Conventional plasticizers deteriorate mechanical and viscoelastic properties of the propellants due to their migration upon aging and long-term storage,which affects reliability and safety properties during exploitati...Conventional plasticizers deteriorate mechanical and viscoelastic properties of the propellants due to their migration upon aging and long-term storage,which affects reliability and safety properties during exploitation.To address this issue,conventional plasticizer,dioctyl adipate(DOA),is replaced by reactive one,castor oil(CO).In addition,three different types of HTPB were used to obtain propellants with designed viscoelastic and mechanical properties.The CO increased propellants viscosity,without a significant impact on the propellant processability,regardless to the type of prepolymer.Conversely,mechanical properties were different depending on the type of resin,which were further analyzed by gel permeation chromatography(GPC).Addition of CO formed a denser polymer network and shifted T_(g) to higher values,compared to the compositions with DOA.The tensile strength of CO-containing propellants was lower at +20℃ and +50℃ compared to the reference compositions,while the strain at maximum load and strain at break were significantly increased with pronounced plastic deformation,especially for samples at -30℃.The inclusion of CO in the propellants composition gives more room for adjusting a wide range of mechanical properties.展开更多
Appropriate drying process with optimized controlling of drying parameters plays a vital role in the improvement of the quality and performance of propellant products.However,few research on solvent transport dynamics...Appropriate drying process with optimized controlling of drying parameters plays a vital role in the improvement of the quality and performance of propellant products.However,few research on solvent transport dynamics within NC-based propellants was reported,and its effect on the evolution of mechanical properties was not interpreted yet.This study is conducted to gain a comprehensive understanding of hot-air drying for NC-based propellants and clarify the effect of temperature on solvent transport behavior and further the change of mechanical properties during drying.The drying kinetic curves show the drying time required is decreased but the steady solvent content is increased and the drying rate is obviously increased with the increase of hot-air temperatures,indicating hot-air temperatures have a significant effect on drying kinetics.A modified drying model was established,and results show it is more appropriate to describe solvent transport behavior within NC-based propellants.Moreover,two linear equations were established to exhibit the relationship between solvent content and its effect on the change of tensile properties,and the decrease of residual solvent content causes an obvious increase of tensile strength and tensile modulus of propellant products,indicating its mechanical properties can be partly improved by adjustment of residual solvent content.The outcomes can be used to clarify solvent transport mechanisms and optimize drying process parameters of double-based gun propellants.展开更多
To simplify the composite propellant formulation and address the current issue of the single-functionality present in existing additives,the multi-cyano,amine-based polybutadiene(AEHTPB-CN)was prepared based on AEHTPB...To simplify the composite propellant formulation and address the current issue of the single-functionality present in existing additives,the multi-cyano,amine-based polybutadiene(AEHTPB-CN)was prepared based on AEHTPB by adopting appropriate synthesis strategies.By replacing 10% of HTPB binder in the propellant formulation,it can effectively enhance the interfacial bond strength between the propellant binder matrix and solid fillers(AP(ammonium perchlorate)and RDX(cyclotrimethylene-trinitramine)),the mechanical properties of the HTPB/AP/RDX/Al propellant were superior to blank control propellant with an improvement of 35.4% in tensile strength,62.0% enhancement in elongation at break,and reduce the propellant burn rate by 10.7% with any energy loss.The function mechanism of AEHTPB-CN was systematically elucidated through experiments and computer simulation techniques.The results show that the tertiary amine group in AEHTPB-CN can react with AP to form ammonium ionic bonds,and the hydroxyl and cyano groups can form hydrogen bonding interactions with AP,which enables AEHTPB-CN to be firmly adsorbed on the AP surface through chemical and physical interactions.For RDX,the interfacial bonding effect of AEHTPB-CN is attributed to their ability to form C-H···N≡C weak hydrogen bonding interaction between the cyano group and RDX methylene group.展开更多
