Investigating the Mechanical Properties of RDX Crystals Using Nano‐Indentation

The shock sensitivity of RDX is of major interest for the development of insensitive munitions. Previous research has implied that internal defects that form within RDX crystals have a strong sensitising effect, increasing the probability of shock initiation. During the NATO Reduced sensitivity RDX Round Robin (R⁴) program the number of internal defects within RDX crystals of differing qualities were assessed by optical microscopy and a scoring system. The results suggested that RDX crystals with many internal defects were more sensitive. Studies investigating the mechanical properties of bulk RDX have shown that lots consisting of poorer crystals are weaker. This study investigates the mechanical properties of individual crystals from different RDX lots using nano‐indentation. It is shown that crystals with many internal defects have reduced modulus of elasticity, stiffness and prone to greater deformation under applied load. The results also show a correlation between these parameters and previously reported shock sensitivity data.     

Characterization of Granular and Polymer‐Embedded RDX Grades: Floret Tests

In an attempt to further contribute to the characterization of explosive compositions, small scale Floret tests were performed using four RDX grades, differing in product quality. A Floret test provides a measure – by indentation of a copper block – of detonation spreading or the initiability and shock wave divergence and is applied in particular to explosives used in initiation trains. Both as‐received RDX and PBXs (based on the AFX‐757 composition, a hard target penetrator explosive) containing these RDX grades were tested in the Floret test set‐up. It was found that the Floret test method, when applied to granular, as‐received RDX, was not able to discriminate between the overall RDX product qualities on the basis of the resulting volume of the indentation in the copper block. For the Floret test data of the PBX samples, a division into two parts, where one of the RDX lots shows a lower dent volume compared to the other RDX lots tested. Based on the results presented in this paper with granular RDX and a PBX composition and earlier results with a different type of PBX (based on PBXN‐109, an insensitive high explosive used in a wide range of munitions), the Floret test could be developed into a screening test for shock sensitivity and product quality, without the need for complex and large volume casting of specific PBX compositions.     

Quantitative Characterization of Internal Defects in RDX Crystals

Size, shape, internal defects are very important properties of explosives crystals. These parameters play a role on both the explosive formulation processing and the detonic behavior of the explosive formulations. The use of explosive crystals free of solvent inclusions leads to decrease the shock sensitivity of cast explosive formulations. Many efforts for processing such high quality explosive crystals have been done and are still in progress. Qualitative observations of internal crystal defects can be performed by optical microscopy with matching refractive index. The purpose of this paper is to provide two accurate quantitative tools for internal crystal defects measurements. The first method is based on accurate measurements of the crystal apparent density. The second method records the mass of the species entrapped in the crystal internal cavities. Experiments are performed on two RDX batches. The strong correlation recorded between the results of the two complementary methods validates the measurements. Apparent density measurements provide an accurate global characterization of the internal defects population of a crystal batch sorting the crystals in function of their apparent density. The second method is a tool to identify the species entrapped in the crystals.     

Reduced Sensitivity RDX Obtained From Bachmann RDX

In recent years much interest has been generated in a quality of reduced sensitivity RDX (RS‐RDX), like I‐RDX^® which, when incorporated in cast cure and even pressable plastic bonded explosives (PBX compositions), can confer reduced shock sensitivity as measured through gap test. At crystal level, lot of work has been done to try to determine which property or properties may explain the behaviour of the corresponding cast PBX composition. But up to now, and despite an international inter‐laboratory comparison (Round Robin) of seven lots of RDX from five different manufacturers conducted from 2003 to 2005, even if some techniques lead to interesting results, there is no dedicated specification to apply to RS‐RDX. This quality (I‐RDX^®) has proved to retain its low sensitivity even after ageing, which does not seem to be the case for standard RDX produced by the Bachmann process (when re‐crystallized under I‐RDX conditions in order to obtain RS‐RDX). It has been shown that the higher sensitivity of RDX produced by the Bachmann process, or the evolution of sensitivity after ageing of RS‐RDX produced from Bachmann RDX may be linked to the presence of octogen (HMX) during the crystallization process. In order to check such hypothesis, low HMX content RDX produced by the Bachmann process has been prepared and evaluated in cast PBX composition (PBX N 109). Results of the characterization of such quality of RDX and its evaluation in cast PBX composition as well as ageing behaviour are presented and discussed; there are indications that removal of HMX from Bachmann RDX may lead to RS‐RDX, which retains its RS character even after ageing.     

