WeiJia Hu,
YanQing Wu*,
FengLei Huang* and
XinJie Wang
State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing, China. E-mail: wuyqing@bit.edu.cn; huangfl@bit.edu.cn
First published on 12th July 2018
Phase transition of HMX single crystals is the very first process prior to chemical reaction and ignition of polymer-bonded explosives (PBX). A mesoscale β ↔ δ phase transition model is developed to investigate the role of solid phase transformation on the thermo-mechanical behavior of HMX single crystals. The model captures nonlinear elasticity, dislocation-based crystalline plasticity and temperature-dependent phase transition. Phase transition evolutions of HMX subjected to different heating rates with a certain hydrostatic pressure were investigated based on the finite element software ABAQUS. The simulated results showed that with the thermal heating and cooling boundary conditions, the β ↔ δ phase transition state is reversible, but its path is irreversible. The path-dependence of the β ↔ δ phase transition is reflected by the residual strain and stress that comes into being in the absence of mechanical constraints for 1 mm size HMX single crystals during a temperature cycle. Moreover, the β → δ phase transition is inhibited by higher temperature gradients and hydrostatic pressure. As the β-phase of HMX crystal converts to the δ-phase, the crystal volume expands due to the larger expansion coefficients of δ-HMX so that the stress concentration can be found at the sample center.
Abundant research has been done about the β–δ phase transition of HMX by experiments and molecular dynamics. Experiment methods for measuring or observing phase transition of HMX are shown as follow: Raman spectroscopy, thermogravimetric analysis, Fourier Infrared Method (FTIR),7,8 second harmonic generation (SHG),9–13 differential scanning calorimetry (DSC),14,15 X-ray diffraction (XRD),16–18 diamond anvil cell (DAC).19 Henson et al.12 quantitatively analyzed the two phases according to the intensity of the SHG signal. As the SHG signal is symmetry forbidden, δ phase therefore has a nonzero volumetric second order nonlinear polarizability. Then they established a model for studying the thermodynamics of the phase transition of HMX based on the experiments.11 The model is embedded in the crystal constitutive model to investigate the phase transition under thermal cook-off in this study. Aaron et al.20 checked the kinetic parameters of the second order reversible phase transition model and the Prout–Tompkins cook-off model by the ALE3D algorithm, and simulated thermal ignition, thermal explosion. The calculated results were consistent with the DSC and ODTX experimental data. The modified model can predict the phase transition and chemical reaction process of energetic materials. Alan et al.21 heated from ambient temperature to 573 K at different heating rates for DSC experiment. They also verified the second order reversible β → δ phase transition model of HMX. They thought that phase transformation was more likely to nucleate at the crystal defect. It indicated that the activation energy of the defect-free crystal was higher than that of the defective crystal. Smilowitz et al.16 found that the HMX sample could fully revert back to β phase by cooling the sample to temperature below the δ phase stability point. They believed the phase transition process included reversible nucleation and growth. They also found some cracks were generated after the reversible phase transition. As the cracks will increase the probability of the ignition of the HMX, the reversible phase transition of the HMX is necessary to study. During cook-off, temperature gradients will lead to pressure gradients which in turn will drive phase transition and chemical decomposition, thus affecting ignition time and location.22 Multi-point measured temperature cook-off tests were carried out at different heating rates by Chen Lang et al.23 They also used a multi-step reaction kinetics model to simulate the revolution of the chemical reaction products (β-HMX, δ-HMX, final gas products). They found that the phase transition of HMX had an influence on the temperature of the explosives and would affect the ignition of the explosive.
In this work, we develop a mesoscale constitutive model by considering temperature dependent phase transition to analyze the response of phase transition in HMX under thermal cook-off and hydrostatic pressure. This paper has three main objectives: (1) understanding the irreversibility of the phase transition path; (2) investigating the onset temperature of phase transition; (3) probing into the thermal–mechanical response under cook-off process.
F = FeFp = ReUeFp | (1) |
According to (1), the velocity gradient L is written as,
L = ḞF−1 = Ω + ReRe−1;Ω = ṘeRe−1 | (2) |
(3) |
In order to express the crystal plastic constitutive equations through slip systems, the resolved shear stress τ(α) is based on Schmid law.
