204 (Chemical Thermodynamics for Meals and Materials capacity difference, ACr4 = Cray ~ Cra) is approximately constant aud equal to 4.6 Jmot"K", The element B melts at 2,300K, but the heat of fusion is unknown. The heat ‘capacities of the pure liquid and solid B are equal. It was found in an experiment with a id solution of Ny = 0.22 that in cooling the frst slid crystals appeared at 1,700K. ‘Calculate the heat of fusion of B. 4. A and B have negligible mutual solid solubilities in the solid state and their phase diagram shows a eutectic transformation. The liquid phase at 1 atm is represented by the equation e T\ imot! oF <2sn (tesla “The following information is known A T= 1,S00K AH 4 = 15,100 mol“! ACh) =O Bi Ty=1200K AH, = 11,100/mot™! Crp." 9 Develop equations of the liquidus of the above system and explain how to find the eutectic temperature and composition using the equations developed. 43. Ternary Systems 43.1. Composition Triangles Temary systems are those possessing three components, Therefore there are four independent variables inthe A-B-C teary system : ‘© Temperature © Pressure ‘© Two composition variables (Third one is not independent since the sum of the mole (or mass) fractions is unity : N+ Ne + Nc= 1). Construction of a complete diagram which represents all these variables would require a four-dimensional space. However, if the pressure is assumed constant (customarily at 1 ‘atm, the system can be represented by a three dimensional diagram with three independent variables, ie., temperature and two composition variables. In plotting three dimensional diagrams, it is customary thatthe compositions are represented by triangular coordinates in ‘ horizontal plane and the temperature in a vertical axis. Phase equilibria can be expressed in this space of the triangular prism. ‘Temperature TPhase Diagrams 205 For plotting temary compositions, it is common to employ an equilateral composition triangle with coordinates in terms of either mole fraction or weight percent of the three ‘components. c /\ Tre ‘Three pure components are represented by the apices, A, B and C. Binary compositions are represented along the edges : eA point on the line B-C is ‘composed entirely of components B and C without A. ‘+ Points inside the triangle represent mixtures ofall three components, We now discuss several different methods of determining the proportions of three ‘components represented by a point inthe triangle. ‘Method 1 ‘© Draw lines through P parallel to ‘each of the sides ofthe triangle. Bh BAC Proportion of A aa AB BC MB K ~ 5 7 AC” BC206 (Chemical Thermodynamic for Metals and Materials ‘© Draw lines through P parallel to each ofthe sides ofthe triangle. ‘© Notice that each side is now divided into three parts © Ifthe side A-B is chosen, 2B ion of A = 2B Proportion of A = 2 Proportion of B = 8% AB ab Proportion of C =< port a a a 5 3 ‘The composition can also be found from the sides B-C and A-C. The two end parts of each line represent the proportions of the components atthe opposite ends and the ‘middle part represents the proportion of the third component. iia} ‘* Draw lines from apices through P to the opposite sides of the triangle. B ‘Ac Proportion of B _ Ca. Proportion of CB Proportion of C _ Ab Proportion of A BC All the methods presented above are based on the same principle: Le. the material balance using the lever rule. Therefore these are not limited to equilateral triangles, but equally valid for scalene triangles which frequently appear when dealing with subsystems.Phase Diagrams 207 Consider the subsystem XYZ. within the system ABC. c w Points X, ¥ and Z are mixtures of A, B and C and the composition ofeach point can be determined by one ofthe methods described above. ‘© Since the point P is inside the subsystem XYZ, it may be considered as a mixture of X, YandZ: Proportion of X Proportion of Y Proportion of Z oe XZ 2 XZ Xe xz Another important relationship which can be drawn from composition triangles is that “If any two mixtures (or solutions) or components are mixed together, the composition of ‘the resultant mixture lies on the straight line which joins the original two compositions.” c . If the component C is added to the binary mixture D, the composition of the resultant temary mixture lies on the line ©. If the component B is added to the temary mixture X, the composition of the mixture lies on th line XB. If the two temary mixtures, Y and Z, are ‘mixed together, the composition of the ‘mixture lies on the line YZ. Inall cases, the position ofthe resultant mixture on the line is determined by the lever rule,208 Chemical Thermodynamic for Meal and Maras ‘As explained earlier, the temperature is represented by an axis