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The evaporation characteristics of unsymmetrical dimethylhydrazine droplets with different initial diameters in a subcritical environment were experimentally investigated with the temperature–pressure separation technique. The evaporation processes of unsymmetrical dimethylhydrazine droplets with different initial diameters in this environment have the same general pattern. All the studied droplets exhibit a short transient heating phase and a steady-state evaporation phase obeying d2. Notably, the expansion of the transient heating phase gradually increases with increasing ambient pressure. The change in diameter squared ∆d2max increases from 1.03% at 1 MPa to 12.48% at 5 MPa. Under subcritical conditions, the evaporation rate decreases linearly with decreasing droplet diameter, and the droplet evaporation lifetime increases linearly. Changes in the initial droplet diameter may still have a large effect on droplets smaller than those studied here. When the ambient pressure is not greater than 3 MPa, the change in the steady-state evaporation time for both medium- and large-diameter droplets accounts for more than 70% of the variation in the droplet evaporation lifetime. As the ambient pressure increases to 4 MPa and 5 MPa, the percentage of the change in the transient heating time contributing to the variation in the droplet evaporation lifetime gradually increases to more than 45%.

Unsymmetrical dimethylhydrazine (UDMH) is a common liquid propellant widely used in rocket engines and other applications. The safety of UDMH in service is affected by its slow oxidation during long-term storage to form impurities such as dimethylamine (DMA) and formaldehyde dimethylhydrazone (FDH). How these impurities affect combustion performance is not known, and in order to assess these effects, the present experiments investigated the combustion characteristics of self-igniting fuels and carried out ignition delay time measurements and flame propagation velocity measurements of pure UDMH and its denatured mixtures in a nitrogen tetroxide (NTO) atmosphere. This experiment was carried out to measure the delay time of hedge ignition of pure UDMH and qualitative analysis of its flame propagation properties under vacuum conditions at room temperature (T = 293 K). Ignition delay time measurements and flame propagation characterization were performed under the same experimental conditions for UDMH mixed with 1%, 5% and 10% FDH, UDMH mixed with 1%, 5% and 10% H2O, UDMH mixed with 1%, 5% and 10% DMA, as well as for UDMH mixed with the same proportions of the three substances (1%, 5% and 10%). The flame propagation characteristics were analyzed. The results showed that the incorporation of DMA, H2O and FDH in different proportions could inhibit the combustion of UDMH to varying degrees and prolong its ignition delay time. It is worth noting that the introduction of FDH had the least effect on it, and the least effect was observed at a concentration of 1%. In contrast, the effect of DMA on UDMH is more obvious, and the addition of H2O has the largest increase in the ignition delay time of UDMH. In the flame propagation experiment, the flame of the experimental group adding H2O can no longer fill the whole experimental window, while the other experimental groups can still make the window full of flame. Combined with the measurements of the ignition delay time, it can be seen that the moisture content has the greatest effect on the combustion characteristics.

In this study, mesoporous TiO2 with various hydrolysis rates were prepared and combined with H2O2 for the photodegradation of unsymmetrical dimethylhydrazine (UDMH) under VUV irradiation. Results showed that the mesoporous TiO2 synthesized by the hydrolysis in water (MT100) exhibited a good mesoporous structure and the largest specific surface area (178.85 m2 g−1). Consequently, MT100 showed the best degradation efficiency, with the rate constant (k) for VUV/MT100 and VUV/MT100/H2O2 of 0.0185 and 0.2595 min−1, respectively, which was 1.4 and 4.0 times of that of P25. The addition of H2O2 significantly enhanced the degradation efficiency by photoactivation of H2O2 and the synergistic effect. The rate constant and the mineralization rate (after a 3-h treatment) increased by 13 and 3.8 times when 40 mM H2O2 was added into VUV/MT100. The weak alkaline condition (pH = 9) would facilitate the degradation of UDMH. The ⋅OH was the key oxidizing species in VUV/MT100/H2O2. Eight intermediates were detected during the degradation and the possible pathways of UDMH degradation in VUV/MT100/H2O2 process were proposed. VUV/MT100/H2O2 provides an efficient method to degrade UDMH.

A series of GO/g-C3N4 aerogel materials were prepared by the methods of ultrasonic peeling, solution cross-linking and freeze-drying, and the proportion of raw materials were optimized. The materials were characterized by SEM, XRD, and UV-vis absorption spectrum. The photocatalytic activity was evaluated by the degradation of unsymmetrical dimethylhydrazine (UDMH) wastewater. The pure g-C3N4 aerogel was dominated by mesoporous structure. As the graphene oxide (GO) ratio increases, the layered structure and macroporous structure of the material gradually increase, and all show strong adsorption performance. When the mass fraction of GO is 25%, the photocatalytic degradation of UDMH wastewater is the best and the performance is stable after 5 cycles, the photocatalytic activity is only reduced by 7.15%. Through the study on the energy band structure, characterization of photoelectric effect and PL spectrum, the results show that the g-C3N4 molecular orbital energy level and band gap (Eg) were impacted by the cross-linking between the π-π bond of GO layers and the aromatic ring of g-C3N4, which improve the response performance to visible light. The metallic properties of GO facilitate the rapid separation of photogenerated electron-hole pairs and improve the photocatalytic activity. According to the band gap calculation and the intrinsic molecular orbital of the material, the main active species for GOCN photocatalytic degradation of UDMH wastewater are ·O-2 and h+.

