Revealing Al-O/Al-F reaction dynamic effects on the combustion of aluminum nanoparticles in oxygen/fluorine containing environments:A reactive molecular dynamics study meshing together experimental validation

Improving the energy conversion efficiency in metallic fuel(e.g.,Al)combustion is always desirable but challenging,which often involves redox reactions of aluminum(Al)with various mixed oxidizing environments.For instance,Al-O reaction is the most common pathway to release limited energy while Al-F reaction has received much attentions to enhance Al combustion efficiency.However,microscopic understanding of the Al-O/Al-F reaction dynamics remains unsolved,which is fundamentally necessary to further improve Al combustion efficiency.In this work,for the first time,Al-O/Al-F reaction dynamic effects on the combustion of aluminum nanoparticles(n-Al)in oxygen/fluorine containing environments have been revealed via reactive molecular dynamics(RMD)simulations meshing together combustion experiments.Three RMD simulation systems of Al core/O_(2)/HF,n-Al/O_(2)/HF,and n-Al/O_(2)/CF4 with oxygen percentage ranging from 0%to 100%have been performed.The n-Al combustion in mixed O_(2)/CF_4 environments have been conducted by constant volume combustion experiments.RMD results show that Al-O reaction exhibits kinetic benefits while Al-F reaction owns thermodynamic benefits for n-Al combustion.In n-Al/O_(2)/HF,Al-O reaction gives faster energy release rate than Al-F reaction(1.1 times).The optimal energy release efficiency can be achieved with suitable oxygen percentage of 10%and 50%for n-Al/O_(2)/HF and n-Al/O_(2)/CF_4,respectively.In combustion experiments,90%of oxygen percentage can optimally enhance the peak pressure,pressurization rate and combustion heat.Importantly,Al-O reaction prefers to occur on the surface regions while Al-F reaction prefers to proceed in the interior regions of n-Al,confirming the kinetic/thermodynamic benefits of Al-O/Al-F reactions.The synergistic effect of Al-O/Al-F reaction for greatly enhancing n-Al combustion efficiency is demonstrated at atomicscale,which is beneficial for optimizing the combustion performance of metallic fuel.

Fabrication and characterization of multi-scale coated boron powders with improved combustion performance:A brief review

Boron has high mass and volume calorific values,but it is difficult to ignite and has low combustion efficiency.This literature review summarizes the strategies that are used to solve the above-mentioned problems,which include coatings of boron by using fluoride compounds,energetic composites,metal fuels,and metal oxides.Coating techniques include recrystallization,dual-solvent,phase transfer,electrospinning,etc.As one of the effective coating agents,the fluorine compounds can react with the oxide shell of boron powder.In comparison,the energetic composites can effectively improve the flame temperature of boron powder and enhance the evaporation efficiency of oxide film as a condensed product.Metals and metal oxides would react with boron powder to form metal borides with a lower ignition point,which could reduce its ignition temperature.

Bimetallic CoNi single atoms supported on three-dimensionally ordered mesoporous chromia:highly active catalysts for n-hexane combustion

Developing the alternative supported noble metal catalysts with low cost,high catalytic efficiency,and good resistance toward carbon dioxide and water vapor is critically demanded for the oxidative removal of volatile organic compounds(VOCs).In this work,we prepared the mesoporous chromia-supported bimetallic Co and Ni single-atom(Co_(1)Ni_(1)/meso-Cr_(2)O_(3))and bimetallic Co and Ni nanoparticle(Co_(NP)Ni_(NP)/mesoCr_(2)O_(3))catalysts adopting the one-pot polyvinyl pyrrolidone(PVP)-and polyvinyl alcohol(PVA)-protecting approaches,respectively.The results indicate that the Co_(1)Ni_(1)/meso-Cr_(2)O_(3)catalyst exhibited the best catalytic activity for n-hexane(C_(6)H_(14))combustion(T_(50%)and T_(90%)were 239 and 263℃ at a space velocity of 40,000 mL g^(-1)h^(-1);apparent activation energy and specific reaction rate at 260℃ were 54.7 kJ mol^(-1)and 4.3×10^(-7)mol g^(-1)_(cat)s^(-1),respectively),which was associated with its higher(Cr^(5+)+Cr^(6+))amount,large n-hexane adsorption capacity,and good lattice oxygen mobility that could enhance the deep oxidation of n-hexane,in which Ni_(1) was beneficial for the enhancements in surface lattice oxygen mobility and low-temperature reducibility,while Co_(1) preferred to generate higher contents of the high-valence states of chromium and surface oxygen species as well as adsorption and activation of n-hexane.n-Hexane combustion takes place via the Mars van Krevelen(MvK)mechanism,and its reaction pathways are as follows:n-hexane→olefins or 3-hexyl hydroperoxide→3-hexanone,2-hexanone or 2,5-dimethyltetrahydrofuran→2-methyloxirane or 2-ethyl-oxetane→acrylic acid→CO_x→CO_(2)and H_(2)O.

