Microstructural Differences between Virgin and Recycled Lots of PBX 9502

PBX 9502 is an insensitive high explosive formulated comprised of 95 wt% TATB and 5 wt% Kel‐F 800^TM binder. Due to the relatively high cost of manufacturing TATB (triaminotrinitrobenzene), methods for reclaiming TATB from PBX 9502 machine cuttings were previously developed. Reclaimed PBX 9502 was mixed with ~ 50% virgin PBX 9502 to produce “recycled” lots of PBX 9502. Several studies have shown significant differences between the mechanical properties of virgin and recycled lots of PBX 9502, and postulated that the differences were related to various aspects of TATB particle size and distribution. The purpose of this study is to show that these differences in mechanical properties are related to differences in the distribution of TATB within the microstructure of PBX 9502. Ultimately, a better understanding of these properties may lead to selected formulation changes for future rebuilds, Lifetime Extension Programs (LEP) and/or candidate replacements to enhance engineering and physics performance.     

Time‐Evolution of TATB‐Based Irreversible Thermal Expansion (Ratchet Growth)

TATB is an insensitive high explosive, attractive for use because of its safety aspects. TATB compactions, with or without binder, undergo irreversible volume expansion (or ratchet growth) upon thermal cycling. In the past, experimental elucidation of this phenomenon has focused on irreversible expansion as a function of the number of thermal excursions over a given temperature range, where growth is asymptotic with increasing cycle number. In this paper, we demonstrate that ratchet growth also occurs as a function of time at constant temperature, and that growth is substantial at elevated temperatures. We have measured strain response in PBX 9502, a TATB‐based composite, by performing thermal‐cycling tests with different durations at high temperature. Irreversible growth arises from the thermal ramps themselves (increasing and decreasing), as well as from the subsequent isotherms. PBX 9502 specimens with previously‐identified TATB texture/orientation were used in order to eliminate and/or evaluate texture as a variable. Measurements were also performed on dry‐pressed TATB (no binder) to confirm that expansion as a function of time (constant temperature) is not caused by the binder. A simple analysis of the time‐response data demonstrates consistency in the results. We propose that the primary driving force for irreversible expansion is the proximity of the current strain value (due to thermal history) to the strain saturation point of the current cycle (i.e. strain at infinite high‐temperature hold times or an infinite number of cycles). Such tests should aid in the understanding and modeling of ratchet growth response in these materials.     

Highly Thermal Stable TATB‐based Aluminized Explosives Realizing Optimized Balance between Thermal Stability and Detonation Performance

In this work, a series of TATB‐based aluminized explosives were formulated from 1, 3, 5‐triamino‐2, 4, 6‐trinitrobenzene (TATB), aluminum powders and polymeric binders. The thermal stability, heat of detonation, detonation velocity and pressure of the TATB based aluminized (TATB/Al) explosives were systematically investigated by cook‐off, constant temperature calorimeter, electrometric method and manganin piezo resistance gauge, respectively. The selected PBX‐3 (70 wt% TATB/25 wt% Al/5 wt% fluorine resin) achieved optimized balance between thermal stability and detonation performance, with the thermal runaway temperature around 583 K. The thermal ignition of TATB‐based aluminized explosive occurred at the edge of the cylinder according to the experimental and numerical simulations. Moreover, the critical thermal runaway temperature for PBX‐3 was calculated based on the Semenov's thermal explosion theory and the thermal decomposition kinetic parameters of the explosive, which was consistent with the experimental value.     

