Phase-Separating Binary Polymer Mixtures: The Degeneracy of the Virial Coefficients and Their Extraction from Phase Diagrams.

The Edmond-Ogston model for phase separation in binary polymer mixtures is based on a truncated virial expansion of the Helmholtz free energy up to the second-order terms in the concentration of the polymers. The second virial coefficients (B 11, B 12, B 22) are the three parameters of the model. Analytical solutions are presented for the critical point and the spinodal in terms of molar concentrations. The calculation of the binodal is simplified by splitting the problem into a part that can be solved analytically and a (two-dimensional) problem that generally needs to be solved numerically, except in some specific cases. The slope of the tie-lines is identified as a suitable parameter that can be varied between two well-defined limits (close to and far away from the critical point) to perform the numerical part of the calculation systematically. Surprisingly, the analysis reveals a degenerate behavior within the model in the sense that a critical point or tie-line corresponds to an infinite set of triplets of second virial coefficients (B 11, B 12, B 22). Since the Edmond-Ogston model is equivalent to the Flory-Huggins model up to the second order of the expansion in the concentrations, this degeneracy is also present in the Flory-Huggins model. However, as long as the virial coefficients predict the correct critical point, the shape of the binodal is relatively insensitive to the specific choice of the virial coefficients, except in a narrow range of values for the cross-virial coefficient B 12.

Introduction

Phase separation of a binary mixture of polymers in a common solvent into two liquid phases is a well-established phenomenon and is discussed in many recent[1−3] and older reviews.[4−9] It is a topic of both fundamental interest and practical importance, with applications in diverse fields like polymer physics,[10−17] cell biology,[18−21] and food technology.[22−25] Particularly, when phase separation is incomplete on a macroscopic scale (also known as microphase separation), phase-separated polymer mixtures show properties that the individual polymers do not possess,[26] for example, large deformation and rupture properties in gelled phase-separated systems.

The simplest theoretical descriptions of phase separation in polymer mixtures are the Flory–Huggins[27] and the Edmond–Ogston models.[28] Such models are useful because they are the minimal models necessary to capture all of the essential physics and properties of phase separation with reasonable accuracy. Clark showed that both models are equivalent up to the second order of the expansion in the concentrations.[29] The present paper focuses on the Edmond–Ogston model rather than on the Flory–Huggins model because the former has a slightly more straightforward basis in thermodynamics, is not formulated on a lattice, and can in principle be readily extended to higher-order terms in concentration.

The Edmond–Ogston model is based on a truncated virial expansion of the Helmholtz free energy up to the second-order terms in the concentration of the polymers[28,30−32] and is therefore sometimes referred to as the virial model. The use of the Helmholtz free energy implies that the demixing of the mixed polymer solution does not cause a change in the total volume of the system, which is reasonable as the typical system under consideration consists mostly of solvent. The three parameters in the model, describing the pair interactions between the polymers, are the so-called virial coefficients (B11, B12, B22). In principle, the virial coefficients can be obtained experimentally from, e.g., membrane osmometry,[9] static light scattering,[33] or analytical ultracentrifugation.[34] It is noted that these measurements are often experimentally challenging for reasons depending on the specific technique used.

Also, the small number of parameters involved raises the hope of being able to generate a database of virial coefficients that allow for a fair (if not fully quantitative) prediction of the phase behavior for a wide range of binary polymer mixtures. Such a database could be generated by extracting the virial coefficients from experimental data. This requires a thorough understanding of the mathematical structure of these models. However, some gaps exist within this area that need to be filled. The database does not require the highest level of accuracy but needs to be sufficiently precise to guide a researcher evaluating a large number of potential biopolymer combinations.

In a recent paper,[31] a number of new results were obtained for the Edmond–Ogston model (analytical expressions for the critical point and for the binodal in the “symmetrical” case, where B11 = B22). It was shown that provided one of the virial coefficients is known, the other two virial coefficients can be determined from either (1) the location of the critical point or (2) the composition of a pair of co-existing phases.[31] If none of the virial coefficients is known, an infinite number of solutions for the triplets of virial coefficients (B11, <span class="Chemical">B12, B22) is found. It is shown here that this stems from a degeneracy in the mathematical formulation of the problem, where all of the triplets derived from the specific properties (1) or (2) above are located on lines in (B11, <span class="Chemical">B12, B22)-space or B-space. These lines in B-space intersect at a single point, corresponding to the actual set of virial coefficients. It is noted that given the equivalence of Edmond–Ogston and Flory–Huggins models, this degeneracy is also essentially present in the latter model.

