Phase behaviour near the order-disorder transition (ODT) of 58 model h
ydrocarbon diblock copolymers, representing four different systems, is
summarized. Six distinct ordered-state microstructures are reported,
including hexagonally modulated lamellae (HML), hexagonally perforated
layers (HPL) and a bicontinuous cubic morphology with Ia ($) over bar
3d space group symmetry. Two non-classical parameters, epsilon and ($
) over bar N, control the occurrence and distribution of these phases,
in addition to the classical variables f and N-chi, where f, chi and
N are the composition, segment-segment interaction parameter and degre
e of polymerization, respectively. epsilon accounts for differences in
the conformational and volume-filling characteristics of each block.
Conformational asymmetry, epsilon not equal 1, produces an asymmetric
phase diagram around f = 1/2. The importance of fluctuation effects ar
e inversely related to the magnitude of ($) over bar N, a type of Ginz
burg parameter that is proportional to N. As ($) over bar N decreases,
the bicontinuous Ia ($) over bar 3d phase appears adjacent to the ODT
. Development of this cubic phase can be rationalized based on chain-p
acking frustration near the lamellar hexagonal state. Apparently the I
a ($) over bar 3d cubic state is stabilized by fluctuations since it d
isappears when ($) over bar N becomes large. These findings provide ne
w insights into the origins of phase complexity in condensed soft matt
er.