OXFORD POL PHA G0. 40: OO) R. Koningsveld W. H. Stockmayer See blesOXFORD Great Clarendon Street, Oxford OX2 6DP Oxford University Press isa department ofthe University of Oxford, It furthers the University’s objective of excellence in research, scholarship, ‘and education by publishing worldwide in ‘Oxford New York Athens Auckland Bangkok Bogoté Buenos Aires Calcutta Cape Town Chennai Dares Salaam Delhi Florence Hong Kong Istanbul Karachi Kuala Lumpur Madrid Melbourne Mexico City Mumbai Nairobi Paris $io Paulo Singapore Taipei Tokyo Toronto Warsaw with associated companies in Berlin Ibadan (Oxford isa registered trade mark of Oxford University Press in the UK and in certain other countries Published inthe United States by Oxford University Press, Inc, New York OR Koningsveld, WH. Stockmayer, and. Nies, 2001 ‘The moral rights of the author have been asserted Database right Oxford University ress (maker) Fest published 2001 All rights reserved. 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Tite, ‘TPIO87.K66 2001 668.9—de21_00-066567 13579108642 ISBN 0 19 855635 7 (Hardback) ISBN 0 19 855634 9 (Paperback) ‘Typeset by Integra Sofiware Services Pvt. Ltd, Pondicherry, India Printed in Great Britain on acid free paper by ‘The Bath Press, AvonThis book is dedicated to the memory of Giinther Rehage, physical chemist par excellence, inspiring teacher and true friend, and of James A. Beattie, master of Gibbsian thermodynamicsContents Preface Glossary of symbols and abbreviations PART 1 Principles of Heterogeneous Equilibrium 1 Single-component systems 1.1 ‘Thermodynamic laws 1.2 Conditions for equilibrium between phases 1.3 Equilibrium curves 14 Further remarks on the p(T) diagram 1.5 Vapoutliquid equilibrium: p(V) diagram 1.6 Supercooling; irst- and second-order phase transitions 1.7 Exercises 2 Mixtures 2.1 Chemical potentials 22. The phase rule 23. Exercises 3 Binary systems, Bakhuis Roozeboom diagram 3.1 Phase rule 3.2 Two-phase equilibria 3.3 Three-phase equilibrium 3.4 ‘The Bakhuis Roozeboom p(7,x2) space diagram; phase diagrams 3.5._Rules for equilibrium curves and metastable extensions 3.6 Supercooling and vitrification 3.7 Exercises 4 Binary systems, partial miscibility inthe liquid phase, and supercritical phenomena 4.1 Introduction 42. Liquid/iquid equilibrium 43. Bakhuis Roozeboom diagram witha partially miscible liquid phase 44 Solidfiquid/iquid equilibrium 4.5 Supercritical phenomena; solubility enhancement 46 Exercises 5 Binary systems, solid solutions, and compounds 5.1 Solid solutions 45 4s 45 48 55 61-—_——- Vili, Contents 6.2. Partial misc 63. Crystalline phases 5.2 Compounds 5.3. Exercises ‘Ternary and multicomponent systems 6.1 Introduction 6.4 Appearance of vapour phases 65. Exercises PART 2 Simple Modelling 2 Modelling partial miscibility and solid/liquid equilibrium 7.1 Introduction 7.2. Liquid/liquid equilibrium 73. Solidfliquid equilibrium 74 Exercises PART3 Heterogeneous Equilibrium in 8 10 Macromolecular Systems Introduction 8.1 General remarks 8.2. Free enthalpy of mixing 83. Exercises Partial miscibility of strictly binary polymer systems 9.1 Introduction 9.2 Demixing of strictly binary systems 9.3 Binary polymer solutions 9.4 Binary polymer mixtures (blends) 9.5 Determination of cloud points 9.6 Blends containing statistical copolymers 9.7 Upper and lower critical miscibility (UCST and LCST) 98 Exercises Partial miscibility of quasi-binary polymer systems 10.1 General principles 10.2 Quasi-binary polymer solutions 10.3 Equilibrium among three liquid phases 10.4 Quasi-binary polymer blends 10.5 The theta temperature 10.6 Exercises ‘The influence of pressure 11.1 Introduction 11.2 Vapour/liquid equilibrium involving polymer solutions. 68 n 9 9 81 ao 97 98 101 101 lol 109, 13 117 117 18, 121 122 122 122 125 129 131 132 135 135 137 137 138 44 152 156 159 161 161 16111.3 Liquid/tiquid equilibrium in the absence of vapour 168 114 Exercises: m 12. Solid/liquid equilibrium m 12.1 Introduction in 12.2. Soli/liquid equilibrium in homopolymer systems im 123 Interference of solubility curve and miscibility gap 10s 124 Other factors 180 12,5 Copolymers 181 12.6 Exercises 182 13. (Quasi-)ternary polymer systems 184 13.1 Introduction ie 13.2 Two solvents, one polymer ie 13.3. One solvent, two polymers in 134. Three polymers 130 13.5. Exercises 192 14 Fractionation of polymers rf 14.1 Introduction 198 14.2 Fractionation by distribution among two liquid phases. 