Thermodynamics of HMX Polymorphs and HMX/RDX Mixtures

Myint, Philip C.; Nichols, Albert L.

doi:10.1021/acs.iecr.6b03697

Thermodynamics of HMX Polymorphs and HMX/RDX Mixtures

Journal Article · Fri Dec 09 00:00:00 EST 2016 · Industrial and Engineering Chemistry Research

DOI:https://doi.org/10.1021/acs.iecr.6b03697· OSTI ID:1438669

^[1]; Nichols, Albert L. ^[2]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Design Physics Division
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Materials Science Division

In this paper, we present thermodynamic models for the five most commonly studied phases of the energetic material octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX): liquid HMX and four solid polymorphs (α-, β-, γ-, and δ-HMX). We show results for the density, heat capacity, bulk modulus, and sound speed, as well as a phase diagram that illustrates the temperature and pressure regions over which the various HMX phases are most thermodynamically stable. The models are based on the same equation of state presented in our recently published paper [Myint et al., Ind. Eng. Chem. Res., 2016, 55, 2252] on another energetic material, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). We combine our HMX and RDX models together so that the equation of state can also be applied to liquid and solid mixtures of HMX/RDX. This allows us to generate an HMX/RDX phase diagram and calculate the enthalpy change associated with a few different kinds of phase transitions that these mixtures may undergo. Our paper is the first to present a single equation of state that is capable of modeling both pure HMX and HMX/RDX mixtures. A distinct feature of HMX is the strongly metastable nature of its polymorphs. This has caused some ambiguity in the literature regarding the thermodynamic stability of α-HMX. Finally, by examining possible arrangements for the relative order of the six different solid-solid transition (α–β, α–γ, α–δ, β–γ, β–δ, and γ–δ) temperatures, we conclude that α-HMX must be thermodynamically stable so that the HMX phase diagram must have an α phase region.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Sponsoring Organization:: Dept. of Defense (DoD) (United States); USDOE

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1438669

Report Number(s):: LLNL-JRNL--703524

Journal Information:: Industrial and Engineering Chemistry Research, Journal Name: Industrial and Engineering Chemistry Research Journal Issue: 1 Vol. 56; ISSN 0888-5885

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Possible pre-phase transition of the α-HMX crystal observed by the variation of hydrogen-bonding network under high pressures Zhao, Xiao; Zhu, Weihua CrystEngComm, Vol. 22, Issue 2 https://doi.org/10.1039/c9ce01492f	journal	January 2020
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Non-Schmid effect of pressure on plastic deformation in molecular crystal HMX Pal, Anirban; Picu, Catalin R. Journal of Applied Physics, Vol. 125, Issue 21 https://doi.org/10.1063/1.5092285	journal	June 2019
Dislocation cross slip in molecular crystal cyclotetramethylene tetranitramine (β-HMX) Khan, Mohammad; Picu, Catalin R. Journal of Applied Physics, Vol. 126, Issue 15 https://doi.org/10.1063/1.5114940	journal	October 2019
Dislocation energy and line tension in molecular crystal cyclotetramethylene tetranitramine (β-HMX) Khan, Mohammad; Picu, Catalin R. Journal of Applied Physics, Vol. 127, Issue 5 https://doi.org/10.1063/1.5140195	journal	February 2020
Peierls–Nabarro stresses of dislocations in monoclinic cyclotetramethylene tetranitramine ( β -HMX) Pal, Anirban; Picu, Catalin R. Modelling and Simulation in Materials Science and Engineering, Vol. 26, Issue 4 https://doi.org/10.1088/1361-651x/aab45a	journal	April 2018
Dislocation mobility and critical stresses at finite temperatures in molecular crystal cyclotetramethylene tetranitramine ( β -HMX) Khan, Mohammad; Pal, Anirban; Picu, Catalin R. Modelling and Simulation in Materials Science and Engineering, Vol. 26, Issue 8 https://doi.org/10.1088/1361-651x/aae7c0	journal	November 2018

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