Networks mechanical properties

Figure 15 Concept of biomimetic design of a tnodular cross-linker, based on double-looped UPy motifs, for enhancing network mechanical properties. (Reproduced from Ref. 45. American Chemical Society, 2007.)...

An agreement with experimental results was obtained by taking into account the increased effective fraction of the filler, Veff, due to the glassy interphase of the bound epoxide layer and assuming a co-continuous morphology of the epoxy-silica hybrid network. Mechanical properties in dependence on the phase continuity are treated by parallel and series models for bicontinuous morphology and discontinuous phases, respectively. The equivalent box model (EBM) developed by Takayanagi (13) (eqs 2-5) and Davies model (14) (eq. 6) were used to compare the experimental data with the theory (9). 

Scanlan, J. C., Webster, D. C., Crain, A. L., Correlation between Network Mechanical Properties and Physical Properties in Polyester-Urethane Coatings (R. R. Gould, qA.), ACS Symp. Series, No. 648 222-234 (1996)... 

Sanabria-DeLong, N., Crosby, A.J., Tew, G.N., 2008. Photo-cross-finked PLA-PEO-PLA hydrogels from self-assembled physical networks mechanical properties and influence of assumed constitutive relationships. Biomacromolecules 9 (10), 2784—2791. 

We noted above that the presence of monomer with a functionality greater than 2 results in branched polymer chains. This in turn produces a three-dimensional network of polymer under certain circumstances. The solubility and mechanical behavior of such materials depend critically on whether the extent of polymerization is above or below the threshold for the formation of this network. The threshold is described as the gel point, since the reaction mixture sets up or gels at this point. We have previously introduced the term thermosetting to describe these cross-linked polymeric materials. Because their mechanical properties are largely unaffected by temperature variations-in contrast to thermoplastic materials which become more fluid on heating-step-growth polymers that exceed the gel point are widely used as engineering materials. 

Hyperbranched polyurethanes are constmcted using phenol-blocked trifunctional monomers in combination with 4-methylbenzyl alcohol for end capping (11). Polyurethane interpenetrating polymer networks (IPNs) are mixtures of two cross-linked polymer networks, prepared by latex blending, sequential polymerization, or simultaneous polymerization. IPNs have improved mechanical properties, as weU as thermal stabiHties, compared to the single cross-linked polymers. In pseudo-IPNs, only one of the involved polymers is cross-linked. Numerous polymers are involved in the formation of polyurethane-derived IPNs (12). 

The surface energy of silicones, the liquid nature of the silicone polymers, the mechanical properties of the filled networks, the relative insensitivity to temperature variations from well below zero to very high, and the inherent or added reactivity towards specific substrates, are among the properties that have contributed to the success of silicone materials as adhesives, sealants, coatings, encapsulants, etc. 

As one example, in thin films of Na or K salts of PS-based ionomers cast from a nonpolar solvent, THF, shear deformation is only present when the ion content is near to or above the critical ion content of about 6 mol% and the TEM scan of Fig. 3, for a sample of 8.2 mol% demonstrates this but, for a THF-cast sample of a divalent Ca-salt of an SPS ionomer, having only an ion content of 4.1 mol%, both shear deformation zones and crazes are developed upon tensile straining in contrast to only crazing for the monovalent K-salt. This is evident from the TEM scans of Fig. 5. For the Ca-salt, one sees both an unfibrillated shear deformation zone, and, within this zone, a typical fibrillated craze. The Ca-salt also develops a much more extended rubbery plateau region than Na or K salts in storage modulus versus temperature curves and this is another indication that a stronger and more stable ionic network is present when divalent ions replace monovalent ones. Still another indication that the presence of divalent counterions can enhance mechanical properties comes from... 

Dusek K (1971) in Shompff AJ, Newmann S (eds) Polymer Networks. Structure and Mechanical Properties. Plenum Press, New York, p245... 

A large number of SAHs described in the literature combine synthetic and natural macromolecules in the network structure. The natural components are usually starch, cellulose, and their derivatives. It is assumed that introduction of rigid chains can improve mechanical properties (strength, elasticity) of SAH in the swollen state. Radical graft polymerization is one of the ways to obtain such SAH. 

It should be noted that for polymerization-modified perlite the strength parameters of the composition algo go up with the increasing initial particle size. [164]. In some studies it has been shown that the filler modification effect on the mechanical properties of composites is maximum when only a portion of the filler surface is given the polymerophilic properties (cf., e.g. [166-168]). The reason lies in the specifics of the boundary layer formation in the polymer-filler systems and formation of a secondary filler network . In principle, the patchy polymerophilic behavior of the filler in relation to the matrix should also have place in the failing polymerization-modified perlite. 

As an organic polymer, poly(tetramethylene oxide) was also used for the preparation of ceramers. The mechanical properties in these cases were much improved in comparison with those for hybrids from polysiloxanes. In these poly (tetramethylene oxide)-silica hybrids, the effect of the number of functional triethoxysilyl groups was examined [13]. As shown in Fig. 2, more multifunctional organic polymer produced more crosslinked hybrid networks. This means that the more rigid the structure in the hybrids is, the higher the modulus and the lower swelling property. 

---