Phase Diagrams 57 i errr ¢ is an invariant point in the ternary system, where all the four phas coexist, with zero degree of freedom. When the liquid has this composition, a four-phase eutectic reaction occurs isothermally Le—>a+pry 2.9 QUATERNARY PHASE DIAGRAMS With increasing complexity of industrial alloys, mul-component systems, in which the umber of components may be more than ree a EATHINE impor tance, A quaternary system comprises four components A B,C and D. After omitting the pressure variable, there are still Four variables to be shown on a ‘graphical representation. If the temperature is kept constant, a three-dimensional regular tetrahedron (Fig. 24) can show the phase relations. The Tour compo- ness ae Toged atthe Four omer. A, B, C and D, the six sides of the tetrahedron represent the six binaries AB, AC, AD, BC, BDvand CD, and the four faces of the seaedron are isotemal seco of the four temnaries ABC, ‘ABD, ACD and BCD. Any composition inside the quaternary space has all the four components in it. The equilibrium between four phases in the quaternary space is represented by a tie-tetrahedron (similar to the tie-triangle in ternary systems). A tie-tetrahedron ean be of any irregular shape. The equilibrium be- tween a, B. x and o phases is schematically sketched in Fig. 2.24. sees A ie Figure 2.24 The composition tetrahedron for the quaternary system A-B-C-D. ‘A tie-tetrahedron depicting four-phase equilibrium lies within58_ Physical Merallurey For two-dimensional_representation, the concentration of one of the components and temperature is to be kept constant. Figure 2.25 shows an isothermal section of the Fe-Cr-V-C system at 700°C and at a constant C content of 0.2 wt%. MaxCg, MiCoand MC 4 are alloy carbides, with M standing for (Fe, Cr, V). ABC is the triangular section of a tie-tetrahedron, showing a four- phase equilibrium. \ 20, —— \ a+Mc atMC+MysCy 7 15 ' & % Z % % 4 ‘° , 3 _ ms ae 8 10 t ' ie Yo : a a+MCHM,C, A\O ot Maes 2 ie , os +M,Cy#M, ? otM;C3 o JL 0 6 9 12 ' Weight Percent Chromium Figure 2.25 Fe-Cr-V-C quaternary isothermal section at 700°C and al a constant carbon content of 0.2 wis 2.10 EXPERIMENTAL DETERMINATION OF PHASE. DIAGRAMS A variety of physical techniques are used forthe experimental determination of phase diagratis. Among these, the more important are: i) thermal analysis, i) microscopic examination, and Gil) xray difraction. Other auxiliary techniques ae diatometry,electical resistivity and! mag- netic measurementsPhase Diagrams _59 Determination of the liquidus and the solidus Thergral analysis is by far the most important method employed for determining the liquid-solid TaNSTOT= ‘mations. The method is based on the fact that evolution or absorption of heat occurs during a phase change, When the temperature Of an alloy sample is plotted as a function of time during heating or cooling, abrupt changes in sTope of the plot occur at poinis corresponding to the start or finish of a phase change. igure 3.26 Haetates sone tical eS TIRE 7200 : for a_pure tal. As the liquid is cooled to the freezing point, solidification ESE Tost to the surroundings. so that the temperatgre of the sample remains constant. The cooling curve becomes horizontal ‘and qemains so, Will the solidi- fan is sang Tet songs tan eth abrupt change in slope at the boint of completion ofthe salidificaion. Often, a liquid may supercool below the freezing point. But once solidification starts, heat evolution raises the sample temperature back to the freezing point as loot coher —>= é i Time ‘Temperature ‘Temperature Time Time © d Figure 2.26 Thermal analysis. Cooling curves (a) for a pure metal without supercooling, (b) for a pure metal with supercooling, to fers ae aly and fora hypoateee ly.« preceeded alley60 Physical Metallurgy When heating a pure solid metal, similar breaks in the heating curve occur. In the horizontal part of the curve, the heat input is used up.for the latent heat _ssobed ducing ming. No supetheaing is known to oc. The mere Spondi wizontil part of the cooling and heating curves must coincide. This gives the true freezing/melting point of the metal. “Figure 2.26c is the cooling curve for the solidification of a solid solution, The first arrest indicating an abrupt decrease in the cooling rate occurs as the liquidus temperature 7) is crossed. There is no horizontal portion in the cooling curve here, as solidification occurs range of temperature between the liquidus and the solidus, The second arrest is observed at the solidus tempera- tue when the cooling rate starts to increase again, Figure 2.26d is the cooling curve for a proeutectic binary alloy, The first arrest occurs at the liquidus temperature and the cooling rate decreases. At the eutectic temperature T,, the cooling curve becomes horizontal, as the invariant eutectic reaction occur isothermally. The cooling rate increases again, when the aici eal tiation ts complet he elloy hes acy tha einai go! sitiqn, only the horizontal partin the cooling curve is seen, corresponding to the eulgctic solidification. In principle, a epetic alloy shoul show 2 simi behaviour. However, the Prenerenor rounding preven tbe padiesic Teaction from going to completion isothermally. The horizontal part in the cool- ing curve may not be cl fined, « ‘The Felleging precautons ore tnben in determining. cooling curves 1. gga Sucwations oF temperature inthe Furnace shoul be avoided. 2. The rate_of cooling must be as slow as feasible for near equilibrium conditions to be achieved Sr 3. The molten alloy should be stirréd for uniform temperature and to reduce. supercoofing. supercooling. 