BDNPF/A增塑剂的性能及其应用

BDNPF/A具有适宜的密度和黏度,与众多的推进剂和炸药组分相容性良好。BDNPF/A毒性与一般硝基化合物类似;安定性好,在配方中替代NG,可降低配方的冲击敏感性;能量适中,具有出色的氧平衡和热平衡数值,在配方中替代惰性增塑剂,可显著改善配方的燃速和比冲。BDNPF/A在DB、CMDB等推进剂配方和PBX、PAX系列炸药配方中都得到了广泛应用,是制备钝感含能材料的必要含能增塑剂之一。     

Thermal and Sensitivity Study of Dihydroxyl Ammonium 5,5′‐Bistetrazole‐1,1′‐diolate (TKX‐50)‐based Melt Cast Explosive Formulations

Dihydroxyl ammonium 5,5′‐bistetrazole‐1,1′‐diolate (TKX‐50) is a promising energetic material with predicted performance similar to RDX as well as to CL‐20. In the present study, TKX‐50 was evaluated as a possible replacement for RDX in TNT‐based, aluminized as well as non‐aluminized melt cast formulations. Thermal analysis reveals the compatibility of TKX‐50 with benchmark explosives like RDX and TNT in explosive formulations. This paper describes the thermal and sensitivity study of TKX‐50 with RDX and TNT‐based melt cast explosives. The result indicated that TKX‐50 can be effectively used as a RDX replacement in melt cast explosive formulations. TKX‐50/TNT‐based aluminized composition shows more thermal stability than RDX/TNT based composition, which clearly indicated the usefulness of TKX‐50 in melt cast explosive formulations.     

Plasticizers derived from cardanol: synthesis and plasticization properties for polyvinyl chloride(PVC)

Two natural plasticizers derived from cardanol (CD), cardanol acetate (CA) and epoxidized cardanol acetate (ECA), were synthesized and characterized by ¹H NMR and ¹³C NMR. The plasticizing effects of the obtained plasticizers on semi-rigid polyvinylchloride (PVC) formulations were also investigated. Two commercial phthalate ester plasticizers, dioctyl terephthalate (DOTP) and diisononyl phthalate (DINP), were used as controls. Mechanical and thermal properties, compatibility, thermal stability, microstructure, and workability were assessed by dynamic mechanical analysis (DMA), mechanical analysis, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and dynamic stability analysis, respectively. Results indicated that the natural plasticizer ECA had overallsuperior flexibility, compatibility, thermal stability, and workability comparable to both controls. The obtained CA and ECA have lower volatility resistance and similar extraction and exudation resistance than that of DOTP and DINP. The CA was further blended with DOTP in soft PVC films. Results of DMA, TGA and mechanicalanalysis indicated that CA can serve as a secondary plasticizer to improve the related properties of soft PVC formulations. These CD derived plasticizers show promise as an alternative to fully or partially replace petroleum-based plasticizers.     

Composite Propellant Based on a New Nitrate Ester

Composite propellants based on the solid nitrate ester 2,3‐hydroxymethyl‐2,3‐dinitro‐1,4‐butanediol tetranitrate (SMX) were theoretically and experimentally examined and compared to formulations based on ammonium perchlorate (AP). Thermochemical equilibrium calculations show that aluminized SMX‐based formulations can achieve theoretical sea level specific impulse values upwards of 260 s. Both ignition sensitivity (tested via drop weight impact, electrostatic discharge, and BAM friction) and physical properties (hardness and thermal properties) are comparable to those of the AP‐based formulations. However, the SMX‐based formulation could be detonated using a high explosive donor charge in contact with the propellant. Differential scanning calorimetry of the SMX‐based propellant indicated an exotherm onset of 140 °C, which corresponds to the known decomposition temperature of SMX. The propellant has a high burning rate of 1.57 cm s⁻¹ at 6.89 MPa, with a pressure exponent of 0.85. This high pressure sensitivity might be addressed using various energetic and/or stabilizing additives. With good performance and high density, SMX‐based composite propellants may offer a promising perchlorate‐free alternative to existing AP‐based formulations.     

