Divalent properties

These monomers provide a means for introducing carboxyl groups into copolymers. In copolymers these acids can improve adhesion properties, improve freeze-thaw and mechanical stability of polymer dispersions, provide stability in alkalies (including ammonia), increase resistance to attack by oils, and provide reactive centers for cross-linking by divalent metal ions, diamines, or epoxides. 

Although rare-earth ions are mosdy trivalent, lanthanides can exist in the divalent or tetravalent state when the electronic configuration is close to the stable empty, half-fUed, or completely fiUed sheUs. Thus samarium, europium, thuUum, and ytterbium can exist as divalent cations in certain environments. On the other hand, tetravalent cerium, praseodymium, and terbium are found, even as oxides where trivalent and tetravalent states often coexist. The stabili2ation of the different valence states for particular rare earths is sometimes used for separation from the other trivalent lanthanides. The chemicals properties of the di- and tetravalent ions are significantly different. 

In aqueous solutions, trivalent lanthanides ate very stable whereas only a limited number of lanthanides exhibit a stable divalent or tetravalent state. Practically, only Ce and Eu " exist in aqueous solutions. The properties of these cations ate very different from the properties of the trivalent lanthanides. For example, Ce" " is mote acidic and cetium(IV) hydroxide precipitates at pH 1. Eu " is less acidic and eutopium(II) hydroxide does not precipitate at pH 7—8.5, whereas trivalent lanthanide hydroxides do. Some industrial separations ate based on these phenomena. 

Separation Processes. The product of ore digestion contains the rare earths in the same ratio as that in which they were originally present in the ore, with few exceptions, because of the similarity in chemical properties. The various processes for separating individual rare earth from naturally occurring rare-earth mixtures essentially utilize small differences in acidity resulting from the decrease in ionic radius from lanthanum to lutetium. The acidity differences influence the solubiUties of salts, the hydrolysis of cations, and the formation of complex species so as to allow separation by fractional crystallization, fractional precipitation, ion exchange, and solvent extraction. In addition, the existence of tetravalent and divalent species for cerium and europium, respectively, is useful because the chemical behavior of these ions is markedly different from that of the trivalent species. 

Selective Reduction. In aqueous solution, europium(III) [22541 -18-0] reduction to europium(II) [16910-54-6] is carried out by treatment with amalgams or zinc, or by continuous electrolytic reduction. Photochemical reduction has also been proposed. When reduced to the divalent state, europium exhibits chemical properties similar to the alkaline-earth elements and can be selectively precipitated as a sulfate, for example. This process is highly selective and allows production of high purity europium fromlow europium content solutions (see Calcium compounds Strontiumand strontium compounds). 

Divalent manganese compounds are stable in acidic solutions but are readily oxidized under alkaline conditions. Most soluble forms of manganese that occur in nature are of the divalent state. Manganese(Il) compounds are characteristically pink to colorless, with the exception of MnO and MnS which are green, and Mn(OH)2, which is white. The physical properties of selected manganese(Il) compounds are given in Table 6. 

Polyethers. Antibiotics within this family contain a number of cycHc ether and ketal units and have a carboxyHc acid group. They form complexes with mono- and divalent cations that ate soluble ia aoapolar organic solvents. They iateract with bacterial cell membranes and allow cations to pass through the membranes causiag cell death. Because of this property they have been classified as ionophores. Monensia, lasalocid, and maduramicia are examples of polyethers that are used commercially as anticoccidial agents ia poultry and as growth promotants ia mmiaants. 

Electroanalytical chemistry is one of the areas where advantage of the unique properties of SAMs is clear, and where excellent advanced analytical strategies can be utilized, especially when coupled with more complex SAM architectures. There are a number of examples where redox reactions are used to detect biomaterials (357,358), and where guest—host chemistry has been used to exploit specific interactions (356,359). Ion-selective electrodes are an apphcation where SAMs may provide new technologies. Selectivity to divalent cations such as Cu " but not to trivalent ions such as Fe " has been demonstrated (360). 

Monovalent cations are compatible with CMC and have Httle effect on solution properties when added in moderate amounts. An exception is sUver ion, which precipitates CMC. Divalent cations show borderline behavior and trivalent cations form insoluble salts or gels. The effects vary with the specific cation and counterion, pH, DS, and manner in which the CMC and salt are brought into contact. High DS (0.9—1.2) CMCs are more tolerant of monovalent salts than lower DS types, and CMC in solution tolerates higher quantities of added salt than dry CMC added to a brine solution. 

Zweiwelligkeit,/. two-wave property, zweiwertig, a. bivalent, divalent. Zweiwertigkeit, /, bivalence. 

The type of counterion present in an ionomer may, or may not, have a significant effect of properties. For polyethylene-based ionomers, where the presence of crystallinity has an appreciable effect on properties, the type of counterion present does not appear to have a significant effect on either modulus or tensile strength, as Fig. 4 indicates. However, in amorphous ionomers, the effects of changing the counterion from a monovalent one, as in Na or K, to a divalent one, such as Ca, may be appreciable. 

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... 

The theory of Leibler holds for mainly compatible systems. Leibler developed a mean field formalism to study the interfacial properties of two polymers, A and B with an A-B copolymer. An expression for interfacial tension reduction was developed by Noolandi and Hong [ 18] based on thermodynamics to explain the emulsifying effect of the A-b-B in immiscible A-B blends (A-A-b-B-B). [18,19]. The expression for interfacial tension reduction Ar) in a binary lend upon the addition of divalent copolymer is given by ... 

Sintered and sprayed ceramic anodes have been developed for cathodic protection applications. The ceramic anodes are composed of a group of materials classified as ferrites with iron oxide as the principal component. The electrochemical properties of divalent metal oxide ferrites in the composition range 0- lA/O-0-9Fe2O3 where M represents a divalent metal, e.g. Mg, Zn, Mn, Co or Ni, have been examined by Wakabayashi and Akoi" . They found that nickel ferrite exhibited the lowest consumption rate in 3% NaCl (of 1 56 g A y at 500 Am and that an increase in the NiO content to 40mol 7o, i.e. O NiO-O-bFejO, reduced the dissolution rate to 0-4gA y at the expense of an increase in the material resistivity from 0-02 to 0-3 ohm cm. 

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