Ionic clusters/clustering

A gas phase ionic cluster can be described as a core ion solvated by one or more neutral atoms or molecules... 

X-ray diffraction work (11,15) shows that there is an ionomer peak at 4°C which is absent in the acid precursor. This low, broad peak is not affected by annealing or ion type and persists up to 300°C. Since the 4°C peak corresponds to a spacing of about 2.5 nm, it is reasonable to propose a stmctural feature of this dimension in the ionomer. The concept of ionic clusters was initially suggested to explain the large effects on properties of relatively sparse ionic species (1). The exact size of the clusters has been the subject of much debate and has been discussed in a substantial body of Hterature (3,4,18—20). A theoretical treatment has shown that various models can give rise to supramoleculat stmctures containing ionic multiplets which ate about 10 nm in diameter (19). 

Ethylene—Dicarboxylic Acid Copolymers. Partial neutralization of copolymers containing carboxyls in pairs on adjacent carbons, eg, ethylene—maleic acid, has been described (11). Surprisingly, there is no increase in stiffness related to neutralization. Salts with divalent metal cations are not melt processible. The close spacing of the paired carboxyl groups has resulted in ionic cluster morphology which is distinct from that of the commercial ionomer family. 

One of the most remarkable results from the molecular simulation studies of aqueous electrolyte solutions was that no additional molecular forces needed to be introduced to prevent the much smaller ions (Na has a molecular diameter of less than 0.2 nm) from permeating the membrane, while permitting the larger water molecules (about 0.3 nm in diameter) to permeate the membrane. This appeared to be due to the large ionic clusters formed. The ions were surrounded by water molecules, thus increasing their effective size quite considerably to almost 1 nm. A typical cluster formed due to the interaction between the ions and a polar solvent is shown in Fig. 7. These clusters were found to be quite stable, with a fairly high energy of desolvation. The inability of the ions to permeate the membrane is also shown... 

FIG. 7 Example of an ionic cluster formed by ions being surrounded by molecules of a polar solvent (methanol) [25]. 

The ionic clusters observed are not limited to aqueous electrolyte solutions only. In fact very similar results were obtained for methanolic solutions as well [25]. This shows that sufficiently large and stable ionic clusters are a fairly common occurrence whenever ions are dissolved in polar solvents. The clusters are an essential factor in the facilitation of reverse osmosis purification. Since many industrially important solutions include ions in polar solvents, it is important to account for them in separation involving such solvents. 

Studies of PMMA-based ionomers also demonstrate the influence of thermal treatment on deformation modes (16). For Na salts of PMMA-based ionomers of 6 and 12 mol% that were cast from DMF, only crazes were observed on straining. However, after an additional heat treatment (48 h at 160°C), which also removes any DMF solvent that is present, shear deformation zones are induced. Hence, the ionic cluster phase, which was destroyed by the polar solvent, has been restored by the heat treatment. 

The mechanical properties of ionomers are generally superior to those of the homopolymer or copolymer from which the ionomer has been synthesized. This is particularly so when the ion content is near to or above the critical value at which the ionic cluster phase becomes dominant over the multiplet-containing matrix phase. The greater strength and stability of such ionomers is a result of efficient ionic-type crosslinking and an enhanced entanglement strand density. 

Figure 4. Two representations (on the left) of cation motion in a polymer electrolyte assisted by polymer chain motion only, and two (on the right) showing cation motion taking account of ionic cluster contributions.

The presence of ions in an otherwise organic matrix is not thermodynamically stable. As a result these materials undergo slight phase separation in which the ions cluster together in aggregates. These ionic clusters are quite... 

The representation of an essentially infinite framework by a finite SCF treated cluster of atoms, (with or without point-ions), inevitably leads to the problem of how to truncate the model-molecule . Previous attempts at this have included using hydrogen atoms l and ghost atoms . Other possibilities include leaving the electron from the broken bond in an open shell, or closing this shell to form an ionic cluster. A series of calculations were performed to test which was the host physically realistic, and computationally viable, solution to this problem for this system. 

Ethylene ionomers consist of copolymers of ethylene and an organic add, such as methacrylic acid, the acid moieties of which have been neutralized to form a metal salt. The metal salts from neighboring chains tend to form clusters, such as the one shown schematically in Fig. 18.3. The net result is the overall structure shown in Fig. 18.2 g), in which the ionic clusters form weak crosslinks between adjacent chains. Ionomers also contain short and long chain branches, which are similar to those found in low density polyethylene. 

Species concentrations are shown in Figure 12. At 34 GPa (2.0g/cc), H2O is the predominant species, with H30+ and OH having mole fractions of ca. 5%. In addition, some aggregation has occurred in which neutral and ionic clusters containing up to six oxygens have formed. The concentrations of OH and H30+ are low for all densities investigated and nonexistent at 95 and 115 GPa (2.8 and 3.0g/cc, respectively). The calculated lifetimes for these species are well below 10 fs for the same thermodynamic conditions (less than 8 fs at 34 GPa). At pressures of 95 and 115 GPa, the increase in the O-H bond distance leads to the formation of extensive bond networks (Figure 13). These networks consist entirely of O-H bonds, whereas 0-0 and H-H bonds were not found to be present at any point. 

Figure 4.34. The cluster [Mo6C1i4]2 is shown. Numerous compounds are known which contain this group as a negative ionic cluster. Six Cl atoms were added to the six vertexes of the white octahedron shown in Fig. 4.32.

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