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Disclination unbinding transition from the hexatic N+6 phase to the nematic phase in discotic
liquid crystals
C Giannessi
Maurice KlCman
Institut Curie, Section de Physique et Chimie, 11 rue Pierre et Marie Curie, 75231 Paris CCdex, France and
Laboratoire de Physiques des Solides, UniversitC Paris-Sud, 91405 Orsay, France
Abstract
Defects are local breakings of symmetry in an ordered medium. The physics of defects
has long been reduced to the study of dislocations in solids, and to the main physical
phenomena they are responsible for, like plastic deformation. Dislocations break
translational symmetries. Disclinations break rotational symmetries and are the basic
defects of media with continuous symmetries, like liquid crystals. In this review, it is
stressed how their study has contributed to a renewal of the physics of defects. Static
and dynamic properties in the nematic, cholesteric, blue, smectic and columnar phases
of liquid crystals are described in detail, up to the most recent results, for small-molecule
thermotropic liquid crystals as well as for lyotropic and polymeric liquid crystals. We
also discuss the homotopy classification of defects, including point defects, and compare
it with the Volterra classification; finally we present the curved-crystal description of
frustration in the light of the relevant situation in liquid crystals. The usefulness of
the concepts introduced for liquid crystals for the study of other systems (structural
problems in biology, dissipative structures, magnetic domains, etc) is also emphasised.
Contents
Page
1. Introduction 557
1.1. An overview of the theory of defects 557
1.2. Liquid crystals: materials, symmetries 559
1.3. Liquid crystals: free energy 563
1.4. The scope of this review 566
2. Static properties of defects. General considerations 567
2.1. The Volterra process for solid media 567
2.2. The Volterra process for partially ordered fluids 568
3. Static defects in smectic phases 569
3.1. Simple disclinations in smectics 569
3.2. Dislocations in smectics 570
3.3. Focal domains 577
3.4. Layer instabilities and defects 582
3.5. Defects in layered media other than SmA: generalities 583
3.6. Defects in SmC phases; bulk specimens 584
3.7. Defects in SmC* phases; bulk specimens 588
3.8. SmC and SmC" free suspended films 589
3.9. Lamellar phases with long-range and short-range 2D positional
order 589
4. Plasticity of smectic phases 590
4.1. SmA phases 590
4.2. SmB phases 596
4.3. Hexatic smectics 597
5. Defects in columnar phases 597
5.1. Developable domains and disclinations 598
5.2. Dislocations, walls and grain boundaries 602
6. Defects in nematics and cholesterics 605
6.1. Disclinations and singular points: a summary 605
6.2. Recent results on disclinations 606
6.3. Disclinations: dynamics 607
6.4. Chiral nematics (cholesterics) 609
6.5. Biaxial nematics 613
6.6. Polymeric nematics 615
7. The classification of defects by algebraic topology methods 62 1
7.1. The essentials of the topological classification of defects, and
examples 62 1
7.2. Other results concerning the topological theory of defects 625
7.3. Defects with partial topological definition (semi-defects) 628
7.4. Surface defects, cores and the use of the exact homotopy sequence
in various problems involving defects 629
8. Defects in media with frustrated symmetries 632
8.1. Generalities 632
8.2. Frustrated liquid crystals 635
8.3. Curved space representation of double twist 64 1
References 646
Defects in liquid crystals 557
1. Introduction
Research in liquid crystals has been a very active field for almost twenty years, despite
several decades of somnolence; it has contributed considerably to our understanding
of a number of important topics in condensed matter physics. The large variety of
different phases displayed by thousands of liquid crystalline materials synthesised by
the chemists has led physicists to investigate at least two major fields in which major
advances have thus been made: phase transition theory (global symmetry breakings)
and defect theory (local symmetry breakings). This review will try to cover the major
developments in the field of defects in liquid crystals over the last ten years; however,
most of the concepts are not restricted to these materials and consequently we shall
be led, in some instances, to consider other condensed systems. It will repeatedly be
apparent that defects are not only some sort of mischievous object that perturbs
perfection and which should be avoided as much as possible, as the name defect would
seem to indicate: they also have unique and beautiful properties which means they
are essential to the understanding of phase transitions, disordered systems, frustrated
media, convective instabilities, some biological shapes, etc. Historically, liquid crystals
have been the mould in which many of these new features of defects took shape. But
in their own right defects in liquid crystals constitute a beautiful field of research which
is far from being exhausted.
(very clever) attempts, until Frank brought this subject afresh to the attention of
physicists in his much quoted 1958 paper; he coined the word disinclination (now
disclination) and indicated the kinship of this subject to that of dislocations.
Briefly stated, while dislocations are topologically related to symmetries of transla-
tion of ordered phases of condensed matter physics, disclinations are related to their
symmetries of rotation. Such a connection implies a number of similar questions in
both fields of research (in that respect the relevance of metallurgical concepts in the
physics of disclinations has to be recognised) while the differences pave the way for
problems of a somewhat different, and unexpected, nature.
As dislocations, disclinations are sources of internal strains, and are therefore in
general metastable entities. Comparing dislocations and disclinations energies, the
latter appear to-be as relevant as or more relevant than dislocations not only in liquid
crystals but also in spin systems, phases of biological materials and various other
systems often characterised by the presence of continuous symmetries. Typical ques-
tions like the nature of the core, the presence of kinks on the defect lines, their
interactions, growth, movement, multiplication, splitting, can be asked. The answers
are not mere replicates or extensions of the known answers for dislocations. In
particular there is a complex and beautiful topological interplay between dislocations
and disclinations (when they coexist in the same material) which reverberates between
splitting and mobility mechanisms. Also, since fluidity is an essential property of liquid
crystals, concepts pertaining to metallurgy and hydrodynamics must be used simul-
taneously, in a very original way. In contradistinction to the case of liquid crystals,
the basic mechanisms that rule the mobility of spin disclinations (called Bloch lines)
in ferrimagnetic garnets are well understood (Malozemoff and Slonczewski 1979), but
much remains to be done in investigating their interactions with the lattice defects
(dislocations, precipitates, etc).
The doubled-sided nature of the defect concept (topology on one hand, strains and
stresses on the other) is best reflected in the Volterra process of defect fabrication,
which yields the so-called Volterra classification of line defects (each defect type
corresponds to an element of symmetry (translation and rotation) it breaks), and opens
the way to a discussion of the energetical stability of a defect. In that respect the
Volterra process has some advantage over a more recent approach to the classification
of defects which uses the so-called homotopy groups of algebraic topology (Toulouse
and Kliman 1976), and deals therefore only with the topological stability of defects.
This is, however, treated in a somewhat deeper way in this approach, since difficulties
like the non-commutativity of the symmetries of rotation, or the relationships between
dislocations and disclinations, do disappear completely. Another great advantage of
the homotopy approach is that it applies to defects in all ordered media and can be
generalised to point-like, planar defects and configurations. It also extends to vortices
and other defects in superfluids and all sorts of isotropic materials that have gauge
symmetries.
Phase transitions are often driven by defects, which within this perspective can be
considered as condensates of fluctuations. Kosterlitz and Thouless (1972) have
described in this way the transition in a 2 D X - Y model, which invokes magnetic
vortices (disclinations); more recent models that use the splitting of dislocations in
two disclinations, describe a new 2 D phase, the so-called hexatic phase (Halperin and
Nelson 1978) whose existence is ascertained in some smectic materials. Evidence of
the same type of phenomenon in 3D is less clear; however, the vortical rotons of
Hiritier et a1 (1979) in superfluid 3He and 4He, which are condensates of solid-like
Defects in iiquid crystals 559
fluctuations, may play a role in the liquid-solid transition. Similarly the martensitic
transformation involves the creation of defects, as well as the classical description of
the solid-liquid transition (for a review of this last topic, see Halperin (1981)).
Finally disclinations are met in configurations resulting from competing interactions
which are geometrically incompatible at molecular scale; examples are, amorphous
metals, where local pentagonal packing of atoms cannot extend in space homo-
geneously, and blue phases of liquid crystals, whose complex structure results from a
balance between incompatible cholesteric and nematic ordering. In all these cases this
'frustration' can be given a geometrical representation by a 'crystal' in a 3D curved
space (KlCman and Sadoc (1979)); disclinations are the tools which are useful to
decurve this space and obtain structures in real space. This is indeed no surprise for
dislocation researchers, who have known for a long time that dislocation densities can
be represented by torsion in a non-Riemannian manifold, and disclination densities
can be represented by curvature (Kondo 1955, Bilbey et a1 1955, Bilby 1960, Kroner
1981). But the interesting fact is that we have at our disposal physical realisations of
curvature.
o /
/ o
HllC5 /
HnC5
which orders in a columnar LC phase between T = 69 "C and T = 122 "C. One will
easily recognise that a character common to all molecules is the coexistence of a rigid
560 M Kle'man
central part (usually benzene rings) and of flexible exterior parts. These ingredients
seem indeed necessary to obtain a LC phase. Most of the LCS studied today consist
of elongated molecules. Some amphiphilic compounds, like block copolymers (e.g.
polystyrene-polyethylene) give rise to thermotropic phases. A number of polymers
give thermotropic LC phases. They fall into two classes: main-chain polymers, made
of mesogenic monomers in line and side-chain polymers, i.e. a non-mesogenic backbone
along which mesogenic molecules are grafted at periodic repeat distances (figure 1).
Some of these new LC phases, like Kevlar, are most important industrially; their study
is expanding rapidly (cf Cifferi et a1 1982, and the Proceedings of the First Conference
on Liquid Crystal Polymers, Bordeaux, 1987, published in Mol. Cryst. Liq. Cryst.
February 1988).
(ii) Lyotropic liquid crystals, made of organic elongated molecules associated with
other molecules like water, oil, alcohol, etc. Rigid rods in solution (e.g. tobacco mosaic
virus TMV) or semi-rigid polymers in solution (e.g. molecules of biological origin like
PBLG, xanthan or DNA), display LC phases which are mostly nematic or cholesteric.
Another, wide class, of lyotropic phases is obtained from amphiphilic molecules, with
a polar head (hydrophilic) and a paraffinic tail (hydrophobic) in water and/or oil.
Typical molecules are lecithin, Na laurate, sodium decylsulphate ( SDS), pentaethylene-
glycol dodecylether ( c ~ ~ E o a~ non-ionic
), surfactant. With water, they act as surfactants
and build liquid or solid interfaces with fascinating spatial arrangements, a number
of them having the same symmetries as thermotropic LCS, others extending the realm
of LC order.
random, the point group is P = D 2 ,but many other possibilities exist, with P being a
subgroup of the group of rotations O(3)t). While uniaxial nematics are most common,
biaxial phases have been discovered only recently, in lyotropic systems and in polymeric
nematics (Yu and Saupe 1980a, b, Windle et a1 1985, Hessel and Finkelmann 1986).
A cholesteric N* is a twisted nematic, i.e. the building blocks rotate with a constant
pitch along some direction. It is made of chiral mesogenic molecules or can be obtained
by introducing in a nematic some quantity of chiral molecules. Most recent studies
+
of N * phases concern lyotropic materials (surfactants water: Yu and Saupe (1984b),
Figueiredo Net0 et a1 (1984, 1985); cholesteric mesophases of biological origin like
DNA in water: Livolant and Bouligand (1986) etc).
(ii) Smectic phases. These are lamellar phases, made either of molecules stacked
parallel one to another (thermotropic) or of bilayers of amphiphilic molecules separated
by water or oil (for instance, soaps, from which they take their name). Smectics are
therefore one-dimensional solids (in the direction perpendicular to the layers); different
types of ordering in the layers lead to various smectic types, either liquid-like (SmA,
SmC; see figures 3(a) and (6)) or solid-like (SmB sensu stricto, etc). In SmB hexatic,
SmI or SmF, the order inside one layer does not propagate coherently (figure 3(c));
we have 2D short-range order and 2D or 3D bond orientational order with some
unusual phase transitions where defects play an important role; since it is easy to
achieve monolayer samples, or at least samples containing a few layers, the physics
of these phase transitions has been quite active in recent years (Prost 1984). For a
review on 2D order in smectics, see Helfrich and Heppke (1980). All smectic phases
are reviewed from the point of view of order and textures in the beautifully illustrated
book of Gray and Goodby (1984). SmA phases have been the standard medium for
the study of defects relevant to the layered structure only (focal conics).
As there are twisted nematics N*, smectic phases made of chiral molecules may
have a helical pitch superimposed on the layer periodicity (SmC*, for instance).
(iii) Columnar phases (also called canonic phases). They arise either with discotic
molecules (which stack in columns which arrange in a 2D ordered lattice), or with
amphiphilic molecules arranged in infinite cylinders either direct (water outside) or
inverse (water inside), forming 2D hexagonal lattices (figure 4). These latter phases
have long been known in the soap industry. Discotic phases are a more recent discovery;
their study has again emphasised the importance of geometry in defect theory, a fact
already known since Friedels analysis of focal conics in smectics.
t We follow the Landau and Liftshitz (1962) notation for the groups.
562 M Kle'man
(C)
Figure 4. ( a ) Discotic hexagonal phase; ( b ) and (c) lyotropic hexagonal phases (direct
and inverse).
(iv) Blue phases. Blue phases were first characterised in myristate cholesterol by
Saupe (1969); it is a bluish (hence the name), optically isotropic phase, with cubic
symmetry, made of chiral molecules, stable in a small temperature range between the
isotropic (liquid) and the cholesteric phase. The lattice parameter is of the order of
the pitch. Intense research on blue phases started only in the early 1980s, and has
proved remarkably rewarding. There are in fact three blue phases, noted BP I, I1 and
I11 (temperature increasing). BP I and BP I1 are cubic ( B P I is probably simple cubic
and BP I1 BCC) and grow with beautiful crystalline shapes (Barbet-Massin et a1 1984);
BPIII (blue fog) is isotropic but with a short-range order extending over a length
comparable with the pitch. The importance of blue phases stems from the fact that
they are frustrated phases: the molecules have the tendency, in their ground state, to
twist in all directions (this is called double-twist; in N" there is only one helicoidal
axis), but this geometry is non-crystallographic and thus forbidden to extend infinitely.
Defects in liquid crystals 563
There is therefore some characteristic length on which the unfrustrated geometry can
extend, but not beyond; the medium is then made of domains of size 6, separated by
boundaries which can be analysed topologically in terms of defects. However, the
whole structure is thermodynamically stable. The term frustration was first introduced
for spin lattices (Toulouse 1977b), then applied to spin glasses, amorphous media and
to the complex alloys (phases of Frank and Kasper (1959)) which are the analogues
of BPS in metals. Blue phases offer an example where the geometrical content of
frustration shows up clearly (figure 5 ) . It has been proposed that the blue fog is an
icosahedral liquid quasi-crystalline phase (Hornreich and Shtrikman 1986) similar to
the aperiodic quasi-crystals of A1-Mn alloys first discovered by Shechtman et a1 (1984).
Figure 5. ( a ) Cholesteric phase N * . One axis of helicity (simple twist). We use the nail
convention (Frank) to represent a director at some angle from the plane of the drawing,
assuming that the head of the nail (which is along the principal molecular axis) is on the
side of the observer. Here the cholesteric is right-handed. ( b ) A molecular local arrange-
ment with double-twist (along the axis of the cylindrical region); ( c ) frustration of
double-twist between the cylinders, with the defects as in ( d ) ,along the ternary axis. This
geometry is believed to occur in blue phases.
564 M Kleman
Twist
Figure 6. The basic distortions of a director field: ( a ) splay only; ( b ) twist only; ( c ) bend
only.
where cy is the angle of rotation and d the thickness; n x curl n, the bend density ( K 3
bend constant), is the only non-vanishing gradient in figure 6 ( c ) .
K24;the constant of saddle-splay, governs a gradient term which, by Stokes' theorem,
amounts to a surface term. This is why it is not always considered. However, it plays
an important role when new boundaries are created, or when the boundary area scales
faster that v213,v being the volume. A large positive K24stabilises blue phases (KlCman
1985b). The geometrical meaning of the gradient term itself is very simple when n is
normal to a surface (as in SmA, where it is the normal to the layers, or in water-surfactant
systems, where it is the normal to the interfaces). We have
= f div(n div n
c1c2 + n x curl n ) (4)
where cl and c2are the principal curvatures of the surface, and e1u2its Gaussian
curvature.
In a smectic, the free energy has to be supplemented by a term which describes
the layer elasticity. In a SmA it is:
where U is the elastic displacement of the layer, measured along its normal. It is tacitly
assumed in equation (5) that when the SmA is deformed n remains normal to the
layer. d u / d n is the derivative of U along the normal. In addition, note that the Frank
free energy simplifies in a SmA, where n is along the normals to the layers. For this
geometrical condition we can write:
n curl n = 0
so that twist is identical to zero (except in the cores of defects, where the layering is
broken). It can also be shown that the bend contribution is small compared with other
contributions, except when the radius of curvature of layers is small compared with
A , = (K1/B)'I2.
566 M Kleman
If the medium is biaxial, QIj is still traceless but with three different eigenvalues;
Hence the Landau-Ginzburg energy is more complicated than equation (3).
Other free-energy densities have been derived when the order parameter has
components other than a pure nematic one. We shall not have to refer to them in
general, although our approach to the topology of defects requires a detailed knowledge
of the order parameter. But it will be apparent that our approach to the toplogy of
defects in fact provides details of the concept of order parameter.
