Solid Propellant Research Articles

Trinitroethyl hydrazides of dicarbonic acids – Energetic compounds with high oxygen and nitrogen content

AbstractMany currently used energetic materials need to be replaced with new compounds due to toxicity or other drawbacks. Among these is the oxidizer ammonium perchlorate, often used in solid state propellants, which itself, as well as its combustion products, poses health and environmental issues. Herein, three new polynitro energetic compounds are presented containing trinitroethyl moieties. Starting from easily available starting materials, such as malonic acid ethylester, diglycolic and diaminodiacetic acid, simple and straightforward syntheses were performed to obtain first the corresponding hydrazides and subsequently the trinitroethyl hydrazides in good yields and high purity. These compounds have a positive oxygen balance (assuming to the formation of CO), a high oxygen and nitrogen content and moderate densities. Full characterization was performed by NMR spectroscopy, vibrational analysis and elemental analysis. By using the Gaussian program package, the heats of formation were calculated and the energetic parameters were estimated utilizing the EXPLO5 computer code.

A novel dynamic simulation method for investigating the hygroscopicity of Ammonium perchlorate

Ammonium perchlorate (AP) is a widely used oxidizer, extensively employed in solid propellants with excellent combustion properties. Ultrafine AP has better combustion properties, but its strong hygroscopicity and high sensitivity hinder its application. To safely and efficiently explore the hygroscopicity of ultrafine AP, this paper proposes a novel molecular dynamics (MD) simulation approach. By analyzing the movement of water molecules, fluctuations in average hydrogen bond strength, and the influence of non-covalent intermolecular forces throughout the moisture absorption process, this study presents a comprehensive overview of the hygroscopic properties of ultrafine AP across relative humidity (RH) levels spanning from 10 % to 100 %, and temperatures ranging between 273 K and 373 K. It was found that temperature has a more significant impact on the hygroscopicity of AP compared to RH. During the hygroscopic process of AP, Van der Waals interactions hindered the water absorption of AP, while electrostatic forces promoted its hygroscopic properties. The hygroscopicity of AP reached a maximum when the temperature exceeded 333 K, and plateaued as the increase of RH. The proposed moisture simulation method facilitates the secure and effective forecasting of moisture absorption in AP-based materials across various temperature and RH environments, thereby greatly expediting research on enhancing the moisture resistance of ultrafine AP.

Thermal shock triggers microexplosion combustion in graded fuel and oxidizer encapsulation microspheres with improved combustion efficiency

The combustion agglomeration of aluminum (Al) and the long heat and mass transfer distance between Al and oxidizer cause serious two-phase flow loss and slag accumulation in the engine of solid propellants. Here, we present an effective strategy by in-situ encapsulating graded nano-aluminum (nAl) and micron-aluminum (μAl) in ammonium perchlorate (AP) simultaneously by using hydroxymethyl cellulose (HMC) as adhesive and constructing a compact coupling fuel oxidizer complex high-energy microsphere (μAl/nAl@AP/HMC) to enhance the energy release efficiency and combustion efficiency. Compared with physical mixture (PM), the ignition delay time and combustion time of μAl/nAl@AP/HMC microspheres are reduced by 69.58 % and 69.87 %, owing to the decomposition process control of AP through the adsorption and spatial constraint effect on the interface between metal fuels and oxidizer. Furthermore, the nAl embedded in the AP surface forms a hot spot around the μAl to promote the combustion reaction, thereby shortening the cavitation threshold and tensile limit time of μAl and accelerating the occurrence of microexplosion. Microexplosion effect in μAl/nAl@AP/HMC microsphere significantly weakens combustion agglomeration and improves combustion efficiency and energy release efficiency by sharp shrinkage of combustion condensation products, which addresses the challenges on energy output and combustion efficiency in high-density solid propellants.