Investigation of Crystal Morphology and Shock Sensitivity of Cyclotrimethylenetrinitramine Suspension by Rheology

Crystal morphology and shock sensitivity of a series of cyclotrimethylenetrinitramine (RDX) particles suspended from ethylene glycol were investigated. Flow rheology was employed to measure the rheological properties of the suspensions at constant temperature; it was observed that the stress‐shear rate and viscosity behavior of the suspensions were controlled by the particle morphology. The viscosity of the RDX suspensions changed with the roundness/smoothness of RDX crystals at all applied shear rates. The suspensions containing crystals with smoother morphology showed reduced viscosity. When the viscosity data was compared to the shock sensitivity results from the RS‐RDX Round Robin study, a good correlation was obtained. This study has validated the use of flow rheology to indicate the morphology and shock sensitivity of crystalline particles.     

RDX and HMX with Reduced Sensitivity Towards Shock Initiation–RS‐RDX and RS‐HMX

Reduced Sensitivity RDX (RS‐RDX) has received a lot of attention and interest from the explosive community in the recent years. There are several producers of RS‐RDX, most of them using a direct nitration (Woolwich process) for the RDX synthesis, while Chemring Nobel uses the Bachmann process. The processes for obtaining the RS properties probably differ between the various producers. Chemring Nobel has also developed an HMX quality that shows Reduced Sensitivity (RS‐HMX) of different particle size distributions. The shock sensitivity is at the same level as for RS‐RDX in comparable compositions. Reduced shock sensitivity has been obtained for RS‐RDX and Reduced Sensitivity (RS‐HMX) in both pressable and cast‐cured compositions. By using a pressable composition, it is possible to get the results from a BICT gap test faster than from a cast‐cured composition that has to go through a curing process. Chemring Nobel in cooperation with FFI have performed an extensive accelerated ageing testing of RS‐RDX produced by the Bachmann process. The samples have been aged at 60 and 70 °C and the shock sensitivity tested by two different gap tests. The results demonstrate that the Chemring Nobel RS‐RDX retain the insensitivity towards shock during ageing and show no degradation at all. Accelerated ageing testing of RS‐HMX has also been performed and shows no degradation in the shock sensitivity.     

Confocal Scanning Laser Microscopic Study of the RDX Defect Structure in Deformed Polymer‐Bonded Explosives

The influence of an explosion‐driven deformation on the defect structure in RDX crystals embedded in a polymer‐bonded explosive was investigated by means of confocal scanning laser microscopy. The images were compared to the defect structure in the as‐received RDX grades, embedded in an epoxy resin. In this way it is possible to qualitatively analyze the changes in defect structure of the RDX crystals that were induced by the explosion‐driven deformation. For the first time, these data therefore provide experimental confirmation of how shock waves mechanically interact with energetic crystals – a topic that, up to now, was only explored by means of simulations.     

The Effect of RDX Crystal Defect Structure on Mechanical Response of a Polymer‐Bonded Explosive

An explosive composition, derived from AFX‐757, was systematically varied by using three different qualities of Class I RDX. The effect of internal defect structure of the RDX crystal on the shock sensitivity of a polymer bonded explosive is generally accepted (Doherty and Watt, 2008). Here the response to a mechanical non‐shock stimulus is studied using an explosion‐driven deformation test as well as the ballistic impact chamber. No correlation between RDX crystal quality and deformation sensitivity is observed. The DDT behavior (Deflagration to Detonation Transition) of the three plastic bonded explosives, although similar in composition, is distinct regarding the rate of diameter increase in the explosion‐driven deformation test. Recovered polymer bonded explosive from the explosion‐driven deformation test responds equally fast or slower in the ballistic impact chamber. Based on our experimental results the shear rate threshold as a single parameter describing mechanical sensitivity is challenged, and preference is given to the development of an ignition criterion based on inter‐granular sliding friction under the action of a normal pressure.     

