Anomalous thermal stability of atomic destruction fragments in polymer nanocomposites

Abstract

Thermal destruction of composites of ureaformaldehyde (UPR) and polyester resins (PER) with silicon dioxide nanoparticles having a specific surface area of 280 m2/g, titanium dioxide and titanosilicate with a specific surface area of 40 and 48 m2/g, respectively, when a filler content is no more than 5.0 wt% have been studied. The investigations were performed using The thermally programmed mass spectrometry method with registration of the masses of desorbed atomic fragments in the 10 ‒ 200 m/z range. It was established that during the main polymer mass destruction at 150 ‒ 350 oC, along with low temperature decomposition products, anomalously high thermal resistance of a number of atomic fragments of polymer chains and cross-links are recorded. The atomic composition of destruction fragments and their desorption temperature in the range 400 ‒ 700 oС were determined. It was established that in composites of ureaformaldehyde resin with SiO2 and TiO2 nanoparticles the high temperature resistance of fragments with m/z 27 exhibits due to the formation of strong bonds among the Si and Ti surface sites and the nitrogen atoms of the polymer. Such thermal stability is not realized in resin loading with (Si/Ti)O2 nanoparticles. In composites of polyester resin with silica a high-temperature destruction of oxygen atoms from polyester chains realizes at temperatures of 290 ‒ 400 oC and a low-intensity wide destruction band takes place in the temperature range 400 ‒ 700 oC. In addition, in the temperature range of 400-700 oC cross-links are destroyed with the release of benzene rings and styrene molecules. It was established that anomalously high-temperature desorption is typical for atomic fragments of the polymer structure attached to surface Si and Ti sites through nitrogen or carbon atoms from the polymer structure. Thus, in UPR composites with silicon and titanium oxides, strong chemical nitride bonds of the form Si-N≡C-H and Ti-N≡C-H are formed, which demonstrate anomalously high heat resistance. It is shown that in composites of polyester resin with silicon dioxide nanoparticles, the high-temperature destruction of fragments is due to their desorption from the surface of silicon dioxide particles when breaking their bonds with silicon atoms. Thus, polymer matrices have been determined, in which atomic fragments of the macromolecule, binding to the surface centers of fillers, significantly weaken the thermal destruction of composites due to the formation of strong chemical and coordination bonds.