Experimental measurement and molecular dynamics simulation analysis of thermal aging performance in composite solid propellants

As a complex mixed system, the aging mechanism of high-energy composite materials involves the aging of each component itself, interactions between components, and transformation of microstructural and thermodynamic properties. The study of a single component or performance parameter has great limitations for elaborating the cognitive complexity of aging processes, making it difficult to reveal the underlying principles of physicochemical property transformation. Thus, it can only be applied as an empirical summary. In view of this, this study comprehensively utilized numerical analysis and experimental detection to explore the evolution of micromolecular conformation and changes in macro aging performance from four aspects of composite systems, including binder aging, plasticizer migration, bond interface debonding, and mechanical property transformation. There was good consistency observed between molecular simulation and thermal aging experiments, indicating that there was basically no post curing process for HTPB propellants using TDI as the curing agent. In the early stage of aging, scission chain was the main process and, in the later stage of aging, oxidation crosslinking the main process. Oxidative crosslinking increased the mean square radius of gyration and glass transition temperature of the binder system, reduced the peak value of radial distribution function, and revealed the reason for the change of propellant hardness and CC and CO double bond content. However, chain degradation increased the number of polar groups, enhanced intermolecular polarity, reduced the solubility parameter, and increased the free volume fraction of the mixed system and the dioctyl sebacate diffusion coefficient. This resulted in an increase in the tangent value of the HTPB propellant loss angle from 0.43 to 0.44° and a decrease in the glass transition temperature from 203.3 to 202.0 K. The binding energy at the interfaces of AP/HTPB and Al/HTPB increased first and then decreased, which was consistent with SEM images of bonding interfaces. The joint effect of binding energy and mechanical properties of the binder system promoted the transformation of the stress-strain curve of aging propellant.

MOF-74 derivatives spinel CuCo2O4/C with d-band center modulation for accelerating ammonium perchlorate thermolysis

As one of main components of solid propellant, ammonium perchlorate (AP) shows slow sluggish decomposition kinetics with unconcentrated heat release. In the past, researchers have done a lot of work using spinel oxides as combustion modifiers to improve the combustion performance of AP. However, AP decomposition process is very complicated, and the relationship between intrinsic activity of cobalt-based spinel catalysts and AP combustion process is still unclear. In this paper, a series of cobalt-based spinel structure catalysts, MCo2O4/C, were prepared by pyrolysis of cobalt-containing bimetal MOF-74 and used as AP combustion catalysts. All of them showed excellent catalytic performance, among which CuCo2O4/C had the best catalytic activity. It effectively reduces the activation energy of the reaction, speeds up the reaction rate, and reduces the peak temperature of the AP decomposition reaction by 161.2 ℃, and the reaction rate k is 10.28 times of Co3O4/C. XPS and NH3-TPD tests indicate that substitution CoTd2+ with Cu2+ increases the ratio of Co3+/Co2+ and enhance interaction between NH3 and catalyst. The essential reason is that Cu–O-Co corner sharing effect changes electron distribution and enhances CoOh3+ Lewis acidity accompanied with the proximity of d-band center to EF by density functional theory calculations.

Analysis of the mechanical response of solid rocket engine propellant under acceleration shock

The increased-range solid rocket engine of new ammunition often needs to withstand extremely high acceleration overload, leading to damage to the propellant’s structural integrity. To address this issue, this paper constructs a nonlinear viscoelastic constitutive model for the CMDB propellant by using low- and high-strain rate mechanical property tests. Combined with the secondary development of explicit dynamics and numerical simulation technology, the mechanical response of a certain type of solid rocket propellant under different acceleration impacts is analyzed. The results show that under acceleration impact loads, the propellant will compress, rebound, and recover over time, continuously cycling. Its axial displacement, maximum equivalent stress, and maximum equivalent strain exhibit irregular sinusoidal wave-like periodic cycles. Looking at the time when the peaks appear, the time when the maximum equivalent stress appears always lags behind the time when the maximum axial displacement peak appears. Due to the viscous effect of the viscoelastic material of the propellant, the time when the equivalent strain peak appears will lag behind the equivalent stress. Because of the material’s damping effect, both the peak values of the maximum equivalent stress and equivalent strain decrease over time. Under continuous high acceleration impact loads, this viscous damping phenomenon continuously diminishes, and the peak value of the propellant’s axial displacement gradually increases.