94 14.3 Fractional crystallization and dissolution 198 144 Fractionation by size-exclusion chromatography 200 145° Exercises 4 15 Miscellaneous phase transitions a 15.1 Introduction a 15.2 Mesophases; block copolymers zo 15.3. Mesophases; liquid-crystalline polymers 207 15.4 Equilibrium swelling of networks a 15.5. Glass transition aia 15.6 Flow oi 15.7 Thin films 20 Appendix 1 Spinodals and critical points 21 Appendix 2 Simple modelling for small-molecule systems 204 A2.1 Introduction 24 2.2 Eutectic behaviour 24 2.3 Partial miscibility 25 A24 Compounds 6 Appendix 3 Calculation of cloud-point, shadow, and coexistence curves in macromolecular systems 228 A3.1_ Molar-mass distributions 2s A3.2_ Coexistence conditions for (quasi-)binary systems 232 3.3 Coexistence conditions for (quasi-)ternary systems 236 A34_ Alternative procedures 240 Contents ixX Contents ‘Appendix 4 Simple modelling of equilibria in polymeric systems 256 dL Introduction 256 ‘A42 Practically binary polymer solutions 256 ‘A43. Polymer blends 262 ‘Add Quasi-binary iquid-erystalline polymer systems 268, ‘Appendix 5 Numerial evaluation of interaction parameters 2m ‘AS.1 Introduction mm 'A52_ Concentration and molar-mass dependence m AS3. Solubility parameters 273 A54 Chemical potentials 215 ‘ASS Higher derivatives of AG mn ‘A5.6 Sedimentation equilibrium 279 5.7 (Quasi-)ternary systems 279 A58 Copolymers 280 ‘A59- Interface analysis 281 Appendix 6 Molecular basis ofthe interaction parameter 282 285 Answers to exercises References 325 Index aPreface ‘The understanding and control of phase relationships isan increasingly import- ant requirement of modem polymer science and engineering. This fact has ’been the chief motivation of the authors in undertaking to prepare the present text. Increasing numbers of high-performance materials are polymer blends, ‘made by mixing two or more ingredients. For example, by the end of 1988, industrial production of such blends in the United States had risen to 20 percent of all polymeric materials, with a growth rate twice that of the total polymer figure; and this trend has continued. Several reasons for this development can be recognized. Probably foremost isthe prospect of substantial improvements in performance characteristics such as rigidity, toughness, abrasion resistance, chemical and flame resistance, heat resistance, and ease of processing. In addition, blends may offer possible economic bonuses such as lower cost, easier recycling, relatively rapid commercalization when based on already available constituents, and greater versatility of tailoring to match users’ needs. ‘A good summary of the practical importance of polymer blends is found on pp. 83-87 of arecent committee report entitled Polymer Science and Engineer- ing: The Shifting Research Frontier, National Academy Press. Washington, DC, 1994 ‘According to the properties desired, polymer blends as used may be either homogeneous polymer ‘alloys” or (more commonly) partially miscible, more or less finely dispersed two-phase materials. I is thus evident that polymet/ polymer compatibility is a central technical question (though of course not the only one) in the field of polymer blends ‘The production and processing of polymers are also influenced by the presence of phase separation and segregation, which may be either necessary or highly undesirable. For example, proper orientation and crystallization conditions are needed to secure useful fibres and films; on the other hand, segregation of highly viscous phases during a polymerization process may lead to catastrophic consequences like plugged lines or overheated reactors. Phase relationships are no less important in analytical and research laboratories 0 (isolated system, U and V constant) (11a) [dU]sy <0 (system at constant $ and V) carb) [Grp <0 (system at constant T and p) (le) [4ATny $0 (system at constant T and V) «id where the inequalities denote the direction of natural processes. Thus an JRolated system tends towards a maximum entropy; and a system Kept at con- Rant and p reaches equilibrium when its free enthalpy has attained its min jmum possible value consistent with the specified 7 and p. ‘One-component systems may consist of: one phase (crystalline solid: anisotropic liquid (‘Tiau liquid; or vapour) ‘eto phases (solid/liquid, eg. melting ice; liquid/vapour, ¢B~ boiling benzene; solid/vapour, e.g., subliming CO2) ‘etree phases (solid/iguid vapour, eg. water at 0.006 bat and +75 x 10-2°C; solid a/solid bivapour, eg, elemental sulfur at 10° bar and 956°C; anisotropic liquid isotropic liquid/vapour, &8 p-methoxycin- namic acid (0.06 bar; 185°C). For a two-phase one-component syst and b) the equilibrium conditions are: id crystal’; isotropic tem (with the phases indicated by 4 =P (mechanical equilibrium) (12a) 7, =T=T (thermal equilibrium) (126) (120) Gna = Gmb pies of phases a and b, respect- denote the molar free enthall (Je) by considering & where Gnas Gmb the last condition from ively, at Tand p. We can derive Equilibrium between phases 5"ponent systems sm containing Me moles of the substance in phase q closed one-component syste hat the total free enthalpy (an extensive quantity!) and ny moles in phase b, $0 of the system is G = mGnat MGme Now consider the transfer ofan infinitesimal phase to the other, = dng dn under the equilibrium (and p being constant), and G mu: we have aG= which (since dng is arbitrary in sign) leads to (12) ‘Similar arguments for three-phase equilibrium give (mechanical equilibrium) (thermal equilibrium) Gna = Gus = Gre 4.3 Equilibrium curves From (10b) we readily obtain the partial derivatives: From (8b) we have (ar)-7(er), = Gnade + Gaps = (Gna ~ Gnp)4a a3) quantity of the substance from one (14) conditions of Tand p. Since Ga and Gro remain fixed ist maintain its minimum equilibrium value, (sy (16a) (166) (160) (7) (18a) (18b) ay) (20) ay interms of the constant-pressure heat capacity C,. We may also note the mixed second derivative,-_() _ #6 _ fav (i, BTop (ir), 2), ic tots ne a the usefal Marvell relations. We donot have space 10 rive several intuitively credible stability conditions, tere without bo le stability conditions, stated here without av" Bp), $9 (oon-negative compressibility) 2) pO (non-negative heat capacity) ey The following inequalities involving vapourliquid (1/6) equiibru Joa ing vapour/liquid (v/é) equilibrium are Vous > Vine @3) Snw 2 Se 26) which become equalities at the vapour/liquid critical point Tp; and far from the critical conditions: Vy: Vic. It is also usually true that the molar volume of the liquid is larger than that of the Solid, Vm > Vas but there are a few exceptions including, of course, water; and we have Say > Smy Except for Be single almost incredible exception of ‘He between about 0.1K and The above equations dictate the shapes of curves for G(T) at constant p and. Gy(p) at constant 7, Fig. 1a and b. The drawn slopes and curvatures ae seen to be consistent with the non-negative nature of Sp and Vj, and with the negative curvatures as required by (19), (20), (23), and (24). These plots, though conceptually clear in describing phase relationships, are not of great practical use, as Fig. 1a gives the equilibrium transition temperatures at only a single pressure. We really need a family of such curves, one for each pressure, which in three-dimensional space would generate a surface Gy(T,p) on which two- phase equilibrium curves would appear as discontinuities in slope. The projec- tion ofthese curves onto the p-7 plane generates a practically useful diagram. Figure le provides a schematic illustration, ‘An exact thermodynamic relation for the slope of @ p(T) curve describing two-phase equilibrium in a one-component system is Clapeyron’s equation ap) AS 5 OH & J, AV” TAV 2) Where the subscript ‘eq’ denotes the phase equilibrium condition and AS, AV, AH refer to differences atthe T, p of the two-phase equilibrium point considered. To derive the Clapeyron equation, we apply (12c) to two-phase equilibrium states (phases a and b) at T, p and T + dT, p + dp. We have Gna(T.P) = Gaal T oP) iaMTsP)+dGny at T+ d7,p + dp and Gua(T,p) +4Gina Equilibrium curves 7 Fig.1 Molar enthalpy (Gibbs tree ‘energy) Ge, fora single-component ‘substance, showing slope and ‘curvature required by (17)-(22) (a) asatunction of Tat constant p, ‘equlrium meting and boting ports: TT’ (0) a8 a function of pat constant T, equilbrum boling and meling pressures: py, Py (6) Equiibrium molar fre enthalpy surface of a pure substance in Gq(T.p) space, The two-phase ‘equitria slv, sf, and tv are space ‘curves which intersect at the nan- vvaviants//v tpl point a. Projection ‘onto the p(T) plane isaiso shown, hich isthe phase diagram in Fig. 28 Single-component systems Hence, dna = dGuus and, by (100), ~SyaAT + Vind? = ~Sn dT + Vn dp ea which rearranges to ASn _ AS QVm AV 29) Observe that the molar quantities are not necessary, since only ratios are required. The final form of (27) above is based on combination of (10a) ang (12c), which gives Howe _ SH Sub — Sma = AS = a [Another commonly used symbol for this special enthalpy change, Aff, is (from the old name latent hea). : ‘We ean now construct the pressure-temperature diagram for a typical single-component system (Fig. 2). The steep slope of the solid/liquid equilib. rium curve is due tothe relatively small difference between Vn,e and Vg. AS mentioned earlier, this difference is usually positive, making dp/aT positive in View of (27) and the almost universal A, > O for fusion; the few exceptions include 130, Bi, Si, and Ga which show a negative slope for the ‘melting curve’ because in those cases AV < 0. 'A majority of solids kept under atmospheric pressure melt o aliquid upon heating: ie, the triple point, at which solid, liquid and vapour phases are in equilibrium, occurs at pressure less than I bar. However, some substances Fig.2. p(T) phase diagram fora pure have their triple points at pressures higher than I bar (e., NH,Cl, CO:,C) and substance showing tne irple Pol (A) herefore sublime (pass without melting from the solid into the vapour phase) . when heated under atmospheric pressure. Under pressures greater than the triple point value, they can of course melt directly into the liquid state upon heating. triple point Te 1.4. Further remarks on the p(T) diagram Each of the three curves in Fig, 2 describes the loci of a two-phase equilibrium. and obeys one of the conditions: Gna = Gat Gg = Guy (120) Gna = Gay At the intersection of any two of these curves, two conditions are simultan- cously satisfied: Gms = Gane = Gray (16) ‘Thus the third condition of (12c) is automatically satisfied, and so the third curve must also pass through the same point of intersection (the triple point).Ata triple point the three enthalpies of transition are not independent, and the same is true of the volume and entropy changes; for, as is true of all state functions, the relations fare, fone far-o 00 hold for any eyelic path. Henee, for example, Lay + Lee + Lea = 0 oe) or, more specifically, Lisublimation) = L(fusion) + L(vaporization) (2) Many possible processes can be simply understood from the p(T) diagram. For example, if an unsaturated vapour is slowly and isothermally compressed by aprocess starting at point ain Fig. 2, a two-phase vapour/liquid equilibrium pressure is reached at point A’ und the vapour starts to condense toa liquid. Itis 4 general finding that the pressure will not rise further until all the vapour has been transformed into liquid. In Chapter 2 we shall see thatthe phase rule pres cribes such behaviour. When all the material has been liquefied, the pressure can again increase (e.g., to point d). Thus the equilibrium pressure of a two- ‘phase one-component system does not depend on the relative or total amounts of the two phases. (This behaviour serves as a criterion of purty, since itis not