Recent advances in catalytic combustion of AP-based composite solid propellants

Composite solid propellants(CSPs) have widely been used as main energy source for propelling the rockets in both space and military applications. Internal ballistic parameters of rockets like characteristic exhaust velocity, specific impulse, thrust, burning rate etc., are measured to assess and control the performance of rocket motors. The burn rate of solid propellants has been considered as most vital parameter for design of solid rocket motors to meet specific mission requirements. The burning rate of solid propellants can be tailored by using different constituents, extent of oxidizer loading and its particle size and more commonly by incorporating suitable combustion catalysts. Various metal oxides(MOs),complexes, metal powders and metal alloys have shown positive catalytic behaviour during the combustion of CSPs. These are usually solid-state catalysts that play multiple roles in combustion of CSPs such as reduction in activation energy, enhancement of rate of reaction, modification of sequences in reaction-phase, influence on condensed-phase combustion and participation in combustion process in gas-phase reactions. The application of nanoscale catalysts in CSPs has increased considerably in recent past due to their superior catalytic properties as compared to their bulk-sized counterparts. A large surface-to-volume ratio and quantum size effect of nanocatalysts are considered to be plausible reasons for improving the combustion characteristics of propellants. Several efforts have been made to produce nanoscale combustion catalysts for advanced propellant formulations to improve their energetics. The work done so far is largely scattered. In this review, an effort has been made to introduce various combustion catalysts having at least a metallic entity. Recent developments of nanoscale combustion catalysts with their specific merits are discussed. The combustion chemistry of a typical CSP is briefly discussed for providing a better understanding on role of combustion catalysts in burning rate enhancement. Available information on different types of combustion nanocatalysts is also presented with critical comments.

Cu–Co–O nano-catalysts as a burn rate modifier for composite solid propellants

Nano-catalysts containing copper–cobalt oxides(Cu–Co–O) have been synthesized by the citric acid(CA) complexing method. Copper(II) nitrate and Cobalt(II) nitrate were employed in different molar ratios as the starting reactants to prepare three types of nano-catalysts. Well crystalline nano-catalysts were produced after a period of 3 hours by the calcination of CA–Cu–Co–O precursors at 550 °C. The phase morphologies and crystal composition of synthesized nano-catalysts were examined using Scanning Electron Microscope(SEM), Energy Dispersive Spectroscopy(EDS) and Fourier Transform Infrared Spectroscopy(FTIR) methods. The particle size of nano-catalysts was observed in the range of 90 nm–200 nm. The prepared nano-catalysts were used to formulate propellant samples of various compositions which showed high reactivity toward the combustion of HTPB/AP-based composite solid propellants. The catalytic effects on the decomposition of propellant samples were found to be significant at higher temperatures. The combustion characteristics of composite solid propellants were significantly improved by the incorporation of nano-catalysts. Out of the three catalysts studied in the present work, Cu Co-I was found to be the better catalyst in regard to thermal decomposition and burning nature of composite solid propellants. The improved performance of composite solid propellant can be attributed to the high crystallinity, low agglomeration and lowering the decomposition temperature of oxidizer by the addition of Cu Co-I nano-catalyst.

Experimental study of Al agglomeration on solid propellant burning surface and condensed combustion products

Aluminum(Al) particles are commonly added to energetic materials including propellants,explosives and pyrotechnics to increase the overall energy density of the composite,but aluminum agglomeration on the combustion surface may lower the combustion efficiency of propellants,resulting in a loss in twophase flow.Therefore,it is necessary to understand the agglomeration mechanism of aluminum particles on the combustion surface.In this paper,a high-pressure sealed combustion chamber is constructed,and high-speed camera is used to capture the whole process of aluminum accumulation,aggregation and agglomeration on the combustion surface,and the secondary agglomeration process near the combustion surface.The microscopic morphology and chemical composition of the condensed combustion products(CCPs) are then studied by using scanning electron microscopy coupled with energy dispersive(SEM-EDS) method.Results show that there are three main types of condensed combustion products:small smoke oxide particles oxidized by aluminum vapor,usually less than 1 μm;typical agglomerates formed by the combustion of aluminum agglomerates;carbonized agglomerates that are widely distributed,usually formed by irregular movements of aluminum agglomerates.The particle size of condensed combustion products is measured by laser particle size meter.As the pressure increases from 0.5 MPa to 1.0 MPa in nitrogen,the mass average particle size of aluminum agglomerates decreases by 49.7%.As the ambient gas is changed from 0.5 MPa nitrogen to 0.5 MPa air,the mass average particle size of aluminum agglomerates decreases by 67.3%.Results show that as the ambient pressure increases,the higher oxygen content can improve combustion efficiency and reduce the average agglomeration size of aluminum particles.