We shall introduce static defects in liquid crystals without using the full power of the
homotopy classification; we shall rather present experimental results (observations)
and theoretical analysis essentially at the same time as they appeared historically. This
presentation has the advantage of emphasising the extraordinary variety of the physical
properties of defects in relationship with the molecular properties. For example,
disclinations in N phases appear quite different whether they are studied in short
molecules (usual) nematics or in polymeric nematics, even when they belong to the
same class of local breaking of the symmetry group. Such differences show up in the
core properties and in the relative importance of splay, bend and twist distortions
around the defect. The natural guide in such an approach is the well known Volterra
classification of defects, which works perfectly well for dislocations and to some extent
for disclinations. The necessity of introducing topology will become apparent during
this presentation, as we want to take inspiration from the methods devised for physical
metallurgy; this path has also the advantage of providing us with texture analysis
which is widely used to characterise the nature of a phase by simple observation of
its defects (Demus and Richter 1978, Gray and Goodby 1984).
I
Figure 7. The Volterra process for a line defect (6, n) in a solid.
568 M Klkman
I
1 6 *
I I
of the cut surface with respect to each other by a supplementary quantity fl x 6,i.e.
introducing a dislocation of Burgers vector b = SL x 6 perpendicular to the disclination.
Such a process would require a large energy in a solid. In a nematic, the dispersion
of the dislocation into infinitesimal defects db relaxes this energy and is in fact the
process by which fl follows the line L to its new position. Observe also as a consequence
that the movement of a disclination in a liquid is accompanied by a general process
of emission (absorption) of dislocations.
Consider now a curved line L in a nematic. fl will vary from point to point along
L in order to decrease the stresses, but at the expense of the presence of static
infinitesimal dislocations attached to the line. Consider, as in figure 8(b), two points
P and Q = P + tds infinitesimally close on L. The dislocation introduced by the
variation of position of SZ from P to Q is, by reasoning on the cut surface as above,
equal to:
d b = n x Q M -fl x PM=fl x t ds (6)
where M is any point on the cut surface.
Note that the angular variations of the director n about the disclination line can
be understood as being caused by this density of dislocations attached to the line.
This point of view is developed in Klkman (1983b, ch. 6 ) . Such an effect is quite clear
in a smectic, where a static dislocation db located between two layers creates a mutual
glide of the layers, and consequently a curvature of the layers. A density n of
dislocations of such a type leads indeed to a curvature 1/R measured in a plane
perpendicular to the dislocation lines, and which is proportional to n (figure 8(c)).
This approach is in fact much akin to the approach of curvature in bent crystals made
by Nye as early as 1953; in this approach the density n of dislocations introduces extra
matter to an extent that compensates exactly for the strains; accordingly the resulting
bent crystal has a constant density and is unstressed at a scale of the order of the
distance between dislocations.
Finally, while infinitesimal dislocations translate fl along the disclination line,
infinitesimal disclinations change its direction. For example they can be invoked to
describe the wedge character along the entire length of disclinations in cholesterics.
la)
Figure 10. Disclinations A and B can smoothly approach one another and annihilate.
of elasticity obtained by minimising the sum of the terms of equations (3) and ( 5 ) .
The dominant terms read:
K , AC\:u= B a 2 u / a z 2 (7)
where
A, = a2/ax2-+ a2/ay2.
One will notice by the presence of fourth-order derivatives how different this equation
is from the equation of standard elasticity.
3.2.1. Edge dislocation. The straight edge dislocation (figure 1 1 ) has been considered
by de Gennes (1972) and KlCman and Williams (1974). The strain a u / a x and the
energy per unit length of line is:
d u l d x = $&[ b/(Az)] exp( - x 2 / 4 A z )
W = Klb2/2Ar,+ W,
where A = (K1/B) is a penetration length, W, the contribution of the core to the
total energy and b = ndo. Different core models will be discussed as a function of
A / d o . This quantity is usually of the order of unity, but can be much smaller in some
materials where the layers are very flexible ( K1small), like non-ionic surfactants + water
(Oswald and Allain 1985) or lamellar phases close to microemulsions (de Gennes and
Taupin 1982).
The strain 13 = a u / d x is strong inside two parabolas x2 = *4AZ, and weak outside.
Its variation with x and z is special to the elasticity of equation ( 7 ) .
The energy varies as the square of the Burgers vector, which should favour
dislocations of small Burgers vector ( n = 1 ) . However, some observations indicate
that dislocations of the same sign gather into dislocations of huge Burgers vectors.
This might be explained with a core model which is split into two disclinations L1 and
L2 of opposite signs, as in figure 1 2 ( a ) (such a splitting was proposed long ago by
Friedel (1964) for dislocations in graphite). In this model, r, is of the order of the
distance between L , and L 2 , and scales like b ; the elastic energy is then proportional
to b, and the core energy reads:
W,= ( 1 r K , / 2 )In b / 2 d o + w, (9)
where w, is a new core energy for the disclinations which does not depend on b. The
first term on the right-hand side of equation ( 9 ) is pure curvature energy (of L 2 , where
the layers are parallel). Strain energy of L , can also be minimised (at the expense of
curvature energy) by some instability along the line, which can also be described as
some (longitudinal) splitting of the line into focal domains (see 0 3.4).
572 M Kleman
Figure 12. Splitting of an edge dislocation into disclinations of opposite signs. ( a ) Usual
model, A = d o ; ( 6 ) anisotropic core in a low K , lyotropic smectic.
The core model which has been discussed has to be modified when A/do is very
small (Allain and KlCman 1987); the core extension & along the z axis is still the
distance at which the width of the parabolas x2= f 4Az reaches do (in this region the
curvature of the layers is larger than l / d o and the linear analysis of the distortions
fails), but this quantity & = di/A is now much different from & = rc = b and the core
is anisotropic (figure 12(b)). Note that .$ does not depend on n. Such anisotropic
configurations of cores probably exist in small K 1 layered systems, and they have
already been observed in 2D layered systems formed by the roll electrohydrodynamic
instabilities of nematics (Ribotta and Joets 1984); the quantity analogous to A is here
the frequency of the AC voltage which drives the instability. When A is small, the
extended dislocation core plays a major role in the shear of the varicose electrodynamic
instability.
Edge dislocations are present in homeotropic wedges where they gather along the
mid-sample tilt grain boundary. Their mean distance A is then simply related to their
Burgers vectors and wedge angle (cf figure 26):
A = b/a. (10)
In this geometry energetic reasons (Pershan and Prost 1975) would rather favour
dislocations of small Burgers vector, as is found experimentally (Meyer et al (1978),
Defects in liquid crystals 573
Chan and Webb (1981a), Bourdon (1980), see also the recent experiments of Nallet
and Prost (1987) in a lyotropic SmA with a very large repeat distance -1000 A).
3.2.2. Screw dislocations. An obvious displacement field for a screw dislocation is, as
in usual dislocation theory:
U = b9/21r. (11)
The line energy, calculated to second order in a SmA, is zero, the smaller the Burgers
vector, the better this approximation. Thus, to this order, screw dislocations are objects
whose energy is restricted to a core energy: screw dislocations of small Burgers vector
have indeed a very small energy and are experimentally extremely frequent; they have
been observed with a density of 1O8cm- in different lyotropic SmAs by electron
microscopy of freeze-fractured specimens, which cleave easily along the interfaces of
the paraffinic chains (KlCman et a1 1977, Allain 1985). In these conditions screw
dislocations piercing the cleavage surfaces determine cleavage steps which gather in
rivers (figure 13) as in usual crystals (Friedel 1964, ch. 12). They have also been
observed by optical microscopy in homeotropic samples of SmA, near the SmC
transition (Meyer et a1 1978, Bourdon 1980). It is interesting to notice that in the latter
observations, edge dislocations finite segments are often visible (figure 14): at each
end of the segments there is a vertical screw dislocation segment continuing the
dislocation line, with of course the same Burgers vector. The absence of a smooth
variation (at least on an optical length) from the edge to the screw part of the line is
a further indication of the small energy of the screw dislocation; at the same time any
fluctuation in shape of the screw segment is difficult, which can be ascribed to a large
configurational line tension of the screw line. A calculation by Bourdon et a1 (1981)
gives:
T= 0.004Bb2 In(21rdAlrf) (12)
for a line of length d pinned at its extremities. A screw line resists curvature by
developing a configurational forcef= T/ R, where R is the radius of imposed curvature;
curvature arises (see D 4.1.2.) when the layers experience a compressive stress a,which
induces a Peach and Kohler force on the line f = a b (for this concept, see Friedel
Figure 13. Screw dislocations, steps and rivers on a cleavage surface of a non-ionic lyotropic
surfactant (freeze-fracture; courtesy M Allain).
574 M Klkman
Figure 14. Edge dislocation segments in a SmA thermotropic phase. Polarising microscope
photography, courtesy L Bourdon.
(1964) pp 31 and 34; some subtleties concerning its use in the case of liquid crystals
have been emphasised by Lejcek (1986)).
Taking into account higher order elasticity, screw dislocations are well understood
in two limits:
(i) in the vincinity of a SmA-nematic second order transition, A = ( K 1 / B )
becomes very large since B = 0 in the nematic phase; in the limit of B = 0 we must
have a vanishing density of splay, i.e. any geometry must obey the condition div n = 0,
which means, for a system in which the director field n is perpendicular to a surface
(the layers), that the mean curvature of the layers vanishes everywhere (see KIiman
(1983a ch. 5); the layers take the shape of minimal surfaces. For an isolated screw
dislocation the solution is a helicoid, whose equation reads:
cp= -b8/27r+z (13)
where cp = cp(r) is a phase variable constant on each layer, z is the coordinate along
the dislocation, and 8 a polar angle. Clearly cp + cp - b when 8 + 8 + 27r at constant z.
Equation (13) is in fact the same as (1 l), with U = z - cp, but now the solution is valid
to any order. The energy reads:
W = Bb4/ 128(r, - R - 2 )+ w, (14)
where R is the external radius of the sample. W does not diverge when R + C O and
the b4 behaviour ensures that only dislocations of very small Burgers vector are stable,
which differentiates them greatly from edge dislocations. Also, the order of magnitude
of (10) is 1000times smaller than that of the edge dislocation of the same Burgers vector.
(ii) When B is large compared with K1 (i.e. any interesting length in the problem
is larger than A ) , the layers prefer to stack with constant thickness do, i.e. parallel to
each other. Then & / a n must be taken to be equal to zero. Such a geometry has been
studied by Frank and Kliman (see Kliman (1983a) ch. 5). It consists of a parent layer
having the shape of a helicoid, with periodicity b, and a set of layers parallel to the
parent layer and stacked at constant distance do from each other. Let us emphasise
the difference with the former model: when div n =0, all the layers are helicoids;
Defects in liquid crystals 575
therefore, if b = ndo there are n such helicoids that fill the space; in the continuous
limit we have ( 1 1 ) . Clearly the axis r = 0, on which all these helicoids meet, is a
singular axis, and a core model has to be devised. However, when & / a n = 0, there is
only one layer in the shape of a helicoid, passing through the axis r = O , and no
singularity. The normals to the set of parallel layers are straight lines: note the analogy
between the set of layers and a set of wavefronts, between normals and light rays.
There is therefore a focal surface enveloped by the normals; in fact, the normals meet
two helices C, and C2 of pitch b, which are singular lines of the geometry and cusp
lines of the focal surface. C,and C, are the only visible singularities: the layers fold
around these lines as around disclinations (see figure 15). This is another example in
which two disclinations of opposite rotations couple to give a dislocation. This double
helix geometry has been observed by Williams (1975) in some SmA samples, with
dislocations of huge Burgers' vectors (figure 16). An estimation of the energy of the
screw dislocation split into a double helix leads to:
W=1.81K1+10-2Bb2+w, (15)
per unit length of screw line. The first term refers to the energy of the configuration
of the disclination type around the helices; the second term refers to those long-range
deformations created by the screw line outside the cylindrical region enclosed by the
helices: in this region splay is unimportant, and this term is in fact akin to the energy
calculated above (equation (14)), with rc = b/2 ( w , is a core energy). It can be shown
that the splitting in a double helix is favoured only for large enough Burgers' vectors
(i.e. b = 25do and above); this is why it is possible to observe this beautiful geometry
quite easily in experiments.
b/2n
Figure 15. Screw dislocation split into two helical disclinations C , and C2 of strength
S = f : transverse (above) and meridian cuts of the geometry of the layers. 5 = b/27r.
A measures the distance of the layer to the parent layer A = 0, which is a helicoid.
576 M Klkman
Figure 16. Screw dislocation of huge Burgers vector split into a double helix. Courtesy
C Williams.
Pleiner (1988) has recently calculated in their full generality the role of non-linear
terms in the energy of screw dislocations. His conclusions are that there is a large
contribution of bend elasticity near the core, and that two parallel screw dislocations
of same sign attract through a potential which varies logarithmically with distance.
The standard core model for a screw dislocation of Burgers vector unity in a
lyotropic is indicated in figure 17. Its advantage is to maintain a clear separation
between water and aliphatic chains, either water in the core (as in figure 17), or,
alternatively, aliphatic chains on the core. The core is in fact a sort of extended pore
in a unique membrane (there is only one layer, connected by the helical geometry). It
a unique membrane (there is only one layer, connected by the helical geometry). It
explains rapid diffusitivity in the bulk of amphiphilic molecules, which do not have
Figure 17. The core model for an elementary screw dislocation in a lyotropic medium.
Defects in liquid crystals 577
to jump through water to pass through the medium, and of water (pipe diffusion). If
n > 1, one can imagine n superimposed helices. But a definitive model of the core has
still to be worked out in this case.
Morawietz and Demus (1987) have argued that the growth of the SmA phase in
the shape of b6tonnets (Friedels term) occurs with a screw dislocation, very similar
to the mechanism of growth in usual solids.
3.2.3. Interaction between a microscopic impurity and a dislocation. The static deforma-
tion field of an impurity in a smectic phase and its interaction with a dislocation has
been studied by Lejcek (1986).
3.3.1. A quick reminder of the geometry of focal domains. Domains built on cofocal
conics are the most frequent non-trivial arrangements of parallel layers met in smectics
at the scale of the optical microscope observations. The condition of parallelism
implies curl n = 0, n being the normals to the surface: there is no twist (necurl n = 0)
or bend ( n x curl n = 0) deformations in focal domains, and n does not change as it
moves parallel to itself. It is the fundamental geometry which best relaxes imposed
boundary conditions in a smectic phase with liquid layers (i.e. where one layer easily
glides upon another, at no compressive elastic expense, only curvature energy). Thus
geometries of parallel layers are observed in SmAs and SmCs; this is essentially under
the form of focal conic domains (Friedel and Grandjean 1910), where the layers have
negative Gaussian curvature. Note however that spherical layers are also observed,
either between focal domains, or in free droplets, in both cases at small scale lengths
(Sethna and KlCman 1982, Lavrentovich 1986a).
Consider a set L of parallel (but non-planar) layers: as a general result, this set is
singular on the centres of curvature C1and C2of the layer surfaces; all parallel layers
have the same normals and the same C, and C, on a given normal; C1and C2generate
the evolute F of L, formed of two sheets F1and F 2 . In geometrical optics, F is called
the focal surface of L; it is indeed also the envelope of the normals to L. A pictorial
discussion of some topics in the theory of surfaces, quite useful for a thorough
understanding of what follows, can be found in Hilbert and Cohn-Vossens book
(1952); the interested reader who wants to go into more depth should read Darbouxs
remarkable treatise (1888, reprinted 1954).
The singularities of a set of parallel layers can be two- one- or zero-dimensional.
Two-dimensional singularities of parallel layers have never been observed; a onc-
dimensional subset of a 2D focal surface F is sometimes visible, the rest of the focal
surface being virtual. We have met such a situation when previously discussing the
splitting of screw dislocations into two helices (cf also KlCman (1983a) ch. 5).
A zero-dimensional singularity occurs only when the layers are spherical.
If both sheets of the focal surface are lines (one-dimensional singularity), then it
can be proved (Darboux 1954) that the two focal lines are cofocal conics (one ellipse
578 M Klkman
and one hyperbola, or two parabolas), and that the layers are Dupin cyclides (figure
Wa)).
Special cases of Dupin cyclides occur when: (i) the hyperbola is at infinity and the
cofocal circle E is a straight line; the layers form a set of parallel circular cylinders
about E. (ii) The hyperbola H is reduced to a straight line and the circle E is of finite
radius, R, centred on H ; the Dupin cyclides are nested tori centred on E, which is a
singularity of the same type as in (i) (figure 18(b)). The singularities of H consist in
conical points of layers, with a solid angle at the apex which tends to 27r at long
distances, hence the singularity on H becomes negligible at some distance of the plane
of the circle. (iii) Parabolic focal domains (Rosenblatt et a1 1977). The limiting case
of PFDS has not been studied by Friedel and Grandjean. The distortion of the layers
is extremely weak, except in the region where the parabolas cross (see the excellent
computed plots of the distortions in Rosenblatt et a l ) . PFDS are of small energy, and
are easily formed (figure 1 8 ( c ) ) .
The generic case has been well described quite often, and we refer the reader to
the classical reviews on the subject, starting with Friedel (1922).
3.3.2. Textures made of focal domains. The huge majority of observed focal domains
contains only those parts of the Dupin cyclides with negative Gaussian curvature, i.e.
those parts where the surface locally looks like a saddle. A few exceptions have been
observed (Meunier and Billard 1969, Zasadzinsky et a1 1985), where the surface is
I ,
Figure 18. Focal domains. ( a ) General case; ( b )toric domains; (c) parabolic focal domains:
a frequent association of PFDS, as it occurs in strongly dilated homeotropic samples.
