Thermochemical Code Research Articles

A Novel Method for Assessment of the Velocity of Detonation for Primary Explosives

AbstractPrimary explosives are hazardous energetic materials with considerable sensitivities to external stimuli such as impact, friction, flame, heat, electric spark, and shock. A novel correlation has been introduced for prediction of detonation velocities of different hazardous primary explosives. The needed data for the new model are the loading density, the heat of detonation, the sum of the moles of gaseous products per gram of explosive and the average molecular weight of gaseous products. Decomposition products were specified based on the oxygen balance of primary explosives. Cross‐validation of the model and the statistical parameters were used for evaluating the goodness‐of‐fit, goodness‐of‐prediction, accuracy, and precision of the new model. The statistical parameters of the new model, as compared to the outputs of one of the best available thermochemical computer codes, confirm the higher reliability of the new correlation.

X-ray radiative transfer in protoplanetary disks

Context. The X-ray luminosities of T Tauri stars are about two to four orders of magnitude higher than the luminosity of the contemporary Sun. As these stars are born in clusters, their disks are not only irradiated by their parent star but also by an X-ray background field produced by the cluster members. Aims. We aim to quantify the impact of X-ray background fields produced by young embedded clusters on the chemical structure of disks. Further, we want to investigate the importance of the dust for X-ray radiative transfer in disks. Methods. We present a new X-ray radiative transfer module for the radiation thermo-chemical disk code PRODIMO (PROtoplanetary DIsk MOdel), which includes X-ray scattering and absorption by both the gas and dust component. The X-ray dust opacities can be calculated for various dust compositions and dust-size distributions. For the X-ray radiative transfer we consider irradiation by the star and by X-ray background fields. To study the impact of X-rays on the chemical structure of disks we use the well established disk ionization tracers N2H+ and HCO+. Results. For evolved dust populations (e.g. grain growth), X-ray opacities are mostly dominated by the gas; only for photon energies E ≳ 5−10 keV do dust opacities become relevant. Consequently the local disk X-ray radiation field is only affected in dense regions close to the disk midplane. X-ray background fields can dominate the local X-ray disk ionization rate for disk radii r ≳ 20 au. However, the N2H+ and HCO+ column densities are only significantly affected in cases of low cosmic-ray ionization rates (≲10-19 s-1), or if the background flux is at least a factor of ten higher than the flux level of ≈10-5 erg cm-2 s-1 expected for clusters typical for the solar vicinity. Conclusions. Observable signatures of X-ray background fields in low-mass star-formation regions, like Taurus, are only expected for cluster members experiencing a strong X-ray background field (e.g. due to their location within the cluster). For the majority of the cluster members, the X-ray background field has relatively little impact on the disk chemical structure.

CN rings in full protoplanetary disks around young stars as probes of disk structure

Aims. Bright ring-like structure emission of the CN molecule has been observed in protoplanetary disks. We investigate whether such structures are due to the morphology of the disk itself or if they are instead an intrinsic feature of CN emission. With the intention of using CN as a diagnostic, we also address to which physical and chemical parameters CN is most sensitive. Methods. A set of disk models were run for different stellar spectra, masses, and physical structures via the 2D thermochemical code DALI. An updated chemical network that accounts for the most relevant CN reactions was adopted. Results. Ring-shaped emission is found to be a common feature of all adopted models; the highest abundance is found in the upper outer regions of the disk, and the column density peaks at 30−100 AU for T Tauri stars with standard accretion rates. Higher mass disks generally show brighter CN. Higher UV fields, such as those appropriate for T Tauri stars with high accretion rates or for Herbig Ae stars or for higher disk flaring, generally result in brighter and larger rings. These trends are due to the main formation paths of CN, which all start with vibrationally excited H\hbox{$_2^*$} molecules, that are produced through far ultraviolet (FUV) pumping of H2. The model results compare well with observed disk-integrated CN fluxes and the observed location of the CN ring for the TW Hya disk. Conclusions. CN rings are produced naturally in protoplanetary disks and do not require a specific underlying disk structure such as a dust cavity or gap. The strong link between FUV flux and CN emission can provide critical information regarding the vertical structure of the disk and the distribution of dust grains which affects the UV penetration, and could help to break some degeneracies in the SED fitting. In contrast with C2H or c-C3H2, the CN flux is not very sensitive to carbon and oxygen depletion.