Study on the Detonation Danger of Solid Propellants

A measurement system to study shock initiation behavior of solid propellants was established experimentally. By using this system, the study on shock initiation to the recovered solid propellants with micro damage was performed, especially on the deflagration to denonation transition (DDT) process of solid propellants under both the strong and weak conditions of restriction. The experimental results show that there is a fully compression region in DDT process..

Energetic Opportunities of Solid Composite Propellants Containing Some Hypothetic Furazano-[3,4-d]-pyridazine-based Derivatives

Six furazano-[3,4-d]-pyridazine-based derivatives as main compounds in solid composite propellants have been investigated.It was shown that the use of some furazano-[3,4-d]-pyridazine-based derivatives as main compounds in solid composite propellants can considerably increase ballistic parameters compared with HMX if the compounds under consideration contain difluoramine groups.And the use of the compounds under consideration may be successful only in the presence of an active binder and 10%-30% of AP or ADN as additional oxidizers.

Microwave Attenuation of Solid Propellant Exhaust Plume in Oblique Orientation

Aim To investigate the effects of the incident orientation on the microwave attenuation. Methods Attenuation allowing microwave signal transmitting in an oblique or vertical direction through the solid propellant exhaust plume was computed, and the experiments were performed utilizing a lab scale solid rocket motor with a fully expanded nozzle. Results The predicted results accord well with the experimental results. Conclusion The microwave attenuation in the oblique path is greater than that in the vertical path.

Experimental Investigation on Basic Prototype of Solid Propellant Impulsive Microthrusters

A new type of impulsive microthruster and its measurement system were designed for the aim of testing the performance of a basic prototype of solid propellant impulsive microthruster. Two sets of tests were conducted. The tests show that the ignitor and the main charge of the microthruster match well, the dynamic and static capability of the test and measurement meets the test requirement and the result is creditable. The measured technical characteristics of the microthruster are that the ignition delay time is shorter than 0 3?ms, the total impulse is over 3?N·s, the operational time is shorter than 16?ms and the mass ratio of the thruster is 0 216.

Effect of neutral polymeric bonding agent on tensile mechanical properties and damage evolution of NEPE propellant

Introducing Neutral Polymeric bonding agents(NPBA) into the Nitrate Ester Plasticized Polyether(NEPE)propellant could improve the adhesion between filler/matrix interface, thereby contributing to the development of new generations of the NEPE propellant with better mechanical properties. Therefore,understanding the effects of NPBA on the deformation and damage evolution of the NEPE propellant is fundamental to material design and applications. This paper studies the uniaxial tensile and stress relaxation responses of the NEPE propellant with different amounts of NPBA. The damage evolution in terms of interface debonding is further investigated using a cohesive-zone model(CZM). Experimental results show that the initial modulus and strength of the NEPE propellant increase with the increasing amount of NPBA while the elongation decreases. Meanwhile, the relaxation rate slows down and a higher long-term equilibrium modulus is reached. Experimental and numerical analyses indicate that interface debonding and crack propagation along filler-matrix interface are the dominant damage mechanism for the samples with a low amount of NPBA, while damage localization and crack advancement through the matrix are predominant for the ones with a high amount of NPBA. Finally, crosslinking density tests and simulation results also show that the effect of the bonding agent is interfacial rather than due to the overall crosslinking density change of the binder.

A New Simulation Method for 3D Propellant Grain Burn Analysis of Solid Rocket Motor

Describes a new computer program (Regress-3D) to simulate the regression of complex 3D grain cavity and calculate the burning surface area. It has a large region of applicability in solid rocket motor design and has made new improvements compared with other available codes. User can easily and rapidly build his initial grain shapes and then obtain geometric information of his design. Considering with the calclulting results, redesigning can be performed as desire until reaching at the satisfied result. Advantages and disadvantages of this method are also discussed.

Effects of Metal and Composite Metal Nanopowders on the Thermal Decomposition of Ammonium Perchlorate (AP) and the Ammonium Perchlorate/Hydroxyterminated Polybutadiene (AP/HTPB) Composite Solid Propellant

Effects of metal (Ni, Cu, Al) and composite metal (NiB, NiCu, NiCuB) nanopowders on the thermal decomposition of ammonium perchlorate (AP) and composite solid propellant ammonium perchlorate/hydroxyterminated polybutadiene (AP/HTPB) were studied by thermal analysis (DTA). The results show that metal and composite metal nanopowders all have good catalytic effects on the thermal decomposition of AP and AP/HTPB composite solid propellant. The effects of metal nanopowders on the thermal decomposition of AP are less than those of the composite metal nanopowders. The effects of metal and composite metal nanopowders on the thermal decomposition of AP are different from those on the thermal decomposition of the AP/HTPB composite solid propellant.

