Surface morphologies of Mg-Gd alloy particle during its reactions with O_(2) and Teflon

Mg-Gd alloy particle has exhibited its unique combustion properties as the fuel of Mg/Teflon/Viton(MTV).Mg-Gd alloy/Teflon/Viton(MGTV)could burn at lower ambient pressure than MTV.To further investigate the reaction of MGTV in air,it was investigated via thermo gravity-differential scanning calorimetry(TG-DSC).Meanwhile,the morphologies and element distributions on the alloy surface during the reaction of MGTV in air were investigated via scanning electronic microscope-mapping-electronic differential spectrometer.Meanwhile,a similar experimental protocol on the Mg-Gd alloy particle during oxidation was also applied.The results showed that owning to a protective oxide shell,the onset oxidation temperature of Mg-Gd alloy is higher than Mg.However,the onset oxidation temperature of the exceeded Mg-Gd alloy in MGTV is significantly lower than that of the exceeded Mg in MTV.It was due to the existence of GdOF,which could significantly lower the oxidation temperature of the exceeded fuel.Furthermore,a possible reaction mechanism was proposed.The fascinating oxidation properties of Mg-Gd alloy suggested its promising applications in energetic materials.

New insights in nano-copper chromite catalyzing ultrafine AP:Evaluation of dispersity and mixing uniformity

Improving the application of nanomaterials has always been a research hotspot in the field of energetic materials(EMs)due to their obvious catalytic effect on the EMs,especially the uniformly dispersed nanomaterials.However,few studies have reported the dispersion of nanomaterials.In this study,the dispersity and mixing uniformity of nano-CuCr_(2)O_(4)was evaluated based on the difference of solid UV light absorption between the nano-catalytic materials and EMs.The nano-CuCr_(2)O_(4)/ultrafine AP composites with different dispersity of nano-CuCr_(2)O_(4)were prepared by manual grinding and mechanical grinding with different grinding strength and griding time.And then,the absorbance of different samples at 212 nm was obtained by solid UV testing due to the high repeatability of the absorbance at 210-214 nm for three parallel experiments,and the dispersity of different samples was calculated through the established difference equation.Furthermore,the samples were characterized by XRD,IR,SEM,EDS,DSC and TG-MS,which confirmed that different mixing methods did not change the structure of the samples(XRD and IR),and the mixing uniformity improved with the increase of grinding strength and grinding time(SEM and EDS).The scientificity and feasibility of the difference equation were further verified by DSC.The dispersity of nano-CuCr_(2)O_(4)exhibits a positive intrinsic relationship with its catalytic performance,and the uniformly dispersed nano-CuCr_(2)O_(4)significantly reduces the thermal decomposition temperature of ultrafine AP from 367.7 to 338.8℃.The TG-MS patterns show that the dispersed nano-CuCr_(2)O_(4)advanced the thermal decomposition process of ultrafine AP by about 700 s,especially in the high temperature decomposition stage,and the more concentrated energy release characteristic is beneficial to further enhance the energy performance of AP-based propellants.The above conclusions show that the evaluation method of dispersity based on solid UV curves could provide new ideas for the dispersity characterization of nano-catalytic materials in EMs,which is expected to be widely used in the field of EMs.

Interfacial reinforcement of core-shell HMX@energetic polymer composites featuring enhanced thermal and safety performance

The weak interface interaction and solid-solid phase transition have long been a conundrum for 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane(HMX)-based polymer-bonded explosives(PBX).A two-step strategy that involves the pretreatment of HMX to endow—OH groups on the surface via polyalcohol bonding agent modification and in situ coating with nitrate ester-containing polymer,was proposed to address the problem.Two types of energetic polyether—glycidyl azide polymer(GAP)and nitrate modified GAP(GNP)were grafted onto HMX crystal based on isocyanate addition reaction bridged through neutral polymeric bonding agent(NPBA)layer.The morphology and structure of the HMX-based composites were characterized in detail and the core-shell structure was validated.The grafted polymers obviously enhanced the adhesion force between HMX crystals and fluoropolymer(F2314)binder.Due to the interfacial reinforcement among the components,the two HMX-based composites exhibited a remarkable increment of phase transition peak temperature by 10.2°C and 19.6°C with no more than 1.5%shell content,respectively.Furthermore,the impact and friction sensitivity of the composites decreased significantly as a result of the barrier produced by the grafted polymers.These findings will enhance the future prospects for the interface design of energetic composites aiming to solve the weak interface and safety concerns.

