Phase Diagrams for Ceramists Emest M. Levin, Carl R, Robbins and Howard F, McMurdie Compiled at the National Bureau of Standards Margie K. Reser, Editor © Copyright, 1964, by The American Ceramic Society 4065 N. High St, Columbus, Ohio 43214 Pribted in U.S. A. Price $18General Discussion General Discussion of Phase Diagrams l_ GLOSSARY (1) Alkemade (Van Rijn van Alitemade) Theo rem: The direction of falling temperature om the boundary curve of two intersecting primary phase areas is always away from the Alkemade line (see (2)). If the Alkemade line intersects the boundary curve, the point of intersection represents a temperature maximtm on the boundary curve. If the Alzemade tine does not intersect the boundary curve, then the maximum on the boundary curve is represeated by that ead which if prolonged would intersect the Alltemade line, (2) Alkemade Line: In a teraary phase di gram a straight lice connecting the composition points af two primary pases whose areas are adjacent and the intersection of which forms a boundary cur (8) Boundary Line (Curre): The intersection of adjoining liquidus surfaces in a ternary phase dia gram, The area endosed by a series of boundary lines is termed a primary phase area. (4) Components (of a System): The smallest number of independently variable chemical constituents necessary aad suficient to express the composition of each phase present in any state of equilftcium. Zero and negative quantities of the compocents are pemmissible in expressing the composition ofa phase. (5) Composition (or Compatibility) Tetrahedron: In the phase diagram of a condensed quatemary sys tem, the four triangular planes conzecting the composi- ons of four solid phases which can coexist in equi- go | 57 e 1 1 Feevetyas keg a ata as a ‘cUNTI9e@) to, L—Comparison of Geophysical Laboratory Tem geratre Sal of (014 nd Inertational Temperstare Seale Of lear wick thas of che Iotersational Temperature Seale of 1048, (A) a a tne, 107-—ine 1648; CB) a = Geo pbyeial [later 1088. Worium with liquid. The composition of the liquid is represented by a quaternary invariant point, which may ie within the composition tetrahedron (eutectic point) or outside the tetrahedron (peritectic or reaction point) (6) Composition (or Compatibility) Txisngle: Tr the phase diagram of a condensed ternary system the three joins conzecting the composition poiats af the three primary phases whose liquidus surfaces mest at 2 point. TE a the diagram of a terdary system, all of the Alle made lines (see (2)) be constructed, the ternary dia. fram wil be divided into a number of composition Tangles, If the three substances designating the vertices of any of these triangles are not miscible ia the solid state, they represent the Sal equilibrium prod- ‘ects of cxystlliration at the solidus temperature for compositions within the triangle, When crystalline sold solutions exist between any ofthe thee substances, the final products of crystallization may be reduced in ‘samber by one or two, (7) Condensed System: One in which the va- por pressures of the solid and liquid phases preseat are ‘egligible or scall in comparison to the atmospheric pressure. For such systems, e.., the refractory oxide ‘ones, 28 the pressure may be considered constant, one degree of freedom is lost, and the phase rule may be modified accordingly: The sum of the aumber of phases plus the mumber of degrees of freedom equals the sum of the number of compotents plus ane (instead af two). (6) Congruent Melting Point: At a specified pressure, the temperature at whieh a solid substance ‘hanged to a liquid of identical chemical composition, (9) Conjugate Phase: One of two phases ic equilibrium with each other defining a conode (see (10). (19) Conode (or Tie Line): For a particular temperature, the straight line connecting the comoosi- tions of to (conjugate) phases in equilforium with each other. (11) Critical Pressure: In a one componest system, the unique pressure at which the Hiquid and ‘vapor phases become identical (12) Critical Temperature: In a oxe component system, the unique temperature at which the liquid ad vapor phases become identical. At the extical temperature the system passes from a heterogeneous state to a Komogeneous. phase. Ahove the critical temperature ao liquid phase can exist however great ‘the pressure,Definitions (13) Degrees of Freedom (or Variance): “The ‘umber of intensive variables which can be altered in- dependently and arbitrarily without briaging about the disappearance of a pase or the formatioa of a new one called the number of degrees af freedom of a system." Intensive variables are those which are independent of mass, such 28 pressure, temperature, and composition. ‘The aumber of degrees of freedom of a system may also be defined as the “number of variable factors, temperature, pressure, and concentration of the com= ponents, which must be arbitrarily fixed in order that the condition of the system may be perfectly defined.” A system is termed invariant, mono-variaat, bi- variant, tri-variant, and so on, according to whether it possesses, respectively, 0, 1, 2, 8, ete, degrees of free- dom. 14) Devitrifeatio ‘material from glass. (18) Enantiotropic Forms: Polymorphic forms (see (49)) which possess an inversion point at whic they are in reversible equilibrium, that is, they are interconvertible; for example, a- and £-2Ca0°Si0, and a- and f-quartz In such cases the vapor-pres- sure curves intersect below the melting poiat of the ‘bighest temperature polymorphic form, (16) Equilibrium: “From the theoretical, thermo- dyzamic standpoint, the conditions for equilibrium can be exactly and precisely defined; because fc reversible process, 20 useful energy passes from of into che system. From the practical, experimental standpoint, bor- ever, the actual attainment of aa equilibrium state with- in a system may be very dificult to assess, Three criteria have been used variously either singly or tor gether: (1) The time eriterion, based on the constancy fof phase properties with the passage of time; (2) the approach from two directions criterion, yielding under the same conditions pases of identical properties, e from undersaturation and supersaturation, or from rais- ing and lowering the temperature to the same value: and (3) the attainment by differeat procedures criter- fon, producing phases having the same properties whea the same conditions, with respect to the variants, are reached. None of these criteria ere entirely adequate for ex- cluding metastable relationships, Ta silicate systems, in particular, metastable equilibrium is common an ‘may persist for long periods of time ard at high tem- peratures. In the final analycis, interpretation and judgment by the investigator are of prime importance. (17) Eutectic: A eutectic represents an in- variant (unique temperature, pressure, composition) point for a system at which the phase reaction on the addition or removal of feat results in an increase or decrease, respectively, of the proportion of liquid to + The formation of crystalline LF, H, MacDougall, “Thermodynamics and Chem ‘Jehn Wiley aad Sons, New York, 1939. ‘Alexander Findlay, A. 3. Campbell, and wader "Theory" in “Sclenved Bibliograniy," solid. phases, without change af festectic temperature the composition of the liquid phase jm equiliorium with the solid phases can always be ex pressed in terms of positive quantities af solid is thet combination of com- oueats ina simple system having the lovest aeltag Temperature of aay f2U0 of the compocents and located atthe intersection ofthe