Far-infrared HD emission as a measure of protoplanetary disk mass

Protoplanetary disks around young stars are the sites of planet formation. While the dust mass can be estimated using standard methods, determining the gas mass - and thus the amount of material available to form giant planets - has proven to be very difficult. Hydrogen deuteride (HD) is a promising alternative to the commonly-used gas mass tracer, CO. We aim to examine the robustness of HD as tracer of the disk gas mass, specifically the effect of gas mass on the HD FIR emission and its sensitivity to the vertical structure. Deuterium chemistry reactions relevant for HD were implemented in the thermochemical code DALI and models were run for a range of disk masses and vertical structures. The HD J=1-0 line intensity depends directly on the gas mass through a sublinear power law relation with a slope of ~0.8. Assuming no prior knowledge about the vertical structure of a disk and using only the HD 1-0 flux, gas masses can be estimated to within a factor of 2 for low mass disks (M$_{\rm disk} < 10^{-3}$ M$_\odot$). For more massive disks, this uncertainty increases to more than an order of magnitude. Adding the HD 2-1 line or independent information about the vertical structure can reduce this uncertainty to a factor of ~3 for all disk masses. For TW Hya, using the radial and vertical structure from Kama et al. 2016b the observations constrain the gas mass to $6\cdot10^{-3}$ M$_\odot$ < M$_{\rm disk} < 9\cdot10^{-3}$ M$_\odot$. Future observations require a 5$\sigma$ sensitivity of $1.8\cdot10^{-20}$ W m$^{-2}$ ($2.5\cdot10^{-20}$ W m$^{-2}$) and a spectral resolving power R > 300 (1000) to detect HD 1-0 (HD 2-1) for all disk masses above $10^{-5}$ M$_\odot$ with a line-to-continuum ratio > 0.01. These results show that HD can be used as an independent gas mass tracer with a relatively low uncertainty and should be considered as an important science goal for future FIR missions.

The Synthesis of Energetic Compound on 4,4′‐((2,4,6‐trinitro‐1,3‐phenylene)bis(oxy)) bis(1,3‐dinitrobenzene)(ZXC‐5): Thermally Stable Explosive with Outstanding Properties

AbstractThe novel, thermally stable explosive 4,4′‐((2,4,6‐trinitro‐1,3‐phenylene)bis(oxy))bis(1,3‐dinitrobenzene) (Be referred to as ZXC‐5 in our laboratory) has been reported. ZXC‐5 can be synthesized by a simple synthetic method (The total synthesis of ZXC‐5 requires only two steps and the total yield of ZXC‐5 is more than 89 %) and shows the superior detonation performances (detonation pressure, detonation velocity, sensitivity toward mechanical stimuli, and temperature of decomposition). The structure of ZXC‐5 was characterized by multinuclear (1H, 13C) NMR and mass spectrometry. The structure in the crystalline state was confirmed by low‐temperature single‐crystal X‐ray diffraction. From the calculated standard molar enthalpy of formation and the measured densities, the detonation properties were predicted by using the EXPLO5 V6.01 thermochemical computer code. The sensitivity of ZXC‐5 towards impact, electrostatic discharge, and friction were also measured.

