Crosslink mobility

In their work on a specific class of amine-crosslinked epoxy thermosets, Lesser and Crawford [140,141] found that Tg was affected strongly by Mc, by the average crosslink functionality fav (because of the effects of crosslink mobility, as will be discussed in Section 1 l.B.3.a for the equilibrium shear modulus Ge°), and by the chain stiffness. Their data were best represented by Equation 6.18, where Tg(° ) and C, were treated as fitting parameters. 

If the rubbery equilibrium shear modulus does not show evidence of crosslink mobility for some other family of thermosets, then the factor (fav-2)/fav would drop out of Equation 6.18, so that the dependence of Tg on network architecture would be expressed more simply, just in tenns of Mc. It could, in that case, be expressed equivalently as in Equations 6.16 and 6.17. For thermosets known to or expected to manifest crosslink mobility, it should, then, generally be possible to combine the functional form of the dependence on fav shown in Equation 6.18 with Equation 6.16, to obtain Equation 6.19 which is an alternative form for the relationship for the Tg of thermosets manifesting crosslink mobility. 

Also, the theory does not directly address the role of entanglements, but treats them in the manner of Flory and Erman (12-13) as imposing restrictions on crosslink mobility. We regard it as an open question as to whether this approach is adequate for accounting for the effect of entanglements and its local variation on influencing local swelling. 

Obviously the theory Is not quantitatively correct. But It does Indicate a need to rethink current Ideas about stress-induced crystallization. It shows that stress regeneration at low temperatures need not Involve a morphological change. It demonstrates that crosslink mobility and wrong-way chains can have extremely Important consequences. And It demonstrates a necessity for extensive, reliable experimental data on a number of polymer networks. 

The tightrope situation that arises from balancing high mobility, low crystallinity, and optimum crosslinking is often dealt with by using copolymers rather than homopolymers. With chain composition as an additional variable, molecules can be tailored better for specific application situations. 

Fig. 22. Nomialized pull-off energy measured for polyethylene-polyethylene contact measured using the SFA. (a) P versus rate of crack propagation for PE-PE contact. Change in the rate of separation does not seem to affect the measured pull-off force, (b) Normalized pull-off energy, Pn as a function of contact time for PE-PE contact. At shorter contact times, P does not significantly depend on contact time. However, as the surfaces remain in contact for long times, the pull-off energy increases with time. In seinicrystalline PE, the crystalline domains act as physical crosslinks for the relatively mobile amorphous domains. These amorphous domains can interdiffuse across the interface and thereby increase the adhesion of the interface. This time dependence of the adhesion strength is different from viscoelastic behavior in the sense that it is independent of rate of crack propagation.

The porosity and permeability of CP are the most important factors determining their ability to sorb and immobilize BAS. For solving these problems, it was necessary to synthesize various types of porous and permeable CP differing in the mobility of elements of the crosslinked structure and in the rigidity of the polymer backbone. For biological problems related to the application of CP as biosorbents, it has been found necessary to use CP with a marked structural inhomogeneity. 

In this case, the elements of the crosslinked structure exhibit higher mobility, the permeability of the crosslinked structure depends on the degree of hydration. It should be noted that the pore size in hydrated crosslinked copolymers is determined by small-angle X-ray scattering or with the aid of electron microscopy using special methods of preparation for the CP samples [15],... 

The steady structure determined by the value of Kw (Fig. 1) for the entire class of carboxylic CP obtained by precipitation copolymerization is one of the most important factors determining the possibility of reversible bonding of proteins absorbed by carboxylic CP with a high sorption capacity [16,19]. Thus, for the MA-HHTT system (Fig. 2), a complete desorption of enzyme is carried out on crosslinked copolymers characterized by low Kw values. In crosslinked structures exhibiting looser structure (Kw P 1), owing to the mobility of chain fragments of CP especially in the process of desorption, the macromolecules of sorbed protein are irreversibly captured as a result of a marked polyfunctional interaction. 

In order to study the mobility of elements of crosslinked structure of CP, it is suitable to use their microdisperse forms [30-35]. On the one hand, in potentiome-tric titration the equilibrium is quickly attained for these forms and on the other hand the effect of light scattering in spectral methods of investigation (e.g., polarized luminescence) can be greatly decreased. 

The possibility of conformational changes in chains between chemical junctions for weakly crosslinked CP in ionization is confirmed also by the investigation of the kinetic mobility of elements of the reticular structure by polarized luminescence [32, 33]. Polarized luminescence is used for the study of relaxation properties of structural elements with covalently bonded luminescent labels [44,45]. For a microdisperse form of a macroreticular MA-EDMA (2.5 mol% EDMA) copolymer (Fig. 9 a, curves 1 and 2), as compared to linear PM A, the inner structure of chain parts is more stable and the conformational transition is more distinct. A similar kind of dependence is also observed for a weakly crosslinked AA-EDMA (2.5 mol%) copolymer (Fig. 9b, curves 4 and 5). 

The interpretation of the relationships obtained here is based on the same principles of polyfunctional interaction between CP and organic ions which are considered in sections 3.1-3.3. The dispersion of CP grains to a certain size (1-10 pm) yields particles retaining the ability of polyfunctional interaction with organic ions. Simultaneously with increasing dispersion, the mobility of elements of the crosslinked structure also increases, which favors additional interaction. Further dispersion of CP (d 0.1 pm) gives so weak networks that the spatial effect of polyfunctional interaction with organic ions drastically decreases similar to linear polyelectrolytes [64]. 

Small deformations of the polymers will not cause undue stretching of the randomly coiled chains between crosslinks. Therefore, the established theory of rubber elasticity [8, 23, 24, 25] is applicable if the strands are freely fluctuating. At temperatures well above their glass transition, the molecular strands are usually quite mobile. Under these premises the Young s modulus of the rubberlike polymer in thermal equilibrium is given by ... 

Naphthalenedisulfonate-acetonitrile as the only mobile phase with a silica column coated with a crosslinked aminofluorocarbon polymer has proven to be an effective combination for the separation of aliphatic anionic surfactants. Indirect conductivity and photometric detection modes are used to monitor these analytes. The retention of these surfactants is found to depend on both the ionic strength and the organic solvent content of the mobile phase. The mechanism of retention is considered to be a combination of both reverse phase and ion exchange processes. Selective separation of both alkanesulfonates and... 

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