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.

Shock Initiation Experiments with Modeling on a DNAN Based MeltCast Insensitive Explosive

2,4-dinitroanisole(DNAN)is a good replacement for 2,4,6-trinitrotoluene(TNT)in melt-cast explosives due to its superior insensitivity.With the increasing use of DNAN-based melt-cast explosives,the prediction of reaction violence and hazard assessment of the explosives subjected to shock is of great significance.This study investigated the shock initiation characteristics for a DNAN-based melt-cast explosive,DHFA,using the one-dimensional Lagrangian apparatus.The embedded manganin gauges in the apparatus record the pressure histories at four Lagrangian positions and show that shock-todetonation transition in DHFA needs a high input shock pressure.The experimental data are analyzed to calibrate the Ignition and Growth model.The calibration is performed using an objective function based on both pressure history and the arrival time of shock.Good agreement between experimental and calculated pressure histories indicates the high accuracy of the calibrated parameters with the optimization method.

Hydrodechlorination of trifluoro-trichloroethane to chlorotrifluoroethylene:Revealing the deactivation mechanism and regeneration strategy of Pd-Cu/AC catalyst

Chlorotrifluoroethylene(CTFE)is a vital fluorinated olefinic monomer produced through the catalytic hydrodechlorination of trichlorotrifluoroethane(CFC-113),an eco-friendly process.However,hydrodechlorination catalysts for olefin production often suffer from poor stability.The Pd/AC catalyst and Pd-Cu/AC catalyst prepared by co-impregnation method exhibited poor stability,Pd-Cu/AC catalyst with CFC-113 conversion dropping to around 37%after 50 h of hydrodechlorination reaction.Brunauer-Emmett-Teller,transmission electron microscopy,X-ray photoelectron spectroscopy,and X-ray diffraction of fresh and deactivated Pd/AC catalysts indicate that the deactivation of Pd/AC catalysts is due to high-temperature agglomeration of Pd.Comparative analysis of fresh and deactivated Pd-Cu/AC catalysts using Brunauer-Emmett-Teller,transmission electron microscopy,and thermogravimetric analysis techniques revealed decreased dispersion of active sites,reduced surface area,catalyst aggregation deactivation,and a significant decrease in Cu content.Furthermore,the results of NH3-TPD revealed that the acid sites of the catalyst increased significantly.X-ray diffraction spectra indicated the formation of new species,basic copper chloride(Cu_(2)(OH)_(3)Cl),during the reaction.As the reaction progressed,these new species agglomerated,leading to a gradual loss of catalyst activity.Moreover,the deactivated catalyst was successfully reactivated using a simple alkaline washing method.

Revealing the correlation between adsorption energy and activation energy to predict the catalytic activity of metal oxides for HMX using DFT

Traditional selection of combustion catalysis is time-consuming and labor-intensive.Theoretical calculation is expected to resolve this problem.The adsorption energy of HMX and O atoms on 13 metal oxides was calculated using DMol3,since HMX and O are key substances in decomposition process.And the relationship between the adsorption energy of HMX,O on metal oxides(TiO_(2),Al_(2)O_(3),PbO,CuO,Fe_(2)O_(3),Co_(3)O_(4),Bi_(2)O_(3),NiO)and experimental T30 values(time required for the decomposition depth of HMX to reach 30%)was depicted as volcano plot.Thus,the T30 values of other metal oxides was predicted based on their adsorption energy on volcano plot and validated by previous experimental data.Further,the adsorption energy of HMX on ZrO_(2)and MnO_(2)was predicted based on the linear relationship between surface energy and adsorption energy,and T30 values were estimated based on volcano plot.The apparent activation energy data of HMX/MgO,HMX/SnO_(2),HMX/ZrO_(2),and HMX/MnO_(2)obtained from DSC experiments are basically consistent with our predicted T30 values,indicating that it is feasible to predict the catalytic activity based on the adsorption calculation,and it is expected that these simple structural properties can predict adsorption energy to reduce the large quantities of computation and experiment cost.

Shock Raman spectra and structural transformation of powdered TKX-50 by the plate impact experiments combined with real-time Raman detection

As an energetic material of great interest,the work capacity of dihydroxylammonium 5,5’-bistetrazole-1,1’-diolate(TKX-50)has been questioned recently.Although some research groups have explored the reasons for the low working ability of TKX-50,the plane impact experiment on powdered TKX-50 is obviously closer to the practical application,and the conclusions based on this are more guiding.Hence,we performed shock Hugoniot measurements of powdered TKX-50 between 5.65 and 16.29 GPa.The plane impact experiments of powdered TKX-50 were carried out and the shocked Raman spectra were collected.By Raman spectroscopy analysis,a new peak of powdered TKX-50 was found between19.47 GPa and 24.96 GPa,which may be caused by decomposition/phase transition and was related with the low work capacity.