The properties of the phase diagram are described by a set of nonlinear algebraic equations that are, even numerically, not trivial to solve. It turns out that progress can be made by parametrization of the governing equations by introducing the slope of the tie-lines (i.e., the lines connecting the co-existing phases located on the binodal in the phase diagram) as a new parameter. By introducing this parameter, a symmetry property of the equations is revealed, thereby simplifying the original problem to basically a two-dimensional problem. We have chosen to sketch the main line of thought in the main text and have given the mathematical details of the derivations in the Appendices I–X.

Results and Discussion

Characteristics of the Phase Diagram

The overall phase diagram of a binary polymer mixture in a common solvent displays a number of key features (see Figure ). The binodal indicates the border between the stable and metastable regions, whereas the spinodal separates the metastable and unstable regions in the diagram.[35] Binodal and spinodal share a common tangent at the critical point, which is the only point where the stable region directly borders the unstable region. In the metastable region, phase separation takes place via a nucleation and growth mechanism and only proceeds when concentration fluctuations are large enough to overcome the free energy barrier that hinders phase separation. In the unstable region, phase separation takes place spontaneously by a process called spinodal decomposition, when concentration fluctuations increase unhindered because no free energy barrier exists. In the stable region, no phase separation occurs. A polymer mixture formulated to be in either the metastable or unstable region ultimately separates in a pair of distinct co-existing phases, which can be displayed in the phase diagram as being connected through a so-called tie-line. Any mixture formulated along the same tie-line ends up with compositionally identical pairs of co-existing phases, the difference being their relative volumes that can be derived from the so-called lever rule. Furthermore, all mixtures formulated along the same tie-line have identical osmotic pressure because all of these separate in the same pair of co-existing phases (albeit at different relative volumes) that have the same osmotic pressure. A more detailed explanation on the calculation of the critical point, spinodal, binodal, tie-lines, and phase volumes is given below. In a previous study,[31] we have derived several characteristics of the phase diagram in dimensionless concentration units. In the next sections, these results are extended and given in terms of molar concentrations, allowing for a more direct comparison with experimental phase diagrams. Molar concentrations were chosen because this allows for virial coefficients, osmotic pressure, and chemical potential to be expressed in familiar units as well.

Figure 1

Typical phase diagram for a polymer mixture for (B11, B12, B22) = (1, 3, 4) (m3/mol). The binodal (red solid line) separates the stable region (below the binodal) from the metastable and unstable regions. The unstable region can be found above the spinodal (blue dashed line). The binodal and spinodal intersect at the critical point (solid circle), where they share a common tangent. The tie-lines (dashed-dotted line) connect the co-existing phases located on the binodal. The mixture (c1, c2) phase-separates along a tie-line connecting phases I and II with phase volumes VI and VII, which can be determined from the length of line segments L1 and L2 and the lever rule (cf. eq ).

Typical phase diagram for a <span class="Chemical">polymer mixture for (B11, <span class="Chemical">B12, B22) = (1, 3, 4) (m3/mol). The binodal (red solid line) separates the stable region (below the binodal) from the metastable and unstable regions. The unstable region can be found above the spinodal (blue dashed line). The binodal and spinodal intersect at the critical point (solid circle), where they share a common tangent. The tie-lines (dashed-dotted line) connect the co-existing phases located on the binodal. The mixture (c1, c2) phase-separates along a tie-line connecting phases I and II with phase volumes VI and VII, which can be determined from the length of line segments L1 and L2 and the lever rule (cf. eq ).

Governing Equations

In the present model, the Helmholtz free energy F(J) of the mixture readswhere R is the gas constant (J K–1 mol–1), T is the absolute temperature (K), V is the total volume of the system (m3), n1 and n2 are the number of moles (mol) of polymers 1 and 2, respectively, B11 is the second virial coefficient of polymer 1 (m3 mol–1), B22 is the second virial coefficient of polymer 2 (m3 mol–1), and B12 is the second cross-virial coefficient between polymer 1 and polymer 2 (m3 mol–1). Only situations where all virial coefficients are positive are considered. Although only the terms up to the second order in the concentration are taken into account, this simple model still captures all essentials of phase separation with fair accuracy. The above expression for the Helmholtz energy leads to a set of co-existence equations that are the same as derived earlier by Edmond and Ogston.[28] If higher accuracy is required, this model can be straightforwardly extended to include higher-order concentration terms in a consistent way. For the Flory–Huggins model, such an extension is not obvious as binary interaction parameters already show up in the higher-order concentration terms, and the Maxwell relation does not seem to be fulfilled (see Appendix I). It is noted that the higher-order virial coefficients are difficult to be determined experimentally because they reflect the effects of interactions between three polymer particles for the third order, between four for the fourth order, etc. The contribution of such higher-order interactions is usually small, especially in the dilute-to-semidilute regime, making an extension to higher-order concentration terms to be of limited practical value.

