Effect of precompression on isothermal decomposition kinetics of pure and doped potassium bromate

Pure and doped samples of potassium bromate (KBrO₃) were subjected to precompression and their thermal decomposition kinetics was studied by thermogravimetry at 668 K. The samples decomposed in two stages governed by the same rate law (contracting square equation), but with different rate constants, k ₁ (for a α ≤ 0.45) and k ₂ (for α ≥ 0.45), as in the case of uncompressed samples. The rate constants k ₁ and k ₂ decreased dramatically on precompression, the decrease being higher for doped samples. Cation dopants (Ba²⁺, Al³⁺) caused more desensitization effect than the anion dopants ( \textSO₄ ^2- {\text{SO}}_{4}{}^{ 2- } , PO₄ ³⁻) of the same magnitude of charge and concentration. The results favor ionic diffusion mechanism proposed earlier on the basis of doping studies.     

Influence of the organic layer thickness in (Metal-Assisted) secondary ion mass spectrometry using Ga+ and C 60 + projectiles

This article investigates the influence of the organic film thickness on the characteristic and molecular ion yields of polystyrene (PS), in combination with two different substrates (Si, Au) or gold condensation (MetA-SIMS), and for atomic (Ga⁺) and polyatomic (C ₆₀ ⁺ ) projectile bombardment. PS oligomer (m/z ～ 2000 Da) layers were prepared with various thicknesses ranging from 1 up to 45 nm on both substrates. Pristine samples on Si were also metallized by evaporating gold with three different thicknesses (0.5, 2, and 6 nm). Secondary ion mass spectrometry was performed using 12 keV atomic Ga⁺ and C ₆₀ ⁺ projectiles. The results show that upon Ga⁺ bombardment, the yield of the fingerprint fragment C₇H ₇ ⁺ increases as the PS coverage increases and reaches its maximum for a thickness that corresponds to a complete monolayer (～3.5 nm). Beyond the maximum, the yields decrease strongly and become constant for layers thicker than 12 nm. In contrast, upon C ₆₀ ⁺ bombardment, the C₇H ₇ ⁺ yields increase up to the monolayer coverage and they remain constant for higher thicknesses. A strong yield enhancement is confirmed upon Ga⁺ analysis of gold-metallized layers but yields decrease continuously with the gold coverage for C ₆₀ ⁺ bombardment. Upon Ga⁺ bombardment, the maximum PS fingerprint ion yields are obtained using a monolayer spin-coated on gold, whereas for C ₆₀ ⁺ , the best results are obtained with at least one monolayer, irrespective of the substrate and without any other treatment. The different behaviors are tentatively explained by arguments involving the different energy deposition mechanisms of both projectiles.