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.     

Soil burial degradation of new bio‐based additives. Part II. plasticized poly(vinyl chloride) films

Commercial sunflower oil was epoxidized, and the epoxidized oil (ESO) was used as a new thermal stabilizer for poly(vinyl chloride) (PVC). Plasticized formulations stabilized with ESO and epoxidized soya bean oil as a commercial stabilizer were evaluated for comparison. Two plasticizers were used, dioctyl phthalate and diisononyl adipate. The aging of the PVC samples was investigated in landfill soil for 24 months. The modifications of the structure of the polymer were followed by Fourier, transform infrared spectroscopy. Furthermore, the variations of density and mechanical properties (tensile and Shore D hardness) were considered, and the variations of the mass of the samples, the glass transition temperature (T_g), the molar mass distribution, and the weight loss were followed as a function of duration of soil burial. The morphological changes were tracked by scanning electron microscopy. Results showed that the nature of the plasticizer and heat stabilizer affects the properties of PVC as well as the phenomena of migration and biodegradation. J. VINYL ADDIT. TECHNOL., 19:183‐191, 2013. © 2013 Society of Plastics Engineers     

Optimizing the mixture blending for castable aluminized plastic-bonded explosives

Castable aluminized plastic-bonded explosive (PBX) is a multiple components blending. To find an optimum mixture blending (formulation) for PBX to meet several required specifications is formidable. This is due to the fact that there are unlimited candidate formulations from which an appropriate one could be chosen. In general, trial and error type of engineering judgement is still the primary approach to reach the desired goal. This paper, however, employs a statistical approach named Mixture Experiments as well as an optimization routine called Eureka to find the optimum formulation, which meets five required specifications. Finally, two confirmation runs are performed. The results justify that the theroretical solution derived from the systematic statistical approach is indeed applicable.     

Development of a Pyrolysis-Gas Chromatographic Method for characterization of plastic-bonded explosives

As part of a program to develop chemical tests which can be used to complement existing tests for mechanical properties, propellant ballistic performance, and explosive sensitivity, a detailed experimental procedure is presented for analysis of plastic-bonded explosives (PBX's) by the coupled method of pyrolysis-gas chromatography (PyGC). The method involves grinding the cooled PBX, pressing a controlled quantity on a pyrolysis wire, performing Curic-Point pyrolysis, and detecting the products after separation by gas chromatography. PyGC results are presented to show the capability of the method to differentiate aged and unaged samples of PBX's and to differentiate stabilized and unstabilized PBX's based on RDX. Also included are results from several series of reproductibility studies, which suggest that the method may require only minor modifications before it can be implemented for regular screening of these complex formulations.     

Mechanical Properties of Smokeless Composite Rocket Propellants Based on Prilled Ammonium Dinitramide

Ammonium dinitramide (ADN) is a high performance solid oxidizer of interest for use in high impulse and smokeless composite rocket propellant formulations. While rocket propellants based on ADN may be both efficient, clean burning, and environmentally benign, ADN suffers from several notable disadvantages such as pronounced hygroscopicity, significant impact and friction sensitivity, moderate thermal instability, and numerous compatibility issues. Prilled ADN is now a commercially available and convenient product that addresses some of these disadvantages by lowering the specific surface area and thereby improving handling, processing, and stability. In this work, we report the preparation, friction and impact sensitivity and mechanical properties of several smokeless propellant formulations based on prilled ADN and isocyanate cured and plasticized glycidyl azide polymer (GAP) or polycaprolactone‐polyether. We found such propellants to have very poor mechanical properties in unmodified form and to display somewhat unreliable curing. However, by incorporation of octogen (HMX) and a neutral polymeric bonding agent (NPBA), the mechanical properties of such smokeless formulations were significantly improved. Impact and friction sensitivities of these propellants compare satisfactorily with conventional propellants based on ammonium perchlorate (AP) and inert binder systems.     