Combustion crack-network reaction evolution model for highly-confined explosives

The evolution behavior of combustion crack reaction of highly confined solid explosives after non-shock ignition is governed by multiple dynamic processes,including intrinsic combustion of explosives,crack propagation,and rapid growth of combustion surface area.Here,the pressure increase can accelerate the combustion rate of explosives,and the crack propagation can enlarge the combustion surface area.The coupling between these two effects leads to the self-enhanced combustion of explosive charge system,which is the key mechanism for the reaction development after ignition.In this study,combustion cracknetwork(CCN) model is established to describe the evolution of combustion crack reaction of highly confined solid explosives after non-shock ignition and quantify the reaction violence.The feasibility of the model is verified by comparing the computational and experimental results.The results reveal that an increase in charge structure size causes an increase in the time of crack pressurization and extension of cracks due to the high temperature-generated gas flow and surface combustion during the initial stage of explosive reaction,but when the casing is fractured,the larger the charge structure,the more violent the late reaction and the larger the charge reaction degree.The input pressure has no obvious influence on the final reaction violence.Further,a larger venting hole area leads to better pressure relief effect,which causes slower pressure growth inside casing.Larger reserved ullage volume causes longer lowpressure induction stage,which further restrains the internal pressure growth.Furthermore,the stronger the casing constraint,the more rapid the self-enhanced combustion of the high temperaturegenerated gas,which results in more violent charge reaction and larger charge reaction degree during casing break.Overall,the proposed model can clarify the effects of intrinsic combustion rate of explosives,charge structure size,input pressure,relief area,ullage volume,and constraint strength on the reaction evolution,which can provide theoretical basis for violence evaluation and safety design for ammunition under accident stimulus.

Characterizations and Photocatalytic Activities of Nanocrystalline MTiO_3 (M=Sr, Pb, Co) Prepared via a General Self-propagating Combustion Method

Nanocrystalline MTiO3 （M = St, Pb, Co） were prepared by a general self-pro- pagating combustion method. The samples were characterized by X-ray diffraction （XRD） analysis, scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, N2 adsorption and UV-vis diffuse reflectance spectra （DRS）. The photocatalytic activity of MTiO3 （M = Sr, Pb, Co） was evaluated by the photocatalytic degradation of methyl orange （MO）. MTiO3 （M = Sr, Pb, Co） having the same core element showed distinctly different photocatalytic activity due to the different coordinating atoms. Factors affecting the photocatalytic activity of MTiO3 （M = Sr, Pb, Co） were discussed. It was suggested that the structures of TiO6 octahedra and the electronic property were the predominant factors of the photocatalytic behavior for MTiO3 （M = Sr, Pb, Co）.

Comparative investigations of ternary thermite Al/Fe_(2)O_(3)/CuO and Al/Fe_(2)O_(3)/Bi_(2)O_(3) from pyrolytic,kinetics and combustion behaviors