The second virial coefficient B is defined by[36]where NA is Avogadro’s number (6.02 × 1023 mol–1), w(r) is the potential of mean force as a function of the distance r between segments of <span class="Chemical">polymer i and <span class="Chemical">polymer j, kB is Boltzmann’s constant (1.38 × 10–23 J/K), and T (K) is the absolute temperature. In eq , it is, without loss of generality, assumed that the force is isotropic.

Using the thermodynamic relation for the osmotic pressure Π, the following expression is obtainedwhere c = n/V is the molar concentration of polymer i (mol m–3) with i = 1, 2 for polymers 1 and 2. This is a hyperbola with asymptotes , where c1, = (1/2)(B22 – B12)(B11B22)/B122 and c2, = (1/2)(B11 – B12)(B11B22)/B122.

The chemical potentials μ (with i = 1, 2) relative to the standard chemical potentials are given byIt is noted that eqs and 5 satisfy the Maxwell relation, confirming that the Helmholtz free energy F is a state variableWhen the system separates into two phases, I and II, the following co-existence equations hold[35]Alternatively, eq can be formulated in terms of the chemical potential μs and the partial molar volume υs of the solvent using the thermodynamic identityIt is noted that the Gibbs phase rule for binary mixtures (see Appendix II) in principle allows for a three-phase equilibrium without any degrees of freedom left and therefore corresponds to a fixed composition of the three co-existing phases. This situation is not taken into consideration.

From the conservation of mass for both polymers, two additional equations are found that correspond to the so-called lever ruleandwhere cI and cII denote the molar concentrations of polymer i in phases I and II, respectively, and c still reflects the total concentrations of polymer i (with i = 1, 2). Here, γ is defined aswhere VI is the volume of phase I and VII is the volume of phase II.

Equations and 12 correspond to the lever rulewhere VT is the total volume after phase separation. L1 and L2 are the line segment lengths on the tie-line on which the <span class="Chemical">polymer mixture (c1, c2) would be located without phase separation (cf. Figure ). From eqs –9 and 3–5, the following co-existence equations are found from which the co-existing phases can be calculatedThe criterion for phase separation is given by[37]This set of equations (eqs –17) is invariant under the transformationwhere k is a constant, and to interpret the physical meaning of this invariance, the special case of a hard-sphere dispersion can be considered. The volume fraction φ1 of a hard-sphere dispersion equals <span class="Species">B11c1/4.[31] This implies that eqs –9 can be written completely in terms of volume fractions, making the phase behavior of hard-sphere mixtures length-scale-independent. In the general case, the physical meaning of the invariance is less obvious but still holds mathematically. This consideration was also the reason for introducing reduced variables (e.g., and ) in the previous study.[31] It is noted that within the Flory–Huggins theory, the governing equations are usually formulated in terms of volume fractions.

Critical Point

There are different expressions available relating the molar concentrations of the critical point (c1,, c2,) to the virial coefficients. By means of stability analysis,[38] the critical point was previously found to be a solution of a third-order polynomial in terms of (either eq A.8 or eq 40 in Dewi et al.[31])orThese two expressions are equivalent and can easily be converted into each other by division by a factor . It is also noted that the substitution (B11, <span class="Chemical">B12, B22, S) → (B22, <span class="Chemical">B12, B11, 1/S) transforms eq into eq and vice versa. Here, −S corresponds to the slope of the binodal and spinodal at the critical point (in molar concentration units), which is given bywith(Note that to simplify the notation, the accent for the slope in molar coordinates was dropped in the present paper. Therefore, the quantity referred to as −S in the present paper is the same as −Sc′ in the previous work.[31,32]) Explicit expressions were derived for the coordinates of the critical point (eqs 47 and 48 in Dewi et al.[31]), which read in molar concentration unitsThe equivalence of the second and third terms in eqs and 25 is demonstrated in Appendix III and requires the use of eq 20 or 21. The expressions in the third terms in eqs and 25 are the most convenient ones to be used when working in molar concentrations.

The invariance of eqs –17 under multiplication of the virial coefficient B by the same factor k (cf. eq ) further implies that the slope −S at the critical point remains the same under this transformation. However, the critical point, binodal, and spinodal shift simultaneously by a factor 1/k closer to the origin (cf. Figure ). The explicit expressions for the critical point, eqs and 25, can also be used to verify the useful relation given in the work of Edmond and Ogston (eq 5a,b in Edmond and Ogston[28]), which reads in the present notationIn Appendix IV, it is demonstrated that these equations are equivalent to eq or 21. Since the critical point (c1,, c2,) is determined from two equations containing three virial coefficients (B11, <span class="Chemical">B12, B22), it follows that for every critical point there is an infinite number of solutions for the virial coefficients triplets (B11, <span class="Chemical">B12, B22) that correspond with this critical point. Therefore, to uniquely determine the virial coefficients from just the location of the critical point, at least one of the virial coefficients should be known.[31] Suppose that triplet (B11, B12, B22) gives the same critical point as triplet (B11*, B12*, B22*), they have to satisfy the relationas a consequence of eqs and 25. This corresponds to a line in “virial coefficient space” or B-space that can be written in vector notation aswith λ1 being any real number, while ensuring that and that all B’s are larger than zero. A support vector can be found by choosing an arbitrary real value for B11 (i.e., B11 = 1) from which B12 and B22 can be calculated from eqs and 25 or 26 and 27. All triplets (B11*, B12*, B22*) lead to the same critical point with the slope −S at the critical point, as is demonstrated in Appendix V. Note that for this to be a critical point as well, the new virial coefficients also have to satisfy the criterion with the third-order polynomial for the critical point (cf. eq ).which is also proven in Appendix V.