Microstructure and interaction in aluminum hydrides@polydopamine composites and interfacial improvement with GAP adhesive.

The reduction of interfacial interaction and the deterioration of processing properties of aluminum hydrides (AlH3) is the main challenges preventing its practical application. Here, a simple and effective core-shell structure aluminum hydrides@polydopamine (AlH3@PDA) complex was constructed through in-situ polymerization. The evolution of element states on the surface of AlH3 conducted by X-ray photoelectron spectroscopy indicated the successful introduction of PDA to form the core@shell structure, the thickness of the PDA coated layer increased with the increasing PDA dosage from 0.1 to 1.6% in mass fraction, and the maximum of thickness is 50nm in TEM testing. Py GC/MS results proved that the increase of dopamine concentration leads to higher proportions of self-assemble units, whereas lower dopamine concentrations favor higher levels of chemical bonded components. Regarding whether PDA is a covalent polymer or a noncovalent aggregate of some species, the formation of intermediates, such as dopaminechrome and 5,6-dihydroxyindole played an important role to coordination interaction with AlH3 in FTIR, Raman, and UV-Vis spectra testing. Compared with pure AlH3, the formation of organic PDA coating improved AlH3 heat resistance. The adhesion work with GAP adhesive was also improved from 107.02J/m2 of pure AlH3 to 111.13mJ/m2 of AlH3@PDA-5 complex. This paper provides well support for further practical application of AlH3 in solid propellants.

Preparation and Reactivity of Core-Shell Al@CL-20 Composites Embedded with Graphene-Based Complexes as Catalysts.

Incomplete combustion of Al in solid propellants can be effectively resolved by coating of an oxidizer at the microscale. In this paper, Al@CL-20 composites with polydopamine as the interfacial layer were prepared using this strategy. The structure, heat of reaction, thermal decomposition properties, and combustion performances of these composites under the effects of graphene oxide (GO) and graphene-based carbohydrazide complexes (GO-CHZ-M, M = Co2+, Ni2+) have been comprehensively investigated. The experimental results show that the heat of reaction of Al@CL-20 is 6482 J g-1, which is 561 J g-1 higher than that of the corresponding mechanical mixture. The presence of GO-CHZ-Co can further increase the heat of reaction of Al@CL-20 to 6729 J g-1 with a decreased activation energy by about 54.8%. Under the synergistic effect of interfacial control and GO-CHZ-M, the ignition delay time of Al@CL-20-Co decreases from 5.1 to 4.2 ms. Besides, the D50 of the combustion condensed products (CCPs) decreased from 5.62 to 4.33 μm, indicating the combustion efficiency of Al is greatly improved.

Synthesis of propellant grade HHTPB by hydrogenation of HTPB using Pd-activated charcoal as catalyst

To derive more performance from the conventional composite propellant based on hydroxyl-terminated polybutadiene (HTPB) and ammonium perchlorate (AP), it is envisaged to hydrogenate HTPB, which increases the H/C (hydrogen to carbon ratio) of the base polymer. This paper attempts to describe the partial hydrogenation of HTPB using a catalytic method that uses palladium supported by activated charcoal as a catalyst and HTPB polymer as a precursor. HTPB has a hydroxyl value of 41.0 mg KOH/g with a number-average molecular weight (Mn) of 6150, polydispersity (PD) of 2.25 was used as a precursor. Iso-propyl alcohol (IPA) and toluene were used as a solvent media to disperse the HTPB polymer during hydrogenation. The estimate revealed an increase in specific impulse (ISP) up to 1.2 s with ∼37 % hydrogenated HTPB (HHTPB) as binder in composite solid propellants. Partial hydrogenation is only attempted to retain other process capabilities essential for realizing a defect-free solid propellant grain with good structural integrity. In contrast, others attempted to reach near saturation. A reactor capacity of 100 ml, operating at 60 bar pressure, was used to synthesize HHTPB, and the extent of hydrogenation was controlled based on the numerous experiments varying the reactor parameters like operating temperature, operating pressure, and solvent-to-polymer ratio for a given catalyst concentration. Detailed characterization of the end product by FTIR, 1H NMR and 13C NMR to reveal the degree of hydrogenation along with generic polymer characteristics. The measured hydroxyl value of HHTPB is comparable with HTPB; however, a marginal increase in molecular weight and polydispersity was noticed at 37 % conversion, wherein other researchers found a loss in -OH value. Thermogravimetry analysis revealed that no significant change in the gasification rate. A slight increase in the H/C ratio and calorific value was observed for HHTPB compared to HTPB. Despite the increase in viscosity of HHTPB, the increase in the vinyl-type functional distribution of HHTPB aids for better process-ability during propellant processing. However, the propellant formulation should be optimized with the help of plasticizers, solid loading, etc., to achieve the required properties.