Progress on the application of graphene-based composites toward energetic materials:A review

Carbon material is an important additive in energetic materials.Graphene is a monolayer carbon material in which carbon atoms are arranged in two-dimensional honeycomb structure,who has special optical,electrical,and mechanical properties.Recently,the application of graphene-based composites in energetic materials has received extensive attention.This review mainly summarizes the applications of graphene and graphene-based nanomaterials in energetic materials.The effects of these materials on the thermal stability,sensitivity,mechanical property,ignition and combustion of energetic materials were discussed.Furthermore,the progress of functionalized modification of graphene has been summarized,including covalent bonding modification and doping modification.These studies show that graphenebased materials exhibit excellent performances and might emerge as promising candidate for energetic materials.

Thermochemistry on Coordination Behavior of Neodymium Chloride Hydrate with Diethylammonium Diethyldithiocarbamate

The complex of neodymium chloride lower hydrate with diethylammonium diethyldithiocarbamate (D-DDC) was synthesized conveniently in absolute alcohol and dry N_2 atmosphere. The title complex was identified as Et_2NH_2[Nd(S_2CNEt_2)_4] by chemical and elemental analyses and the bonding characteristics of which was characterized by IR. The enthalpies of solution of neodymium chloride hydrate and D-DDC in absolute alcohol at 298.15 K and the enthalpies change of liquid-phase reaction of formation for Et_2NH_2[Nd (S_2CNEt_2)_4] at different temperatures were determined by microcalorimetry. On the basis of experimental and calculated results, three thermodynamic parameters (the activation enthalpy, the activation entropy and the activation free energy), the rate constant and three kinetic parameters (the apparent activation energy, the pre-exponential constant and the reaction order) of liquid-phase reaction of formation were obtained. The enthalpy change of the solid-phase title reaction at 298.15 K was calculated by a thermochemical cycle.

Research on 2D Model of Capillary Discharge Plasma

The physical process of capillary discharge in a PE tube utilized in electro-thermal-chemical(ETC)guns was investigated.ETC guns can enhance the ignition and combustion of propellant in order to reduce the ignition delay and increase muzzle velocity of the projectile.A key component in ETC gun is the capillary plasma source.In this paper,a 2D steady state model of discharge was built by using magnetic hydrodynamics method.It took the plasma energy balance,material ablation,mass and momentum conservations in a quasi-neutral plasma region into account.Also,the effect of different compositions and PE concentration distribution were considered.In order to evaluate the validation of this model,the simulation results are compared with former works.

Explosion characteristics of aluminum-based activated fuels containing fluorine

Measuring the dust explosion characteristics of aluminum-based activated fuels was a prerequisite for developing effective prevention and control measures.In this paper,ignition sensitivity,flame propagation behaviors and explosion severity of aluminum/polytetrafluoroethylene(Al/PTFE)compositions including 2 PT(2.80 wt.%F),4 PT(7.18 wt.%F)and 8 PT(11.90 wt.%F)were studied.When the content of F increased from 2.80 wt.%to 11.90 wt.%,the minimum explosive concentration MEC decreased from380 g/m^(3)to 140 g/m^(3),due to the dual effects of increased internal active aluminum and enhanced reactivity.The average flame propagation velocities increased as the percentage of F increased.The maximum explosion pressure Pmof 500 g/m3aluminum-based activated fuels increased from 247 k Pa to299 kPa.Scanning electron microscopy demonstrated that with the increase of PTFE content,the reaction was more complete.On this basis,the explosion mechanism of aluminum-based activated fuels was revealed.