trve of mixtures.) The p-T plane is divided into three areas, within each of which the substance is stable as a one-phase system. The curves separating these areas from each other delineate two-phase equilibria and obey Clapeyron's equation (27). ‘There is a single pressure and a single temperature (triple point) permitting three phases in equilibrium. Under these conditions the G(T) curves of Fig. 1a assume the location sketched in Fig. 3a, We note that the vapour is the most stable phase at T > Ty whereas the solid has the lowest Gy at T < Ty. Consequently, cooling an unsaturated vapour at p* and passing Ti, in the process will be accompanied by a vs phase transition, It can be seen in Fig. 1c that a similar situation exists when a two-phase system (e.g. &) is cooled while the equilibrium is maintained, in other words, with an appropriate change of the pressure. The extension of the é/v curve in Ga(p, 7) space beyond the triple point lies above the surface representing the stable solid phase, s. As a consequence, the fv equilibrium is less stable in that (p,7) region and, passing Ty in the process, the system will usually undergo a phase transition é + v — s. This statement is valid also for the other two two-phase equilibrium curves (s/v and s/é) and can be formulated quite generally as follows. If two two-phase equilibrium curves intersect, a new phase must appear and both, or at least one, of the original phases disappears. In the later case, another two-phase curve is followed (c.g., sv, if T and p of an flv equilibrium are lowered beyond the triple point). Figure 2 supplies further details of the slopes of the two-phase curves ‘meeting in the triple point. At pressure p, the three Gu(7) curves will have The p(T) diagram 9 Fig. 3. (a), (0) Necessary course of Ga(7) curvesin the vicinity ofthe triple point (see Fig 2); (c) (7) diagram showing the correct location of tha a/c equilibrium curve (ower line) and the impossible course (upper line); (@illustration ofthe impossibility of the ‘extension of equilibrium alc according tothe upper curve in).10 Single-component systems Fig.4Furherillutration of the Correct (top) and incorrect (bottom) textension ofa two-phase equilibrum ‘curve beyond a triple point. the appearance of Fig. 3b and we see thatthe (equilibrium (M) occuyy ap T < TS and ata larger value of Gy than that ofthe Solid phase, which i qe most stable. This argument demonstrates that the extension of a two-phaye curve beyond a triple point must lie between the other two intersecting tue. hase curves. ‘An alternative derivation of this important rule is suggested by Figs, 3¢ ang 4. Consider the aicequilibrium at 7). The heavy curves represent the situation in accordance with the extension rule stated above. Ifthe a/c equilibrium occurred at an equilibrium pressure lower than that of the equilibrium a/b, there would have to be tWo Gy curves (a and (a) in Fig. 34). Since Gy is, at constant 7, 4 single-valued function of p, such a situation is not possible, Hence, shifting ‘curve a to (a) would then only move the intersection a/b to a pressure lower than that of (ale), and the original equilibrium situation is recovered. “These considerations can further be illustrated with (29) and (32), The volume changes forthe transitions s —+ v and & —+ ydo.not differ much so that the difference in slope ofthe two two-phase curves at Ti largely determined by the value of Aly. Thus, the sublimation curve has the larger slope at 7 and, ‘consequently, the extension ofthe flv curve at T”< Ty, must ie above the p( 77) ‘curve for s/v. This statement is exemplified by the following kind of experi- ‘ment, Most liquids can be supercooled below the triple point (e.g, point K, Fig. 2) and kept in this metastable condition for some time. Imagine connecting bulb withthe supercooled liquid through an initially evacuated tube toa bulb containing crystals of the same substance atthe same temperature. After atime it will be observed that the second bulb gains weight atthe expense ofthe first ‘one. Evidently the supercooled liquid (point K in Fig. 2) has a higher vapour pressure than the crystalline solid (point L) atthe same temperature, Two quite ‘general rules can be stated: 1. The more stable phase has the lower equilibrium vapour pressure. 