Laser‐Induced Deflagration of Unconfined HMX – The Effect of Energetic Binders

The effect of three energetic binders [poly(3‐methyl‐3‐nitratomethyloxetane (polyNIMMO), polyglycidyl nitrate (polyGLYN) and an energetic polyphosphazene (PPZ‐E) – all at 10%] on the unconfined laser‐induced deflagration of cyclotetramethylene tetranitramine, commonly known as High Melting point Explosive (HMX) by a near IR (NIR) diode laser (801 nm) has been examined. Hydroxyl terminated polybutadiene (HTPB) and PPZ (the precursor to PPZ‐E – before nitration) were used as reference materials. The formulations required the addition of an optical sensitizer – carbon black (CB) – for ignition. At the designated threshold flux density of 2.3 kW cm⁻², a minimum of ∼1 wt.‐% CB was needed for the reliable ignition of unbound HMX and its formulations with polyGLYN, PPZ‐E and PPZ. Under similar conditions HMX/polyNIMMO and HMX/HTPB required 3% CB. Ignition maps (ignition time versus laser flux density) have been constructed for the five formulations. Comparison of ignition times and ignition energy densities for HMX and HMX/polyGLYN showed this binder to have only a marginal effect. In contrast, HTPB, PPZ and PPZ‐E all retarded HMX ignition at the threshold flux density, but showed negligible effect at higher flux densities. As PPZ and PPZ‐E produced both similar delays in the ignition time and similar increases in the flame development times (10–90%) at the threshold flux density, the inhibition of the HMX ignition by these PPZs appears to be largely independent of the polymer energy content. Such characteristics could be useful for high performance and insensitive energetic formulations. PolyNIMMO (3% CB) increased the ignition time of HMX only slightly at 2.3 kW cm⁻². However, at this threshold flux level the HMX flame development times with polyNIMMO or HTPB were much longer than that for the unbound material; this effect is attributed to the enhanced CB content.     

Synthesis and Characterization of CNT Composites for Laser‐Generated Ultrasonic Waves

In the last few years, extensive progress in ultrasonic wave generation by using multiwalled carbon nanotubes (MWCNTs) in combination with polydimethylsiloxane (PDMS), functional composites, has been achieved. Due to high optical absorption of MWCNTs as perfect absorbers for laser beams and the high thermal expansion coefficient of PDMS, a compact transducer for ultrasonic wave generation at higher frequency can be realized. This study reports a novel method to synthesize MWCNT–PDMS composites deposited on a glass substrate by spray coating, which is done in a short time of 2 h. The layers (0.9–32.2 µm) show low optical transmission properties of 13.9–0.0% at a wavelength of 1047 nm. Apart from using a 1% Triton‐X‐100 stock solution and then diluted to a 0.1% relatively nonhazardous solution, no toxic chemicals are used. The Triton‐X‐100 solution is not hazardous for lab handling and is a commonly used lab detergent for the treatment of biological cells. The achieved sound pressure level is 3.4 MPa with a frequency bandwidth of 9.7 MHz. These results show the potential for a fast and nontoxic production of laser‐generated ultrasonic transducers, which can be used well in the field of nondestructive material testing of layered materials or in medicine with an appropriate frequency range.     

Characterization of acrylic acid‐grafted PP membranes prepared by plasma‐induced graft polymerization

Acrylic acid (AA)‐g‐polypropylene (PP) membranes were prepared by grafting AA on to a microporous PP membrane via plasma‐induced graft polymerization. The grafting of AA to the PP membrane was investigated using Fourier transform infrared spectroscopy (FTIR). Pore‐filling of the membranes was confirmed by field emission‐scanning electron microscopy (FESEM) and energy dispersing X‐ray (EDX). Ion exchange capacity (IEC), membrane electric resistance, transport number and water content were measured and analyzed as a function of grafting reaction time. The prepared AA‐g‐PP membranes showed moderate electrochemical properties as a cation‐exchange membrane. In particular, membranes with a degree of grafting of 155% showed good electrical properties, with an IEC of 2.77 mmol/g dry membrane, an electric resistance of 0.4 Ω cm² and a transport number of 0.96. Chronopotentiometric measurements indicated that AA‐g‐PP membranes, with a high IEC had a sufficient conducting region in the membrane. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis and Characterization of 1‐Nitroguanyl‐3‐nitro‐5‐amino‐1,2,4‐triazole