The severe erosion and inadequate mechanical strength are prominent challenges for high-energy gun propellants.To address it,novel PTW@PDA composites was prepared by polydopamine(PDA)-modifying onto potassium titanate...The severe erosion and inadequate mechanical strength are prominent challenges for high-energy gun propellants.To address it,novel PTW@PDA composites was prepared by polydopamine(PDA)-modifying onto potassium titanate whisker(PTW,K_(2)Ti_(6)O_(13)),and after was incorporated into gun propellant as erosion-reducing and mechanical-reinforcing fillers.The interfacial characterizations results indicated that as-prepared PTW@PDA composites exhibits an enhanced surface compatible with propellant matrix,thereby facilitating their dispersion into propellants more effectively than raw PTW materials.Compared to original propellants,PTW@PDA-modified propellants exhibited significant less erosion,with a Ti-Kbased protective coating being detected on the eroded steel.And 0.5 wt%and 1.0 wt%addition of PTW@PDA significantly improved impact,compressive and tensile strength of propellants.Despite the inevitably reduction in relative force,PTW@PDA slightly increase propellant burning rate while exerting little adverse impact on propellant dynamic activity.This strategy can provide a promising alternative to develop high-energy gun propellant with less erosion and more mechanical strength.展开更多
Drying is a complicated physical process which involves simultaneous heat and mass transfer in the removal of solvents inside propellants.Inappropriate drying techniques may result in the formation of a hard skin laye...Drying is a complicated physical process which involves simultaneous heat and mass transfer in the removal of solvents inside propellants.Inappropriate drying techniques may result in the formation of a hard skin layer near the surface to block the free access of most solvent through for long stick propellants with large web thickness,which lead to lower drying efficiency and worse drying quality.This study aims to gain a comprehensive understanding of drying process and clarify the mechanism of the blocked layer near the propellant surface.A new three-dimensional coupled heat and mass transfer(3D-CHMT)model was successfully developed under transient conditions.The drying experiment results show that the 3DCHMT model could be applied to describe the drying process well since the relative error of the content of solvent between simulation and experiment values is only 5.5%.The solvent behavior simulation demonstrates that the mass transfer process can be divided into super-fast(SF)and subsequent minorfast(MF)stages,and the SF stage is vital to the prevention of the blocked layer against the free access for solvent molecules inside propellant grains.The effective solvent diffusion coefficient(Deff)of the propellant surface initially increases from 3.4×10^(-6)to 5.3×10^(-6)m^(2)/s as the temperature increases,and then decreases to 4.1×10^(-8)m^(2)/s at 60-100 min.The value of Deffof surface between 0-1.4 mm has a unique trend of change compared with other regions,and it is much lower than that of the internal at100 min under simulation conditions.Meanwhile,the temperature of the propellant surface increases rapidly at the SF stage(0-100 min)and then very slowly thereafter.Both the evolution of Deffand temperature distribution demonstrate that the blocked layer near the propellant surface has been formed in the time period of approximately 0-100 min and its thickness is about 1.4 mm.To mitigate the formation of blocked layer and improve its drying quality of finial propellant products effectively,it should be initially dried at lower drying temperature(30-40℃)in 0-100 min and then dried at higher drying temperature(50-60℃)to reduce drying time for later drying process in double base gun propellants.The present results can provide theoretical guidance for drying process and optimization of drying parameters for long stick propellants with large web thickness.展开更多
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 ve...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.展开更多