To develop new energy enhancement energetic materials with great combustion performance and thermal stability,two kinds of ternary thermite,Al/Fe_(2)O_(3)/CuO and Al/Fe_(2)O_(3)/Bi_(2)O_(3),were prepared and analyzed via mechanical ball milling.The samples were characterized by SEM,XRD,TG-DSC,constant volume and constant pressure combustion experiments.The first exothermic peaks of Al/Fe_(2)O_(3)/CuO and Al/Fe_(2)O_(3)/Bi_(2)O_(3) appear at 579°C and 564.5°C,respectively.The corresponding activation energies are similar.The corresponding mechanism functions are set as G(a) = [-ln(1-a)]^(3/4) and G(a) =[-ln(1-a)]2/3,respectively,which belong to the Avrami-Erofeev equation.Al/Fe_(2)O_(3)/CuO has better thermal safety.For small dose samples,its critical temperature of thermal explosion is 121.05°C higher than that of Al/Fe_(2)O_(3)/Bi_(2)O_(3).During combustion,the flame of Al/Fe_(2)O_(3)/CuO is spherical,and the main products are FeAl_(2)O_(4) and Cu.The flame of Al/Fe_(2)O_(3)/Bi_(2)O_(3)is jet-like,and the main products are Al_(2)O_(3),Bi and Fe.Al/Fe_(2)O_(3)/Bi_(2)O_(3)has better ignition and gas production performance.Its average ignition energy is 4.2 J lower than that of Al/Fe_(2)O_(3)/CuO.Its average step-up rate is 28.29 MPa/s,which is much higher than 6.84 MPa/s of Al/Fe_(2)O_(3)/CuO.This paper provides a reference for studying the thermal safety and combustion performance of ternary thermite.

Tungsten combustion in impact initiated W-Al composite based on W(Al) super-saturated solid solution

Element W can effectively improve the density of energetic structural materials. However, W is an inert element and does not combust in air. To change the reaction characteristics of W, 60 at.% Al was introduced into W through mechanical alloying. XRD analysis shows that after 50 h of ball milling, the diffraction peak of Al completely disappears and W(Al60) super-saturated solid solution powder is obtained. Further observation by HAADF and HRTEM reveals that the W(Al60) super-saturated solid solution powder is a mixture of solid solution and amorphous phase. Based on the good thermal stability of W(Al60) alloy powder below 1000℃, W(Al60)-Al composite was synthesized by hot pressing process.Impact initiation experiments suggest that the W(Al60)-Al composite has excellent reaction characteristics, and multiple types of tungsten oxides are detected in the reaction products, showing that the modified W is combustible in air. Due to the combustion of tungsten, the energy release rate of the W(Al60)-Al composite at speed of 1362 m/s reaches 2.71 kJ/g.

Combustion characteristics of unburned pulverized coal and its reaction kinetics with CO2

The combustion characteristics of two kinds of unburned pulverized coal (UPC) made from bituminous coal and anthracite were investigated by thermogravimetric analysis under air. The reaction kinetics mechanisms between UPC and CO2 in an isothermal experiment in the temperature range 1000–1100°C were investigated. The combustion performance of unburned pulverized coal made from bituminous coal (BUPC) was better than that of unburned pulverized coal made from anthracite (AUPC). The combustion characteristic indexes (S) of BUPC and AUPC are 0.47 × 10^-6 and 0.34 × 10^-6 %2·min^-2·°C^-3, respectively, and the combustion reaction apparent activation energies are 91.94 and 102.63 kJ·mol^-1, respectively. The reaction mechanism of BUPC with CO2 is random nucleation and growth, and the apparent activation energy is 96.24 kJ·mol^-1. By contrast, the reaction mechanism of AUPC with CO2 follows the shrinkage spherical function model and the apparent activation energy is 133.55 kJ·mol^-1.

Combustion behavior and mechanism of molecular perovskite energetic material DAP-4-based composites with metal fuel Al

Combined with the oxidizer anions and fuel cations,molecular perovskite energetic materials show a good potential.In this work,the combustion behavior and mechanism of metal fuel aluminium(Al)with molecular perovskite energetic material(H_(2)dabco)[NH4(ClO_(4))_(3)](DAP-4)as a high-energy oxidant was investigated.The DAP-4 based composites with metal fuel Al were designed and fabricated by the different mass ratios.Results showed that DAP-4 exhibits a good oxygen-supplied capacity for enhancing the combustion performance of Al.The maximum combustion heat of DAP-4/Al-3 at the Al/O mass ratio of 38:62 is up to 10,412 J/g in the inert gas,which is higher than those of other ratios and the mixtures of other energetic materials and Al.The evolution of pressure output,pressurization rate,and flame temperature was monitored for DAP-4/Al with different mass ratios.Composites DAP-4/Al/F were characterized by burning rates.The combustion reaction mechanism of metal fuel Al with DAP-4 as a high-energy oxidant was provided.DAP-4 was ignited firstly and released acid and oxidizing gases,which corroded Al_(2)O_(3)shells on Al particle surfaces and accelerated the combustion reaction with Al to release a lot of energy.This work offered a new idea that molecular perovskite energetic materials have great potential in the high-energy Al-based solid rocket propellants.