Defects in liquid crystals 579
locally spherical. Most of them relate to free surfaces. The reason for the predominance
of saddle surfaces is probably because they have less curvature energy, since the splay
term reads 4Kl(uI+ u2)2 for a surface of principal curvatures u1= 1/ R1 and u2= 1/ R 2 .
It is therefore an advantage to have uluz< 0. Conditions of growth can also play a role.
In an actual sample of SmA, focal domains are the rule, rather than the exception,
except if great care is taken to produce a single crystal, generally in the form of a
homeotropic sample. Focal domains appear either complete (as described above), or
fragmented (the ellipse or the hyperbola being incomplete) or limited between two
cones with apexes on the hyperbola, etc. But they cannot tile space: this is forbidden
by their shape; in fact, in most instances, they associate according to rules that have
been described by Friedel and which can be satisfied entirely in an often-encountered
geometry (Friedel 1922, Williams 1976)-the geometry of a tilt grain boundary; this
we will now go on to describe.
Consider, as in the scheme of figure 19, two single crystals of SmA which meet
along a plane bisecting the normals to the layers on both sides; the plane is necessarily
a region where the order parameter experiences a strong variation. Assuming that this
variation occurs elastically, this requires an energy ( K,/B)12f( a ) with f(a )= a 3 for
vanishing angles (de Gennes 1974) but tending to a constant for not too small angles.
This is large compared with two other possibilities: introducing dislocations in the
plane, or focal domains. Let us consider these two possibilities.
I
Figure 19. A grain boundary in a SmA with smooth variation of the layers through the
boundary.
(i) Dislocations. A grain boundary can be split into dislocations (Friedel 1964).
This is a usual situation in solid crystals. Call a the angle between the layers on both
sides, and assume that the parallel edge dislocations of Burgers vector b are located
at a distance d = b / a from one another. The energy per dislocation unit length being
of the order of K l b 2 / A r , ,the energy per unit area is approximately (K1B)12when
rc = b. This solution is chosen in low-angle grain boundaries, and occurs in homeotropic
samples where the boundaries are not always strictly parallel (figure 26).
(ii) Focal domains. In this geometry, the ellipses are in the plane of the grain
boundary and the hyperbolas have asymptotic directions perpendicular to the layers
on both sides of the boundary; therefore they belong to planes perpendicular to the
boundary and the axis of rotation, and all have the same eccentricity e H . The ellipses
580 M Klkman
therefore have eccentricities eE = e i ,and have parallel major axes. Furthermore, they
are in contact, in order that the focal domains they carry fill space best. These focal
domains are tangential along the molecular directions which join these contacts to the
points at infinity along the asymptotic directions (figure 20), therefore they match
together with a vanishingly small energy, so that they tend to multiply, and focal
domains of smaller and smaller size could hierarchically appear between larger focal
domains and fill in the gaps, down to some size where the multiplication of singularity
lines should no longer be favoured.
Figure 20. A grain boundary in a SmA crystal. The layers are perpendicular to the long
singular lines which are hyperbolas belonging to focal domains whose ellipses are in the
grain boundary. Courtesy C Williams.
This iterative filling of the boundary with ellipses all of the same elongation and
the same eccentricity does satisfy the first of Friedels laws of association (if two focal
domains are in contact, they are tangential to each other along the common generator
of their boundaries). The second of Friedels laws (law of corresponding cones) states
that the cones of generators which have a common apex M belonging to two conics
must coincide. This is achieved in the geometry of the grain boundary if the contacts
M between ellipses are either along the major axes, or along the minor axes. This
seems to be the case in the observations of Williams and Kliman (1975) in CBOOA.
In lecithin, some observations from freeze-fractured specimens suggest a minimum
size of the order of 1000 A (KICman et a1 1977a, b).
Bidaux et a1 (1973) have considered the (simpler) iterative problem of circles; it
corresponds to the case of a zero disorientation angle a with hyperbolas reduced to
straight lines; Friedels second law is satisfied for any contact between circles. The
problem of the iteration of circles is known in mathematics as Apollonius problem.
Let g ( p ) be the number of circles of radius R > p, when the iteration reaches circles
of radius p. We have a scaling law g(p)--p- with t of the order of $ (numerical
calculation). Bidaux et al show that the energy per unit area then scales as:
U - ( K , B ) * (I/L)*- (16)
where L is the size of the largest circles, 1 the size of the smallest ones. Note that,
when a # 0, because of Friedels second law, the perimeter P ( p ) should increase more
slowly when p decreases, i.e. t should increase with a. Hence U decreases with a,at
constant L and 1. This supports the fact that grain boundaries, except for very small
angles, are split into focal domains (figure 20).
Defects in liquid crystals 581
In a grain boundary, the hyperbolas meet at infinity. The case when they all meet
at a finite distance is no different in principle: the planar layers between the focal
domains are replaced by spherical layers centred on the point of intersection of the
hyperbolas (Sethna and KlCman 1982).
The principal textures made of focal domains are described in Friedel (1922).
Amongst them let us quote the textures d bbtonnets, which appear at the isotropic-SmA
transition: (these b4tonnets are complex nuclei of SmA phase), the polygonal textures,
the fan textures, the Grandjean terraces (often decorated with small focal domains),
etc (for illustrations, see Gray and Goodby (1984)).
3.3.3. Energy of focal domains. The energy of the region of size A surrounding the
focal lines is difficult to calculate, since it is a singular region. It is reasonable to take
it of the order of K1 per unit length of line. The curvature energy of the bulk domain
has been calculated by KlCman (1977, 1983a), using Darbouxs method of local axes
at each point M of each layer (Mx, and Mx2 along the lines of principal curvature,
Mz along the normal). The fundamental quadratic form of a Dupin cyclide reads in
these axes:
ds2 = A du2+ B2 du2 (17)
with
A = ba2/ ((+I - ~ 2 ) B = kbq1 /((TI - ~ 2 )
(18)
(TI = 1/R1= ( C COS U - z)- a , = l / R , = ( a cosu-z)-l
where c = a - b and e = c / a ( a and b are the major and minor axes of the ellipse); U
and U parameterise each layer z, where z is measured along any normal to the layers.
Formulae are different for parabolic focal domains.
For small eccentricities, the bulk energy of a focal domain reads:
w = ~ T K , (-I e 2 ) K ( e 2 ) aIn a / r c (19)
where K ( e 2 ) is the complete elliptic integral of the first kind and rc is a core radius;
W is a decreasing function of e (for small values of e, as in equation (19) but also for
large es) for a given value of the major axis a (the domain volume scales like ab).
Hence, the situation in which the Dupin cyclides degenerate into tori is not stable:
the tori which are visible in real samples must be stabilised by some external factor,
generally surface anchoring forces, or topological forces (the transformation from a
torus to a generic cyclide requires a change in the nature of the core; this topological
barrier is indeed equivalent to the transition from a wedge disclination (the circle) to
a twist disclination (the ellipse) and requires the absorption or the emission of a
dislocation line (see 90 6.3.1., 7.1.2); it might be high).
For a parabolic focal domain confined to a cylinder of radius R, the bulk energy
reads:
W = 47rfK, In( R 2 / 4 f r , ) . (20)
Parabolic focal domains have smaller energy, for a given volume, than any other
type of domain. In fact, PFDS appear in all sorts of geometries. They build instability
in the strong non-linear stage of the undulation which appears when homeotropic
samples are submitted to large dilations (Rosenblatt et a1 1977, Oswald et a1 1982),
exist down to microscopic sizes (Clark and Hurd 1982) and have been observed in
thermotropic and in lyotropic smectics (Asher and Pershan 1979, Scudieri et a1 1979)
(see figure 18 above).
582 M Kliman
Equations (19) and (20) refer to isolated focal domains, which do not carry any
elastic energy of compression of layers. The iterative fillings of space by focal domains
necessitates some energy of that sort, which is included in a calculation like the one
leading to equation (16).
P L Pi
'Lx
Figure 21. Paired dislocations of same sign in a smectic (model for oily streaks); ( a )
transverse cut; ( b ) longitudinal cut; with instabilities displayed.
and has as such been invoked to explain the stability of pores in layers, micelles, etc
and of various lyotropic phases. For example, micelles are favoured by K24> 0
(Turkevich et a1 1984) in certain ranges of concentration of water versus surfactant;
recentiy Helfrich (1986) has advocated a < 0 to explain the stability of cubic phases.
This is related to the fact that the saddle-splay term factorises the Gaussian curvature
(equation (4)), hence K24> 0 favours positive Gaussian curvature, i.e. surfaces which
are locally spherical while K24 < 0 favours saddle-shaped structures. Such structures
with negative Gaussian curvature occur locally in pores (which have the geometry of
the inner part of a torus) or in the cores of screw dislocations of lyotropic materials.
Saddle-shaped structures were first discussed by Scriven (1977) for microemulsions,
and Helfrich (1981) argued that is negative in lecithin, where lattices of pores in
layers have been observed (Harbich et a1 1978). If this is true, this might also explain
the strong tendency of lecithin to grow in water in myelinic shapes which easily curve
into helical shapes, like flexible polymers (Friedel 1927, Sakurai et a1 1985).
that they have short-range (in-plane only) positional correlations of the molecules, but
keep long-range ( 2 D or 3D) bond-orientational order. Finally SmA and incommensur-
ate thermotropic smectic phases (for a recent review of their structural properties, see
Hardouin et a1 (1983) and the more theoretical paper by Prost (1984))are still practically
not investigated for their textures; however, some lyotropic phases of similar symmetries
( P p equivalent to SmB, and ribbon phases) have been studied by freeze-fracture
techniques (see, for example Ruppel and Sackmann (1983)). We shall therefore
highlight the essential problems raised by the smectic new phases, rather than describe
in detail the textures and defects (for such a purpose see Gray and Goodby 1984).
Finally some smectic phases of chiral nature show up phenomena believed to be
typical of frustration (Carlson et a1 1988). We shall discuss them in 9 8.
3.6.1. Disclinations of the tripodjield. The Volterra process proves useful in investigating
the configurations corresponding to the breaking of the symmetries of rotation: (i) the
n axis is a 2rr axis of rotation for the field t (and the associated field N ) ; (ii) the N
axis is a twofold axis for the n field and the t field (figure 22). We study the associated
defects in turn. More details and figures can be found in Allet et a1 (1978), Bouligand
and KlCman (1979) and Bourdon et a1 (1982).
/ f
(i) Defects of the t field were observed a long time ago (Taylor et a1 1970) and
constitute the elements of the schlieren textures of SmCs. The distribution of t about
the corresponding disclination lines, which are perpendicular to the layers, is similar
to the director distribution about wedge lines of integral strength in nematics. We use
the notation m(2rr), m(-27r) for these m lines.
Defects in liquid crystals 585
c f-
(ii) Defects which simultaneously affect the n field (i.e. the lamellar structure) and
the t field (i.e. the director field) will be noted l ( * ~ ) 1(*257),
, and called 1 lines. In
the simplest case, the distortions of the t and n fields are coupled as in figure 23(a),
which represents an I ( + T ) wedge line, which is a S = ++for the t and the n fields
separately. Figure 23(b) represents an imperfect line in the sense that it has wedge
character for the n field and twist character for the t field; it can be obtained as follows:
assume that N is at some angle from L and create a disclination of the n field about
L, letting the t field attach unperturbed to the layers. A surface discontinuity of the t
field appears on the layer bound by L. Each molecule located on one side of the
discontinuity is then rotated by an angle 2 a about n and allowed to relax; there appears
a twist disclination for t along L, which can also be described as a NCel wall of angle
2a; if any layer surrounding L is unwound on a plane, the directions t(m) and t ( - 0 0 )
make an angle 2 a (figure 23(c)). Such NCel walls in l ( + v )and l ( - ~ )lines have been
observed and calculated (width, energy) by Allet e? a1 (1978) in DOBCP. Hinov (1984)
has calculated the effect of a magnetic field on such lines, and shown that the partial
twist character can disappear above some threshold field.
NCel walls have a definite chirality; NCel walls of opposite chiralities are separated
by m lines (figure 23(d)) transverse to the 1 lines, which possibly form loops by joining
two transverse m lines (wedge) by two twist m lines. When cooling a specimen from
the nematic phase to the SmC phase such disclination loops often remain: they delimit
regions of opposite chiralities.
3.6.2. Focal conics. Focal domains exist in SmC phases for the same reason they do
in SmAs: layers can easily glide one upon another, and have a minimal energy when
they remain a constant distance apart. But focal lines can also be defined topologically:
they are disclination lines of mixed character (wedge and twist), with rotation vector
vector along N (Bourdon et a1 1982). In the present context of SmC phases, focal
ellipses are I ( T ) lines of mixed character. Many situations can occur for the t field,
the two extreme ones being, for a toric domain, the following: (i) N is parallel to the
singular circle everywhere: we have in any section the configuration of a perfect wedge
I( 5 7 ) ; the axis of the focal domain is an axial S = +1 line for the t field (i.e. an m(257)
line); it is this axial disclination which curves N along the singular circle.
(ii) N has a constant direction at infinity: the local I ( T ) line along the singular circle
is of mixed, variable, character, with a varying with the polar angle cp of the circle as
shown in figure 24(a). 2 a is discontinuous for cp = 5712 and cp = 3 v / 2 , which fact
necessitates the presence of two wedge m lines, which are of strength S = -1 (see
figure 24( 6 ) ) . The two m lines are attached to the singular circle; therefore they pass
through all the layers surrounding the I ( v ) line and reach the axis of the toric domain,
either at the same point (this is energetically the most probable situation, and it has
been observed and analysed first by PCrez et a1 (1978)), or in two different points
which must therefore be the extremities of a S = + 1 , m ( 2 n ) line segment, along the axis.
The case of a general focal domain is more difficult. It has been discussed at length
when N is uniform at infinity (Bourdon et a1 1982).
R aN
587
Figure 24. Line singularities in a focal domain of a SmC phase; see text.
a1 1978), because of the compressional stresses near the core which trigger the transition
in this region at a slightly higher temperature TL> To: the medium is then locally
biaxial, which is enough to provide for a strong optical contrast of the lines. Many
observations of the physical properties of the lines (relationship with m lines, visibility
of finite segments of edge lines continuing along screw lines, different mobility in the
SmA and SmC phases, etc (Bartolino and Durand 1978, Bourdon 1980)) have been
made with the help of this technique. Screw lines seen head-on are also visible.
Some calculations of the line energy and speculations on the core of the screw
dislocations have been made (KlBman and Lejcek 1980). The energy per unit length
of line reads:
W = [(A12A21)2/2/a](b2/4~)j32r;2 (21)
where, with
K =$All(A12A21)1/2
we have
and r, is some length related to the core radius. For the definition of the involved
elastic coefficients see KlBman (1983a ch. 7). W goes to zero when j3 + 0, i.e. in the
SmA limit of the anisotropy of the coefficients. The same authors propose that the
core is liquid, and that the molecular configuration in its vicinity is an m ( 2 ~ line
)
centred on it and screened at a short distance by an m( - 2 ~ line.
) The same model
has been proposed independently, on experimental grounds, by Ishikawa et a1 (1984).
588 M Kliman
Figure 25. Dechiralisation lines in a SmC* phase (courtesy Monique Brunet). Planar
anchoring on both lamellae.
Defects in liquid crystals 5 89
unwinding of the twist under an electric field proceeds by motion and annihilation of
these disclinations, and has been studied in great detail, both experimentally and
theoretically, by the Czech group (Glogarova er a1 1983, Lejcek 1985, Fousek and
Lejcek 1986, etc).
It has also been observed that focal conics in a SmC" always contain disclination
lines (Perez et a1 1981, Bourdon et a1 1982). This phenomenon has the same origin
as the similar phenomenon in a SmC.
where u' are anisotropic viscous stresses and g = -apf/au is the force per unit volume
exerted on the layers by their elastic response to any deformation field U of the layers;
in linear elasticity g reads
g = (0, 0, B a2U/dz2-K,A:u). (23)
Defects in liquid crystals 59 1
This force is relaxed by permeation (a diffusive motion of the molecules through the
layers (Helfrich 1969))
A,g = (0, 0, U - 0,) (24)
a process which is also much akin to the percolation of a fluid through a porous
medium, and obeys indeed Darcys law in the stationary and inviscid case
U - vZ = A, aplaz. (25)
The Newtonian viscosity p2 corresponding to the glide of the layers past each other
has been measured on perfect homeotropic samples (Horn and KlCman 1978, Oswald
1986b) at very low shear rates. At larger shear rates the samples do not remain
homeotropic and one always observes a progressive development of a regular array
of parabolic cofocal domains (see figure 18). They are related to the, unavoidable
undulation instability which always sets in, since the equidistance between the plates
cannot be maintained better than the penetration length A during shear. This array
develops in the direction of shear (Oswald and Ben-Abraham 1982). In Horns
experiments, the shear stress U necessary to produce a shear rate y during the
development of domains can be written as
u=A+vy (26)
where the viscosity v is low, of the order of 1 poise, and varies but little with the
proportion of regions filled with focal domains; but the solid friction A increases linearly
with this proportion, up to a value K,/12,where 1 is the size of the domains which fill
the sample. The existence of this yield stress implies that the domains, which are
probably anchored to the surfaces, impede the flow and are distorted under it.
Anomalous viscous behaviours and differences in the Couette profile have also been
reported in the regime before the nucleation of PFDS (Oswald 1986a), which is due to
the coupling of the flow with the forest of screw dislocations.
where permeation has not been taken into account. This relationship implies that (+I3
with
K- =(Vh,) 1/2
(31)
( K - ~is of molecular dimensions) and that the force per unit length necessary to produce
a velocity v is multiplied by a factor K b compared with a classical viscous force pv
F =Kbvv. (32)
(The same type of relationship has been obtained for the climb of dislocations in
Rayleigh-BCnard cells, see Dubois Violette et a1 (1983).) The real situation might well
be in between these two models.
