PHASE DIAGRAMS AND PHASE TRANSFORMATIONS

Binary isomorphous systems Determination of phase composition and phase quantities, lever rule, binary eutectic systems, development of microstructure in eutectic alloys, eutectoid and peritectic reactions. Iron Carbon phase diagram, development of microstructures in iron Carbon alloys, Isothermal transformation diagrams and continuous cooling transformation diagrams.

Components and Phases

Component - chemical species (Fe + C in steel; H2O + NaCl in salt water). Binary alloy 2 two components, Ternary alloy 3, etc. Phase a portion with separate, uniform physical or chemical characteristics Single-phase system: Homogeneous. Two or more phases Mixture or Heterogeneous system. e.g. water + ice, separated by a phase boundary

Solubility Limit
Solvent - host or major component Solute - minor component

Solubility Limit = maximum amount that can be dissolved in a phase (e.g. alcohol has unlimited solubility in water, sugar has a limited solubility, oil is insoluble).

Same concepts for solids: Cu and Ni are mutually soluble in any amount (unlimited solid solubility), while C has a limited solubility in Fe.

Microstructure

Properties of an alloy depend on proportions of the phases and on how they are arranged at the microscopic level. Microstructure: number of phases, their proportions, and their arrangements
Microstructure of cast Iron

Alloy of Fe with 4 wt.% C. There are several phases. The long gray regions are flakes of graphite. The matrix is a fine mixture of BCC Fe and Fe3C compound.
Phase diagrams help understand and predict microstructures
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Phase diagram
Phase diagram - combinations of temperature, pressure or composition for which specific phases exist at equilibrium H2O: diagram shows temperature and pressure at which ice (solid),water (liquid) and steam (gas) exist.

Phase diagram Show what phases exist at equilibrium and what transformations we can expect when we change T, P, or composition Consider binary alloys only Pressure constant at one atmosphere.

Binary Isomorphous System (I)

Assume Complete Solubility

L +L

Three phases : Liquid (L) , solid + liquid (+L), solid () Liquidus line separates liquid from liquid + solid 7 Solidus line separates solid from liquid + solid

Binary Isomorphous Systems (II) Cu-Ni Complete solubility occurs because Cu and Ni have the same crystal structure (FCC), similar radii, electronegativity and valence

Lever Rule
fl =CB/CA =CS -CO / CS Cl =58-50/58-46 =0.67 fs=BA/CA = CO Cl/ CS Cl =50-46/58-46 =0.33
Fraction of liquid of composition 46% Ni = Fraction of solid of composition 58% Ni = 0.67 0.33 100

Binary Isomorphous System (III) One-component: melting occurs at a well-defined temperature. Multi-component: melting occurs over range of temperatures between solidus and liquidus lines. Solid and liquid phases are in equilibrium in this temperature range.

L +L

Liquid solution

Liquid solution + Crystallites of Solid solution

Polycrystal

Solid solution
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Interpretation of Phase Diagrams

Given: temperature + composition determine
1) Phases present

2) Compositions of phases
3) Relative fractions of phases

Composition in a two phase region:

1. Locate composition and temperature 2. Draw tie line or isotherm 3. Note intersection with phase boundaries 4. Read compositions at the intersections
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Liquid and solid phases have these compositions

The Lever Rule

Amounts of each phase in two phase region Locate composition and temperature Draw tie line or isotherm Fraction of a phase = length of tie line to other phase boundary divided by the length of tie line
The lever rule is a mechanical analogy to the mass balance calculation. The tie line in the two-phase region is analogous to a lever balanced on a fulcrum.

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The Lever Rule

Mass fractions: WL = S / (R+S) = (C- Co) / (C - CL) W = R / (R+S) = (Co- CL) / (C - CL)
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Phase compositions and amounts. An example.