Effect of Crystal Quality and Particle Size of HMX on the Creep Resistance for TATB/HMX Composites

Two kinds of reduced sensitivity high explosive 1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocane (RS‐HMX) with different particle sizes were selected to enhance the energy output and the mechanical properties of insensitive high explosive 1,3,5‐triamino‐2,4,6‐trinitrobenzene (TATB). Mechanical sensitivities, dynamic mechanical analysis, and non‐linear time dependent creep behaviors of TATB/HMX composites were investigated and discussed in relation to the structural characteristics. Compared with TATB/conventional HMX (C‐HMX) sample, both the impact and friction sensitivities of TATB/RS‐HMX were reduced. It revealed that TATB/fine grains RS‐HMX composites had the highest storage modulus and minimum steady‐state creep strain rate due to the increased coherence strength and the inhibited slide of the single layer of TATB crystal. The creep resistance also showed clear dependence on the particle size of RS‐HMX. The overall results indicated that RS‐HMX had good potential in high energetic, safe, and load‐bearing material applications.     

Effect of the comonomer content on the solid‐state mechanical and viscoelastic properties of poly(propylene‐co‐1‐butene) films

In this study, we quantified the thermal and solid‐state mechanical and viscoelastic properties of isotactic polypropylene (i‐PP) homopolymer and poly(propylene‐1‐butene) copolymer films having a 1‐butene ratio of 8, 12, and 14 wt %, depending on the comonomer content. The uniaxial tensile creep and stress‐relaxation behaviors of the samples were studied in a dynamic mechanical analyzer at different temperatures. The creep behaviors of the samples were modeled with the four‐element Burger equation, and the long‐term creep strains were predicted with the time–temperature superposition method. The short‐term mechanical properties of the samples were also determined with tensile and impact testing at room temperature. We found that the Young's modulus and ultimate strength values of the samples decreased with increasing amount of 1‐butene in the copolymer structure. On the other hand, the strain at break and impact strength values of the samples improved with increasing amount of 1‐butene. Creep analysis showed that i‐PP exhibited a relatively lower creep strain than the poly(propylene‐co‐1‐butene)s at 30 °C. However, interestingly, we discovered that the temperature increase resulted in different effects on the creep behaviors. We also found that short‐chain branching improved the creep resistance of polypropylene at relatively high temperatures. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46350.     

The Microstructure of TATB‐Based Explosive Formulations During Temperature Cycling Using Ultra‐Small‐Angle X‐Ray Scattering

TATB (1,3,5 triamino‐2,4,6‐trinitrobenzene), an extremely insensitive explosive, is used both in polymer‐bound explosives (PBXs) and as an ultra‐fine pressed powder (UFTATB). Many TATB‐based explosives, including LX‐17, a mixture of TATB and Kel‐F 800 binder, experience an irreversible expansion with temperature cycling known as ratchet growth. Additional voids, with sizes hundreds of nanometers to a few micrometers, account for much of the volume expansion. Measuring these voids is important feedback for hot‐spot theory and for determining the relationship between void size distributions and detonation properties. Also, understanding mechanisms for ratchet growth allows future choice of explosive/binder mixtures to minimize these types of changes, further extending PBX shelf life. This paper presents the void size distributions of LX‐17, UFTATB, and PBXs using commercially available Cytop M, Cytop A, and Hyflon AD60 binders during temperature cycling between −55 and 70 °C. These void size distributions are derived from ultra‐small‐angle X‐ray scattering (USAXS), a technique sensitive to structures from about 2 nm to about 2 μm. Structures with these sizes do not appreciably change in UFTATB. Compared to TATB/Kel‐F 800, Cytop M and Cytop A show relatively small increases in void volume from 0.9 to 1.3% and 0.6 to 1.1%, respectively, while Hyflon fails to prevent irreversible volume expansion (1.2–4.6%). Computational mesoscale models combined with experimental results indicate both high glass transition temperature as well as TATB binder adhesion and wetting are important to minimize ratchet growth.     

