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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

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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.

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The long gray regions are flakes of graphite. There are several phases.Microstructure Properties of an alloy depend on proportions of the phases and on how they are arranged at the microscopic level. Phase diagrams help understand and predict microstructures 4 . and their arrangements Microstructure of cast Iron Alloy of Fe with 4 wt. The matrix is a fine mixture of BCC Fe and Fe3C compound.% C. their proportions. Microstructure: number of phases.

combinations of temperature.Phase diagram Phase diagram . 5 .water (liquid) and steam (gas) exist. pressure or composition for which specific phases exist at equilibrium H2O: diagram shows temperature and pressure at which ice (solid).

or composition Consider binary alloys only Pressure constant at one atmosphere. P.Phase diagram Show what phases exist at equilibrium and what transformations we can expect when we change T. 6 .

solid () Liquidus line separates liquid from liquid + solid 7 Solidus line separates solid from liquid + solid . solid + liquid (+L).Binary Isomorphous System (I) Assume Complete Solubility L +L  Three phases : Liquid (L) .

Binary Isomorphous Systems (II) Cu-Ni Complete solubility occurs because Cu and Ni have the same crystal structure (FCC). similar radii. electronegativity and valence 8 .

67 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 = 0.33 100 .Lever Rule • fl =CB/CA =CS -CO / CS –Cl =58-50/58-46 =0.

Solid and liquid phases are in equilibrium in this temperature range.Binary Isomorphous System (III) One-component: melting occurs at a well-defined temperature. L +L Liquid solution  Liquid solution + Crystallites of Solid solution Polycrystal Solid solution 10 . Multi-component: melting occurs over range of temperatures between solidus and liquidus lines.

Note intersection with phase boundaries 4.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. Read compositions at the intersections 11 Liquid and solid phases have these compositions . Draw tie line or isotherm 3.

The tie line in the two-phase region is analogous to a lever balanced on a fulcrum.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. 12 .

CL) / (C .CL) W = R / (R+S) = (Co.CL) 13 .The Lever Rule Mass fractions: WL = S / (R+S) = (C.Co) / (C .

68 14 W = (Co.Co) / (C . % Mass fractions: WL = (C. C = 42.CL) = 0.Phase compositions and amounts. An example.5 wt. CL = 31.CL) / (C .32 . Co = 35 wt.5 wt.CL) = 0. %. %.

Microstructure in isomorphous alloys Equilibrium (very slow) cooling 15 .

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

Binary Eutectic Systems (I) alloys with limited solubility .

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

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

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

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steels are alloys of Iron (Fe) and Carbon (C). up to around 7% Carbon.Iron–Iron Carbide (Fe–Fe3C) Phase Diagram In their simplest form. but we will only consider the steel part of the diagram. The Fe-C phase diagram is a fairly complex one. .

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Steels and Irons .

consists of two phases) consists of alternate layers of ferrite and cementite in the proportion 87:13 by weight. Si) with carbon content up to 2% intended for wrought products or semi products.steels. .76% C (up to 2% C). Mn. Now. Si) with carbon content over 2% intended for castings. There are three groups of steels according to carbon content: .hypereutectoid steels contain more than 0.76% C .g. Perlite is formed from austenite at eutectoid temperature (A1) 727°C upon slow cooling.hypoeutectoid steels containing less than 0. we consider only a part of Fe-Fe3C diagram referring to steel. Perlite is a structure (i. Steel is an alloy of carbon and iron and other alloying elements (e. . Cast iron is an alloy of carbon and iron and other alloying elements (e.e. Mn.g.eutectoid steel with carbon content about 0.cast irons.76% .On a base of Fe-Fe 3C diagram we can divide iron-carbon alloys into: .

petrochemical equipment. knives.): 12-20 wt% Cr.Classification.2.008 wt % C in α−ferrite at room T • Steels: 0.008 .6.5 wt %) heavy equipment casing . Cast iron: 2. etc.14 .7 wt % (usually < 4. Three types of ferrous alloys: • Iron: less than 0.14 wt % C (usually < 1 wt % ) α-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.

within several years) into α-Fe and C (graphite) at 650 . but decomposes (very slowly.14 wt %.700 °C .solid solution of C in BCC Fe • Stable form of iron at room temperature. • Transforms to BCC δ-ferrite at 1395 °C • Is not stable below the eutectoid temperature (727 ° C) unless cooled rapidly δ-ferrite solid solution of C in BCC Fe • The same structure as α-ferrite • Stable only at high T. it remains as a compound indefinitely at room T.022 wt% • Transforms to FCC γ-austenite at 912 °C γ-austenite . above 1394 °C • Melts at 1538 °C Fe3C (iron carbide or cementite) • This intermetallic compound is metastable. • The maximum solubility of C is 0.solid solution of C in FCC Fe • The maximum solubility of C is 2.α-ferrite .

Development of microstructures in iron– Carbon alloys .

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

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

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

Continuous Cooling Transformation (CCT) Diagrams .

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

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