The synthesis of 1‐nitroguanyl‐3‐nitro‐5‐amino‐1,2,4‐triazole (ANTA‐NQ) ( 1 ) with good yield and high purity is described. DSC analysis showed that the material displays good thermal stability. An X‐ray crystallographic analysis confirms the structure of this material, as well as displays intramolecular hydrogen bonding. A gas pycnometry density for this material was measured to be 1.79 g cm⁻³. The heat of formation of this material was also measured. These data, along with the molecular formula were used as inputs to calculate the detonation velocity and detonation pressure using the Cheetah thermochemical code. The sensitivity of this material towards impact, spark and friction was also measured, as well as its vacuum thermal stability. The 3‐azido derivative 2 was also prepared and its properties are described as well. The above data show that (ANTA‐NQ) may be a high performing material with low sensitivity and good thermal stability.     

Salts of Tetrazolone – Synthesis and Properties of Insensitive Energetic Materials

Tetrazolone (5‐oxotetrazole, 1 ) is formed by diazotization of 5‐aminotetrazole in the presence of CuSO₄. Nitrogen‐rich salts such as guanidinium ( 2 ), 1‐aminoguanidinium ( 3 ), 1,3‐diamino‐guanidinium ( 4 ), 1,3,5‐triamino‐guanidinium ( 5 ), ammonium ( 6 ), hydrazinium ( 7 ) and the hydroxylammonium ( 8 ) salts of tetrazolone were prepared by facile deprotonation or metathesis reactions. All compounds were characterized by single‐crystal X‐ray diffraction, vibrational spectroscopy (IR and Raman), multinuclear NMR spectroscopy, elemental analysis and DSC measurements. The heats of formation of 2–8 were calculated using the atomization method based on CBS‐4M enthalpies. With these values and the experimental (X‐ray) densities several detonation parameters such as the detonation pressure, velocity, energy and temperature were computed using the EXPLO5 code (V.5.04). In addition, the sensitivities towards impact, friction and electrical discharge were tested using the BAM drop hammer and friction tester as well as a small scale electrical discharge device.     

Energetic Salts of 5‐(5‐Azido‐1H‐1,2,4‐triazol‐3‐yl)tetrazole

Several metal and nitrogen‐rich salts of the recently presented 5‐(5‐azido‐1H‐1,2,4‐triazol‐3‐yl)tetrazole (AzTT), including silver ( 1 ), copper(I) ( 2 ), potassium ( 3 ), cesium ( 4 ), copper(II) ( 7 ), ammonium ( 8 ), and guanidinium ( 9 ), as well as the respective double‐salts of 3 , 4 , 8 and 9 , were prepared and well characterized by IR and multinuclear (¹H, ¹³C, ¹⁴N) NMR spectroscopy, DSC, mass spectrometry, elemental analysis and one ( 4 ) additionally by single‐crystal X‐ray diffraction. The sensitivities towards impact, friction and electrostatic discharge were determined according to BAM standards, revealing most of the metal salts as highly sensitive and the nitrogen‐rich salts as insensitive. The metal salts were further tested for their ability of being primary explosives.     

Estimated Detonation Velocities for TKX‐50, MAD‐X1, BDNAPM,BTNPM, TKX‐55, and DAAF using the Laser–induced Air Shock from Energetic Materials Technique

Since new energetic materials are initially produced in very small quantities for both safety and cost reasons, laboratory‐scale methods for characterizing their performance are essential for determining the most promising candidates for scale‐up. Laser‐induced air shock from energetic materials (LASEM) is a promising new method for estimating the detonation velocity of novel explosives using milligram amounts of material, while simultaneously investigating their high temperature chemical reactions. LASEM has been applied to 6 new explosives for the first time: TKX‐50, MAD−X1, BDNAPM, BTNPM, TKX‐55, and DAAF. Emission spectroscopy of the laser excited materials revealed the formation of the high pressure bands of C₂ during the ensuing exothermic reactions. The low thermal sensitivity of the materials also led to unusual laser‐material interactions, visualized with high‐speed video. The estimated detonation velocities for the 6 explosives were compared to predicted values from EXPLO5 and CHEETAH. The LASEM results suggest that TKX‐55, BDNAPM, and BTNPM have higher detonation velocities than predicted by the thermochemical codes, while the estimated detonation velocities for MAD−X1 and TKX‐50 are slightly lower than those predicted.     

