Domain microphase

Other PDMS—sihca-based hybrids have been reported (16,17) and related to the ceramer hybrids (10—12,17). Using differential scanning calorimetry, dynamic mechanical analysis, and saxs, the microstmcture of these PDMS hybrids was determined to be microphase-separated, in that the polysiUcate domains (of ca 3 nm in diameter) behave as network cross-link junctions dispersed within the PDMS oligomer-rich phase. The distance between these... 

Microdomain stmcture is a consequence of microphase separation. It is associated with processability and performance of block copolymer as TPE, pressure sensitive adhesive, etc. The size of the domain decreases as temperature increases [184,185]. At processing temperature they are in a disordered state, melt viscosity becomes low with great advantage in processability. At service temperamre, they are in ordered state and the dispersed domain of plastic blocks acts as reinforcing filler for the matrix polymer [186]. This transition is a thermodynamic transition and is controlled by counterbalanced physical factors, e.g., energetics and entropy. 

Cakmak M. and Wang M.D., Structure development in the tubular blown film of PP/EPDM thermoplastic elastomer, Antec 89, 47th Annual Tech. Conference of SPE, New York, May 1, 1989, 1756. Hashimoto T., Todo A., Itoi H., and Kawai H. Domain boundary structure of styrene-isoprene block copolymer films cast from solution. 2. Quantitative estimation of the interfacial thickness of lamellar microphase systems. Macromolecules, 10, 377, 1977. 

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.

Table II shows Tg data obtained from DSC traces of the PHEMA-1 -PIB networks. The traces showed two Tgs indicating microphase separation into PHEMA and PIB domains. The presence of the PHEMA Tg at - 110°C indicates complete desilylation of all networks. The Tgs for the reference PIBs (see footnote a in Table II) are lower than the Tgs of the PIB incorporated into the network. This may be due to the flexible PIB chain-ends embedded in the glassy PHEMA matrix. The increase in the Tg of the PIB phase in the network with increasing % PIB is most likely due to an increase in crosslink density.

Drug Release from PHEMA-l-PIB Networks. Amphiphilic networks due to their distinct microphase separated hydrophobic-hydrophilic domain structure posses potential for biomedical applications. Similar microphase separated materials such as poly(HEMA- -styrene-6-HEMA), poly(HEMA-6-dimethylsiloxane- -HEMA), and poly(HEMA-6-butadiene- -HEMA) triblock copolymers have demonstrated better antithromogenic properties to any of the respective homopolymers (5-S). Amphiphilic networks are speculated to demonstrate better biocompatibility than either PIB or PHEMA because of their hydrophilic-hydrophobic microdomain structure. These unique structures may also be useful as swellable drug delivery matrices for both hydrophilic and lipophilic drugs due to their amphiphilic nature. Preliminary experiments with theophylline as a model for a water soluble drug were conducted to determine the release characteristics of the system. Experiments with lipophilic drugs are the subject of ongoing research. 

In microphase-separated systems, ESR spectra may consist of a superposition of two contributions, from nitroxides in both fast and slow-tumbling regimes. Such spectra provide evidence for the presence of two types of domains with different dynamics and transition temperatures. This case was detected for a HAS-derived nitroxide radical in heterophasic polyfacrylonitrile-butadiene-styrene) (ABS) as shown in Figure 5, the fast and slow components in the ESR spectrum measured represent nitroxide radicals located in butadiene-rich (B-rich) and styrene/acrylonitrile-rich (SAN-rich) domains, respectively [40]. These two components were determined by deconvoluting the ESR spectrum of HAS-NO measured at 300 K. 

Several structure sizes caused by microphase separation occurring in the induction period as well as by crystallization were determined as a function of annealing time in order to determine how crystallization proceeds [9,18]. The characteristic wavelength A = 27r/Qm was obtained from the peak positions Qm of SAXS while the average size of the dense domains, probably having a liquid crystalline nematic structure as will be explained later, was estimated as follows. The dense domain size >i for the early stage of SD was calculated from the spatial density correlation function y(r) defined by Debye and Buche[50]... 

The complete parallel orientation makes the excluded volume zero while the complete perpendicular orientation gives the maximum value. Doi s theory predicts that such parallel orientation does not occur homogeneously in the system, but it involves an SD-type microphase separation into the oriented and unoriented domains. These theoretical predictions actually agree with our observations as described in the previous section. 

Fig.49 Composition distribution dependence of reduced domain spacing, D/D0, of PS- -P2VP with single microphase-separated structure. Do = 60.8 nm is domain spacing of parent copolymer with Mn = 125 kg/mol. Hatched region macrophase separation. From [160], Copyright 2003 American Chemical Society...

Further evidence for microphase separahon has been seen by AFM. As expected, BPSH 00, with no ionic regions, displays no significant features in its AFM image. For BPSH 20, isolated ionic clusters have dimensions of 10-25 nm. These clusters are even more readily discerned from the non-ionic matrix in BPSH 40, but the domains appear to remain relatively segregated from each other. In the case of BPSH 50 and 60, connections between domains are clearly visible, especially in the case of the latter sample. It also should be noted, however, that these samples were in a dehydrated state. Therefore, it might be expected that even in the case of the lower acid content samples, it is likely that some channel formation between ionic domains will still occur upon the uptake of water. This can be clearly seen in its linear conductivity behavior as a function of disulfonated monomer (i.e., the percolation threshold has been reached by at least 20-30% content of disulfonated monomer). 

Little characterization of 17 and 18 is available in the open literature. In the case of 19 and 20, both pol5dmides displayed microphase separation in contrast to statistically, main-chain sulfonated polyimides for which little, if any, microphase separation is observed. Eor 19, hydrophilic domains were seen to be on the order of 5 nm in size. Similarly, 20 (where x = 3, y = 10, n = 50) with a... 

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