two ssiuity curves jn bisary system and of the three solubility surfaces (18) Butectoid: An invariant point (see (24) composed solely of eystaline phases, at walsh the phase reaction oo chalge of heat content af soastant temperature reaute ia 4 cage in proporcans of the sold phases eactly analogous to teat at eutectic rice (oe (17) 2 which oot ofthe phacens gad (G9) Glass: Ta eee phace equine sien tlats refers to superecoled laud. (20) Heterogeneous Equilibria: 4 system ie heterogeneous and itn Beterogeneousequiltrama wheat it comin of two oF Tore homogeneous porous (phases) ia equitram with each other. Ta the eal ‘consideration of the phase rule, changes in equilibrium Gue to eles, agai, capdlay, and provational forces are ant considered, But oaly thowe changes du to temperature, presure, and concesttiea, Gi). Homogeneous Ziuiioriun? A system is homogeneous aad is ix homogeneous equlfbsias when it consiste of one phate and all process or rectons cecuring ‘wihin i are in reresibie equlfmamn, A Homegensous phase need oot consist of one stamie ot Bolster species, ein the singe phace poem so. Gin corde wiation, Nav, Cla, O™ OS HO, fod assocated tolesies tay all be pret Sat the ‘actions involving them are at equliclam, (22) Incongreent Melting Point: At 2 spect fed pestre the temperstize at which oot solld pance transforms into another solld phe pls aliquid phase both of diferent chemical compositions ta the age inal substance, (23) Indiferent Point: Ta « two ot moce come govent syste the special conditions where two phases Become identical fo composition and the system loses tne degree of freedom. ‘Typical cases icc the mani, toa or minimom ina solid olution series andthe melt {bg plat of congroeaty sxelig compouna (2s) Invatant Point: ‘The particular condi- tious within system, i terms of presere, temperature, and composition, for which the system poureaes 6 degrees of freedom (see (13)) constitute the invariant points Stated diferentiy, at an invariant point, 20 inde- pendent changes in the state ofthe sytem ca be made. (35). Inversion Point: The temoeatare at srica ooe pelymorpbic form ofa substance (ee (49)) Changes into another under invariant conditions (26), Isobar: ‘The locus of all points of constant presnue. (2t) Tsotract: For compositions within a ter- sary system the locus of ll lanes of constant index of niacinDefinitions (28) Tsopleth: A line i a phase diagram of constant composition, (29) Isopiethal Study: The method of con- idering the changes occurring in a system iu mbich the ‘composition variable is held constant and the tem ure varied (30) Isotherm: In a ternary system the locus of all poincs om the liquidus of constant temperacure. (G1) Isothermal Study: The method of con- sidering the changes occurring in a system in which the temperature variable is beld constant and the composi- tion (or pressure) is varied. (32) Join: The region of a phase diagram rep- resenting all mixtures that can be formed from a given number of selected compositions. 4 join may be binary (straight line), ternary (plane), ete, depending on the number of selected compositions, which need not be compounds. Each selected compesitioa, bower must be incapable of formatica from the others. (93) Le Chatelier’s Taeorem: If a system in equilibrium is disturbed, a reaction tends to take place hich opposes the effect of the disturbance, ie, one bby which the effec is partially annulled. The theorem of Le Chatelier is an important augment ‘o the phase rule for it enables one to predict qualitatively the effect of external changes on the equilibrium of a system. (34). Lerer Rule (or Center of Gravity Principle) When a particular compesition separates into only two phases, the given composition and that ofthe two phases ‘ace colinear; furthermore, the amounts of the two Separated phases are inversely proportioral ta their Gistances from the given composition. Thus, in the adjacent Szure, 4 and B represeat the compositions of two phases formed from composition C: Amt. of dX length AC = Amt. of B X length BCor 4/8 = BC/AC — AC 8 (35) Liquidus: The locus of temperature-com- position points representing the maximem solubility {Saturation} of a solid phase ia the liquid phase. Tn a binary system, itp aline; and ina ternary system, its a suriace, asually curved, At temperatures above the liquidus, the syitem is completely liquid, and a point fon the liquids represents equilibrium between liquid ‘and, in general, one crystalline phase (the primary one). (36) Metastable Phase: "4 phase exists meta- stably in asystem if it would aot be present at final (thermodynamic) equilibrium, under unchanged con- ditions, and if the system is not approaching thermo- iynamie equilibria at an observable rate. (G7) Monotopic Forms: [2 certsin instances af polymarphisa (see (42), the vapor-pressure curves of the to forms do aot meat below the melting point. ‘They, therefore, lack a stable inversion point, and the form with the higher vapor pressure is metastable with respect tothe other at all trperatures below the melt- ing point. Such forms are called monotropic and are rot interconversibe, (38) Periteede Poiat: (28) at whieh An invariant point (see 1 composition of the liquid phase in equilibrium with the solid phases cannot be expressed, in terms of positive quantities of the solid phases, ‘Whereas the composition of a eutectic point always lies between or within the composition limits of the solid phases in equilibrium with liguid, the composition of a peritectic point always lies outside the composition limits “At a peritectic point the intersecting univariant carves do aot produce a minimum point on the liquidus curveas fora eutectic. (28) Peritectoid: As invariant point (see (24)) composéd entirely of crystalline phases, at whica the ‘phase reactions oa change of heat content at constant, temperature are exactly analogous to those at 2 peri- tectic point (see (38)), in whieh one of the phases is (40) Phase: Aay portion, including the whole, of & system which ia physiedly homogeneous within itself and bounded by a suriace so that it is mechani- cally separable from aay ether portions. A. separable portion ceed not form a continuous body, a8 for ex: ple, one liquid dispersed in another ‘A system composed of one phase is a homogeneous system; a system composed of more than one pase is heterogeneous; aud in order forthe phase rule to apely, cach puase must be ia homogeneous a8 well as hetero geneous equiibriam. Gl) Phase Rule: For a system in equilibrium, the sum af the number of phases plus the oumber of Gegrees of freedom must equal the sum of the number of components plus two, or P+ F = C+ 2, (G2) Piercing Point: Ins quaternary system, the interection of s univariant curve with a ternary Joint (e (2)) at a poine other than ternary invariant point. The univariant curve represents the composi~ Hons of guide that ean exist in equilibrium with three particular sold phases. The composition ofthese said phases asualy ail lie im the place of the ternary join FF the intersection is a ternary invariant poiat, but they Caonot alli in thet plane ifthe intersection isa piere- fg point. 