Theories of Liquid Crystalline Polymers

65

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 dierence 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 eorts 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 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 dierent 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 . (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

66

Liquid Crystalline Polymers

x/y x

(a)

(b)

Figure 2.4. A rigid rod in the Flory lattice. (a) a rod making an angle to the director; (b) the rod divided into y sub-particles.

particle is aligned o the director the value of y increases. Therefore, y can be regarded as a measure of a rods deviation o the director. y is called the o-orientation degree or disorder degree. Assume that the total number of cells in the system is n0 and (j 1) rods have been placed in the lattice. They have occupied x(j 1) lattice cells and hence n0 x(j 1) lattice cells remain unoccupied. In this case, there are j ways to put the j -th rod into the lattice j = [n x(j 1)]Nj
(xyj )

Pj

(yj 1)

(2.29)

where yj is the number of the sub-particles of the rod; the rst term represents the number of ways of putting the rst basic unit of the rst sub-particle into the lattice which is the number of unoccupied cells. Pj is the ways of putting the rst unit of remaining (y 1) sub-particles; Nj is the number of ways of placing the remaining (x yj ) units entering into the lattice. First we will work out Pj . Once the rst sub-particles position is determined each of other sub-particles must be the closest neighbor to the preceding sub-particle shown in Figure 2.4. In addition, the rst unit must be immediately next to the last unit of the preceding sub-particle. The probability of such an arrangement is the volume fraction of unoccupied cells in the system, so that Pj = [n x(j 1)] . n (2.30)

All units of each sub-particle must be in same row of the cell. Once the rst 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). There are two possibilities: the cell may be unoccupied and is allowed to enter in; the other possibility is that it has been occupied by the rst unit of a sub-particle

Theories of Liquid Crystalline Polymers

67

of another rod and is not allowed to enter in. The possibility Nj of emptiness for the cell is the fraction of empty cells in both empty cells and total number of sub-particles. Thus Nj is Nj = [n x(j 1)] [n x(j 1) y (j 1)]

[n x(j 1)] , = [n (x y )(j 1)]

(2.31)

where y is the average of y of the (j 1) rods already in the system, y (j 1) is the total number of sub-particles already in the lattice, i.e., the total number of the rst unit of all the sub-particles. Substitute Pj and Nj to Equation 2.29 one obtains j = [n x(j 1)]Nj =
(xyj )

Pj

(yj 1)

[n x(j 1)]x {[n (x y )(j 1)](xyj ) n(yj 1) } [n x(j 1)]![n (x y )j ]! . yj 1) (n xj )![n (x y )(j 1)]!n(

(2.32)

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

j ,
j =1

(2.33)

where the factor of (1/np !) is introduced to avoid repeatedly counting identical rods. Substituting Equation 2.32 into Equation 2.33 gives Zcomb = np )! (ns + y , n y 1) ns !np !n p ( (2.34)

where ns = n xnp is the number of empty cells left in the system which are occupied by solvent molecules. It is shown that both the numerator and denominator in Equation 2.34 increases as the o-orientation degree y increases, but the denominator increases more rapidly. As a result, Zcomb decreases with increasing y . It illustrates that if the disorder of conguration of rods in the system increases, the excluded volume occupied by each rod increases and the space

68

Liquid Crystalline Polymers

in which rods can move freely decreases. Therefore, the collision between particles increases and the entropy decreases, reducing the stability of the system. Inversely, if y decreases, the degree of orientation along the director becomes high, hence Zcomb becomes great and the contribution to the energy reduction accordingly becomes important. In fact, the above-mentioned equation is valid only for the perfectly ordered case, i.e., the rods are all aligned in parallel. This illustrates that the Flory theory works well for concentrated solutions. Another contribution to the total partition function of the system arises from the orientation, i.e., Zorient Zorient =
y

y np npy

npy

(2.35)

where npy is the number of rods with o-orientation degree y, y is the solid angle fraction associated with y , and npy /np represents the orientation distribution function. The average of y is given by y =
y

ynpy np

(2.36)

It is illustrated from Equation 2.35 that if the system is in a perfectly ordered state, y = 1; thus npy = np , Zorient becomes very small. Otherwise, the system is in disorder ( y = x) then y = npy /np and Zorient = 1. According to the Florys (1956) approximation, when the orientational order is high, npy /np is important only in the range . Assume that npy /np is uniform within the range. When > , npy /np is zero. In the y /x)2 . Therefore, range the solid angle becomes approximately ( Zorient ( y /x)2np . (2.37)

The fact that the orientational partition function Zorient increases as y increases can be understood. Suppose the next neighbor of each cell in a lattice is six. If the orientation is random each basic unit of a particle has ve 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. In the perfectly ordered state, after the rst unit is put into the lattice the remaining units enter the lattice via the same direction. The contribution to the system entropy is about zero, and thus is not favored, taking only the orientational entropy into account. Therefore, the fundamental reason

Theories of Liquid Crystalline Polymers

69

for rigid rods to form a liquid crystal phase must be attributed to the steric repulsion eect between the rods. Consequently, the partition function is given by 2n np )! ( y /x) p (ns + y Z = Zcomb Zorient = . (2.38) y 1) ns !np !nnp ( The equation describes the dependence of the partition function on np (the number or concentration of rods), x (the axial ratio or degree of polymerization of rods), and y (the averaged o-orientation degree). From the partition function one can nd the critical concentrations of phase separation of the underlying system as a function of the axial ratio and other quantities which are of interest.

