Nanocomposites polymer chains

Intercalated nanocomposites When the polymer chains intercalate into the clay gallery gaps but are unable to break down the layered structure, they are called intercalated nanocomposites (Figure 2.6a). 

Since the possibility of direct melt intercalation was first demonstrated [11], melt intercalation has become a method of preparation of the intercalated polymer/ layered silicate nanocomposites (PLSNCs). This process involves annealing, statically or under shear, a mixture of the polymer and organically modified layered fillers (OMLFs) above the softening point of the polymer. During annealing, the polymer chains diffused from the bulk polymer melt into the nano-galleries between the layered fillers. 

The rheological properties of insitu polymerized nanocomposites with end-tethered polymer chains were first described by Krisnamoorti and Giannelis [33]. The flow behavior of PCL- and Nylon 6-based nanocomposites differed extremely from that of the corresponding neat matrices, whereas the thermorheological properties of the nanocomposites were entirely determined by the behavior of the matrices [33]. The slope of G (co) and G"(co) versus flxco is much smaller than 2 and 1, respectively. Values of 2 and 1 are expected for linear mono-dispersed polymer melts, and the large deviation, especially in the presence of a very small amount of layered silicate loading, may be due to the formation of a network structure in the molten... 

Galgali and his colleagues [46] have also shown that the typical rheological response in nanocomposites arises from frictional interactions between the silicate layers and not from the immobilization of confined polymer chains between the silicate layers. They have also shown a dramatic decrease in the creep compliance for the PP-based nanocomposite with 9 wt% MMT. They showed a dramatic three orders of magnitude drop in the zero shear viscosity beyond the apparent yield stress, suggesting that the solid-like behavior in the quiescent state is a result of the percolated structure of the layered silicate. 

PDMS nanocomposites with layered mica-type silicates were also reported.374 A two-step sol-gel process of the in situ precipitation of silica led to the development of siloxane-based nanocomposites with particularly high transparencies.3 5 Some unusual nanocomposites prepared by threading polymer chains through zeolites, mesoporous silica, or silica nanotubes were reviewed.3 6 Poly(4-vinylpyridine) nanocross-linked by octa(propylglycidyl ether) polyhedral oligomeric silsesquioxane was reported.377... 

Beside planar surfaces, Patten et al. [310-312] and Hallensleben et al. [313, 314, 322] prepared weU-defined nanocomposites by ATRSIP of from silica and gold nanoparticles. After spin-coating a solution of the polymer decorated particles onto mica, Hallensleben was able to image the single particles with the individual grafted polymer chains (Pig. 9.33). 

In exfoliated nanocomposites, delaminated structures are obtained if a large number of polymer chains are present between the layers and the layers stand >10 nm apart. Thus, the interlayer expansion is comparable to the radius of gyration of the polymer rather than that of an extended chain, as in the case of intercalated hybrids [35]. 

In the case of 34NBR, the polymer chains have H-bonding interactions with the clay along with van der Waals interactions. These in turn improve the thermal stability of the nanocomposite. 

The dynamic mechanical thermal analyzer (DMTA) is an important tool for studying the structure-property relationships in polymer nanocomposites. DMTA essentially probes the relaxations in polymers, thereby providing a method to understand the mechanical behavior and the molecular structure of these materials under various conditions of stress and temperature. The dynamics of polymer chain relaxation or molecular mobility of polymer main chains and side chains is one of the factors that determine the viscoelastic properties of polymeric macromolecules. The temperature dependence of molecular mobility is characterized by different transitions in which a certain mode of chain motion occurs. A reduction of the tan 8 peak height, a shift of the peak position to higher temperatures, an extra hump or peak in the tan 8 curve above the glass transition temperature (Tg), and a relatively high value of the storage modulus often are reported in support of the dispersion process of the layered silicate. 

At the co-deposition of nanocomposite components formation of M/SC particles proceeds simultaneously with formation of a dielectric matrix, and the relationship between these processes determines the nanocomposite structure. This problem has been in detail investigated for the case of M/SC nanoparticles formation in polymer matrices. Synthesis of nanocomposite films by simultaneous PVD of polytetrafluoroethylene (PTFE) and Au has been carried out in works [62-64], Polymer and metal were sputtered under action of Ar ions and then the obtained vapors were deposited on substrates (quartz, glass, silica, mica, etc.) at various temperatures. Here, it is necessary to note that polymer sputtering cannot be considered as only physical process PFTE polymer chains destruct under action of high-energy ions, and formed chemically active low-molecular fragments are then deposited and polymerized on a substrate surface. 

The nature of the organomodifier plays a role in the existence of true nanocomposite structures (intercalated for 15A and 30B, exfoliated for 25A, microcomposite for 10A), cone calorimeter results associated with x-ray diffraction (XRD) suggest that increased flame retardancy are more dependent on physical and thermal cross-linking of clay particles and polymer chains than on formation of nanocomposite structure. However, it can be concluded that the role of clay is crucial since PHRR values are reduced up to 70% in the presence of clays. 

Rheology of various polymer layered-silicate nanocomposites - intercalated, exfoliated and end-tethered exfoliated (prepared by in-situ polymerization from reactive groups tethered to the silicate surface), have been performed in a conventional melt-state rheometer in both oscillatory and steady shear modes. These experimental studies have provided insight into the relaxation of polymer chains when confined by the layers of inorganic silicates, as well as the role of shear in orienting the layered nanocomposites. 

Fig. 20. Schematic diagram describing the end-tethered nanocomposites. The layered silicates are highly anisotropic with a thickness of lnm and lateral dimensions (length and width) ranging from -100 nm to a few microns. The polymer chains are tethered to the surface via ionic interactions between the silicate layer and the polymer-end. Adapted from Ref. [54].

Polymer silicate nanocomposites offer unique possibilities as model systems to study confined polymers or polymer brushes. The main advantages of these systems are (a) the structure and dynamics of nanoconfined polymer chains can be conveniently probed by conventional analytical techniques (such as scattering, DSC, NMR, dielectric spectroscopy, melt rheology) (b) a wide range of different polymers can be inserted in the interlayer or end-grafted to the silicate... 

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