The chemistry of episodic accretion in embedded objects

Episodic accretion is an important process in the evolution of young stars and their environment. The observed strong luminosity bursts of young stellar objects likely have a long lasting impact on the chemical evolution of the disk and envelope structure. We want to investigate observational signatures of the chemical evolution in the post-burst phase for embedded sources. With such signatures it is possible to identify targets that experienced a recent luminosity burst. We present a new model for episodic accretion chemistry based on the 2D, radiation thermo-chemical disk code ProDiMo. We have extended ProDiMo with a proper treatment for envelope structures. For a representative Class I model, we calculated the chemical abundances in the post-burst phase and produced synthetic observables like intensity maps and radial profiles. During a burst many chemical species, like CO, sublimate from the dust surfaces. As the burst ends they freeze out again (post-burst phase). This freeze-out happens from inside-out due to the radial density gradient in the disk and envelope structure. This inside-out freeze-out produces clear observational signatures in spectral line emission, like rings and distinct features in the slope of radial intensity profiles. We fitted synthetic C18O J=2-1 observations with single and two component fits and find that post-burst images are much better matched by the latter. Comparing the quality of such fits allows identification of post-burst targets in a model-independent way. Our models confirm that it is possible to identify post-burst objects from spatially resolved CO observations. However, to derive proper statistics, like frequencies of bursts, from observations it is important to consider aspects like the inclination and structure of the target and also dust properties as those have a significant impact on the freeze-out timescale.

Stellar energetic particle ionization in protoplanetary disks around T Tauri stars

Anomalies in the abundance measurements of short lived radionuclides in meteorites indicate that the protosolar nebulae was irradiated by a high amount of energetic particles (E$\gtrsim$10 MeV). The particle flux of the contemporary Sun cannot explain these anomalies. However, similar to T Tauri stars the young Sun was more active and probably produced enough high energy particles to explain those anomalies. We want to study the interaction of stellar energetic particles with the gas component of the disk and identify possible observational tracers of this interaction. We use a 2D radiation thermo-chemical protoplanetary disk code to model a disk representative for T Tauri stars. We use a particle energy distribution derived from solar flare observations and an enhanced stellar particle flux proposed for T Tauri stars. For this particle spectrum we calculate the stellar particle ionization rate throughout the disk with an accurate particle transport model. We study the impact of stellar particles for models with varying X-ray and cosmic-ray ionization rates. We find that stellar particle ionization has a significant impact on the abundances of the common disk ionization tracers HCO$^+$ and N$_2$H$^+$, especially in models with low cosmic-ray ionization rates. In contrast to cosmic rays and X-rays, stellar particles cannot reach the midplane of the disk. Therefore molecular ions residing in the disk surface layers are more affected by stellar particle ionization than molecular ions tracing the cold layers/midplane of the disk. Spatially resolved observations of molecular ions tracing different vertical layers of the disk allow to disentangle the contribution of stellar particle ionization from other competing ionization sources. Modeling such observations with a model like the one presented here allows to constrain the stellar particle flux in disks around T Tauri stars.

ALMA unveils rings and gaps in the protoplanetary system HD 169142: signatures of two giant protoplanets

The protoplanetary system HD 169142 is one of the few cases where a potential candidate protoplanet has been recently detected via direct imaging. To study the interaction between the protoplanet and the disk itself observations of the gas and dust surface density structure are needed. This paper reports new ALMA observations of the dust continuum at 1.3\,mm, $^{12}$CO, $^{13}$CO and C$^{18}$O $J=2-1$ emission from the system HD 169142 at angular resolution of $\sim 0".18 - 0".28$ ($\sim 20\,$au$ - 33\,$au). The dust continuum emission reveals a double-ring structure with an inner ring between $0".17-0".28$ ($\sim 20 - 35\,$au) and an outer ring between $0".48-0".64$ ($\sim 56 - 83\,$au). The size and position of the inner ring is in good agreement with previous polarimetric observations in the near-infrared and is consistent with dust trapping by a massive planet. No dust emission is detected inside the inner dust cavity ($R \lesssim 20\,$au) or within the dust gap ($\sim 35 - 56\,$au). In contrast, the channel maps of the $J=2-1$ line of the three CO isotopologues reveal the presence of gas inside the dust cavity and dust gap. The gaseous disk is also much larger than the compact dust emission extending to $\sim 1'.5$ ($\sim 180\,$au) in radius. This difference and the sharp drop of the continuum emission at large radii point to radial drift of large dust grains ($>$ \micron-size). Using the thermo-chemical disk code \textsc{dali}, the continuum and the CO isotopologues emission are modelled to quantitatively measure the gas and dust surface densities. The resulting gas surface density is reduced by a factor of $\sim 30-40$ inward of the dust gap. The gas and dust distribution hint at the presence of multiple planets shaping the disk structure via dynamical clearing (dust cavity and gap) and dust trapping (double ring dust distribution).

