Coupling effect on the thermal hazard assessment of hazardous chemical materials via calorimetric technologies and simulation approaches

The coupling effect of heat absorption and release exists in the thermal decomposition of a few chemical materials.However,the impact of the above coupling on thermal hazard assessment is not considered in the literature studies.In this work,nitroguanidine(NQ)and 1,3,5-trinitro-1,3,5-triazine(RDX)are selected as representative materials to explore the influence of the coupling effect on the thermal hazard assessment of chemical materials.The linear heating experiments of NQ and RDX are carried out by a microcalorimeter and synchronous thermal analyser.The thermal decomposition curves are decoupled by advanced thermokinetics software.The thermal decomposition and kinetic parameters before and after decoupling are calculated.The results of TG experiment show that both NQ and RDX began to lose mass during the endothermic stage.The endothermic melting and exothermic decomposition of NQ and RDX are coupled within this stage.The coupling effect has different degrees of influence on its initial decomposition temperature and safety parameters.Compared with the parameters in the coupling state,the initial decomposition temperature and adiabatic induction period after decoupling decrease.The self-accelerating decomposition temperature increases,and internal thermal runaway time decreases.In the thermal hazard assessment of chemical materials with coupling effects,the calculated parameters after decoupling should be taken as an important safety index。

Effect of neutral polymeric bonding agent on tensile mechanical properties and damage evolution of NEPE propellant

Introducing Neutral Polymeric bonding agents(NPBA) into the Nitrate Ester Plasticized Polyether(NEPE)propellant could improve the adhesion between filler/matrix interface, thereby contributing to the development of new generations of the NEPE propellant with better mechanical properties. Therefore,understanding the effects of NPBA on the deformation and damage evolution of the NEPE propellant is fundamental to material design and applications. This paper studies the uniaxial tensile and stress relaxation responses of the NEPE propellant with different amounts of NPBA. The damage evolution in terms of interface debonding is further investigated using a cohesive-zone model(CZM). Experimental results show that the initial modulus and strength of the NEPE propellant increase with the increasing amount of NPBA while the elongation decreases. Meanwhile, the relaxation rate slows down and a higher long-term equilibrium modulus is reached. Experimental and numerical analyses indicate that interface debonding and crack propagation along filler-matrix interface are the dominant damage mechanism for the samples with a low amount of NPBA, while damage localization and crack advancement through the matrix are predominant for the ones with a high amount of NPBA. Finally, crosslinking density tests and simulation results also show that the effect of the bonding agent is interfacial rather than due to the overall crosslinking density change of the binder.

Hazard evaluation of ignition sensitivity and explosion severity for three typical MH_(2) (M=Mg,Ti,Zr)of energetic materials

MgH_(2),TiH_(2),and ZrH_(2) are three typical metal hydrides that have been gradually applied to composite explosives and propellants as additives in recent years.To evaluate ignition sensitivity and explosion severity,the Hartmann device and spherical pressure vessel were used to test ignition energy and explosion pressure,respectively.The results showed that the ignition sensitivity of ZrH_(2),TiH_(2) and MgH_(2) gradually increased.When the concentration of MgH_(2) is 83.0 g/m^(3) in Hartmann device,the ignition energy attained a minimum of 10.0 mJ.The explosion pressure of MgH_(2) were 1.44 times and 1.76 times that of TiH_(2) and ZrH_(2),respectively,and the explosion pressure rising rate were 3.97 times and 9.96 times that of TiH_(2) and ZrH_(2),respectively,through the spherical pressure vessel.It indicated that the reaction reactivity and reaction rate of MgH_(2) were higher than that of TiH_(2) and ZrH_(2).In addition,to conduct in edepth theoretical analysis of ignition sensitivity and explosion severity,gas production and combustion heat per unit mass of ZrH_(2),TiH_(2) and MgH_(2) were tested by mercury manometer and oxygen bomb calorimetry.The experimental results revealed that MgH_(2) had a relatively high gas production per unit mass(5.15 mL/g),while TiH_(2) and ZrH_(2) both had a gas production of less than 2.0 mL/g.Their thermal stability gradually increased,leading to a gradual increase in ignition energy.Furthermore,compared with theoretical combustion heat,the combustion ratio of MgH_(2),TiH_(2) and ZrH_(2) was more than 96.0%,with combustion heat value of 29.96,20.94 and 12.22 MJ/kg,respectively,which was consistent with the explosion pressure and explosion severity test results.