2.2.2.

Formation of the liquid crystal phase

From the partition function in Equation 2.38 the free energy can be obtained as F = ln Z = ns ln(1 ) + np ln kB T np ) ln 1 (ns + y 1y x x + np ( y 1) 2np ln y . x (2.39)

For the isotropic system y = x and Equation 2.39 becomes F = ns ln(1 ) + np ln kB T where xnp n ns 1= n = are the volume fractions of solvents and rods, respectively. The relation of the partition function and o-orientation degree y in Equation 2.39 is depicted in Figure 2.5 where x = 100. Each curve corresponds to a dierent volume fraction. As shown in Figure 2.5, for the volume fraction of rods less than critical value (here = 0.0784) e.g., = 0.060, Z increases monotonously with increasing y . In other words, the more disorder the higher Z . x + np ( y 1), (2.40)

70

Liquid Crystalline Polymers

Figure 2.5. The partition function vs. o-orientation degree of a rod system of axial ratio x = 100. (Modied from Flory, 1956.)

. If Zmax is greater than Z0 , As > there is a maximum Zmax with y the value for y = x, then Zmax gives the equilibrium state; otherwise, it is the meta-equilibrium state. Another conclusion from Figure 2.5 is that the y value at Z = Zmax is much less than x/2, even for = . As increases, y at Z = Zmax decreases. 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. If and x are great enough, there are two extremes in Z . The maximal value is associated with the stable (or meta-stable) states, in which y is less than that at the minimum Z . Dierentiate F in Equation 2.39 with respect to y and make d( ln Z )/d y equal to zero. The y for the two extremes are given by x 2 = 1 exp . (2.41) (x y ) y There are two solutions for y . The smaller solution corresponds to the stable or meta-stable state in which Z is at a maximum, as shown in Figure 2.5. The dependence of on y can be obtained numerically.

Theories of Liquid Crystalline Polymers

71

To obtain the critical value of when the system starts to appear in the meta-stable state, i.e., the minimum value of for the existence of liquid crystal state, let d =0 dy and is given implicitly by x = y + y
2

[exp(2/y ) 1] , 2 2 y 2 y

(2.42)

where y is the value at = , or = 1 1 exp (2.43)

Substituting 2.42 into 2.41 Flory et al., in their 1956 approximation, obtained the critical as the function of the axial ratio x 8 x 1 2 x . (2.44)

If x > 10, the error of the approximation in the above equation is less than 2%. It is concluded from Equation 2.44 that the larger the axial ratio of rods x, the less is . Equation 2.44 is the well-known Flory formula which is widely used in the study of liquid crystalline polymers. It should be pointed out that is only the minimal solution of Equation 2.41 at which the partition function rst shows a maximum. At this volume fraction , Zmax is actually less than the Z at the disordered state ( y = x). 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 2.43 that as increases up to = 1, i.e., the neat polymer system, y = 2. Substituting y = 2 into Equation 2.42 the axial ratio is x = 2e = 5.44, which is approximately the minimum axial ratio of rods that the systems are able to show a liquid crystal phase.

2.2.3.

Two phase equilibrium

According to the above analyses, when the concentration of rods in the solvent increases beyond , phase separation occurs, and the biphasic

72

Liquid Crystalline Polymers

coexistence of liquid crystal and isotropic phases appears. The chemical potentials of each component must be equal at the coexistence of two phases, i.e., s = s (2.45) p = p, where the subscript s is designated for the solvent while p is for the rigid rods, and and are the chemical potentials at the isotropic and liquid crystal phase, respectively. According to Equation 2.38, the derivative of ( ln Z ) with respect to the volume fraction ns of the solvent gives
0 y 1) ( ( y s s ) = ln(1 ) + ln 1 1 RT x x

(2.46)

At equilibrium d( ln Z )/dy = 0. Replace the last term by 2/y from Equation 2.41 and thus Equation 2.46 becomes
0 ( ( y 1) 2 s s ) = ln(1 ) + + . RT x y

(2.47)

The chemical potential for solvents in the isotropic phase is (s 0 1 s) = ln(1 ) + 1 RT x . (2.48)

Similarly, the chemical potential of rods in the liquid crystal and in the isotropic phase are given respectively by
0 ( p p ) = ln RT

+ ( y 1) + 2 2 ln

y x

(2.49)

and

(p 0 p) = ln RT

+ (x 1).

(2.50)

The equilibrium state of coexistence of two phases is governed by the following set of equations ln(1 ) + ln x ( 1 y 1) 2 + = ln(1 ) + 1 x y x

y + ( y 1) + 2 2 ln = ln x

(2.51)

+ (x 1).

Theories of Liquid Crystalline Polymers

73

Figure 2.6.