143)" Potymorphism: The proverty possessed by some substances of exstisg in more than one eryatal frm, all forms being of the same chemical composition but airing ia crystalline structure and physical prop- erties, and yielding identical iquid or gaseous phases on Jung or evaporating. (42) Primary Phase: The only crystalline phase which can exist in equilibrium with liquid of 2 given empostion. The primary phase isthe Erst crystalline pase to appear om cooling a composition from the liquid fate; or converely, iti the last crystalline phase to isappear on beating composition to melting (se. alo, Boundary Line (9) and Liquidus (33). (4a). Primary Phase Region: The locus of all conpsitns ia pe aga Bavag 8 commos ps sary phase (Ge) Pseudo System: It is frequently, coave- nicat or necessary to refer to portions of a binary or ferry, ete, system which are aot (tue) subsystems (Gee Ga))., Ta sued instances the term pseudo binary, or peeudo ternary, etc. i use.Phaze Rule For example, in Fig. “XIV, 3Ca0- Alr-2Ca0- SiO; is a pseudo binary system and AKO-C40 “AKO: 2810¢ BAhO1-2Si03 is a pseudo ternary system, A ternary system must consist of componests and be bouaded by three binary systems. Ia the pseudo ternary system cited, one of the Boundary lines, 3ANOs-2SiOrCa0: ANO#2S0,, is only a pseuda binary system, a8 no combination af Ce0- AlOr-2Si0s and 2AL0s-25i a svhich may be vaned in composition within date limits ‘without the appearance of an adaitional phase (48) Solidus: The locus of temperature-com- positon pint ina system at temperatures above wich Sclid and liquid are is equiliam and below which the syste completely sold, fo binary diagrams ssthout sod solation, iia stright tne, representing constant temperature, and mith solid solutiows, ts 8 curved line or eombination of carved and straight lines {ieemze a tercary systems, the solidus ie represented bya fae plane ort carved surface, respectively 48) Subsystem: Any portion of a binary, te acy, ete. srater which saa be tested as an independ. ete. system. Te atlected su0- stances dosguating the subsystem aust be components for the subsystem (see (4) in the CaQ-AlsOr binary system (Fig. 231), the limealtmine sompounds ith ongrueatly melticg points form binary svetems mith sech other. for example, the Ca0-24lOrCa0 Ais and the Ca0-Ca0-AlsOr systems; sod fm the toraary system Ca0-ALOrSiO; (Fig, XIV), the binary joins, Foch a8 Ca0-SiOrCab)-AlOs 25i0y are true. binary systems, and the three conerueneiy melting compound G20-$i0s, Ca0-A1i0y- 2810, and 2020 -AlsOy SiOy ‘whose corazon boundary lines meet in-a eutectic, ont :eiste «tre ternary system. ($0) System: Any portion of the material uni- corse which can be folated completely and arbitrary from the rest for coasideration of the changes which rmay occur within i under varying conditions ‘The term syctom iv oued in two senses: te zener aed the pe the general seve, one species a system by vaming the chosen compoaenta, for example, the binary system Ca0-Al.0s, or the ternary system: K,O-E:Or#0. In the specific sense, one may desig- nate restricted portions of a "seneral"” system for study or discourse. Thus one may refer to an i+ variant system or bi-variant system, ete, in which the restriction is based on the degrees of freedom (see (19), One may also refer to 2 one phase (homogensous) system (for example, system water vapor) oF to 8 tro Phase (heterogeneous) system (for example, system calcium discate-liquid), ete, in waich ease the restric. Yon is based on the number of phases present. Finally. oue may refer to a system in which the restriction is based on chernical composition, for example, the system 20 per cent LigO-SiO,-S0 percent LiO-B.O;, The use of the term system to designate a particular chemical composition is not cecessary and should be avoided, 1 the definition of system be kent ia mind, the varied use of the word need not be confusing and can easily be interpreted in context, See Conode (10) ‘See Degrees of Freedom (13), (1) TleLine: (52) Variance: lL THE PHASE RULE (1) Statement ‘The basis of all work on equilibrium diagrams course, the phase rule of Willard Gibbs. Tts use has been greatly facilitated by the interpretations of Rooze- boom,’ Schreinemakers,' and others, Extensive ex plazations are to be found ia textbooks on physical Chemistry or books devoted exclusively to the phase rule (see V. Selected Bibliography, (1). ‘The diagram known variously as phase diagram, equilibrium diagram, etc, is esseatially a graphical expression of the phase rule. Equation (1) gives the ‘usual mathematical form af the phase rule, PeFac+2 a G = sumber of components of system, B = sumber of phases presene 8: equilibrism, FF degrees of freedom (Yarianes) of system, ‘The terms used in equation (1) as wel as others nee- essary to an understanding and application of the phase rule are defined in the Glossary. (2). Limitations ‘The phase rule applies only to equilibrium states ofa system which require both homogeneous equifbruan rrithin each phase and heterogeneous equilibrium be- frveen co-eisting phases. The phase rule dees not depend on the sature of the components of onthe nate and amousts of the phases present, but only ou theit umbers; or does it give information concerning rates of reactions “A system in equilibrium always obeys the paase rule, but conformance, in itself, is aot a suficent test Ter equilibrium, because of the possible existence nonequilibrium phases and conditions. Non-confor- sisace with the phase rule, however, is proof that equi- onium conditions do aot exist ‘The pase rule provides the basis for the clasifca- tion, atcordiog to sumber af components, of the di- verse cases of chemical equilibrium. F the number of components be known, which is usually the case for a spectied system, the sum of the number of phates and the muraber af degrees of freedom is fixed at C plus 2. ‘The aumber of camponeats plus two also represents the maximum aumber of phases that can coexist at equildrium, as the degrees of freedom (F) can aever be fees than 0 (at invariant conditions), 4(a) J. W. Gibbs, “Equilibrium of Heterogeneous Sub- stances” Trans. Conn, Asad. Seu, 3 108-248, 040-604 Graig), (& J. WW, Gibbs, The Collected Works of J. Willard Gibbs, Vol, Zp. SHSTL. Longmans, Greesi and Con, New York, 1038) Wz W. 5. Roozeboor, Dis heterogenen Gleichgewichte, 6 vols. F, Vigmeg Co, Son, Brauaseaweig, 111. VE al i, Schetinemakers, “Miceakracale a Systeres- eeiee het. Chem, s0 (2) 188-99: 8 [9] O47 76; 82 (of 813-30 C1008).One- and Two-Component Systems Ill, INTERPRETATION OF DIAGRAMS (1). One-Component Systems The indepeadeat variables in a one-component sy tem are limited ta teperatare and pressure because the composition is xed. [e follows from the pbase rule chat the system is biariant if one phase is present, tnivariant if tro phases are present and invariant three are present. A diagram of 4 ose-component system in hich the independent variables, temperature dd presute are the abscsea and ord ¥ is shown in Fig, IL, Te following facts are observed: (i) Curve Fd (uaivariant) isthe sublimation eurve for modification 4 (2) Curve 4-B (usivariant) is the sublimation curve formodifeation 3B, {@) Curve 8-C (univariant) is the vapor pre curve forthe liquid. (2) Curve d-D (univariant) is the transition cur for modifications A and 3 and represents the change of the trasition pein wih pressure, (@)_ Curve 8-E (univariant) is the melting curve for modification 2 and presents the change of the melting point with presture. (6) Poict (invariant) is the transition point for the two crystalline modifcations, Tt is called a triple point since tis the point at which three phases (two Solids and vapor) are in equibrium, (7). Point B is the triple point (invariant) for the ‘equilibrium between crystalline modification B, liquid, 24 vapor. (8) The system is bivariant in all parts not on these lines their ntersetions "a dealing with refractory substances i ia at present iempossite, with