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Title: Kinetics of the γ–δ phase transition in energetic nitramine-octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine

Abstract

The solid, secondary explosive nitramine-octahydro-1,3,5,7-tetranitro-1,3,5,7 or HMX has four different stable polymorphs which have different molecular conformations, crystalline structures, and densities, making structural phase transitions between these nontrivial. Previous studies of the kinetics of the β–δ HMX structural transition found this to happen by a nucleation and growth mechanism, where growth was governed by the heat of fusion, or melting, even though the phase transition temperature is more than 100 K below the melting point. A theory known as virtual melting could easily justify this since the large volume difference in the two phases creates a strain at their interface that can lower the melting point to the phase transition temperature through a relaxation of the elastic energy. To learn more about structural phase transitions in organic crystalline solids and virtual melting, here we use time-resolved X-ray diffraction to study another structural phase transition in HMX, γ–δ. Again, second order kinetics are observed which fit to the same nucleation and growth model associated with growth by melting even though the volume change in this transition is too small to lower the melting point by interfacial strain. To account for this, we present a more general model illustrating that melting overmore » a very thin layer at the interface between the two phases reduces the total interfacial energy and is therefore thermodynamically favorable and can drive the structural phase transition in the absence of large volume changes. Finally, our work supports the idea that virtual melting may be a more generally applicable mechanism for structural phase transitions in organic crystalline solids.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [2];  [1];  [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Iowa State Univ., Ames, IA (United States). Dept. of Aerospace Engineering, Mechanical Engineering, and Material Science and Engineering
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1499348
Report Number(s):
LA-UR-17-30452
Journal ID: ISSN 0021-9606
Grant/Contract Number:  
89233218CNA000001
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 6; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Bowlan, Pamela Renee, Henson, Bryan Fayne, Smilowitz, Laura Beth, Levitas, Valery, Suvorova, Natalya Alexandra, and Oschwald, David M. Kinetics of the γ–δ phase transition in energetic nitramine-octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine. United States: N. p., 2019. Web. doi:10.1063/1.5080010.
Bowlan, Pamela Renee, Henson, Bryan Fayne, Smilowitz, Laura Beth, Levitas, Valery, Suvorova, Natalya Alexandra, & Oschwald, David M. Kinetics of the γ–δ phase transition in energetic nitramine-octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine. United States. doi:10.1063/1.5080010.
Bowlan, Pamela Renee, Henson, Bryan Fayne, Smilowitz, Laura Beth, Levitas, Valery, Suvorova, Natalya Alexandra, and Oschwald, David M. Thu . "Kinetics of the γ–δ phase transition in energetic nitramine-octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine". United States. doi:10.1063/1.5080010. https://www.osti.gov/servlets/purl/1499348.
@article{osti_1499348,
title = {Kinetics of the γ–δ phase transition in energetic nitramine-octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine},
author = {Bowlan, Pamela Renee and Henson, Bryan Fayne and Smilowitz, Laura Beth and Levitas, Valery and Suvorova, Natalya Alexandra and Oschwald, David M.},
abstractNote = {The solid, secondary explosive nitramine-octahydro-1,3,5,7-tetranitro-1,3,5,7 or HMX has four different stable polymorphs which have different molecular conformations, crystalline structures, and densities, making structural phase transitions between these nontrivial. Previous studies of the kinetics of the β–δ HMX structural transition found this to happen by a nucleation and growth mechanism, where growth was governed by the heat of fusion, or melting, even though the phase transition temperature is more than 100 K below the melting point. A theory known as virtual melting could easily justify this since the large volume difference in the two phases creates a strain at their interface that can lower the melting point to the phase transition temperature through a relaxation of the elastic energy. To learn more about structural phase transitions in organic crystalline solids and virtual melting, here we use time-resolved X-ray diffraction to study another structural phase transition in HMX, γ–δ. Again, second order kinetics are observed which fit to the same nucleation and growth model associated with growth by melting even though the volume change in this transition is too small to lower the melting point by interfacial strain. To account for this, we present a more general model illustrating that melting over a very thin layer at the interface between the two phases reduces the total interfacial energy and is therefore thermodynamically favorable and can drive the structural phase transition in the absence of large volume changes. Finally, our work supports the idea that virtual melting may be a more generally applicable mechanism for structural phase transitions in organic crystalline solids.},
doi = {10.1063/1.5080010},
journal = {Journal of Chemical Physics},
number = 6,
volume = 150,
place = {United States},
year = {2019},
month = {2}
}