Ablative laser propulsion, the propellants and measuring parameters: A brief review

Keeping in view the weightage of electric propulsion over chemical propulsion, materials from metals to polymers and liquid (water) have been tested as propellants in ablative laser propulsion. This emerging propulsion technique can be widely used for aerospace applications like debris removal in the range of cm, pointing micro and nano satellites, laser micro thrusters for spacecraft attitude, and orbit control. Laser propulsion can become a less expensive alternative to chemical propulsion. In this review, we compile the work done in ablative laser propulsion and different modes of propulsion along with the efficiency of different propellants. We summarize the optimized propulsive parameters with solid propellants and liquid propellants along with the efficiencies and theories of laser thrusters with optimized specific impulses. The article provides precise developments done in the field of ablative laser propulsion and deep insights into the analysis done between the different propellants used recently in ablative laser propulsion.

Nitramino-polymer with ether bridges and 1,2,3-triazole subunits incorporated into the polymer chain

The creation of novel energetic polymers for future advanced solid composite propellants and gunpowder is an urgent area of modern research. A simple and effective waste-free cycloaddition reaction between dialkyne and diazide comonomers, both bearing nitramine groups, for the synthesis of an energetic polymer containing explosophoric units in the polymer chain has been described. Neither solvent nor catalyst is required for the production of this polymer, the comonomers used are readily available, and the product does not need any purification, and, importantly, this protocol scales well. The resulting polymer, C1Z1, (C14H22N12O8)n, was comprehensively characterized by spectral and physico-chemical methods. Compatibility with energetic plasticizers (NG, DNDEG, DANPE), thermochemical characteristics and combustion features indicate the prospects of target polymer C1Z1 (density, ρ = 1.484 g/cm3; onset temperatures is 230 °C; positive enthalpy of the formation, ΔHf0 = +636 kJ/kg; burning rate at 10 MPa is 9.5 mm/s) as a binder base for energetic materials. Comparison of C1Z1 with nitrocellulose (NC) and their compositions with plasticizers revealed the advantages of C1Z1.

Simulation study on the breakup process of kerosene Gel Jet in transverse airflow

The gel propellant not only inherits the characteristics of liquid propellants, such as high specific impulse, multiple ignition capabilities, and adjustable thrust, but also offers an advantage type of solid propellants, including reduced risk of leakage, long-term storage feasibility, and ease of maintenance. In this study, numerical simulations were conducted to investigate the atomization and mixing process of kerosene gel jets in high-speed crossflows. The study reveals that the jet breakup process primarily involves two forms of breakup: columnar breakup dominated by Rayleigh Taylor’s unstable wave and surface breakup dominated by Kelvin Helmholtz’s unstable wave. These two forms coexist, complement each other, and interact with each other. The numerical simulation of the kerosene gel breakup process provides favorable support for studying its combustion characteristics in the rotating detonation engine.

Exploring the combustion mechanism of single micron-sized aluminum particles with a numerical model

In this work, we explore the combustion mechanism of single micron-sized aluminum particles using a numerical model. The Burcat database and Catoire mechanism is considered as the thermodynamic data and the kinetic mechanism for our numerical model of aluminum combustion. Two independent experiments, including particle temperature profiles, ignition delay and burning time, are selected to evaluate the performance of the numerical model. The model shows great agreement for all considered properties. A parametric study is further conducted to identify the effect of involved physical parameters on the combustion process. The diffusion coefficient (D) of oxidizers and the activation energy of surface kinetics (Esurf) and evaporation coefficient (α) of aluminum impact the particle temperature the most. Burning time is most sensitive to the activation energy of surface kinetics (Esurf). The optical measurement in a solid propellant combustion indicates that the contact angle of the oxide cap on Al particle is between 10° and 20°. It is found that the selection of contact angle of the oxide cap significantly impacts the prediction of combustion time and residual of active aluminum. The current work highlights the importance of physical properties on the prediction of Al combustion, suggesting that more detailed evaluation from experiments and theory is encouraged.

