Artificial ageing of double base rocket propellant

The ageing of double base rocket propellants (DB rocket propellants), which is a consequence of chemical reactions and physical processes that take place over time, has significant effect on their relevant properties (e.g. chemical composition, mechanical properties, ballistic properties, etc.). The changes of relevant properties limit the safe and reliable service life of DB rocket propellants. This is the reason why numerous research efforts are devoted to finding out reliable methods to measure the changes caused by ageing, to assess the quality at a given moment of time, and to predict remaining life-time of DB rocket propellants. In this work we studied dynamic mechanical properties of DB rocket propellant artificially aged at elevated temperatures, in order to detect and quantify changes in dynamic mechanical properties caused by the ageing. Dynamic mechanical properties were studied using dynamic mechanical analyser (DMA). The results obtained have shown that the ageing causes significant changes of DMA curve’s shape and positions. These changes are quantified by following some characteristic points on DMA curves (e.g. glass transition temperatures; storage modulus, loss modulus and tanδ at characteristic temperatures, etc.). It has been found out that the most sensitive parameters to the ageing process are: storage modulus at viscoelastic and softening region, peak width and height on loss modulus curve, glass transition and softening temperature, and tanδ at viscoelastic region.     

Thermal decomposition studies of catalysed double base propellants

To understand the rote of lead salts of organic acids in the combustion of double base rocket propellants, thermal decomposition behaviour of propellants was studied bydta andtg methods. Catalysed propellants decomposed at lower temperatures than the control. Percent thermal decomposition of propellants containing lead salts was also higher. Rate constants were higher and energy of activation was lower for catalysed propellants. Results obtained suggest that condensed phase reactions may be the site for the action of lead salts in the combustion of double base propellants     

Reactive Nanocomposites as Versatile Additives for Composite Propellants

A new approach to improve the performance of composite propellants was developed in which reactive nanocomposites (RNCs) are used as replacements for aluminum powders in composite solid rocket propellants. The new materials are mechanically activated nanothermites comprising of nano‐powders of aluminum as the fuel as well as oxides of copper, iron, molybdenum, or nickel as the oxidizer. The obtained RNCs were characterized using X‐ray diffraction, scanning electron microscopy, and laser diffraction particle size analyzer. The obtained RNCs were used for preparation of modified composite solid rocket propellants (CSRPs). Burning rate, thermal decomposition behavior, heat of combustion, sensitivity, and mechanical properties of CSRPs were determined. The results showed increases in the combustion energy and the burning rate of the modified propellants were achieved, and that RNCs can be considered to be promising multi‐function additives for composite solid rocket propellants. In addition, the mechanical properties and sensitivities of the modified propellants are within the desired range.     

Influence of strain rate on the compressive yield stress of CMDB propellant at low,intermediate and high strain rates

The mechanical properties of composite modified double base (CMDB) propellant significantly depend on the strain rate. In particular, the yield stress increases dramatically at higher strain rates. To study this behaviour, low, intermediate and high strain rate compression testing (1.7 × 10⁻⁴ to 4 × 10³ s⁻¹) of CMDB propellant at room temperature was conducted by using a universal testing machine, a hydraulic testing machine and a split Hopkinson pressure bar (SHPB) system, respectively. The yield stress was observed to increase bilinearly with the logarithm of strain rate, with a sharp increase in slope at a strain rate of 5 × 10¹ s⁻¹, which was supported by dynamic mechanical analysis (DMA) testing. The Ree-Eyring model, involving two rate-activated processes, was employed to predict the yield behaviour of CMDB propellant over a wide range of strain rates. The predictions are in excellent agreement with the experimental data.     

Study on the influence of ageing on chemical and mechanical properties of N,N′-dimethyl-N,N′-diphenylcarbamide stabilized propellants

Double-base propellants undergo chemical, physical and mechanical changes upon ageing, leading to changes in ballistic performance and presenting explosive hazards. This report studies the variation of chemical and mechanical properties of aged N,N′-dimethyl-N,N′-diphenylcarbamide (methyl centralite) stabilized propellants in order to simulate and evaluate the natural ageing throughout the artificial one. Therefore, a comparative study of stabilizer depletion, plasticizers content, heat of combustion and mechanical properties such as storage modulus, loss modulus and damping of naturally and artificially aged propellants has been carried out by the following techniques: high-performance liquid chromatography (HPLC), thermogravimetric analyzer (TG), calorimeter of combustion and dynamic mechanical analyzer (DMA), respectively. The results obtained show that all properties are closely connected. In addition, the determination of stabilizer depletion, plasticizers evaporation, decrease of heat of combustion and mechanical properties are very useful for a better understanding of the decomposition and ageing behaviour of propellants. The HPLC investigation of stabilizer has shown good stability of the propellants. The results obtained for DMA have shown that some considerable changes of the mechanical and viscoelastic properties of the propellants occurred during ageing. These results confirm the results obtained by TG for the reduction of the nitroglycerine amount and the decrease of the heat of combustion.     