Phase diagrams for various rod axial ratios. (From Flory & Ronca, 1979a.)

and Equation 2.43, where and are the volume fraction of rods in the liquid crystal and isotropic phase, respectively. For various axial ratios x of the rods the numerical solutions of the above set of equations are summarized in Figure 2.6. The following important conclusions can be obtained from Figure 2.6: (1) Those rigid molecules capable of showing a stable liquid crystal phase must have the axial ratio greater than x = 6.7. This value is somewhat greater than the estimated value of x = 5.44. We have emphasized that the estimate of the minimum axial ratio for forming a liquid crystal phase (x = 5.44) is that at which the partition function starts to take a maximum. (2) At the equilibrium state, the volume fraction of rods in the two phases decreases as the axial ratio x increases. The volume fraction of the liquid crystal phase is slightly greater than that of the isotropic phase, the ratio between these two critical volume fractions increases with increasing x, but is always less than 1.56. For enough large x, the critical volume fractions are respectively = 8 , x = 12.5 . x

74

Liquid Crystalline Polymers

Figure 2.7. Critical volume fraction vs. axial ratio. (Modied from Flory, 1961. Reproduced by permission of John Wiley & Sons, Inc.)

(3) y /x increases smoothly as x increases, however, the variation is not great. The value of y /x is very small which illustrates that the ordering in the liquid crystal phase is very high. An experiment was carried out for PBLG to verify the theory. PBLG molecules in solution adopt an extended -helical conformation so that they are rigid rods. In Figure 2.7, the critical volume fractions of PBLG in solvents (Flory, 1961) were depicted as a function of the axial ratio. The curve A is for at which the liquid crystal phase starts to appear while the curve B is for at which the isotropic phase completely disappears and the system becomes entirely a liquid crystal. The solid curve is the theoretical expectation while the dashed line is the experimental result. Both are in good agreement. 2.2.4. Eect of soft interaction between molecules

Later Flory further took the two soft interactions between the molecules into account. The anisotropic interaction is associated with molecular orientations while the isotropic one is irrelevant of the molecular orientation. In fact, the anisotropic interaction was the basis of another well-known theory in liquid crystals MaierSaupe theory (Maier & Saupe, 1959). Flory successfully captured the essence of the theory.

Theories of Liquid Crystalline Polymers

75

First we introduce the isotropic interaction which results from the mixing of rods and solvents. The previous theory, without the mixing contribution to entropy, is only applicable to an athermal system. If there is a mixing entropy contribution, the free energy in Equation 2.39 is implemented by a term ns , where is the FloryHuggins interaction parameter. Flory called the mixing term the isotropic soft interaction to distinguish it from the steric interaction of rods. 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 , and y
2 y 1) 2 ( 1 + + = ln(1 ) + 1 x y x

ln(1 ) + ln x = ln

+ 2

+ ( y 1) + 2 2 ln x

y + x(1 )2 x (2.52)

+ (x 1) + x(1 )2 .

Figure 2.8 shows the numerical result of the rod/solvent system for the rod axial ratio x = 100. The ordinate is the FloryHuggins parameter and the abscissa is the volume fraction of rigid rods. For negative , the two phase equilibrium is basically independent of . A positive has a signicant eect on the two-phase equilibrium. The diagram can be divided into three regions: in Region I the concentration is small and the system is in a single isotropic phase; in Region II the system is in the liquid crystal phase; and in Region III both the liquid crystal and isotropic phases coexist. For less than, say, 0.07, the region of biphasic coexistence is narrow, / = 1.5. For greater than 0.07 the volume fraction dierence between the two phases becomes larger. Figure 2.9 shows the experimental results of the PBLG/dimethyl formamide(DMF)-methanol system (Nakajama et al., 1968). The axial ratios were 150 and 350, respectively, and the value was controlled by varying the concentration of methanol. The more methanol the greater is . It was shown that for small concentrations of methanol, the biphasic range is narrow. As the volume fraction of methanol increases (up to 0.100.12) the biphasic range becomes wider.

76

Liquid Crystalline Polymers

0.2

0.1

LC

II

0 I + LC LC

LC + LC

LC

0.1 I + LC 0.2 0 0.2 0.4

0.6 0.8 1.0 III

Figure 2.8.

Phase diagram for rod axial ratio of 100. (From Flory, 1956.)

Figure 2.9. Experimental phase diagram of PBLG/dimethyl formamide(DMF)methanol system. (Modied from Nakajama et al., 1968.)

Theories of Liquid Crystalline Polymers

77

Figure 2.10.

The phase equilibrium vs. temperature. (From Miller et al., 1974.)

The value of varies with the temperature, i.e., decreases as the temperature increases. Wee & Miller (1971) examined the phase equilibrium as a function of temperature. The results are shown in Figure 2.10. For temperatures below 35 C the phase diagram is basically the same as the Flory theory; while at higher temperatures, the curve deects to a high concentration regime. This phenomenon was observed in a system of cellulose derivatives (Navard et al., 1981). Warner and Flory (1980) found that the introduction of the anisotropic attractive force predicts this eect. This anisotropic interaction associated with molecular orientation is expressed by 1 2 xnp S 2 T T , (2.53)

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 r6 ()2 , where r is the distance of neighboring rods.