Revisiting the initial reaction rates for TMS combustion and a new evidence for metastable silica nanoparticles in the gas-phase synthesis

Nanomaterials from gas-phase synthesis are tapping into new fields of application in research and industry due to their unique size-dependent properties. To produce tailored nanoparticles, the synthesis starting from the precursor decomposition to the particle formation must be fully understood. Tetramethylsilane is used as a precursor for the synthesis of silica nanomaterials in flames. The precursor starts to decompose by H-abstraction. Reaction rates for H-abstraction of tetramethylsilane (TMS) by +O/+H/+OH radicals are determined by means of quantum chemical calculations. The rate expressions are obtained in the temperature range from 300 to 1400 K: kH =  6,025,735 (T/K)2.1731exp(-(+2613.840 K)/T) cm3mol−1s−1 for the total bimolecular reaction coefficient of TMS with hydrogen atoms, kOH =  10,179,818 (T/K)1.7790 exp(-(+152.739 K)/T) cm3mol−1s−1 for TMS with OH radicals, and kO =  93,100 (T/K)2.4797 exp(-(+889.166 K)/T) cm3mol−1s−1 for TMS with O(3P) radicals, respectively. The reaction rates are implemented into the TMS reaction mechanism of Janbazi et al. [1], and a better agreement of the TMS reactivity in the flame is achieved. Experiments are conducted to obtain the mass deposition rates with a Quartz-Crystal-Microbalance (QCM) in a wide range of different equivalence ratios. The equivalence ratio is varied between ϕ = 0.6–1.2, and precursor amounts of 400, 600 and 800 ppm are used. These QCM-experiments are complementary to the MBMS-studies from Karakaya et al. [1–3] but use the same flame conditions to extend the data set. The results reveal that metastable particles exist in the reaction zone of the flame. Depending on flame conditions, their concentration decreases towards the end of the reaction zone, but particles subsequently grow again in the recombination zone of the flame. The mechanisms, which describe the reactivity of the metastable nanoparticles, are tentatively proposed. The understanding of the mechanisms can open up the way for tailored nanoparticles with different structures and stoichiometries

Kinetics of thermal decomposition of PMMA at different heating rates and in a wide temperature range

Using the methods of differential mass-spectrometric thermal analysis (DMSTA), thermogravimetric analysis (TGA), microscale combustion calorimetry (MCC), and fast pyrolysis (FP), thermal decomposition of high-molecular-weight polymethylmetacrylate (PMMA) has been investigated in the temperature range of 315÷500 °C. Based on these data, the kinetic parameters (the activation energy, the pre-exponential factor) were obtained of a one-step pyrolysis reaction in supposition of a first-order reaction using simple mathematical fitting and an iso-conversion method. Validity of the obtained kinetic parameters was verified by comparing the experimental data on dependence of the decomposition rate on temperature in the broad range of the heating rates with the results of simulating the above dependence, using these kinetic parameters. These parameters, obtained in the broad temperature range, may be further used in numerical simulation of PMMA combustion under fire conditions and for assessing the polymer’s flammability