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# Theories of Liquid Crystalline Polymers

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The contribution from Russian scientists is worthy of special mention. We will introduce their theory later. It should be pointed out that to meet the second virial approximation, molecules must have a large L/D so that at the transition the solution is dilute. For molecules of axial ratio less than 10 the theory does not work well. In addition, the Onsager value of the density diﬀerence at the nematic — isotropic transition is greater than the experimental data. Introducing higher virial terms may extend the Onsager theory to concentrated solutions (Khokhlov & Semenov, 1981). The Flory theory discussed in the next section is another important theory on rigid liquid crystalline polymers. Because of its clear picture of the lattice model and the incorporation of the Onsager theory, it has become a basic method for the theoretical study of liquid crystalline polymers. As a result of the constant eﬀorts of Flory and his co-workers, the theory has been applied to binary and poly-disperse systems and also includes the “soft” interactions.

2.2.

FLORY THEORY FOR RIGID — ROD LIQUID CRYSTALLINE POLYMERS Partition function of a rigid rod solution

2.2.1.

Flory (1956, 1984) adopted the lattice model. The Flory theory starts with the partition function of systems consisting of rigid rods and solvent molecules. Assume the long axis of the rigid rods makes an angle ψ with respect to the director of the system and the director is along one principal axis of the cubic lattice. Divide each rod into x basic units of equal width. Each basic unit occupies one cell in the lattice. x is actually the axial ratio of the rods. For simplicity, suppose that the dimension of a solvent molecule is compatible to the size of a cell lattice. In this section we adopt the same assignations as Flory. These may be diﬀerent from those used in the preceding section by Onsager. In order to put a rod into the lattice, a postulate is made, which suggests that each rigid rod be divided into y sub-particles as shown in Figure 2.4b y = x sin θ. (2.28)

Each sub-particle has x/y basic unit and its long axis is along the director. If a particle is perfectly aligned along the director, y is zero. As a

There are two possibilities: the cell may be unoccupied and is allowed to enter in. The probability of such an arrangement is the volume fraction of unoccupied cells in the system.4. Assume that the total number of cells in the system is n0 and (j − 1) rods have been placed in the lattice. Therefore. the other possibility is that it has been occupied by the ﬁrst unit of a sub-particle . Once the ﬁrst unit has been put into the lattice (the cell must be unoccupied and is allowed to put in) each of remaining units must be positioned immediately next to preceding unit (the cell must be unoccupied). so that Pj = [n − x(j − 1)] . (b) the rod divided into y sub-particles. the ﬁrst term represents the number of ways of putting the ﬁrst basic unit of the ﬁrst sub-particle into the lattice which is the number of unoccupied cells. y can be regarded as a measure of a rod’s deviation oﬀ the director.29) where yj is the number of the sub-particles of the rod. First we will work out Pj . n (2. Once the ﬁrst sub-particle’s position is determined each of other sub-particles must be the closest neighbor to the preceding sub-particle shown in Figure 2. They have occupied x(j − 1) lattice cells and hence n0 − x(j − 1) lattice cells remain unoccupied. In this case. (2.4. In addition.66 Liquid Crystalline Polymers x Ψ x/y x (a) (b) Figure 2.30) All units of each sub-particle must be in same row of the cell. there are νj ways to put the j -th rod into the lattice νj = [n − x(j − 1)]Nj (x−yj ) Pj (yj −1) . (a) a rod making an angle Ψ to the director. A rigid rod in the Flory lattice. Pj is the ways of putting the ﬁrst unit of remaining (y − 1) sub-particles. the ﬁrst unit must be immediately next to the last unit of the preceding sub-particle. particle is aligned oﬀ the director the value of y increases. Nj is the number of ways of placing the remaining (x − yj ) units entering into the lattice. y is called the oﬀ-orientation degree or disorder degree.