Figure 2

Illustration of the scaling behavior of the equations. Taking (B11, B12, B22) = (1/k, 3/k, 4/k) (m3/mol) for k = 1–4, it is observed that the corresponding critical point (solid circle), spinodal (blue dashed line), binodal (red solid line), and tie-lines (dashed-dotted line) shift in the phase diagram from the bottom left to the top right for k = 1–4. All curves superimpose on the curves for k = 1, if the axes (c1, c2) are scaled as (c1/k, c2/k).

Illustration of the scaling behavior of the equations. Taking (B11, <span class="Chemical">B12, B22) = (1/k, 3/k, 4/k) (m3/mol) for k = 1–4, it is observed that the corresponding critical point (solid circle), spinodal (blue dashed line), binodal (red solid line), and tie-lines (dashed-dotted line) shift in the phase diagram from the bottom left to the top right for k = 1–4. All curves superimpose on the curves for k = 1, if the axes (c1, c2) are scaled as (c1/k, c2/k).

Spinodal

The condition for the spinodal (c1,sp, c2,sp) is given by (see, e.g., Ersch et al.[30] or Dewi et al.[31])or[30]Therefore, every point on the spinodal can be written in the following formwhere −Ssp is the tangent to the spinodal in this point and Ssp ranges from ∞ to 0, as can be demonstrated by substituting eq in eq . Now, it is easy to determine the asym<span class="Chemical">ptotes of the spinodal. For , the absolute value of the slope of the spinodal behaves as Ssp → ∞ and c2,sp → ∞. For , the absolute value of the slope of the spinodal behaves as Ssp → 0 and c1,sp → ∞. Note that due to the phase separation criterion in eq , the asym<span class="Chemical">ptotes for phase-separating mixtures are always found at positive (and physically relevant) concentrations c1,sp and c2,sp.

Tie-Lines

Suppose that the molar composition of two co-existing phases (c1I, c2I) and (c1II, c2II) are known. These values can be substituted in eqs –17, and a set of three linear equations in the three virial coefficients are obtained asWhen the virial coefficients are considered as the variables, the determinant of these sets of equations equals zero (cf. eq 104 in Dewi et al.[31]), leading to the conclusion that there is not a unique solution but an infinite number of solutions for the virial coefficients (B11, <span class="Chemical">B12, B22). The condition for having an infinite number of solutions is expressed by the conditionInterestingly, this equation does not contain the virial coefficients explicitly and provides an excellent check on the accuracy of the experimental or numerical determination of the composition of the co-existing phases, since it holds for all co-existing phases. The set of virial coefficients (B11, <span class="Chemical">B12, B22) can be obtained from eqs and 36, when one of the virial coefficients is known.

If phase separation takes place, eqs –36 can be used to determine the composition of the co-existing phases. In a previous study, it was shown that the composition of the co-existing phases could be determined numerically using the method of steepest descent.[31] Here, it is shown that the structure of the equations for the co-existing phases becomes clearer by introducing the slope of the tie-lines explicitly. As a first step, corresponding to the requirement of equal o<span class="Chemical">smotic pressure for the co-existing phases, eq is written asThe slope of the tie-lines −S is given bywhere the tie-lines connect the co-existing phases (c1I, c2I) and (c1II, c2II). The last term in eq follows directly from eq . (Note that S is defined here in terms of molar units and is the same as the parameter S′ used in Dewi et al.[31]). By introducing (c1,, c2) as the midpoint of the tie-line by

equation can be rewritten <span class="Chemical">asAfter introducing the variables (c1,, c2,) asequations –42 can be combined, and the following relation is obtained

This can be written, using eq and refraining from a formulation in terms of midpoints of the tie-lines again, as