Machine Learning in Combustion: Optimization of Fuel Combustion of Rockets

Application of Machine Learning (ML) Techniques in research has seen a drastic increase in past few years and the main aspect of it in the rocket propulsion is to understand the combustion process and finding various methos to optimize it. This paper provides an overview of the relationship between machine learning and combustion with a specific focus on optimizing the rocket fuel combustion. The introduction presents an overview of Combustion and various ways which the ML is associated with it. Subsequently, the paper also discusses about the various ML algorithms which extends its discussions with the supervised, unsupervised and semi-supervised learning techniques and some of its types. An overview of different types of rocket engine is presented for the understanding of the characteristics, advantages and disadvantages of the commonly used rocket engines such as solid, liquid and hybrid propellant ones. Focusing on rocket fuel combustion, the discussion extends to various methods of optimization of the combustion process. Finally, the paper presents comprehensive results and discussions derived from the studies conducted on rocket fuel combustion optimization.

Overview of the Current State of Physical-Mathematical Modelling of Solid Fuel Combustion Processes

This study provides a comprehensive introduction to the combustion of solid propellants. We conduct a thorough review of existing physical-mathematical models related to solid fuel combustion processes. Additionally, we explore the heat propagation within the solid phase, examine the physical chemical processes in the k–phase, and investigate the fundamental solution of the heat conduction equation in a multiphase (k–phase) medium. The heat conduction equation plays a crucial role in governing the temperature distribution within a given material, and a profound understanding of its fundamental solution is essential for various engineering and scientific applications. In this research, we expand our analysis to a multiphase scenario, considering different phases with distinct thermal properties coexisting.

Kinetic models of HMX decomposition via chemical reaction neural network

1,3,5,7-Tetranitro-1,3,5,7-tetrazocane (HMX) is commonly used in solid propellants and explosives as energetic materials. The study of its kinetics and decomposition mechanism is of great significance to its application in the aerospace industries. This work investigates the thermal decomposition of HMX based on the combined thermogravimetric (TG) measurements and chemical reaction neural network (CRNN). Two compact kinetic models for HMX are introduced, with one consisting of four substances and a single global reaction (4–1 model) and the other consisting of four substances and four reactions (4–4 model). In the 4–1 model, the calculated activation energy is 328.44 kJ·mol−1, which agrees with the experimental value. As for the 4–4 model, the substances and reactions are assigned based on a skeleton mechanism involving reactions of N-N and C-N bond cleavage and HONO elimination. Moreover, the catalytic effects of TiO2 and Al2O3 on HMX are well simulated using the aforementioned kinetic models. The CRNN models can reproduce the peak temperature with a reduced activation energy, but the initial decomposition temperature is overestimated owing to the complex nature of catalytic impact. This work presents the application of the CRNN model to obtain a decomposition mechanism of HMX, highlighting its efficacy in accurately capturing the thermal decomposition behavior. The potential extension of CRNN to kinetic modeling of other energetic materials is anticipated in future studies.