Thus Nj is Nj = [n − x(j − 1)] [n − x(j − 1) − y ¯(j − 1)] [n − x(j − 1)] .32) Assume there are np identical rigid rods in the system and the contribution of the np rods to the partition function of the system can be written as Zcomb 1 = np ! np νj . The possibility Nj of emptiness for the cell is the fraction of empty cells in both empty cells and total number of sub-particles. Zcomb decreases with increasing y ¯. yj −1) (n − xj )![n − (x − y ¯)(j − 1)]!n(¯ (2. It illustrates that if the disorder of conﬁguration of rods in the system increases.33 gives Zcomb = ¯np )! (ns + y . j =1 (2. Substitute Pj and Nj to Equation 2..33) where the factor of (1/np !) is introduced to avoid repeatedly counting identical rods.32 into Equation 2.34 increases as the oﬀ-orientation degree y ¯ increases. = [n − (x − y ¯)(j − 1)] (2. y ¯(j − 1) is the total number of sub-particles already in the lattice.29 one obtains νj = [n − x(j − 1)]Nj = ≈ (x−yj ) Pj (yj −1) [n − x(j − 1)]x {[n − (x − y ¯)(j − 1)](x−yj ) n(yj −1) } [n − x(j − 1)]![n − (x − y ¯)j ]! . the excluded volume occupied by each rod increases and the space .e. the total number of the ﬁrst unit of all the sub-particles.Theories of Liquid Crystalline Polymers 67 of another rod and is not allowed to enter in. As a result. but the denominator increases more rapidly. n y −1) ns !np !n p (¯ (2.31) where y ¯ is the average of y of the (j − 1) rods already in the system.34) where ns = n − xnp is the number of empty cells left in the system which are occupied by solvent molecules. i. Substituting Equation 2. It is shown that both the numerator and denominator in Equation 2.

taking only the orientational entropy into account. hence Zcomb becomes great and the contribution to the energy reduction accordingly becomes important. the system is in disorder (¯ y = x) then ωy = npy /np and Zorient = 1. after the ﬁrst unit is put into the lattice the remaining units enter the lattice via the same direction. and npy /np represents the orientation distribution function. thus npy = np .36) It is illustrated from Equation 2. Zorient Zorient = y ω y np npy npy . the collision between particles increases and the entropy decreases. Therefore. (2. Zorient becomes very small. and thus is not favored. In the y /x)2 . Suppose the next neighbor of each cell in a lattice is six. In the perfectly ordered state. The average of y is given by y ¯= y ynpy np (2. Therefore. Otherwise. The contribution to the system entropy is about zero.68 Liquid Crystalline Polymers in which rods can move freely decreases. the above-mentioned equation is valid only for the perfectly ordered case.35) where npy is the number of rods with oﬀ-orientation degree y. i. y = 1. According to the Flory’s (1956) approximation. This illustrates that the Flory theory works well for concentrated solutions. (2. the rods are all aligned in parallel.37) ¯ The fact that the orientational partition function Zorient increases as y increases can be understood. the fundamental reason .e. If the orientation is random each basic unit of a particle has ﬁve ways and hence the particle of x units has 5x ways to enter into the lattice and thus the contribution to the entropy of the system is kB x ln 5.. when the orientational order is high. Another contribution to the total partition function of the system arises from the orientation. In fact. Assume that npy /np is uniform within the range. Inversely. ωy is the solid angle fraction associated with y ¯. Therefore. if y ¯ decreases. npy /np is zero. range θ ≤ θ′ the solid angle becomes approximately (¯ Zorient ≈ (¯ y /x)2np . npy /np is important only in the range θ ≪ θ′ . When θ > θ′ . i..e. reducing the stability of the system. the degree of orientation along the director becomes high.35 that if the system is in a perfectly ordered state.