Rings, rings, rings: what does CN tell us?

AbstractCN emission lines are among the brightest, and have been observed in the last 20 years with single dish observations. With modern interferometers, we are now able to spatially resolve CN emission, which often shows ring-like structures. We investigate whether such structures trace the morphology of the disks, or if they have a chemical origin. By using the thermochemical code DALI, we conclude that CN formation is triggered by the existence of vibrationally excited H2*, produced by FUV pumping of H2. Herbig stars therefore generally have larger rings and higher CN fluxes than TTauri. Disks with higher masses and flaring also show stronger CN emission and larger rings. CN observations could in the future provide important constraints on some important disk physical parameters. The results of the models are well consistent with the spatially resolved CN observations to-date available.

Estimated Detonation Velocities for TKX‐50, MAD‐X1, BDNAPM, BTNPM, TKX‐55, and DAAF using the Laser–induced Air Shock from Energetic Materials Technique

AbstractSince new energetic materials are initially produced in very small quantities for both safety and cost reasons, laboratory‐scale methods for characterizing their performance are essential for determining the most promising candidates for scale‐up. Laser‐induced air shock from energetic materials (LASEM) is a promising new method for estimating the detonation velocity of novel explosives using milligram amounts of material, while simultaneously investigating their high temperature chemical reactions. LASEM has been applied to 6 new explosives for the first time: TKX‐50, MAD−X1, BDNAPM, BTNPM, TKX‐55, and DAAF. Emission spectroscopy of the laser excited materials revealed the formation of the high pressure bands of C2 during the ensuing exothermic reactions. The low thermal sensitivity of the materials also led to unusual laser‐material interactions, visualized with high‐speed video. The estimated detonation velocities for the 6 explosives were compared to predicted values from EXPLO5 and CHEETAH. The LASEM results suggest that TKX‐55, BDNAPM, and BTNPM have higher detonation velocities than predicted by the thermochemical codes, while the estimated detonation velocities for MAD−X1 and TKX‐50 are slightly lower than those predicted.

14,16,34,36,54,56,74,76-Octanitro-2,4,6,8-tetraoxa-1,3,5,7(1,3)-tetrabenzenacyclooctaphane and its derivatives: thermally stable explosives with outstanding properties

Herein, the novel, thermally stable explosive 14,16,34,36,54,56,74,76-octanitro-2,4,6,8-tetraoxa-1,3,5,7(1,3)-tetrabenzenacyclooctaphane (4a) and its derivatives are reported.

Simulating sympathetic detonation using the hydrodynamic models and constitutive equations

A Sympathetic detonation (SD) is a detonation of an explosive charge by a nearby explosion. Most of times it is unintended while the impact of blast fragments or strong shock waves from the initiating donor explosive is the cause of SD. We investigate the SD of a cylindrical explosive charge (64 % RDX, 20 % Al, 16 % HTPB) contained in a steel casing. The constitutive relations for high explosive are obtained from a thermo-chemical code that provides the size effect data without the rate stick data typically used for building the rate law and equation of state. A full size SD test of eight pallet-packaged artillery shells is performed that provides the pressure data while the hydrodynamic model with proper constitutive relations for reactive materials and the fragmentation model for steel casing is conducted to replicate the experimental findings. The work presents a novel effort to accurately model and reproduce the sympathetic detonation event with a reduced experimental effort.

Laser-shocked energetic materials with metal additives: evaluation of chemistry and detonation performance.

A focused, nanosecond-pulsed laser has been used to ablate, atomize, ionize, and excite milligram quantities of metal-doped energetic materials that undergo exothermic reactions in the laser-induced plasma. The subsequent shock wave expansion in the air above the sample has been monitored using high-speed schlieren imaging in a recently developed technique, laser-induced air shock from energetic materials (LASEM). The method enables the estimation of detonation velocities based on the measured laser-induced air-shock velocities and has previously been demonstrated for organic military explosives. Here, the LASEM technique has been extended to explosive formulations with metal additives. A comparison of the measured laser-induced air-shock velocities for TNT, RDX, DNTF, and LLM-172 doped with Al or B to the detonation velocities predicted by the thermochemical code CHEETAH for inert or active metal participation demonstrates that LASEM has potential for predicting the early time (<10 μs) participation of metal additives in detonation events. The LASEM results show that while Al is mostly inert at early times in the detonation event (confirmed from large-scale detonation testing), B is active-and reducing the amount of hydrogen present during the early chemical reactions increases the resulting estimated detonation velocities.