Co = 35 wt. %, CL = 31.5 wt. %, C = 42.5 wt. % Mass fractions: WL = (C- Co) / (C - CL) = 0.68
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W = (Co- CL) / (C - CL) = 0.32

Microstructure in isomorphous alloys

Equilibrium (very slow) cooling

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Solidification in the solid + liquid phase occurs gradually upon cooling from the liquidus line. The composition of the solid and the liquid change gradually during cooling (as can be determined by the tieline method.) Nuclei of the solid phase form and they grow to consume all the liquid at the solidus line.

Binary Eutectic Systems (I) alloys with limited solubility

Binary Eutectic Systems (II)

Three single phase regions (a solid solution of Ag in Cu matrix, b = solid solution of Cu in Ag marix, L - liquid) Three two-phase regions (a + L, b +L, a+b) Solvus line separates one solid solution from a mixture ofsolid solutions. Solvus line shows limit of solubility

Binary Eutectic Systems (IV) Eutectic reaction transition between liquid and mixture of two solid phases, a + b at eutectic concentration CE. The melting point of the eutectic alloy is lower than that of the components (eutectic = easy to melt in Greek). At most two phases can be in equilibrium within a phase field. Three phases (L, a, b) may be in equilibrium only only at a few points along the eutectic isotherm. Single-phase regions are separated by 2-phase regions.

Peritectic reaction
A peritectic reaction - solid phase and liquid phase will together form a second solid phase at a particular temperature and composition upon cooling, e.g. L + These reactions are rather slow as the product phase will form at the boundary between the two reacting phases thus separating them, and slowing down any further reaction. Peritectics are not as common as eutectics and eutectiods, but do occur in some alloy systems. There is one in the Fe- C system that we will consider later.

IronIron Carbide (FeFe3C) Phase Diagram

In their simplest form, steels are alloys of Iron (Fe) and Carbon (C). The Fe-C phase diagram is a fairly complex one, but we will only consider the steel part of the diagram, up to around 7% Carbon.

Steels and Irons

On a base of Fe-Fe 3C diagram we can divide iron-carbon alloys into: - steels, - cast irons.

Steel is an alloy of carbon and iron and other alloying elements (e.g. Mn, Si)
with carbon content up to 2% intended for wrought products or semi products.

Cast iron is an alloy of carbon and iron and other alloying elements (e.g. Mn,
Si) with carbon content over 2% intended for castings. Now, we consider only a part of Fe-Fe3C diagram referring to steel. Perlite is a structure (i.e. consists of two phases) consists of alternate layers of ferrite and cementite in the proportion 87:13 by weight. Perlite is formed from austenite at eutectoid temperature (A1) 727C upon slow cooling.

There are three groups of steels according to carbon content: - hypoeutectoid steels containing less than 0.76% C - eutectoid steel with carbon content about 0.76% - hypereutectoid steels contain more than 0.76% C (up to 2% C).

Classification. Three types of ferrous alloys:

Iron: less than 0.008 wt % C in ferrite at room T

Steels: 0.008 - 2.14 wt % C (usually < 1 wt % )

-ferrite + Fe3C at room T Examples of tool steel (tools for cutting other metals): Fe + 1wt % C + 2 wt% Cr Fe + 1 wt% C + 5 wt% W + 6 wt % Mo Stainless steel (food processing equipment, knives, petrochemical equipment, etc.): 12-20 wt% Cr.

Cast iron: 2.14 - 6.7 wt % (usually < 4.5 wt %)

heavy equipment casing

-ferrite - solid solution of C in BCC Fe

Stable form of iron at room temperature. The maximum solubility of C is 0.022 wt% Transforms to FCC -austenite at 912 C

-austenite - solid solution of C in FCC Fe

The maximum solubility of C is 2.14 wt %. Transforms to BCC -ferrite at 1395 C Is not stable below the eutectoid temperature (727 C) unless cooled rapidly
-ferrite solid solution of C in BCC Fe

The same structure as -ferrite Stable only at high T, above 1394 C Melts at 1538 C

Fe3C (iron carbide or cementite)