Also, the definition in eq can be rearranged asThe expression for eqs and 46 can be combined using matrix notation asBy adding and subtracting the rows in eq , the above matrix equation can be rearranged in the formIntroducing the parameter S may seem like a step back, since it adds a fourth equation to the co-existence eqs –17. However, the expressions for (c1,, c2,), eq , can be used to rewrite eqs and 17 in a solvable form (see Appendix VI)As a result, the original three co-existence eqs –17 are now replaced by four equations (eqs –50). The solutions of eqs –50 can be expressed in terms of the so-called Lambert-W function,[39] previously already invoked to solve the symmetrical case where B11 = B22,[31] aswhere, for the remainder of this paper, the (arbitrary) convention is used that the “lower right” phase with c1I > c1, and c2I < c2, is labeled I and the “upper left” phase with c1II < c1, and c2II > c2, is labeled II, in line with Figure . This convention can be used because the co-existing phases (c1I, c2I) and (c1II, c2II) should always be in diagonally opposite quadrants relative to the point (c1,, c2,). Substitution of eq in eq leads toEquation becomes in this notationProgress has been made by parametrization of the problem, where the original four-variable problem (c1I, c2I, c1II, c2II) has been effectively reduced to a two-variable problem ((c1I, c2I) in eq ), where S acts as a parameter that has to be chosen in the interval [S,S∞] or [S∞,S], depending on whether S or S∞ is <span class="Chemical">smaller. Here, S∞ is the absolute value of the slope of the tie-line in molar units far away from the critical point, as demonstrated in the Appendix VII section (cf. eq 115 in Dewi et al.[31])Once (c1I, c2I) is determined for a certain S, the values for (c1II, c2II) can be determined analytically from eq . Note that in the symmetrical case, where S = 1 for all tie-lines, the solution is given directly in Dewi et al.[31] Care has to be taken that the correct branch of the Lambert-W function is chosen, W–1 or W0, as indicated in eqs and 52. In addition, the parametrization of the problem reveals the symmetry properties of the equations that are hidden in the initial co-existence equations. These symmetry properties allow us to find explicit solutions for specific cases, but these expressions in eq still have to be solved numerically in the general case to find the properties of the phase diagram. It should also be emphasized that eq is invariant under the transformation (c1I, c2I, S) ↔ (c2II, c1II, 1/S). Table summarizes the values for (c1,, c2,) in three well-defined limits of S. Note that the matrix in eq simplifies in the symmetrical case, where B11 = B22 ≡ B, S = 1, and , and eq reduces to

Table 1

Values for (c1,, c2) in Three Well-Defined Limits of S

Sm = Sc	Sm

leading to diagonalization of the matrixSubstitution of eq in eqs –50 leads to the analytical result for the binodal that was previously reported for the symmetrical case as[31]where (c1,, c2,) represent the coordinates of the binodal.

Although other formal limits exist in which the matrix in eq diagonalizes as(when c1 and/or c2 → ∞, or when B12 → ∞ for a fixed critical point), both limits are unphysical in the sense that they describe situations in which the total equivalent hard-sphere volume fraction φ = (B11c1 + B22c2)/4 is vastly larger than O(1). Since the maximum packing for hard spheres is about 0.7, depending on the details, it is reasonable to expect that (B11c1 + B22c2)/4 should not exceed a value of O(1) by many orders in other cases. Therefore, the cases for these formal limits are not addressed here, except for a short note on the behavior of the slope of the tie-lines in one of these limits in the next section.

Degeneracy in the Virial Coefficients for the Critical Point

Consider two sets of virial coefficients that give rise to the same critical point, (B11, B12, B22) and (B11*, B12*, B22*). Using eq , an expression for S∞ can be obtainedandWhen B12 ≠ B12*, it follows that S∞ ≠ S∞*, which means that the tie-lines far away from the critical point are generally not parallel to each other for two sets of virial coefficients that give rise to the same critical point. However, numerical evidence shows that the changes in the slope of the tie-lines tend to be modest over most of the range of B12. This is quantified below.

From eqs and 27 and the requirement that (B11, B22) > 0, a bound on B12, can be directly derived asUsing the following expressions that were derived from eqs and 25the slope of the tie-line far away from the critical point, −S∞, can be written asorFor large B12, the above equation can be expanded in a Taylor series to linear order asFrom eq , it follows that S∞ → S for B12 → ∞ and S∞/S – 1 decays proportionally to 1/B12 for large B12. S∞/S varies only in a relatively narrow range of B12 close to the value where one of the pair B11 and B22 becomes zero. The phase separation criterion behaves for large B12 asTherefore, as B12 increases to large values, the phase separation criterion reaches its critical value of 1, edging closer and closer to stability.

Figure shows the behavior of eqs and 67 for a specific choice of virial coefficients.

Figure 3

(Solid line) |S∞/S–1| and (dashed-dotted line) as a function of B12 for a fixed critical point with c1, = 2.0521 mol/m3, c2, = 0.0445 mol/m3, and S = 0.0777; (dotted line) limits for large B12 according to eqs and 67; and (red solid circle) |S∞/S–1| for the systems for which the phase diagrams are described in Figure .

