Terminology CL 404 : Material Science

Component: Chemically recognizable species (Fe and C in carbon steel) Phase: a portion of a system that has uniform physical and chemical characteristics. Phases are separated from each other by definite phase boundaries A phase may contain one or more component Not necessary that there be a difference in both physical and chemical characteristics. E : !ater and ice are identical in chemical ma"eup but considered as a separate phases Polymorphism (FCC# $CC structures) : Each of these structure is considered to be a separate phase %ystem %pecific body of a material under consideration (or) %eries of possible alloys consisting of same components !ithout regard to alloy composition (iron&carbon system) 'omogenous (%ingle Phase) (heterogeneous system (t!o or more phases)

9. Phase Diagrams

Terminology

Microstructure
/he properties of an alloy depends on microstructure !hich is specified by Number of phases /heir proportions /heir arrangement in space ,icrostructure depends on +ariables such as Alloying elements present /heir concentration 'eat treatment of an alloy

%ol+ent: ,a-or component %olute: ,inor component %olubility .imit: At specific temp# there is a ma imum conc. of solute atoms that may dissol+e in the gi+en sol+ent to form a solid solution. /his is true for many alloy atoms. /his is similar to dissolution of sugar in !ater. (0efer Figure). /he solubility limit changes !ith temp. *
Note: 2e+elopment of an microstructure of an alloy is related to the characteristics of phase diagrams. /hat3s !hy !e are interested in understanding the phase diagrams

Equilibrium and metastable

E4uilibrium: Free energy is minimum at specified combination of /# P and composition. /he characteristics of the system do not change !ith time %ufficient time is re4uired to achie+e e4uilibrium. ,etastable: A state along the path to the e4uilibrium may appear to be stable Phase e4uilibrium
Free energy Metastable state Equilibrium coordinate

One component (Unary Phase diagram)

Composition 7 held constant Phase diagram for pure substance P# / are +ariables At any point on the phase boundary# t!o phases on either side are in e4uilibrium Point 898 7 triple point(in+ariant point. 'ere three phases are in e4uilibrium. /riple point (/ : );*.<6 = > P :6.?1 <?&* atm) /hese phase diagrams for many substances ha+e been determined e perimentally. For substances such as carbon# multiple solid phases e ist (allotropes) and so !e ha+e other triple points 6

Binary Phase Diagram

/emperature# composition are +ariable parameters Pressure 7 constant $inary phase diagram helps us to understand and predict microstructure(ha+ing e4m (non e4m characteristics) ,icrostructure de+elop from phase transformation Appearance(disappearance of phase /ransition from one phase to other phase
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Binary Isomorphous systems

Asomorphous system: Complete solid solubility of the t!o components (both in the li4uid and solid phases) /hree different phase regions %olid (), .i4uid (L) and solidB.i4uid (+L)

.i4uidus line (%eparates .i4uid from .i4uid B %olid) %olidus line (%eparates %olid from .i4uid B %olid)

Binary Isomorphous systems

For Cu and Ni system# -Phase %ubstitutional solid solution (FCC crystal structure) At temp. belo! <?@?DC# Cu and Ni soluble in each other in the solid state for all composition. /his is mainly due to both Cu and Ni ha+e same FCC structure and identical atomic radii and electronegati+ity. ,etallic alloys# solid solutions are represented by Eree" letters (,,) 9ne component system: ,elting occurs at a !ell defined temp. ,ulti&component system: ,elting occurs o+er the range of temp.

Interpretation o Phase diagram

Phases Present 2etermination of phase compositions /he relati+e fraction of the phases

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!o" o Phases Present

Fery simple .ocate the temp. 7 composition point on the diagram and note the phase (s) !ith !hich the corresponding phase is labeled.

#inding composition in $%phase region

.ocate composition and temp. in diagram An t!o phase region# dra! the tie line or isotherm at that temp Note intersection !ith phase boundaries and read the compositions at the intersections. /he li4uid and solid phases ha+e these compositions.