This intermetallic compound is metastable, it remains as a compound indefinitely at room T, but decomposes (very slowly, within several years) into -Fe and C (graphite) at 650 - 700 C

Development of microstructures in iron Carbon alloys

Isothermal Transformation (or TTT) Diagrams (Temperature, Time, and % Transformation)

 At close to Ae1temperature, coarse pearlite forms at close to Ae1temperature due to low driving force or nucleation rate. At higher under coolings or lower temperature finer pearlite forms. At the nose of TTT diagram very fine pearlite forms Close to the eutectoid temperature, the under cooling is low so that the driving force for the transformation is small. However, as the under cooling increases transformation accelerates until the maximum rate is obtained at thenoseof the curve. Below this temperature the driving force for transformation continues to increase but the reaction is now impeded by slow diffusion. This is why TTT curve takes on aC shape with mostrapid over all transformation at some intermediate temperature.

 Pearlitictransformationisreconstructive.Atagiventemperature(sayT1)t hetransformationstartsafteranincubationperiod(t2,atT1).Locusoft2ford ifferentfordifferenttemperatureiscalledtransformationstartline.After50 %transformationlocusofthattime(t3atT1)fordifferenttemperaturesiscal led50%transformationline.Whiletransformationcompletesthattime(t4a tT1)iscalledtransformationfinish,locusofthatiscalledtransformationfini shline.ThereforeTTTdiagramconsistsofdifferentisopercentagelinesofw hich1%,50%and99%transformationlinesareshowninthediagram. Athightemperaturewhileunderloolingislowformcoarsepearlite.Attheno setemperaturefinepearliteandupperbainiteformsimultaneouslythought hemechanismsoftheirformationareentirelydifferent.Thenoseistheresult ofsuperimpositionoftwotransformationnosesthatcanbeshownschemati callyasbelowoneforpearliticreactionotherforbainiticreaction. UpperbainiteformsathightemperatureclosetothenoseofTTTdiagramwh ilethelowerbainiteformsatlowertemperaturebutaboveMStemperature.

Continuous Cooling Transformation (CCT) Diagrams

General features of CCT diagrams

1. CCT diagram depends on composition of steel, nature of cooling, austenite grain size, extent of austenite homogenising, as well as austenitisingtemperature and time. 2. Similar to TTT diagrams there are different regions for different transformation (i.e. cementite/ferrite, pearlite, bainiteand martensite). There are transformation start and transformation finish line and isopercentagelines. However depending on factors mentioned earlier some of the transformation may be absent or some transformation may be incomplete. 3. In general for ferrite, pearliteand bainite transformation start and finish temperature moves towards lower temperature and transformation time towards higher timing in comparison to isothermal transformation. Transformation curve moves down and right.

4.Thebainitereactioncanbesufficientlyretardedsuchthattransformationtakesshelt ercompletelyunderpearlitictransformationincaseofeutectoidplaincarbonsteel andthereforebainiteregionvanishes.Howeverinothersteelitmaybepartiallyshe ltered.Thereforebainiticregionobservedinnoneutectoidplaincarbonsteelorall oysteels. 5.Ccurvesnosemovetolowertemperatureandlongertime.Soactualcriticalcoolingr aterequiredtoavoiddiffusionaltransformationduringcontinuouscoolingislesst hanasprescribedbyTTTdiagram.Actualhardenabilityishigherthanthatpredict edbyTTT. 6.MStemperatureisunaffectedbytheconventionalcoolingrate,however,itcanbelo weredatlowercoolingrateifcoolingcurvessuchthatausteniteenricheswithcarbo nduetobainiteorferriteformation(inhypoeutectoidsteel).OntheotherhandMSc angoupforlowercoolingratesuchthataustenitebecomeleanincarbonduetocarbi deseparation(inhypereutectiodsteel). 7. Large variety of microstructure like ferrite/cementite/carbide +pearlite+bainite+martensite can be obtained in suitable cooling rate. It is not feasible or limited in case of isothermal transformation.