Changes in Pore Size Distribution upon Thermal Cycling of TATB‐based Explosives Measured by Ultra‐Small Angle X‐Ray Scattering

Hot‐spot models of initiation and detonation show that voids or porosity ranging from nanometer to micrometer in size within highly insensitive energetic materials affect initiability and detonation properties. Thus, the knowledge of the void size distribution, and how it changes with the volume expansion seen with temperature cycling, are important to understanding the properties of the insensitive explosive 1,3,5‐triamino‐2,4,6‐trinitrobenzene (TATB). In this paper, void size distributions in the 2 nm to 2 μm regime, obtained from small‐angle X‐ray scattering measurements, are presented for LX‐17‐1, PBX‐9502, and ultra‐fine TATB formulations, both as processed and after thermal cycling. Two peaks were observed in the void size distribution: a narrow peak between 7–10 nm and a broad peak between 20 nm and about 1 mm. The first peak was attributed to porosity intrinsic to the TATB crystallites. The larger pores were believed to be intercrystalline, a result of incomplete consolidation during processing and pressing. After thermal cycling, these specimens showed an increase in both the number and size of these larger pores. These results illuminate the nature of the void distributions in these TATB‐based explosives from 2 nm to 2 μm and provide empirical experimental input for computational models of initiation and detonation.     

Augmenting the performance of acrylonitrile–butadiene–styrene plastics for low‐noise dynamic applications

The main objective of this study was to enhance the performance of acrylonitrile–butadiene–styrene (ABS) plastics for dynamic structural applications, including those of automobile relevance. First, ABS was modified by blending with maleic anhydride grafted styrene–ethylene–butadiene–styrene block copolymer (MA‐g‐SEBS) in various proportions. Squeaking noise characteristics were evaluated by measurement of the frictional behavior in an in‐house fabricated friction testing apparatus, and the results are explained on the basis of the change in surface energy upon modification. Detailed dynamic mechanical analyses (strain, frequency, and temperature sweep) revealed significant improvements in the damping characteristics of the modified ABS, especially that modified with 10 wt % MA‐g‐SEBS, without much sacrifice in its mechanical strength. The modulus values predicted with Kerner's model of the blends were well correlated with the morphological changes upon modification. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Improving the aging resistance of styrene‐butadiene‐styrene tri‐block copolymer and application in polymer‐modified asphalt

Thermal oxidation process of styrene‐butadiene‐styrene (SBS) copolymer was studied by using a variety of analytical and spectroscopic methods including thermal analysis, dynamic mechanical analysis and FTIR spectroscopy. The experimental results indicate that the thermal oxidation process of SBS is a free radical self‐catalyzed reaction containing four steps (initiation, growth, transfer, and termination of the chain) with both crosslinking and scission and the latter is confirmed to be the main process. The antioxidants 1010 as scavenger of free radicals and 168 acting decomposition of hydroperoxides were used to improve the oxidation aging resistance of SBS copolymer. It has been found that synergic effect of 1010 and 168 may be the best in practice and 0.2 wt % 1010 + 0.4 wt % 168 can effectively prevent SBS from the thermal oxidation at certain temperature. Furthermore, the aging resistance of the SBS‐modified asphalt was improved by addition of complex antioxidants. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Replication of sub‐micron features using amorphous thermoplastics

A comprehensive experimental study was carried out to replicate sub‐micron features using the injection molding technique. For the experiments, five different plastic materials were selected according to their flow properties. The materials were polycarbonate (PC), styrene‐butadiene block copolymer (SBS), impact modified poly(methyl methacrylate), methyl methacrylate‐acrylonitrile‐butadiene‐styrene polymer (MABS), and cyclic olefin copolymer (COC). Nanofeatures down to 200‐nm line width and with aspect ratios (aspect ratio = depth/width) of 1:1 could be replicated. In all selected materials, the greatest differences between the materials emerged when the aspect ratio increased to 2:1. The most favorable results were obtained with the use of high flow polycarbonate as the molding material. The best replication results were achieved when melt and mold temperatures were higher than normal values.     