Assessing Blending of Non‐Newtonian Fluids in Static Mixers by Planar Laser‐Induced Fluorescence and Electrical Resistance Tomography

Planar laser‐induced fluorescence (PLIF) and electrical resistance tomography (ERT) were applied simultaneously to monitor the mixing performance of a KM static mixer for the blending of non‐Newtonian fluids of dissimilar rheologies in the laminar regime. The areal distribution method was used to obtain quantitative information from the ERT tomograms and the PLIF images. Comparison of the ERT and PLIF results demonstrates the ability of ERT to detect the mixing performance in cases of poor mixing within the resolution of the measurement, though the accuracy decreases as the condition of perfect mixing is approached. Thus, ERT has the potential to detect poor mixing within the confines of its resolution limit and the required conductivity contrast, providing potential rapid at‐line measurement for industrial practitioners.     

Laboratory‐Scale Method for Estimating Explosive Performance from Laser‐Induced Shock Waves

A new laboratory‐scale method for predicting explosive performance (e.g., detonation velocity and pressure) based on milligram quantities of material is demonstrated. This technique is based on schlieren imaging of the shock wave generated in air by the formation of a laser‐induced plasma on the surface of an energetic material residue. The shock wave from each laser ablation event is tracked for more than 100 μs using a high‐speed camera. A suite of conventional energetic materials including DNAN, TNT, HNS, TATB, NTO, PETN, RDX, HMX, and CL‐20 was used to develop calibration curves relating the characteristic shock velocity for each energetic material to several detonation parameters. A strong linear correlation between the laser‐induced shock velocity and the measured performance from full‐scale detonation testing has been observed. The Laser‐induced Air Shock from Energetic Materials (LASEM) method was validated using nitrocellulose, FOX‐7, nano‐RDX, three military formulations, and three novel high‐nitrogen explosives currently under development. This method is a potential screening tool for the development of new energetic materials and formulations prior to larger‐scale detonative testing. The main advantages are the small quantity of material required (a few milligrams or less per laser shot), the ease with which hundreds of measurements per day can be obtained, and the ability to estimate explosive performance without detonating the material (reducing cost and safety requirements).     

The High‐Pressure Characterization of Energetic Materials: Diaminotetrazolium Nitrate (HDAT‐NO3)

In‐situ high‐pressure room temperature synchrotron X‐ray diffraction and optical Raman and infrared spectroscopy were used to examine the structural properties, equation of state, and vibrational dynamics of diaminotetrazolium nitrate (HDAT‐NO₃). The X‐ray measurements show that the pressure–volume relations remain smooth to 12 GPa. X‐ray diffraction measurements at pressures above 12 GPa were not possible in this study because of sample decomposition resulting from several factors. X‐ray diffraction reveals no indication of a phase transition to at least 12 GPa, but slight variations in the c/b unit cell ratio suggests modifications within the hydrogen bonding sub‐lattice. Vibrational measurements show the ambient phase of HDAT‐NO₃ to remain the dominant phase to 33 GPa.     

Iodine Pentoxide Nano‐rods for High Density Energetic Materials

The iodine pentoxide is one of the most advanced oxidizers for nanostructured energetic formulations among the thermites due to the highest energy release per volume 25.7 kJ cm⁻³. The size and shape of iodine pentoxide particles have a strong impact on the pressurization rates during the reaction. Although micro‐sized iodine pentoxide particles are commercially available, nano‐sized particles, which are desired for various nano‐energetic applications, are not available on the market. Conventional wet chemical methods are unable to produce iodine pentoxide nanoparticles due to high solubility in water. In this study, we demonstrate fabrication of iodine pentoxide nano‐rods by high energy mechanical treatment of micro‐sized I₂O₅ particles. Tuning the energy dose in high‐energy ball milling is allowing to produce I₂O₅ nano‐rods with diameter of 50–100 nm and length of 300–600 nm. The produced nano‐rods exhibited 10 % smaller decomposition energy compared to the precursor of micro particles. The experiments showed that the nano‐energetic materials prepared with nano‐sized I₂O₅ rods have pressure discharge value of 43.4 MPa g⁻¹ which is two times higher than using commercial iodine pentoxide particles.     