a few exceptions, to measure drecdy the vapor preesre of the solid and li phases. It is possible, however, o construct diagrams for refractory Substances showing qualitatively the vapor pressure fcr the diferect phases i the temperature-stabity rla- tons are known because the unstable phase always has 4 higher vapor prrssre than the stable phase even Fro, IT Phase relations in a one though the vapor pressure is infinitesimally small (2) Two-Component Systems ‘Two-component systems have three independent variables, camely, temperature, pressure, and composi- vyagor presture remains vary low for temperature, the pressure variable acd the vapor phase may be elimizated from consideration. Systems with the pressure variable eliminated are called condensed-systems. The reduced phase rule by which such systems may be represented is shown in equation (2) in which P ceiers only to solid and liquid phases. PaR=Chi @ In bioary systems under these conditions three eoex- isting phases produce an invariant condition, two a anivariant condition, and one a biveriant condition. Tn representicg condensed binary systems it is cus. tomary to make the erdinate the temperature scale and the abscissa the composition scale, In Fig. IIT, the intersection of the ordinate with the abscissa at Ty rep- resents 100 percent Si (and 0 percent 3); the inter section at T, represents 100 percent 5; (and 0 percent 5). The scale as labeled, readiog from left to right, refers to percentage of S: present; the percentage of S, tepreseated by any poiat equals 100 ~ Ss, Tue com- position variable is usually given in weight percent or tole percent, according to convenience; occasionally ix ‘weight fraction or mole fraction. (A) Binary Systems Without Solid Solutions (e)_ No Compounds Present In Fig. IITs shown a simple type of condensed binary system with (1) no intermediate compounds, (2) com- plete solubility in the quid state, and (9) no solubility tion) between the solid phases. The sariant point of the eutectic type where phases (components Sy and S;) and liquid (cf composition 40% 5, 60% Si are i equilibrium. change in either vanable will couse one or more phases isappear. The curves F-C; and G-C, determine the position of univariant equilibrium, The coexistence ff both phases (one solid and one liquid) caa be main- tained with change of one variable if a compensatory change is made in the other. the proportion of the two phases changing accordingly. The waivariant bound- Sry defines tie quantitative relations ofthe variables, in Fig. I, the vervical boundaries represent one- component systems. The solid phases, Si and Ss, representing these components have sharp melting points at the temperatures F and G, respectively Elsewhere, the F.C and GC; liquidus) carves separate the one phase (iguld) region from the areas where both solid and liquid are present. ‘The diference between a one-phase region and a re- ion representing two or more phases in equifbrium is a basic concept in the interpretation of phase diagramsMechanics of Crystallization Sg Tea as oa ta G0e* 3, comeasition 3: Fic, UL—Two-component system without intermediate ‘sompouds or Zoli rolutions, Every location within a one phase region, such as ia the Geld designated Liguid ia Fig, 1, represents an actual state of the system, in terms of temperature and concentration variables. Locations within « to- phase region, however, do cot represent actual states, Sut merely correspond to the overall chemical composi tion of two phases in equilfrium with each other, sample, points in the fields designated Liquid + S., Lignid + Sy and S; + Sy in Fig. IIE. The bro-phase areas are, in effect, gaps or voids in which no single homogeneous phase can exist, To construct isobaric diagrams, i is necessary and sufficient to know the om phase-egion bourdaries.” Meckanes of Cryctallcaion: Changes in the syster itdstrated in Fig, TIT may be followed by varying tither temperature or composition. On eating, a mass of composition C, wil show sharp melting at the temperature Ty, This is the lowest temperature in this system at which Hguid is ix equilibrium with solids (the eutectic temperature). Conversely, 2 homogeneous liquid of his composition wil exystalize completely at this same temperature, on cooling, provided equiforiuam condivoes are maintained, Since neither of the vari ables, temperature or composition, canbe chaaged without the complete disappearance of one or more haces, the point Gis an invariant point. A liquid of composition Aon cooling under equi- Nbrium conditions from a temperature above 7 will be- have quite diferently. ‘The substance will remaia a omogentous liguid until temperature Ty is reached, when the Grst infinitesimal amount of tke solid with composition 5, will crystallize. Upon further cooling, Si il eostinue to crystallize while the composition of the liquid flows eurve C-C\. 2 See J.8, Marsh, under "Theory" in Selected Bibli- ography, Pat V. 10 At any temperature the composition of the liquid coexisting with the solid is represented by the point of intersection of the horizontal line corresponding to that joerature with the Kquidus curve. The relative amounts of solid and liquid coexisting are represented by the relative lengths of the temperature horizcintal from the composition of the initial material to iaters tion with the liquidus and with the vertical, SF ree spectively. Thus, composition 4 at the temperature T, will consist ofa solid of composition S, and aliquid of in the ratio of line lengths Br-Cy! dB, With further cooling, solid 5; will continue to crystal- lize until the temperature of the extecti, C, is reached. ‘he material will remain, because of the heat of erystal- ation, et that temperature until completely eystal- lized into a misture of solids 5) and Sy The ratio of the amounts of the two solid substances can be found by the same lever rule S'S: = -Sy/d-S, IE the two solids, Sy and S; (Fig. IMD), are mixed in such propartion as represented by polat A and are heated, 20 reaction will take place until the temperature TT, of the intersection of the isopleth and the solidus is reached. At this temperature a Liquid of composition C, which contains both S\ and Sis formed, The quan tity of liquid C, formed at T; is measured by the line AvBy and the ratio of solid to liquid is B-C/d.-B,. ‘At temperature T; the racia of solid to liquid is By Cy/- ‘ArBy, and the composition of the liquid is given at Ci, the intersection of the tie line ay-C; with the liquidus F.C, As the temperature is raised, the amount of solid decreases and the liquid increases, the liquid be- coming richer in. At dT aelow Ty, only a very small amount of solid remains and the composition of the liquid has changed from C, to C. At Ty the solid is completely melted and the liquid is of composition 4, ‘The relative amounts of liquid and solid S present at various temperatures irom T to T; for the substance of composition d are shown in Fig. IV. This igure serves fairly well to illustrate the use of the lever rule. The compositions, S, and S, and the composition corre sponding to C, are special cases to whiea curves of the type of Fig. IV do not apply since melting of these com- positions takes place at definite temperatures and not Over temperature intervals, The above statements regarding the crystallization of melts are true only if the rate of cooling is sufficiently slow to allow eouilibrium to be attained at every stant. A rapid rate of cooling will lead to quite dif ferent results The liquidus boundary curve shows the effect of soluble impurities on the melting point of pure com- pounds. This effect can be shown by an isothermal study of thessolid, Sj. Ifa charge of S, (Fig. ITT) is held ‘constant at temperature 7: and a small amount of Sy is added, a srail amount of liquid of composition Z will be formed. As the amount af S; is increased, the amount of liquid Z increases, When sulficent ux, S,, has been added to bring the total composition to L, the solid phase, Sj, disappears and the charge becomes extirely ‘Therefore, ¢ small amount of soluble impurity the melting temperature from F to Ty. ig lowersBinary Systems with Solid Solutions saat Toeoae pe ae fer ctl mal won i e209 4 29 0 6 Pastel mich sind wa Fro, 1V.