Phase microphase separation structure

Table II shows Tgs obtained from DSC traces. (Footnotes a and b in Table II show T s values of three reference polymers two PIBs, whose Mns are similar to the Mns of MA-PIB-MA used in the network synthesis, and a PDMAAm the difference in the Tg for the Mn=4,000 and 9,300 PIBs is due to the dependence of Tg on Mn(72)). The DSC traces of the networks exhibited two Tgs, one in the range of -63 to -52 °C (PIB domains) and another in the range of 90 to 115 °C (PDMAAm domains) indicating microphase separated structures. The Tgs associated with the PIB phase in the PDMAAm-1-PIB networks were higher than those of the reference homoPIBs which may be due to PIB chain-ends embedded in the glassy PDMAAm phase restricting segmental mobility. The Tg of the PIB phase in the PDMAAm-1-PIB increases by increasing the PIB content which may be due to an increase in crosslink density. In contrast, the Tg for the PDMAAm phase in the network decreases upon increasing the PIB content. Interaction of the (-CH2-CH-) moiety of the PDMAAm with the flexible PIB and thus the formation of a more flexible structure may explain this phenomenon.

In addition to the previously mentioned driving forces that determine the bulk state phase behavior of block copolymers, two additional factors play a role in block copolymer thin films the surface/interface energies as well as the interplay between the film thickness t and the natural period, Lo, of the bulk microphase-separated structures [14,41,42], Due to these two additional factors, a very sophisticated picture has emerged from the various theoretical and experimental efforts that have been made in order to describe... 

UsingTEM to identify blend morphology, two diblocks with/ps 0.8 that form cubic-packed spherical phases and cylindrical phases respectively in the pure copolymer were found not to macrophase separate in a blend with d = 2.2, but to form single domain structures (cylinders or spheres) in the blend (Koizumi et al. 1994c). Similarly, blending a diblock with fK = 0.26 with one with fK = 0.64 (d = 1.2) led to uniform microphase-separated structures, with a lamellar phase induced in the 50 50 blend. Vilesov et al. (1994) also observed that blending two PS-PB diblocks with approximately inverse compositions (i.e. 22wt% PS and 72 wt% PS) induces a lamellar phase in the 50 50 blend. These examples all correspond to case (i). 

The increase of the solvent concentration in SB41 films on raising the partial pressure of chloroform vapor, and the related loss of long-range order, can be explained in terms of the so-called dilution approximation for the bulk block copolymer phases [167, 168], The above results clearly demonstrate the high sensitivity of the polymer-polymer interactions towards solvent content. Therefore, the microphase-separated structures in swollen block copolymer films can be used as a qualitative measure of the degree of swelling of the films [49, 166],... 

Figure 18c displays swelling kinetics of two SV films with the same initial thickness but different microphase-separated structures. The curves show up to 10% larger swelling (smaller poi) of SV films with the initial bulk lamella morphology as compared to the films with the non-bulk micelle phase [119],... 

We note that earlier research focused on the similarities of defect interaction and their motion in block copolymers and thermotropic nematics or smectics [181, 182], Thermotropic liquid crystals, however, are one-component homogeneous systems and are characterized by a non-conserved orientational order parameter. In contrast, in block copolymers the local concentration difference between two components is essentially conserved. In this respect, the microphase-separated structures in block copolymers are anticipated to have close similarities to lyotropic systems, which are composed of a polar medium (water) and a non-polar medium (surfactant structure). The phases of the lyotropic systems (such as lamella, cylinder, or micellar phases) are determined by the surfactant concentration. Similarly to lyotropic phases, the morphology in block copolymers is ascertained by the volume fraction of the components and their interaction. Therefore, in lyotropic systems and in block copolymers, the dynamics and annihilation of structural defects require a change in the local concentration difference between components as well as a change in the orientational order. Consequently, if single defect transformations could be monitored in real time and space, block copolymers could be considered as suitable model systems for studying transport mechanisms and phase transitions in 2D fluid materials such as membranes [183], lyotropic liquid crystals [184], and microemulsions [185],... 

This approach towards nanostructured inorganic-organic hybrid materials is the first one to allow the synthesis of inverse-topology systems, in which the hydrophobic polymer blocks represent the outside of the microphase-separated structure. After solidification of the inorganic sol, the hydrophobic phase can be swollen with organic solvents. This procedure allows the isolation of colloidal objects, such as spheres or ceramic rods (see Fig. 12), from one another, which are sterically stabilized, because the hydrophihc block is firmly anchored in the ceramic material [45]. 

Columnar mesomorphic behavior is observed for compound 78 because the associated lateral groups disturb the formation of smectic layers and the hydrophilic lateral chain and the hydrophobic core unit form microphase-separated structures. A variety of block molecules capable of forming mesophases have been prepared and examined in relation to phase-separated association [164]. 

Figure 9. Microphase separated structure of a diluted polysiloxane in the SmC phase according to [40].

Boudouris et al. also observed microphase-separated structures in poly(3-dodecylthiophene-l7-lactic acid) diblock copolymers 34 after short periods of thermal annealing. The PT blocks retained their crystallinity within the nanos-tructured phases, and chemical etching of the poly(lactic acid) block resulted in the formation of nanoporous PT films. 

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