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Works referenced in this record:

Effect of Initial Microstructure on Final Intergranular Phase Distribution in Liquid-Phase-Sintered Ceramics
journal, January 1999


Study of the kinetics of solid-solid phase transitions in HMX
conference, January 2018

  • Bowlan, P.; Smilowitz, L.; Henson, B. F.
  • SHOCK COMPRESSION OF CONDENSED MATTER - 2017: Proceedings of the Conference of the American Physical Society Topical Group on Shock Compression of Condensed Matter, AIP Conference Proceedings
  • DOI: 10.1063/1.5044961

Structure of the fourth form of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (γ-HMX), 2C4H8N8O8.0.5H2O
journal, September 1985

  • Main, P.; Cobbledick, R. E.; Small, R. W. H.
  • Acta Crystallographica Section C Crystal Structure Communications, Vol. 41, Issue 9
  • DOI: 10.1107/s0108270185007739

A phase-field approach to nonequilibrium phase transformations in elastic solids via an intermediate phase (melt) allowing for interface stresses
journal, January 2016

  • Momeni, Kasra; Levitas, Valery I.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 17
  • DOI: 10.1039/c6cp00943c

Shock relief
journal, August 2012


The β–δ phase transition in the energetic nitramine octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine: Thermodynamics
journal, August 2002

  • Henson, B. F.; Smilowitz, L.; Asay, B. W.
  • The Journal of Chemical Physics, Vol. 117, Issue 8, p. 3780-3788
  • DOI: 10.1063/1.1495398

Pressure-temperature dependence of the .beta.-.delta. polymorph interconversion in octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine
journal, December 1980

  • Landers, A. G.; Brill, T. B.
  • The Journal of Physical Chemistry, Vol. 84, Issue 26
  • DOI: 10.1021/j100463a015

Single-step production and formulation of HMX nanocrystals
journal, August 2012


Metastability and Instability of Organic Crystalline Substances
journal, February 2008

  • Randzio, Stanislaw L.; Kutner, Andrzej
  • The Journal of Physical Chemistry B, Vol. 112, Issue 5
  • DOI: 10.1021/jp077161a

The β–δ phase transition in the energetic nitramine-octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine: Kinetics
journal, August 2002

  • Smilowitz, L.; Henson, B. F.; Asay, B. W.
  • The Journal of Chemical Physics, Vol. 117, Issue 8, p. 3789-3798
  • DOI: 10.1063/1.1495399

Stabilization of Nanoscale Quasi-Liquid Interfacial Films in Inorganic Materials: A Review and Critical Assessment
journal, May 2007


Origins and Applications of London Dispersion Forces and Hamaker Constants in Ceramics
journal, September 2000


Virtual melting as a new mechanism of stress relaxation under high strain rate loading
journal, July 2012

  • Levitas, V. I.; Ravelo, R.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 33
  • DOI: 10.1073/pnas.1203285109

On the Difference in Impact Sensitivity of Beta and Delta HMX
journal, October 2003

  • Asay, Blaine; Henson, Bryan; Smilowitz, Laura
  • Journal of Energetic Materials, Vol. 21, Issue 4
  • DOI: 10.1080/713770434

Melting and superheating of crystalline solids: From bulk to nanocrystals
journal, November 2007


Submicron-Sized Gamma-HMX: 1. Preparation and Initial Characterization
journal, June 2007


The Strong Influence of Internal Stresses on the Nucleation of a Nanosized, Deeply Undercooled Melt at a Solid–Solid Phase Interface
journal, March 2015

  • Momeni, Kasra; Levitas, Valery I.; Warren, James A.
  • Nano Letters, Vol. 15, Issue 4
  • DOI: 10.1021/nl504380c

Propagating phase interface with intermediate interfacial phase: Phase field approach
journal, May 2014


Solid−Solid Phase Transformation via Internal Stress-induced Virtual Melting, Significantly below the Melting Temperature. Application to HMX Energetic Crystal
journal, May 2006

  • Levitas, Valery I.; Henson, Bryan F.; Smilowitz, Laura B.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 20
  • DOI: 10.1021/jp057438b

Two-step nucleation mechanism in solid–solid phase transitions
journal, September 2014

  • Peng, Yi; Wang, Feng; Wang, Ziren
  • Nature Materials, Vol. 14, Issue 1
  • DOI: 10.1038/nmat4083

Thermal analysis of the phases of HMX using X-ray diffraction
journal, January 1993