High‐performance waterborne coatings based on epoxy‐acrylic‐graft‐copolymer‐modified polyurethane dispersions

Polyurethane dispersions (PUDs) have been an active area of research since the early 1940s because of legislative restrictions on the use of organic solvents in conventional solvent‐based products and also because PUDs exhibit almost the same high performance levels as solvent‐borne polyurethanes. In the present study, properties of conventional waterborne PUDs are modified with epoxy‐acrylic graft copolymer blocks. The epoxy‐acrylic graft copolymers were first modified with ethylene diamine to give amine‐terminated blocks which in turn reacted with isocyanate‐terminated prepolymer (prepolymer mixing process) to give modified PUDs. Several experimental sets were prepared with varying compositions. The experimental sets were also prepared using conventional poly(ethylene glycol) blocks and ethylene diamine chain‐extenders. The physico‐chemical properties and film characteristics of the experimental sets show the dramatic improvement in important mechanical properties of PUDs due to grafting with epoxy‐acrylic copolymer blocks. Copyright © 2004 Society of Chemical Industry     

Blends of poly(2,6‐dimethyl‐1,4‐phenylene oxide)/polyamide 6 toughened by maleated polystyrene‐based copolymers: Mechanical properties,morphology, and rheology

Poly(2,6‐dimethyl‐1,4‐phenylene oxide)/polyamide 6 (PPO/PA6 30/70) blends were impact modified by addition of three kinds of maleated polystyrene‐based copolymers, i.e., maleated styrene‐ethylene‐butylene‐styrene copolymer (SEBS‐g‐MA), maleated methyl methacrylate‐butadiene‐styrene copolymer (MBS‐g‐MA), and maleated acrylonitrile‐butadiene‐styrene copolymer (ABS‐g‐MA). The mechanical properties, morphology and rheological behavior of the impact modified PPO/PA6 blends were investigated. The selective location of the maleated copolymers in one phase or at interface accounted for the different toughening effects of the maleated copolymer, which is closely related to their molecular structure and composition. SEBS‐g‐MA was uniformly dispersed in PPO phase and greatly toughened PPO/PA6 blends even at low temperature. MBS‐g‐MA particles were mainly dispersed in the PA6 phase and around the PPO phase, resulting in a significant enhancement of the notched Izod impact strength of PPO/PA6 blends from 45 J/m to 281 J/m at the MBS‐g‐MA content of 20 phr. In comparison, the ABS‐g‐MA was mainly dispersed in PA6 phase without much influencing the original mechanical properties of the PPO/PA6 blend. The different molecule structure and selective location of the maleated copolymers in the blends were reflected by the change of rheological behavior as well. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Magnetite‐functionalized graphene/poly(styrene‐butadiene‐styrene) composites: thermal and mechanical properties

Advanced polymer composites containing organic–inorganic fillers are gaining increasing attention due to their multifunctional applications. In this work, poly(styrene‐butadiene‐styrene) (SBS) composites containing magnetite‐functionalized graphene (FG) were prepared by a dissolution ? dispersion ? precipitation solution method. Evidently, through morphology studies, amounts of FG were well distributed in the SBS matrix. Improvements in neat SBS properties with respect to FG loading in terms of thermal stability, creep recovery and mechanical properties are presented. As expected, the addition of FG improved the thermal stability and mechanical properties of the composites. The yield strength and Young's modulus of the SBS increased by 66% and 146% at 5 wt% filler loading which can be attributed to the reinforcing nature of FG. Similarly, an increase in the storage and loss modulus of the composites showed a reinforcement effect of the filler even at low concentration. The results also showed the significant role of FG in improving the creep and recovery performance of the SBS copolymer. Creep deformation decreased with filler loading but increased with temperature. © 2017 Society of Chemical Industry     

Blends of bisphenol A polycarbonate and rubber‐toughened styrene–maleic anhydride copolymers