Reaction dynamics in the combustion synthesis system of Al-CrO_3-Al_2O_3-NaF-N_2-O_2

A new material with heat-resistant and adiabatic characteristics and high strength was prepared using the combustion synthesis method by mixed powders of CrO3, Al, Al2O3, and NaF in atmospheric gas. The reaction dynamic process of the Al-CrO3-NaF-Al2O3-N2-O2 new material system by the combustion synthesis method was discussed based on the observation results by SEM, EDS, and XRD in combination with the combustion front quenching method （CFQM） and the relation curves between reaction free enthalpies and the corresponding temperatures. The combustion synthesis mechanism and the formation reasons of the phase in the combustion product were analyzed.

Effect of carbon dioxide on oxy-fuel combustion of hydrogen sulfide:An experimental and kinetic modeling

CO_(2) is an important component in the acid gas and it is necessary to study the effect of CO_(2) presence on the oxy-fuel combustion of H_(2)S with particular focus on the formation of carbonyl sulfide(COS).The oxyfuel combustion of acid gas was conducted in a coaxial jet double channel burner.The distribution of flame temperature and products under stoichiometric condition along axial(R=0.0)and radial at about 3.0 mm(R=0.75)were analyzed,respectively.The Chemkin-Pro software was used to analyze the rate of production(ROP)for gas products and the reaction pathway of acid gas combustion.Both experimental and simulation results showed that acid gas combustion experienced the H2S chemical decomposition,H_(2)S oxidation and accompanied by H_(2) oxidation.The CO_(2) presence reduced the peak flame temperature and triggered the formation of COS in the flame area.COS formation at R=0.0 was mainly through the reaction of CO_(2) and CO with sulfur species,whereas at R=0.75 it was through the reaction of CO with sulfur species.The ROP results indicated that H_(2) was mainly from H_(2)O decomposition in the H_(2)S oxidation stage,and COS was formed by the reaction of CO_(2) with H_(2)S.ROP and other detailed analysis further revealed the role of H,OH and SH radicals in each stage of H_(2)S conversion.This study revealed the COS formation mechanisms with CO_(2) presence in the oxy-fuel combustion of H_(2)S and could offer important insights for pollutant control.

Reaction mechanism of self-propagating magnesiothermic reduction of ZrB_2 powders

Fine zirconium diboride （ZrB2） powders with high purity were successfully prepared by combustion synthesis through magnesiothermic reduction process in Mg-B2O3-ZrO2 system. The reaction mechanism was investigated by differential thermal analysis and quenching experiment. The results show that the whole magnesio-thermic reduction process includes three stages： first, molten B2O3 and Mg formed above the temperature of 650 ℃, and glassy B2O3 and solid ZrO2 particles were coated on the surface of the molten Mg; thus, the hollow balls can be formed when the molten Mg was exuded under capillary function. Second, ZrO2 particles reacted with molten Mg to form Zr and MgO with dissolution-precip-itation mechanism, which released a large amount of heat to induce the diffusion reaction between B203 and Mg to form B and MgO. Last, Zr reacted with B to form ZrB2 grains. The preparation of ZrB2 by self-propagating syn-thesis in Mg-B2O3-ZrO2 system is a solid-liquid-liquid reaction.