—Variation in amounts of liquid anc solid phase, 5, upon heating composition 4 of Fig. Tit from the temperature Ty 10 Ty + dT along the rements In’ temperas phase, 5), respectively Further additions of S. completely dissolve and the composition ofthe liquid varies until point Ais reached tvhen the solid phase, S,. na longer dissolves. that is, the liquid is saturated with S,. Further additions of Sedo not dissolve and the relative amount of liquid de: cresces; the mass approaches 2 complete solid as the total composition approaches S;, Since the curve F.C, represents solutions saturated with Si, and the curve G-C), solutions saturated. with, Sp the intersection C; (eutectic) must represent a solu tion saturated with both solids. The curves are, thus, solubility curves or freezing point curves. () Compounds Preset ‘Three types of binary diacrams with compounds, are shown in Fig. V. Figure V(4) showsa compound. 5.Ss, which decomposes at T, into the solids, S, and S.. Figure V(B) shows a compound, 5,S;, with an incongra- ent melting point; that is, ic decomposes at Ty into a solid, 5, and liquid, C, neither of which has the com: position of the original compound, Ficure V(C) shows compourd, 5,5; which melts congruently. that is, the liquid resulting from the melting of S\S, is of the same composition as the solid, 5\S., ‘The system represented in Fic, iC) may conven- ieatly be divided inco two svstems or subsystems, one containing S, and S,S- as its compogents, the other Sit and Sp Both may be studied in the same manner as Fig. ITE (©) Binary Systems with Solid Solutions (a) Meckanies of Crystallization Figure VI represents the case of simple solid solution. where the melting point of is depressed by 8 und that of Bisraised by 4. The composition at the tempera- ture, fo, weil consist entirely of liquid. If this mele és allowed to cool along the isopleth to the temperature, Ti, a solid of composition SS, crystallizes out af the solu: un oy 3 35 Fro, V,—Two-componsnt systeas wi compounds pes- ant. (jane compound, 5S, decomposes af a tepera> fore belo the eutectic temperature; (3), the com: ound, Sc, decomooses at a temperature above thet of Fhe ete fe compound, Si, 1s sable at ts tacking pont 38 Compt Complete solid solution with- irmum in 2 binary sys rd represents the comm bosition af the liquid phase and is called the figuiduscarve. Lite L-SS-SS-SSe-Zrepre= sents the composition ofthe solid phase and Giealled the solidus curve, The te fines, Ssple SSrLs,and SSeLs, show the conus gate relation of quid and solid phase for ‘hres temperatures fy, Tn Ts sat that the solid is richer in 4 than t temperature Ty the liquid has a solution a composition tion, Tt is apps is the liquid . composition of Zy and the sol ‘Se: and the ratio of slid to liquid is L-2/95-X, As the temperature falls from T, to T: the isopieth ‘SS, to SS, with the compositions of liquid from L, to For the system to maintain equilibrium in cooling, crystal of solid solution must change in composition continuously throughout its mass, ‘There is a constant interchange of material between solid and liquid phases aad s constant change in com- position in all parts af the solid as cooling progresses. ‘The solid is thus increasing in concentration of B along SSS, while the liguid is increasing in concentra. tion of B slong Ly-Lz, Simultaneously the amount of solid is inereasing and the amount of liquid decreasing the total composition of the system, of course, remain ing constant, The last drop of liquid has the eompo- sition Land the total solid the composition SS. ‘Fractional crystallization can be obtained between Ty and T; by removing the solid phase at any tempers- ture hetween ThandBinary Systems with Immiscible Liquids (8) Types of Spstems Figures VI, VIZ and VIII show types of solid-salution diagrams. Ta the case of binary solid solutions with a maximum of misimum (Fig. VII), the maximum or miniroum point on the curve is not an invariant point, as can be seen from the following argument. In 3 ‘wo-component, condensed system (pressure constant), PLF=C+land Fo3—P, In order for the system to be invariant (F = 0), three phases must exist in equilibrium, Such a condition, however, can never exist in a solid-solution series as shown in Fig. Vil, because there are never more than two phases presest, ive, solid solution and liquid solution. The system ca fat zo point become invariant, and the equilibrium curves ‘must be continuous, in contrast to a “true” invariant point (eutectic or peritectic) which is 2 point of discontinuity on the curve. ‘Such points desiguating maxima and minima, cluding the melting points of congruently melting com- pounds, at which two phases become identical in car position are known as indifferent points.* ‘Figure VIII shows two cases where wo solid solutions are present, [a Fig, VITIC4) at point c there are two Vig Fra. inary ‘with 2 single solid solution. (4), landbuch der. Meisliphysit. Edited by Georg Slasing Val TE, Die becerogenen Gleichge- wwichte, by Radol! Voge p. 241, Kzademische Veringsgestlschate, Berlin, 19 ase 3 AS ¢ Fro, VITI_—Solid solutions showing conjugate relatio biog,” The two solid solutions, Sand Sp baves conjugare flation to each stter im area 2.é-r-y. The sel solutions: ig areas E-ave and mde have a conjugate relation to the Sorresponding liquid phages present in theee areas, solid colutions of compositions 2 and 6 and a ligule of composition c, This aumber of phases (3) preseat ia a condensed two-component system makes the point ¢ fan invariant point which satisfies the definition of a featectic, Is Fig, VIII(B) at point ¢ there are two solid solutions of compositions @ and 6 and a liquid solution of composition c, Point cin Fig. VIEI(2) is also an in- variant poiat, but it differs from thet ix VITI(4) be- cause there is Solid in equilibrium with liquid both above and below the temperature of the invariant point. The relationship is therefore called peritectic in distinction from eutectic. ‘Marsh? has pointed out that complete insolubitity in the solid state, as indicated on many bypothetieal and actual binary diagrams, is highly improbable. It vill be observed that this compilation chows many’ bi- sary diagrams of the silicates and refractory orides ia which there is ao indication of solid solubility, that is, 10 solid solution, In many cases selubility is so slight that evidentes of it cannot be obtained or the scale of the diagram is insufident to show it, Im too many in- stances, however, the relations in the solid state have not beea sufficeatly explored. Data of this kind are important to the ceramic engineer and technologist as ‘well as to the petrologist, and are becoming more prom {neat in lteratare © Binary Systems with Immiscible Liquids Ta some systems two liquid solutions can exist equilioriam as shows by the area o-bcin Fig, IX. The extremities of