2. Phase stability changes ata point of intersection of two-phase equilibrium curves, eg. v+ 6. ‘Asa consequence, the three two-phase equilibrium curves intersecting at the triple point must do so at angles all less than 180°, so that extension of any one ‘of them leads toa new stable phase at equilibrium and the disappearance of at least one phase. In Fig. 4 (top) we see that a decrease of T will turn the two- phase equilibrium bc into a, according tothe phase reaction: b+ ¢ —» a and thus give rise to the formation ofa new stable phase. The same process would bbe accompanied by the phase reaction b {@, ¢ ifthe two-phase curve ble would incorrectly extend into the one-phase ¢ range, in which case no new phase is formed, We shall see later that similar useful rules can be formulated for binary systems and, in fact, for systems containing any number of components; see Sections 3.5 and 6.2.5.2 and Reef. 3,55, Exploration of the p(T) field to higher pressures very often reveals the existence of polymorphism: different crystal structures ofa substance become stable phases indifferent areasofthe diagram, Thereader will probably recallthe rich p(T) diagram for water, with several triple points involving two differ- ent solid forms and the liquid, or thre different sold forms. For high polymers, ofplat roy 50 700 300 00 Fig. 5. Pressur-temporture phase re phase agra or polsrauroathyere) Noe the Change of pressure sea between ne ohalvscl Rodagran The Vol fon sax fatter urcoain an teretre shown mparteses, Vou raves cannot be senih thet becase ty occur at screen reser triple points involving a vapour phase would occur only at meaninglessly low pressures, and have not been observed, However, polymorphism isnotunknown, though perhaps rarer than in the world of smaller molecules, and the equilibrium curves are usually also harder to establish experimentally, forkinetic reasons. A relatively diversified p(T) diagram is found inthe case of poly(tetrafluoroethy- Tene), which shows no less than four different crystalline phases (Fig. 5). Additional features are found in p(T) diagrams for substances capable of forming liquid crystals. An example is given in Fig. 6 for p-methoxycinnamic acid: there is a triple point at 169 °C for equilibrium among crystalline solid, nematic liquid, and vapour, and a second one at 185°C involving nematic liquid, isotropic liquid, and vapour. 1.5 Vapour/liquid equilibrium: p(V) diagram The Helmholtz free energy, (9a), is illuminating for discussion of isothermal p(V) behaviour. From (9b) we obtain the derivatives ‘an (w), PA ov}, Isotherms of A(V) and p(V) are sketched in Figs. 7a and b, respectively, and show the necessary behaviour for vapourMliquid (»/¢) equilibrium. Thus, (12a) requires that the slope of the A(V) curve be the same atthe volumes correspond- ing tothe two phases in equilibrium. Moreover, (1c) requires, by (9a)and (10a), @3) G4) (A+pV), =A+PV 5) Ay ~Ac= PVs VO) Vapourhiquid equilibrium 11 160 200 Fig. 6 Pressure-temperature phase ‘dagram for pmethoxyeinnamic ci”. Fig.7__The relationship between the Helmholtz free eneray A (a) and pressure pb) as a function of Vat constant T.i 12 Single-component systems sn esta tn tii ha Spin “ich se ha ni i oes A ee eta voones is eats neeeeae con, ee on ogi Ses ihe tee System is univariant (see Section 2.2) and T has already been chosen, the pressure must remain constant at p* as Tong as the two phases coexist Le until the volume reaches the value V;* at point ‘A’. Upon: further ‘decrease of V' the one-phase Tiquid region (e.g. t0 point d) the pressure rises again, quite steeply because ofthe small compressibility of liquids. Between points A’ and BY of Fig. 7b, where the system consists of two phases, we can write (as for any extensive property; compare (13)) V = mVaxe + Vine ing one mole of the substance, this becomes point B’ i For a system contai 