(Solid line) |S∞/S–1| and (dashed-dotted line) as a function of <span class="Chemical">B12 for a fixed critical point with c1, = 2.0521 mol/m3, c2, = 0.0445 mol/m3, and S = 0.0777; (dotted line) limits for large <span class="Chemical">B12 according to eqs and 67; and (red solid circle) |S∞/S–1| for the systems for which the phase diagrams are described in Figure .

Figure 6

Binodal A corresponds to (B11, B12, B22) = (0.0052, 3.2000, 29.9146) (m3/mol). Binodal B corresponds to (B11, B12, B22) = (1.00, 16.00, 194.71) (m3/mol). Binodal C corresponds to (B11, B12, B22) = (5.9774, 80, 1017.5) (m3/mol). All three binodals have the same critical point (solid circle) located at (c1,, c2,c) = (2.0521, 0.0445) (mol/m3). It shows that binodal A does not superimpose with binodal B or C. The binodals B and C do superimpose for all practical purposes and their tie-lines are very close. The spinodals (blue dashed line), binodals (red solid line), and tie-lines (dashed-dotted line) are indicated by labels A, B, and C. These systems are also indicated in Figure , which plotted |S∞/S – 1| for tie-lines far away from the critical point.

Degeneracy in the Virial Coefficients for a Single Tie-Line

In case the composition of the co-existing phases is known, but none of the virial coefficients is known, an infinite number of solutions is found for the virial coefficients. It can be shown (the Appendix VIII section) that the same tie-line (or co-existing phases) is obtained for two triplets of virial coefficients (B11, <span class="Chemical">B12, B22) and (B11′, <span class="Chemical">B12′, B22′), provided(which is similar to eq ). This corresponds to a line in B-space that can be written in vector notation aswith λ2 being any real number, ensuring that and all B’s are larger than zero. A support vector can be found by choosing an arbitrary real value for B11 (i.e., B11 = 1) from which B12 and B22 can be calculated from eqs and 36.

Removing Degeneracy in Virial Coefficients Using More Than One Experimental Result: Intersection of the Lines in B-Space

In the previous sections, it was shown that a single data point (like the critical point or a tie-line) is insufficient to determine a unique set of virial coefficients. There is always a line in B-space that satisfies the requirements for one of these requirements. Next, the use of two data points (a critical point and a tie-line or two tie-lines) to obtain a unique set is discussed. It is shown that this approach is possible in theory, as it involves finding the intersection of two nonparallel lines in B-space, but it requires an experimental accuracy that is not likely to be achieved in practice. The case where the critical point and one of the tie-lines are known is considered below, but the example can easily be ada<span class="Chemical">pted for the case where two tie-lines are known.

First, consider a phase diagram that is characterized by a set of virial coefficients (B11, B12, B22). As the discussion in the previous sections has shown, each critical point (cf. eq ) or tie-line (cf. eq ) in the diagram can be represented by triplets of virial coefficients situated on lines in B-space. These lines fan out from a single point in B-space that corresponds with the actual virial coefficients (B11, B12, B22). In theory, no more than two lines in B-space are needed to determine the actual triplet (B11, B12, B22).

Next, consider the inverse case: two sets of virial coefficients that satisfy the individual requirements for a critical point and a tie-line are known and are points on lines in B-space that give rise to the same critical point or tie-line. The intersection of the two lines of individual solutions, P and P, is the common solution and can be found fromFrom the discussion above, it can be concluded that in the nonsymmetrical case (B11 ≠ B22), in theory, two tie-lines or a tie-line and a critical point can be used to determine a unique set of virial coefficients. In practice, however, the range over which S varies is <span class="Chemical">small and the experimental inaccuracy in the determination of the composition of the co-existing phases is too high to exploit this approach.

Sensitivity of the Shape of the Phase Diagram to the Choice of the Virial Coefficients in Degenerate Cases

Above, it was established that in the general case it is possible to have an infinite number of combinations of virial coefficients that give rise to the same feature in a phase diagram (a critical point, a tie-line). It was also established that two features (the critical point + a tie-line, two tie-lines) fix the choice of the virial coefficients and therefore the phase diagram. For the special symmetric case (B11 = B22), a single feature is sufficient to fix the choice of the virial coefficients.

What was not established is whether the phase diagram in the first case (virial coefficients based on a single feature) is sensitive to the choice of a triplet (B11, <span class="Chemical">B12, B22) on the corresponding line in B-space. Numerical calculations are presented below to address this question. The near-symmetrical and asymmetrical cases are distinguished.