A review: Multidimensional internal plasticization of molecular structure in energetic polymer

In the field of propellant and polymer-bonded explosives (PBX), energetic polymers may bring poor mechanical properties for bulky groups and polarity. To get rid of the defects, plasticizers with low molecular weight can enhance the flexibility and processability of propellants through monotonous mixing. However, the migration of plasticizers over time may severely disrupt the mechanical property of energetic polymers. In contrast to general plasticization, internal plasticization can regulate flexibility from the perspective of molecular structure. In this context, this review focuses on the internal plasticization of energetic polymers from different dimensions. Hopefully, this review can provide some inspiration for designing energetic polymers to optimize the mechanical properties from various dimensions and integrate them for further research.     

Transparency of rubber‐toughened polymer blend containing plasticizer

Transparency and its temperature dependence were studied for rubber‐toughened polymer blends composed of poly(methyl methacrylate), core–shell latex–rubber particles, and plasticizers such as tricresyl phosphate and di(2‐ethylhexyl)adipate. The transparency of the blends was found to be improved by the addition of the plasticizers. This phenomenon is attributed to the uneven distribution of the plasticizer in the blends. Furthermore, it was found that the plasticizers improve the transparency in a wide temperature range, because the plasticizer addition reduces the difference in the thermal expansion, and thus the temperature dependence of the refractive index, between poly(methyl methacrylate) and the rubber phases. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40775.     

PBX9501热感度、热膨胀及力学性能的分子动力学模拟

采用分子动力学模拟研究了不同温度和压强条件下PBX9501炸药的热感度、热膨胀和力学性能。通过体系中各组分最大引发键键长的变化判断温度对其热感度的影响;预测了PBX9501体系在不同温度下的热膨胀系数;采用静态力学理论分析其力学性能随温度和压强的变化。结果表明,在295~450K,随温度的升高,PBX9501炸药的敏感性增大,且在375K时其引发键的最大键长显著增大;热膨胀系数随温度升高而减小;随温度升高其脆性越明显,随压强的增加其韧性越好。     

Rocket Propellants with Reduced Smoke and High Burning Rates

Rocket propellants with reduced smoke and high burning rates recommend themselves for use in a rocket motor for high accelerating tactical missiles. They serve for an improved camouflage on the battle field and may enable guidance control due to the higher transmission of their rocket plume compared to traditional aluminized composite propellants. In this contribution the material based ranges of performance and properties of three non aluminized rocket propellants will be introduced and compared to each other. The selected formulations based on AP/HTPB; AP/PU/TMETN and AP/HMX/GAP/TMETN have roughly the same specific impulse of I_SP = 2430 Ns/kg at 70:1 expansion ratio. The burning rates in the pressure range from 10–18 MPa vary from to 26–33 mm/s for the AP/HTPB propellant, 52–68 mm/s for the formulation based on AP/PU/TMETN and 28–39 mm/s for the propellant based on AP/HMX/GAP. With 58% and 20% AP-contents the propellants with nitrate ester plasticizers create a much smaller secondary signature than the AP/HTPB representative containing 86% AP. Their disadvantage, however, is the connection of high performance to a high level of energetic plasticizer. For this reason, the very fast burning propellant based on AP/PU/TMETN is endowed with a low elastic modulus and is limited to a grain configuration which isn't exposed too much to the fast and turbulent airstream. The mechanical properties of the AP/HMX/GAP-propellant are as good or better as those of the AP/HTPB propellant. The first one exhibits the same performance and burn rates as the composite representative but produces only one fifth of HCl exhaust. For this reason it is recommended for missile applications, which must have high accelerating power together with a significantly reduced plume signature and smoke production.     

