On the mechanisms of heterogeneous recombination of nitrogen and oxygen atoms

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Abstract

The problem of heterogeneous recombination of nitrogen and oxygen atoms is considered. An analysis of the processes influencing the results of measurements of the recombination probability was carried out. The work presents the authors’ data on heterogeneous recombination of atoms in the temperature range of 300–3000 K and pressures of 0.01–50 hPa (mbar). The probabilities of heterogeneous recombination of O and N atoms on the surface of quartz were measured using the method of resonance fluorescence spectroscopy (RFS) under strictly controlled conditions at temperatures of 300–1000 K and pressures of 0.01–10 hPa in IBHF reactors. The pressure and temperature regions where recombination occurs predominantly according to the Langmuir-Hinshelwood or Rydil-Ely scheme have been determined. In experiments at the VAT-104 TsAGI installation in the temperature range of 1000–3000 K and pressures of 5–50 hPa, the effective values of the rate constant of joint heterogeneous recombination Kw of nitrogen and oxygen atoms were determined using measurements of specific heat flows. Coatings with a surface layer similar in composition to quartz and a number of high-temperature ceramics based on hafnium (zirconium) borides were studied. Studies of ceramics have shown that heterogeneous recombination also occurs at temperatures of 2500–3000 K. A new mechanism of heterogeneous recombination of nitrogen and oxygen atoms is considered. Under the influence of a high-speed plasma flow, the ceramics are oxidized and a layer of hafnium (zirconium) oxide polycrystals is formed. The observed jump in temperature by ≈1000 K and heat flux up to 4–5 times is caused by the catalytic activity of the tetragonal and cubic phases of HfO2 (ZrO2) polycrystals. The high catalytic activity of the oxide layer is apparently explained by a new recombination mechanism associated with the incorporation of nitrogen and oxygen atoms into the crystal lattice (formation of a solid solution).

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About the authors

S. N. Kozlov

Emanuel Institute of Biochemical Physics, Rus. Ac. Sci.

Author for correspondence.
Email: kozlovse@yandex.ru
Russian Federation, Moscow

B. E. Zhestkov

Central Aerohydrodynamic Institute; Moscow Aviation Institute (National Research University)

Email: kozlovse@yandex.ru
Russian Federation, Zhukovsky; Moscow

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Supplementary files

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2. Fig. 1. a ‒ Setup for measuring the probability of heterogeneous recombination of atoms: 1 - quartz reactor with heated walls for temperatures of 300-700 K; 2 - furnace; 3 - source of resonant radiation; 4-5 - receivers of resonant radiation; 6 - microwave resonator providing gas dissociation in the quartz branch 7, 8 - pressure sensor; 9 - electronic signal processing system; 10 - computer. b ‒ another version of the setup 1 - quartz reactor with cooled walls; 2 - quartz "shirt"; 3 - sample under study; 4 - heater; 5 - microwave generator resonator; 6 - source of resonant radiation; 7 - receivers of resonant radiation; 8 - pressure sensor; 9 - electronic signal processing unit; 10 - registration system computer; 11 ‒ quartz branch of the reactor for freezing the reaction products. Point A in both figures indicates the location of registration of the atoms being studied.

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3. Fig. 2. Diagram of the VAT-104 wind tunnel: 1 - working gas flow meter, 2 - working gas flow regulator system, 3 - high-frequency induction gas heater, 4 - high-frequency generator, 5 - wind tunnel nozzle, 6 - mirror for measuring the temperature distribution of the front surface of the test sample, 7, 8 - coordinate mechanisms, 9 - optical windows, 10 - pyrometer, 11 - video camera for recording the flow mode around the model, 12 - thermal imager, 13 - heat exchanger, 14 - pressure sensor connection points, 15 - vacuum system, 16 ‒ working chamber.

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4. Fig. 3. Dependence of the probability of recombination of γ oxygen atoms on pressure at temperatures of 417–650 K in a mixture with the initial composition of 10% O2 + 90% He.

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5. Fig. 4. Dependence of the probability of recombination of γ nitrogen atoms on pressure at temperatures of 300–658 K in a mixture with an initial composition of 20% N2 + 80% He.

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6. Fig. 5. Photo of testing a ceramic sample in the VAT-104 ADT.

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7. Fig. 6. Temperature increase of the sample during heating, oxidation and formation of a highly catalytic oxide layer.

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8. Fig. 7. Dependence of the temperature of the ceramic sample on the pressure in the heater.

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9. Fig. 8. Dependence of the brightness temperature of the sample on the pressure in the heater during air plasma flow.

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10. Fig. 9. Dependence of the brightness temperature of the sample on the pressure in the heater during flowing nitrogen plasma.

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