Fabrication and thermal decomposition of glycidyl azide polymer modified nitrocellulose double base propellants

Glycidyl azide polymer(GAP) with the advantages of non-volatility and excellent thermal stability is a candidate as a replacement for nitroglycerine(NG) in a double base propellant. The GAP-NC double base propellants were formulated with GAP and nitrocellulose(NC) fibers. Tensile test and SEM characterization indicated that GAP-NC propellants had a homogeneous structure. Thermogravimetric analysis of GAP-NC propellants revealed that the onset decomposition temperature reached a high level ranging from 192.9 to 194.6 °C, which indicated that the substitution of NG with GAP contributed to the safe storage and process operations for double base propellant. The result analysis of decomposition products of GAP-NC propellants showed that the main gas decomposition products of the propellants were NO, NO_2, CO, CO_2, NH_3, CH_4, HCN, N_2, CH_2O and C_2H_4O. The thermal decomposition process of the specimens was proposed.     

Synthesis,anti‐migration and burning rate catalytic mechanism of ferrocene‐based compounds

One of the most important components of solid rocket propellant is the burning rate catalysts (BRC) which enhance burning rate of solid composite propellant. Low‐pressure exponents and stable burning rate are the key features of an excellent solid propellant. Addition of BRC to the propellant results in the increase of burning rate of the propellant and decrease in pressure exponents. Among all BRC, ferrocene‐based BRC have attracted much attention because of their better microscopic homogeneities in distribution, ignitability of the propellants and good compatibility with organic binder. However, the main barrier for the development and practical applications of ferrocene‐based BRC is their migration property. This article reviews the field and highlights recent progress. Copyright © 2014 John Wiley & Sons, Ltd.     

Thermal behavior and decomposition kinetics of composite solid propellants in the presence of amide burning rate suppressants

The employment of burning rate suppressants in the solid rocket propellant formulation is long known. Different research activities have been conducted to well understand the mechanism of suppression, but literature about the action of oxamide (OXA) and azodicarbonamide (ADA) on the thermal decomposition of composite propellant is still scarce. The focus of this study is on investigating the effect of burning rate suppressants on the thermal behavior and decomposition kinetics of composite solid propellants. Thermogravimetric analysis (TG) and differential thermal analysis have been used to identify the changes in the thermal and kinetic behaviors of coolant-based propellants. Two main decomposition stages were observed. It was found that OXA played an inhibition effect on both stages, whereas the ADA acts as a catalyst in the first stage and as coolant in the second one. The activation energy dependent on the conversion rate was estimated by two model-free integral methods: Kissinger–Akahira–Sunose (KAS) and Flynn–Wall–Ozawa (FWO) based on the TG data obtained at different heating rates. The mechanism of action of coolants on the decomposition of solid propellants was confirmed by the kinetic investigation as well.     

The influence of porosity of ammonium perchlorate (AP) on the thermomechanical and thermal properties of the AP/polyvinylchloride (PVC) composite propellants

The influence of porous ammonium perchlorate (P_OAP) on the thermomechanical and combustion behavior of solid rocket propellants based on polyvinylchloride binder has been investigated. Differential scanning calorimetry, differential thermogravimetry, dynamic mechanical thermal analysis, and scanning electronic microscopy measurements were used for thermomechanical and thermal decomposition properties assessment. The results obtained indicate that lower glass transitions of the propellants and catalytic effect of combustion are obtained with P_OAP.     

Thermogravimetric analysis of cobalt sulfate

Morpholine is a base of moderate strength, comparable with that of ammonia, and capable of forming -onium-type salts. Extensive studies [1,2] have been made on the thermal stability of ammonium perchlorate because of its technological use as an oxidant in solid state rocket propellants. The preparation, characterization and thermal behaviour of morpholinium perchlorate are reported in this note. The study was followed by XRD, IR, TG, DTA and mass spectral techniques.     

RDX/AMMO推进剂的分子动力学

Molecular dynamics simulations have been performed to investigate well-known ener-getic material cyclotrimethylene trinitramine (RDX) crystal, 3-azidomethyl-3-methyloxetane (AMMO) and RDX/AMMO propellant. The results show that the binding energies on differ-ent crystalline surface of RDX changes in the order of (010)>(100)>(001). The interactions between RDX and AMMO have been analyzed by means of pair correlation functions. The mechanical properties of RDX/AMMO propellant, i.e. elastic coefficients, modulus, Cauchypressure, and Poisson's ratio, etc., have been obtained. It is found that mechanical properties are effectively improved by adding some amounts of AMMO polymers, and the overall effect of AMMO on three crystalline surfaces of RDX changes in the order of (100)>(010)>(001). The energetic properties of RDX/AMMO propellant have also been calculated and the results show that compared with the pure RDX crystal, the standard theoretical specific impulse of RDX/AMMO propellant decrease, but they are still superior to those of double base propellant.     