(4) |
The Orowan equation34 is in the description of shear strain rate for rate-dependent crystal plasticity,
(α) = ρm(α)b(α)(α) | (5) |
(6) |
Two distinct processes contribute to the strain rate: nucleation of dislocation loops and growth of existing loops.36 At low strain rates, increases in dislocation density are usually attributed to multiplication of existing dislocations via a process called multiple cross glide.37 However, for solids under extremely large shear stresses the nucleation of dislocations at stress concentrations must be considered.38 At higher stresses, multiplication of dislocations will operate simultaneously with the nucleation. Then the rate of mobile dislocation density can be expressed as,
(7) |
The threshold shear stress τ0 and τc are affected by temperature.39 When the temperature increases, the threshold shear stress will increase.
(8) |
In thermo-elasticity, elastic strain and entropy specify the thermodynamic state. The internal energy per unit mass is expanded in terms of elastic strain tensor and entropy.41 At constant entropy, higher-order elastic constants may be used to approximate internal energy increments,
(9) |
(10) |
The relationship between unrotated Cauchy stress rate and the elastic strain rate tensor e can be obtained from eqn (9)
(11) |
As proved by Johnson and Bammann,41 the Cauchy stress rate L, is material frame indifferent and can be expressed as:
= − Wσ + σW | (12) |
Then, the complete expression of the rate-dependent constitutive model equation is obtained by,
(13) |
A small amount of data is obtained on the higher-order elastic constants of single crystal β-HMX, which are important to describe ∂/∂e in eqn (13). The nonlinear elastic response of β-HMX single crystals is assumed to be dependent on the pressure and temperature
(14) |
Bulk modulus K is pressure and temperature dependent. The pressure and temperature dependent relation of elastic constants ∂/∂P and ∂/∂T can be obtained by molecular dynamic simulations are performed using COMPASS field of force for β-HMX single crystals.43
In the process of the phase transition, the stress depends on the mole fraction of the β-HMX and the δ-HMX,
σ = λσδ-HMX + (1 − λ)σβ-HMX | (15) |
To complete the thermo-dynamic description, the temperature is given by,
(16) |
CV = 667.7 + 0.88T (J kg−1 K−2) | (17) |
All the parameters employed in the model are listed in Table 1 and 2.
C11 | C12 | C22 | C13 | C23 | C33 | C44 | C45 | C55 | C16 | C26 | C36 | C66 |
---|---|---|---|---|---|---|---|---|---|---|---|---|
20.8 | 4.0 | 26.9 | 13.0 | 6.6 | 17.6 | 2.9 | 3.0 | 3.8 | 0.6 | −1.5 | 0.1 | 6.6 |
b (m) | ρm0 (m−2) | M (m−2) | τ0 (Pa) | H (Pa) | v0 (m s−1) | τc (Pa) | A (m2 Pa2) | Sd (Pa) |
---|---|---|---|---|---|---|---|---|
7.1332 × 10−10 | 1.4 × 1010 | 1.23 × 1012 | 1.2 × 106 | 1010 | 3280 | 1.56 × 106 | 10−9 | 0.17 × 109 |
(18) |
(19) |
The first step in eqn (18) represents the nucleation kinetics from either β or δ phases. The second and third step represent the growth of the new, stable phase in either direction, with kinetics modeled as second order in both mass fractions. The phase transition velocity vph can be obtained,
vph = k1 + [β0(k2 − k−2) − (k1 + k−1)]x + β0(k−2 − k2)x2 | (20) |
x = [δ]/β0;β0 = 0.0064 mol cm−3 | (21) |
All the parameters used in the phase transition model are listed in Table 3.
Q (m3 mol−1) | S (J mol−1 K) | U (kJ mol−1) | V (m3 mol−1) | |
---|---|---|---|---|
k1 | 1.00 | 144.44 | 207.691 | 1.14 × 10−5 |
k−1 | 1.00 | 121.68 | 197.891 | 0.00 |
k2 | 3.00 × 10−10 | 149.85 | 79.700 | 2.33 × 10−5 |
k−2 | 3.00 × 10−10 | 127.09 | 69.900 | 1.19 × 10−5 |
The overall phase transition fraction of the crystal, which means the fraction of new generated δ-HMX, is plotted in Fig. 3(a). Obviously that in a temperature cycle, β ↔ δ phase transition state is reversible, but its path is irreversible. A and B in Fig. 3(a) respectively represent the beginning points of β → δ and δ → β phase transition. The temperature of the A and B states correspond to 432 K and 426 K. There is a volume expansion due to the decrease of the density from 1.90 (for β phase) to 1.76 g cm−3 (for δ phase), accompanying the β → δ phase transition. This may result in the generation of cracks, which will not disappearance during the δ → β phase transition. The cracks change the physical and chemical properties of the crystal so that the crystal can't convert back to the initial β phase. Another evidence is that negligible residual strain and stress appear in the crystal when subjected to a temperature cycle. Fig. 3(b) shows the evolution of the averaged volumetric strain of the crystal. Averaged volumetric strain is zero at first time and increases with rising temperature. After β → δ phase transition, the volumetric strain will increase more quickly. When the temperature loading on outer boundary begins to decrease, the volumetric strain has a slight increase around 500 K for that the temperature of the internal crystal is still rising on the influence of thermal conduction. Then the volumetric strain decreases to 0.025 after the temperature loading drops to 300 K and keeps for a while. This means that the crystal has residual volume expansion, which may be caused by damage such as cracks.