perpendicular to the plane of the composition triangle. The point Sin the diagram below left represents a temary mixture ‘of the composition P at the temperature 7. (Recall thatthe pressure is assumed constant in this type of composition-temperature coordinates). The diagram below right isan example of the three dimensional temary phase diagram drawn using the composition tangle ~ temperature coordinates. Isothermal pla r we t c A B A ‘The point P inthe equilateral composition diagram represents a temary mixture of components A, B and C. Prove that e Proportion of A === ¥ ‘Ad P Pb F Proportion of B = 22 Proportion of C =P ; c ad Bx _yd_ Pa ion of A =e = 24 £4 The proport a Propo Fe A= FE The proportions of B and C can be obtained in similar way.Phase Diagrams 20 a A ‘The point P represents a ternary alloy. 1). When pure A is added to the alloy, in which irection does the overall composition change? 2) When pure A precipitates out, in which direction does the composition of the remaining alloy change? B G c 1) FromPtoA 2) FromPtoa Example 3 ‘The Gibbs phase rule is of use in phase equilibrium studies of multicomponent systems. 1) Determine the maximum number of phases which can coexist in equilibrium in @ ternary system. 2). For condensed systems the effect of pressure is negligible in many cases. Therefore, when the pressure is fixed at 1 atm, the number of variables of the system is reduced by one unit. When equilibrium conditions of a temary system at a constant pressure are represented in the space of the composition trimgle - temperature prism, prove the following: 8) Four phase equilibria are represented by points. ') Three phase equilibria are represented by lines. ©) Two phase equillbria are represented by surfaces. 4) Single phase equilibria are represented by spaces. 1) From the Gibbs phase rule, ¢ = 3 (teary system) f= 0 (the maximum number of phases ‘occurs at zero degree of freedom.) = ‘A maximum of five phases can coexist in equilibrium.210 (Chemical Thermodynamic for Meals and Marios 2) Ifthe pressure is fixed ata constant value, i =ptl I plels Explanation No degree of freedom : Neither composition nor temperature can be 8) | 4| 3 | 0 | chosen freely. tn other words four phases can exist together in equilibrium only at a fixed composition and temperature: invariant ‘One degree of freedom : One variable (either the concentration of | b) | 3 | 3 | 1 | one of the components or temperature) can be freely varied, and then all others are fixed: univariant ‘Two degrees of freedom : Two variables are at our discretion, and © |? | | ? | the rest are then fixed: bivariant ‘Three degrees of freedom : Three variables ean be varied freely: | 1] 3 | 3 [ee Afer choosing & compastion of the temary system, temperature can sil be varied while maintaining single phase sate: srivariant Exercises 1. Fig. A below shows the composition triangle of the ABC temary system, Determine the ‘composition of the mixture represented by the point P. A Fig. B - cB c 2. A mixture represented by the point P in Fig. B above is to be prepared by mixing the mixtures X and Y, Determine the ratio of X to Y to obtain the right composition. The composition of each point is given in the following table: ABC P 35% 40% «25% X 20% 70% 10% ¥ 40% 30% 30%Phase Diagrams au 43.2. Polythermal Projections ‘This figure represents a simple ternary phase diagram. However, it has the disadvantage that fines inthe figure are not seen in true length, and hence itis difficult to obtain quantitative information. ‘There re two ways to solve this problem: 1) A two dimensional representation of the temary liquidus surface on the base 2) Two dimensional isothermal diagrams which represent isothermal plane intersections ‘with various surfaces (liquidus, solidus, etc). ‘The first method consists of a polythermal projection of all features (liquidus, ete) down ‘onto the base composition triangle. ‘The figure below shows such a polythermal projection of a simple temary eutectic system ‘without solid solution lke the one represented by the figure above. ¢ Inthe figure, 4 point a : BC binary eutectic point 6 : AC binary eutectic point ¢ : AB binary eutectic point ¢ : ABC temary eutectic22 Chemical Thermodynamics for Meals and Materials Now, let's examine crystallisation paths of this simple temary system, If a liquid of composition p is allowed to cool, ‘+ The liquid solution remains liquid until the system temperature reaches the liquidus. ‘© Atthe liquidus, pure solid A begins to crystals. ‘+ As the temperature decreases further, solid A continues to precipitate out of the liquid, tnd hence the liquid is depleted in A and the liquid composition changes along the line 4. ‘+ At, the second phase