The effect of viscoplastic deformation of the energetic material HMX on the mechanical, thermal, and ignition response of a two-phase (HMX and Estane) polymer bonded explosive (PBX) is analyzed. Specific attention is given to the high strain rate response of the material during the first passage of the stress wave when impacted by a constant velocity piston. PBX microstructures are subjected to impact loading from a constant velocity piston traveling at a rate of 50 to 200 m/s using a 2D cohesive finite element (CFEM) framework. The initial focus is to fully quantify the effect that viscoplastic HMX has on the behavior of a PBX composite, a thorough thermo-mechanical analysis is performed. The thermal response of the PBX specimens having viscoplastic HMX is characterized by a significant reduction in average heating, peak temperature rise, and the number or amount of material experiencing localized heating (hotspots). This reduction in heating is found to be accomplished through the mechanism of greatly reducing the density of fracture in the PBX. The second focus of this work is to evaluate the ignition sensitivity of these materials to determine the effect, if any, of the viscoplastic HMX. Viscoplastic HMX is shown to increase the minimum load duration, mean load duration, and range of critical load durations required for ignition. A 3D crystal plasticity framework is employed to quantify the potential heterogeneities in the stress and temperature field resulting from the inherent crystalline anisotropy of the HMX grains. It is found that in a densely packed HMX, the heterogeneities due to material anisotropy can contribute to increased stress gradients and localized temperature rise. Finally, the 2D framework is used to study a hypothetical composite containing HMX grains suspended in an aluminum matrix. This investigation focuses not on the feasibility of producing such a composite, but on determining whether such an arrangement would be advantageous from a mechanical and ignition sensitivity standpoint. Results indicate that this hypothetical composite would be considerably less sensitive than a similar PBX.

This work explores the computational modeling of electromechanical problems using peridynamics and in particular, its application in studying the potential of carbon nanotube (CNT) reinforced nanocomposites for the purpose of sensing deformation and damage in materials. Peridynamics, a non-local continuum theory which was originally formulated for modeling problems in solid mechanics, has been extended in this research to electromechanical fields and applied to study the electromechanical properties of CNT nanocomposites at multiple length scales. Piezoresistivity is the coupling between the electrical properties of a material and applied mechanical loads, more specifically the change in resistance in response to deformation. This can include both, a geometric effect due to change in dimensions as well as the change in resistivity of the material itself. Nanocomposites referred to in this work are materials which consist of CNTs dispersed in a binding polymer matrix. The origins of the extraordinary piezoresistive properties of nanocomposites lie at the nanoscale where the non-local phenomenon of electron hopping plays a significant role in establishing the properties of the nanocomposite along with CNT network formation and inherent piezoresistivity of CNTs themselves. Electron hopping or tunneling allows for a current to flow between neighboring CNTs even when they are not in contact, provided the energy barrier for electrons to hop is small enough. This phenomenon is highly nonlinear with respect to the intertube distance and is also dependent on other factors such as the potential barrier of the polymer matrix. To investigate this in more detail, peridynamic simulations are first employed to study the piezoresistivity at the CNT bundle scale by considering a nanoscale representative volume element (RVE) of CNTs within polymer matrix, and by explicitly modeling electron hopping effects. This is done by introducing electron hopping bonds and it is shown that the conductivity and the non-local length scale parameter in peridynamics (the horizon) can be derived from a purely physics based model rather than assuming an ad-hoc value. Piezoresistivity can be characterized as a function of the deformation and damage within the material and thereby used as an in-situ indicator of the structural health of the material. As such, a material system for which real time in-situ monitoring may be useful is polymer bonded explosives. While these materials are designed for detonation under conditions of a strong shock, they can be damaged or even ignited under certain low magnitude impact scenarios such as during accidental drop or transportation. Since these materials are a heterogeneous system consisting of explosive grains within a polymer matrix binder, it is proposed that CNTs can be dispersed within the binder medium leading to an inherently piezoresistive hybrid nanocomposite bonded explosive material (NCBX) material which can then be monitored for a continuous assessment of deformation and damage within the material. To explore the potential use of CNT nanocomposites for this novel application, peridynamic simulations are carried out at the microscale level, first under quasistatic conditions and subsequently under dynamic conditions to allow the propagation of elastic waves. Peridynamics equations, which can be discretized to obtain a meshless method are particularly suited to this problem as the explicit modeling of crack initiation and propagation at the microscale is essential to understanding the properties of this material. Moreover, many other parameters such as electrical conductivity of the grain and the properties of the grain-binder interface are studied to understand their effect on the piezoresistive response of the material. For example, it is found that conductivity of the grain plays a major role in the piezoresistive response since it affects the preferential pathways of current density depending on the relative ease of flow through grain vs. binder. The results of this work are promising and are two fold. Peridynamics is found to be an effective method to model such materials, both at the nanoscale and the microscale. It alleviates some of difficulties faced by traditional finite element methods in the modeling of damage in materials and can be extended to coupled fields with relative ease. Secondly, simulations presented in this work show that there is much promise in this novel application of nanocomposites in the field of structural health monitoring of polymer bonded explosives. / Ph. D.