Fabrication of electrostatic safety copper azide film with in situ growing MOF

Due to its extremely low electrostatic sensitivity,copper azide primary explosive is greatly limited in practical applications.In this study,a composite film with Cu-MOF in-situ growth on carbon nanofilm was prepared by electrospinning and solvothermal methods,and CNF@Cu-N3film with electrostatic safety was obtained by carbonization and azide later.Its electrostatic sensitivity(E50)was greatly increased from 0.05 mJ of raw materials to 4.06 mJ,and still maintained a good detonation performance which could successfully detonate the CL-20 secondary explosive.This is mainly due to the synergistic effect of the carbon film and the MOF structure,which greatly improves the conductivity of the entire system and the uniform distribution of copper particles,providing a new preparation strategy for metal azide film that is suitable for the micro-initiator device.

Polyurethane-degrading fungi from soils contaminated with rocket propellant and their ability to decompose alkyne terminated polybutadiene with urethane

A large amount of propellant materials are produced every year,and storage and disposal of these propellant materials seriously contributes to environmental pollution.Alkyne terminated polybutadiene with urethane segments(PUPB)is the macromolecule backbone of these propellant materials,and degradation of PUPB is central to the eco-friendly treatment of propellant materials.In this study,we isolated a polyurethane(PU)-and PUPB-degrading fungus from soils contaminated with rocket propellant,and the fungus H14 was identified as Fusarium solani(Mart.)Sacc.based on macro-and micro-morphology as well as phylogenetic analyses.The ability of F.solani H14 to degrade PU film and PUPB patches was evaluated via mass loss,scanning electron microscopy(SEM)and enzyme production ability.Mass loss analyses revealed a 25.8%reduction in mass of PU and 1.3%reduction in mass of PUPB after F.solani H14 was incubated with PU and PUPB for 90 days,respectively.We found that F.solani H14 mycelia significantly colonized both PU and PUPB.SEM images showed that the surface of PU films and PUPB patches formed holes,underwent folding and experienced damage as well as irregular fissuring from the erosion of fungal hypha.Moreover,two possible degradative enzymes,lipase and esterase,were produced by F.solani.Our study opens a new avenue of research for eco-friendly treatments of explosive materials and propellants.This paper represents the first article on the degradation of PUPB patches.

Regio-and Stereoselective Polymerization of Bio-based Ocimene by Rare-Earth Metal Catalysts

Coordination polymerization of renewable β-ocimene has been investigated using asymmetric diiminophosphinate lutetium complex1, β-diketiminate yttrium complex 2, bis(phosphino)carbazolide yttrium complex 3, half-sandwich benzyl fluorenyl scandium complex 4 and pyridyl-methylene-fluorenyl rare-metal complexes 5a–5c. Complexes 1, 4 and 5a–5c show trans-1,2-regioselectivities and high activities, of which 5c exhibits excellent isoselectivity(mmmm>99%). Conversely, complexes 2 and 3 promote β-ocimene polymerization to produce isotactic cis-1,4-polyocimenes(cis-1,4>99%, mm>95%). Diblock copolymers cis-1,4-PIP-block-cis-1,4-POc and cis-1,4-PBD-block-cis-1,4-POc are obtained in one-pot reactions of β-ocimene with isoprene and butadiene using complex 3. Epoxidation and hydroxylation of polyocimene afford functionalized polyolefins with enhanced T_(g)(from-20 ℃ to 79 ℃ and 74 ℃) and hydrophilicity.

Theoretical predict structure and property of the novel CL-20/2,4-DNI cocrystal by systematic search approach

Cocrystallization integrates the merits of high energy and insensitivity between energetic molecules to obtain energetics with satisfying performance.However,how to obtain supramolecular synthons accurately and rapidly for predicting the structure and property of cocrystal remains a challenging problem.In this research,an efficient systematic search approach to predict CL-20/2,4-DNI cocrystal has been proposed that 2,4-DNI revolves around CL-20 with a stoichiometric ratio of 1:1 in accordance with the specified rules(hydrogen bond length:2.2-3.0 Å;search radius:6.5 Å;the number of hydrogen bond:1-3).Eight possible supramolecular synthons were obtained by combining quantum chemistry with molecular mechanics.Crystal structure prediction indicated that there are four structures in cocrystal,namely P21/c,P212121,Pbca and Pna21,and CL-20/2,4-DNI cocrystal is likely to be P21/c and the corresponding cell parameters are Z=4,a=8.28 Å,b=12.17 Å,c=20.42 Å,α=90°,β=96.94°,γ=90°,and ρ=1.9353 g/cm^(3).To further study the intermolecular interaction of CL-20/2,4-DNI cocrystal,a series of theoretical analyses were employed including intermolecular interaction energy,electrostatic potential(ESP),Density of State(DOS),Hirshfeld surface analysis.The C-H…O hydrogen bonds are demonstrated as the predominant driving forces in the cocrystal formation.The mechanical properties and detonation properties of CL-20/2,4-DNI cocrystal implies that the cocrystal shows better ductility and excellent detonation performances(9257 m/s,39.27 GPa)and can serve as a promising energetic material.Cocrystal structure predicted was compared with the experimental one to verify the accuracy of systematic search approach.There is a less than 8.8%error between experiment and predict results,indicating the systematic search approach has extremely high reliability and accuracy.The systematic search approach can be a new strategy to search supramolecular synthons and identify structures effectively and does have the potential to promote the development of energetic cocrystal by theoretical design.