B appears, and the liquid composition moves along the curve ge. Until it reaches the temary eutectic pointe, both A and B crystals. ‘© Ate, solid phases A, B and C crysallise and the temperature remains constant until all, liquid has exhausted, ‘+The final product will consist of large crystals of A and B which have crystallised before reaching the pointe, and smal crystals of eutectic structure of A, B and C which hhave crystallised atthe point € ‘The polythermal projection is generally given with constant temperature lines as shown in the following figure: ‘These Lines are called liquidus isotherms. The intersections of adjoining liquidus surfaces like ae, be and ce are called the boundary curves. When a liquid whose composition lies in the region surrounded by Aceb is cooled, the first crystalline phase that appears is A, and hence A is called the primary phase and the region Aceb is the primary field of A. In this field, solid A is the ast solid to disappear when any composition within this field is heated, Similarly,B and C are primary phases in their respective primary fields, Baec and Caeb. In multicomponent systems, compounds are frequently formed between components. The following phase diagrams are for ABC temary system forming a binary compound AB which melts congruently, as itis stable at its melting point‘Phase Diagrams 213 ‘The straight line C-AB is called an Alkemade line. An Alkemade line divides a temary composition triangle into two sub-composition triangles. The final phases produced by cquilibrium crystallisation of any composition within one of these sub-triangles are those indicated by the apices of the triangle, For instance, any composition within the composition triangle A-C-AB results in producing phases A, C and AB at equilibrium. The crossing point on the boundary curve ef'by the Alkemade line isthe maximum in temperature on the ‘curve ef, and the points ¢ and f are eutectic, and each sub-compositon triangle can be ‘treated as a true temary system, The Alkemade line in this case represents a true binary system of C and AB, The arrows in the diagram indicate directions of decreasing temperature, ‘The following phase diagrams are for ABC ternary system forming a binary compound AB which melts incongruent, as it s unstable at its melting point :24 (Chemicol Thermodynamics for Metals and Materials In this case, the Alkemade line C-AB does not ross the boundary curve (ef) between these primary phases. Now, we state the Alkemade theorem in a more general form : ‘The direction of falling temperature on the boundary curve of two intersecting primary phase areas is always away from the Alkemade line, ‘© If the Alkemade line intersects the boundary curve, the point of intersection represents a temperature maximum on the boundary curve, ‘© If the Alkemade line does not intersect the boundary curve, then temperature ‘maximum on the curve is represented by that end which if prolonged would intersect the Alkemade line, Now, it is obvious from the Alkemade theorem that for the case of the incongruently- melting compound as shown above only the point e is eutectic. It is also apparent by ‘examining the above phase diagrams for the congruently-melting compound and the incongrucntly-melting compound thatthe composition ofthe compound li ‘© within the primary field ofthe compound ifit has a congruent melting point, and ‘© outside the primary fed ofthe compound ift hasan incongruent melting point. ‘The ternary invariant points (¢.g, ¢ and fin the above diagrams) that appear in a system without solid solution are either ternary eutectics or ternary peritectics. Whether it is eutectic or peritectic is determined by the directions of falling temperatures along the boundary curves. ‘© Ifan invariant point is the minimum point in temperature along all three boundary curves, itis a ternary eutectic. ‘© Ifthe point isnot the minimum point, itis a ternary peritectic. In the previous diagrams, points e and f for the congruently-melting compound are both temary eutectic. On the other hand, forthe incongruentiy-melting compound the point eis the temary eutectic, whereas the point fis the ternary peritectic, ‘Alkemade lines are also called in many different ways including conjugation lines and joins. ‘Both Alkemade lines and Alkemade triangles (composition triangles produced by Alkemade lines) are of use in the understanding of ternary systems, They play an essential role in understanding crystallisation or heating paths: ‘This figure is a simple temary phase diagram which shows a temary eutectic at the point e. Explain the crystallisation path of each of liquids represented by the points p, q, and 1. Explain also the change in (1) liquid ‘composition, (2) mean solid composition, 3) solid phase(s), (4) instantaneous ‘composition of solids crystallising, and (8) change in the ratio of liquid to solid phases,Phase Diagrams as ‘As the whole diagram is an Alkemade triangle and point ¢ is the temary eutectic, all crystallisation curves of this ternary system should terminate at this temary eutectic. However, binary liquid compositions such as points p and s terminate their respective binary eutectic, cand a. ) 2 Point p ‘+ The system remains liquid until the temperature reaches liquidus. ‘© Atthe liquidus, solid B begins to crystallse. © As the temperature decreases, solid B continues to crystallise and the liquid composition changes toward point c along the line pc. ‘© The ratio of solid (B) to liquid at the moment the liquid composition arrives at point cis represented by the lever rule, plo. ‘*Atpointc, both A and B co-crysallise forming eutectic structure until all liquid {is consumed. The temperature remains constant during this eutectic reaction : L = Ay + By Point q * At the liquidus solid B begins to crystallise As the temperature decreases, solid B continues to crystallise and the liquid composition moves straight 2 ‘away from B along the straight line 4 qu. ¢ At point 1, the second phase A appears © With further cooling, the crystallisation path follows the. boundary curve ue with crystallisation ofboth A and B. ‘© At point w which is an arbitrary point on the boundary curve we, the mean ‘composition of the solid is represented by the point x. Proportions of solid A and solid B are determined by the ever rule; (Solid A)(solid B) = s-B/A-x. The ratio of liquid to solid is also given by the lever rule = quxtw-g. ‘+ The instantaneous composition of the solid phases crystallising at w can be determined by drawing the tangent to the curve ue at w and finding the intersection of the tangent with line AB. Therefore, point = represents the instantaneous composition ofthe solid phases. * At pointe, the eutectic crystallisation occurs : ez ye B L = Ay + By + Cw During the eutectic reaction, the mean composition of the solid phases changes ‘along the line yg. The solid composition reaches point q when the liquid is ‘completely consumed by the eutectic crystallisation.216 (Chemical Thermodynamics for Metals and Maeials ‘In summary, the liquid composition changes along the path quove, whereas the ‘mean composition of solid phases follows the path Buyq. ‘+The final structure of the system after complete solidification consists of large crystals of A and B which have been crystallised during the path quwe and a mixture of small crystals of A, B and C (eutectic structure). 3) Pointr ‘* The crystallisation path can be determined in the same manner as the above case, However, the second phase crystallisng in this case is C instead of B. This figure is a phase diagram of ABC temary system which forms two binary ‘compounds, AC and BC. 1) Why isan Alkemade ine connecting A and BC not drawn? 2) Describe crystallisation paths of liquid compositions pq and r, 3) Describe heating paths of mean solid compositions of pq and r. 4) Would the compounds AC and BC melt congruently or incongruently? 1) Because the primary fiels of A and BC are notin contact with each other, and hence these two fields do not form a boundary curve. 2) Pointp ‘As point p lies in the Alkemade triangle C-AC-BC, the final solid phases in equilibrium should be C, AC and BC, From the figure given below,27 a (On touching the liquidus at p, solid C begins to crystallse. From p tox, solid C continues to erystalise ‘Atsx, solid compound AC appears. From x tof, both AC and C crystals. ‘As the mean composition of the solid crystallised out between p and fis given by point f there is some liquid left when crystallisation path arrives at f ‘© Atf the final solidification takes place through a peritectic reaction : AC and BC crysallise out together at the expense of liquid and portion of C. This can easily be seen from the Alkemade triangle C-AC-BC. During the peritectic reaction, the ‘mean solid composition moves from &to p. ‘+ At completion of the solidification at point; the final solid phases in equilibrium are C, AC and BC, since the mean composition of the system lies within the Alkemade triamgle C-AC-BC as mentioned earlier. Point q ‘As point q lies in the Alkemade triangle AC-BC-B, the final solid phases in equilibrium should be AC, BC and B. Refer to the figure given below: ‘© Ontouching the liquidus at q solid C begins to crystallise. From q tox, solid C continues to crystallse, ‘At, solid AC appears From x tof, AC and C crystallise out together. ‘As the mean composition of te solid crystallised out between q and fis given by point