Understanding the alkyl effect of geminal dinitropropyl ester energetic plasticizers on hydroxyl terminated polybutadiene(HTPB):Simultaneous tuning on low temperature behavior and processability

Geminal dinitropropyl ester plasticizers(DNPEPs) possess excellent energetic performances which provide good potentials as insensitive plasticizer. In this study, we design and synthesize DNPEPs with different alkane chain parts, and systematically investigate their structure-property relationships.Results show that DNPEPs have impact sensitivities all higher than 25.2 J, thermal decomposition temperatures all higher than 254 ℃, and glass transition temperatures(T_(g)) lower than-90 ℃.Furthermore, the effects of DNPEPs as plasticizer are studied on hydroxyl terminated polybutadiene(HTPB) in detail, including the viscosity, glass transition temperatures and others. It is noteworthy that 2,2-dinitropropyl nonanoate(DNPNc) among these DNPEPs exhibits the most expected simultaneous tuning effects on both viscosity and T_(g) of HTPB systems, providing favorable potentials to replace the conventional plastizers as dioctyl sebacate(DOS) in the HTPB based propellants and explosives.

A review on the high energy oxidizer ammonium dinitramide:Its synthesis,thermal decomposition,hygroscopicity,and application in energetic materials

Ammonium dinitramide(ADN)is considered as a potential substitute for ammonium perchlorate in energetic materials due to its high density,positive oxygen balance,and halogen-free characteristics.However,its application has been severely limited because of its strong hygroscopicity,difficult storage,and incompatibility with isocyanate curing agents.In order to better bloom the advantages of the highly energetic and environment-friendly ADN in the fields of energetic materials,an in-depth analysis of the current situation and discussion of key research points are particularly important.In this paper,a detailed overview on the synthesis,thermal decomposition,hygroscopic mechanism,and antihygroscopicity of ADN has been discussed,its application in powdes and explosives are also presented,and its future research directions are proposed.

Modification of SDOF model for reinforced concrete beams under close-in explosion

In this paper,a modified single-degree-of-freedom(SDOF)model of reinforced concrete(RC)beams under close-in explosion is proposed by developing the specific impulse equivalent method and flexural resistance calculation method.The equivalent uniform specific impulse was obtained based on the local conservation of momentum and global conservation of kinetic energy.Additionally,the influence of load uniformity,boundary condition and complex material behaviors(e.g.strain rate effect,hardening/softening and hoop-confined effect)was considered in the resistance calculation process by establishing a novel relationship between external force,bending moment,curvature and deflection successively.The accuracy of the proposed model was verified by carrying out field explosion tests on four RC beams with the scaled distances of 0.5 m/kg~(1/3)and 0.75 m/kg~(1/3).The test data in other literatures were also used for validation.As a result,the equivalent load implies that the blast load near the mid-span of beams would contribute more to the maximum displacement,which was also observed in the tests.Moreover,both the resistance model and test results declare that when the blast load becomes more concentrated,the ultimate resistance would become lower,and the compressive concrete would be more prone to softening and crushing.Finally,based on the modified SDOF model,the calculated maximum displacements agreed well with the test data in this paper and other literatures.This work fully proves the rationality of the modified SDOF method,which will contribute to a more accurate damage assessment of RC structures under close-in explosion.

Microfluidic assisted 90%loading CL-20 spherical particles:Enhancing self-sustaining combustion performance

The performance of the chemical fuel determines the altitude,range and longevity of spacecraft in air and space exploration.Promising alternatives(e.g.,hypergolic ionic liquids or high-energy composites)with high-energy density,heat of formation and fast initial rate are considered as potential chemical fuels.As the high-energy density material,hexanitrohexaazaisowurtzitane(CL-20)often serves as secondary explosive with poor self-propagating combustion behaviors.Herein,90%loading CL-20 microspheres with uniform particle sizes are precisely prepared by microfluid method,which exhibit unique hierarchical structure.The morphology,thermal behaviors,as well as combustion performance were further investigated.The results demonstrated that as-prepared spherical particles exhibit prominent thermal compatibility,and the enhanced self-sustaining combustion performance.This work provides an efficient method achieving the uniform high-energy density particles with excellent self-sustaining combustion performance.

RDX crystals with high sphericity prepared by resonance acoustic mixing assisted solvent etching technology

In order to obtain high-quality spherical RDX crystal particles,the RDX crystals were suspended in a mixed solvent of cyclohexanone and cyclohexane,subsequently a solvent etching study was carried out under the action of vibration/acoustic flow coupled flow field,which generated by resonance acoustic mixing.The effects of solvent ratio,temperature,acceleration and experiment time on morphology as well as particle size of RDX crystals were studied.Not only were the morphology,particle size distribution and crystal form of RDX crystals determined,but also the thermal decomposition performance and mechanical sensitivity of spherical RDX were examined and discussed.Results indicated that under the process of solvent/non-solvent volume ratio at 1:2,temperature of 40℃,acceleration of 40 g and experiment time of 4 h,α-type RDX crystal with sphericity of 0.92 can be obtained.Furthermore,the median particle size(D_(50))of spherical RDX crystals is 215.8 μm with a unimodal particle size distribution(size span 1.34).For one thing,the thermal decomposition peak temperature of spherical RDX is about 2.5℃ higher than that of raw RDX,and apparent activation energy reaches 444.68 kJ/mol.For another thing,impact sensitivity and friction sensitivity of spherical RDX are 18.18% and 33.33% lower than that of raw RDX,respectively.It demonstrates that safety of spherical RDX under thermal,impact and friction stimuli has been improved.