Investigation of aluminum particle ignition dynamics in various propellant environments

The ignition delay of aluminum particles can be profoundly influenced by the agglomeration and combustion characteristics of solid propellants. In this experimental study, the ignition of individual aluminum particles in nitrate ester plasticized polyether (NEPE) and hydroxyl‑terminated polybutadiene (HTPB) propellant atmospheres was examined using laser ignition tests and high-speed photography. Focus was directed at the effects of the atmospheric composition, pressure, and aluminum particle size (500, 800 and 1000 µm). It was observed that the non-homogeneous reaction heat generation and convective heat exchange rates during particle ignition could be increased by increasing the CO2 content or ambient temperature, resulting in a shorter ignition delay time. This explains why aluminum particles tended to burn more efficiently in nitrate ester plasticized polyether than in hydroxyl‑terminated polybutadiene. In addition, it was found that the ignition delay time decreased with increasing pressure and was inversely proportional to the particle size squared. An ignition model for aluminum particle ignition in a multi-component atmosphere was developed and validated to describe the temperature change and energy transfer during ignition. The calculated ignition delay times were found to be within 5% of the experimental values. The model also showed that increasing the ambient temperature was more effective than increasing the CO2 content at enhancing ignition, and that CO2 was more effective than O2, which was itself more effective than H2O. Overall, this study provides useful insight into the ignition characteristics of aluminum particles in different propellant environments. The results could be used to develop more effective propellant formulations, optimize combustion processes, and improve safety in the handling and use of aluminum-based propellants.

Effect of Using Fractals as Grain Configuration on the Performance of Solid Rocket Motors

Grain design is a very crucial consideration for determining the performance of solid propellant rocket motors. A rocket’s performance and combustion characteristics (thrust profile, chamber pressure variation, propellant mass flow rate, and sliver among other important performance parameters) depend very strongly on the grain configuration. We propose fractal shapes (Koch star, Koch snowflake, Gosper, and Cesaro) as new port geometries and theoretically predict their performance using simulations based on the fast-marching method implemented in the open-source software Open-Motor. The initial thrust for fractal geometry grains was found to be significantly higher than the commonly used industry standard BATES and Finosyl ports. The fractal grains also showed a significant decrease in sliver as compared to the Finocyl port that is generally used to increase performance as compared to the circular BATES ports. Especially, The Koch snowflake port had a drastically lower sliver. These new grain geometries proposed in this work can be used for applications in which low initiation and ignition times along with high initial thrust are crucial. Moreover, these geometries can improve the performance of the solid rocket motor (SRM) owing to their better regression characteristics which promise complete utilization of the entire grain web.

Thermal structural damage and thermal decomposition characterization of GAP propellants with nitrate ester plasticizers

AbstractGAP and nitrate ester compounds are introduced into the solid propellant formulation as energetic binders and energetic plasticizing agents, respectively, to further enhance the energy level of solid propellants. However, under abnormal thermal conditions, various components within GAP propellants, especially nitrate ester plasticizers, can collectively result in the generation of a large number of voids within the propellant due to factors such as thermal stress and slow component decomposition. This phenomenon can impact the safety of solid rocket engines, necessitating research into their thermal decomposition processes and thermal damage structures. In this study, the thermal decomposition characteristics and gas products of GAP propellants with different nitrate ester plasticizer formulations were investigated using DSC‐TG and FT‐IR. The damage structure of GAP propellants heated under unignited conditions was studied through Micro‐CT, examining the influence of heating conditions and nitrate ester plasticizers on the thermal damage structure of GAP propellants. During heating, the thermal damage structure of GAP propellants was found to include voids generated within the GAP binder and cracks at the interface between the GAP binder and particles, with nitroglycerin as a plasticizer exacerbating the thermal damage of GAP propellants (about 2.2–2.9 times).

Synchronized measurement method of burning rate and combustion temperature of a solid propellant specimen

To characterize the combustion properties of solid propellants, the synchronized measurement method of burning rate and combustion temperature is proposed combined shadow imaging and radiation imaging. Using spectroscopic and filtering imaging, shadow and radiation images of a solid propellant specimen are obtained synchronously. Burning rate is calculated by burning surface movement velocity of shadow images, and combustion temperature is calculated by radiation image thermometry. Measurement accuracies of burning rate and combustion temperature of the solid propellant specimen are validated by other independent measurement methods. On this basis, the synchronized measurements of burning rate and combustion temperature of different formulations of solid propellant specimens under different working conditions are carried out. The results show that the influence on burning rate and combustion temperature of pressure and formulas is different. Therefore, the synchronized measurement of burning rate and combustion temperature can provide more direct data support for the evaluation of solid propellant combustion performance.