f thee is some liquid left when crystallisation path arrives at ‘© Atfha peritectic reaction takes place: AC and BC crystallise out together at the expense of C and portion of liquid. During the peritectic reaction, the mean solid ‘composition moves from k to m.218 Chemical Thermodynamics or Meals and Materials a € B ‘+ From/to g, AC and BC crystalise out together, and the mean solid composition ‘moves from mto ‘© Atg, a eutectic reaction takes place until the last portion of liquid is completely ‘consumed ; three solid phases AC, BC and B crystallise out together to form & eutectic structure, ‘© During the eutectic reaction at g the mean solid composition changes from 7 to @ ‘© At completion of the solidification at point g, the final solid phases in ‘equilibrium are AC, BC and B since the mean composition of the system lies within the Alkemade triangle AC-BC-B as mentioned earlier. Point r As point r lies in the Alkemade triangle AC-A-B, the final solid phases in ‘equilibrium should be AC, A and B. Referring to the figure given below: ‘On touching the liquidus at r, solid AC begins to crystallise. From r to z, solid AC continues to crystals. Atz, solid A appears, From zto h, both AC and A crystallise. AAs the mean composition of the solid crystallised out between r and his given by point, there is some liquid left when crystallisation path arrives ath ‘Ath, the final solidification takes place through a eutectic reaction: AC, A and B crystallise out together to form a eutectic structure. During the eutectic reaction, the mean solid composition moves from k tor. eeeee .Phase Diagrams 219 a € B 3) Heating from below the liquidus can be considered as the opposite to cooling from above the liquidus. Heating path of composition p is illustrated below. Others may be determined inthe same manner. ‘Mean solid composition of p ‘At the peritectic point f the peritectic reaction of AC and BC reacting form both C ‘and liquid phase proceeds until BC is consumed completely. This occurs isothermally. The composition of the liquid phase formed by this peritectic reaction is that of point ‘+ Above the peritectic temperature, solids C and AC continue to dissolve into the liquid phase, and the liquid composition changes from fto x. ‘© When the liquid reaches point x, solid AC has completely dissolved and C is the only solid phase left ‘© As the temperature increases, solid C continues to dissolve and the liquid ‘composition moves from x top. ‘© When the liquid reaches point p, solid C has completely dissolved and the system 4) Both AC and BC melt incongruently, as the stoichiometric compositions of these ‘compounds lie outside their respective primary fields.20 (Chemical Thermodynamics for Metals and Materials Referring to the figure given below, 1) Determine whether binary compound and temary compounds & and @ melt ccongruently or incongruently. 2) Drawall Alkemade lines. 3) Determine the crystallisation path ofa liquid of composition p. ¢ OS a B 1). The binary compound 5 and the temary compound ¢ melt congruently, since they are ‘within their respective primary fields, but the ternary compound «melts incongruently as it is ouside its primary field. 2) Allthe Alkemade lines are given inthe following diagram. 3) Crystallsation path (Refer tothe figure given below) : ‘© When the temperature reaches the liquidus, 8 phase begin to crystalise. ‘+ Phase 5 continues to erystallise out until the liquid composition contacts the ‘boundary curve between 8 and P at point k © Atk, phase appears, and thereafter 8 and Bi crystallise together with the liquid ‘composition changing along the path km. © Atpoint m, a teary peritectic reaction occurs isothermally. L+8+Boe ‘There ae three possible results after completion ofthe above peritectic reaction 1) The liquid is exhausted before either 8 or B, and hence solidification is completed at point. 2) 5 phase is exhausted first, and crystallisation continues along the path mo. 3) B phase is exhausted firs, and crystallisation continues along the path me.Phase Diagrams a Which is the case depends on within which Alkemade triangle the total ‘composition lies. Since point p lies within the triangle 6-e-B(6), solidification should terminate at point m. c Exercises 1. Discuss the crystallisation paths of the overall liquid compositions p and q in the following temary phase diagram : c fs AB(Chemical Termodynamies for Meals and Maerias 2. Shown below is the phase diagram of the SiO,-CaO-ALO, system.