Formation of the liquid crystal phase From the partition function in Equation 2.5 where x = 100.40) . respectively.39 becomes F = ns ln(1 − φ) + np ln kB T where xnp n ns 1−φ= n φ= are the volume fractions of solvents and rods.. for the volume fraction of rods less than critical value φ∗ (here φ∗ = 0. (2. Each curve corresponds to a diﬀerent volume fraction. x (2. the more disorder the higher Z .0784) e.Theories of Liquid Crystalline Polymers 69 for rigid rods to form a liquid crystal phase must be attributed to the steric repulsion eﬀect between the rods.g.2.060. (2. The relation of the partition function and oﬀ-orientation degree y ¯ in Equation 2. Z increases monotonously with increasing y . Consequently.5. the partition function is given by 2n ¯np )! (¯ y /x) p (ns + y Z = Zcomb Zorient = . From the partition function one can ﬁnd the critical concentrations of phase separation of the underlying system as a function of the axial ratio and other quantities which are of interest.39) For the isotropic system y = x and Equation 2. φ x + np (¯ y − 1). In other words.38) y −1) ns !np !nnp (¯ The equation describes the dependence of the partition function on np (the number or concentration of rods).2. φ = 0.38 the free energy can be obtained as F = − ln Z = ns ln(1 − φ) + np ln kB T ¯np ) ln 1 − φ − (ns + y 1−y ¯ x φ x + np (¯ y − 1) − 2np ln y ¯ .39 is depicted in Figure 2. and y ¯ (the averaged oﬀ-orientation degree). As shown in Figure 2. x (the axial ratio or degree of polymerization of rods). 2.

(2. The dependence of φ on y ¯ can be obtained numerically.) ¯. as shown in Figure 2. in which y ¯ is less than that at the minimum Z . The smaller solution corresponds to the stable or meta-stable state in which Z is at a maximum. As φ increases. If φ and x are great enough. y ¯ at Z = Zmax decreases.5 is that the y ¯ value at Z = Zmax is much less than x/2. (Modiﬁed from Flory. As φ > φ∗ there is a maximum Zmax with y the value for y ¯ = x. Diﬀerentiate F in Equation 2. The y ¯ for the two extremes are given by x −2 φ= 1 − exp . then Zmax gives the equilibrium state. otherwise.39 with respect to y ¯ and make d(− ln Z )/d¯ y equal to zero. there are two extremes in Z . 1956. If Zmax is greater than Z0 . The maximal value is associated with the stable (or meta-stable) states. The partition function vs.70 Liquid Crystalline Polymers Figure 2. it is the meta-equilibrium state.5. oﬀ-orientation degree of a rod system of axial ratio x = 100. Another conclusion from Figure 2. It is illustrated that when the system transforms from the disordered state (¯ y = x) to the liquid crystal state. y ¯ changes abruptly to x/2. even for φ = φ∗ . .5.41) (x − y ¯) y ¯ There are two solutions for y ¯.

It should be pointed out that φ∗ is only the minimal solution of Equation 2. i.Theories of Liquid Crystalline Polymers 71 To obtain the critical value of φ∗ when the system starts to appear in the meta-stable state. in their 1956 approximation. the minimum value of φ for the existence of liquid crystal state.41 Flory et al. At this volume fraction φ∗ .. 2 2 y∗ −2 y∗ (2.e.42) where y ∗ is the value at φ = φ∗ . i.43) Substituting 2. and the biphasic . the less is φ∗ .44 that the larger the axial ratio of rods x. which is approximately the minimum axial ratio of rods that the systems are able to show a liquid crystal phase. Substituting y ∗ = 2 into Equation 2.44. Two phase equilibrium According to the above analyses. (2. the neat polymer system. 2. The system is at a meta-stable state only when the volume fraction further increases to a greater value in which the system is indeed at a stable state. It is shown in Equation 2.. the error of the approximation in the above equation is less than 2%.43 that as φ∗ increases up to φ∗ = 1.. It is concluded from Equation 2.e.3. Equation 2. when the concentration of rods in the solvent increases beyond φ∗ . or φ∗ = 1 − 1 − exp (2.41 at which the partition function ﬁrst shows a maximum.44 is the well-known Flory formula which is widely used in the study of liquid crystalline polymers.42 into 2. phase separation occurs. y ∗ = 2.2.42 the axial ratio is x = 2e = 5. obtained the critical φ∗ as the function of the axial ratio x φ∗ ≈ 8 x 1− 2 x . Zmax is actually less than the Z at the disordered state (¯ y = x). let dφ =0 dy ¯ and φ∗ is given implicitly by x = y∗ + y∗ 2 [exp(2/y ∗ ) − 1] .44) If x > 10.