The morphology and mechanical properties of polycarbonate (PC) blends with rubber‐toughened styrene–maleic anhydride copolymer materials (TSMA) were investigated and compared with the properties of blends of PC with acrylonitrile–butadiene–styrene (ABS) materials. The PC/TSMA blends showed similar composition dependence of properties as the comparable PC/ABS blends. Polycarbonate blends with TSMA exhibited higher notched Izod impact toughness than pure PC under sharp‐notched conditions but the improvements are somewhat less than observed for similar blends with ABS. Since PC is known for its impact toughness except under sharp‐notched conditions, this represents a significant advantage of the rubber‐modified blends. PC blends with styrene–maleic anhydride copolymer (SMA) were compared to those with a styrene–acrylonitrile copolymer (SAN). The trends in blend morphology and mechanical properties were found to be qualitatively similar for the two types of copolymers. PC/SMA blends are nearly transparent or slightly pearlescent. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1508–1515, 1999     

Neutron Diffraction Measurements and Micromechanical Modelling of Temperature‐Dependent Variations in TATB Lattice Parameters

Triaminotrinitrobenzene (TATB) is a highly anisotropic molecular crystal used in several plastic‐bonded explosive (PBX) formulations. TATB‐based explosives exhibit irreversible volume expansion (“ratchet growth”) when thermally cycled. A theoretical understanding of the relationship between anisotropy of the crystal, crystal orientation distribution (texture) of polycrystalline aggregates, and the intergranular interactions leading to this irreversible growth is necessary to accurately develop physics‐based predictive models for TATB‐based PBXs under various thermal environments. In this work, TATB lattice parameters were measured using neutron diffraction during thermal cycling of loose powder and a pressed pellet. The measured lattice parameters help clarify conflicting reports in the literature as these new results are more consistent with one set of previous results than another. The lattice parameters of pressed TATB were also measured as a function of temperature, showing some differences from the powder. This data is used along with anisotropic single‐crystal stiffness moduli reported in the literature to model the nominal stresses associated with intergranular constraints during thermal expansion. The texture of both specimens were characterized and the pressed pellet exhibits preferential orientation of (001) poles along the pressing direction, whereas no preferred orientation was found for the loose powder. Finally, thermal strains for single‐crystal TATB computed from lattice parameter data for the powder is input to a self‐consistent micromechanical model, which predicts the lattice parameters of the constrained TATB crystals within the pellet. The agreement of these model results with the diffraction data obtained from the pellet is discussed along with future directions of research.     

Toughening study of fire‐retardant high‐impact polystyrene

Fire‐retardant high‐impact polystyrene (HIPS) was modified by melt blending with varying amounts of three types of tougheners. The effects of the tougheners on the properties of the fire‐retardant HIPS were studied by mechanical, combustion tests, and thermogravimetric analysis. The morphologies of fracture surfaces and char layers were characterized through scanning electron microscopy. The results show that the impact properties of styrene–butadiene–styrene (SBS)‐containing composites were better than those of ethylene–propylene–diene monomer (EPDM)‐containing or ethylene–vinyl acetate copolymer (EVA)‐containing composites. The tensile strength and flexural modulus of the fire‐retardant HIPS decreased evidently with the addition of tougheners. It is found that the compatibility between SBS copolymer and HIPS matrix was best among the three types of tougheners. The addition of SBS had little influence on the thermal property, residue, flammability, and morphology of char layer of the fire‐retardant HIPS, but the addition of EPDM rubber or EVA brought adverse influence on the residue, flammability, and morphology of char layer of the fire‐retardant HIPS, especially for EPDM. Copyright © 2009 John Wiley & Sons, Ltd.     

Structural Defect Evolution of TATB‐Based Compounds Induced by Processing Operations and Thermal Treatments

2,4,6‐Triamino‐1,3,5‐trinitrobenzene (TATB) compounds are commonly used in high performance explosives because of their thermal stability and high detonation velocities compared to other materials. The insensitivity and mechanical properties are related to the stability of their crystalline structure. Crystallographic structure and structural defects evolution of TATB and TATB‐based compounds were studied by X‐ray diffraction for powders, molding powders, and pressed compounds, using Rietveld refinement. The effects of synthesis conditions, thermal treatments, coating and pressing operations on the structure of TATB compounds were evaluated. The results show that the pressing operation results in anisotropic crystallite size, leading to an increase of the structural defects density. It could be due to the anisotropic mechanical response of the TATB crystal under pressure, possibly plasticity. Finally, it is shown that increasing thermal treatment temperature on TATB powders decreases the structural defects density.     