A measurement of the mobility of edge dislocations in climb leads to a direct
measurement of the order of magnitude of A,. This is achieved in Bartolino and
Durands experiments (1977a, b), where a sudden strain is applied on a homeotropic
Defects in liquid crystals 593
sample; a lattice of parallel edge dislocations is created in the non-linear stage of the
resulting dilation instability, which relaxes with a relaxation time
r = ( d / m )Bpdo (33)
where p is the linear density of parallel dislocations, and do the Burgers' vector, which
experimentally is observed to be equal to one layer. A, can also be measured by the
'lubrication wedge' method (Oswald and K16man 1982), which is described in figure
26: when a liquid is sheared between two planar surfaces making a small angle a, it
is well known that a large pressure is set up, which is at the origin of the lubrication
process; by replacing the liquid by a homeotropic SmA, one expects an even more
spectacular effect since, apart from the easy flow of the layers past each other, there
is a genuine solid-iike resistance perpendicular to the layers. The lubrication set up
with shear y = v / d is also equivalent to a compression process with a vertical velocity
v, = cyv imposed on one of the plates. One observes then that the dislocations move
with constant velocity in the plane of the subgrain boundary where they sit, after a
transient time:
T= (d/cym)B
Typical values obtained this way are given in table 1. One will notice that the A,s are
all of the same order of magnitude but that the activation energies U differ widely.
Note, however, that in lecithin, the measurement of typical annealing times in wedge
specimens leads to A,- (Chan and Webb 1981a), much smaller than in the other
materials.
When a homeotropic sample is submitted to a constant load (compressive creep),
the edge dislocations climb under the u33stress, but also multiply, probably by a
mechanism where edge segments form Frank and Read mills (Friedel 1964) about
their screw parts (which are not affected by uS3stress). Also, as we shall see now,
screw lines pinned on the glass plates can suffer helical instabilities which generate
edge loops.
Helical instabilities of screw lines have been predicted by Bourdon er a1 (1981)
and seem to have been observed only in thermotropic smectics (Oswald and KlCman
1984). The mechanism is described in figure 27: the U,, stress is relaxed (above some
displacement threshold of the order of d o ) by the production of a helical turn which
Table 1.
/
/
--
I A
1 -
A
/
Figure 27. Helical instability of screw dislocation lines in smectics.
4.1.3. Glide of dislocations. Screw dislocations move parallel to themselves under the
action of configurational forces f , = ba,, or fx = ba,, ,
A screw dislocation moving parallel to itself with velocity vo in the x direction
provokes a backflow very akin to the backflow set up by the motion of a cylinder of
radius 5 in a liquid; .there is however, in addition, an important 21, component which
brings matter from one layer to the next, by a helical motion which avoids permeation;
as a result, permeation is practically non-existent outside the core (Pleiner 1986b).
Hence
V, = ti - v0 auldx. (34)
There are therefore two contributions to the drag force which acts on the dislocation
line, a classical Stokes force proportional to p2v0,and a (larger) force due to the U,
components, which reads (Pleiner)
To produce such a large force by the action of mechanical stresses would require
a large ~ 2 3 ,which could exist only near a kink on an edge line. However, if the
dislocation is pinned, and the sample sheared, the velocity field which is set up can
be large enough to couple to the dislocation. This produces an anomalous flow
behaviour and an increase in apparent viscosity which has already been mentioned
(Oswald 1986a). It is not possible to invoke the non-conventional hydrodynamics of
Mazenko er a1 (1982) to explain these anomalies, since p 3 does not show up any l / w
divergence in Mazenkos theory.
Glide of edge dislocations involves a periodic variation of the molecular structure
of the core (Friedel 1975), and the dislocation will tend to lie longer along the most
stable of those structures. Glide involves therefore a finite Peierls stress cr,,b. This
stress should depend on the nature of the core of the dislocation. For elementary edge
dislocations in usual thermotropic smectics, where the core is not expected to be split
into disclinations, this stress should not be too large and the process of formation of
double kinks of screw character (figure 28) would be thermally activated, and limited
by permeation. For multiple edge dislocations in usual thermotropic smectics, and for
edge dislocations of any strength in lyotropics, where the core is split into disclinations,
glide is expected to be very difficult, or even impossible, since such a motion would
require the exchange of dislocations between the two disclinations.. The case of
lyotropics has, however, to be considered apart when K , is very small, i.e. the penetra-
tion length h = ( K , / B ) 2 small compared with the layer repeat distance d o , as is the
Defects in liquid crystals 595
4.1.4. Focal conics. The motion of a disclination requires the emission or the absorption
of dislocations (Friedel and KlCman 1970). This is probably true also for its nucleation
and growth. This makes the rheology of disclinations of the focal conics quite difficult
and in fact largely unknown. However, the nucleation of focal conics, resulting from
instabilities of the flow, and their motion, have been carefully observed. We refer (i)
to the numerous observations of the appearance of parabolic focal domains in homeo-
tropics under dilation and shear (Asher and Pershan 1979, Oswald et al 1982); (ii) to
the observations of permeative flow around an obstacle made by Clark (1978) and (iii)
in planar geometries, to the experiments of Marignan et a1 (1978), Marignan and
596 M Kleman
Parodi (1979, 1983) in alternative shear; focal conics are periodically produced in the
volume of the sample, with their ellipses parallel to the surface. When the amplitude
of the shear is increased, these ellipses move surprisingly easily through the sample
and reach the surface, where they form geometries similar to those observed by Williams.
The motion of the focal conics is worth studying in more detail, inasmuch as it can
be observed directly. The threshold of appearance of the domains has been studied
theoretically (Marignan et a1 1983), and the results seem to be corroborated by
experiments; they can be described as a function of two quantities, N and M :
N = BOg/wT = 1 Og/wr+ (38)
where r,,, is the relaxation time of the order parameter and Os the critical inclination
M = TH (39)
where T~ is the hydrodynamical relaxation time ( rH= L2p/D, where L is the thickness
of the sample and p the density), w is the shear frequency. There are two regimes.
(i) When M < lo-, i.e. at low frequencies of shear Hz to lo2 Hz) Os is of
the order of a few degrees and varies like w l * , i.e. N is constant. The ellipses do not
change eccentricity at lo-* Hz when they move under small-amplitude shears, which
indicates a large amount of fairly easy permeation, while the layers bend elastically.
This is probably possible because the layers are firmly anchored at their extremities
on the glass plates. At frequencies of the order of 10*Hz, the geometry seems to
involve more plastic relaxation of the focal conics, which change shape when moving.
(ii) When M is large, N = M-4; but this regime has not been studied.
The study of the threshold at low frequency enabled Marignan to measure T+ as
a function of temperature, and obtain this way the critical behaviour of B in ~ O C B .
This yields B -c. T23as expected from de Gennes theory.
4.2. SmBphases
The crystalline nature of the SmB phase consists in a compact hexagonal structure
with a stacking of the layers of the ABAB type (Levelut er a1 1974,1977). The anisotropy
is very large ( a / c = 6), which explains the existence of a very small energy of coupling
between layers, and the presence of numerous small-energy stacking faults. The
dislocations of the basal plane, with Burgers vector along a, are therefore easily
dissociated into Shockley partials. The anisotropy reflects also in the elastic coefficients;
C44=lo6 erg cmP3,while the other elastic coefficients are lo3 to lo4 times bigger. At
very low applied deformations ( E < Cagnon and Durand 1980, 1981) under a
constant shear rate i. in the layers the SmB phase of 40.8 (butoxyl benzylidene
octylaniline) has a Newtonian response with an effective viscosity of the order of lo7
poise, i.e. reacts as a plastic solid. The corresponding shear stress which develops is
very small ( U < 200 dyn ~ m - ~ this
) ; suggests a regime of microplasticity. In a creep
experiment under large applied shear stresses ( U > 2000 dyn ~ m - the ~ )creep rate varies
in an exponential way, and suggests according to Oswald (1985) a model of thermally
activated glide of the basal dislocations. In this model the activated process is due to
the crossing of the forest of screw dislocations perpendicular to the layer ( b s = c). The
Peach and Kohler force drags indeed the basal dislocations whose Burgers vector b,
*
has a component f b along the shear, with a force F = ub along the shear direction;
the activation energy is the energy of the jogs formed at the crossing ( U = 0.6 eV,
including the energy of constriction of the basal dislocation lines). Comparison of
Defects in liquid crystals 597
experiments with theory leads to a density p d of active basal dislocations of the order
of 10 cm-, a dissociation width of 40 A and a stacking fault energy of lo- erg cm-.
Microplasticity experiments are explained in this frame by assuming that the basal
dislocations move so little that they have many crossings back. The density of disloca-
tions is very high and can probably be explained by the curvatures of the layers, which
introduce matching dislocations of the type described long ago by Nye (1953) for
curved crystals (see figure 8(c)). Nyes relationship between p and R, namely p = 1/ Rb
leads to R = 1 cm, which indicates that very small curvatures, which are not unthinkable
in such an anisotropic liquid-like material, can be indeed at their origin. There is also
a possibility that (largest) spontaneous curvatures are relaxed by vacancies and inter-
stitials, which would give rise to a Nabarro creep at much smaller characteristic lengths.
While numerous chemical syntheses of new discotic molecules have been performed
in recent years, the study of the physical properties of the mesomorphic thermotropic
phases associated with these molecules is as yet largely undeveloped. The book edited
by Helfrich and Heppke in 1980 still provides a relevant bibliographical introduction
to the chemical and structural properties of discotic molecules (see Billard (1980), also
Luz et a1 (1985), who puts emphasis on NMR methods of investigation). This slow
start is explained by the difficulties met in these syntheses, and the fact that obtaining
well aligned samples is often a question of luck. Some discotic materials, which have
an easily alignable high-temperature nematic phase, should give good single crystals
of columnar phases also at low temperature, oriented at will, but these materials are
not easily available. Freely suspended discotic strands have been obtained from
triphenylene hexadodecanoate (van Winkle and Clark 1982), where the columns are
along the strand, allowing for precise x-ray study. Finally, mesomorphic lyotropic
hexagonal phases have also been little studied, but are of fundamental interest, since
they show up phase transitions (hex e= isotropic or nematic micellar; hex e= lamellar)
which necessitate changes in the topology of the layers through mechanisms involving
defects (Gruner et al 1985).
While we know up to now only hexagonal lyotropic columnar phases, thermotropic
phases differ from each other by the nature of the columnar stacking, the tilt of the
molecular discs with respect to the column axis (Frank and Chandrasekhar 1980), the
rotation of the molecules and finally the density modulation along the columns (cf
de Gennes 1983, Godrhche et a1 1985). But we shall limit ourselves to a description
of the defects in the case of flexible, liquid columns, with untilted molecules; the
conclusions apply, largely unchanged, to hexagonal lyotropic phases.
598 M Klkman
We will discuss in order: (i) the developable domains, whose deformation field
implies only curvature elasticity and which are the analogue for these 1 D liquid phases
of the 2D liquid smectic A phases focal domains; (ii) defects which imply positional
elasticity (dislocations, walls). The most conspicuous defects in the polarising micro-
scope are straight disclinations (they are special developable domains), grain boun-
daries probably analysable in dislocations, walls analysable in dislocations and small
developable domains (figure 29).
Figure 29. Typical textures in a discotic hexagonal phase. Polarising microscope observa-
tion, courtesy P Oswald. ( a ) Planar texture; ( b )homeotropic texture, with grain boundaries,
and straight disclinations evidenced by their shadows.
Defects in liquid crystals 599
a columnar phase with only curvature deformations, inasmuch as planar textures (figure
29( a ) ) are very similar to the fan textures of smectics. In fact Monge surfaces are not
Dupin cyclides, except in the special case of the sphere and of the cylinder. Therefore
the analogy is mistaken (but is it not possible, a contrario, that fan textures could
involve Monge surfaces?). The simplest singularities involving only curvature energy
in a columnar phase are developable surfaces, and not focal conics, as we show in what
follows.
The columns C form parallel lines on a Monge surface; their normal trajectories
X are therefore geodesics. One can show that X and C curves are also lines of curvature
of the Monge surfaces. Two Monge surfaces are either parallel or intersect along a
C, which is a line of curvature on both of them; according to Joachimstahls theorem
(cf Darboux 1954), they therefore cut with a constant angle along C ; this is precisely
the condition of non-angular distortion we wished to satisfy in planes II perpendicular
to the Cs. Since the columns are also parallel, there are no local elastic distortions in
the planes II at all.
Figure 30 represents two infinitesimally close planes II; D is their line of intersection,
which envelops a space curve L when II moves. The infinitesimal motion of II can
be divided into a motion of pure rotation about 0, namely dq, and a motion about a
normal v to II passing through the point of contact of D with L, namely d$; II is the
osculating plane to L, and v is the binormal.
Consider any column C : its centre of curvature is on D, and its osculating plane
perpendicular to D. The curvature of the columns reads:
l/R=ltxcurl tl=dq/ds (40)
where t is a unit vector (director) along the column, and s the curvilinear abscissa on
C. Similarly, the curvature l l p of L in M (see figure 30) reads:
l / p = d$/du (41)
where u is the curvilinear abscissa on L. Properties of reciprocity exist between L and
C, namely:
p/T= -T/R (42)
where T and T are the torsions of C and L, oriented by the motion of II. The curvature
1/R of C becomes infinite on D, whose locus is consequently the singularity of the
600 M Kleman
set of parallel Cs. D describes a developable surface (figure 31) which limits the
domain of existence of columns. We call it a developable domain. L is the cuspidal
edge of the developable surface. For a complete theory, see KlCman (1980b).
Numerous examples of developable domains can be found in Bouligand (1980).
The curvature energy of a columnar phase is the same as the curvature energy of
a nematic, with the director t defined as above. In a developable domain we have:
div t = 0 t.curlt=O (43)
since there is conservation of the column flux and since the columns are parallel. The
only contribution comes therefore from bend and can be calculated as some integral
on L. We have:
where W, is a surface energy (of the developable surface) and where the y axis is
along the straight line D ( n ) in each plane n. Call 1, and 1, some lengths typical of
the domain; we have:
where b is some molecular length (a cut-off length near the developable surface);
=I
R I , Idc/pI, the average torsion of L, is a quantity which measures the strength of
the developable domain and depends on the torsion of L. If L is a planar curve,
1/ r = 0 and W = 0: this is indeed what we expect, because if L is planar the associated
developable surface is the plane containing L, and the columnar phase is perfect.
A remarkable fact is that the bulk term of W does not depend on the curvature of L ;
5
R, = Idalp1 is, however, an interesting quantity, which measures some intrinsic twist
of the columnar crystal about t along L.
Developable domains are classified in Klkman (1980).
5.1.2. Simple types of developable domains. We discuss disclinations and twisted points.
(i) Disclinations. If the developable surface is a circular cylinder K, we get the
simplest type of defect, the S = +1 wedge disclination (figure 3 2 ) . The intersections
of a plane containing a circular section of the cylinder with the half plane n are the
half tangents to K. The columns C are the evolutes of K. Assuming now that the
Figure 31. A developable domain: global geometry. L, the cuspidal edge, is the envelope
of the straight lines D which generate the ruled surface which limits the developable domain.
Defects in liquid crystals 601
Figure 32. The S = + 1 disclination in a columnar mesophase; the columns are along the
evolutes of the cylinder K.
ILz
Figure 33. The two possible positions L, and L, of wedge S = f disclinations in a hexagonal
columnar mesophase.
602 M Kleman
-
here a geometry whose twist has a definite sign, while the twist density t curl t is
vanishing by virtue of equation (43). Twisted points have not yet been observed.
pf = -
e
1 -+-
au au
B(dx a
+c-
~ ) ~ [:(:; I;:::
-+-
2)::
---
where U and U are the x and y components of the elastic displacement in the plane
perpendicular to the columns (along z ) and B and C two positive stiffness coefficients.
This equation assumes that the columns are liquid-like and relax to a constant density
in a finite time; however, in some geometries (when the stress a,, differs from zero)
this relaxation requires exchange of molecules between columns, a process which is
not elastic and is not supposed to take place quickly: in such case, a more general
expression of pfel is required, with a displacement w explicitly introduced.
For small distortions, the curvature energy density reads:
(-+ -)
pfc = f K l a2u a2u + f K,( - +fK,[
a2U - A) +(
(e) $)2].
(47)
axaz ayaz ayaz axaz ax2
We discuss below dislocations and walls of small disorientation in the frame of
this second-order elasticity for small distortions; this is of course not a good approxima-
tion for large curvatures (as they appear in developable domains); but even small
distortions might require in some cases a more elaborate free energy density, including
third-order elasticity (second-order terms display cylindrical symmetry; hexagonal
symmetry appears only in third-order terms). For example, the shape of the free
droplets which grow around disclinations (Oswald and KlCman 1981) or the growth
of instabilities above their threshold (dilation instability, buckling instability, KlCman
and Oswald (1982)) are probably governed by those terms (Frank 1982); the onset of
buckling instability should also be very sensitive to the plane of bending of the columns
forced by the experimental set-up.
which is akin to the equation for an edge dislocation in a smectic and can be discussed
similarly. At a distance from the core larger than A , = ( K , / B ) , the K , term is
Defects in liquid crystals 603
negligible, and we recover exactly the smectic equation, governed here by the charac-
teristic penetration length h3= ( K3/B)/; if K3 is very large (as claimed by Cagnon
et a1 (1984)), the elastic distortions extend in a large parabola (of width h3) whose
axis is along the y direction. At distances from the core smaller than A I ,the displace-
ment field reads approximately:
b b
u ( y , z ) =-+-tan- zhl/xh3. (49)
4 2
This core structure is quite novel; one expects a large core energy, since A l is large,
possibly relaxed by a Peierls-type splitting, which would introduce the columns free
ends. Direct microscopic observations are clearly needed to go further.