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For single phase region# read the composition is straight for!ard

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&mount ('elati(e #raction) o phases

Gsing .e+er rule .ocate composition and temp. in diagram An t!o phase region dra! the tie line or isotherm Fraction of a phase is determined by ta"ing the length of the tie line to the phase boundary for the other phase# and di+iding by the total length of the tie line H. : %((0B%) H. : (C 7Co)((C&C.) /he le+er rule is a mechanical analogy to the mass balance calculation. /he tie line in the t!o phase region is analogous to a le+er balanced on a fulcrum.

Deri(ation o )e(er rule

9nly t!o phases are present# the sum of their mass fraction must be e4ual to <.? H. B H : H/ (<.?) ,ass of one of the components (either Cu or Ni) that is present in the phase : ,ass of that component in that alloy H.C. B H C : H/Co

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*olume raction
Phase amount in +olume fraction is more preferred than mass fraction Folume fraction can be determined by e amining the microstructure Properties of a multiphase alloy may be estimated on the basis of +ol. fraction. Con+erting mass fraction into +olume fraction

Problem
A Cu&Ni alloy of composition ;? !tI Ni 7 *? !tI Cu is slo!ly heated from a temperature of <*??C
At !hat temp does the first li4uid phase formJ Hhat is the composition of this li4uid phaseJ At !hat temp does complete melting of the alloy occurJ Hhat is the composition of the last solid remaining prior to complete meltingJ

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Problem

De(elopment o microstructure in isomorphous alloys

E4uilibrium cooling (%lo! cooling). He are pro+iding sufficient time for the system to attain e4m. a. <*??DC: complete li4uid !ith *5I Ni &65I Cu b. K<)6?DC: First solid begin to form ( 7 16I Ni) c. K<)5?DC: 7 1*INi and .& *)I Ni d. K<))?DC: .ast li4uid to solidify e. Complete solid phase (*5I Cu)

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De(elopment o microstructure in isomorphous alloys

Non&E4uilibrium cooling (Fast cooling) Compositional read-ustment for change in temperature occur +ia diffusion (time dependent phenomenon) $ut solidification in+ol+es fast cooling rates. 2iffusion in solid state is +ery lo!. %o the ne! layers that solidify on top of the e isting grains ha+e the e4uilibrium composition at that temperature. /his leads to formation of layered (cored) grains

De(elopment o microstructure in isomorphous alloys

/ie&line method to determine the composition of the solid phase is in+alid /he tie line method !or"s for the li4uid phase# !here diffusion is fast %olidus line is shifted to the right (higher Ni contents)# solidification is complete at lo!er /# the outer part of the grains are richer in lo!&melting component (Cu) Gpon heating grain boundaries !ill melt first. /his can lead to premature mechanical failure /he distribution of the t!o elements !ithin the grains is non& uniform Concentration gradients are established across the grains. /he centre of each grain# !hich is the first part to freeze is rich in high melting element (Ni) !hereas the concentration of the lo! melting element increases !ith position from this region to the grain boundary. )? /his is termed as cored structure.

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Binary Eutectic systems

Eutectic reaction: /ransistion b(! li4uid and mi ture of t!o solid phases# L B M at eutectic concentration CE

Binary Eutectic systems

For Ag&Cu system

Eutectic isotherm

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Binary Eutectic systems

/hree single phase regions L & solid solution of Ag in Cu matri M & solid solution of Cu in Ag matri . 7 .i4uid /hree t!o phase regions (LB.# MB.# LB M) %ol+us line separates one solid solution from a mi ture of solid solutions. %ol+us line sho!s limit of solubility Eutectic(in+ariant point: .i4uid and t!o solid phases co& e ist in e4m at the eutectic composition CE and the eutectic temp /E

Binary Eutectic systems

/he melting point of the eutectic alloy is lo!er than that of the components (eutectic :easy to melt in Eree") /hree phases are in e4m along the eutectic isotherm

