Exfoliated clay

Clays are usually cation-exchangeable aluminosilicates, and exfoliated clay particles have a platelet shape with nanoscopic size. Cast protein-clay films on electrodes have been used to immobilize proteins. The Clay/Mb electrode has good electrocatalytic properties for the reduction of oxygen and hydrogen peroxide [236] and the biosensors can also be made based on these properties. 

The same group carried out ATRP of EA in bulk at 90°C in the presence of organically modified nanoclay as an additive. They found remarkable enhancement in the rate of polymerization as compared with the ATRP of EA without nanoclay. Interestingly, the resulting nanocomposites had exfoliated clay particles, as evident from WAXD and studies [80]. 

Figure 7 shows the representative bright field HRTEM images of nanocomposites of NR and unmodified montmorillonite (NR/NA) prepared by different processing and curing techniques. It is apparent that the methodology followed to prepare the nanocomposites by latex blending facilitates the formation of exfoliated clay structure, even with unmodified nanoclays. It has been reported in the literature that hydration of montmorillonite clay leads to extensive delamination and breakdown of silicate layers [94, 95]. It has also been shown that NA disperses fully into the individual layers in its dilute aqueous dispersion (clay concentration <10%)... 

Hbaieb et al. [260] recently suggested that Mori-Tanaka and 2D FEM models do not predict accurately the elastic modulus of real clay/PNCs. The Mori-Tanaka model underestimates the stiffness at higher volume fractions (>5%) and overestimates the stiffness of exfoliated clay/PNCs. 

A good state of dispersion of the organoclay has been found in the CR matrix. The exfoliated structure can be directly observed from the of the OMMT-filled CR composite (left-hand image in Fig. 30). It is noticed from this micrograph that all silicate layers are exfoliated and distributed very nicely throughout the whole rubber matrix. It is also observed that some of the exfoliated clay platelets form a house of cards structure (right-hand image in Fig. 30). 

It is a common phenomenon that the intercalated-exfoliated clay coexists in the bulk and in the interface of a blend. Previous studies of polymer blend-clay systems usually show that the clay resides either at the interface [81] or in the bulk [82]. The simultaneous existence of clay layers in the interface and bulk allows two functions to be attributed to the nanoclay particles one as a compatibilizer because the clays are being accumulated at the interface, and the other as a nanofiller that can reinforce the rubber polymer and subsequently improve the mechanical properties of the compound. The firm existence of the exfoliated clay layers and an interconnected chain-like structure at the interface of CR and EPDM (as evident from Fig. 42a, b) surely affects the interfacial energy between CR and EPDM, and these arrangements seem to enhance the compatibility between the two rubbers. 

In this type of system, the polymer chains are constrained by a surface. They can lie between two hard surfaces such as in the galleries within two parallel clay platelets (as is illustrated in Figure 7), have one layer absorbed on to a hard surface as a coating, with the other free (as in Figure 8), they can be absorbed by the surfaces of exfoliated clay platelets (Figure 9), or by the surface of a solid reinforcing particle completely surrounded by an elastomeric phase (Figure 10). 

Figure 16.24 shows the schematic representation of dispersed clay particles in a polymer matrix. Conventionally dispersed clay has aggregated layers in face-to-face form. Intercalated clay composites have one or more layers of polymer inserted into the clay host gallery. Exfoliated polymer/clay nanocomposites have low clay content (lower than intercalated clay composites which have clay content -50%). It was found that 1 wt% exfoliated clay such as hectorite, montmorillonite, or fluorohectorite increases the tensile modulus of epoxy resin by 50-65%. ... 

Generally, polymer nanocomposites can be obtained through two routes the first one is the polymerization of monomers in contact with the exfoliated clay and the second one uses existing transformation processes to produce nanocomposites, for example, by a reactive extrusion. There are, however, problems present due to the lack of affinity of the clay-polymer system because of the hydrophilic character of the particles. It is then necessary to treat the clay chemically to increase its affinity with the polymer matrix. This constitutes another whole area of research in the nanocomposites production. 

The HCP model implies that in diluted systems ( < 0.005, where exfoliated clay platelets may freely rotate), individual HCPs are dispersed in a polymeric matrix and values of the interaction parameters are constant. As the concentration increases, the domains of reduced mobility around HCPs begin to overlap, macromolecules with bulk properties disappear, and the interactions change with clay content. Above the encompassed clay platelet volume fraction, rot = Q.99 p 0.005, there is a second critical concentration, Wmax 3.6 wt% or (/>max 0.015, at which the clay platelets with adsorbed solidified organic phase begin to overlap. Due to platelet crowding, CPNC approaching this concentration forms stacks thus, the assumption that individual exfoliated platelets are present is no longer valid. 

Since nanoparticles in PNC are orders of magnitude smaller than conventional reinforcements, the models developed for composites are not applicable to nanocomposites. However, development of a universal model for PNC is challenging since the shape, size, and dispersion of the nanoparticles vary widely from one system to another. On the one hand, exfoliated clay provides vast surface areas of solid particles (ca. 800 m /g) with a large aspect ratio that adsorb and solidify a substantial amount of the matrix polymer, but on the other hand, the mesoscale intercalated clay stacks have a much smaller specific surface area and small aspect ratio. However, in both these cases the particle-particle and particle-matrix interactions are much more important than in conventional composites, affecting the rheological and mechanical behavior. Thus, the PNC models must include the thermodynamic interactions, often neglected for standard composites. 

Plasticizers used for TPS can also exfoliate clay during processing. Maksimov et al. [239] investigated an unmodified-montmorillonite (MMT)-filled... 

Mixtures of clay platelets and polymer chains compose a colloidal system. Thus in the melt state, the propensity for the clay to be stably dispersed at the level of individual disks (an exfoliated clay dispersion) is dictated by clay, polymer, stabilizer, and compatibilizer potential interactions and the entropic effects of orientational disorder and confinement. An isometric dimension of clay platelets also has implications for stability because liquid crystalline phases may form. In addition, the very high melt viscosity of polypropylene and the colloidal size of clay imply slow particulate dynamics, thus equilibrium structures may be attained only very gradually. Agglomerated and networked clay structures may also lead to nonequilibrium behavior such as trapped states, aging, and glassy dynamics. 

Fang et al [89] have also used Pickering emulsion polymerization (Figure 14.12a) fabricate clay-coated PANI particles by employing exfoliated clay sheets as a stabilizer. PANI particles with a fairly broad size distribution indicate a quite rough surface, which is composed of exfoliated clay sheets (Figure 14.12b). The PANI/clay nanocomposite particles have been employed as an ER material and exhibit similar ER behavior (Eigure 14.12c) to other typical ER systems. 

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