(iii) Screw dislocation. Taking the line along the x axis, the only relevant displace-
ment is U , which obeys the equation:
c d2U
- ?= K 2 - d4U 2 + d4 U
K3-z.
2 ay ay2 az dz
The calculation goes as above, with two characteristic lengths A;= ( 2 K 2 / C ) 2and
A: = (2K3/C)l2. In the region in the vicinity of the line (in a range of order Ah), there
is essentially twist deformation; the core region has the remarkable feature that there
is no necessity to introduce any physical singularity on the columns (figure 35). A jog
of molecular size on a screw dislocation introduces one free end; this should be in
practice a way of relaxing stresses which require a large divergence term div i.
it
Figure 35. Screw dislocation in a columnar mesophase.
604 M Kleman
5.2.2. Walls. Let us first distinguish two broad classes of walls (Bouligand 1980). Walls
of the first class are singularity walls; walls of the second class are planes II common
to two developable domains (figure 36). Together they form characteristic fan textures
which have been observed in lyotropic hexagonal phases, where they are due to
instabilities following desiccation (Rogers and Winsor 1969, Saupe 1977) and in
thermotropic phases, where they are also probably due to some elastic dilation instabil-
ity. They were first explained by Merucci (1976).
Walls of the first type divide in: curvature walls (cw), walls with developable
domains ( DDW), and discontinuity walls (DW), in ascending order of disorientation
angle. They can be symmetric or asymmetric, in which latter case they probably contain
dislocations. Low-angle grain boundaries are probably always split into dislocations,
as well as grain boundaries (always observed in homeotropic specimens). We will
discuss briefly the curvature walls (for details see Oswald and KlCman (1981)).
We assume as in figure 36 that the columns are planar and call 0 the angle of the
director t with the z axis perpendicular to the wall. The free energy density reads:
Minimising this expression and restricting ourselves to small angles 0 yields the first
integral :
W = $0:(
K3E). (54)
The O 3 behaviour indicates that such walls would be stable only for small values
of 0,;they are indeed observed for 06 15 O in thermotropic and lyotropic specimens.
\ cylinders
For these cw, as well as for DW and DDW, the inner structure of the wall deserves
more detailed microscopic studies.
situated in a region with no singularity of R in the so-called 'good crystal'; the integral
taken on this manifold is an integer. 4 v N represents the flux through a sphere of unit
radius centred at the origin of the vector n at any point of this closed surface, transported
to the origin; therefore N is the algebraic number of times this unit sphere is covered
in the considered mapping. Since the integral is a third power of n, the sign of N
depends on the (arbitrary) sign given to the director. Now assume that the singular
point makes a complete turn around a half-integral line: n changes sign after completion
of the loop, and N also. Therefore the singular point which has changed sign would
now annihilate with another singular point of strength N. This mutual collapse would
not have occurred before completion of the turn.
Singular points were first considered in ferromagnets by Feldtkeller (1964, 1965),
who introduced the above mapping on a unit sphere; soon afterwards Doring (1968)
calculated their energy. These are now of great importance in the physics of domains
and walls (Malozemoff and Slonczewski 1979). Equation ( 5 5 ) was first given by KlCman
(1970) for nematics and rediscovered by Blaha (1976) in his study of vortons (which
are singular points at the terminations of singular lines) in 3He-A.
Singular points can also be classified as vector field singularities (PoincarC sin-
gularities) as shown by Nabarro (1972). They have been observed and studied by
polarising microscopy in nematic-filled capillaries, first by Williams et a1 (1972, 1973)
and more recently by Melzer et a1 (1977a, b).
6.3.1. Mobility of an isolated disclination. A local analysis of the mobility can be made
in terms of the Peach-Koehler force (KlCman 1983b). Eshelby has argued that the
force on a disclination in a nematic LC is, unlike its namesake for a dislocation in a
solid, not a fictitious configurational force, but a real force. Formally, this is a
consequence of the near identity of the Ericksen stress and the appropriate energy-
momentum tensor.
A global analysis of the mobility is easy if we assume that the motion of the line
does not involve any backflow, but only a rotation of the director. The theory has
been worked out by Imura and Okano (1973) and de Gennes (1976), along very similar
lines. In the simple model of Imura et al, let
be the entropy production due to a disclination moving with constant velocity uo along
the x direction, y = a 3 - a 2 being a viscosity coefficient and cp some angle which
describes the orientation of the director about the line. By definition of the friction
coefficient J; we write U =fui.
Since there is no backflow, and assuming isotropic Frank elasticity, cp obeys the
equation
Then, for distances r from the disclination larger than r, = K / yuo, the second term in
the left-hand side of equation ( 5 6 ) is negligible, and the orientation of the director
about the moving line is the same as about the line at rest, namely
cp = cpo+ s tan-' [ y / ( x- u o t ) ] . (57)
608 M Kleman
(+
= 2 L
= -yuo In -
2 10
f = yW/2K (59)
where W = r K S 2 In L/ro is the energy per unit length of the line, L the size of the
sample and ro a core radius which has no reason to be equal to the core radius at
rest and which is necessarily.equa1 to or larger than rl . This theory assumes dissipation
for r > ro.
Geurst et a1 (1975) have studied experimentally the velocity U of a straight twist
Jisclination under the action of a magnetic field. It is easy to show by scaling argumellts
that uo depends on the magnetic field as follows
intuitive model for the dynamic splitting of the core has been suggested by Kltman
(1984; see figure 16). Note that r 3 / r ,= v y / K lo4; hence the splitting affects a quite
2-
in a time T ~ =yL2. The ratio r f / r ,goes like r 3 / r , . In the presence of a magnetic field,
it is the largest of the two times, Tf or r H =y / x a H 2 which dictates the relaxation
behaviour. Generally, T H >> T ~ .
(iv) The study of the dynamics of line defects in nematics has recently been extended
to the effect of electric fields (Cladis et a1 1987).
6.3.2. Nucleation and relaxation of disclinations in large shear $ow. Graziano and
Mackley (1984b) have experimentally put into evidence several regimes in a homeo-
tropic sample of MBBA under shear. At very low shear rate ( y < 1 s-l) the molecules
align along the velocity flow, in the manner described by Hilltrop and Fischer (1976),
up to saturation of their orientation. At slightly higher shear rate, disclinations nucleate
(see also Cladis and Torza 1976) in the form of closed loops of thicks and thins. Thins
nucleate in the boundary layers. These loops elongate in the flow and tumble, due to
the gradient of the velocity field. At y 10 s-' the entire field of view is covered with
2-
a complete mesh-like network of interacting lines. After cessation of the shear, they
relax by collapsing to points (this is the case for thins and nodeless thicks) or by
breaking at the nodes and shortening (thicks). An interesting observation is that the
contrast of the thins broadens when the shear stops; this observation is consistent with
the idea that the dynamic core is different from the static one, but now the static core
is larger, probably because the lines considered by Graziano et a1 are along the flow,
and not transverse as in 6.3.1.
6.4.2. Edge dislocations. These are observed in many situations, and in particular in
the Grandjean-Can0 geometry (Cano 1968) in which a cholesteric is inserted in a
wedge with parallel anchoring. The number of cholesteric layers increases therefore
from the edge of the dihedron outwards; this increase is relieved by a number of
discontinuities of the twist, which can be analysed in terms of x twist disclinations
parallel to the dihedron (de Gennes 1968). As shown by Bouligand (1974b), the line
closest to the edge has the configuration of a classical nematic twist line (this is a
region where the thickness of the specimen is smaller than the pitch), while the following
ones are dislocations split into two opposite wedge disclinations of strengths 14,either
a 7- and a A + coupled at a distance p/4 (figure 37a), forming a dislocation of Burgers
vector b = p / 2 (also a ~ ( i )or
) ,a A + and A - coupled at a distance p / 2 (figure 37(b)),
forming a dislocation of Burgers vector p (also a ~ ( 1 ) ) Note
. that other couplings (a
A - T + at d =p/4, a T-T+ at d = p / 2 , figure 37(c)) would lead to the same Burgers
vectors, but they are not observed. No doubt this is related partly to the gain in energy
due to the continuous cores.
.................. .. --
, - - - -- -
___-- - ,l .......................
any positive or negative integer. One can show (Bouligand and KlCman 1970) that
the strength S of the ,y disclination generated along the axis is S = 1 - m / 2 , and that
b = -pS (figure 38(a)). Rault (1973, 1974a) has shown experimentally that this simple
model should be modified in most cases by letting the molecules 'escape' along the
axis. For a ,y(+l), this escape is possible everywhere except in singular points distant
from p / 2 (figure 38(b)). For a ,y(-l), the escape of the A-director can be complete
(figure 38(c)), so that the only remaining singularities are those of the T and of the y,
directors, but they are immaterial. The same remark is true of course for the ,y(-1).
The generating pattern is interesting in that it can be modified at will in order to
introduce another singularity at some distance from the axis (figure 39). This is a way
to study in particular the configuration of helical pairs of disclination lines (note that
if m = 2, there is no singularity on the axis itself).
e
-4 ,;p
m =4
.
I-
0 .
Figure 38. Helical defects in a cholesteric. ( a ) Defect along the helical axis (see text); ( b )
Rault model of a x ( + 1) with partial escape; ( c ) Rault model of a x( - 1 ) with total escape
of the h director.
----------
there exists a fault plane in the medium marking their cut surface, after the manner
of stacking faults in solids. However, it is possible to pair two disclinations of opposite
signs (a, -Cl) at a constant distance in order that they cancel their effects at a large
distance. They are then linked by a small ribbon of infinitesimal defects (Friedel and
KlCman 1969, 1970). Note furthermore that such a coupling (a, -a)is a mode of
splitting of a dislocation, of Burgers vector b = at x d, where t is tangent to the line,
i.e. also a x disclination. No wonder therefore that the pair can curve at will, since
this is a property of a x line (and of a dislocation).
These pairings have already been illustrated; they are observed also in the kinks
of the dislocations and in closed loops. Bouligand (1974a) has given a complete
analysis of such observations, which can be quite often understood in physical terms
Defects in liquid crystals 613
6.4.5. Textures and double twist, Cholesterics display large textures of the focal conic
type, since they are layered media, with, however, more flexible mutual arrangements
than in smectics, since the pitch can be modified elastically at lower cost than the
thickness of the layers in a SmA (see Bouligand 1972b, 1973a, b).
Another important ingredient in the description of the textures of cholesterics is
the role of double-twist, which can happen locally as a helicoidal instability of small
energy (Lequeux 1986, Lequeux and KlCman 1988). This role of double twist is
probably enhanced by a large positive KZ4(KlCman 1987).
n is the strong director, that the biaxiality is weak ( m and t are weak directors) and
that t is perpendicular to the lamellar correlation. We can therefore imagine, as a
possible application of this isomorphism, that n and m lines couple like A and 7 lines
in order to form wedge disclinations of the t type, as in figure 40, according to the
algebraic rule n(f) m(f) = t ( 4 ) .
Two n(f), two m(5) or two t(f) couple to form lines similar to the S = *1 lines of
the uniaxial nematics, which cannot have a continuous core, since an escape in the
third dimension of n would not allow m and t to escape at the same time. There is
+
of course topological equivalence between n( 1) and n ( - l ) , as there is between
S = + 1 and S = -1 in a uniaxial nematic. As in cholesterics, we have to go to n(*2),
m(k2), t ( ~ t 2lines
) to get complete escape of the local frame, and a continuous core.
A considerable difference between NBs and N s is that singular points are not
topologically stable in NBs (see 0 7). Therefore a defect loop L of the type pictured
in figure 41, which is obtained by a rotational symmetry of the pattern of a n(+f), say,
does not exist without another defect along the axis of revolution M, because the loop
cannot shrink to a singular point as in a uniaxial phase. M is a defect of the type
n ( + l ) . The whole pattern is of course reminiscent of a focal conic in a SmA. In other
words, we expect that some kinds of disclination loops couple systematically with
S = + 1 defects.
Figure 40. ( a ) The three directors m, n and t of a biaxial nematic having the anisotropy
of a parallelepiped. ( b ) The coupling of two lines of types n and m leads to a line of
type t.
Figure 42. Pure twist stripes appearing in the Freedericks transition for splay in a nematic
solution of PRLG (courtesy D Srajer, F Lonberg and R B Meyer). (Applied field 3.4 kG;
periodicity 125 p m . )
chains (A4 = 1000) one observes a typical small molecule liquid crystal (SMLC) thread
texture, with thins (IS1 =$) and thicks (IS/ = 1). In the course of time the threads have
a tendency to disappear and be replaced by a well resolved texture of Friedel's nuclei
(plage ci noyaux, with only integral lines and singular points). However, for longer
chains ( M = 10 000 and more) there are very few integral lines or nuclei, and most of
the defects are half-integral lines, either loops floating in the bulk and tending to
collapse in a few minutes after their appearance (these loops have a twist character)
or lines attached to either the glass covers or (in free droplets) the free boundary. In
this last case one can observe directly that the size of the cores of S = +:wedge segments
is much larger than the size of the cores of S = -4 wedge segments (Mazelet and
KlCman 1986).
The interpretation relies on two related effects: (i) K1 is large in this product
( K ,= 3 x dyn; Sun et a1 1984), because of the scarcity of chain ends, while K 2
has its usual SMLC values ( K 2 = 3 x lo-' dyn). K , is probably small too. (ii) The cores
of S = + i wedge lines are clusters of chain ends (a large part of the necessary splay
deformation tends to be concentrated here); chain ends accumulate differently near a
S=-'l ine, where the chains align parallel to the core of a three-arm star. Fayolle et
a1 (1979) have observed a slightly different homopolyester and corroborate some of
these observations.
The fact that K , is large compared with K 2 and K , should lead, by an argument
of continuum elasticity, to a spreading on large distances of splay deformation,
according to Meyer (1982) who explains this way the formation of splay domains of
width R separated by disclinations where twist-bend deformation is highly concen-
trated. This argument is certainly true for a one-dimensional deformation, where we
expect R = ( K ,,I K23)d ( d being some radius, where twist-bend concentrates, of the
order of the transverse size of the specimen, K2, some elasticity modulus which involves
only K 2 and K,). But it may happen that there are local molecular mechanisms of
relaxing splay deformation which do not enter in the framework of continuum elasticity,
as for example the formation of hairpins (de Gennes 1977) or the concentration of
chain ends in dislocation cores. In the first case, the effective splay modulus could be
strongly reduced if the activation energy of formation of hairpins is small; this is the
only possible mechanism in the infinite chain limit, and for very long molecules, like
DNA. We discuss the second mechanism in more detail below.
The same polyesters also display 90" Bloch walls (we use a terminology borrowed
from the study of magnetic walls), in which the molecules rotate about an axis
perpendicular to the wall, with practically pure twist. This indicates that K 2 is small,
and provides an example of 1 D geometry of the type alluded to above. The domains
on both sides contain bend and splay spread all over.
Very thin films (a few hundred .$) of the same polyester, spread over a convenient
substrate and afterwards quenched (at a moderate rate) show up in high-voltage electron
microscopy an alternation of nematically ordered and disordered stripes, with a
periodicity comparable with the molecular length (Mazelet et al 1988). The stripes
become quickly amorphous under electron irradiation, but keep their individuality;
they are still visible by thickness contrast in electron microscopy. This effect had
indeed allowed Thomas et a1 (1985) to make the first observation of such stripes, but
in a random copolyester.
Finally, let us indicate the observation of anisotropic droplets in a nematic-nematic
phase separation, in a mixture of a side-chained polysiloxane with a SMLC nematic
(Casagrande et a1 1987). These very unusual objects seem akin to the tactoids quite
618 M Klkman
frequently observed in lyotropic polymers of rigid rods (Bernal et a1 1941). Here they
are explained as resulting from the competition between a low interfacial energy and
elastic energy of the nematic matrix.
(ii) Models for wedge disclinations S = ib. It has been proposed by Mazelet and
Kleman (1986) that the large-scale off -core observations of half-integral wedge segments
in free droplets have to be explained by the anisotropy of the Frank coefficient, for
example on the basis of the models of Nityananda and Ranganath (1980) as in figure
43(a). Such models are derived in the frame of the standard elasticity of SMLC nematics;
but in the limit of very long chains, we have to take into account a contribution of the
compressibility E-' (Taratuta and Meyer 1987), which dominates splay contribution
on lengths smaller than
A, = 2 ~K1(/ E)'/* (64)
E has not been measured in the polyesters we consider, but one expects that E scales
like the inverse length of the molecule, as long as there are no entanglements (L< Le);
taking then E = lo7 erg ~ m - K ~1,= dyn we get A, of the order of a few hundred
A. We show that it is also a typical size of the core when K 1 is large, so that the
model of the core has to be 'elastic' essentially. Of course the calculations are valid
as long as the core is not much larger than the molecular length L.
Figure 43. (a) A core model for the three-arm star observed in S = -4 wedge lines. ( b )
Core model for a S = +fwedge line.