Safety analysis on truing process of solid propellant

In order to investigate safety character of solid propellant, the truing process was analyzed by a thermalmechanical coupled finite element method. Based on the viscoelastic integral constitutive relation, the temperature response in truing process was calculated. The result showed that the maximum temperature in solid propellant truing process could attain up to 65 ℃ when the truing velocity was 10 mm/s and the truing thickness was 1 mm, and there was no remarkable temperature change under the truing thickness of 1.0 mm, 1.5 mm and 2.5 mm. The hazard in truing process of solid propellant was mainly close to the edge of cutting area.

Estimation of Enthalpy of Formation Using Benson’s Group Addition and Functional Group Correction

The enthalpies of formation of solid organic compounds containing carbon,nitrogen,oxygen,and hydrogen were estimated using two suggested descriptor sets,separately,by machine learning methods.The two descriptor sets are both composed of descriptors of Benson’s groups and corrected groups.The main differences between them are that one is generated based on atoms and the other is based on bonds.An in-house program was specially written in Java to extract all the descriptors with a function to ensure that each atom(or bond)of a molecule is represented by Benson’s groups once for an atom-based(or bond-based)descriptor set.Multiple linear regression and partial least squares were used,separately,to build models to predict the enthalpy of formation for two descriptor sets.The combination of the models constructed by two descriptor sets based on the atoms and the bonds achieved the best-predicted results in this paper,and the corresponding results of the test set are better than that in the literature,from which the original data were retrieved.Further,a small data set of fluorinated molecules was collected,and satisfactory results were also obtained for these molecules containing fluorine with the assistance of the former data set.

Elaborative collection of condensed combustion products of solid propellants:Towards a real Solid Rocket Motor(SRM)operational environment

A novel constant-pressure and constant-quenching distance Condensed Combustion Products(CCPs)collection system was developed,coupled with a timing control system,to collect the CCPs formed in the course of burning of aluminum-based composite propellants.The effects of adiabatic graphite plating,collection zone,quenching distance,time series of collection,and propellant burning rate on the microscopic morphology,particle size distribution and unburned aluminum content of CCPs were investigated.It was verified that the graphite plating can provide a high-fidelity high-temperature environment for propellant combustion.The combustion efficiency is improved by 2.44% compared to the bare propellant case.The time series of collection has a significant effect on the combustion efficiency of aluminum,and the combustion efficiency of aluminum in the thermal state(1.2-2.4 s)is 2.75% higher than that in the cold state(0-1.2 s).Similarly,the characteristics of the CCPs in different collection zones are different.At the quenching distance of 5 mm,the combustion efficiency of aluminum in the core zone(85.39%)is much lower than that in the outer zone(92.07%),while the particle size of the CCPs in the core zone(172μm)is larger than that in the outer zone(41μm).This indicates that the core zone is more likely to produce large-sized and incompletely burned agglomerates during the propellant combustion process.Different burning rates also lead to a significant difference in particle size distribution and combustion efficiency.High burning rates result in higher combustion efficiency.A detailed sequence of the elaborative collection process of CCPs is proposed,mainly including the setting of ignition delay time,burning rate,working pressure,plating length and time series of collection.The findings of this study are expected to provide a reliable tool for the evaluation of the combustion efficiency of solid propellants.

Ultrasensitive methyl salicylate gas sensing determined by Pd-doped SnO_(2)

Efficient chemicalwarfare agents(CWAs)detection is required to protect people from the cWAs in war and terrorism.In this work,a Pd-doped SnO_(2)nanoparticles-based gas sensor was developed to detect a nerve agent simulant named methyl salicylate.The sensing measurements of methyl salicylate under different Pd doping amounts found that the 0.5 at.%Pd-doped SnO_(2)exhibited a significant improvement in the detection of methyl salicylate at the ppb(1ppb=10-9)level,and the response value to 160 ppb methyl salicylate is 0.72 at 250℃.Compared with the pure SnO_(2),the response value is increased by 4.5 times,which could be attributed to the influence of the noble metal Pd on the oxygen state and its catalytic effect.In addition,the 0.5at.%Pd-doped SnO_(2)sensor still has an obvious response to 16ppb methyl salicylate with a response value of 0.13,indicating the lower detection limit of the sensor.