On the Reliability of Sensitivity Test Methods for Submicrometer‐Sized RDX and HMX Particles

Submicrometer‐sized RDX and HMX crystals were produced by electrospray crystallization and submicrometer‐sized RDX crystals were produced by plasma‐assisted crystallization. Impact and friction sensitivity tests and ballistic impact chamber tests were performed to determine the product sensitivity. Rather than reflecting the quality of the particles, we found the sensitivity tests to be unreliable for submicrometer particles. The used impact test was not accurate enough, while in the friction and ballistic impact chamber tests the submicrometer‐sized crystals were distributed among the grooves of the porcelain plate or among the grains of the sandpaper used in these tests. These observations stress the need for revisiting the current standards used for determining the hazardous properties like friction and impact sensitivity of energetic materials in the case, where the sample consists of submicrometer‐sized crystals. Recommendations were suggested to develop new test methods that only use the interactions between the particles and therefore allow the application of sensitivity tests for submicrometer/nano‐sized energetic materials.     

Effects of Additives on ε‐HNIW Crystal Morphology and Impact Sensitivity

Crystals of γ‐HNIW were transformed into crystals of ε‐HNIW by application of a drowning‐out process in the presence of different additives, namely ethylene glycol, triacetin, and aminoacetic acid. They show different effects on the crystal morphology of ε‐HNIW and cause less angular and more regular structures. Investigation of the sensitivities of the different ε‐HNIW crystals shows that their angles and regularity have an influence on the impact sensitivity. Aminoacetic acid selectively inhibits the growth of individual ε‐HNIW crystal faces to modify the morphology into spherical shape, these ε‐HNIW crystals are of much lower sensitivity, even compared with general RDX and HMX explosives.     

Shock Sensitivity of Pressed RDX‐Based Plastic Bonded Explosives under Short‐Duration and High‐Pressure Impact Tests

The shock sensitivities of plastic bonded explosives were studied with a thin flyer impact test by using two types of pressed RDX. The thin flyer, driven by an electrically exploding plasma, exerts a short‐duration, high‐pressure pulse to the samples to trigger a shock‐to‐detonation process. It was found that the duration and magnitude of the incident shock strongly influence the dominant mode of hot‐spot formation, promoting a fast pore collapsing mechanism while suppressing other slower shear or friction mechanisms, as proposed by Chakravarty et al. [1]. The pressed PBX based on reduced sensitivity RDX had higher shock threshold pressure, compared to the pressed PBX based on commercial RDX. The difference was observed even with a certain portion of external extragranular defects. It is postulated that the internal crystal defects are more efficient than the external porosity in terms of the rapid reaction of hot spots.     

Reduced Sensitivity RDX (RS‐RDX) in Pressed Formulations: Respective Effects of Intra‐Granular Pores,Extra‐Granular Pores and Pore Sizes

Reduced sensitivity RDX (RS‐RDX) particles are now available from several manufacturers. But a clear understanding of this reduced sensitivity behavior is not yet available. RS‐RDX particles are usually employed in cast formulations to reduce their shock sensitivity. The use of RS‐RDX in pressed formulations is more recent and does not always give reduced sensitivity formulations.     

Relationship Between RDX Properties and Sensitivity

An interlaboratory comparison of seven lots of commercially available RDX was conducted to determine what properties of the nitramine particles can be used to assess whether the RDX has relatively high or relatively low sensitivity. The materials chosen for the study were selected to give a range of HMX content, manufacturing process and reported shock sensitivity. The results of two different shock sensitivity tests conducted on a PBX made with the RDX lots in the study showed that there are measurable differences in the shock sensitivity of the PBXs, but the impact sensitivity for all of the lots is essentially the same. Impact sensitivity is not a good predictor of shock sensitivity for these types of RDX. Although most RDX that exhibits RS has low HMX content, that characteristic alone is not sufficient to guarantee low sensitivity. A range of additional analytical chemistry tests were conducted on the material; two of these (HPLC and DSC) are discussed within.     