For a S = +i (figure 43(b)), we assume that the core elastic energy is minimised
by a clustering reminiscent of the geometry of a crystal bent under the effect of a
density of dislocations ( 0 2.2 and figure 8(c)): the polymer chains are represented by
half straight lines, which are the analogues of the extra atomic rows in Nye's model;
d, the mean distance between chains, plays the role of the lattice parameter in the
transverse direction; the chain ends ate dislocation segments of the lattice, the whole
dislocation lines being along the core. The total (elastic) energy of the core is in this
geometry essentially restricted to the interaction energy between chain ends. If 1 is
-
the mean distance between the corresponding dislocations, we have 1 (drm)1'2,where
Defects in liquid crystals 619
rm is the size of the cluster. Hence for the total core energy
E dr, r,
W,=- In - (65)
8 d
and for the total line energy
W = W,+ K23 In A/ r,
where K z 3 is a bend-twist constant and A a typical distance between disclinations.
Minimising with respect to r,, one finds
-1
r m = -8(K 2 3 ,+In?) A23
Ed
where A23 = 2 7 ~K( 2 3 /E). This is of course a very large core, because of the ratio
A23 / d, which is anyway large, even if is much smaller than A,.
The model of an S = -4 (figure 43(a)) does involve chain ends in a quite different
way, with chains probably escaping vertically along the core and the three-arm-star
walls.
Non-singular integral lines would have an elastic energy larger than the elastic
energy (core included) of the singular half-integral lines, because of a large K , . This
is why they are not observed.
(iii) Observations in copolyesters. Observations of disclinations seem to be at vari-
ance with those reported above for homopolyesters. Mackley et a1 (1981) interpret
theirs as demonstrating the existence of numerous disclinations with strengths S = 1, *
in the classical plage & noyaux (schlieren texture). The core itself is rather large, and
the whole contrast is much fuzzier than in a usual plage Ci noyaux; this could be due
to a gradient of chain ends on large scales. However, little more can be said, because
we ignore even the order of magnitude of the molecular weight. Noel et al (1984)
have also reported schlieren textures with integral and half-integral lines in another
copolyester.
Graziano and Mackley (1984a) and Aldermann er a1 (1985) have reported on the
changes in optical textures under controlled shearing experiments together with the
subsequent relaxation behaviour at the cessation of flow. Some observations, like
the nucleation and multiplication of defects, are reminiscent of those observed in SMLC
nematics by the same authors, at least at low shearing rates. But others appear unique
to LCPS, in particular the fact that the shear has a significant and specific effect on
the microscopic texture, and presumably the microstructure. More precisely, Graziano
et a1 describe: (i) the appearance of a worm texture, a kind of disordered polydomain
texture at the scale of a few micrometres, i.e. inferior to the size of the specimens and
independent of it; the worm density increases with increasing shear rate, (ii) a sharp
transition between the worm texture to a birefringent texture (with optical axes along
the direction of shear), called ordered texture, made presumably of a very high density
of suboptical oriented defects of the type seen in the worm texture. The shear rates
at which these transitions occur decrease with decreasing temperature and decreasing
thickness of the sample. Finally the relaxation behaviour is very peculiar, and consists,
in high enough molecular weight nematics (A4= 20 000), of a banded texture perpen-
dicular to the shear direction, after cessation of shear in the ordered texture; the banded
texture relaxes to the worm texture and back finally to the quiescent original state with
few disclinations. The banded texture itself seems to be a specific uniform texture
which, like all other textures observed, always occurs with the same specific characteris-
tics under a given set of shear and thermal conditions.
620 M Klbman
Banded structures (of another sort?) were observed in thin films of random CO-
polyesters by diffraction contrast in electron microscopy (Donald and Windle 1984a, b).
Annealed specimens show up walls which tend to be either parallel or perpendicular
to the original shear direction, with a characteristic rotation of the molecules out of
the plane, interpreted by the authors as the splay-splay compensation of the type
alluded to above (Meyer 1982). Comparison of electron and optical microscopy
pictures, and x-ray diffraction patterns have led the authors to infer that the copolyesters
they have observed are biaxial, with orientation correlations about all three axes
(multiaxiality). It is quite possible that the copolyesters used by Mackley et al (1981)
in their large-scale shearing experiments are also biaxial. This property has implications
for new observations of the disclination lines, and it might well be that the important
differences observed between the textures in copolyesters and those in homopolyesters
are related to the different natures of the molecular correlations.
Precholesteric states and hierarchical textures: banded textures have been observed
at the isotropic cholesteric transition of DNA in solution, when the transition is driven
by a slight desiccation of the sample. These banded textures show up also in concen-
trated solutions. Their geometry has been studied by Livolant (1984, 1987); since they
appear between the isotropic and the cholesteric state, they have, as expected, some
resemblance to the blue phases which will be discussed later, i.e. they result from
phenomena of the frustration of the cholesteric order. Essentially these bands are
complex supermolecular arrangements of bundles of molecular lines twisted along
their length. Geometrically, equal bundles can pack together and form ordered (parallel
bundles or twisted bundles) or disordered arrangements on high scales. It is therefore
feasible that bands are high-scale hierarchical arrangements of bundles of lower scale.
Livolant has also observed self-assemblies with very large pitch of large hexagonal
packings of PRLG.
Hierarchies of organisation have been observed in collagen, which has a cholesteric
phase (Gathercole and Keller 1982).
(iii) Rheological properties of cholesteric polymers under shear and relaxation. They
are a subject of constant study since the pioneering work of Kiss and Porter (1980)
who provided evidence for the existence of three regimes under shear in a solution of
PBLG in meta-cresol: (i) at low shear, appearance of defects elongated in the direction
of shear; (ii) at intermediate shear, multiplication of the defects and existence of a
negativ'e first normal-stress difference N , = u l l- u22 (measured in a plate-cone
geometry); (iii) at high shears, N , is again positive. Bands perpendicular to the shear
direction appear in relaxation in the first regime, but show up directly in the second
regime, during shear. These experiments have been done subsequently, with the same
results, in hydroxypropylcellulose liquid crystals in water (Navard 1986). The suc-
cession of regimes and the appearance of bands bear some resemblance to the
phenomena observed when shearing a nematic copolymer (see above). Note finally
that Donald et a1 (1986) have observed that the bands in HPC can relax subsequently
to a texture of parabolic focal domains.
7.1.I. Uniaxial nematics and abelian homotopy groups f o r line and point defects. Consider
a Burgers' circuit r surrounding a disclination line L (as in figure 9 ( d ) ) ; if the
configuration of the director is planar, the mapping of the director on a unit circle C
(see figure 9 ( e ) ) is enough to tell us about the nature of the singularity. If the
configuration is three-dimensional, an evident generalisation is to map the director on
a unit two-dimensional sphere S 2 : the image of an S = =kiline is therefore a path y
on S 2 between two antipodal points, which represent in some way the same director
622 M Kleman
n = -n. Take the convention of identifying antipodal points on S2;one obtains a new
manifold, called the projective plane P 2 , representative of the topological properties
of the order parameter of a nematic, and whose topology has been much studied by
the geometers (see for example Hilbert and Cohn-Vossen 1952). On P 2 the path y is
closed. If the Burgers circuit r is displaced in space without ever traversing L, its
image y moves on P 2 in a continuous manner; it cannot be reduced to a point and
cannot vanish in a continuous motion. The contrary would indeed mean that there
would be a continuous way to transform a singular ib line into a non-singular one.
Therefore topologically stable defect lines are represented on P2 by classes of closed
paths which are non-homotopic to zero. It is not very difficult to convince oneself
(figure 44) that there is only one class of such paths on P 2 : any oriented closed path
which is not in the null class (like yo) is homotopic to y = AB. For example y- = BA
is homotopic to y (rotate the line y by moving its end points A and B along the
circle, always keeping them diametrically opposite, until A comes in B and B in A.
This is a continuous motion). Also the product of two oriented paths, both non-
homotopic to zero, is in the null class.
B
Figure 44. Types of loops on the projective plane P 2
of ordered media have a fundamental group R I (V) which is non-abelian. This character
introduces a new degree of complexity in the non-linear topological behaviour of line
defects(see next section).
The ordered media whose corresponding fundamental group ITl is abelian are in
fact very few. Apart from nematics and amorphous ferromagnets, there are the various
superfluid phases of 3He and 4He, whose order parameter is defined through a gauge
group. For the discussion of their disclinations, see Volovik and Mineyev (1977) and
Bailin and Love (1978).
Topological stability, just discussed, and energetical stability, are different concepts.
Consider the simple example of usual nematics, made of short molecules, the energetical
stability of defects meets the criteria of topological stability, and in particular integral
lines have generally a continuous configuration. The situation is different in some
nematic polymers, where the configurations required by the escape of the core are very
high in energy, and are rarely observed.
b=2d (69)
the only constraint being on d, which must be such that b is a permitted Burgers
vector. This relationship does express the group theoretical law of multiplication of
two opposite twofold rotational symmetries at a distance d ; they result in a translation.
Figure 45 illustrates a different case, but of the same nature. The same type of group
theoretical relationship applies for a kink on a disclination (figure 46). It is visible
indeed that the difference between figure 46(a) and ( 6 ) is just in the displacement of
. ...
Figure 45. Splitting of a dislocation into two disclinations (with respectively five-membered
and seven-membered rings around their cores) in a 2D hexagonal lattice.
624 M Kleman
ti
L, L2
t
L1
Figure 46. To illustrate the relation between kinks on disclinations and dislocations (see
the text).
one of the wedge disclinations of the pair to another position, but with its end still
attached to the twist segment, which we call here a kink. The scheme of figure 46(b)
applies here to the case when b is a permitted Burgers vector, but it can be easily
generalised to a curved disclination (figure 8( b ) ) ; equation (69) then generalises to
db = Cl x d s (70)
a relation which holds for a nematic, as we already know.
The presence of dislocations at kinks is well illustrated experimentally in hexagonal
columnar mesophases: we know from 5 that S = +$wedge disclinations form easily
in these media, while twist disclination lines are never observed. But kinks might be
present, to which dislocations are attached, forming, rather than a well defined grain
boundary, a pair of lines which disperse far away from the kink, as observed by Oswald
(see the illustration in KlCman (1983a)).
Let us now notice that opposite disclinations, when merging, do not necessarily
form a dislocation (figure IO); they can also anneal. It appears indeed that the final
result depends in fact on the path followed by the two disclinations which are to meet.
More generally, the relative motion of two defects has topological implications. For
example the Burgers vector of a dislocation changes sign when this dislocation makes
a complete turn about a half-integral disclination (Frank 1969) (see figure 47). Consider
Figure 47. A dislocation changes sign wher, circumnavigating about a half-integral disclina-
tion in a layered medium.
Defects in liquid crystals 625
Final position
Initial position
7.2.2. The fundamental group. We have discussed above some specific features of the
interaction between defects of non-commutative symmetry invariants. The same
phenomena receive a quite simple and illuminating description in terms of homotopy
classes. Call a, the class of homotopy of a given defect and let it accomplish a complete
turn around a defect of class c. It is possible to show by methods of algebraic topology
that it has acquired a new class of homotopy az= ca,c-'. If a, and c commute, nothing
is changed. But in the general case the same defect can take any of the classes of
homotopy belonging to the same class of conjugacy of II,. More generally, consider
two defects of homotopy classes a and by belonging to the classes of conjugacy C ( a )
and C ( b )in II,. Note that ai, bi and ci are any homotopy classess belonging to C ( a ) ,
C ( b ) and C(c) respectively. Then:
(i) if a, rotates around c, its class of homotopy changes after a complete turn and
becomes aj = caic-';
(ii) if a and b merge, the resulting defect belongs to a class of homotopy in
C ( a ) C ( b ) . The product C ( a ) C ( b )does not define in general a unique conjugacy
class in I l l . Hence the defect resulting from the coalescence is not uniquely defined
even in the sense of the topological theory of defects;
(iii) if a and 6 cross, they stay connected by a defect belonging to the class of
homotopy c = aba-'b-'. There is no obstruction to crossing if c = 1, i.e. if a and b
commute (Po6naru and Toulouse 1977, KlCman 1977b). The set of all elements of II,
of the form aba-lb-' form the so-called commutator subgroup K, which is the largest
normal abelian subgroup of II,.
The non-trivial defects pertaining to the conjugacy classes of K of II,(V) are
special: they can always be split into two defects which, after some turn of one of
them about a third one, can annhilate (Trebin 1982).
The set of conjugacy classes form a group, the so-called homology group H,( V) =
II,( V)/ K, with K as unit element. H,( V) is abelian.
As an illustration of a non-abelian fundamental group, consider cholesterics, whose
defects have been classified by the Volterra process in 0 6.4, and biaxial nematics
(0 6.5), whose order parameter is the same. The topological classifications are due
respectively to Toulouse for NBs (1977a) and the Mineyev and Volorik (1978) for
cholesterics; the fundamental group is the quaternion group Q = - I * e , , * e 2 , (--e2),
* e 3 , containing eight elements and five conjugacy classes c ~ { I } C0{-1},
, Ck{ek, -ek}
with the combination rules
erez= - e2e1= e3
e1e2e3= - I
( - I ) ~ =I.
Table 2 gives the correspondence between topological classes and Volterra defects in
cholesterics. The correspondence between cholesterics and NBs is in 0 6.5. A very
remarkable fact is that all dislocations whose Burgers' vector b equals 2np enter the
Defects in liquid crystals 627
Table 2,
b = 2np +
b = (2n 1)p b = ( n+ 4 ) p
,y(S=2n) ,y(S=2n+l) ,y ( S = n + f )
7 (S=2n) 7 ( S = 2 n + 1) 7(S=n+$)
A (S=2n) A (S=2n+l) A (S=n+f)
null class, i.e. the core singularity can disappear and the configuration be continuous;
this is evidently reminiscent of the behaviour of the integral lines in nematics.
7.2.3. Conjigurations and the homotopy group I13. The distortion fields whose homotopy
class belongs to a non-trivial element of 113(V) are non-singular topologically stable
fields. These so-called configurations or solitons are not, however, observed in
crystals, rod lattices and lamellar systems, because of obstructions to their presence
which result from the integrability conditions of the distortion fields, as noticed by
Gunn and Ma (1980) and Trebin (1983). More precisely, in a crystal lattice, the
periodic nature of the crystal must be respected in any distortion field; in other words
the distortion field pij, defined in continuum by the differential form
must be derived from a displacement field ui(r ) ; this condition ensures that the lattice
vectors close after distortion, and curl p = 0, i.e. in component rotation:
Conditions (73) are the well known compatibility conditions of a distortion field
(Bilby et a1 1955, Kroner 1981). Trebin (1983) has established by employing general
arguments of differential topology that any field obeying these conditions is diffeomor-
phic to a field without configurations, i.e. to the perfect crystal, in three dimensions.
Reciprocally, this implies that any configuration in a crystal is attended by some sort
of singularity of the distortion field, whose density is measured by one of the quantities
which vanishes in (73); for example
bpk = EpqrPkr.4 (74)
measures a density of dislocations, as shown by Kroner (1981). The identity bpkp = 0
is the expression in continuum theory of the fact that a dislocation cannot terminate.
bpk is therefore a component of the infinitesimal Burgers vector of an infinitesimal
dislocation along the direction k, of components blk,b2k,b3k.
Trebins theorem does not apply to media with continuous symmetries only. For
example, He3-A superfluid has an order parameter whose geometrical representation
is a triad of vectors, but there is no condition of the type (73), since He3-A is a liquid
and can suffer any elastic distortion. Therefore there is no obstruction to topological
configurations in He3-A. The same results hold for biaxial nematics NB,nematics and
cholesterics, and we expect topologically stable configurations in these media. The
quantities bpk # 0 which attend these configurations can be interpreted as frozen
infinitesimal dislocation fields on a virtual lattice superimposed on the medium; this
virtual lattice is defined by the natural local frames in He3-A, NB phases and
cholesterics, in the examples above. However, as noted first by Shankar (1977),
628 M Kle'man
configurations in He3-A and nematics, whose order parameter space is of the type P"
or S", are not stable and shrink spontaneously to zero size. This is evident in the frame
of continuous linear elasticity, since there is no natural macroscopic length in such a
theory. Whether lengths introduced by higher-order terms are enough to provide for
high-energy barriers is still an open question. It has been suggested that configurations
are stable in cholesterics, where the pitch offers a natural length (Pisarski and Stein
1980).
7.2.4. More on singular points. These are classified by the elements of n,(V); this
group is isomorphic to the group of integers 2 in nematics and layered media, but is
restricted to the triGia1 element in biaxial nematics, cholesterics and He3-A. Therefore
singular points are not topologically stable in these media. The corresponding invariant
N (see equation ( 5 5 ) ) changes sign with the sign convention on the director n.
Nonetheless we have to distinguish between different singular point geometries which
can bear the same absolute charge INl; for example for IN1 = 1, the hedgehog (in which
the director points radially with the singular point as centre, in a nematic; or in which
the layers are spherical, in a smectic), and the hyperbolic point defect (this is the
configuration at the centre of a toric focal domain). It is intriguing to notice that if
an IS1 =; disclination rotates around an N point defect, then after completion of the
turn N-. -N. Trebin and Kutka (1981) have proposed a finer classification of singular
points, by the use of the Morse index, which distinguishes between the various
geometries of the same configuration INI. They have also noticed that a focal domain
can be defined as a singular point, with an inner region of hyperbolic nature, and a
hedgehog exterior, separated by a disclination, which is necessary by an argument
akin to the argument used above for the change of sign of N. In the same spirit, it is
worth noting that Lavrentovich and Terentiev (1987) have observed, in a nematic drop
embedded in the isotropic phase, a transition under a temperature change from a radial
hedgehog to a hyperbolic one with the simultaneous formation of a circular non-singular
disclination. The boundary conditions (homeotropic) do not vary during the transition.
