
o Not an equilibrium compound*
o But, if heated between 650º and 700ºC for several years, it gradually transforms into α-
iron and carbon (graphite)
o Because decomp. of cementite is so slow, virtually all carbon in steel is as Fe3C as
opposed to graphite
 Eutectoid invariant point exists at 0.76 wt% C at 727ºC
 Eutectoid rxn:

 Ferrous alloys = alloys where iron is the prime component (but C and other alloying elements
may be present)
o Three types:
 Iron – contains less than 0.008 wt% C
 Composed almost exclusively of the ferrite phase at room temp
 Steel – between 0.008 and 2.14 wt% C
 Microstructure consists of both α and Fe3C phases
 In reality concentrations rarely pass 1.0 wt%
 Cast iron – between 2.14 and 6.70 wt% C

10.20 DEVELOPMENT OF MICROSTRUCTURE IN IRON-CARBON ALLOYS

 The microstructures produced in steel alloys depends on both the carbon content and the heat
treatment
 We are currently discussing only very, very slow cooling of steel alloys – equilibrium is
continuously maintained
 At the eutectoid concentration of carbon, when austenite is cooled slowly through the eutectoid
temperature, pearlite is formed
o Pearlite is a microstructure consisting of an alternating laminar structure of α and Fe3C
 Relative layer thickness is ~8:1 (α to Fe3C)
o Pearlite exists as grains, within each grain the layers are oriented in the same direction
(variable orientation between colonies)
o Mechanically, pearlite has properties intermediate between soft, ductile ferrite and
hard, brittle cementite
 Formation of pearlite microstructure:
o Composition of parent phase (austenite, 0.76 wt%) is different from either product
phase (α, 0.022 wt%, and Fe3C, 6.70 wt%) and so phase transformation requires there to
be a redistribution of carbon by diffusion
o Carbon atoms diffuse away from the 0.022 wt% ferrite regions and to the 6.70 wt%
cementite layers
 o The pearlite extends from the grain boundary into the unreacted austenite grain

o Layered pearlite forms because carbon atoms need diffuse only minimal distances with
the formation of this structure

Hypoeutectoid Alloys
 Composition C0 is to the LEFT of the the
eutectoid (less carbon than eutectoid
composition)
o Between 0.022 and 0.76 wt% C
 At point c the microstructure consists
entirely of grains of austenite
 In cooling to point d, alpha-ferrite begins
to form (particles) along grain boundaries
o Concentrations of alpha and
gamma phases may be
determined using the
appropriate tie line
 Cooling from point d to e, just above the
eutectoid but still in the alpha + gamma
region, produces an increased fraction of
the alpha phase
o Alpha particles have grown larger
o At this point the compositions of the alpha and gamma phases are determined by
constructing a tie line at the eutectoid temperature (Te)
 Alpha phase contains 0.02 wt% C and gamma phase will be of the eutectoid
composition, 0.76 wt% C
 As temp is cooled below eutectoid (point f), all of the austenite that was present at Te transforms
into pearlite
 The alpha phase will remain unchanged – it exists as a continuous matrix phase surrounding the
isolated pearlite colonies
o This ferrite is called proeutectoid ferrite (formed before the eutectoid temp)
o The ferrite present in pearlite is called eutectoid ferrite
 All hypoeutectoid iron-carbon alloys that are slowly cooled to a temperature below the
eutectoid will have two microconstituents: pearlite and proeutectoid ferrite
  Relative amounts of proeutectoid alpha and pearlite may be determined using lever rule and tie
line that extends from the NO phase boundary to the eutectoid composition (pearlite is the
transformation product of austenite having this composition)

 Fractions of both total alpha (eutectoid + proeutectoid) and cementite are determined using the
lever rule and a tie line that extends across the entirety of the α + Fe3C phase region (from 0.022
to 6.7 wt% C)

Hypereutectoid Alloys
 Alloys with composition between 0.76 and 2.14 wt% C
 At point g, only the austenite phase is present, with a composition of C1
o Only gamma grains exist
 Upon cooling to point h, the cementite phase begins to form along the initial gamma grain
boundaries
o This cementite is called proeutectoid cementite
o The cementite composition remains constant (6.70 wt% C) as the temperature changes
 As the temp is lowered through the eutectoid to point i, all remaining austenite of eutectoid
composition is converted into pearlite
 The resulting microstructure consists of pearlite and proeut. cementite microconstituents
  Relative amounts of both P and proeut. C microconstituents may be computed using a tie line
extending between 0.76 and 6.70 wt% C

10.21 THE INFLUENCE OF OTHER ALLOYING ELEMENTS

 Additions of other alloying elements (ex. Cr, Ni, Ti, etc.) bring about dramatic changes in the
binary iron-iron carbide phase diagram
o Alter the positions of phase boundaries and the shapes of the phase fields —>
dependent on the particular alloying element and its concentraation
 An important change is the shift in the eutectoid with respect to temperature and carbon
concentration
o Thus, adding alloying elements alters the relative fractions of pearlite and the
proeutectoid phase that form
 Steel is usually alloyed to improve its corrosion resistance or to render it amenable to heat
treatment