A nanoparticle formation model considering layered motion based on an electrical explosion experiment with AI wires

To study the evolution of nanoparticles during Al wire electrical explosion,a nanoparticle formation model that considered layered motion was developed,and an experimental system was set up to carry out electrical explosion experiments using 0.1 mm and 0.2 mm Al wires.The characteristic parameters and evolution process during the formation of nanoparticles were calculated and analyzed.The results show that the maximum velocities of the innermost and outermost layers are about 1200 m·s-1and 1600 m·s-1,and the velocity of the middle layer is about 1400 m·s-1,respectively.Most of the nanoparticles are formed in the temperature range of2600 K-2500 K.The characteristic temperature for the formation of Al nanoparticles is~2520K,which is also the characteristic temperature of other parameters.The size distribution range of the formed nanoparticles is 18 to 110 nm,and most of them are around 22 nm.The variation of saturated vapor pressure determines the temperature distribution range of particle nucleation.There is a minimum critical diameter of particles(~25 nm);particles smaller than the critical diameter can grow into larger particles during surface growth.Particle motion has an effect on the surface growth and aggregation process of particles,and also on the distribution area of larger-diameter particles.The simulation results are in good agreement with the experiments.We provide a method to estimate the size and distribution of nanoparticles,which is of great significance to understand the formation process of particles during the evolution of wire electrical explosion.

Extra contribution to the crystal stability of insensitive explosive TATB: The cooperativity of intermolecular interactions

An in-depth analysis on the cooperativity of intermolecular interactions including hydrogen bonding andπ-π stacking in 1,3,5-triamino-2,4,6-trinitrobenzene(TATB) crystal was studied. Two quantities, cooperativity rate and energy, were defined to evaluate the nature and strength of cooperativity in a series of clusters diverging from 1D to 3D prototypes. The origin and mechanism of the cooperative effect were settled to demonstrate that the nature of cooperativity is determined by whether the non-covalent interactions compete or promote with each other, which is manifested by the changing trend of electron transfer. There exists obvious cooperative effect in intra-layer and inter-layer structures as they own the equivalent non-covalent interactions, while anti-cooperative effect is also observed if two interactions correlate with each other. On the whole, in the process of crystal formation, the apparent cooperativity is the check and balance of the two effects, which is capable to support a global interaction among all of molecules and contribute to the stabilization of system. Based on the results, one may get a new insight to understand the relationship between non-covalent interactions and low impact sensitivity.

Numerical simulation of flow field characteristics and the improvement of pressure oscillation of rotating detonation engine

Due to the inherent working mode of rotating detonation engine(RDE),the detonation flow field has the characteristics of pressure oscillation and axial kinetic energy loss,which makes it difficult to design nozzle and improve propulsion performance.Therefore,in order to improve the characteristics of detonation flow field,the three-dimensional numerical simulation of annular chamber and hollow chamber is carried out with premixed hydrogen/air as fuel in this paper,and then tries to combine the two chambers to weaken the oscillation characteristics of detonation flow field through the interaction of detonation flow field,which is a new method to regulate the detonation flow field.The results show that there are four states of velocity vectors at the outlet of annular chamber and hollow chamber,which makes RDE be affected by rolling moment and results in the loss of axial kinetic energy.In the external flow field of combined chamber,the phenomenon of cyclic reflection of expansion wave and compression wave on the free boundary is observed,which results in Mach disk structure.Moreover,the pressure monitoring points are set at the external flow field.The pressure signal shows that the high-frequency pressure oscillation at the external flow field of the combined chamber has been greatly weakened.Compared to the annular chamber,the relative standard deviation(RSD) has been reduced from 14.6% to5.6%.The results thus demonstrate that this method is feasible to adjust the pressure oscillation characteristics of the detonation flow field,and is of great significance to promote the potential of RDE and nozzle design.