<div>Polymer bonded explosives (PBXs) consist of energetic material (EM) crystals embedded inside a polymeric binder. These are highly heterogeneous structures designed to explode under controlled conditions. However, accidental ignition of PBXs leading to deflagration, or even detonation, may take place due to non-shock stimulus such as low velocity impacts and vibration. Thus, assessing the safety of PBXs under non-shock stimulus is very important.</div><div><br></div><div>The ignition in PBXs depends on several microstructural features which include mechanical properties of EM particles and polymeric binder, as well as the adhesive properties of interface between EM particles and binder. It is also sensitive to initial defects in EM particles including cracks or voids. EM particle size distribution, distance between particles and their relative location are also shown to be affecting the ignition behavior of PBXs. This study focuses on PBX composition consisting of HMX as EM and Sylgard or HTPB as polymeric binder. Among several mechanisms of hot-spot formation, this study focuses on frictional heating at cracks or debonded surfaces.</div><div><br></div><div>Finite element simulations are performed on a domain containing a single EM particle embedded inside polymer binder under compressive and tensile loading at 10 m/s. The effect of the binder properties and the particle surface properties, on damage evolution and corresponding temperature rise due to frictional heat generation, is investigated. Two binders, Sylgard and HTPB, while two surface qualities for HMX particle, low and high, are compared. The adhesion strength of the particle-polymer interface is varied and damage evolution is qualitatively compared with experimental results to estimate interfacial energy release rate for HMX-Sylgard and HMX-HTPB interfaces. Simulations of two HMX particles inside Sylgard binder, subjected to vibration loading, are performed to analyze the effect of particle-particle distance and relative location of particles on the damage evolution and frictional heating in the particles.</div><div><br></div><div>The results of impact simulations show that the low surface quality HMX particle inside HTPB is likely to propagate cracks as compared to high surface quality particle. The HMX particle inside Sylgard shows crack propagation irrespective of particle surface quality. The impact simulations with the lower stiffness binder do not show a significant increase in temperature after impact. A polymer with higher stiffness induces more particle damage under impact contributing to a larger temperature rise. Furthermore, high quality surface and higher adhesion strength induces larger stresses and increase the temperature rise. The vibration simulations show that a small particle is less likely to damage when it is shielded by a large particle irrespective of its distance, within 40-200$\mu$m, from the large particle. However, the small particle is likely to damage when it is in parallel to the large particle with respect to loading. The temperature rise in the small particle is higher than the larger particle only in case of parallel configuration. The adhesion between the particles and the polymer has a direct effect on the formation of hot-spots due to friction and through local increase of compressive stresses that may cause a surge in heat generation.</div><div><br></div><div>The energetic materials often show anisotropy in elastic and crystalline properties. Fracture in HMX along the preferred cleavage plane is considered. Anisotropy in the elastic constants is also incorporated in the fracture model. The dependence of pressure on temperature is considered using Mie-Gruneisen equation of state which is shown to be important for damage evolution in HMX at impact velocity of 100 m/s.</div>

<p>The transformation of mechanical energy into thermal energy within composite energetic materials through various thermomechanical mechanisms is thought to lead to the creation of localized areas of intense heating. The growth of these “hot spots” is responsible for the bulk reaction or decomposition of the energetic material. Understanding the formation and growth of these hot spots has been an active area of research particularly for high-speed impact and shock conditions, but further work remains to be done in particular with respect to hot spot formation due to periodic mechanical excitation. Previous literature has established that many potential thermomechanical mechanisms may act at the interface between the constituent components of a composite energetic material. In order to provide further insight and guidance into the design of