Optical spectroscopy to study confined and semi-closed explosions of homogeneous and composite charges

Confined and semi-closed explosions of new class of energetic composites as well as TNT and RDX charges were investigated using optical spectroscopy. These composites are considered as thermobarics when used in layered charges or enhanced blast explosives when pressed. Two methods to estimate fireball temperature histories of both homogeneous and metallized explosives from the spectroscopic data are also presented, compared and analyzed. Fireball temperature results of the charges detonated in a small explosion chamber under air and argon atmospheres, and detonated in a semi-closed bunker are presented and compared with theoretical ones calculated by a thermochemical code. Important conclusions about the fireball temperatures and the physical and chemical phenomena occurring after the detonation of homogeneous explosives and composite formulations are deduced.

TEA: A CODE CALCULATING THERMOCHEMICAL EQUILIBRIUM ABUNDANCES

ABSTRACT We present an open-source Thermochemical Equilibrium Abundances (TEA) code that calculates the abundances of gaseous molecular species. The code is based on the methodology of White et al. and Eriksson. It applies Gibbs free-energy minimization using an iterative, Lagrangian optimization scheme. Given elemental abundances, TEA calculates molecular abundances for a particular temperature and pressure or a list of temperature–pressure pairs. We tested the code against the method of Burrows &amp; Sharp, the free thermochemical equilibrium code Chemical Equilibrium with Applications (CEA), and the example given by Burrows &amp; Sharp. Using their thermodynamic data, TEA reproduces their final abundances, but with higher precision. We also applied the TEA abundance calculations to models of several hot-Jupiter exoplanets, producing expected results. TEA is written in Python in a modular format. There is a start guide, a user manual, and a code document in addition to this theory paper. TEA is available under a reproducible-research, open-source license via https://github.com/dzesmin/TEA.

First-Principles Monte Carlo Simulations of Reaction Equilibria in Compressed Vapors.

Predictive modeling of reaction equilibria presents one of the grand challenges in the field of molecular simulation. Difficulties in the study of such systems arise from the need (i) to accurately model both strong, short-ranged interactions leading to the formation of chemical bonds and weak interactions arising from the environment, and (ii) to sample the range of time scales involving frequent molecular collisions, slow diffusion, and infrequent reactive events. Here we present a novel reactive first-principles Monte Carlo (RxFPMC) approach that allows for investigation of reaction equilibria without the need to prespecify a set of chemical reactions and their ideal-gas equilibrium constants. We apply RxFPMC to investigate a nitrogen/oxygen mixture at T = 3000 K and p = 30 GPa, i.e., conditions that are present in atmospheric lightning strikes and explosions. The RxFPMC simulations show that the solvation environment leads to a significantly enhanced NO concentration that reaches a maximum when oxygen is present in slight excess. In addition, the RxFPMC simulations indicate the formation of NO2 and N2O in mole fractions approaching 1%, whereas N3 and O3 are not observed. The equilibrium distributions obtained from the RxFPMC simulations agree well with those from a thermochemical computer code parametrized to experimental data.

