纳米金属钴粒子的制备及对高氯酸铵热分解的影响

The monodispersed Co nanoparticles were successfully prepared by means of hydrogen plasma method in inert atmosphere. The particle size, specific surface area, crystal structure and morphology of the samples were characterized by transmission electron microscopy （TEM）, BET equation, X-ray diffraction （XRD）, and the corresponding selected area electron diffraction （SAED）. The catalytic effect of Co nanoparticles on the decomposition of ammonium perchlorate （AP） was investigated by differential thermal analyzer （DTA）. Compared with the thermal decomposition of pure AP, the addition of Co nanoparticles （2%-10%, by mass） decreases the decomposition temperature of AP by 145.01-155.72℃. Compared with Co3O4 nano-particles and microsized Co particles, the catalytic effect of Co nanoparticles for AP is stronger. Such effect is attributed to the large specific surface area and its interaction of Co with decomposition intermediate gases. The present work provides useful information for the application of Co nanoparficles in the AP-based propellant.     

纳米MnFe2O4的制备及其对高氯酸铵热分解的催化性能（英文）

Nano-MnFe2O4 particles were synthesized by co-precipitation phase inversion method and low-temperature combustion method respectively, using MnCl2, FeCl3, Mn(NO3)2, Fe(NO3)3, NaOH and C6H8O7. X-ray diffraction (XRD), transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR), thermogravim-etry-differential thermal analysis (TG-DTA) and differential scanning calorimetry (DSC) were used to characterize the structure, morphology, thermal stability of MnFe2O4 and its catalytic performance to ammonium perchlorate. Results showed that single-phased and uniform spinel MnFe2O4 was obtained. The average particle size was about 30 and 20 nm. The infrared absorption peaks appeared at about 420 and 574 cm-1, and the particles were stable below 524 ℃. Using the two prepared catalysts, the higher thermal decomposition temperature of ammonium perchlorate was decreased by 77.3 and 84.9 ℃ respectively, while the apparent decomposition heat was increased by 482.5 and 574.3 J?g?1. The catalytic mechanism could be explained by the favorable electron transfer space provided by outer d orbit of transition metal ions and the high specific surface absorption effect of MnFe2O4 particles.     

Catalytic bed slenderness ratio and ADN/methanol ratio for decomposition and combustion characteristics within ammonium dinitramide(ADN)-based green aerospace thruster

The decomposition and combustion characteristics of ammonium dinitramide(ADN) based non-toxic aerospace propellant are analytically studied to determine the effects of catalytic bed structure(slenderness ratio) and operation parameters(mass fraction ratio of ADN/CH_3OH) on the general performance within the ADN-based thruster. In the present research, the non-equilibrium temperature model is utilized to describe the heat transfer characteristics between the fluid phase and solid phase in the fixed bed. We determined the fluid resistance characteristics in the catalytic bed by experiments involving the method of pressure–mass. We have done the simulation study based on the available results in the literature and found the complex physical and chemical processes within the ADN thruster. Furthermore, an optimized catalytic bed slenderness ratio was observed with a value of 1.75 and the mass fraction ratio of 5.73 significantly influenced the propellant performance.These results could serve as a reference to explore the combustion characteristics within the thruster and the preparation of future propellants.     

High-energy Metal Fuels for Rocket Propulsion:Characterization and Performance

A joint international effort to improve solid propellant performance within the framework of a FP7European Project was described.Several metallized solid rocket propellants,of the broad family AP/HTPB/Metal in the ratio 68/14/18,were experimentally analyzed seeking to optimize the delivered specific impulse by identifying the most suitable high-energy fuel.Keeping the same nominal composition,different metallic fuels(including micrometric and nanometric Al,AlH3,and a variety of dual metal compositions)were characterized,tested,and contrasted to a conventional micrometric aluminum(30μm average grain size)certified for space flights.In order to overcome the intrinsic performance limitations of the matrix AP/HTPB,a new matrix consisting of ADN/GAP satisfying also the need for environmentally benign propellant formulation was considered as well.A comparative analysis between the two solid propellant systems in terms of ideal thermochemistry and experimental combustion properties reveals advantages and disadvantages of both.Overall,it is judged worthwhile to develop ADN/GAP propellants,with or without metallic fuels,to enhance the current status of solid rocket propulsion.Controlling morphology and mechanical properties of ADN/GAP compositions and understanding their flame structure and aggregation/agglomeration properties are the main issues still challenging industrial users.     

