Crosslink energy

The crystal s total crosslink energy is given by the sum of the terms of attraction and repulsion, which (in light of expressions [1.47] and [1.55] given above) gives ... 

Thus, in the expression of the crosslink energy, there is a constant m which needs to be determined. We can find its value by looking at the compressibility coefficient. Imagine that we compress a crystal at the temperature of absolute zero. The variation in internal energy will be ... 

This variation is due only to the change in the crosslink energy. By taking account of the definition of the compressibility coefficient, which is ... 

For simplicity s sake, let us write expression [1.56], of the crosslink energy, in the form ... 

If the other values are known, this expression can be used to calculate the crosslink energy. ... 

Mangipudi et al. [63,88] reported some initial measurements of adhesion strength between semicrystalline PE surfaces. These measurements were done using the SFA as a function of contact time. Interestingly, these data (see Fig. 22) show that the normalized pull-off energy, a measure of intrinsic adhesion strength is increased with time of contact. They suggested the amorphous domains in PE could interdiffuse across the interface and thereby increase the adhesion of the interface. Falsafi et al. [37] also used the JKR technique to study the effect of composition on the adhesion of elastomeric acrylic pressure-sensitive adhesives. The model PSA they used was a crosslinked network of random copolymers of acrylates and acrylic acid, with an acrylic acid content between 2 and 10%. 

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.

There is considerable evidence in the thermoset literature that the fracture energy decreases with increasing crosslink density, consistent with the intuitive result that crosslinking inhibits flow. In the limit of very high crosslink density, where for example we approach the structure of diamond, fracture can occur on a single crystal plane such that... 

Instead of using thermal energy to trigger the hydrogen abstraction mechanism, photo-induced reactions can be also be used to successfully crosslink acrylic PSAs [74-76], In this case, photoactive compounds, such as for example those containing benzophenone, anthraquinone or triazine nuclei are compounded with the polymer or copolymerized as one of the monomers. After drying, the adhesive... 

Once cured, PDMS networks are essentially made of dimethylsiloxane polymeric chains crosslinked with organic linkages. The general and inherent molecular properties of the PDMS polymers are therefore conferred to the silicone network. Low surface energy and flexibility of siloxane segments are two inherent properties very useful in adhesion technology. 

Earlier studies [14,15] clearly reveal that there is a reaction between two polymers and that the extent of reaction depends on the blend ratio. As 50 50 ratio has been found to the optimum (from rheological and infrared studies) ratio for interchain crosslinking, the higher heat of reaction for the NBR-rich blend may be attributed to the cyclization of NBR at higher temperatures. There is an inflection point at 50 50 ratio where maximum interchain crosslinking is expected. Higher viscosity, relaxation time, and stored elastic energy are observed in the preheated blends. A maximum 50-60% of Hypalon in NBR is supposed to be an optimum ratio so far as processibility is concerned. 

Surface crosslinkings could be introduced, surface energy could be increased or decreased, and reactive free radicals [28] and groups [30] could be produced. 

Crosslinking poly (2,2-dinitropropyl acrylate) in plastic-bonded explosives , US At Energy Comm, UCRL-50434 (1968) CA 70, 39419 (1969)... 

Effective molecular mass between crosslinks tvtc/kg mol 1 Tensile yield strength cry/MPa Energy release rate Gic/Jm 2 Half crack opening displacement w = 6/2 = Gic/2cry w/pm Chain contour length (Eq. 7.9) lc/nm... 

Apparently, the width and the length of the deformation zone are simply proportional to the molecular mass of the network strands The more highly crosslinked a polymer, the smaller is its deformation zone. On the other hand, polymers with few crosslinks will exhibit large deformation zones ahead of the growing crack. Since deformation zones pick up energy proportional to their crack... 

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