the "tie line” Zy-L, represent the com- positions of the t¥o solutions which are ia equilibrium at the temperature 7, The point ¢ at temperature T) is a triple point which, in @ two-composent system, is fan invariant point since there are two liquid phacee and fone solid, A, present. The work of Greig hes shown that there are often similar conditions present in certain SiOyrich regions of silicate systems b L Tra \Y ok §| ae & BH. d a8 a Composition a Fro. 1. —Conjugate liquid phates. The troten fines in area G-ive show the conjugate relationship of the £0 {igaid phases for eke two temperatures, Ty aadComplex Binary Systems (O) Binary Systems of « Complex Neture An example ofa hypothetical binary diagram of con- siderable complesity is given in Fig, X¢to illustrate how the courses of crvstallization under equilibrium condi- tions can be visualized, The two components are ol aad B. Component, within the temperature range of the diagram, occurs in 5 enantiotropie forms: liquid, ax, fon ay and ax. Component B ests in only tro forms within this temperature range, liquid and), There is One intermediate compound, 7, which does not exist at the liquidus, In a part of the composition range two Tiguids, L, and Ly, coexist. The components, by defi- tition, melt congruently to form liquids of their own composition, ‘Three vertical lines of constant composition (ison pleths), CD, and E will be considered, (j) Crystallzction along iopleth C: At tempera. tures above point # on the isopiech C, the suostance is a homogeneous liquid. When the temperature drops to point &, separation into two liguids results, the two liquids changing in composition and in relative amounts as the temperature is lowered from # to, At the tem perature represented by point m, for example, the coms potitions of the two liquids correspond to the intersec+ Hons of the horizontal line (tie line) throug poiat m ‘with the boundaries of the deld (points d and «) and the relative amounts of the two liquids, Ly and Ly, are pro- Crystallteation Paths Fic, X.—Hypothetical binary diagram ta llustrate possible phase changes, 13¢ Three-Companent Systems portional to the lengths ms and dom, respectivels ‘At the temperature of point n, crystallization of the phase, m, 2 slid solution, occurs. The coexisting solid dnd liquid have the compositions of the left and right extremities, SS, and Ly, respectively, of the horizontal line chrougi », Further temperature drop results only in changes in compositions and in relative amounts af se two plaeses represented by horizontal lines through the composition at the proper temperature level until point o is reached, at which time the compositions of Solid and liquid are A and a, respectively. At the emperature of point o, the cooling is arrested until all of the liquid of composition a bas crystallized to a mix. ture of the solid solutions, = and ay, ax having the composition of point , and ay having the composition of the point Further cooling through the region from 9 to p re: sults in reaction of the to pases, ay aud ar, the Gu titative relations between compositions and amounts being found as before by passing horizontals through the temperature levels of the reaction to the intersec- tions with the phase-region boundaries. Solid a changes in composition from i to 9’ and a from i to 2. At the temperature of paint p, continued reaction be- ‘oween solids ax and ay results in the complete disag- pearance of Solid solution ay of composition p persists, unchianged jin composition, until the temperature of point @ is eacked, At this point. there is a partial decomposie ‘on of phase ay to form ay of camposition 9; (a eutec- 7d decomposition). These two phases co-enist, con- ‘inwally changing in relative mounts and in coraposi- ‘ons, until point r is reached when another eutec- oid decomposition takes place. Solid ay completely Gsappears, and the new solid solution, , af compo- sition rs farms. At point s, a: is in tura replaced by ta, and the two phases ay and + exist together until the lowest temperature shown ia the diagram is reached. i) Crytalécation along isopleth D: & mass of composition D cooled from above the temperature where it exists asa homogeneous liquid undergoes qualitatively the same changes as did sample C until the temperature represented by point » is reached. Here reactio: tween the solid oy and liquid L tekes place, resulti the re-solution of a and precipitation of a, The phases ay and L coexist, changing in composition with de- creasing temperature until the last bit of liquid. disap- pears at the point w. From w to x only the solid ay is present, At x phase y precipitates from ay, but ar persists through only a very short cooling range whe it reacts with (is resorbed by) phase +, and y persists alone throughout the remaining cooling range shown in the diagram, ‘The phase 7 is a solid solution of intermediate "8 Crysuallzation of any sold solution in equilibrium yt alga slution or wit another sla stuton under Changing temperature condisions requires that conta! faction takes place not only between the matecialscrss- talliging at that inctane but wien ail the solide alzescy qrywtalized.. The diftealty of the attainment of saule “igemum ander suck conitious is obvious, compound of the composition 4,3, which can take sither 4 or B int is struceure in grester than scichio- metric proportions. The compound 4.8, canzot be considered a component of a subsidiary system since it does not melt 29 8 homogeneous liquid but instead ine othe solid solution a on heating Crystallization along ioplth B: Coal of comn- position E results inthe crystallization of sli scution 31 of composition fy at the temperature of point J Changes in composition of the coexistent solid and Tiguid phases tale place until tke temperature of eutectic, C, is reached. Then ax arrest i the celing takes place unt reaction has caused the complete ds appearance of liquid by the crystalization of pases ay and 4 in the proportion indicated by tbe lever pine ciple about point g. Further reactions on cooling are ot sufficiently diferent fram previous descriptions to require comment. (3) Three-Component Systems ‘There are four independent variables in a ternary system, samely, pressure, temperature, and two con centration variables since a ternary solution requires a statement of its composition with respect to two com: ponents before its total composition is fited. Five co- existing phases (a quintuple point) produce au invariant fyitem, four give aa usivariant system, three, a bivari= ant, etc. A complete graphical representation of the ternary system is a very dificult matter. If, however, the vapor pressure is so low as to be nezligible, the ter- nary systems may be treated as condensed systems as was the case sith binary systems, the phase rule again expressed as P+ F = CHI. ‘The compositions cau then be represented by trian- gular coordinates. This method is Tlustrated in Fig, SCL, Ia this figure, each side of the equilateral tangle is divided into 100 parts, each tenth division being inter- seeted by lines parallel to each of the other two sides. ‘A point at the avex, C, is composed wholly of compo- rent C. A point on the base line A-B is composed entirely of campouents and B with none of C. The relative distance of 2 point, such as x, from each of the three apices may be expressed in percentage and it thus may Fepresént a percentage composition of 2 ternary mixture or solution in terms of components 4, B, C. Point X, for example, represents a composition of 45% A, 20% B, and 35% C, whereas