Unsymmetrical dimethylhydrazine (UDMH) is a widely used rocket propellant. Entering the environment or being stored in uncontrolled conditions, UDMH easily forms an enormous variety (at least many dozens) of transformation products. Environmental pollution by UDMH and its transformation products is a major problem in many countries and across the Arctic region. Unfortunately, previous works often use only electron ionization mass spectrometry with a library search, or they consider only the molecular formula to propose the structures of new products. This is quite an unreliable approach. It was demonstrated that a newly proposed artificial intelligence-based workflow allows for the proposal of structures of UDMH transformation products with a greater degree of certainty. The presented free and open-source software with a convenient graphical user interface facilitates the non-target analysis of industrial samples. It has bundled machine learning models for the prediction of retention indices and mass spectra. A critical analysis of whether a combination of several methods of chromatography and mass spectrometry allows us to elucidate the structure of an unknown UDMH transformation product was provided. It was demonstrated that the use of gas chromatographic retention indices for two stationary phases (polar and non-polar) allows for the rejection of false candidates in many cases when only one retention index is not enough. The structures of five previously unknown UDMH transformation products were proposed, and four previously proposed structures were refined.

The TiO2/g-C3N4 composites were prepared by the hydrothermal method with cetyltrimethyl ammonium bromide (CTAB). The influence of CTAB on the structural properties and spectral properties of the composites was studied. The samples were characterized by XRD, TEM, N2 adsorption-desorption, FT-IR, UV-Vis DRS and PL, meanwhile, the samples were used to degrade unsymmetrical dimethyl hydrazine (UDMH) wastewater under visible light. The results show that the crystal structure of TiO2/g-C3N4 composites assisted by CTAB is intact,with smaller particle size of nanoparticles and uniformly distributed on g-C3N4 sheets. The specific surface area of the composites increases and the mesoporous is more abundant, the adsorption ledge of the composites is expanded to 450nm, the recombination rate of hole-electron reduces obviously. Photocatalytic results show that the UDMH degradation efficiency of TiO2/g-C3N4 (CTAB) reaches 83.2% in 120min, which is improved by 13.7% than that of the no CTAB-assisted composites.

Lignin, a large scale by-product of papermaking and bioethanol production, is applied now in various fields. One of the main areas of use is in the development of different adsorbents, including those intended for detoxification of the spills of 1,1-dimethylhydrazine-based rocket fuel. The present work has shown the possibility of oxidative modification of hydrolytic lignin by hydrogen peroxide to improve the efficiency of the adsorbent. The change in functional composition of the modified adsorbent was studied by IR and NMR spectroscopy. It was shown that the oxidative treatment led to an increase in the content of carbonyl and carboxyl groups, which act as the active adsorption centres for hydrazine molecules. The optimum oxidation conditions were found. An increase in treatment duration from 15 to 120 min and in concentration of hydrogen peroxide from 6 to 30% did not have a significant effect on the functional composition and adsorption properties of lignin.

The majority of unsymmetrical dimethylhydrazine (UDMH) treatments produce lots of toxic by-products, among which N-Nitrosodimethylamine (NDMA) is a strong carcinogen. The compositions of the by-products are important for evaluating the treatment efficiency and understanding the UDMH degradation mechanism to achieve UDMH mineralization. The intermediate and end products of UDMH treatment with different oxidants were investigated by using a simple and fast method, solid-phase micro-extraction (SPME) in combination with gas chromatography–mass spectrometry (GC-MS). The effects of several parameters (coating fibre, salt addition, pH, sampling time and desorption time) were studied to optimize analyte recovery. The best response can be attained by the 65 µm PDMS/DVB fibre at pH 7 during 10 min after desorption of 1 min in the GC inlet. The intermediate and final oxidative products of UDMH wastewater treatment with different oxidants (O3, Mn2+/O3, Fe2+/H2O2) were investigated. The results showed that the UDMH treatment with O3 could lead to high yields of NDMA. Metal catalytic ozonation could largely minimize the formation of NDMA. No NDMA was observed in the final decontaminated samples after treatment with Fe2+/H2O2. The NDMA formation and degradation mechanism were discussed based on the intermediates. This study is expected to provide useful information for controlling NDMA formation during UDMH wastewater treatment.

We describe the syntheses and crystal structures of two molecular salts containing the 1,1-dimethylhydrazinium cation, namely 1,1-dimethylhydrazin-1-ium bromide, C2H9N2+·Br−, (I), and 2,2-dimethylhydrazin-1-ium dihydrogen phosphite, C2H9N2+·H2PO3−, (II). In (I), the cation is protonated at the methylated N atom and N—H...Br hydrogen bonds generate [010] chains in the crystal. In (II), the cation is protonated at the terminal N atom and cation-to-anion N—H...O and anion-to-anion O—H...O hydrogen bonds generate (001) sheets.