Ammonium perchlorate-based composite solid propellant formulations with plateau burning rate trends

This paper presents burning rates as a function of pressure of several propellant formulations based on ammonium perchlorate (AP) and hydroxyl-terminated polybutadiene cured by isophorone diisocyanate, many of which exhibit significantly low (nearly zero or negative) values of the pressure exponent of the burning rate in distinct pressure ranges, termed as plateau burning rate trends. The propellants contain a bimodal distribution of AP particles with the size of the coarse and fine particles within narrow ranges whose mean values are widely separated. Two mean sizes of fine particles were considered for the propellant formulations in the present work, namely, 5 and 20 μm. These choices are based on the mid-pressure extinction behavior exhibited by the matrix of fine AP and binder contained in the propellants but when tested alone over a wide range of fine AP size and pressure. The propellants that include the fine AP/binder matrixes exhibiting a mid-pressure extinction, in turn, exhibit the plateau burning rate trends within the corresponding pressure ranges. A plateau is also observed at elevated pressures in the burning rates of some formulations, which is related to the diminishing relative importance of the near-surface leading-edge region of the oxidizer/fuel diffusion flame in the gas-phase combustion zone. The choice of the coarse AP size influences the exact pressure range within the mid-pressure extinction domain of the matrix where the propellant exhibits the plateau burning rate trends. __________ Translated from Fizika Goreniya i Vzryva, Vol. 43, No. 4, pp. 73–81, July–August, 2007.     

Condensed combustion products of aluminized propellants. II. evolution of particles with distance from the burning surface

Condensed combustion products of a model propellant on the basis of ammonium perchlorate and aluminum were studied using the sampling technique. The granulometric composition of combustion products and the content of metal aluminum in particles of size from 1.2 μm to maximum were determined within the pressure range of 0.6–7.5 MPa at a distance from the burning surface up to 190 mm. A multimode structure of mass distributions of oxide particles within the size range of 1.2–40 μm was found. An empirical dependence of burnout of metal aluminum from agglomerates on the residence time of particles in the plume of combustion products of the propellant sample was obtained. Translated fromFizika Goreniya i Vzryva, Vol. 36, No. 4. pp. 66–78, July–August, 2000.     

金属硫化物作为阳极材料对H2S固体氧化物燃料电池性能研究

Two anode catalysts with Pt, MoS2 and composite metal sulfides (MoS2 NiS), are investigated for electrochemical oxidation of hydrogen sulfide in solid oxide fuel cell (SOFC) at temperatures 750-850℃. The catalysts comprising MoS2 and MoS2 NiS exhibited good electrical conductivity and catalytic activity. MoS2 and composite catalysts were found to be more active than Pt, a widely used catalyst for high temperature H2S/O2 fuel cell at 750-850℃. However, MoS2 itself sublimes above 450℃. In contrast, composite catalysts containing both Mo and transition metal (Ni) are shown to be stable and effective in promoting the oxidation of H2S in SOFC up to 850℃. However, electric contact is poor between the platinum current collecting layer and the composite metal sulfide layer, so that the cell performance becomes worse. This problem is overcome by adding conductive Ag powder into the anode layer (forming MoS2 NiS Ag anode material) to increase anode electrical conductance instead of applying a thin laver of platinum on the top of anode.     

Energetic Abilities of Solid Composite Propellants Based on 3,4,5-Trinitropyrazole and Ammonium Dinitramide

The investigation aims at the expansion of the basis of formulations of solid composite propellants by introducing new compositions with lower sensitivity to mechanic impact and improved thermal stability.The formulations based on trinitropyrazole(TNP)contains a binder(a hydrocarbon or active one),aluminum and inorganic oxidizer ADN.The results show that a binary formulation TNP+active binder(18%-19%)(volume fraction)with no metal is well designed which would achieve high specific impulse(at Pc∶Pa=40∶1)of 248s,high density of 1.80g/cm3 and combustion temperature Tcabout 3 450K.In terms of energy,metal-free compositions with TNP lose a bit to those with HMX,only if HMX fraction in formulation is higher than 45%-50%.     