A Novel Cocrystal Explosive of HNIW with Good Comprehensive Properties

In order to improve the safety of the high explosive 2,4,6,8,10,12‐hexanitrohexaazaisowurtzitane (HNIW), we cocrystallized HNIW with the insensitive explosive DNB (1,3‐dinitrobenzene) in a molar ratio 1 : 1 to form a novel cocrystal explosive. Structure determination showed that it belongs to the orthorhombic system with space group Pbca. Therein, layers of DNB alternate with bilayers of HNIW. Analysis of interactions in the cocrystal indicated that the cocrystal is mainly formed by hydrogen bonds and nitro‐aromatic interactions. Moreover, the thermal behavior, sensitivity, and detonation properties of the cocrystal were evaluated. The results implied that the melting point of the cocrystal is 136.6 °C, which means an increase of 45 °C relative that of pure DNB. The predicted detonation velocity and detonation pressure of the cocrystal are 8434 m s⁻¹ and 34 GPa, respectively, which are similar to that of the reported HNIW/TNT cocrystal, but its reduced sensitivity (H₅₀=55 cm) makes it an attractive ingredient in HNIW propellant formulations.     

Understanding the Compatibility of the Energetic Binder PolyNIMMO with Energetic Plasticizers: Experimental and DFT Studies

The development of energetic binders with suitable energetic plasticizers is required to enhance the mechanical properties and to reduce the glass transition temperature of propellant and explosive formulations. The compatibility of the energetic binder poly(3‐nitratomethyl‐3‐methyloxetane) (polyNIMMO) with five different energetic plasticizers viz. bis(2,2‐dinitro propyl)acetal (BDNPA), dinitro‐diaza‐alkanes (DNDA‐57), 1,2,4‐butanetriol trinitrate (BTTN), N‐N‐butyl‐N ‘(2‐nitroxy‐ethyl) nitramine (BuNENA) and diethyleneglycoldinitrate (DEGDN) was studied by differential scanning calorimetry (DSC), rheology, and DFT methods. The results obtained for the pure binder were compared with the results obtained for the binder/plasticizer blend in regard of the decomposition temperature and the format of the peak indicated the compatibility of polyNIMMO with the plasticizers. The glass transition temperatures of the blends were determined by low temperature DSC and showed desirable lowering of glass transition temperature with single peak. The rheological evaluation revealed that the viscosity of the binder is considerably lowered by means of flow behavior upon addition of 20 % (w/w) plasticizer. The addition of BuNENA and DEGDN has maximum effect on the lowering of viscosity of polyNIMMO. The predicted relative trend of interaction energies between plasticizer and binder is well correlated with the corresponding trend of viscosity of binder/plasticizer blends. These experimental studies verified by theoretical methods are valuable to design practical blends of new plasticizers and binders.     

Processability and mechanical properties of commercial PVC plastisols containing low‐environmental‐impact plasticizers

Preliminary results are presented concerning the use of less‐toxic plasticizers such as dioctyl adipate (DOA) and acetyl tributyl citrate (ATBC) in plastisol formulations for rotational molding technology. The DOA and ATBC plasticizers have been studied by comparing the effects of their content, molecular architecture, and polarity on the rheological behavior of liquid plastic systems and on the mechanical properties of the ultimate products prepared with PVCs having different particle sizes and molecular‐weight distributions. Rheological tests have confirmed the differences in solvent power of the diethylhexyl phthalate (DOP), DOA, and ATBC plasticizers. The glass transition temperatures measured on rotomolded samples have shown that the use of ATBC leads to a more nearly rigid system as a consequence of the branched structure and polarity of this plasticizer when compared with DOA. Mechanical tests carried out on final products after natural and forced environmental aging revealed a slight decrease in their performance. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

