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Figure 5.9. Scattering light intensity as a function of the water content (vol%) for PEAPE, BP-AZ-CA, and PEAPE/BP-AZ-CA (1:1, wt:wt) dissolved in THF-H2O media. The scattered light intensity shown here is a ratio of scattered light intensity to incident light intensity. Source: From Deng et al., 2007.

+M+ + MChemical potentials are split up into standard and variable terms, (*i + ii ; + ju _ + n -)/RT + h^/RT + h Ina0 + 2In

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chromophores. The photoinduced deformation study that is discussed in Section 5.4 con rms that the colloids are composed of the two components. Because of the hydrophilicity difference, the two polymeric components are not uniformly distributed in the colloidal spheres. Figure 5.9 shows lightscattering intensity as a function of the water content (vol%) for PEAPE, BPAZ-CA, and PEAPE/BP-AZ-CA (1:1, wt:wt) as the water is slowly added into THF-H2O media. It can be seen that the CWC of PEAPE is much lower than that of BP-AZ-CA (24 vol% for PEAPE and 36 vol% for BP-AZ-CA). CWC of the solution containing both PEAPE and BP-AZ-CA is close to that of PEAPE. By using the method developed by Zhang et al. (1997), the percentage of the associated chains as a function of the water content can be estimated for the single-component system. When the water content reaches 40 vol%, the associated chains of PEAPE are estimated to be 99.5%. For BP-AZ-CA, polymeric chains start to associate at 36 vol% (CWC). Only when the water content reaches 77 vol%, the percentage of the associated chains can reach 99.5%. For the dispersions containing both polymers, the variation of aggregation fraction versus the H2O increment cannot be directly obtained by this method. Although some deviation could be caused by the interaction between the PEAPE and BP-AZ-CA molecules, the tendency of the components to aggregate in order of their hydrophilicity should be maintained. It means that during the water content increasing process, more hydrophobic PEAPE chains will associate rst. A signi cant amount of PEAPE chains in the dispersion has aggregated when

(1-3.39)

the BP-AZ-CA chains start to aggregate. As the water content further increases, the less hydrophobic BP-AZ-CA chains assemble on the PEAPE-dominated cores, which nally results in the formation of the hybrid colloids. The nonuniform distribution of the two components and its in uence on the photoresponsive properties are further discussed in the following section.

Solution Deployment Descriptor (SDD)

+ In y+tX + In Y-,x = In y+ + In y'- (1-3.40) For Ai0 , all the logarithmic terms approach zero. Thus the combination of the standard potentials given by the first terms in Eq. (1.3.40) equals

Depending on the composition and preparation conditions, the azo polymer colloidal spheres can exhibit different photoresponsive properties triggered by the photoisomerization of the azo chromophores. The photoinduced variations are related to both the isomerization features of the azo chromophores and the structures of the colloidal matrices. For colloids containing azobenzene-type chromophores, the photochromic variation caused by isomerization can be measured by UV-vis spectroscopy. As mentioned earlier, the isomerization rate and degree have been used as a tool to monitor the structure variation. Compared with the isolated chains and loose aggregates, the photoinduced isomerization rate and degree are much lower for the colloids in their nal collapsed state, which is due to the compact inner structure after the collapse. For the colloids containing relatively small amount of pseudostilbene-type azo chromophores, the shape of the colloids remains unaltered after the linearly polarized Ar+ laser light irradiation, but the azo chromophores in colloids can be driven by the linearly polarized light to align perpendicularly to the polarization direction. This property is discussed in Section 5.5 together with those observed for the 2-D colloidal arrays. Most signi cant photoresponsive variation is the shape deformation induced by Ar+ laser irradiation, which can be observed for the colloids containing pseudostilbene-type chromophores. This photoresponsive property is discussed in this section in detail.