They explain this phenomenon as being due to a temperature-induced variation of the
Frank constants.
Figure 49. Non-singular semi-defects in a cholesteric phase with various Hopf indexes
(polarising microscopy; courtesy Y Bouligand).
7.4. Surface defects, cores and the use of the exact homotopy sequence in various problems
involving defects
The so-called exact homotopy sequence (EHS, see Steenrod (1951)) is often used as a
powerful tool to compute homotopy groups. Since its geometrical meaning is closely
related to some physical properties of defects at surfaces, at phase transitions, and to
their core properties, we comment on it in some specific examples.
7.4.1. An interesting relationship (KlCman and Michel 1978a, b) between the defects
of the SmC phase and the SmA phase arises from the fact that the point group H,
(reflections excluded) is a subgroup of the point group HA(reflections excluded). This
is easily seen when considering a continuous phase change SmC + SmA, which consists
in tilting the optical axis towards the normal to the layers. Let us therefore assume
that we know the order parameter space VA= V(SmA). To each point in VA we put
in correspondence a one-parameter family of orientations of the SmC phase, by keeping
the orientation of the layers constant but moving the optical axis on a cone about a
normal to the layer; all these positions define a circle S; in mathematical terms S is
thefibre of the fibre bundle with base VA,and bundle Vc = V(SmC): all the orientations
of the SmC phase are indeed reached once and only once when one performs the
former geometrical operation for all the SmA orientations defined by all the points
of v,.
Reciprocally, let us consider the set of all loops on Vc whose homotopy class is
(0, a), i.e. we consider in VA defect lines of type m (the notation ( n , u p ) means that
the considered defect does contain a dislocation part of Burgers vector b = nd,, and
a disclination of strength S = p ~ )We
. know from former considerations that 2 classifies
the dislocations, and 2, the disclinations, since a4 is the trivial defect, whose core is
630 M Kle'man
able to escape in the third dimension. These loops in Vc clearly deal with the
geometrical operation just considered, and we conclude that the fibres S' are all in
the same homotopy class. The 27r disclination lines disappear when the SmC phase
is transformed to the SmA phase. Therefore V A is obtained from Vc by identifying
on Vc all the points of a family of (0, a') loops fibring V,. In the same way, all the
elements in II,( V,) which are in the conjugacy class of (0, a'), or which pertain to the
smallest subgroup containing this conjugacy class, disappear when Vc + V,. This
subgroup consists of the elements (0, 1) and (0, a 2 ) ;it is isomorphic to 2, and constitutes
the kernel of the mapping II,( V,) + II,( V,). Hence
HI ( VA)2. (
1 vC)/z2 = 02 2 (75)
since HI( Vc)= Z 0 2,. Note further that since (0, a') = (0, a')-', an oriented loop of
this class can change orientation after each of its points has performed a closed loop
on Vc. Therefore Vc is not a direct product VAx S': rather it is a situation analogous
to that one in which one obtains a Mobius ribbon by fibring a circle (the base) by a
line segment (the fibre), letting this line segment suffer a *rr rotation along the base.
Equation (75) which states that 2, is the kernel of the isomorphism HI( Vc)+ II,( V,),
is only an element in the sequence which links the homotopy groups of the base, the
fibre and the bundle, namely
.. ~ . ..
~ ~ 2 ( s 1 ) ~ ~ 2 ( v C ) ~ ~ 2 ( v A ) ~ ~ l ( s ' ) ~ ~(76)
~ ( v C ) ~
Its property of exactness means that if three successive elements of the sequence are
considered
1 1
+A-, B - , C+ (77)
the image of the mapping i is equal to the kernel of the mapping j
7.4.2. The fact that Vc is not a direct product of the base V, by the fibre S' implies
that mappings of V, onto Vc (take a point P on V,, map it on some point of the fibre
S ' ( P ) attached to P, and proceed similarly for all the points in the neighbourhood of
P in a smooth way, and so on) are not continuous. A striking physical consequence
of that fact is the following: if one starts from a SmA phase which is sufficiently full
of defects, the transformation to the SmC phase which has the same layers is attended
by the appearance of (0, a') disclination loops, along which, precisely, the mapping
V,+ V, which is achieved by the transformation is not continuous. For example, start
from a droplet in which the SmA layers are piled in concentric spheres (this is a
topologically stable point defect, belonging to 112(V,) = Z ) , and cool it to the SmC
phase; at least two (0, a') lines appear, which begin on the singular point. This
transformation, which has been observed by Kurik and Lavrentovich (1983) is reminis-
cent of the singular gauge-induced transition from a t'Hooft-Polyakov monopole
(t'Hooft 1974, Polyakov 1974) into a Dirac monopole (Dirac 1934) with a singular
string. For more on the relation between singular gauge transformations and defects,
see KlCman, in Kroner (1982).
Defects in liquid crystals 63 1
7.4.3. Mermin et a1 (1978) (see also Volovik (1978) and Mermin (1979)) have estab-
lished the classification of defects at boundaries (when some constraint acts on the
order parameter, like a director field forced to be parallel or homeotropic) or when
the order parameter depends on the length on which the medium is considered. In
both cases one has to introduce two-order parameter spaces VI and V,, say, such that
one of them is included in the other ( V2= VI ). The concept of homotopy has then to
be modified to one of relative homotopy.
Call for example V, the order parameter space restricted to the boundary (S' for
a planar nematic, a point I for a homeotropic one). V2 is included in VI, the order
parameter space of the bulk. Consider the case when the surface defect is a point,
and surround it by a loop y. Compute the homotopy classes of y in IIl(Vl) and in
IT,( V,). If the point defect is the termination of a line defect, then clearly the homotopy
classes so computed must be the same, say a. Conversely, isolated point singularities
are represented by elements b of ITl( V,) which vanish in II,( VI) when the loop y
surrounding the point of the surface is transported in a smooth manner in the bulk.
This corresponds to the operation of inclusion i of V2 in VI. This transport of y clearly
defines a homeomorphism between 111(V2) and II,( Vl); all elements b are in the kernel
of this homeomorphism. Finally, some surface point singularities can be generated
by bulk point singularities arriving on the surface; these objects are truly point
singularities and are not in ker {IT,( V,) +IT,( Vl)}, but are classified by the classes of
homotopy of half-sphere X2embedded in the bulk and whose limiting circles are on
the boundary. These are relative homoropy groups IT,( VI, V,); the limiting circle is
mapped in V,. If the image of 8,in the mapping is entirely in V,, we contract it to
a point in V,; its class of homotopy is the identity element in II,( Vl, Vz). In fact, we
have the EHS:
-2
i2 J2 32
+rI2( V2) n2(Vl)
+ + Vl, V,)+ IT,( V,) nl(VI)--+. (79)
In this sequence, 8 is an operation which consists of considering in V2 only its boundary
X2on the specimen surface. It induces a group homeomorphism between It2(VI, V,)
and IT,( V2).
Using (79), it can be proved that II,(V,, V,) is finally the product (direct or
semi-direct according to the case) of two groups of elements; the first is ker i , and
describes true singular surface points which are not terminations of lines; the second
is the quotient group ITz( Vl)/im i2 and describes singular surface points coming from
the bulk. Surface points which are terminations of lines are in im i l .
This discussion (which can be extended to any dimensionality of surface defects)
shows how complex the classification of these defects can be and how powerful the
homotopy method. Let us take the example of nematic phase with parallel boundary
conditions (Volovik 1978). One has V, = P 2 and V, = S'. Here ker il = Z ; these are
the terminations at the boundary of the disclinations of integer strength which are
non-singular in the bulk but cross the surface with a singular point. IT,( Vl)/im i2 is
equal to Z,but it also classifies the bulk point singularities, which are all topologically
stable on the surface. The rest of the surface singularities are the termination of
half-integer lines. Finally, we have
nz(P2, S' ) = zx z. (80)
A detailed study of surface defects in nematic drops with various boundary condi-
tions has been given by Volovik and Lavrentovich (1983), including the dynamics of
their transformation one into another (see also Candau et al (1973)).
632 M Kleman
Mermin (1977) has introduced the term of boojum to denote the surface sin-
gularities in the superfluid phase of 3He-A. The order parameter is an orthogonal
tripod A , , A,, I ; 1 is perpendicular to the surface. The only topologically stable surface
defects have even strength and are multiples of *47r (rotation of the Ais axes), which
limitation results from the fact that there are no topologically stable point defects in
the bulk. Therefore any boundary singular point which has an odd integral strength
(*27r, *67r, . . .) must be a pinning point of a topologically stable line in the bulk.
Eventually, any boojum ( S = 4n7r) can split into two singular points of odd strength,
linked by a singular line.
Booja in cholesterics have also been discussed (Stein er a1 1978). Assume that
the so-called cholesteric axis is perpendicular to the boundary; therefore V, = S / Z , =
SI.We have U,( V,) = II,( V,) = 1; U,( V,) = 2 ; and U,( V,) = Q, where Q is the quater-
nion group. The inclusion of V, in Vl=SU(2)/Q is not easy to figure out. As in
0 7.2.2 let us introduce I, -I, * e l , *e2 and *e3 the elements of Q. To each conjugacy
class of Q corresponds a certain type of loop included in V. Assume that the class
*e3 represents the ~ ( * f ) lines, the class * e , the A(*$) lines and the class *e2 the
T(*$) lines as in table 1. Clearly, the manifold V, is in the mapping in V, of a Burgers
circuit surrounding a x line. Its homotopy class in IT,( V,)(=Z)is *1 and is +e3 in
111(V,). If V, is surrounded twice (elements of homotopy classes *2 in IT,( V,)), its
homotopy class in V , is -I = (*e3). If it is surrounded three times ( 1 3 in U,( V,)),
its homotopy class in V, is again * e 3 . Only elements *4n in U,(V2) map on I in
II,( V,):they constitute the kernel of the inclusion i and correspond to possible booja.
Here, as above in the 3He-A phase, splittings are possible which would divide the
singular points on the surface in two singular points linked by a ( - I ) , or in four
singular points linked by ( * e , ) lines.
7.4.4. In many instances, it is believed that the singular region of the defect core is
filled with material with an order parameter more symmetric than in the bulk, liable
indeed to display the symmetry of the higher temperature phase. The situation can
be easily handled with the help of an EHS if the transition is second order, in which
case one of the order parameter spaces is included in the other, which is a fibre bundle
on the former. Similar problems happen if the order parameter depends on the scale
on which it is observed (for more details, see Klkman (1983a p 306)).
8.1. Generalities
As already indicated, the term frustration refers to the fact that the competition
between local interactions in matter leads to structural arrangements which are intrinsi-
cally inhomogeneous, on some typical length 6 much larger than molecular or atomic
lengths. Such a situation arises in solids such as metallic glasses, Frank and Kasper
phases (1958, 1959), quasi-crystals, in liquid crystals such as blue phases, Pp,lamellar
phases, SmI films and probably also in cholesteric solutions of biological polymers.
Some biological structures in vivo might quite well benefit from the same type of concept.
Frustrated media have been approached through various points of view. The
thermodynamical viewpoint has been privileged by Hornreich er a1 (1980, 1988) in
their studies of the blue phase and of the hypothetical icosahedral chiral phase
(Hornreich and Shtrikman 1986); using a mean-field Landau approach with an order
Defects in liquid crystals 633
parameter whose amplitude varies in space, they have established the phase diagram
of the various cubic blue phases, and the rules of stability. In their theory the lines
where the quadrupolar order parameter Q vanishes are most probably lines of defects,
in the sense that the order parameter n rotates by some angle multiple of T when
circumnavigating around those lines. But the description can be made continuous
everywhere and the defects inherent to the structure are not visible at first sight. These
defects are, in contradistinction, the essential ingredients of the structural (rather
than thermodynamical) theories of Kliman and Sadoc (1979) and Rivier (1979) for
metallic glasses and Meiboom et a1 (1981,1983) for blue phases, and of the energetical
theories of Carlson et a1 (1988) for the same materials and for the ripple PpJphase
and for thin SmI films. Finally the theories which involve the construction of
unfrustrated crystals in curved spaces introduce defects which decurve those crystals
and are present in the final euclidean frustrated medium. Our review will stress these
aspects of the frustrated media with defects.
We will briefly review the essential ingredients of geometrical frustration in the
case of metallic glasses, for which the concept was first developed (K16man and Sadoc
1979). We consider a system made of equal atoms of physical diameter d, which like
to pack as densely as possible. Such a requirement is certainly achieved locally if four
spheres occupy the four vertices of a regular tetrahedron of edge a = d. Trying to fill
space with such tetrahedra, we assemble them first in bundles of 5 tetrahedra with a
common edge (but they do not fill entirely the space around the common edge; it
remains an angle of approximately 7, which can be filled only by some elastic distortion
of the tetrahedra) and then in bundles of 20 with a common vertex (figure 50), around
which the other vertices form a regular icosahedron.
Such a local icosahedral arrangement has a higher density and a smaller energy
than the more classical FCC and HCP arrangements, as first shown by Frank (1952).
This explains why clusters containing a very small number of molecules possess
icosahedral symmetry. However, this is not a crystallographic symmetry; systems with
local icosahedral symmetry present everywhere are apriori disordered on long distances.
Is it possible to describe the structure of this disorder in more detail?
Icosahedral symmetry is frustrated in our usual, euclidean R 3 space; but this
frustration can be relaxed in a curved space of constant curvature, the 3 D sphere S3,
where it is possible to build a 3D crystal of finite extent since S3 is a finite space,
made of 600 regular tetrahedra, 5 meeting around each edge and 20 around each
vertex, where they form an icosahedron. In Schlafli notation, this 3 D spherical crystal
634 M Kliman
is the ( p , q, r ) polytope, with p = 3, meaning that the facets are triangles, q = 3, meaning
that 3 facets meet at a vertex (i.e. the building block is a tetrahedron) and q = 5 meaning
that 5 tetrahedra meet along an edge. This crystal is nothing other than a 3D analogue
of the 2D dodecahedron: regular pentagons do not fill the plane regularly, but build
a 2D crystal on the sphere S 2 .
The relationship between the (3,3,5) polytope and the amorphous structure can
be understood pictorially as follows: introduce disclinations of strengths which are a
multiple of 2 ~ / 5(in order to respect the (3,3,5) symmetry) along some lines. In this
process, one obtains lines of vertices with coordination number 2 = 14,15,16. . . (figure
51). Along these lines of defects, since extra matter has been introduced, the sphere
is decurved. The purpose is to flatten S 3 completely. Most of the flattening can be
achieved by lines of defects; but the strengths of the lines are prescribed, and the lines
are introduced at random; hence it is impossible to reach a perfect flattening without
straining the matter. The reader is invited to transpose this discussion to a 2D sphere
S 2 tiled with regular pentagons, in order to get a more straightforward physical feeling
for the process. Introduction of extra pentagons decurves the sphere too much and
transforms it locally to a surface of negative curvature; but the introduction of strains
(and stresses) brings the material back to zero curvature (IUCman 1983b).
Another way of understanding the relationship between the curved crystal and the
flat one is to consider a mapping between the substrate spaces which conserves lengths
and angles. Such a mapping is possible (Cartan 1928), and consists geometrically in
a rolling along a line of the curved space on the (tangent) flat one, without slipping
(KlCman 1983b). But such a process can only be achieved along the prescribed line.
The failure to a global mapping is computed by choosing for the prescribed line an
infinitesimally small loop, mapping it on the flat space, and measuring the closure
failure which consists in a translation and a rotation. It is the rotation failure (which
is proportional to the Gaussian curvature of the curved space) which is at the origin
of the disclinations we considered.
Finally, the disordered material can be described as a disordered array of lines
along any of which 2 is constant and larger than 12, embedded in a matrix 2 = 12
(see figure 51, with 2 = 14), where local order is best satisfied. The average distance
between lines, 6, depends on a complex balance between the elastic energy of the bulk
and the energy of the lines of defects, but it is expected that it scales with the radius
of s3.
I
Figure 51. A disclination through an icosahedral packing which changes its coordination
number from Z = 12 to Z = 14.
Defects in liquid crystals 635
BP I1 are cubic phases; they have been observed in freeze fracture experiments (Costello
et a1 1984); their structures seem to be quite well understood (Meiboom et a1 1983);
the building blocks are finite cylinders of double twist, which can arrange locally as
in figure 5( c ) , three of them along the quaternary axes of the cube. If their lateral size
is limited to $,, = 7r/4, they fit nicely along their contacts, but the intermediary region
along the three-fold axis cannot be filled smoothly with molecular directions: a
disclination of strength S = -4 appears in this region. Meiboom et a1 (1981) proved
that the core energy of such a defect is negative if K24 is positive, and explained in
this way the stability of the blue phases. BP 111, also called blue fog (Marcus 1981),
is seemingly a disordered phase; it has been suggested that BP I11 is a disordered array
of soliton lines with local cylindrical double twist along them, with a characteristic
size 6. If this is the case, BP 111 would be a pretransitional region rather than a true
thermodynamic phase. More recently, it has been argued (Hornreich et a1 1986,
Rokhsar and Sethna 1986) on the basis of Landau theory that B P I I I could be, but
without compelling evidence, a thermodynamically stable phase with long-range quasi-
crystalline ordering and icosahedral symmetry.