y represents 15% 4 13% B, and 70% C. ‘By the appropriate construction the coordinates of a point ina triangular diagram can also he read off of any one of the sides. In Fig. XI i the lines XE and XF be constructed parallel to the sides BC and AB, respec- tively, the length CE represents the percentage of (43) in composition X, the length 4 F the percentage of C (35), and the length FE the percentage of B (20). By a similar construction the composition of X, in tems of 4, B, and Coan be read off on the sides BC and AB, The two end segments of each line represent the proportional amounts (in terms of the whole fine) of the substances designated at the opposite ends; the middle segment represents the proportion of the, third sub- seance, no: located on the ine,Typical Simple Ternary Systems station of composition in a ternary sys: tem by means of triangular coordinates, This method of expressing a composition ia terms of three others by the appropriate construction, so a8 to designate the three proportions as segments of a line is not limited to equilateral triangles but is applicable also, to scalene triangles. For example, point .t in Fig, XI can be expressed in terms of , 3, and D on the line BD. The percentage of B = DG X i00/DB = 20; the percentage of D = HB X 100/DB = 52; and the percentage of A = GH X 100/D3 = 28. By rotating the line CE until it were parallel to BD, the prapertions D, and B in X could be determined, similarly, on the sides AD and AB. As will be shown later, whes dealing with subsystems or when tracing the course of crystallization of aliquid, it frequently becomes necessary to express an overa compesition in terms of three others whick do not form an equilateral tangle. ‘A triangular composition diagram also bas the ad- vantage that a series of additions of a third component toa mixture in any ratio of the other two compocer may be represented by 2 straight line from the agex of the third camponeat. In Fig. XI for instance, additions of component B toa mixture of 33% 4, 67% C (paint D) allie or the fine D-B, ‘Temperatures can be represented by lengths perpen dicular to the plane of the composition triangle and ‘therefore cannot be shown directly on a two-dimensional surface, but the temperatures on ane of the tiermal surfaces (usually the liquidus surface) may be indi cated for uniform temperature intervals br isotherms as are elevation contours on topographic maps. The actual solid diagram has an appearance like that of Fig. XI. ‘The liquidus surface is then a series of intersecting sarved surfaces representing the primary phase fields of smpounds ia the system. A primary phase field of a congruently melting ternry compound is a domed sur- face, the highest elevation of which represents the melt- Fro. XUL—Perspective drawing of a space model of ternary system wich @ simple eucectie end a0 ternary compound. in G. Masing, Hancbuct der Metal 206, p. 370, 1997. Vole it, Fig ing point of the compound. Its Geld intersects that of aa adjacent congrueatly melting compound in « sloping valley or boundary line. In the case of an grueatly melting compound the intersection of the primary phave field of the first with that of the second solid isa sloping terrace and not a valley. (A) Termary Systems Without Solid Solutions (a) Typical Cases Ta Fig, XITZ, six typical cases of ternary systems are Figure XIII(A) shows a system without either pounds present, The field 1-4-2- C represents the feld of stability of component C in equilibrium with solution. Solid C is the primary phase for this area and is the last solid to disappear when any composition within this area is heated. Tt is also the first solid phase to appear whex liquids resented by points in this area are caoled, Pointe 1, 2, and 3 are binary eutecties, while point 4 is @ ter- nary eutectic. Lines 1-4, 2-4. and S-4 are known af boundary curves, each of which represents a condition binary or ternary «Typical Simple Ternary Systems cate the direction of falling temperatures, G.A, Rankin and FE. Wright, dim 7, Sc, 4th Se, Of S-phase equilibrium among two soid phases aud liq- uid. |The bvo solid phases at equilorium along 1-4 ats A and C, sloag 2-4 are Cand B, and along 344 are A and 5. “Poit 4 is a quadruple point in a condensed system at which solids a, and 5, C are im equiiories ‘with solution, Tn diagrazas (3), (C), (D), and (2) of Fig, X00T an intermediate binary compound, 48, is present. The straight line which joins this compound to the third component, C, of the ternary system is called an Alke- made line. Alkemade lines divide temary systems {nto composition triangles. The Anal phase: produced by equilibrium crystallization within one of these tr- angles are indicated by the apices of the triangle, For example, in diagrams of Figs, XITI(2), (C), 1D), and (2), the Soal phases within the triangle 4-4B-C are crystalline 4,43, and CG, Ia XIU(F), where a tercary ‘compound {s present with the binary compound, com {ugation lines form four subsidiary triangles, Figure NITI(B) shows a ternary system where the bi- Bary compound AB is stable at its melting point. Ac. cording t0 the theorem of Alkemadet if the tine Co crosses the line 5-8, the point of intersection will be 4 maximum on the boundary 5.3 and the points § and vrill be eutectics and each composition wrangle wil be- have as a true ternary system, «However, CXF does ot eross §-8 but intersects 1-6 and +3 (asia i (C), thes only 6 will be the eutectic. In the case of ed Ppa cats of three-component systems; A and B show hypothetical ietherms. Arrows indi. +39, 18 (1918), 16 . KIII(B), the line Cu forms 2 true binary system with components C and 4B. It divides the ternary system 4-B-C into two terary systems, each of wick may be treated individually. In Fg. XIII(C), however the line C-X erosses the primary phase Geld of another compound, the composition of which does act lic on this line, and therefore the line does aot describe a binary syste, In Fig. XTII(D) the composition of the binary com- pound, iB, les outside the field 45-63 because it has ‘aa incongruent melting point. Ia the binary system ACB it dissociates at a temperature corresponding 9 Point 4 into solid A and'iquid. In the teranry system, 4-B.C the compound 4B is the primary phase ia fed 3-£5-6 ands stable in this field. In Fig. XIIL(Z), 43 dissociates into solids and Bin the binary system 4-3. In the terary system com- pound ZB has a sale ed #5 3s" tisorem by Van Rife Vac Allamade serves as a YeEy eHective guide in regard to temperature changes i Ui interior of ie tangle It the ogous ek oe Sugle which correspoad to the composition of two solid phases be counccted by a line, the temperature at misled thee ae fre pees ca oe click oat 2d vapor rises as the boundary curve approaches this ne Becoming a aazimum at the iuesetion tours a Boundary curve clea ceases tobe stabs sefore ia poise Igreached.” "(W.D. Bancroft, "The Phase Rules Pins Chem i. 129 (1887)_— Crystallization Paths In Fig. XCIII(F), the system bes a binary compound AB and a ternary compound, ABC, exch of which hes 2 ‘congruent melting poiat as their respective composite are within or on the boundaries of the fields ia which they are the primary phases, These simple cases are also applicable to such com= plex systems as the one shown in Fig. XIV. (8) Crystallization Paths!