Oblique Impacts and Friction of HMX and/or TATB‐based PBXs

Transportation, handling, vibrations can lead to dynamic loadings requiring the characterization of the safety of plastic‐bonded explosives (PBX). One of the addressed situations is the fall of explosive on a surface. Knowing that initiation can occur at a lower height during a vertical fall of a projectile on an inclined target than on a horizontal one, devices were developed to determine the critical thresholds. In this paper, data obtained on four HMX and/or TATB‐based PBXs using pendulum drop configurations are detailed. Two analytical models are compared to estimate the heat released by friction at the interface. The model proposed in this paper yields the better agreement with data, and with finite element numerical simulations of the oblique impact on a given PBX. Lastly, the mechanical dissipation at the interface is estimated using this model and the simulations. This paper confirms that PBX/target friction cannot be the heating mechanism leading to initiation during oblique impacts.     

Preparation and properties of PC/SAN alloy modified with styrene‐ethylene‐butylene‐styrene block copolymer

A polycarbonate (PC)/ poly (styrene‐co‐acrylonitrile) (SAN) alloy modified with styrene‐ethylene‐butylene‐styrene (SEBS) block copolymer was prepared and the influence of SEBS content, PC content, and types of modifier on Izod notched impact strength, tensile strength, flexural strength, and Vicat softening temperature was studied. The results showed that the addition of SEBS could obviously increase the Izod notched impact strength and the elongation at break and decrease the tensile and flexural strength and Vicat softening temperature. PC/SAN alloy modified with SEBS had better mechanical properties than the PC/SAN alloy modified with ABS. DSC analysis and SEM photographs revealed that the SEBS was not only distributed in the SAN phase but also distributed in PC phase in a PC/SAN/SEBS alloy while the ABS was mainly distributed in SAN phase in a PC/SAN/ABS alloy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Influences of compatibilizers on rheology and mechanical properties of propylene random copolymer/styrene‐ethylene‐butylene‐styrene block copolymer/organic‐montmorillonite nanocomposites

Propylene random copolymer (PPR)/styrene‐ethylene‐butylene‐styrene block copolymer (SEBS)/compatibilizer/organic‐montmorillonite (OMMT) quaternary nanocomposites and PPR/compatibilizer/OMMT ternary nanocomposites were prepared via two‐stage melt blending and influences of compatibilizers, maleic anhydride (MA) grafted styrene‐ethylene‐butylene‐styrene copolymer (SEBS‐g‐MA), poly(octene‐co‐ethylene) (POE‐g‐MA), or propylene block copolymers (PPB‐g‐MA), on rheology and mechanical properties of the nanocomposites were investigated. The results of X‐ray diffraction measurement and transmission electron microscopy observation showed that OMMT layers were mainly intercalated in the nanocomposites except for the mainly exfoliated structure in the quaternary nanocomposites using POE‐g‐MA as compatibilizer. The nanocomposites exhibited pseudo‐solid like viscoelasticity in low frequencies and shear‐thinning in high shear rates. As far as OMMT dispersion was concerned, POE‐g‐MA was superior to SEBS‐g‐MA and PPB‐g‐MA, which gives rise to the highest viscosities in both the ternary and quaternary nanocomposites. The quaternary nanocomposites containing POE‐g‐MA were endowed with balanced toughness and rigidity. It was suggested that a suitable combination of compatibilizer and SEBS was an essentially important factor for adjusting the OMMT dispersion and distribution, the rheological and mechanical performances of the nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013