Application of Reaction-Bonded Silicon Carbide in Manufacturing of Spacecraft Combustion Chamber

Silicon carbide (SiC) ceramics is a good structural ceramics material, which have a lot of excellent properties such as superior high-temperature strength up to a temperature of 1 350 ℃, chemical stability, good resistance to thermal shock and high abrasion resistance. The silicon carbide ceramics material has so far been used widely for manufacturing various components such as heat exchangers, rolls, rockets combustion chamber. Sintering of ceramics structural parts have many technological method, the reaction-bonded is one of important sintering technology of ceramics structural parts. The preparation of reaction-bonded silicon carbide (RBSC) is based on a reaction sintering process, whereby a compacted body of α-SiC and carbon (graphite) powders is heated in contact with liquid silicon or gas silicon, which impregnates the body, converting the carbon (graphite) to β-SiC which bonds the original alpha grain. This process is characterized by low temperature and a short time sintering, and being appropriate to the preparation of large size and complex-shaped components, and so on. Besides, during compacting process of reaction sintering, it can maintain a stable dimension of ceramics parts. Therefore, the method of reaction-bonded silicon carbide ceramics has been identified as a technology suitable for producing complicated and highly exact dimensions’ ceramics parts. In this paper, the method of reaction-bonded silicon carbide was applied to the manufacturing of a complex-shaped spacecraft combustion chamber of SiC ceramics. SiC and carbon powder of 4～30 μm were chosen as the raw materials, green compacts containing appropriate wt.% carbon were formed using the mold press method, sintering was performed in a graphite electric furnace under an argon atmosphere. It was introduced in detail that the technological parameters and technological flow of reaction sintering silicon carbide ceramics. At the same time, physical and mechanical experiments such as bending strength, coefficient of thermal expansion, coefficient of thermal conductivity, gastight property, heat resisting property etc. have been carried out. The results demonstrated that spacecraft combustion chamber made from reaction sintering of silicon carbide ceramics is feasible and the results of experiment is satisfactory. The strength of high-temperature structural parts made by reaction sintered SiC varied with silicon content; Under the this article testing condition, the optimum silicon content is 10.5% for the part investigated. The method of reaction sintered SiC ceramics is suitable for manufacturing of complicated spacecraft parts with a working temperature of 1 500 ℃.

Welding TiB_2 Ceramies and Metai Mo with Combustion Reaction Technology

Combustion reaction welding, one promising method to weld ceramies and metals, was used to weld TiB2 and Mo. The results showed that the reacted products through combustion reaction were TiB2 and MoB when the Mo contents in reactants were 20 wt pct and 40 wt pct while there was Mo besides MoB and TiB2 when there were 60 wt pct and 80 wt pct Mo in reactants. Diffusion of elements occurred at the interfaces of the two substrates. The interfaces between the reacted and the two substrates were indistinct after being welded. The welding temperature strongly affected properties of the samples. The value of bending strength of the sample with 80 wt pct Mo in reactant welded at 1500℃ was the highest, 368.52 MPa. The highest value of shear strength among all the samples was that of the one with 40 wt pct Mo in reactant vvelded at 1500℃, 50.97 MPa.

Bifurcation characteristics of coal spontaneous combustion and analysis of critical state of gaseous reaction in a packed bed

The numerical model was presented for the coal combustion in the packed bed. The bifurcation characteristic of the ignition-extinction of solid-phase smoldering and tran- sition to flaming was studied for the packed bed of coal.One of the Frank-Kamenetskii parameter β_1 was selected as the control parameter.The computed results show that the bifurcation curve is obviously divided into two zones of solid-phase reaction and gas- phase reaction,and the total process of ignition-extinction presents twice bifurcation cha- racteristic.Moreover,the vanishing of critical state of ignition-extinction is studied.One of the transition points,ε_2=0.05,is numerically solved for the vanishing of critical state.The larger the value of ε_2 is,the easier the gas-phase can react.However,the combustion temperature will decrease with increasing ε_2.The other transition point α_2=0.53 is also ob- tained.With increasing the value of α_2,the combustion temperature of gas-phase reaction is close to the smoldering temperature of coal.When α_2 is infinite,the only reaction occur- ring is the smoldering combustion of solid-phase,and the gas-phase cannot react.

