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PERIODIC AREA MINIMIZATION SURFACES
IN MICROSTRUCTURAL SCIENCE
EDWIN L. THOMAS and SAMUEL P. GIDO
Department of Materials Science and Engineering, and Program in Polymer Science and
Technology, Massachusetts Institute of Technology, Cambridge, MA 02139
Abstract
An A/B block copolymer consists of two macromolecules bonded together. In
forming an equilibrium structure, such a material may separate into distinct phases,
creating domains of component A and of component B. A dominant factor in the
determination of the domain morphology is area-minimization of the intermaterial
surface, subject to fixed volume fractions. Surfaces that satisfy this mathematical
condition are said to have constant mean curvature. The geometry of such surfaces
strongly influences material physical properties. We have discovered domain
structures in microphase-separated diblock copolymers that closely approximate
periodic surfaces of constant mean curvature. Transmission electron microscopy
and computer-simulation are used to deduce the three dimensional microstructure by
comparison of tilt series with two-dimensional image projection simulations of
three-dimensional mathematical models. Two structures are discussed: First is the
double diamond microdomain morphology, associated with a newly discovered
family of triply periodic constant mean curvature surfaces. Second, a doubly
periodic boundary between lamellar microdomains, corresponding to a classically
known minimal surface (Scherk's First Surface), is described.
Introduction
Most multifuctional materials are multiphased; comprised of two or more phases whose
simultaneous presence and mutual arrangement lead to unique properties. Emphasis in
multiphased materials research in recent years has been concerned with the production of
microphase textures of ever finer scale, since novel macroscopic properties can arise from
materials with nanoscale structure. As the size scale of the phase domains decreases, an
increasing percentage of the material is at or near an intermaterial interface. Surface phenomena
which are absent or negligible in the bulk materials then begin to dominate the physics.
Materials which have extremely high interphase surface area per unit volume can exhibit
entirely new physical properties.
In order to exploit such materials we need to learn how to control the size and mutual
arrangement of the microphases. A commonly used route to such ordered micro and
nanocomposites involves directly building up the structure via microlithographic processes.
With this approach process control is critical. An alternative approach is that of self assembly
- the ability of amphiphilic molecules to organize themselves into nanoscale patterns in
response to thermodynamic driving forces[1,2,3]. In our work we employ very large
amphiphiles: diblock copolymers consisting of two chemically different polymer segments.
The mutual repulsion of these segments leads to the formation of periodic nanoscale structure.
This self repulsion arises due to the positive enthalpy of interaction between the different block
monomer units, and is not significantly resisted by the loss of entropy because of the long
chain nature of the molecules. The local segregation of the A and B segments into microphases
occurs in spatially periodic patterns, due to the covalent link between the two types of
segments.
Area-minimization of the A-B intermaterial interface is a dominant factor in determining
the specific microdomain geometry which forms for a particular ratio of A and B block lengths.
Area minimization subject to fixed volume fraction (fixed composition) is the mathematical
Mat. Res. Soc. Symp. Proc. Vol. 175. ©1990 Materials Research Society