Hypergolic propellants based on hydrogen peroxide and organic compounds: historical aspect and current state

The research towards the development of new propellants aims to ensure not only their high performance, but also high environmental compatibility and low toxicity. Considerable attention is paid to the development of hypergolic propellant compositions, the use of which markedly simplifies the engine design and rocket system operation and provides the possibility of their repeated use. Hydrogen peroxide is a promising and nontoxic oxidant. The review summarizes the research and development data concerning the design and application of hypergolic rocket propellants involving hydrogen peroxide, starting from the 1930s and up to now. The data presented in the review could be useful for specialists engaged in the development of prospective high-performance green fuels.     

RDX/BAMO推进剂结合能、力学性质和能量性能的分子动力学模拟

利用分子动力学方法研究了著名的含能材料环三亚甲基三硝胺(RDX)、3,3′-双-(叠氮甲基)-氧杂环丁烷(BAMO)和RDX/BAMO推进剂. 结果表明, BAMO与RDX(010)面之间分子相互作用最强, 其次是(100)和(001)面. 以对相关函数g(r)描述了RDX和BAMO之间的相互作用. 计算了RDX/BAMO推进剂的弹性系数、模量、柯西压、泊松比等性能. 结果表明, BAMO的加入能够改善RDX的弹性力学性能, 相对改善效应的顺序为(100)>(001)>(010). RDX/BAMO推进剂的能量性能结果显示, BAMO的加入降低了RDX的比冲, 但仍高于著名的双基推进剂的比冲.     

Studies on the properties of EPDM–CSE blend containing HTPB for case‐bonded solid rocket motor insulation

Elastomeric blends based on ethylene propylene diene (EPDM) rubber as a primary polymer have been investigated for the thermal insulation of case‐bonded solid rocket motors (SRMs) cast with composite propellant containing hydroxy terminated polybutadiene (HTPB) as a polymeric binder. EPDM rubber found as an attractive candidate for the thermal insulation of case‐bonded SRM due to the advantages such as low specific gravity, improved ageing properties, and longer shelf life. In spite of these advantages, EPDM, a non‐polar rubber, lacks sufficient bonding with the propellant matrix. Bonding properties are found to improve when EPDM is blended with other polar rubbers like polychloroprene, chlorosulphonated polyethylene (CSE), etc. This type of polar polymer when blended with EPDM rubber enhances the insulator‐to‐propellant interface bonding. In the present work, an attempt has been made to study the properties of EPDM–CSE based insulator by incorporating HTPB, a polar polymer as well as a polymeric binder, as an additive to the EPDM–CSE blend by varying the HTPB concentration. Blends prepared were cured and characterized for rheological, mechanical, interface, and thermal properties to study the effect of HTPB addition. This paper reports the preliminary investigation of the properties of EPDM–CSE blend containing HTPB, as a novel and futuristic elastomeric insulation for case‐bonded SRM containing HTPB as propellant binder. Copyright © 2007 John Wiley & Sons, Ltd.     

聚醚环酰胺固体推进剂用键合剂的合成及使用性能

以丙三醇、环氧乙烷、环氧丙烷、氯化亚砜、异氰脲酸等为原料,合成了聚醚环酰胺键合剂。将其应用到推进剂(GAP/HMX/Al/AP)配方中,对成型后的推进剂进行力学性能测试和断面电子显微镜分析。结果表明,此类键合剂可以改善与推进剂中氧化剂的界面粘结性能,有效地提高成型后的推进剂在不同温度下的最大延伸率,但对抗拉伸强度的提高作用不明显。     

Polarographic study on the evolution of the diphenylamine as stabiliser of the solid propellants

Differential pulse polarography (DPP) and square wave voltammetry (SWV) were investigated, in order to know the stability of solid propellants which contain diphenylamine. The simultaneous determination of N-nitrousdiphenylamine (NnDPA), 2-nitrodiphenylamine (2nDPA), 4-nitrodiphenylamine (4nDPA) and 2,4-dinitrodiphenylamine (2,4dnDPA) by DPP and SWV was proposed due to these nitro-derivatives appear during the stabilisation process from degradation of diphenylamine (DPA) used as stabiliser in propellant compositions. The proposed methods were successfully applied to the simple base solid propellant (with nitrocellulose as the only active component), with its stabiliser DPA. In all cases and with both the techniques, detection limits ≤0.01 ppm were obtained.When the usual LC procedure was applied to the real sample, no significant differences were found between the obtained results and those given by the electroanalytical techniques. In addition, the detection limits reached by the electrochemical methods were better than those obtained by LC.Moreover, the proposed procedure can be considered an objective test that would avoid the use of the classic stability tests and would allow one to determine the stability of propellants accurately, faster and cheaper than LC methods.     