LLM-105/CL-20基高能钝感PBX的制备与性能表征

为满足含能材料高能钝感的要求,以CL-20为主体炸药,LLM-105为钝感剂,采用溶液水悬浮法制备了LLM-105质量分数分别为10%、20%、30%的3种LLM-105/CL-20基PBX。通过扫描电子显微镜(SEM)、粉末X射线衍射仪(PXRD)和差示扫描量热仪(DSC)对样品的形貌、晶体结构和热性能进行表征,并测试其机械感度;采用EXPLO5软件计算了其爆轰参数。结果表明,LLM-105/CL-20基PBX样品呈类球形,颗粒密实,粒径约为500μm;PBX中各组分的晶体结构未发生改变;3种配方的热安定性都较好,且随着钝感剂LLM-105含量的增加,LLM-105/CL-20基PBX的热爆炸临界温度呈递增趋势;与原料CL-20相比,3种LLM-105/CL-20基PBX的特性落高分别提高了25.88、33.68、37.18 cm,摩擦爆炸概率分别下降29%、38%、45%;LLM-105质量分数为10%的LLM-105/CL-20基PBX的特性落高与PBX-9501相当,而LLM-105质量分数为20%和30%的LLM-105/CL-20基PBX分别比PBX-9501高16.6%和25.12%;理论爆速分别高381.76、279.2、82.03 m/s。3种配方LLM-105/CL-20基PBX炸药的爆轰性能明显优于PBX-9501。     

Threshold Energy: A Dimensional Extension of the Critical Energy for Jet Attack Application

The critical energy criterion (E_c) developed by Walker and Wasley is widely used to determine the response of explosive submitted to flyer plate impacts. As it has been shown previously to be limited in the pressure range over which it applies, in the number of explosive formulations which appear to obey it and in the range of projectiles covered by it, we have modified twice this criterion. The first modification, taking into account a trend toward lower minimum energy with increasing pressure (pressure fluence) enables it to be applied to explosives previously found to be outside the original criterion and to extend the pressure range. The second modification taking into account a trend toward higher minimum energy with decreasing impact surface area (impact surface dependence) is a bidimensional extension of the critical energy concept. The threshold energy per unit area thus defined allows to predict the shock initiation limits of bare explosives (PBX and cast formulations) impacted by shaped charge jets.     

RDX基铝薄膜炸药与铝粉炸药水下爆炸性能比较

为了减少铝粉炸药在生产过程中因铝粉对环境污染,降低铝粉炸药的撞击感度,提高含铝炸药的成型性及力学性能,将RDX用铝薄膜分层包裹得到新型的铝薄膜混合炸药。将铝薄膜混合炸药与铝粉炸药进行水下爆炸实验与爆速实验,得到两种炸药的爆速与压力时程曲线,经过分析计算得到两种炸药的压力峰值、冲量、冲击波能、气泡脉动周期与气泡能。结果表明：铝薄膜炸药药柱的轴向为RDX与铝薄膜独立贯通的结构,有利于降低混合炸药中添加物对基体炸药爆轰波传播的影响,从而使铝薄膜混合炸药的爆速高于铝粉炸药,导致铝薄膜炸药的冲击波损失系数高于铝粉炸药,使铝薄膜混合炸药的总能量、比气泡能与铝粉炸药相当情况下,其比冲击波能却降低了10.16%～10.33%,计算过程说明铝薄膜混合炸药的C-J压力计算公式具有合理性。     

压装PBX炸药DDT管实验初始反应演化过程分析

在DDT管中采用惰性模拟材料研究电点火头和黑火药产生的初始压力对惰性模拟材料点火端面的影响;采用高速摄像机记录了DDT管内HMX基压装PBX炸药的燃烧发光过程;分析了压装PBX炸药DDT管实验初始反应演化过程。结果表明,电点火头和黑火药产生的初始压力会引起邻近脆性炸药端面裂纹形成和局部破坏,炸药燃烧的火焰沿炸药基体裂纹和炸药与管壁之间的缝隙中传播,压装PBX炸药初始反应演化与缝隙对流燃烧过程密切相关。