重结晶降低RDX感度研究

采用N-甲基吡咯烷酮、二甲基甲酰胺、二甲基亚砜作溶剂,对普通RDX进行重结晶.研究了不同溶剂对RDX晶体形貌、晶体内空穴、位错、残存溶剂的影响,通过扫描电镜和光学显微镜,分析了重结晶RDX晶体的结晶形貌和内部质量,用密度瓶法测试了晶体密度,用10kg落锤测定了撞击感度.结果表明,用二甲基亚砜重结晶制备的RDX有较好的晶体质量,撞击感度最低(54%),晶体密度达1.823g/cm3.     

Production and Sensitivity Evaluation of Nanocrystalline RDX‐based Explosive Compositions

The initiation sensitivity of cyclotrimethylenetrinitramine (RDX) was investigated as a function of crystal size. For this study, RDX powders with mean crystal sizes of ca. 200 and 500 nm were prepared by rapid expansion of supercritical solutions (RESS) with carbon dioxide as the solvent. Initiation sensitivity testing to impact, sustained shock, and electrostatic discharge stimuli was performed on uncoated as well as wax‐coated specimens. The test data revealed that in a direct comparison to coarser grades the nanocrystalline RDX‐based samples were substantially less sensitive to shock and impact stimuli. Furthermore, the 500 nm RDX‐based specimens exhibited the lowest sensitivity values, an indication that minima in shock and impact sensitivities with respect to crystal size exist.     

改性黑索今装药的起爆规律研究

为了研究钝化RDX（黑索今）装药对冲击波响应剧烈程度的变化规律,在改变钝化RDX装药的密度,装药的轴向间隙和径向间隙后,用改进的小隔板实验装置进行测定。结果表明：冲击波响应剧烈程度随着装药密度的增大而增大;在钝化黑索今药装药结构中,轴向间隙和径向间隙都会在不同程度上降低冲击波响应的剧烈程度。     

Research on the Size of Defects inside RDX/HMX Crystal and Shock Sensitivity

Intragranular defects inside RDX/HMX were studied by optical microscopy with matching refractive (OMS), sink‐float method (SFM), and micro‐focus CT (μCT) techniques. OMS results revealed the phenomenon that RDX/HMX had more defects and cracks than RS‐RDX/RS‐HMX. μCT results indicated that RDX/HMX had more defects with larger volume than RS‐RDX/RS‐HMX. The gap test showed that critical shock pressure/gap thickness was 6.4 GPa/19.4 mm for PBX based on RDX, while they were 7.5 GPa/17.5 mm and 8.6 GPa/16.2 mm for PBX based on M‐RDX and RS‐RDX, respectively. Meanwhile, an analysis of the relationship between defects inside RDX/HMX crystal and shock sensitivity was made. Finally, the shock pressure response under impact loading was investigated by discrete element method.     

CL‐20 Evaporative Crystallization under Reduced Pressure

The effect of parameters of the CL‐20 crystallization process carried out by solvent removal by evaporation in vacuo on shape, polymorph type, crystal size, and on their shock sensitivity was studied. The CL‐20 crystallization process by this technique was shown to allow a precise control of the crystallization process parameters and of the process run. The o‐xylene/ ethyl acetate system proved to be highly effective. Selecting suitable values of the parameters such as: pressure, process time, temperature, stirring rate, CL‐20 crystals were obtained in the ε form (even with no need for inoculation of the crystallization system with polymorph ε seeds) and of the shape close to a spherical one. The crystal growth modifiers added allowed to additionally control the shape and size of the CL‐20 crystals formed and to produce crystals of reduced impact and friction sensitivity.     

Energetic Materials: Crystallization,Characterization and Insensitive Plastic Bonded Explosives

The product quality of energetic materials is predominantly determined by the crystallization process applied to produce these materials. It has been demonstrated in the past that the higher the product quality of the solid energetic ingredients, the less sensitive a plastic bonded explosive containing these energetic materials becomes. The application of submicron or nanometric energetic materials is generally considered to further decrease the sensitiveness of explosives. In order to assess the product quality of energetic materials, a range of analytical techniques is available. Recent attempts within the Reduced‐sensitivity RDX Round Robin (R4) have provided the EM community a better insight into these analytical techniques and in some cases a correlation between product quality and shock initiation of plastic bonded explosives containing (RS‐)RDX was identified, which would provide a possibility to discriminate between conventional and reduced sensitivity grades.