Expansion intercalation

Moleculady mixed composites of montmorillonite clay and polyimide which have a higher resistance to gas permeation and a lower coefficient of thermal expansion than ordinary polyimides have been produced (60). These polyimide hybrids were synthesized using montmorillonite intercalated with the ammonium salt of dodecylamine. When polymerized in the presence of dimethyl acetamide and polyamic acid, the resulting dispersion was cast onto glass plates and cured. The cured films were as transparent as polyimide. 

Using dilatometry in parallel with cyclic voltammetry (CV) measurements in lmolL 1 LiC104 EC-l,2-dimethoxy-ethane (DME), Besenhard et al. [87] found that over the voltage range of about 0.8-0.3 V (vs. Li/Li+), the HOPG crystal expands by up to 150 percent. Some of this expansion seems to be reversible, as up to 50 percent contraction due to partial deintercalation of solvated lithium cations was observed on the return step of the CV. It was concluded [87] that film formation occurs via chemical reduction of a solvated graphite intercalation compound (GIC) and that the permselective film (SEI) in fact penetrates into the bulk of the HOPG. It is important to repeat the tests conducted by Besenhard et al. [87] in other EC-based electrolytes in order to determine the severity of this phenomenon. 

A complementary approach has been reported very recently [43]. hi this case negative charges were introduced into the salen ligand Iq (Fig. 14) with the aim of exchanging it on cationic supports, such as a layered double (Zn, Al) hydroxide. The expansion in the basal spacing indicated intercalation, at least partially, of the Ig-Mn complex between the layers of [Zn2,i5Alo,86(OH)6,o2]- The complex was used in the epoxidation of (i )-limonene with molecular oxygen and pivalaldehyde. The use of N-... 

PP-g-MA) silicate nanocomposites and intercalated thermoset silicate nanocomposites for flame-retardant applications were characterised by XRD and TEM [333], XRD, TEM and FTIR were also used in the study of ID CdS nanoparticle-poly(vinyl acetate) nanorod composites prepared by hydrothermal polymerisation and simultaneous sulfidation [334], The CdS nanoparticles were well dispersed in the polymer nanorods. The intercalation of polyaniline (PANI)-DDBSA (dodecylbenzene-sulfonate) into the galleries of organo-montmorillonite (MMT) was confirmed by XRD, and significantly large 4-spacing expansions (13.3-29.6A) were observed for the nanocomposites [335],... 

The catalytic application of clays is related closely to their swelling properties. Appropriate swelling enables the reactant to enter the interlamellar region. The ion exchange is usually performed in aquatic media because the swelling of clays in organic solvents, and thus the expansion of the interlayer space, is limited and it makes it difficult for a bulky metal complex to penetrate between the layers. Nonaqueous intercalation of montmorillonite with a water-sensitive multinuclear manganese complex was achieved, however, with the use of nitromethane as solvent.139 The complex cation is intercalated parallel to the sheets. 

Starting natural graphite from Zavalie deposit in, Ukraine was chemically intercalated in sulfuric acid. Potassium persulphate was used as an oxidizer. Thermal expansion of graphite was performed at 900°C [3], Carbon content in the experimental samples was of about 99.0%. 

This explains why the well-defined diffraction peaks up to the (004) plane are observed (see Figure 9.2). The entropic contribution of the intercalants, which leads to the entropy gain associated with the layer expansion after intercalation of the polymer chains, may not be significant because of the interdigitated layer structure. 

Now it is necessary to understand the meaning of the interlayer expansion in the intercalated nanocomposites. As discussed before, we have to take the interdigitated layer structure into consideration. This structure may suggest that a different... 

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