Thermo-analytical and physico-chemical characterisation of organoclays and polymer-clay nacomposites.

A variety of modified clay minerals have been screened to determine their effectiveness as agents for the production of polystyrene-clay nanocomposites. The n-alkylammonium and n-alkyltrimethylammonium surfactants employed to compatibilise the aluminosilicate layers of the minerals were shown to degrade through a series of stages and mechanisms to yield a hydrocarbon product mixture consisting of a homologous series of saturated and unsaturated hydrocarbons, also, the dehydrocyclisation (DHC) of fragmented alkyl chains was shown to lead to the production of various ring compounds which included substituted cycloalkenes, benzene and toluene.The thermal stability of various cation exchanged modification treatments have been analysed. These organoclays have been characterised by XRD, TGA and TG-MS. The evolved gas analysis conducted by TG-MS was employed to identify which products were being thermally desorbed under thermal events previously seen when using TGA. In particular attention was paid to the activity of these materials with respect to the formation of linear, branched and cyclic aliphatics and aromatics from the feedstock surfactants.Intra-series comparisons of different organoclays showed that as the alkyl chain length of the n-alkylammonium surfactants was increased the concentration of thermal desorption products at approximately 400 °C was also increased. However, characterisation of n-alkyltrimethylammonium exchanged MMT showed that the concentration of thermal desorption products at lower temperatures (approximately 250 °C) increased with alkyl chain length between C[n] = 8 - 16. TG-MS analysis showed that this was mostly due to the DHC of alkyl fragments. These compounds appear to have been largely overlooked in related literature.SWa-1, a clay containing greater concentrations of structural iron, showed higher T[max] values for n-alkylammonium surfactant thermal desorption than similarly exchanged SAz-1. This may be evidence of a current theory that structural iron acts as a radical trap. This is thought to significantly reduce the catalytic activity of the clay's acid sites until higher temperatures. The formulation of polystyrene-clay nanocomposites (PSCNs) by in-situ polymerisation led to various results pertaining to their thermal stability. The relative effectiveness of various initiator species for the production of the most thermally stable PSCNs was AIBN > BPO > SPS > APS > AIBA. Lower radical initiator and organic modifier concentrations led to the production of PSCNs with higher thermal stability. The relative effectiveness of these various organoclays for the production of more thermally stable PSCNs was MCBP-Cn > C15A > C20A " C10A. The preparation method was shown to be effective for producing exfoliated nanocomposites for up to 1 wt% of the various organoclays using AIBN and BPO as initiators. The MCBP-Cn PSCNs remained exfoliated up to 5 wt% , they also showed higher thermal stability when compared with the commercial products, which XRD results showed to remain stacked at organoclay loadings > 1 wt%.A novel one-pot synthesis method for the production of PSCN, by the in-situ polymerisation of PS in the presence of decanamide (an uncharged surfactant) and Na-MMT, was shown to be successful. Whereas, other novel PSCN formulations incorporating N-vinylformamide and the amphoteric surfactant foamtaine SCAB were shown to be encouraging but have, so far, had limited success.In contrast, the analysis of industrially produced unsaturated polyester-clay nanocomposites showed very little increase in the thermal stability of the material. Associated analyses indicated increased dimensional stability of the material, AFM analysis showed that imaging of the clay dispersal was possible by this macroscopic technique. Also, ATR-FTIR analysis of the UPR and UPCN, showed that although not exfoliated the silane modified-MMT had a good synergistic effect on the overall material by reducing the formation of combustion products.The thermal stability and associated studies of kaolin-phenylphosphonic acid (KPPA) complexes was also conducted. PPA was shown to intercalate the kaolin crystal structure forming an expanded phase that exhibited remarkable thermal stability (Tmax = 660 °C). 31P MAS NMR of all the KPPA samples showed three peaks (at +1.2, -3.7 and -7.3 ppm) which represented PPA existing in three non-equivalent bonding states at the kaolin surface. The high thermal stability of these hybrid materials was evident from these studies. This research into the use of covalently bound intercalates in nanocomposite manufacture signifies the necessity for further research.