In this section, we have discussed the stability of the double-twist unfrustrated
geometry in terms of KZ4. If K24 is very large and positive, we expect some domain
of stability for the blue phases. If K24 is not too large, cylinders of double twist cannot
belong to the ground state and are excitations of the cholesteric phase. In terms of
Landau theory these results are discussed as a function of the ratio K = [ / p where 6
is a coherence length and p the pitch. 6, according to Hornreich et a1 (1982), is the
racemic correlation length at the (virtual) isotropic-nematic transition. K is therefore
a dimensionless measure of the tendency to parallel alignment, as opposed to the
helical alignmeht. Our discussion of the polymeric chiral phases will allow us to
deepen this picture. Landau theory tells us that the larger K , the larger the temperature
range of stability of the blue phases, as shown in figure 52. Therefore, in Landau
theory terms, double twist and parallel alignment are already related in some way.
K =</p
8.2.2. Polymeric chiral phases and the chromosome of dinoflagellates: experimental results
and their interpretation. We first mention a few experimental results which point to
the presence of double twist in solutions of polymeric chiral molecules of biological
origin.
(i) Observations of biological cholesterics in vitro. We have already cited the careful
optical observations of Livolant (0 6.7.3). There is little doubt of the presence of double
twist, either of the type discussed above, or of the type described below for the
chromosome of Prorocentrum micans.
Defects in liquid crystals 637
Note also that some spherulites of collagen display a circular line around which
there is local cylindrical double-twist (Giraud-Guille 1988).
(ii) Optical and electron microscopy observations (Livolant and Bouligand 1980) of
the dinoflagellate chromosome (Prorocentrum micans). In this chromosome, D N A takes
a cholesteric arrangement, with the cholesteric axis globally along the axis of the
chromosome. However, one observes also on the periphery a double-helical furrow
with the same helicity as the cholesteric DNA,which indicates the presence of dis-
crepancies with respect to a perfect cholesteric stacking. These discrepancies have
been analysed by KlCman (1985b) using as a starting point the assumption that locally
the double helices of D N A like to be equidistant (see below). The geometry of the
chromosome can indeed be described as follows: there is a central parent surface
(figure 53) built from rectilinear D N A strands which rotate helically about the long
axis of the chromosome. This surface is a helicoid, and can also be described as a
twisted sheet of constant thickness (the thickness being the width of the D N A double
helix with its attending proteins). Place on this twisted sheet, on both sides, another
twisted sheet of the same thickness in contact with the parent surface, made of D N A
helices which have been rotated by some amount about the normal to the parent
surface. Double twist is perfectly satisfied in this region. Continue this process by
successive dispositions of parallel twisted sheets, with helical twist of the D N A about
their common normal. One obtains a double-twist geometry, whose geometrical size
is limited by the focal surface of the common normals to the sheet: in fact, this focal
surface extends outwards along two focal sheets (which are limited by two cuspidal
edges which are precisely the two observed furrows) which are not physically realised;
the geometry is limited grossly by the cylinder which carries the furrows. Beyond,
double twist would decrease and the frustration would be too large. Note the similarity
of this geometry with that one discussed for the screw dislocations of huge Burgers
vectors in SmAs (see figure 15). The furrows are the analogues of the disclination
lines into which the screw dislocation is split.
Figure 53. The parent surface of the model of the dinoflagellate chromosome. It is a
helicoid, ruled with rectilinear DNA strands. The same parent surface can be used for
globular proteins, with rectilinear P-helices (twisted P-sheets).
The double-twist geometry we have just described is, in some sense, orthogonal
to the double-twist cylindrical geometry observed with short chiral molecules. While
this latter one is favoured if K1> K 3 (since div n = 0), the chromosome geometry is
favoured when K , < K 3 (however, n. curl n does not vanish everywhere). The reason
why in the chromosome there is an effective K1 which is small is not straightforward:
K 1 should be infinite in principle in a polymeric liquid crystal with infinitely long
molecules. However, one can argue that many hair pins (figure 41) exist along the
DNA double helix; these hair pins can be favoured by some interaction with the
neighbouring proteins, which leads to local complex structures having this geometry.
A similar geometry of the chromosome has been proposed by Friedel (1984) indepen-
dently, starting from a different point of view.
638 M Kle'man
8.2.3. Polymeric chiral phases and the chromosome of dinojlagellates: identity of double-
twisted local order and equidistance of chains in polymers. In fact, double-twist and
compact stacking are of the same nature. This is shown when considering the geometry
of a-helices at a scale of a few strands. These strands assemble to form a string as in
figure 54 where we have represented the case of seven strands: it is clear that such a
geometry is a geometry of close contact for molecules which are not straight. They
are not parallel, but they are equidistant. Clearly also, the number of neighbours z of
the central molecule depends on the degree of torsion; this number tends to z = 6 when
the molecules become parallel (hexagonal stacking) and there is complete continuity
between double-twist (equidistance) and hexagonal order (parallelism).
These considerations shed a new light on the stability theory of the blue phases.
Figure 52 tells us that BPS are stable when 6 is large compared with p. 6 must in the
present context be understood as the length on which double twist, but also equidistance
of the integral lines of the director n ( r ) , is not frustrated. Therefore the integral lines
of n for short molecules appear here as physical objects.
8.2.4. Chirality in layers. The transition from the SmC" to the SmI" phase of the chiral
thermotropic liquid crystal HOBACPC (hexyloxybenzylidene p'-amino-2-chloropropyl
cinnamate) shows up, in thin films, the formation of droplets with 'booja', as in figure
5 5 , where the director geometry is pictured. According to Langer et a1 (1986), this
phenomenon is because the unfrustrated state has constant curl
curl c = q (82)
where c is a unit vector which is the projection of the director on the layer, and q the
pitch. Such a state cannot exist in a two-dimensional planar surface. Now the total
divergence term -2q curl c in the free energy amounts to a surface term -2q c dl 5
which is largest and negative when c lies parallel to the boundary of the droplet and
points counterclockwise (if q > 0), The addition of these two effects explains why the
boundary of the droplet is singular (.c jumps by an angle 7~ from one droplet to the
next adjacent) and possesses a point defect (a boojum) where the boundary conditions
are badly satisfied.
Figure55. The stable vector field of a tilted SmI* thin film. The vector field is the projection
on the layer of the director field (redrawn from Carlson et al (1988)).
The SmI" film is a very remarkable example of a chiral situation without twist: it
is of course the chirality of the molecules which imposes the total divergence term
-2q curl c ; however, there is no axis of chirality in the layer. But one might expect
that other cases exist where there is some coupling between the surface curvature and
the chirality. For example if a surface takes the shape of a ruled helicoid, the set of
directions defined by the straight lines which generate the helicoid have a definite
chirality, either left or right, according to the chirality of the helicoid. We have met
such a geometry in the model of the chromosome and when discussing screw disloca-
tions with huge Burgers' vectors in a SmA (see figures 15 and 53). Now the same
geometry can be imposed by the chirality of long polymeric molecules, as it does occur
in the twisted p sheets. The polymeric molecules are polypeptidic chains, and their
chirality yields a left twist for the surface. If such surfaces have to pack parallel to
each other, as happens in some models of proteins (see Lotz et al(l982) for conforma-
tional models of silk and keratin, and Salemme (1983)) frustration should become
intolerable at some distance, as in the geometry of the screw dislocation, and a helical
defect of the disclination type appears and bring a natural limit to the stacking.
640 M Kle'man
It has been proposed recently (Bouligand and KlCman 1989) that the stability of
the M2 phase of the chiral compound MHTAC (1-(methyl)-heptyl terephthalidene bis
amino cinnamate, see Levelut et a1 (1983) for phase diagram and x-ray studies) is also
caused by a frustrated coupling between the chirality of the molecule and the layers.
The M2 phase exists, as the blue phase, in a very small interval of temperature just
below the isotropic phase, and above the so-called M I , which is akin to a SmC* phase,
but to some supplementary anisotropy. The MI is quadratic and can be understood
as a SmD phase (Diele et a1 1972) whose cubic symmetry has been broken by the
frustration effect just mentioned.
8.2.5. Smectic ripple phase. This phase was first observed by Sackman et a1 (1980) with
freeze fracture observations, and consists in corrugated bilayers of surfactant in water,
so that there is a one-dimensional periodic density modulation of the chains. In DPCC
(dipalmitoylphosphatidylcholine)the wavelength of this corrugation is 5 = 130 A; the
frustration comes from the fact that the cross-sectional area of the polar heads is
greater than that of the associated chain; this leads to the presence of frustrated regions
in the form of gaps in the packing of the chains (figure 56). Note that this is not the
only geometrical possibility; for example, the competition between the packing of the
chains and that of the heads can be solved by the formation of spherical micelles, or
curved monolayers. Which solution is chosen depends on the material constants of
the surfactant layer, and a small K1 favours the formation of micelles, while a large
one favours planar layers as in Po,.
Figure 56. Periodic defects (gaps) in the packing of the chains in a Pp. phase (redrawn
from Carlson el al (1988)).
The theory of the ripple phase has been developed by Carlson and Sethna (1989);
in the continuous limit, it is a frustrated q'theory, with the presence of a total divergence
term in the free energy. The gaps are the defects required to relieve the frustration.
Other smectic systems with typical frustration effects have been reported, like the
bi-dimensional fluid antiphase SA(freeze fracture observations by Sigaux et a1 (1984)),
and more generally the incommensurate smectic phases with two periodicities (see
Prost (1984) for a review on Landau theory, and Satna et a1 (1985) for optical
observations).
The one-dimensional modulations of the aliphatic chains along the columns
observed in columnar systems (0 5 ) are 1D examples of a similar type of frustration.
8.2.6. Phases of interfaces. The question of the stability of phases of interfaces (colloids,
micelles, hexagonal and cubic phases of surfactants in water and block copolymers,
etc) and of isolated membranes is today a very active field of research, and it is not
yet really known whether the concept of frustration is totally relevant. This type of
explanation has, however, been advanced in the case of the cubic Qa phases (Sadoc
and Charvolin 1986, Charvolin and Sadoc 1987); in such an instance their stability
would result from a conflict between the tendency of the layers to keep as compact as
possible (this implies, in the case of surfactants in water, that opposite monolayers
Defects in liquid crystals 641
are parallel in the bilayers they form, i.e. there is a tendency to the formation of bilayers
separated by water), and the tendency of each monolayer to curve in opposite directions
in order to relax the difference in cross section between the hydrophobic chains and
the hydrophilic heads. The resulting local geometry of the bilayer, in the unfrustrated
zones (where the conflict is best solved), is saddle-shaped.
It has been argued (Klbman 1988) that such a model should apply most probably
when the rigidity K , of the layers is small (comparable with kBT or smaller). In such
a case configurational entropy of the molecules, in particular of the chains, should be
taken into account. At high temperature this entropy can be large enough to stabilise
the L, phase versus the unfrustrated Qmphase, which will show up only at a lower
temperature. It is then easy to show that, for reasons of isotropy, the mean curvature
of the middle surface
H=u,+u2 (83)
between the two monolayers in conflict should vanish in first approximation. This
middle surface is then a minimal surface. Since there exist minimal surfaces which
extend through euclidean space and form periodic lattices, the unfrustrated solution
is a periodic lattice, of one of the types described by Luzzati er al (Luzzati and Spegt
1967, Luzzati et a1 1987). A systematic approach to the geometry of periodic minimal
surfaces has been given by Hyde et a1 (1984) and Andersson et a1 (1984).
The case above ( K , small) might be relevant to non-ionic surfactants, in which the
Q, phase is of small extent or even non-existant, according to the ratio of the lengths
of the hydrophilic and hydrophobic parts. In fact, since the two monolayers on both
sides of the minimal surface cannot be at constant distance through the whole crystal,
one has to take into account the elastic contribution of the variation of the thickness
of the bilayers, which is large since K 1is small. This might also explain the discrepancies
with perfect minimal surfaces.
In fact, the Q, phase can also be stabilised, as first noticed by Helfrich (1981) (see
also Helfrich (1986)), by the existence of a negative K24 saddle-splay term in the free
energy of the bilayers ( a contribution G, where G = u1u2is the Gaussian cur-
vature). K24 is probably positive (but small, comparable with K , ) in non-ionic surfac-
tants. It is large and negative in lecithin and other systems which show up Quphases.
Then it is not necessary to invoke any frustration phenomenon of the form above. The
formation of a topology like that of the Q, phase, which differs from the topology of
the L , or H , phases, is favoured; the integrated energy -K24 1G d V depends indeed
only on the topology, since it is a quantity which is a line integral on each layer. The
importance of this term has been discussed in various cases, not only cubic phases
but also micellar solutions, colloids, microemulsions, etc (see papers in Physics of
Amphiphilic Layers, Springer Proc. in Physics vol. 21 (1987)).
satisfies double twist and is homogeneous throughout space S 3 ; any field obtained by
applying a constant rotation to all n ( r ) of equation (85) is another homogeneous field
and relieves also frustration everywhere, i.e. is homogeneously double twisted, with
pitch p* = 2n-R. A different choice for the n s , like:
n ( r ) = ( 1 / R ) (- X I 9 xo 9 - x3 9 x2 1 (86)
cannot be obtained by rotating the field of equation (85) and has indeed an opposite
pitch p * = -2n-R.
As noticed by KlCman (1985a) the integral lines of (85) or (86) are equidistant
great circles of S 3 (also called Clifford parallels) which are in mutual skew positions.
The integral lines of (85) form a congruence of right Clifford parallels ( p * > 0), while
those of (86) form a congruence of left Clifford parallels ( p * < O ) . Therefore they
achieve homogeneously the double-twist geometry which we discussed in 0 8.2.2. Since
all the great circles are equivalent in S3, now any great circle can be considered as the
axial line of the double twist geometry. Figure 57 shows two neighbouring Clifford
parallels.
Figure 57. Two close Clifford parallels are equidistant and at a constant angle from each
other. They map on the sphere of figure 58 on two points at an angular distance 28.
are conserved in the motion. Bring now a point M of S3 to the origin of the euclidean
space E 3 in which we map the crystal which is homogeneously double twisted in S 3 ,
and let S 3 be tangent to E 3 in M. Then e:, e; and no are in E 3 and can be chosen as
the unit vectors of a reference frame in E 3 . It is then easy to see that the derivative
din, of no in S3 writes in this frame
d.n.
1
I
= n1.1. .- q E .Ilk. nk (87)
where ni,j= dnj/axi is the derivative of n in E 3 . We therefore infer that on S 3 the
free-energy density, computed in the tangent space E 3 , gives
K
pf =- ( n] , .I .- E i,kqnk)2
..
8.3.2. Some standard results in spherical geometry. KlCman (1985a) has described in
more detail the geometry of the great circles of S 3 . Standard references for spherical
geometry (and elliptic geometry, which is obtained by identifying diametrically opposite
points on S 3 ) are Coxeter (1968) and Sommerville (1958). We stress here some results
that have since been used by other authors in the context of various frustrated media
(Nicolis et al 1986, Pansu et a1 1986).
644 M Kle'man
(i) A euclidean 3D space E 3 can be fibred by the parallel lines which are orthogonal
to a given plane E 2 ; similarly, a spherical 3D space S 3 can be fibred by a set of
equidistant great circles which are above a 2D great sphere S2. This is once more the
celebrated Hopf theorem, which more precisely states that any circle belonging to a
set of Clifford parallels which fibre S 3 , either left or right, can be mapped in a unique
way on a great sphere S2. We have used the Hopf theorem above ( 7.3) in another
context.
The distance between two Clifford parallels (both left or both right) can be measured
directly on S 2 . We have
d=R0
where 0 is half the spherical angle between the two points on which the two Clifford
parallels map on S 2 (figure 58).
(ii) Two Clifford parallels which map diametrically opposite points on S 2 are
conjugate in S 3 and at a distance ( r R ) / 2 . The small circles in figure 58 are mappings
of Clifford parallels equidistant to 1 and L, which cover embedded tori (Clifford
surfaces).
L
Figure 58. Mapping on S 2 of Clifford parallels in S 3 . Each point of the sphere S 2 represents
a Clifford parallel (either right or left). Each small circle represents a Clifford surface.
All the Clifford surfaces of this set of small circles are equidistant to the Clifford parallels
1 and L.
Table 3.
Z d,/2R P N
2 0.1666 0.75 3
3 0.1520 0.8453 4
4 0.125 0.8787 6
5 0.0881 0.8961 12
6 0 0.969 m
8.3.4. Some speculations on polymeric systems. The discussion we have so far essentially
concerns chiral molecules. However, there is no conceptual difficulty to extend it to
non-chiral molecules, and in particular molten polymers. We have indeed introduced
two lengths which are of a quite different nature: (i) p* = 6 is a correlation length for
local twist and the fact that the molecules like to be locally twisted does not imply
that they are twisted on long distances; we suggest that some amorphous polymeric
systems might enter this category: their local twist is caused by entropy forces, while
there are forces of contact of van der Waals origin, mostly. The fact that the sign of
p* is not fixed for racemic molecules does not preclude it being a relevant quantity.
(ii) p , the pitch of the cholesteric phase. These two lengths are of course insufficient
to describe the whole family of relevant structural properties; in particular, 5 has to
be larger than the persistence length in order to make our picture coherent. We suggest
the following classification of the structural properties as a function of K = &/p.
Large K : the general trend for large K should be towards disorder of the BP I11
type of disordered polymers. The twisted long-range structure of hexagonal PBLG
alluded to also enter into this category. The effective peffwhich is measured has of
course no relationship with p ; it is imposed by the twisting properties of the hexagonal
domains which become the building entities of the cholesteric order.
Intermediate K : we have double twist as in blue phases BP I and BP 11. The picture
we have given for the chromosome of dinoflagellates also enters this range of values.
Choice between the two double-twist structures depends on other parameters, like K1
or K 3 .
Small K : this is the cholesteric phase.
Very small K : this is the cpxe of nematic order, including biaxial nematic order.
646 M Kliman
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