72 Liquid Crystalline Polymers coexistence of liquid crystal and isotropic phases appears.e.51) + φ(x − 1). where the subscript “s” is designated for the solvent while p is for the rigid rods. RT x y ¯ (2. µs = µ′ s (2.48) Similarly. According to Equation 2. i.38.45) µp = µ′ p.41 and thus Equation 2.50) The equilibrium state of coexistence of two phases is governed by the following set of equations ln(1 − φ′ ) + ln φ′ x φ′ (¯ 1 y − 1) 2 + = ln(1 − φ) + φ 1 − x y ¯ x ′ y ¯ + φ (¯ y − 1) + 2 − 2 ln = ln x φ x (2. respectively.46 becomes 0 (µ′ φ′ (¯ y − 1) 2 s − µs ) = ln(1 − φ′ ) + + .47) The chemical potential for solvents in the isotropic phase is (µs − µ0 1 s) = ln(1 − φ) + φ 1 − RT x .46) At equilibrium d(− ln Z )/dy ¯ = 0. Replace the last term by 2/y ¯ from Equation 2. and µ and µ′ are the chemical potentials at the isotropic and liquid crystal phase. (2..49) and (µp − µ0 p) = ln RT φ x + φ(x − 1). the derivative of (− ln Z ) with respect to the volume fraction ns of the solvent gives 0 y − 1) (µ′ φ′ (¯ y ¯ s − µs ) = ln(1 − φ′ ) + − ln 1 − φ′ 1 − RT x x . . (2. the chemical potential of rods in the liquid crystal and in the isotropic phase are given respectively by 0 (µ′ p − µp ) = ln RT φ′ x + φ′ (¯ y − 1) + 2 − 2 ln y ¯ x (2. (2. The chemical potentials of each component must be equal at the coexistence of two phases.

the critical volume fractions are respectively φ= 8 .) and Equation 2. (From Flory & Ronca. Phase diagrams for various rod axial ratios. This value is somewhat greater than the estimated value of x = 5. We have emphasized that the estimate of the minimum axial ratio for forming a liquid crystal phase (x = 5.Theories of Liquid Crystalline Polymers 73 Figure 2. x . (2) At the equilibrium state.44) is that at which the partition function starts to take a maximum. The following important conclusions can be obtained from Figure 2. 1979a.7. where φ′ and φ are the volume fraction of rods in the liquid crystal and isotropic phase.6. but is always less than 1. The volume fraction of the liquid crystal phase is slightly greater than that of the isotropic phase.56. For enough large x. the volume fraction of rods in the two phases decreases as the axial ratio x increases. For various axial ratios x of the rods the numerical solutions of the above set of equations are summarized in Figure 2.43. the ratio between these two critical volume fractions increases with increasing x.44.6.5 . x φ∗ = 12. respectively.6: (1) Those rigid molecules capable of showing a stable liquid crystal phase must have the axial ratio greater than x = 6.

2. Eﬀect of “soft” interaction between molecules Later Flory further took the two “soft” interactions between the molecules into account. In Figure 2. The anisotropic interaction is associated with molecular orientations while the isotropic one is irrelevant of the molecular orientation.7. 1959). (Modiﬁed from Flory. The solid curve is the theoretical expectation while the dashed line is the experimental result. Reproduced by permission of John Wiley & Sons. however.74 Liquid Crystalline Polymers Figure 2. Inc. the critical volume fractions of PBLG in solvents (Flory. the anisotropic interaction was the basis of another well-known theory in liquid crystals — Maier–Saupe theory (Maier & Saupe. . axial ratio. The curve A is for φ at which the liquid crystal phase starts to appear while the curve B is for φ′ at which the isotropic phase completely disappears and the system becomes entirely a liquid crystal.4. the variation is not great. An experiment was carried out for PBLG to verify the theory. Critical volume fraction vs.) (3) y ¯/x increases smoothly as x increases. 2. PBLG molecules in solution adopt an extended α-helical conformation so that they are rigid rods. In fact. 1961. 1961) were depicted as a function of the axial ratio.7. The value of y ¯/x is very small which illustrates that the ordering in the liquid crystal phase is very high. Both are in good agreement. Flory successfully captured the essence of the theory.