Exploring the methane combustion reaction: A theoretical contribution

This paper represents an attempt to extend the mechanisms of reactions and kinetics of a methane combustion reaction.Three saddle points（SPs） are identified in the reaction CH_4＋ O（~3P） → OH ＋ CH_3 using the complete active space selfconsistent field and the multireference configuration interaction methods with a proper active space. Our calculations give a fairly accurate description of the regions around the twin first-order SPs（~3A＇ and ~3A〞） along the direction of O（~3P） attacking a near-collinear H–CH_3. One second-order SP^（2nd）（~3E） between the above twin SPs is the result of the C_（3v） symmetry Jahn–Teller coupling within the branching space. Further kinetic calculations are performed with the canonical unified statistical theory method with the temperature ranging from 298 K to 1000 K. The rate constants are also reported. The present work reveals the reaction mechanism of hydrogen-abstraction by the O（~3P） from methane, and develops a better understanding for the role of SPs. In addition, a comparison of the reactions of O（~3P） with methane through different channels allows a molecule-level discussion of the reactivity and mechanism of the title reaction.

Effect of particle size of iron on reaction velocity of combustion synthesis of Ti-C-Fe system

Four Ti C Fe powder mixtures, with a same molar ratio but different particle sizes of Fe and Ti, were used to measure the reaction velocity of the combustion synthesis. The results show that in the case of the finer Ti powder used, the reaction velocity of mixture with the finer Fe powder is higher than that with the coarser Fe powder. However, in the case of the coarser Ti powder used, the reaction velocity of mixture with the finer Fe powder is lower than that with the coarser Fe powder. The effect of particle size of Fe powder on reaction velocity can be explained with the previously proposed mechanisms of the combustion synthesis of Ti C Fe system.

Mechanism of mechanical activation for spontaneous combustion of sulfide minerals

In order to uncover the intrinsic reasons for spontaneous combustion of sulfide minerals,representative samples were collected from typical metal mines to carry out the mechanical activation experiment.The structures and heat behaviors of activated samples were characterized by scanning electron microscopy（SEM）,X-ray diffraction（XRD） analysis,and simultaneous thermal analysis（STA）.It is found that the sulfide minerals after mechanical activation show many changes with increased specific surface areas,aggregation phenomenon,decreased diffraction peak intensity,broadened diffraction peak,declined initial temperatures of heat release and self-ignition points.A new theory for explaining the spontaneous combustion of sulfide minerals is put forward：the chemical reaction activity of sulfide minerals is heightened by all kinds of mechanical forces during the mining,and the spontaneous combustion takes place finally under proper environment.

A novel PdNi/Al_2O_3 catalyst prepared by galvanic deposition for low temperature methane combustion

Galvanic deposition method was used to prepare the Pd/Ni-Al2O3-GD catalyst for the combustion of methane under lean conditions. The new catalyst and compared catalysts （Pd/Al2O3-IW, Pd-Ni/Al2O3-IW, Pd/Ni-Al2O3-IW） prepared by incipient wetness impregnation were characterized by N2-physisorption, XRD and TEM to clarify particle size and size distribution of palladium species. Combined O2-TPD and XPS results with the catalytic data, it shows that the surface palladium species with low valence exhibits better combustion performance due to their stronger interaction with support. The results indicate that the galvanic deposition method is an effective route to prepare efficient catalyst for methane combustion, and it also provides useful information for improving the present commercial catalyst.

Spontaneous coal combustion producing carbon dioxide and water

Gas products from the process of coal oxidization and spontaneous combustion have been studied at different temperatures with FTI spectroscopic tests. With temperatures rising to about 30~100 ℃, water and carbon dioxide gas were formed and from about 105~150 ℃, carbon monoxide was produced. Using the DFT B3LYP method with a 6-311G basis set, the reaction system, where spontaneous combustion between coal and oxygen occurs and produces water and monoxide, has been studied, with the geometric configuration for all stagnation points on the potential reaction energy surface optimized. With a frequency analysis and an IRC method, transient formations were tested. Our results indicate that in the reaction of coal oxidization and spontaneous com-bustion producing carbon dioxide and water, oxygen molecules attack carbon atoms of the terminal of the propyl alcohol group on the lateral chain of benzene rings, which causes this propyl alcohol group to produce the acid (-CH2-CH2-COOH) group and water. This acid group continues its break up into carbon dioxide and the (-CH2-CH3) ethyl group. We have come to the conclusion that this water-and-carbon dioxide-production reaction is spontaneous, based on the observation of the energy released by the reaction.