A proposed new diagnostic for Herbig disc geometry

Aims. CO ro-vibrational lines observed from Herbig group II discs are seen to be often broad while the same lines observed from group I discs are often narrow. This difference is not well understood. In this paper we explore the underlying cause for this difference and provide a pathway for a better understanding of the geometry and structure of the inner discs around Herbig Ae/Be stars. Methods. High-spectral-resolution infrared spectra of CO ro-vibrational emission from six Herbig Ae/Be candidate stars were taken with CRIRES (CRyogenic high-resolution InfraRed Echelle Spectrograph) at the VLT (Very Large Telescope). From these spectra, we produce individual and co-added CO ro-vibrational line profiles. We investigate line profile shape differences, and we explore the FWHM (Full Width Half Maximum) variations with J quantum number in the context of disc geometry. Furthermore, we put our new sources into the context of earlier observed sources to study a large sample. For comparison, we also investigate the FWHM variations with J of modelled CO ro-vibrational lines from two typical disc geometries produced with the thermo-chemical disc modelling code ProDiMo. Results. - abbreviated - Comparing dust and gas inner disc geometries (inferred by SED and CO ro-vibrational emission) for the expanded sample of observed Herbig discs, we find no clear correspondence between the SED groups of the sources and their inner CO radius. Conclusions. The FWHM versus J is a potential new gas diagnostic for the inner disc with e.g. a constant FWHM versus J indicating the presence of a large gas hole or gap. Both models and observations indicate the potential of this new diagnostic. - abbreviated -

5,5'-Bis(2,4,6-trinitrophenyl)-2,2'-bi(1,3,4-oxadiazole) (TKX-55): Thermally Stable Explosive with Outstanding Properties.

The novel, thermally stable explosive 5,5'-bis(2,4,6-trinitro-phenyl)-2,2'-bi(1,3,4-oxadiazole) (TKX-55) is reported. This compound can be prepared by means of a facile synthetic procedure and shows outstanding properties (detonation velocity, detonation pressure, sensitivity toward mechanical stimuli, and temperature of decomposition). TKX-55 was isolated and characterized by means of mass spectrometry, multinuclear (1 H, 13 C) NMR spectroscopy, and vibrational spectroscopy (IR and Raman). The structure in the crystalline state was determined by low-temperature single-crystal X-ray diffraction. From the calculated standard molar enthalpy of formation (CBS-4M) and the densities, the Chapman-Jouguet detonation properties were predicted by using the EXPLO5 V6.01 thermochemical computer code. The sensitivity of TKX-55 towards impact, friction, and electrostatic discharge was determined. The shock reactivity (explosiveness) of TKX-55 was measured by applying the small-scale shock reactivity test.

Constrained and extended free energy minimisation for modelling of processes and materials

Computational methods in chemical equilibrium thermodynamics have found numerous application areas in diverse fields such as metallurgy, petrochemistry, the pulp and paper industry, the study of advanced inorganic materials, environmental science and biochemistry. As many of the cases of interest are not actually in equilibrium, there is a need for methods that extend the application area of multiphase equilibrium solvers to non-equilibrium systems. Likewise there is a need for efficient handling of thermochemical systems that are described by parameters other than those most commonly associated with Gibbs energy, namely temperature, pressure and fixed elemental (and charge) balances.In the work computational methods and related theory are presented that can be used with a standard Gibbs energy minimiser to solve advanced thermochemical problems. The actual calculations have been performed using the ChemSheet software, but the presentation has aimed to be generic and applicable to other thermochemical codes that allow the user to define thermodynamic data and the stoichiometries of the constituent species in the system.The examples discussed include electrochemical Donnan equilibrium (particularly applied to aqueous pulp suspensions), surface and interfacial energies of liquid mixtures, systems affected by external magnetic fields and systems with time-dependent reaction extents and diffusion-constrained paraequilibrium. A number of practical applications have been achieved with the models that combine reaction kinetics with partial thermodynamic equilibrium calculation and ion exchange models based on Donnan equilibrium, that have both been applied with success in real-life industrial design and development work with multicomponent, multiphase systems. The method has been successfully applied to liquid surface energies of systems with multiple components and complex non-equilibrium data.

New developments of the CARTE thermochemical code: A two-phase equation of state for nanocarbons

We developed a new equation of state (EOS) for nanocarbons in the thermodynamic range of high explosives detonation products (up to 50 GPa and 4000 K). This EOS was fitted to an extensive database of thermodynamic properties computed by molecular dynamics simulations of nanodiamonds and nano-onions with the LCBOPII potential. We reproduced the detonation properties of a variety of high explosives with the CARTE thermochemical code, including carbon-poor and carbon-rich explosives, with excellent accuracy.