Innovative Metallized Formulations for Solid Rocket Propulsion

Several metallized solid rocket propellants,AP/Metal/HTPB in the ratio 68/18/14,were experimentally analyzed at the Space Propulsion Laboratory of Politecnico di Milano.Effects of the metals(micrometric and nanometric Al,B,Mg,and a variety of dual metals) on the performance of the propellant were studied and contrasted to a conventional micrometric aluminum(30 μm average grain size) taken as reference.It is shown that the propellant microstructure plays a fundamental role in controlling the critical aggregation/agglomeration phenomena occurring below and near the burning surface.Two specific effects of microstructure in terms of steady burning rate and average agglomerate size are illustrated.

Multiscale modeling of heterogeneous propellants from particle packing tograin failure using a surface-based cohesive approach

In the present work, a computational frame- work is established for multiscale modeling and analysis of solid propellants. A packing algorithm, considering the am- monium perchlorate （AP） and aluminum （A1） particles as spheres or discs is developed to match the size distribution and volume fraction of solid propellants. A homogenization theory is employed to compute the mean stress and strain of a representative volume element （RVE）. Using the mean results, a suitable size of RVE is decided. Without consider- ing the interfaces between particles and matrix, several nu- merical simulations of the relaxation of propellants are per- formed. The relaxation effect and the nonlinear mechanical behavior of propellants which are dependent on the applied loads are discussed. A new technology named surface-based cohesive behavior is proposed to describe the phenomenon of particle dewetting consisting of two ingredients： a damage initiation criterion and a damage evolution law. Several ex- amples considering contact damage behavior are computed and also nonlinear behavior caused by damaged interfaces is discussed in this paper. Furthermore the effects of the criti- cal contact stress, initial contact stiffness and contact failure distance on the damaged interface model have been studied.

Controllable combustion behaviors of the laser-controlled solid propellant

Microsatellites have been widely applied in the fields of communication,remote sensing,navigation and science exploration due to its characteristics of low cost,flexible launch mode and short development period.However,conventional solid-propellant have difficulties in starting and interrupting combustion because combustion is autonomously sustained after ignition Herein,we proposed a new type of solid-propellant named laser-controlled solid propellant,which is sensitive to laser irradiation and can be started or interrupted by switching on/off the continuous wave laser.To demonstrate the feasibility and investigate the controllable combustion behaviors under different laser on/off conditions,the combus tion parameters including burning rate,ignition delay time and platform pressure were tested using pressure sensor,high-speed camera and thermographic camera.The results showed that the increase of laser-on or laser-off duration both will lead to the decrease of propellant combustion performance during re-ignition and re-combustion process.This is mainly attributed to the laser attenuation caused by the accumulation of combustion residue and the change of chamber ambient temperature.Simultaneously the multiple ignition tests revealed that the increased chamber ambient temperature after combustion can make up for the energy loss of laser attenuation and expansion of chamber cavity.However,the laser-controlled combustion performance of solid propellant displayed a decrease trend with the addi-tion of ignition times.Nevertheless,the results still exchibited good laser-controlled agility of laser-controlled solid propellant and manifested its inspiring potential in many aspects of space missions.

The properties of Sn-Zn-Al-La fusible alloy for mitigation devices of solid propellant rocket motors

The Al and La elements are added to the Sn9Zn alloy to obtain the fusible alloy for the mitigation devices of solid propellant rocket motors. Differential scanning calorimetry(DSC), metallographic analysis,scanning electron microscopy(SEM), energy dispersive spectroscopy(EDS), tensile testing and fracture analysis were used to study the effect of Al and La elements on the microstructure, melting characteristics, and mechanical properties of the Sn9Zn alloy. Whether the fusible diaphragm can effectively relieve pressure was investigated by the hydrostatic pressure at high-temperature test. Experimental results show that the melting point of the Sn9Zn-0.8Al0·2La and Sn9Zn-3Al0·2La fusible alloys can meet the predetermined working temperature of ventilation. The mechanical properties of those are more than 35% higher than that of the Sn9Zn alloy at-50°C-70°C, and the mechanical strength is reduced by 80% at 175°C. It is proven by the hydrostatic pressure at high-temperature test that the fusible diaphragm can relieve pressure effectively and can be used for the design of the mitigation devices of solid propellant rocket motors.