陶瓷支撑的有机复合膜及其在渗透汽化中的应用(英文)

Pervaporation(PV),as an environmental friendly and energy-saving separation technology,has been received increasing attention in recent years.This article reviews the preparation and application of macroporous ceramic-supported polymer composite pervaporation membranes.The separation materials of polymer/ceramic composite membranes presented here include hydrophobic polydimethylsiloxane(PDMS) and hydrophilic poly(vinyl alcohol)(PVA),chitosan(CS) and polyelectrolytes.The effects of ceramic support treatment,polymer solution properties,interfacial adhesion and incorporating or blending modification on the membrane structure and PV performance are discussed.Two in-situ characterization methods developed for polymer/ceramic composite membranes are also covered in the discussion.The applications of these composite membranes in pervaporation process are summarized as well,which contain the bio-fuels recovery,gasoline desulfuration and PV coupled proc-ess using PDMS/ceramic composite membrane,and dehydration of alcohols and esters using ceramic-supported PVA or PVA-CS composite membrane.Finally,a brief conclusion remark on polymer/ceramic composite mem-branes is given and possible future research is outlined.     

La_(0.8)Sr_(0.2)MnO_3的燃烧法制备及对HMX热分解的影响(英文)

Perovskite-type La0.8Sr0.2MnO3 was prepared by stearic acid gel combustion method. The obtained powders were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scaning electron micrograph (SEM) and X-ray photoelectron spectroscopy (XPS) techniques. The catalytic activity of La0.8Sr0.2MnO3 was investigated on thermal decomposition of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) by thermal gravity-differential scanning calorimetry (TG-DSC) techniques. The experimental results show that La0.8Sr0.2MnO3 is an effective catalyst for HMX thermal decomposition. The surface-adsorbed species such as H2O, OH&;#61485; and adsorbed oxygen (Oad) could result in an advance in the onset temperature of HMX thermal decompo-sition. The mixture system of Mn3+ and Mn4+ ions and lattice oxygen could play key roles for the increase of the decomposition heat of HMX because these exothermic reactions could be catalyzed by La0.8Sr0.2MnO3 between CO and NOx (from the thermal decom-position of HMX) and the oxidation reaction of CO. According to the previous researches and our results, perovskite-type La0.8Sr0.2MnO3 may be used as a novel catalyst or modifier for nitrate ester plasticized polyether (NEPE) propellant.     

NiCu复合金属粉的制备及其催化性能

采用化学还原法制备得到了纳米级NiCu复合金属粉,对其结构进行了表征. 用热分析法研究了纳米NiCu复合金属粉对高氯酸铵(AP)热分解的催化性能. 结果表明,组成为Ni60Cu40的纳米NiCu复合金属粉可使AP的高温和低温热分解温度分别降低140.4和26.8℃,使总表观分解热增至1.29 kJ/g,表现出对AP的高温和低温热分解的显著催化作用. 纳米NiCu复合金属粉的组成对其催化性能有一定影响,以Ni60Cu40的催化效果最强. 纳米NiCu复合金属粉的含量增加,其催化作用增强. 纳米NiCu复合金属粉催化AP热分解的作用机理为：(1) 氧化物在AP热分解起始阶段电子转移过程中的桥梁催化作用;(2) 纳米NiCu复合金属粉与AP分解产物发生反应;(3) 纳米NiCu复合金属粉的表面效应等.     

Evaluation of Nano‐Co3O4 in HTPB‐Based Composite Propellant Formulations

Different propellant compositions were prepared by incorporating nano‐sized cobalt oxide from 0.25 % to 1 % in HTPB/AP/Al‐based composite propellant formulations with 86 % solid loading. The effects on viscosity build‐up, thermal, mechanical and ballistic properties were studied. The findings revealed that by increasing the percentage of nano‐Co₃O₄ in the composition, the end of mix viscosity, the modulus and the tensile strength increased, whereas the elongation decreased accordingly. The thermal property data envisaged a reduction in the decomposition temperature of ammonium perchlorate (AP) as well as formulations based on AP. The ballistic property data revealed an enhanced burning rate from 6.11 mm s⁻¹ (reference composition) to 8.99 mm s⁻¹ at 6.86 MPa and a marginal increase in pressure exponent from 0.35 (reference composition) to 0.42 with 1 % nano‐cobalt oxide.     

