A model Phillips catalyst for ethylene polymerization, prepared by spin coating a Cr(III)(Cr(acac)3) precursor on a silicon wafer, was submitted to an oxidative activation. Laser ablation Fourier transform mass spectrometry provided direct information on molecular species at the silicon wafer surface during activation. At 350 degrees C the chromium precursor was degraded, while chromium oxide species were formed. The chromium concentration decreased with temperature. The activated model catalyst was active for ethylene polymerization. Using complementary techniques (Fourier transform infrared spectroscopy, laser desorption/ionization mass spectrometry), the polymer was identified as crystalline polyethylene. After 1 h of polymerization at 160 degrees C, dome-like structures were observed by atomic force microscopy. Their morphologies were constituted of regions of parallel aligned lamellae of polymer.

The ions generated by laser ablation (LA) of calcium and gadolinium oxoborate GdCa4O(BO3)3 (GdCOB) were investigated by Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS), a powerful tool for the characterization of ionic species produced by laser interaction with solid material. In order to better understand the matter transfer and the mechanism of thin film growth by pulsed-laser deposition (PLD), cationic and anionic clusters generated by UV laser ablation of GdCOB bulk material were studied. Laser ablation of GdCOB leads to the formation of various cluster ions which result from association of CaO, BO and B2O3 building blocks (BB) with different charge carriers (CC): H+, BO+, GdO+ in positive ion mode, and BO2-, OK-, OH-, Cl-, WO3- in negative ion mode. LA-FTICRMS investigations allow us to assign a valence state to each metallic atom included in each BB. A +II chemical state may be associated with calcium and +II and +III ones to boron. UV laser ablation of GdCOB therefore induces reduction processes of boron species in the gas phase. The oxygen reactive atmosphere used during PLD experiments allows the growth of stoichiometric thin films by fixation of oxygen on the ablated species.