TG studies of a composite solid rocket propellant based on HTPB-binder

Thermal decomposition kinetics of solid rocket propellants based on hydroxyl-terminated polybutadiene-HTPB binder was studied by applying the Arrhenius and Flynn-Wall-Ozawa's methods. The thermal decomposition data of the propellant samples were analyzed by thermogravimetric analysis (TG/DTG) at different heating rates in the temperature range of 300-1200 K. TG curves showed that the thermal degradation occurred in three main stages regardless of the plasticizer (DOA) raw material, the partial HTPB/IPDI binder and the total ammonium perchlorate decompositions. The kinetic parameters E _a (activation energy) and A (pre-exponential factor) and the compensation parameter (S _p) were determined. The apparent activation energies obtained from different methods showed a very good agreement. This revised version was published online in August 2006 with corrections to the Cover Date.     

两种形貌纳米Fe2O3对TKX-50热分解的催化性能研究

Energy components used in solid rocket propellants are beneficial for improving the energy performance, and their thermal decomposition characteristics significantly affect the combustion properties of the propellants. As a kind of energetic material with both high energy and low sensitivity (impact and friction), 5, 5'-bistetrazole-1, 1'-diolate (TKX-50) can effectively improve the energy and safety characteristics of solid propellants. Burning catalyst is another important component of solid propellants, which can significantly improve the burning rate of the propellant and reduce the pressure exponent. Among various burning catalysts, nanoscale transition metal oxides can promote the thermal decomposition of the energetic component, thus enhancing the combustion properties of the solid propellant. However, the catalytic effects of nanoscale transition metal oxides with different morphologies on the thermal decomposition of TKX-50 have rarely been studied. Based on the excellent catalytic activity of Fe₂O₃ for TKX-50 thermal decomposition, nano-Fe₂O₃ particles with spherical and tubular microstructures were used for TKX-50 thermal decomposition. The Fe₂O₃ nanoparticles were successfully fabricated via the solvothermal method and characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS) analyses. The XRD, FT-IR, and XPS results confirmed the successful fabrication of spherical and tubular Fe₂O₃ samples. The SEM and TEM images showed that the spherical Fe₂O₃ samples are composed of agglomerated Fe₂O₃ nanoparticles with an average particle size of 110 nm. In addition, the average diameter and length of hollow tubular Fe₂O₃ nanoparticles are 120 nm and 200 nm, respectively. The catalytic activities of spherical and tubular Fe₂O₃ for TKX-50 decomposition were studied by thermogravimetric analysis (TG) and differential scanning calorimetry (DSC) methods. The DSC and TG-DTG curves showed that both tubular and spherical Fe₂O₃ could effectively promote TKX-50 thermal decomposition. The first thermal decomposition peak temperature (T_FDP) of TKX-50 was reduced by 36.5 K and 26.3 K in the presence of tubular and spherical Fe₂O₃, respectively, at 10 K·min⁻¹. The activation energy (E_a) of TKX-50, determined by the iso-conversional method, was significantly reduced in the presence of both tubular and spherical Fe₂O₃. The results indicated that the microstructure of the catalyst has a significant effect on its catalytic performance for TKX-50 thermal decomposition, and that tubular Fe₂O₃ with hollow microstructure possesses better catalytic activity than spherical Fe₂O₃. The excellent catalytic activity of tubular Fe₂O₃ can be attributed to the hollow microstructure, which has more active sites for TKX-50 thermal decomposition.     

Mechanically robust hydrophobized double network hydrogels and their fundamental salt transport properties

Water swollen polymer networks are attractive for applications ranging from tissue regeneration to water purification. For water purification, charged polymers provide excellent ion separation properties. However, many ion exchange membranes (IEMs) are brittle, necessitating the use of thick support materials that ultimately decrease throughput. To this end, novel double network hydrogels (DNHs) with variable water content are prepared and characterized in terms of mechanical and ion transport properties to evaluate their potential utility as tough membrane materials. The first network contains fixed anionic charges, while the other is comprised of a copolymer with varied ratios of hydrophobic ethyl acrylate (EA) and hydrophilic dimethyl acrylamide (DMA) repeat units. Characterization of freestanding DNH films reveals a reduction in water content from 88 to 53 wt% and a simultaneous increase in ultimate stress and strain by ~3.5× and ~4.5×, respectively, for 95%/5% EA/DMA, relative to 100% DMA. Fundamental salt transport properties relevant to water purification, including permeability, solubility, and diffusivity, are measured and systematically compared with conventional membrane materials to inform the development of DNHs for membrane applications. The ability to simultaneously reduce water content and increase mechanical integrity highlights the potential of DNHs as a synthetic platform for future membrane applications.