4. The analysis for composition must be accurate. No contamination must occur from the crucible, thermocouple sheath, 5, eget ys © The solidusis ene only approxirnately from the break in the cooling determination can be carried out by holding the solidified alloy for a long time for homogenization just below the approximate solidus temperature determined from the cooling curve. The alloy is heated again to find the break in the heating curve. This break is at a higher temperature than that determined during cooling, 4s coring effects are removed by homogenization. The thermal analysis is supplemented with microscopic examination. The alloy is heated close to the solidué and quenched to ascertain microscopically the appearance of the first chilled liquid =Phase Diagrans 61 Using the breaks in the cooling and heating curves for a series of compositions eSvering the entire binary range. the liquidus and the solidus boundaries can be fully determined, as illustt in Fig. 2.27 for ar morphous system pure B i pure A e bobidos a i a s K B Figure 2.27 The construction of liquidus and solidus phase boundaries from cooling curves, Each cooling curve (shown in perspective view) corresponds to a single coriposition, Determination of the solvus The common methods for determining the solvus are microscopic examination and x-ray diffraction. A Squies of small EOS of alloys OV aTHETEnY Compositions are prepared and homogentaad They are Tea — In samme cases, the high temperature phases may be retained on quenching. In such cases, subsequent metallographic and x-ray studies at room temperature Gfacloge Gee appenrnce of te Second plnse st soos own eompodton. Ir other cases, the high temperature phase may decompose on quenching. If this happens, room temperature x-ray studies are not sultable. A high temperature x-ray camera may be used, Even after the decomposition during quenching, the metallographic method may be useful, i the wansformed phase isin an easily recognizable form. A phase boundary is first bracketed between two compositions, as illustrated in Fig. 2.28. The exact location of the boundary is determined by snulying Sew many alloy of clonely varvog composition im ts moeiry ies62_Physical Metallurgy Two phases © Single phase oo B ° Initial bracketing ‘Temperature : WL %B ' Figure 2.28 The determination of solvus boundaries by the metallographic and x-ray methods Auxiliary techniques Dilatometry i e volume change associated , with most phase changes. It is common to record the length changes of a ' Specimen as a function of temperature daring heating or cooling. Figure 2.29 13000 ' 9000 Aux 10° 5000 1000 0 200 400-600-800 1000 ‘Temperature, °C % Figure 229 The fractional change in length of a low carbon steel on heating ‘and cooling. The abrupt changes in slope correspond to phase changes.Phase Diagrams _63 shows the length changes in a low carbon steel during heating and cooling. The interpretation of the curve is similar to that for thermal analysis. Note the appreciable thermal hysteresis that occurs during this solid state phase change. The electrical resistivity of a solid solution changes nonlinearly with the concentration ofthe salute. However, the resistivity of a mixture of two phases changes linearly with the volume fraction of the phases. The resistivity of the alloys of a simple eutectic system is shown in Fig. 230a. The abrupt change in slope of this plot indicates the Tocation of a phase boundary (solvus). The eletica esis oF an ordered sold soho i ow ss compare that of the Fandom solid soluion. Figure Z300-shows-the electrical resistivity as a function of composition for the Au-Cu system. The resistivity falls to a minimum ‘at compositions corresponding to the ordered compounds, AuCu and AuCus. ‘An order-disorder transition can thus be identified. 5 eae en aan! Disordered Resistivity,ohm-em x 106 AuCu; AuCu 4. 2507S Atomic Percent Gold a b Figure 2.30 Resistivity changes as a function of composition (a) in a eutectic system, and (b) in a solid solution, where ordering occur. ‘The saturation magnetic intensity ofa ferromagnetic phase is very large as compared oa paramagnetic phase This fact ean be used detect he appearances or disappearance of a phase. if one ofthe phases involved is ferromagnetic. This method is suitable only when it is used in conjunction with one or mote of the other methods described above. SUGGESTED READINGS Metallography and Microstructures, Metals Handbook, Vol. 9, ASM International, Materials Park, Ohio (2000). Prince, A., Alloy Phase Equilibria, Elsevier, Amsterdam (1966). a64 Physical Metallurgy $$ 1, Ina three component system, what is the maximum number of phases that can coexist in equilibrium? Answer: 5 (taking pressure variable into account) 2. Find the atomic % of carbon in mild steel containing 0.2 wt.% C. Answer: 0.92 . A binary eutectic freezes at a fixed temperature, whereas in a ternary system with three-phase equilibrium, freezing is over a range of témpera: ture. Explain why this is so. 4, Explain why coring occurs to a greater extent in Cu-Sn alloys than in Cu-Zn alloys 5. Explain why a eutectic composition does not show coring, whereas a solid solution does. 6. Compare and contrast the phenomena of overheating and burning. 7. Give the invariant reactions (and their names) in the Cu-Zn phase diagram, 8. Explain the relative positions of the Aj line and the corresponding graphite line on the Fe-C diagram, on the basis of free energy composition relationships. Calculate the fractions of proeutectoid ferrite, eutectoid ferrite and total ferrite in a 0.2% C steel Answer: 0.76, 0.21, 0.97. 10. What is the fraction of pearlite in a slowly cooled 0.6% C steel? If the steel contains in addition 1% Mn and 0.5% Si, what is the fraction of pearlite? Answer: 0.77, ~ 0.9. 11. Sketch the microstructural changes that occur in a brass of 37.5% Zn, ‘when cooled slowly from 900°C to room temperature. 12. Draw @ set of cooling curves obtained from thermal analysis of a simple binary eutectic system. 13. Draw heating curves for a proeutectic and a eutectic composition, 9,