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Binary Eutectic systems

Pb-Sn system (Using for soldering applications)

De(elopment o Microstructure (Pb% +n system)

He are considering different composition. $ut the cooling rate is slo! (e4m) in all the cases Case ! Pb rich alloy (? &) I %n) /his is same as isomorphous system (Cu&Ni) system

L + L

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De(elopment o Microstructure
Case ! 0oom temp solubility limit to ma imum solid solubility at eutectic temp $eta phase nucleates as the alpha solid solubility is e ceeded upon crossing the sol+us line

De(elopment o Microstructure
Case ! Eutectic composition No changes abo+e the eutectic temperature At /E# the li4uid transforms to the and phases as per the follo!ing eutectic reaction

L + L +

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De(elopment o Microstructure
At is ob+ious from the eutectic" reaction that composition of both the solid phases is different from that of li4uid phase. /his implies that there must necessarily be a redistribution of the components. /he redistribution is accomplished by atomic diffusion. At is an e4m cooling. 'ence# sufficient time is there for the diffusion to occur# 2iffusion occurs at the eutectic and li4uid interface. /he direction of diffusion of t!o components is sho!n in the figure (%ee ne t slide). Pb is diffusing to!ard alpha layer(Pb rich phase) and %n is diffusing to!ard beta layer (%n rich phase).

De(elopment o Microstructure
" %ince# Pb is diffusing a!ay from this region# it becomes %n rich phase ( phase)

/he alternating layers are formed here. $ecause only for this configuration# atomic diffusion of lead and tin need only occur o+er relati+ely short distances. /his structure is characteristic of the eutectic reaction. /his structure is called eutectic structure . Also called as lamellar structure.

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De(elopment o Microstructure
Case $! All compositions
other that eutectic !hen cooled across eutectic isotherm N. .i4uid (C1 I %n) 9n cooling at point =# primary is formed (same as case AA) 9n further cooling to point .# the composition of the primary alpha is changed. /he composition of both alpha and . could be determined by dra! a isotherm(/ie&line) at that temp *<

De(elopment o Microstructure
Nust abo+e the eutectic isotherm# !e ha+e primary and li4uid !hich ha+e the eutectic comp. 9n further cooling to point m# the li4uid (!hat !e are left !ith) ha+ing eutectic comp. is con+erted in to lamellar structure as per the eutectic reaction. .amellar structure no! consists of and layers. /his alpha is called eutectic . No! a terminology O Microconstituent8 is introduced here. At is element of an microstructure ha+ing an identifiable and characteristic structure. 'ere !e ha+e t!o *) microconstituents 7 Primary alpha and lamellar structure

%lpha comp#

& comp#

%lpha comp#

& comp# ' Eutectic comp

,alculate relati(e amounts o microconstituents

Eutectic microconstituent forms from li4uid ha+ing eutectic comp. (6<.C I %n) Consider eutectic as a separate phase and apply the le+er rule to find the relati+e fraction of primary alpha and eutectic structure He: P((PBP) QEutecticR HL3 : P((PBP) QPrimary R

,alculate Total amounts o Phases

Fraction of phase could be determined by applying le+er rule across the entire B phase field.

HL: (PB0) ((PBPB0) Q phaseR HM : P((PBPB0) Q PhaseR

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Terminal (s" Intermediate solid solutions

/erminal: %olid solutions e ist o+er the composition ranges near the concentration e tremities of the phase diagram ( and phases in Cu&Ag system) Antermediate: it may be found at other than t!o e tremes (Cu&Sn)

Intermediate phases-compounds
Antermetallic compounds that ha+e precise chemical compositions can e ist in some systems Antermetallic compound could be treated li"e any other phase e cept they are not appear as a !ide region but as a +ertical line in the phase diagram. /his diagram can be thought as t!o -oined eutectic diagramsQ,g&,g)Pb and ,g)Pb&PbR.An this case# ,g)Pb can be considered as a component con+ert !tI to atI of ,g)Pb <C !t I ,g&@< !tI Pb : 66.6 atI ,g 7 **.* !tI Pb