safer and more resilient energetic materials, the role of adhesion on hot spot formation for polymer bonded explosives (PBXs), a subset of composite energetic materials, was explored. Single HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazocane) crystals in polymer blocks were subjected to ultrasonic excitation and subsequent heating was captured via infrared thermography. Subsequent testing of HMX PBXs using a drop weight tower captured changes in the sensitivity of the energetic material. Variation of the polymer binder allowed for a range of adhesive and mechanical properties to be examined. These experiments on the role of adhesion under these kinds of excitations provided insight into how mechanical energy is being transformed into localized heating.</p>

<p>  </p> <p>Polymer bonded explosives (PBX) are a particle reinforced composite containing a high solids loading of explosive particulates bound in a polymer matrix. Commercially produced energetic particulates contain some percentage of flaws in the form of contaminants, porosity, and preexisting fractures. Additional large-scale porosity within the composite is generated during PBX formulation. The introduction of novel additive manufacturing techniques to the energetics field alters the known composite structure and introduces a porosity variable that has not been fully characterized. Porosity collapse during deformation is believed to be a predominant mechanism for hotspot formation, which dominates shock initiation behaviors. These phenomena are difficult to experimentally characterize due to inherent small spectral and temporal scales, and as such numerical and computational models are relied upon to inform fundamental physics. Experimental characterization of the behaviors of energetic materials during deformation is necessary to better inform computational studies and improve our understanding of hotspot formation mechanisms. </p> <p>This dissertation experimentally evaluates the high-rate deformation of porosity in individual explosive particulates and within the overall composite structure. This has included the development of a novel micromachining technique for pore generation in energetic single crystals using the focused ion beam (FIB), resulting in precise and controllable porosity generation that is easily reproducible in collaboration with computational studies. FIB was shown to be an effective pore generation technique, verified by assessing surface roughness and pore quality compared to contemporary manufacturing methods. Three experimental subsets are evaluated: surface cracks in HMX single crystals, polygonal pores in HMX single crystals, and large-scale porosity variations in mock vibration assisted print (VAP) produced composites of borosilicate glass beads and Sylgard 184® binder. A single stage light gas gun was used to impact the samples at 400 m/s and the impact event and resultant material response were observed in real time using x-ray phase contrast imaging (PCI). Machined surface cracks were shown to have negligible effect on the final fracture behaviors of HMX crystals. In polygonal pores fractures were shown to originate due to stress concentration during impact followed by otherwise expected brittle fracture behaviors. For wedge-like pores, the shockwave culminates on the front face of the pore and contributed to early fracture in some samples as well as a consistent open fracture opposite the impact along the shockwave direction in later stages of impact. For the blunt rectangular-like pores two differing behaviors were observed, wherein either the pore condensed and fracture at the pore was not seen during the impact event or large open fractures formed at the pore corners opposite the shockwave. The variance in response is attributed to the energy of fracture dissipating somewhere else in the material bulk, like the behaviors observed in the milled slot samples. Finally, additively manufactured PBX deformation behaviors were observed to be dominated by the collapse of the existing ordered porosity in the bulk which occurred at an increased rate relative to the bulk material compression. This resulted in a three-stage progression of deformation, consisting of a rapid collapse of large-scale ordered porosity, followed by the densification of the remaining features, and ultimately ending in compaction of the bulk as the impact projectile fully compressed the samples. Future work includes exploration of further FIB produced pore effects on dynamic fractures, evaluation of printed material deformation behaviors at additional rates, as well as application and evaluation of additional VAP printed material formulations.  </p>