B/Fe_2O_3/NC复合物的制备及其对HTPB/AP推进剂性能的影响

为改善硼粉(B)的性能和纳米氧化铁(Fe_2O_3)在固体推进剂中的分散性,用静电喷雾法制备了B/Fe_2O_3/NC复合物,采用扫描电镜(SEM)表征了复合物的表面形貌,用TG-DSC分析了复合物的热性能及其对HTPB/AP推进剂热性能的影响,并用燃速测试和密闭爆发器实验研究了该复合物对HTPB/AP推进剂燃烧性能的影响。结果表明,所制备的B/Fe_2O_3/NC复合物均以团聚体的形式存在,复合物中B的活性提高,其氧化反应温度提前;团聚硼粉对HTPB/AP推进剂燃烧性能的改善效果明显优于原料硼粉;加入Fe_2O_3后,会进一步改善含硼推进剂的燃烧性能,而且随Fe_2O_3含量的增加,在密闭爆发器中HTPB/AP推进剂达到最高压力所需的时间逐渐减小。当Fe_2O_3的质量分数为8%时,推进剂在常压空气中的燃速最大,为不添加B/Fe_2O_3/NC复合物的HTPB/AP推进剂的2.77倍。B/Fe_2O_3/NC复合物对推进剂的热分解具有一定催化作用,且随Fe_2O_3含量的增加催化作用增强。     

高氯酸铵复合物研究概况

对近年来高氯酸铵(AP)与推进剂燃烧剂、燃烧催化剂、高导热材料碳纳米管(CNTs)组成的复合物的热分解性能进行了总结,介绍了燃烧剂、催化剂和CNTs在含AP推进剂中的应用效果。结合当前含AP推进剂研究现状,认为AP复合处理是改善推进剂燃烧性能、能量性能和工艺性能的新型方法和有效途径,AP复合物具有良好的工程应用前景。     

High‐Fidelity Microstructural Characterization and Performance Modeling of Aluminized Composite Propellant

Image processing and stereological techniques were used to characterize the heterogeneity of composite propellant and inform a predictive burn rate model. Composite propellant samples made up of ammonium perchlorate (AP), hydroxyl‐terminated polybutadiene (HTPB), and aluminum (Al) were faced with an ion mill and imaged with a scanning electron microscope (SEM) and x‐ray tomography (micro‐CT). Properties of both the bulk and individual components of the composite propellant were determined from a variety of image processing tools. An algebraic model, based on the improved Beckstead‐Derr‐Price model developed by Cohen and Strand, was used to predict the steady‐state burning of the aluminized composite propellant. In the presented model the presence of aluminum particles within the propellant was introduced. The thermal effects of aluminum particles are accounted for at the solid‐gas propellant surface interface and aluminum combustion is considered in the gas phase using a single global reaction. Properties derived from image processing were used directly as model inputs, leading to a sample‐specific predictive combustion model.     

纳米ZnO立方体催化AP热分解及其在HTPE推进剂中的应用

为改善高氯酸铵(AP)的性能,从而改善复合固体推进剂的燃烧性能,采用AP辅助的金属有机骨架结构(MOF)热分解法合成纳米ZnO立方体催化剂(n-ZnO/cube);采用XRD、FESEM、TEM等对其形貌进行了表征,分析了其比表面积和孔径分布;采用TG-DTA分析了其对AP热分解的影响;将其加入到HTPE推进剂中,测试了其对推进剂工艺性能、安全性能、力学性能及燃烧性能的影响。结果表明,n-ZnO/cube催化剂具有大的比表面积(70.5m2/g)和大量的孔道结构,将AP热分解的高温分解峰从413℃降至279℃,放热量从584J/g增至1520J/g,分解活化能从151.1kJ/mol降至65.3kJ/mol;将质量分数2%的n-ZnO/cube加入到HTPE推进剂中,推进剂的燃速(20℃,6.86MPa)从12.01mm/s提高到16.16mm/s,工艺性能、安全性能、力学性能、燃速压强指数(0.42,20℃,3~16MPa)、燃速温度敏感系数(2.02×10^-3℃^-1,-55~70℃,6.86MPa)均未受到明显影响,表明纳米ZnO立方体结构对AP热分解表现出良好的催化性能,是HTPE推进剂的一种具有潜力的燃烧调节剂。     

Burning‐rate enhancement of a high‐energy rocket composite solid propellant based on ferrocene‐grafted hydroxyl‐terminated polybutadiene binder

