Volume 45A, number 2 PHYSICS LETTERS 10 September 1973

OPTICAL STUDIES OF THE AMORPHOUS LIQUIDCHOLESTERIC LIQUID

CRYSTAL TRANSITION: THE “BLUE PHASE”

D. COATES and G.W. GRAY

Department of Chemistry, The University, Hull HU6 7RX, England

Received 25 July 1973

Optical studies of various cholesterol derivatives giving cholesteric liquid crystals show that a “blue phase” occurs
for each derivative at the amorphous liquid-cholesteric liquid crystal transition. The structural sigificance of platelets
which occur in the “blue phase” are considered.

From the earliest days of liquid crystallography,
scattered and sometimes conflicting references have
appeared relating to the occurrence of a “metastable
phase” when the amorphous liquids of some choles-
terogens derived from cholesterol are cooled. Lehman
[I], in 1906 reported in very certain terms that such
a phase existed, but Friedel [2] made no mention of
it at all in his classic work of 1922. Later Gray [3] in-
vestigated the situation in the case of the cholesteryl
n-alkanoates and noted that the phase was visible to
the eye in reflected light, but nor visible microscopical-
ly in transmitted light using crossed polarisers; he cal-
led it the “blue homeotropic phase”. The first phase
seen microscopically was the birefringent focal conic
cholesteric texture. Whereas the “blue homeotropic
phase” supercooled, the amorphous liquid did not and
the transition to the “blue homeotropic phase” seen
by eye on cooling, corresponded in temperature to
that of the birefringent cholesteric liquid crystal-
amorphous liquid transition on heating; the “blue
homeotropic phase” was not therefore detected on
heating. Saupe [4] later reported a higher light scatter-
ing and optical activity for a “blue phase” of choles-
teryl p-nonylphenyl carbonate than that for the amor-
phourliquid; he also found it to be optically isotropic
and proposed an idealised model involving a form of
cubic lattice.
More recently the situation has been complicated
by reports of the microscopic observation of platelets
near to the cholesteric-amorphous liquid transition for
some cholesterogens. For example Price and Wendorff
[5] reported white platelets in the case of cholesteryl
myristate. Chistyakov [6] described the observation
of coloured platelets for the same compound and, very
recently, Elser et al. [7] reported and photographed
coloured platelets near to the cholesteric-amorphous
liquid transition for cholesteryl n-alkyl carbonates. In
the latter case, the occurrence of the platelets was
reversible on heating and cooling.
It is therefore apparent that microscopic observ-
ations relating to the cholesteric-amorphous liquid
transition are not self-consistent and constitute a
rather confusing picture. There is much uncertainty
regarding the nature and even existence of the “blue
phase” and the relation between this “phase” and the
more recently observed platelet texture, occurring
around the same temperature region, requires clarifi-
cation. A coordinated optical study of several com-
mon cholesteryl compounds has therefore been under-
taken to try and elucidate the situation.
The compounds, examined as thin films were:
cholesteryl (a) propionate, (b) octanoate, (c) myristate,
(d) palmitate, (e) butyl carbonate, (f) chloride, (g) ben-
zoate, (h) heptyl carbonate.
To facilitate the simultaneous observation of the
“blue phase” by eye and also microscopically in re-
flected light, a black plate was placed under the micro-
scope slide on the hot stage.
The “blue phase” was seen by eye on cooling all
eight amorphous liquids and when viewed microscop
ically violet patches were seen. The violet patches ap
peared exactly when the boundary of the “blue phase”
reached the area illuminated by the light beam. These
patches then gave way to blue platelets, though some-
times they were red or green. At a lower temperature,
the white focal conic cholesteric texture developed in
the platelet texture and the second phase seen by eye
corresponded to this texture. The temperature range

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Volume 45A, number 2 PHYSICS LETTERS
in which the “blue phase” was stable varied but, at
the slow rates of cooling used, was usually < 1°C ex-
cept for (c) and (d) for which it lasted (ca. 4°C) until
the appearance of the smectic phase.
On slow heating of either the focal conic or plane
textures of the cholesteric phase neither the “blue
phase” nor the platelet texture was seen for (c) or (d).
The monotropic cholesteric mesophase of(b) always
crystallized before the transition to the amorphous
liquid, at the slow heating rates employed. The “blue
phase” was, however, detected by eye for the other
five compounds on slow heating and the platelets were
also seen microscopically in the “blue phases”. The
disappearance of the final violet patches corresponded
to the “blue phase”-amorphous liquid boundary pass-
ing completely across the illuminated area.
When the microscope was arranged for rapidly
switching from transmitted to reflected light, it was
found that the “blue phase” could be seen only faint-
ly, if at all, with transmitted light. However, when the
platelets were visible in transmitted light, it became
obvious that only part of the platelet texture was
being seen in reflected light, possibly due to the bright-
ness of those parts. The more uniform colour intensity
obtained with transmitted light showed that the areas
which were apparently black in reflected light also
consisted of coloured platelets.
The important result of these experiments is that
whenever platelets are observed microscopically then
the “blue phase” also exists and occurs over exactly
the same temperature region. Platelets have not been
widely reported possibly because they are diffucult to
see in transmitted light, reflected light being rarely
used in the microscopic study of liquid crystals.
Chistyakov has also noticed that the colour of the
platelets does not change on rotation of the stage, in-
dicating the optic axis of the platelets to be along the
line of sight; rotation of the analyser altered the colour
intensity of the platelets and this indicates that the
platelets rotate the plane of polarisation.
From these observations one can only suppose that
the platelet texture consists of a conglomerate of small
independent regions of differing and changing thick-
116
10 September 1973
ness having a structure of the classic cholesteric type
but of varying pitch length. The orientation of the
helical axes of the regions with respect to the surface
appears to differ as indicated by the different bright-
nesses of similarly coloured regions when viewed with
reflected light. After some supercooling the regions
then form the continuum of the lower energy focal
conic texture.
The platelets would seem to constitute a phase in
which a process of building up (on cooling) or breaking
down (on heating) of the cholesteric order is occurring.
X-ray studies by Wendorff and Price [8] and Rayleigh
scattering studies by Yang [9] also suggest this, but the
precise nature and molecular parameters influencing
this process are not, as yet, understood. As to whether
the platelet texture is always associated with the “blue
phase” is not certain as a result of such a limited study,
but certainly for the compounds studied the two are
compatible. Although the significance and role of the
“blue phase” remain uncertain, the “blue phase” does
exist and where platelets can be seen they occur in the
“blue phase”.
The cholesteric liquid crystal-amorphous liquid
transition is obviously not a simple one and further
work is being undertaken to clarify the situation.
The authors acknowledge with gratitude a main-
tenance grant (to D.C.) from the Science Research
Council, London.
References
1110. Lehmamr, Z. Phys. Chem. 56 (1906) 750.
121 G. Friedel, Ann. de Physique 18 (1922) 273.
131 G.W. Gray, J. Chem. Sot. (1956) 3733.
141 A. Saupe, Mol. Cryst. and Liquid Cryst. 7 (1969) 59.
151 F.P. Price and J.M. Wendorff, J. Phys. Chem. 75 (1971)
2839.
161 LG. Chistyakov and L.A. Gusakova, Kristallografiya
14 (1969) 153.
L71 W. Elser, J.L.W. Pohlmann and P.F. Boyd, Mol. Cryst.
and Liquid Cryst. 20 (1973) 77.
181 J.M. Wendorff and F.P. Price, private communication.
191 C.C. Yang, Phys. Rev. Letters 28 (1972) 955.