0. say. It was shown that for small concentrations of methanol. φ′ and y 2 y − 1) 2 φ′ (¯ 1 + + χφ′ = ln(1 − φ) + φ 1 − x y ¯ x ln(1 − φ′ ) + ln φ′ x = ln + χφ2 + φ′ (¯ y − 1) + 2 − 2 ln φ x y ¯ + χx(1 − φ′ )2 x (2. At the coexistence of the two phases the chemical potentials of the rods and solvents in both the liquid crystals phase and isotropic phase must be ¯ holds equal and thus the following set of equations for φ.. the region of biphasic coexistence is narrow. As the volume fraction of methanol increases (up to 0. the free energy in Equation 2. The diagram can be divided into three regions: in Region I the concentration is small and the system is in a single isotropic phase. For negative χ.10–0.5. the biphasic range is narrow. is only applicable to an athermal system. .07 the volume fraction diﬀerence between the two phases becomes larger.07. The ordinate is the Flory–Huggins parameter χ and the abscissa is the volume fraction of rigid rods. Figure 2. in Region II the system is in the liquid crystal phase. The axial ratios were 150 and 350. and the χ value was controlled by varying the concentration of methanol. The previous theory.39 is implemented by a term χφns . Figure 2. respectively.Theories of Liquid Crystalline Polymers 75 First we introduce the isotropic interaction which results from the mixing of rods and solvents.52) + φ(x − 1) + χx(1 − φ)2 . and in Region III both the liquid crystal and isotropic phases coexist. For χ less than. the two phase equilibrium is basically independent of χ. The more methanol the greater is χ.12) the biphasic range becomes wider.9 shows the experimental results of the PBLG/dimethyl formamide(DMF)-methanol system (Nakajama et al. A positive χ has a signiﬁcant eﬀect on the two-phase equilibrium. where χ is the Flory–Huggins interaction parameter. φ∗∗ /φ∗ = 1. without the mixing contribution to entropy. If there is a mixing entropy contribution.8 shows the numerical result of the rod/solvent system for the rod axial ratio x = 100. 1968). Flory called the mixing term the isotropic “soft” interaction to distinguish it from the steric interaction of rods. For χ greater than 0.

1 I + LCЉ 0.2 0 0.2 –0.) Figure 2. (From Flory.0 III Figure 2.9. Experimental phase diagram of PBLG/dimethyl formamide(DMF)methanol system.6 0.4 0.8. 1956.2 0.) . (Modiﬁed from Nakajama et al.76 Liquid Crystalline Polymers –0. Phase diagram for rod axial ratio of 100.8 1..1 I LC II 0 I + LCЈ LCЈ LCЈ + LCЉ LCЉ 0. 1968.

53) where S is the order parameter and T ∗ is the characteristic temperature which is a function of the anisotropy of the longitudinal and transverse electric susceptibilities kB T ∗ ∝ r−6 (∆α)2 . where r is the distance of neighboring rods. This anisotropic interaction associated with molecular orientation is expressed by − 1 2 xnp φS 2 T ∗ T .e. .Theories of Liquid Crystalline Polymers 77 Figure 2.) The value of χ varies with the temperature.. while at higher temperatures. the curve deﬂects to a high concentration regime. temperature. For temperatures below 35 ◦ C the phase diagram is basically the same as the Flory theory. Wee & Miller (1971) examined the phase equilibrium as a function of temperature. i. (From Miller et al. (2.10. χ decreases as the temperature increases. The phase equilibrium vs.10. This phenomenon was observed in a system of cellulose derivatives (Navard et al. 1981).. 1974.. The results are shown in Figure 2. Warner and Flory (1980) found that the introduction of the anisotropic attractive force predicts this eﬀect.