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Other In(ariant reactions

Eutectic L +
Cooling

,ongruent (s" Incongruent Trans ormation

Congruent No compositional Changes Ancongruent At least one phase !ill e perience a change in composition

Eutectoid
Cooling +

Peritectic
Cooling L +

%uffi Oic8 : in+ol+es one li4uid phase %uffi :8oid8 : An+ol+es only solid phases

E : allotropic transformations# melting of pure component

Eutectic# eutectoid transformation# melting of alloy (isomorphous)

Peritectoid
Cooling +

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Problem
%pecify temp and comp. points at !hich all eutectics# eutectoids# peritectics and congruent phase transformation occur. Also# for each# !rite the reaction upon cooling.

.ibbs Phase 'ule

Construction of phase diagram and principles go+erning the conditions for phase e4uilibria described by la! of thermodynamics Phase rule: PBF : CBN P: No. of phases that !ill coe ist !ithin a system at e4m. F: No. of degrees of freedom or e ternally controlled +ariables (P# /# comp.) (No. of +ariables that can be changed independently !(o altering the no. of phases that coe ist at e4m. C: No. of components in the system. Components are normally elements or stable compounds. ,aterials at the t!o e tremities of the horizontal compositional a is N& No. of non&compositional +ariables (/ and P) F: C&PB) (for one component system) F:C&PB (binary system. N is reduced to < as the pressure is constant

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.ibbs Phase 'ule

Cu&Ag system F:C&PB< %ingle phase region (, ) F:)&<B< :). 9nly t!o parameters are re4uired to completely describe the system /!o phase region F: )&)B< : <. Either temp. or comp. of one of the t!o phases is to be specified to completely define the system

Iron%Iron ,arbide diagram

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Iron%Iron ,arbide diagram

He are considering only till 6.;? !tI of C as all the commercial steels a+ailable in the mar"et ha+ing carbon content less than 6.;? !tI. 'ere carbon form is graphite Alpha ferrite
'a+ing $CC structure ? = to C<? TC C is located at interstitial positions (?#?#<()) center of edges (space a+ailable : ?.<C AT) %ize of carbon is ?.;< AT 2ue to this size difference# the solubility is +ery limited (?.?) !tI at ;)5 TC)

Iron%Iron ,arbide diagram

2elta ferrite
$CC <1<? TC &<5*5 TC %olubility ?.< at <1C* TC

Cementite
Fe*C Comple orthorhombic crystal structure 6.6; !tI C 7 )5 atI C

Eamma U austenite
'a+ing FCC structure C<? TC & <1<? TC An alloy form ;)5 TC & <1C* TC C is located at (?#?#<()) ( (<() V V) center of diagonal. Foid si e &?.5) A T %olubility is ?.< at <1C* TC

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*arious in(ariant reactions

Peritectic: At <1C* TC upon cooling (?.< !tI C# $CC) B . (?.5I) : (?.<@I# FCC) Eutectic ! At <<5? TC upon cooling . (1.*I) : (<.;I# FCC) B Fe*C (comple orthorhombic# 6.6;I C) Eutectoid ! At ;)5 TC

Microstructure De(elopment

Case ! eutectoid composition .amellar structure (alternating alpha and Fe*C layers) is called Pearlite

Note: 9f this# Eutectoid is +ery important as most of the phases comes into picture at this phase field. ,ost of the commercial steel are manufactured based on this region of phase diagram

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Microstructure De(elopment
(ypoeutectoid alloys! Comp. of an alloy less than eutectoid 'ere proeutectoid alpha is formed at the grain boundaries in order to reduce the higher free energy associated !ith it

Microstructure De(elopment
Case ! 'ypereutectoid Alloys 'ere proeutectoid Fe*C is formed at grain boundaries

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&mount o phase
Similar to Eutectic system ()efer Slides ** and *$)

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