When the heating rate is not high enough, the β → δ phase transition can't finish completely during a temperature cycle. Prolonging the maximum temperature time in the thermal cycle can increase the β → δ phase transition degree. Fig. 4 shows the temperature loading on outer boundary at 1.5 K min−1 with different maximum temperature time.
Fig. 5 shows the evolution of the phase transition fraction (δ-HMX) and volumetric strain. When the heating rate is not high enough, the inner crystal temperature has no enough time to rise to phase transition onset temperature, which leads to the incomplete β → δ phase transition. If the temperature is maintained for a while at the plateau value, the crystal temperature will be homogenized because of thermal conduction and the temperature gradient will decrease, then the fraction of the δ-HMX will rise. The longer the maximum temperature lasts, the higher the phase transition fraction is. Volumetric stain increases with the rising temperature and resides after a temperature cycle. Obviously the temperature homogenization caused by thermal conduction contributes to the β → δ phase transition.
Based on thermal conduction, the temperature gradient will be generated in the HMX crystal with the variable temperature. Temperature gradient has a significant influence on the phase transition. The phase transition fraction contour, and the temperature gradient of HMX crystal are shown in Fig. 6. The four pictures in Fig. 6(a) and four curves in Fig. 6(b) correspond to the four points in the Fig. 4, respectively. From Fig. 6(b), the max temperature of the sample is 435 K at t = 90 min. At this time, the β → δ phase transition begins from the boundary as the temperature of the six faces of the sample is the highest. With the influence of the thermal conduction, the temperature of the center of the sample rises, which makes the fraction of the δ-HMX increase to 1. After t = 100 min, the temperature loading on outer boundary begins to decrease. At t = 165 min, the temperature on the outer surfaces of the sample is 426 K and the δ → β has been finished. Finally, the sample converts to β phase totally. While the temperature gradient is high, the temperature are not identical at different location of the sample. Because the phase transition is mainly related to temperature, the phase transition is not homogeneous when the temperature gradient is high. The temperature gradient has an inhibitory effect on phase transition.
Fig. 6 (a) The phase transition fraction contour of δ-HMX; (b) the temperature gradient from the outer boundary to crystal center. |
Fig. 8(a) shows the fraction of δ-HMX changes with the temperature, the linear fit for the natural logarithm of the heating rates and phase transition onset temperature is plotted in Fig. 8(b). High heating rate results in big temperature gradient, which inhibits phase transition in crystal. Moreover, the activation energy of the crystal will change with the temperature, so that the phase transition velocity will be different with different heating rates.
Fig. 8 (a) The phase transition changes with temperature at different heating rates; (b) the linear fit for the natural logarithm of the heating rates and phase transition onset temperature. |
In order to analyze the influence of hydrostatic pressure on β → δ phase transition, the six outer surfaces of the HMX crystal are loaded by constant hydrostatic pressure ranging from 0 to 50 MPa, with the same heating rate of 1 K min−1. The time-varying hydrostatic pressure and temperature are shown in Fig. 9.
