Cross-linked density distribution

Effect of Cross-Link Density Distribution on the Engineering Behavior of Epoxies... 

The NMR quantities defining the contrast of NMR images depend on various macroscopic and microscopic physical and chemical parameters of the investigated samples that affect the nuclear spin interactions or molecular transport parameters. They can be classified as internal and external. Moreover, they can be state parameters that are stationary quantities like stress, strain, moduli of shear and compression, cross-link density, distribution and agglomeration of filler particles, molecular orientation, fibril orientation and domain size distribution. 

Figure 17 Cross-link density distribution of primary polymer chains with respect to their birth conversion. ...

Figure 18(a) presents normalized proton DQ buildup functions of end-linked polydimethylsiloxane model networks prepared by mixing and subsequent cross-linking of very short and rather long chains. Such bimodal networks are known to consist of clusters of highly cross-linked regions embedded in a long-chain elastomer matrix. The buildup curves as well as the cross-link density distributions (i.e., the distributions of D s) derived from these show clear bimodal... 

First, in composites with high fiber concentrations, there is little matrix in the system that is not near a fiber surface. Inasmuch as polymerization processes are influenced by the diffusion of free radicals from initiators and from reactive sites, and because free radicals can be deactivated when they are intercepted at solid boundaries, the high interfacial area of a prepolymerized composite represents a radically different environment from a conventional bulk polymerization reactor, where solid boundaries are few and very distant from the regions in which most of the polymerization takes place. The polymer molecular weight distribution and cross-link density produced under such diffusion-controlled conditions will differ appreciably from those in bulk polymerizations. 

Wootthikanokkhan and Clythong have studied the effects of additive distribution and its effect on the distribution of cross-link density in NR-acrylic rubber (AR) blends [38]. The formulations of the four blends is given in Table 11.15. 

St and divinylbenzene (DVB) were polymerized in a dispersion of acryl-amide-methacrylic acid-methylenebisacrylamide terpolymer particles (25). Fine polystyrene particles were formed in/on each seed terpolymer particle. The former was smaller by about one-twentieth than the latter. The distribution of polystyrene particles depended on the cross-link density. Different amounts of St and DVB were charged in the seeded polymerization, and the resulting composite particles were used for protein adsorption measurement to assess the hydrophobicity of the particle surface. The adsorbed amount was almost proportional to the amount of St and DVB charged. In contrast, cells were less stimulated by the 5% St-containing particle than by the 0% St-containing one, that is, the seed particle. This phenomenon is attributed to selective protein adsorption on the 5% St-containing particle (26). 

Compared with chemical cross-linking of PE, radiation curing produces a different product in many respects. The chemical cross-linking is done at temperatures near 125°C (257°F), where the polymer is in the molten state. Consequently, the cross-link density in the chemically cross-linked polyethylene is almost uniformly distributed, while there are relatively few cross-links in the crystalline fraction of the radiation cross-linked PE. The crystalline fraction of the radiation-processed polyethylene is greater than that in the chemically cured product. ... 

Radiation cross-linking of polyethylene requires considerably less overall energy and less space, and is faster, more efficient, and environmentally more acceptable. Chemically cross-linked PE contains chemicals, which are by-products of the curing system. These often have adverse effects on the dielectric properties and, in some cases, are simply not acceptable. The disadvantage of electron beam cross-linking is a more or less nonuniform dose distribution. This can happen particularly in thicker objects due to intrinsic dose-depth profiles of electron beams. Another problem can be a nonuniformity of rotation of cylindrical objects as they traverse a scanned electron beam. However, the mechanical properties often depend on the mean cross-link density. ... 

Most MIPs show a heterogeneous distribution of binding sites and can be considered as polyclonal in their nature. In non-covalent imprinting, the amorphous material contains binding sites which are not identical because they may have different cross-linking density or accessibility. Moreover, the monomer (M) and the template molecule (A) may form complexes of different stoichiometry (MnA) in the pre-polymerization mixture [5]... 

Cross-link density and parameters relating to the network structure can be measured by NMR by analysis of the transverse relaxation decay (cf. Section 1.3) and the longitudinal relaxation in the rotating frame [67]. Combined with spatial resolution, the model-based analysis of relaxation yields maps of cross-link density and related parameters [68]. Often the statistical distribution of relaxation parameters over all pixels provides a reduced data set with sufficient information for sample characterization and discrimination [68]. 

---