We
report on the formation of a bicontinuous double diamond (DD)
structure in ternary blends of poly(styrene-b-isoprene)
(SI) diblock copolymers with chains of different lengths merely in
a polyisoprene block. Certainly, the materials revealing the DD structure
with mesoscopic length scale have strongly been expected due to high
potential for applications; however, it is difficult to form owing
to thermodynamically evident disadvantages such as wider surface area
and larger domain thickness variation, particularly for monodisperse
copolymers. The DD structure was successfully formed for ternary blends
composed of three parent diblock copolymers; SI-L (M = 190k, φs = 0.46), SI-G (M =
151k, φs = 0.62), and SI-C (M =
124k, φs = 0.73), resulting in covering the overall
composition range 0.57 ≤ φs ≤ 0.60, where φss denotes volume fractions of polystyrene
blocks. Four-branched double network structure with space group symmetry
of Pn3̅m was clearly proved
by transmission electron microscopy (TEM) observation aided by computer
simulation, combined with diffracted data by small angle X-ray scattering.
In addition, TEM tomography gave direct information concerning interwoven
double networks and four-branching nature of the diamond framework.
The effect of molecular weight distribution of ABC linear terpolymers on the formation of periodic structures was investigated. Three poly(isoprene-b-styrene-b-2-vinylpridine) triblockterpolymers with molecular weights of 26k, 96k, and 150k were blended variously. Three-phase, four-layer lamellar structures were observed when polydispersity index (PDI) was low, but it has been found that simple lamellar structure with flat surface transforms into an undulated lamellar one, where two interfaces, i.e., I/S and S/P, are both undulated, and they are synchronizing each other if PDI exceeds the critical value. This new structure could be formed due to the periodic and "weak" localization of three chains along the domain interfaces, which produces periodic surfaces with nonconstant mean curvatures. With further increase of PDI, the blend macroscopically phase-separated into different microphase-separated structures.
The problem of the paradoxical motion of the falling chain is considered. Laboratory and numerical experiments are performed with the initially folded configurations. The velocity and the acceleration of the falling tip are analysed. It is shown that if the acceleration of the chain tip exceeds the gravitational acceleration g, it results in the appearance of a sharp peak in the time evolution of the tip velocity. An approximate analytical formula describing the rising part of the peak is presented and reasons for its limited applicability are discussed.
Hexagonally
packed coaxial triply helical domains with a mesoscopic
length scale in matrices were created from an S1IS2P tetrablock terpolymer/Sh homopolymer blend system,
wherein S1, S2, and Sh denote polystyrene,
I is polyisoprene, and P represents poly(2-vinylpyridine). Two terpolymers,
i.e., S1IS2P-3 (S1/I/S2/P = 0.50/0.17/0.19/0.14, M = 134k) and S1IS2P-4 (S1/I/S2/P = 0.58/0.16/0.10/0.16, M = 173k), were blended with Sh (M = 3k) at various concentrations. In the S1IS2P-3/Sh = 80/20 blend, the helical domain of P (o.d.=
19 nm; h.p. = 34 nm) was displayed by TEM, and the helical I phase
(o.d. = 55 nm; i.d. = 29 nm; h.p. = 34 nm) was clearly demonstrated
by 3D-TEM tomography. Essentially the same structure was confirmed
to be created from the S1IS2P-4/Sh blend. These findings point out that S2 chains fill the
gap between the I and P helices, and hence the intermediate S phase
also has a helical nature. Moreover, it is worth noting that grains
composed of hexagonally packed helices reveal homochirality.
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