The High‐Pressure Characterization of Energetic Materials: 1,4‐Dimethyl‐5‐Aminotetrazolium 5‐Nitrotetrazolate

In‐situ high‐pressure room temperature synchrotron X‐ray diffraction and infrared microspectroscopy were used to examine the structural and vibrational properties and the equation of state of 1,4‐dimethyl‐5‐aminotetrazolium 5‐nitrotetrazolate (DMATNT). The X‐ray measurements show a smoothly varying pressure‐volume relationship to 20 GPa. However, the anisotropic ratios of the unit cell parameters reveal a discontinuity near 3.3 GPa, which can be attributed to an irreversible isostructural phase transition. A significant increase in the Infrared spectral intensity near this pressure coupled with Dayvdov splitting of the NO₂ bending and scissoring modes suggest the transition results in a skewing of the NO₂ groups and increasing asymmetry of the hydrogen bonding sublattice.     

The High‐Pressure Characterization of Energetic Materials: 2‐Methyl‐5‐Nitramino‐2H‐Tetrazole

The isothermal structural properties, equation of state, and vibrational dynamics of 2MNT were studied under high‐pressure using synchrotron XRD and optical Raman and IR microspectroscopy. Analysis of the XRD patterns revealed no indication of a phase transition to near 15 GPa and the pressure‐volume isotherm remained smooth to 15 GPa. Near 15 GPa, significant sample damage was observed from the X‐ray beam which precluded the acquisition of patterns above this pressure. XRD and Raman spectroscopic measurements showed the monoclinic ambient condition phase of 2MNT remains the dominant phase to near 20 GPa, although a shift of the NO₂ IR active vibrational modes to lower frequencies suggested a subtle geometry modification not reflected in the XRD data.     

The High‐Pressure Characterization of Energetic Materials: 1‐Methyl‐5‐Nitramino‐1H‐Tetrazole

Pressure–volume relations and optical Raman and Infrared spectra of polycrystalline 1MNT have been obtained under quasi‐hydrostatic conditions up to 16 and 40 GPa, respectively, by using diamond anvil cell, synchrotron‐based angle‐resolved X‐ray diffraction, and microspectroscopy. The X‐ray measurements show that the pressure–volume relations remain smooth up to 16 GPa at room temperature, while vibrational measurements show no evidence of a phase transition to near 40 GPa. Anomalous increases of several vibrational intensities and bandwidths suggest that subtle molecular distortions and structural modifications occur in the crystal as pressure increases. Decompression experiments indicate the structural modifications are reversible.     

Effect of Temperature,Density and Confinement on Deflagration to Detonation Transition of an HMX‐Based Explosive

In order to obtain the characteristics of the deflagration‐to‐detonation transition (DDT) of PBX‐2 (an HMX‐based explosive) under different conditions, DDT tests were carried out as a function of charge density, temperature, and shell confinement. In these tests, the energetic materials were electrically ignited. The DDT response characteristics for PBX‐2 with 53 % and 99 % of theoretical maximum density (TMD) were evaluated by different shell thickness confinements at ambient temperature and at 85 °C. The test results with different densities, confinements and temperatures exhibited a wide range of reaction violence. Firstly, at both ambient temperature and at 85 °C under 10 and 20 mm shell thickness confinement, PBX‐2 did not undergo fully DDT at 99 % TMD, only a low velocity detonation (LVD) occurred. Secondly, PBX‐2 at 53 % TMD underwent DDT, and significant influence on the minimum run distance to detonation by the shell confinement thickness was observed. Strong confinement is favorable for the transition of DDT but the confinement does not influence reaction degree. Thirdly, the reaction degree of PBX‐2 at 85 °C was remarkably lower than that at ambient temperature. This insensitizing effect of temperature is induced by the melting and flowing of bonders which reduces the porosity and inhibits an important step of DDT, namely, high turbulent combustion.     