Experimental Investigation on Combustion Performance of Solid Propellant Subjected to Erosion of Particles with Different Concentrations

A test device with rectangular channel is developed to study the combustion performance of solid propellant in high temperature particles erosion.The flowfields in this newdevice and a test device with circular channels are simulated numerically.The particle erosion experiments in these two devices are carried out under different particle concentrations.The results showthat the test device with rectangular channel can effectively improve the clarity and precision of combustion diagnosis image and can be used for research on combustion performance of solid propellant under lowconcentration particle erosion;the circular channel device has good particle convergent effect,provides high concentration particle erosion,and can be used for research on the combustion performance of solid propellant under high concentration particle erosion.The experiment data indicates that the propellant burning rate does not change obviously in lower particle concentration;the propellant with lower static burning rate increases remarkably under particle erosion,while the propellant with high static burning rate is not sensitive to the particle erosion.

Ballistic Properties of Some Low Solid Loading Butalites Formulations

The ballistic properties of a low solid loading composite solid propellant family （Butalites） was studied experimentally by using propellant formulations based on hydroxy-terminated polybutadiene pre-polymer （HTPB） as fuel binder main backbone, mono and bi-modal system ammonium perchlorate oxidizer （AP）, copper chromite （CC） as burning rate accelerator and aluminum powder （A1） as metallic fuel. Higher pressures and AP contents as well as smaller AP particle size were found to increase burning rate. The same behavior verified with AI and CC addition. A significant increase of burning rate was recorded when CC added to the aluminized formulations compared with the non-aluminized of the same oxidizer solid loading and particle size.

Combustion Properties of Some High Solid Loading Butalites Compositions

The combustion （ballistic） properties of a high solid loading composite solid propellant family （Butalites） was studied experimentally by using propellant formulations based on hydroxy-terminated polybutadiene pre-polymer （HTPB） as a fuel binder main backbone, bimodal system ammonium perchlorate oxidizer （AP） and aluminum powder （AI） as metallic fuel. Burning rates were doubled at various pressures, when solids loading （AP and 17% A1） were increased from 80 to 88% and the measured characteristic velocity values were increased by about 100m/sec. The pressure exponent （n） values were lower with 80-85% solids loading. The burning rates were increased by about 2-5% when comparing the data obtained by static firing with those obtained by the strand burner method.

The Influence of Aziridine on the Aging of Composite Solid Rocket Propellant

Aging of a solid composite propellant containing HTPB/AP/AL was performed in order to validate the conformance of the accelerated aging data to the Arrhenius law. The main objective of the work was to examine the influence of the aziridine bonding agents family on the propellant aging. Aging of the prepared propellant samples was conducted as follows: 1. Four samples, one free of bonding agents, and three containing aziridine based bonding agents MAPO,HX-752, MAT4 were aged at 65°C. 2. Another four samples based on HX-752, MAT4 with different curing agents were aged at 65°C. The measured mechanical properties of the free bonding agent propellant samples were very far from the specifications and this illustrates the importance of the bonding agents in both the preparation and the aging phases.The prepared bonding agent 'MAT4' gave remarkable improvements of the mechanical properties comparing with HX-752 and MAPO. The aziridine bonding agents family inhibited the rate of decomposition of the propellant during the aging periods and supported the propellant matrix against decomposition at the elevate temperatures. Using of HMDI as curing agent gave slight better mechanical properties to the IPDI.

Infrared radiation signature of exhaust plume from solid propellants with different energy characteristics

The infrared radiation signature of the plume from solid propellants with different energy characteristics is not the same. Three kinds of double-base propellants of different energy characteristics are chosen to measure the infrared spectral radiance from 1000 cm 1 to 4500 cm 1 of their plumes. The radiative spectrum is obtained in the tests. The experimental results indicate that the infrared radiation of the plume is determined by the energy characteristics of the propellant. The radiative transfer calculation models of the exhaust plume for the solid propellants are established. By including the chemical reaction source term and the radiation source term into the energy equation, the plume field and the radiative transfer are solved in a coupled way. The calculated results are consistent with the experimental data, so the reliability of the models is confirmed. The temperature distribution and the extent of the afterburning of the plume are distinct for the propellants of different energy characteristics, therefore the plume radiation varies for different propellants. The temperature of the fluid cell in the plume will increase or decrease to some extent by the influence of the radiation term.

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.