36a) Vn = (1 =a Wing + 0Vne 66) Am = (1 =) + Ame Where x, is the amount in moles of substance in the vapour phase. Elimination of x, between the two equations yields @7) Which is the equation of a straight line passing through points A and B of Fig. 7a and lying below the curve ACEDB, as it must since the condition of equilib- rium in a system of fixed volume and temperature is (d4)py <0 «tay ‘The unstable one-phase curve ACEDB has a central portion, between the inflexion points C and D, displaying negative curvature of the function A(V). From (34) this is seen to correspond to negative compressibility and therefore to a violation of the stability criterion (23), and is called a region of instability, In Fig. 7b this region ies between points C’ and D’. The portions AC and DB of the A(V) curve are called metastable and can actually be observed for limited periods of time under suitable conditions (‘superheated liquids’ and ‘super- cooled vapours"), The special points C and D, or C’ and DY, are called spinodal points (see Appendix 1), and correspond to the limits of instability: (wr) - Cer, In the two-phase region the relative quantities of the two phases can be seen from (36a) to be given by 0 (spinodal condition) (38) Se Vary ae 9) an example of the lever rule.Supercooling; phase transitions 13 aa). =0 (critical condition) (40) In accordance with this condition, the critical p(V/) isotherm has a point inflexion with a horizontal tangent rake Ucoronber grin 2 the critical point. Values ofthe critical tener, volume, and presse TVs and tay eciaeea a substance to substance, but the dimensionless ratio % =). Vi, URT. fra oe from invariant (a8 would be consistent with the principle of conespunding states*! »» lying in the range 0.27-0.29 for ‘Most substances (R is the gas constant). The Van der Waals equation of state is somewhat off the mark, predicting a value of 0.375. A typical p-V diagram fora simple fd including the critical region is shown in Fig, 8 forthe example of methane, CH, Above the eitical temperature 7. the distinction between lgud and vapour is lost, and there is only a single fluid phase, often called a supercritical fluid (especially when under pressures moderately above p), As seen in Fig iis Possible to pass from a vapour (e.g., point a) to aliquid (point d )by a path such as abcd, involving isobaric heating to a supercritical temperature, followed by isothermal compression and eventual isobaric cooling, along which note phase states occur, Superritical fluids may have considerable solvent power and thus have been involved in some useful applications, including liquid chromatography, oil extraction processes, and decaffeination of coffee beans", 1.6 Superoooling; first- and second-order phase transitions Crystallization of polymers requires disentanglement and alignment of the chains, and therefore requires @ long enough time so that at any practical rate of cooling from the melt there will be observable supercooling before crystals, form, Thus, metastable amorphous states may exist for long times. Indeed, the molecular architecture of some polymers (e.g., atactic polystyrene and atactie poly(methy! methacrylate) isso iregular that crystallization does not occur at all. Such materials exist as highly viscous liquids as well as supercooled crystallizable polymers. As the temperature is lowered, a glass transition vitrification’) occurs over a rather narrow temperature range, where flow ceases for any practical time scale and where both the thermal expansion and the heat capacity fall to lower values. The glass transition moves to higher temperature when the pressure is raised®. ‘The phase transitions which are the subject of the classical theory of heterogeneous equilibria are known as first-order transitions, because they ‘are accompanied by discontinuities in the frst derivative of G with respect to T ot p, as seen in Fig. 1. Thus, according to (17) and (18), Vand S change abruptly at a first-order phase transition. If the glass transition were really 1000700 10SCS Fig. 8 Pressure-consiy clagram for ‘methane. Solid curves: gathers for Indicated temperatures (in). Dash- ‘ot curve: vapourfiqud coexistence ‘region wit eriical point (0) at 191 K ‘and 46 bar",14 Single-component systems assified as a second-order transition, since the gy, 3. (OVIOT), and Cp. are Second derivatives Showing discontinuities, (OV! = Gui sowing nenon is Fund in polymeric systems when Fst ang: An der transitions interfere (Chapter 15). ae sharp, it could be cl 1.7 Exercises vas ien gases donot condense ad do 00% show cia 1 rove that Hea 6 uae has a tiple pont at 136-C among Pa ela apou. The wo-phase cure for nme a a falape of 21 bak andthe volume chan aor ae wo.8Sem/mole. Calculate the molar entropy ie aessethe nematic isotopic wansition, stating the wns of yourqnet 4, Which solid phase of poy(tetaluorocthylene) (PTFE) has the hgnes densiy is. 3)? 1 ns Te nt of PTFE under atmospheric pressure, Tx = 6017 tae nme of te molten polymer is 31.8em"mol CF>, and that of ir saline phase I (as determined from X-ray measurements on unis SReensions) is 243cm/mol CF2. The slope of the melting curve $0.2 bar/"C. Find the heat and entropy of fusion per mole of CF in Susi. (Note: The piven data are for PTFE crystallized from the met, correct Mtoe crystallinity.) Somewhat different results are found for “virgin as-polymerized material : ‘5, The known triple points of water occur at the following temperatures and 2. The pressures®: Phases" Temperature (‘C) Pressure wn 4001 4.58 Tor va 220 207 MPa va 347 213 MPa naw 243 344 MPa we “170 346 MPa wim 40.16 625 MPa wenn 4816 2.20GPa wv 2.45 ca. 22GPa "Roman numerals refer to forms of ice. Sketch the p(7) diagram, using dashed lines where you are guessing. 6. Integrate Clapeyron's equation to estimate the limiting value of the vapour pressure p when T’ —+ 0. Assume AH of evaporation to be independent of ;p and to depend linearly on T. Neglect the molar volume of the liquid phase with respect to that of the vapour, which can be assumed to be ideal. 7. At the vapour/liquid critical point of a fluid, the surface tension o of the -vapour/liquid interface must vanish since the two phases become identical. If experimental data for the surface tension of a molten polymer as a func= tion of temperature are extrapolated, a temperature is found where the ; extrapolated surface tension vanishes, and this could be regarded as defining 4 vapour/liquid critical temperature for the polymer.(@) For molten linear polyethylene, the surface tension at -+150°C is ‘measured to be 28.1 x 10-* N/m, and at this temperature the tempera- {ure coefficient isdo/4 = —58 x 10-® N/m°C. Assuming that o varies linearly with temperature over the entire range, find by extrapolation the presumed critical temperature of this polymer, (©) Actually the linear relation suggested in part (a) cannot hold up to the critical point, for it implies a non-vanishing surface enthalpy at the critical point. A better relation is o = K(T ~ 7), where the exponent bis about 1.25, Assuming this relation, finda better extrapolated critical temperature for polyethylene. (©) Speculate on the nature ofthe fluid polymer phase at this unattainable critical condition. ‘The stable crystalline form of polyethylene at atmospheric pressure is orthorhombic (or), and the melting, point (for linear materials) is about 145°C. Recently a triple point has been confirmed for the polymer, at about 245°C and a pressure of about 4.5 x 10° bar, te third phase is @ hexagonal crystalline phase (hex)®. Using the quantities (per mol CH2) estimated below and employing (27), sketch the p(T) diagram in the neighbourhood of the triple point. V = 16.4cm>; Vey = 14.0.cm; Vaex = 14.6cm*; entropies of fusion: AS scp = 2.4 cal/K; ASje, = 1.Teal/K. ‘The phase diagram of p-ethoxybenzoic acid shows two triple points as follows: solid/nematic liquid (&,Y/isotropic liquid (6): 195°C, 6 bar solid/smectic liquid (Cim)/nematic liquid: 197.5°C, 90 bar. = Ata pressure of 150 bar two-phase transitions occur at 198.5°C, 203°C, and 213°C. Sketch the p(T) diagram covering the range 190-220 °C and 0-200 bar”. Exercises 15