Near-Symmetrical Cases

In near-symmetrical cases, where B11 ≈ B22, the binodal is almost mirror-symmetrical relative to the line c1 = c2. This is illustrated in Figure , where the phase diagrams are calculated for the different sets of virial coefficients (B11, <span class="Chemical">B12, B22) = (4, 3, 1) (m3/mol) and (B11, <span class="Chemical">B12, B22) = (1, 3, 4) (m3/mol). Figure shows that the binodals nearly superimpose, although the tie-lines and spinodals are distinctly different. It is noted that the spinodal is sensitive to the choice of the virial coefficients, as was to be expected from the expressions for their asymptotic values (see discussion below eq ).

Figure 4

(Red solid line) Binodal A for (B11, B12, B22) = (4, 3, 1) (m3/mol) corresponding to critical point A and binodal B for (B11, B12, B22) = (1, 3, 4) (m3/mol) corresponding to critical point B. Critical point B is mirror-symmetrical to critical point A relative to the line c1 = c2. Binodal C for (B11, B12, B22) = (1, 1.948, 1) (m3/mol) corresponds to the critical point located on the line c1 = c2 intersecting binodal A. It shows that binodal A, B, and C are nearly mirror-symmetrical relative to the line c1 = c2 and superimpose within the numerical error. Note that for binodals A, B, and C, the ratio B11/B22 is 4, 1/4, and 1, respectively. The corresponding spinodals ((blue dashed line) labeled A, B, and C) and tie-lines ((dashed-dotted line) labeled A, B, and C) are distinctly different from each other.

In near-symmetrical cases, it is possible to find a binodal for a symmetric case, where B11 = B22, that nearly overlaps the original binodal; in this example, B11 = B22 = 1 (m3/mol), B22 = 1.948 (m3/mol) was used. The method to determine the virial coefficients to find the corresponding symmetrical binodal is described in the Appendix IX section (eq ).

Clearly Asymmetrical Cases

Typically, B11 and B22 differ substantially (B11 ≪ B22 or B11 ≫ B22) and the binodal becomes asymmetric. Even though each point on the binodal can be interpreted as a new critical point for a different set of virial coefficients (cf. Appendix X), the binodals through this new critical point generally do not superimpose on the binodal of the original critical point. This is illustrated in Figure .

Figure 5

Binodal A and critical point A corresponding to (B11, B12, B22) = (1.54, 4.00, 5.85) (m3/mol). Binodal B and critical point B corresponding to (B11, B12, B22) = (1.00, 16.00, 194.71) (m3/mol). Here, the critical point B is selected on binodal A. It shows that binodal A and binodal B do not superimpose. Note that for binodal A, we have B11/B22 = 0.263 and for binodal B, we have B11/B22 = 0.005. The spinodals (blue dashed line), binodals (red solid line), and tie-lines (dashed-dotted line) corresponding to critical points A and B (solid circle) are indicated by labels A and B.

Binodal A and critical point A corresponding to (B11, <span class="Chemical">B12, B22) = (1.54, 4.00, 5.85) (m3/mol). Binodal B and critical point B corresponding to (B11, <span class="Chemical">B12, B22) = (1.00, 16.00, 194.71) (m3/mol). Here, the critical point B is selected on binodal A. It shows that binodal A and binodal B do not superimpose. Note that for binodal A, we have B11/B22 = 0.263 and for binodal B, we have B11/B22 = 0.005. The spinodals (blue dashed line), binodals (red solid line), and tie-lines (dashed-dotted line) corresponding to critical points A and B (solid circle) are indicated by labels A and B.

Focusing on binodals for the same critical point, but different virial coefficient combinations (cf. Figure ), it was shown that S is the same (Appendix V). Triplets of virial coefficients that lead to the same critical point do not lead to the same slope of the tie-lines far away from the critical point, −S∞ = −√(B11/B22). As a result, triplets of virial coefficients that lead to the same critical point do not lead to the same phase diagram. In practice, S∞ only varies significantly if either B11 or B22 get very close to zero. When <span class="Chemical">B12 → ∞, we find that the binodal converges to the analytical expression given in eq . It is noted that when <span class="Chemical">B12 → ∞, all tie-lines become parallel to each other with a slope −S and the phase diagrams for a fixed critical point converge to the same phase diagram for B12 → ∞. This is illustrated in Figure . Three phase diagrams are shown for the virial coefficient triplets. Label A: (B11, B12, B22) = (0.0052, 3.2000, 29.9146) (m3/mol), label B: (B11, B12, B22) = (1.00, 16.00, 194.71) (m3/mol), and label C: (B11, B12, B22) = (5.9774, 80, 1017.5) (m3/mol). These parameter combinations share the same critical point (c1,, c2,) = (2.0521, 0.0445) (mol/m3). The spinodals are sensitive to the choice of the virial coefficients. The spinodal and tie-lines B and C nearly superimpose, whereas A and B are clearly different. The same is true for the binodals, although the differences are smaller. One could question whether any of the differences would be sufficiently large to be discerned experimentally. Also, the tie-lines are sensitive to the choice of the virial coefficients. The slope −S∞ = −√(B11/B22) of the tie-lines increases when moving away from the critical point (binodal A: S∞ = 0.013; binodal B: S∞ = 0.071; binodal C: S∞ = 0.274).