From the literature,19 the β → δ phase transition onset temperature is positively correlated with the pressure, which means the phase transition is inhibited by pressure. Fig. 10(a) shows the evolution of the phase transition under different hydrostatic pressure. It is clear that the phase transition will delay when the crystal suffers hydrostatic pressure. According to the phase equilibrium PT relation of the Clapeyron equation (eqn (22)), dP/dT is equal to the product of latent heat of the phase transition divided by the temperature and the molar volume difference through phase transition.47
dP/dT = L/(TΔV);L = TΔS | (22) |
ΔV = Vβ − Vδ = 1.14 × 10−5 m3 mol−1,ΔS = Sβ − Sδ = 30.78 J (mol−1 K−1) | (23) |
Fig. 10 (a) The evolution of the phase transition under different hydrostatic pressure; (b) the phase transition onset temperature under different hydrostatic pressure. |
It will be obtained that,
dT/dP = 0.37 (K MPa−1) | (24) |
The β → δ phase transition onset temperature under different hydrostatic pressure is plotted in Fig. 10(b). The pressure and temperature relations are fitted. The results show the relationship between pressure and temperature, which is close to the linear relationship in the phase transition. The simulation results are fitted with a straight slope,
dT/dP = 0.33 (K MPa−1) | (25) |
From the eqn (24) and (25), it is obvious that the theoretical and simulated values are in good agreements.
Fig. 11 (a) The stress–strain curves under different heating rates; (b) the phase transition curves under different heating rates; (c) the plastic strain under different heating rates. |
Fig. 12 shows the stress contour of HMX before and after β → δ phase transition under different heating rates. The max tensile stress has a great increase after β → δ phase transition and increases more quickly with rising heating rates. The maximum stress of the crystal is at the center before phase transition and at the boundary after phase transition. The β → δ phase transition leads to a great volume expansion so that there will be stress concentration at the center of the crystal. The localized stress increase leads to the generation of hot spots. Phase transition makes the crystal more sensitive.
Fig. 12 The stress contour of HMX before (left hand) and after (right hand) phase transition under different heating rates. |
The evolution of three principle strains of HMX crystal are plotted in Fig. 13. As the HMX single crystal is anisotropic, the principle strains are different along three principle directions. The total strain is equal to the elastic strain plus the thermal strain and the plastic strain, where the thermal strain plays a major role under cook-off process. The higher the heating rate is, the greater the total strain is. The three principle strains increase quicker after phase transition due to the bigger thermal expansion coefficients of δ phase. The third principle strain ε33 is negative before the inflection point, which means the crystal is compressed before the β → δ phase transition. After the β → δ phase transition, the explosive is in a stretched state along the third direction, which may result in the generation of cracks along this direction.
The volumetric strains of the sample at different heating rates are shown in Fig. 14. Obviously that the crystal has an apparent volumetric expansion with the rising temperature. The volumetric expansion is mainly caused by elastic expansion and thermal expansion. The volumetric strain is bigger with higher heating rate. After phase transition, the volumetric strain increases faster, which reveals that the phase transition results in an apparent volumetric expansion. As the final environmental temperature are the same, the volumetric strain are stable at 0.04 for a while, which are mainly caused by phase transition and thermal expansion. Volumetric strain has a slight increase at last due to the elastic strain, which will increase with the rise of plastic strain.
As the temperature rises and decreases, β ↔ δ phase transition state is reversible, but its path is irreversible. The β → δ and δ → β phase transition onset temperature are different. Negligible residual strain and stress still exist in the crystal after a temperature cycle. Moreover, when the heating rate is not high enough for the β → δ phase transition to finish completely, prolonging the maximum temperature time in the thermal cycle will increase the phase transition degree. The longer the maximum temperature lasts, the smaller the temperature gradient is. The inner crystal temperature has enough time to rise to the β → δ phase transition threshold. Small temperature gradient contributes to β → δ phase transition.
The β → δ phase transition is inhibited by great temperature gradient and hydrostatic pressure. The activation energy changes with temperature. With the rising heating rate, the great temperature gradient is generated in the crystal, which may lead to a delay of the β → δ phase transition nucleation. The natural logarithm of the heating rates and phase transition onset temperature are linear. The phase transition onset temperature increases with a rising hydrostatic pressure by a relation of dT/dP = 0.33 (K MPa−1).
As the β-HMX crystal converts to δ phase, the crystal volume expands due to the larger expansion coefficients of δ-HMX. The crystal changes from a compressed state to a stretched state along the third principle direction after phase transition, which may lead to the generation of cracks. The anisotropic thermal expansion and phase transition result in stress increases and concentration. When this stress reaches a critical level, plastic slip initiates, which shows phase transition facilitates plastic slip. Localized high stress and temperature will play an important role in the generation of the hot spots. The β → δ phase transition will result in increased sensitivity to HMX.
In the present work, chemical reaction and thermal damage have not been taken into account in the developed phase-transition model, which will be considered in our future work for better understanding explosion initiation for high explosives.
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