Four different samples of ferrocene‐grafted hydroxyl‐terminated polybutadiene (Fc‐HTPB), containing 0.20, 0.52, 0.90, and 1.50 wt % iron, were synthesized by the Friedel–Crafts alkylation of ferrocene with hydroxyl‐terminated polybutadiene (HTPB) in the presence of AlCl₃ as a (Lewis acid) catalyst. The effects of the reaction conditions on the extent of ferrocene substitution were investigated. The Fc‐HTPBs were characterized by IR, ultraviolet–visible, ¹H‐NMR, and ¹³C‐NMR spectra. The iron content and number of hydroxyl groups were estimated, and the properties, including thermal degradation, viscosity, and propellant burning rates (BRs), were also studied. The thermogravimetric data indicated two major weight loss stages around 395 and 500°C. These two weight losses were due to the depolymerization and decomposition of the cyclized product, respectively, with increasing temperature. The Fc‐HTPB was cured with toluene diisocyanate and isophorone diisocyanate separately with butanediol–trimethylolpropane crosslinker to study their mechanical properties. Better mechanical properties were obtained for the gumstock of Fc‐HTPB polyurethanes with higher NCO/OH ratios. The BRs of the ammonium perchlorate (AP)‐based propellant compositions having these Fc‐HTPBs (without dilution) as a binder were much higher (8.66 mm/s) than those achieved with the HTPB/AP propellant (5.4 mm/s). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Differential Scanning Calorimetric Study of HTPB based Composite Propellants in Presence of Nano Ferric Oxide

A comparative study of the thermal decomposition of ammonium perchlorate (AP)/hydroxy terminated polybutadiene (HTPB) based composite propellants has been carried out in presence and absence of nano iron oxide at different heating rates in a dynamic nitrogen atmosphere using differential scanning calorimetry. The pronounced effect was a lowering of the high temperature decomposition by 49 °C. A higher heat release up to 40% was observed in presence of nano ferric oxide (3.5 nm). The kinetic parameters were evaluated using the Kissinger method. The increase of the rate constant in the catalyzed propellant confirmed the enhancement of the catalytic activity of ammonium perchlorate. The scanning electron micrographs of nano Fe₂O₃ incorporated in HTPB revealed a well‐separated characteristic necklace‐like structure of α‐Fe₂O₃ particles at high magnification.     

铜铬类催化剂对HTPE低易损推进剂燃烧性能的影响

采用差示扫描量热仪(DSC)研究了铜铬类燃速催化剂(亚铬酸铜CC01和铜铬复合氧化物CC02)对端羟基聚醚(HTPE)低易损推进剂中的高氯酸铵(AP)、改性硝酸铵(AN)、HTPE黏合剂体系热分解性能的影响。结果表明,加入少量的CC01和CC02均使AP高温分解峰温明显降低了16和29.7℃,AP高温分解活化能依次降低了16.65和22.59kJ/mol,均可提高AP的高温分解反应速率。CC01和CC02均使AN的热分解峰向低温方向依次前移了52.3和53.6℃,均降低了AN的分解活化能,使AN的热分解反应速率提高了3~4倍。CC01和CC02对HTPE黏合剂体系的热分解影响较小。在AP/AN/Al/HTPE低易损推进剂中,分别添加质量分数0.5%的CC01和CC02可显著提高HTPE低易损推进剂在3~15MPa下的燃速,可使推进剂在7MPa下的燃速分别提高34.1%和43.4%,但CC01和CC02对HTPE低易损推进剂在3~9MPa下的压强指数几乎无影响,而9~15MPa下的压强指数有所降低。     

储氢合金/AP/HTPB推进剂的热分解性能

采用TG-DTG、DSC以及动力学分析方法研究了储氢合金/AP/HTPB推进剂的热分解性能。结果表明,相对于Al/AP/HTPB推进剂,储氢合金/AP/HTPB推进剂的热分解温度降低,放热量提高;A20/AP/HTPB推进剂的凝聚相反应程度提高2.44%,第二、三温区的热分解活化能(Kissinger法)分别降低4.06%和22.63%;A30/AP/HTPB推进剂的凝聚相反应程度提高10.61%,第二、三温区的热分解活化能(Kissinger法)分别降低30.89%和38.87%。储氢合金对AP/HTPB推进剂的热分解有催化作用,并且该催化作用随着储氢合金中Mg0.45Ni0.05B0.5Hx含量的增加而增强。