Conclusions

This paper investigated the solutions of the Edmond–Ogston model, a virial model that takes into account virial coefficients up to the second order and which can be used to describe phase separation in binary mixtures of polymers in a common solvent. The real strength of this model is for relatively low polymer concentrations. The model becomes more qualitative when the polymer concentrations exceed the overlap concentrations and a description of the polymer blend in terms of single polymer particles with pair interactions starts to fail and other models to describe the physics of polymer mixtures should be introduced. While some results for the Edmond–Ogston model, in particular, the expression for the critical point, were obtained previously in a normalized form,[31,32] the present analysis is done in experimentally accessible coordinates like molar concentrations.

A parametrization is introduced that essentially allows for an evaluation of the composition of the co-existing phases at constant o<span class="Chemical">smotic pressure in a natural way. The parameterization simplifies the analysis and reduces the calculation effectively from a four-variable problem into a two-variable problem. Moreover, the parameterization reveals the symmetry of the mathematical structure of the equations and the pivotal role that is played by the so-called Lambert-W functions. The reformulation of the problem also reveals why an exact solution to the problem can be given for the symmetrical case (B11 = B22).

Furthermore, the present formulation of the problem revealed that individual properties of the phase diagram (e.g., the critical point or tie-line) are described by an infinite number of triplets (B11, <span class="Chemical">B12, B22) of virial coefficients. The properties of these triplets were investigated and were found to be represented by straight lines in “B-space”. If the features of the phase diagram are determined with infinite precision, two properties of the phase diagram (e.g., two tie-lines, one tie-line plus a critical point) suffice to determine the actual virial coefficients. In practice, the data is not accurate enough to achieve this, echoing an observation previously made by Clark.[29]

It is found that nearly any choice of virial coefficients gives rise to the same critical point and a similar phase diagram. The binodal and tie-lines for all of these choices almost superimpose, making it unlikely that one could distinguish between the calculated binodals experimentally. The calculated spinodals do depend on the choices of virial coefficients but are experimentally less accessible. Only for choices where B11 or B22 nearly vanish (before they become negative), meaningful differences are observed between phase diagrams.

It was also established that every point on the binodal can be considered as a critical point for another choice of virial coefficients. However, generally, the binodals through these critical points do not superimpose, exce<span class="Chemical">pt if the values of B11 and B22 are close, leading to a nearly symmetrical binodal.

Although the present paper focused on the Edmond–Ogston model, the observations should essentially hold for the Flory–Huggins model too, given the equivalence between both models up to the second order of the expansion in the concentrations as identified by Clark.[29]

The present paper also provides a procedure to calculate the various properties of the phase diagram, in particular the tie-lines. The critical point and spinodal can be calculated analytically through eqs , 25, and 33. The present results indicate that the best method to calculate the properties of the binodal and tie-lines involves the following steps

Calculate the minimum and maximum slope of the tie-lines, −S, and −S using eqs , 23, and 54 (note that S is not necessarily <span class="Chemical">smaller than S∞)

Choose the slope −S of an intermediate tie-line having a value between −S and −S

Calculate c1, and c2, using eq

Solve matrix eq for c1I and c2I

Determine c1II and c2II by means of eq

From a practical point of view, the present results indicate that although the two coordinates for the critical point are insufficient to determine the model parameters accurately, they are sufficient to determine most features of the phase diagram with fair accuracy. The shape of the binodal seems to be least sensitive to the choice of the virial coefficients in the Edmond–Ogston model. The slope of the tie-lines shows variations only in a relatively narrow range of values for <span class="Chemical">B12. The spinodal is the most sensitive to the choice of the three virial coefficients.

The obtained results reveal the intricacies of the Edmond–Ogston model, especially in the context of degeneracies within the model. This deeper understanding of the model helps to assess the possibilities and limitations of the use of phase diagrams from the literature to extract virial coefficients and in this way build a database of parameters to describe the phase behavior of many <span class="Chemical">polymer mixtures.

Table 2

Matching of Terms between Flory–Huggins and Extended Edmond–Ogston Models

extended Edmond–Ogston model parameters	Flory–Huggins model parameters, from eq 76	Flory–Huggins model parameters, from eq 77	Flory–Huggins model parameters, from eq 78
c1
c2
B11	υs(1 – 2χ10)p12
B22	υs(1 – 2χ20)p22
B12
C111
C112
C122
C222