® G) Simple systems: Gees'%® states that “the erys- tallization curve desotes the locus of points which represent the compositions of the solutions formed on cooling any given solution from any given temperature to the temperuture (quintuple poiat in ease of ternary systems) at which it becomes solid, under the assump- Yon that 0 phase is removed during the cooling.” ‘The relations of solid phases to liquid phases of any sys- tem that does not have solid solutions are known whes, the liguidus of the system is determined for all som. positions. The liquidus is the temperature at which the first solid (primary phase) appears on cooling under equilibrium conditions. A knowledge of the erystal- lization curve or the melting curve (the reverse of the crystallization curve) for any particular melt is very valuable in the stadiy of the fring af ceramic bodies. A few types of crystallization curves wil be deseribed us- ing the diagrams and terms given by Andersen.'% In Fig. XV, point m is the ternary eutectic and all crystallization curves of this system are terminated at this point. If a liquid of composition « is chesem and allowed to cool, the system remains Hguid until the liquidus is reached, at which temperature the solid, 4, begins to crystallize. The course of the erystallizatic curve from this point to boundary m- follows a straight ine draws through 4 and a. This is true for all erys- tallization curves where solid solutions are not present, As the liquid changes in composition fram a to 6, solid A crystallizes, At 5, a second phase appears aud the crystallization curve follows boundary fom arith phases A and C crystallizing together. At point m, the tem- erature remains constant with solid phases 4, B, and C ceystalliziag together until all liquid bas disappeared, ‘Tue final product will be a mixture of large crystals of A and C, and small crystals (eutectic mixture) of A,B, and C, ‘The composition of the solids crystallizing at any instant along é-mis given at the poiat where the tangent to the crystallization curve intersects that side of the ‘composition triangle representing the two solid phases coexisting. For example, at 6, it is indicated By the intersection of the tangent to the carve mist at the point 6 with the line 4-C at point 8”, The ratio of A to Cis given by the lever 8”-C/b"".4. The mean composition of the two solid phases that have erystal- 53 (a) W. ©, Geer, "Crystallization in Three-Component Systems." J. Pig, Chem, 8, 257-87 (1904). GY otat A 7 Fig, XIV —Thres-component system, AlOr-Ca0-SiOy, showing (2) boundary curves as solid lines, (2) composition lines (Aikiemade lines) as dashed lines. Tze Sal product of crystalization (on slow cooling) of ternary solutions Of this system always consists of thres solid phases whose fickés of stability are adjaceat. The same three solid phases will be the Saal product of crystallisation rox any folutioa whose composition lies within the triangle (com. orion tian) formed By Une! Jing te comoscose Of these three phases. in compound designations, © SCAG, A = ANOn S = SiO GA Rankia acd BR Waight, dm, J. Sci, dth Ser, 39, 62 (1015), (See Fig. 690 for revised ‘and redcawa diagram.) 8 Fic, XV.—Coure of crystalizatioe in a scape ternary system Oy Anderson, dim J. Sci, 4 Sen, 30, ear csi lized between points 5 and m is represented by the intersection of 2 line drawn through m acd and the side of the composition triangle at 4’, In this case itis amixture of d and Cia the proportion /-C/8'-4. The ‘mean composition af the total solid rrhich separates out between a and m (before B begins to crystallize) ia de- termined by drawing a line through m and a to the side of the composition triangle at a’.Mechanics of Crystallization-Térmary Systems During eutectic crystallization at m, the composition of the total solids changes from a’ to a, reaching the lat- ter point as the last drop of liquid disappears, ‘The method of calculating the amounes of solid sepa, rating between various temperatures by the use of tne lever rule as shown in the preceding paragraphs is the same as described in the case of the binary system. Fer example, in cooling a melt of original composition 44 from the liquidus temperature to poiat 5, the ratio of the amount of solid 4 crystallized ta the total amouat of the system is equal to a4/4-5 whereas the ratio of the amount of liquid of composition remaining at b is equal to o-A/4-5. Similarly, the relative amount of solid of mean composition a’ crystallized between ¢ and im (before B has begun to crystallize) is equal to a-m/- a/-m and the relative amount of liquid of eutectic com- position is equal toa-a'/a’-m, ‘The case ofa ternary system with a binary compound stable at its meiting point is discussed in connection with Fig. XIII(B). The exystalization in each sube system would be treated in the same manser as the above case, (System with ternary peritectice Ta Pig, XVT the ternary eutectic point m and the peritectic point, o, le om the same side of the conjugation line, CB, aud the binary eutectic points, i and j, lie on opposite sides. The Geld of A (A-j-0-8) extends across the conjugation ine, CAB, hence the system C-AB is not a true binary system. The tempergture along line om decreases according to the theorem of Allemade toward m, and 9 is aot 2 eutectic but a peritectic, In cooling a melt of composition a, solid phase 4 crystallizes out along a4. From 5 to 0, d and AB crystallize together and as the total composition of the solid separated between a and o ia given at a’, there ‘must be liquid left when o is reached. _The poiat a is within the composition triangle A- AB-C, and the final products of crystallization must be these three phases. It is evident from the diagram that the th 18 ZB, and C. Thesefore, the final solidification of com- Position « ust take place at o and not at m since a liev in the compositoa triangle witose solid phase areas meet ate. During the final soidifcation at o, sold phases Cand 4B crystallize while some of the phase, 4, is re- sorbed or dissolved. ‘The melt, «on the conjugstion Hae C.dB crystal lizes as follows: Along c4, 4 separates; along bo, and 4B seperate together; at , Cand AB separate aad 4 complealy diaoives, the al products of costal ation being only 4B and C. Ceystalization ati ‘variant points frequently involves more than physical processes and may involve chemical reactfons as well. At o, for example, with melt ¢ the following chemal reaction must secur: (solid) + B Ga liquid) = 43 (alg). ‘The melt, d, on the left of the conjugation ine in the composition triangle B-AB-C, crystallizes as follows: Along dz, A separates; along eo, Cand 4 crystallize together; at o, A dissolves and 4 is formed (tempera ture remains constant until all of diseppeas); along om, 4B acd C crystallize together. At m, the fact products of exystallization are 43, 3, and C, which is to be expected because the point dife in the composi, tion triangle 3-4B-C. The mean composition of the solid separating between d and o is represented by 4 At the moment at which all of 4 has disappeared at o and before exystallization begias to proceed long e-m, the mean composition of the solid has changed from a to d” and is composed of C and 4B. Along om, the ean composition of the solid changes from 4” to d” and daring the final erstalization at m from d” to d. (8) Systems with bath binary and lernary erilctice: Jn Fig. XVI, the quecrupie points, & and j, and the ‘quintuple points and m, lie on the same side of the Alt Kemadeline, C-AB. A meltof composition crystallizes asfollows: Along «+b, A separates;at thecompound dB begins to crystallize and d to cediesolve (the intersection Fra, XVI.—Ternary system containing a binary compound unstable st ce meting PO. Andersen. Am. J. Sei, 4h Ser. 39. 493 ibis.