* Discuss solidification paths for the compositions p,q and r indicated on the diagram, * “Phase diagrams for ceramists”, E.M. Levin, C.R, Robbins and H.F. McMurdie, ‘The American Ceramic Society, Inc. (1964), p21943.3, Isothermal Sections ‘The following figure represents a simple temary phase diagram. However, it has the disadvantage that lines in the figure are not seen in true length, and hence itis difficult to ‘obtain quantitative information, In order to solve this problem, the polythermal projection method was discussed in the previous section (Section 4.3.2), In this section, the other method, namely, two dimensional ‘isothermal diagrams are discussed. First, wo discuss a simple temary eutectic system without solid solution as shown above, ‘The following figures show isothermal seetions ata number of diferent temperatures : NK 7 B i T; is lower than the melting point of B and C, but higher than that of A.coy (Chemical Thermodynamic for Meals and Materials 1, is the eutectic temperature of B- C binary system.Polythermal projections of the liquidus discussed in section 4.3.2, do not provide information on the compositions of solid phases if solid solutions or non-stoichiometric compounds are formed at equilibrium. For providing this information, the method of isothermal section is particularly useful. The following figure represents a simple ternary ‘eutectic system with terminal solid solutions formed.ns (Chemical Thermodmamie for Metals and Materials + If the overall composition lies within one of the solid solution regions, the alloy will ‘exist asthe corresponding solid solution © Ifthe composition lies within one of two-phase regions, say, 6 and liquid phases, both B and liquid phases will coexist. ‘Now a question arises as to how to determine the compositions of | phase and the liquid ‘phase which are in equilibrium with each other. The usual practice is to include fie lines in the isothermal sections, which join the composition points of conjugate phases which coexist in equilibrium at a given temperature and pressure, Tie lines are in fact common tangents to the Gibbs free energy surfaces of the phases that coexist in equilibrium. Let’s assume that a and B phases, both of which form solid solutions, coexist. The following figure shows two arbitrary surfaces, and B : > ‘Common tangent plane Line confecting ‘wa contact pointsPhase Diagrams 2 ‘A common tangent plane shown above produces @ pair of contact points. By rolling the plane on the surfaces, an infinite number of pairs of contact points are generated. Mapping on a reference plane of lines which connect selected conjugate pairs will show how contact points on one surface correspond to those on the other surface. ‘At a given temperature, the Gibbs free energy of each phase in a temary system may be represented in a graphical form with the composition triangle as base andthe free energy as vertical axis. Then it would look like this | | f an (f| } \ eI | | x ‘The phases that would exist at equilibrium and the compositions of the phases are determined by the contact points of a common tangent plane to their Gibbs free energy surfaces, Connection of the contact points forms a tie line. In temary system, & common tangent plane can contact two Gibbs free energy surfaces at an infinite number of points, and hence an infinite number of te lines are generated. However, a common tangent plane ‘to three Gibbs free energy surfaces generates only one set of contact points. Connection of these points forms ate-riangle. “The following is an example of an isothermal section showing a number of lines20 (Chemical Thermodynamic for Metals and Materials B c = cc W/ In construction of isothermal sections or isothermal ternary phase diagrams a tie triangle together with contacting single phase and two-phase areas play an important role. In fact it may be considered as a building block of isothermal phase diagrams. Isothermal ternary phase diagrams are composed of a number of these building blocks. ‘Shown below is an example of a tie-riangle with adjacent single and two phase areas Determine relative proportion of each phase that exist at equilibrium for a system of overall composition ofp in the diagram 2. Determine the fraction of « phase that exist at equilibrium for the overall composition of ¢. 3. Arete boundary curves a the a phase comer corect?1) Fraction of a phase = 2% 2). Fraction of phase = 3) Both extensions of the boundary curves ofthe single phase areas must project either into the triangle (y comer), or outside triangle ( comer), ‘but not in mix. The o comer is wrong. Exercises 1. Prove tha tie lines must not cross each other within any two phase region. 2. ABC temary system forms three binary eutectics and a temary eutectic as shown below. Discuss equilibrium cooling paths for the overall compositions p, q and r indicated in the diagram, Discuss also the change in microstructure that should occur during cooling,