Modeling and Simulation of Laser‐Induced Ignition of RDX Using Detailed Chemical Kinetics

A laser‐induced ignition model of RDX is developed, in which a detailed chemical kinetics scheme, containing 45 species and 231 reactions, is employed to describe the reaction in the gas phase. The model is spatially one‐dimensional and includes the transient development of two regions: the condensed phase and the gas phase. The condensed phase is composed of solid RDX, liquid RDX, and some decomposition products. The main physicochemical processes include melting, decomposation, vaporization, and radiation absorption. The gas phase is composed of RDX vapor and reaction products and the main processes include convection, diffusion, heat conduction, chemical reaction, and radiation absorption. With interfacial boundary conditions, the governing parameters for the condensed phase are conservation equations of energy and species concentration, whereas those for the gas phase are the conservation equations of mass, momentum, energy, and species concentration. A finite difference program using FORTRAN is compiled and numerical simulation is carried out. The ignition process of RDX is discussed from the distribution and evolution of temperature and species concentration. The model can provide a reasonable prediction of the phenomenon that the flame moves towards the surface immediately after ignition, and then departed from the surface.     

Surface modification of polyethylene by plasma pretreatment and UV‐induced graft polymerization for improvement of antithrombogenicity

The purpose of this study was to enhance blood compatibility of polyethylene (PE) films. Glycidyl methacrylate (GMA) was grafted onto the surface of PE by Ar plasma pretreatment and UV‐induced graft polymerization without photo‐initiator, then heparin was immobilized onto the poly (glycidyl methacrylate) segments. The surface compositions and microstructure of GMA graft polymerized PE films were studied by X‐ray photoelectron spectroscopy (XPS) and Attenuated Total Reflectance Fourier Transfer Infrared (ATR‐FTIR) spectroscopy. It was confirmed that heparin was successfully immobilized onto the surface of PE films by XPS analysis. The antithrombogenicity of the samples was determined by the activated partial thromboplastin time (APTT), prothrombin time (PT), thrombin time (TT), and plasma recalcification time (PRT) tests and platelet adhesion experiment. Results indicated that the antithrombogenicity of modified PE was improved remarkably. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2014–2018, 2004     

Plasma‐induced,solid‐state polymerization of N‐isopropylacrylamide

The radio‐frequency plasma‐initiated polymerization of N‐isopropylacrylamide (NIPAM) in the solid state was performed. The isolated linear polymer was characterized by ¹³C‐NMR, ¹H‐NMR, and Fourier transform infrared spectroscopy, and the effects of selected operational plasma parameters (discharge power and time) on the conversion rates were studied. Reversible transitions at the volume‐phase‐transition temperatures of the swelled poly(N‐isopropylacrylamide) hydrogels were investigated by differential scanning calorimetry. The surface morphologies before and after plasma treatment were followed by scanning electron microscopy. With the obtained X‐ray diffraction results, we propose a solid‐state plasma polymerization mechanism for the NIPAM. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Improvement of the interfacial adhesion between PBO fibers and PPESK matrices using plasma‐induced coating

This work deals with the plasma‐induced coating process on the surface of PBO fibers to obtain a strong interfacial adhesion between the poly(p‐phenylene benzobisoxazole) (PBO) fibers and the poly(phthalazinone ether sulfone ketone) (PPESK) matrices. The process consisted of four steps: (a) plasma preactivation of PBO fibers; (b) immersion in an epoxy resin solution; (c) drying and then soaking with the PPESK solution; (d) shaped by compression molding technique. The orthogonal experiments used in this study enable the determination of the significant experimental parameters that influence efficiency of the process by comparing the values of ILSS. The order of their influences was the concentration > power > treating time > treating pressure. The results of the interlaminar shear strength (ILSS) and water absorption showed that the ILSS of the composite increased by 56.5% after coating, meanwhile the water absorption declined to 0.32%. The changes of the surface chemical composition, the surface morphology, and the surface free energy of fibers were studied by FTIR spectroscopy, atomic force microscope (AFM), and dynamic contact angle analysis (DCAA), respectively. Fracture mechanism of the composite was examined by scanning electron microscope (SEM). The results indicated that plasma‐induced coating process was an efficient method to enhance the interfacial adhesion of PBO fibers and PPESK matrices. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012