The monolithic foamed propellants with high densities were prepared by casting and two-step foaming processes.Glycidyl azide polymer(GAP)and isocyanate were used as the binder system and 2,4,6,8,10,12-hexanitro-2,4,6,...The monolithic foamed propellants with high densities were prepared by casting and two-step foaming processes.Glycidyl azide polymer(GAP)and isocyanate were used as the binder system and 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane(HNIW,CL-20)was employed as the energetic component.The newly designed formulation containing 60%CL-20 produced a force constant of 1077 J/g and low flame temperature of 2817 K.Two foamed propellants with densities of 1.32 g/cm^(3)and 1.53 g/cm^(3)were fabricated by a confined foaming process and examined by closed bomb tests.The results revealed that porosity significantly affects burning performance.A size effect on combustion behaviors was observed for the foamed propellant with 5.56%porosity,and a double-hump progressive dynamic vivacity curve was obtained.At last,the 30 mm gun test was carried out to demonstrate the interior ballistic performance,and the muzzle velocity increased by 120 m/s at the same maximum chamber pressure when monolithic propellant was added in the charge.展开更多
The experimental values of the enthalpy of formation of two isomeric 3,4-and 3,5-dinitro-1-(trinitromethyl)-1H-pyrazoles have been obtained(261.5±5.0and 246.4±6.7kJ/mol for crystalline 3,4-and 3,5-dinitro-1-...The experimental values of the enthalpy of formation of two isomeric 3,4-and 3,5-dinitro-1-(trinitromethyl)-1H-pyrazoles have been obtained(261.5±5.0and 246.4±6.7kJ/mol for crystalline 3,4-and 3,5-dinitro-1-(trinitromethyl)-1H-pyrazoles,respectively).The ballistic effectiveness of these potential oxidizers in composite solid propellants was studied.It is shown that these two oxidizers may be successfully applied in metal-free compositions or with a small content of metal.For the bottom stage 3,4-dinitro-1-(trinitromethyl)-1H-pyrazole is a bit better than 3,5-dinitro-1-(trinitromethyl)-1H-pyrazole,for the upper stage the both oxidizers show the equal ballistic parameters.These oxidizers allow to create metal-free solid composite propellants with the binder percentage not lower than 19%(volume fraction),with I3spequal to 256.5-257.0sat density equal to 1.72-1.74g/cm^3.展开更多
A kind of phase change material(PCM)-based nanocomposite was prepared and added into high energy propellants containing RDX as additives to investigate its effect on thermal decomposition and burning characteristic of...A kind of phase change material(PCM)-based nanocomposite was prepared and added into high energy propellants containing RDX as additives to investigate its effect on thermal decomposition and burning characteristic of high energy propellants.The effect of PCM-based nanocomposites on thermal decomposition of high energy propellants is investigated by TG/DSC-FTIR-MS technology.Due to the delayed protection effect(PCM-based nanocomposites can absorb lots of heat at the range of certain temperature when it undergoes structure change or phase transitions)of PCM-based nanocomposites under the thermal decomposition condition,the thermal stability of high energy propellants modified with PCMbased nanocomposites is improved.At the same time,the concentration of N2,NO2,H2O and CO_(2)is increased during thermal decomposition of high energy propellants whereas NO and CO is decreased.The burning gaseous products and burning characteristic of high energy propellants are studied by the combination of closed bomb test and Fourier transform infrared spectrum.The main burning gaseous products are N2,CO_(2),CO,H2O,CH4,etc.After the high energy propellant modified with PCM-based nanocomposites,the concentration of CH4is increased while CO,CO_(2) and H2O is decreased under the high-pressure burning condition.The progressivity factor of high energy propellants is increased by22.2%compared with the control sample while the maximum pressure is merely decreased 1.25%after the addition of the PCM-based nanocomposite,thus PCM-based nanocomposites can be used to adjust the burning process and improve the burning progressivity of high energy propellants.This study is expected to boost the practical application of PCM-based nanocomposite to the propellant formulation and effectively control the burning characteristic of high energy propellants.展开更多
The thermal decomposition of ammonium perchlorate (AP) with Al and Zn metallic particles was studied at different heating rates in dry air atmosphere and the combustion behavior of AP/Al/Zn propellant was evaluated. T...The thermal decomposition of ammonium perchlorate (AP) with Al and Zn metallic particles was studied at different heating rates in dry air atmosphere and the combustion behavior of AP/Al/Zn propellant was evaluated. The exothermic reaction kinetics was studied by differential thermal analysis (DTA) in non-isothermal conditions and compare with the thermal decomposition of pure AP and AP/aluminum particles analyzed in the same experimental conditions. The Arrhenius parameters were estimated according to the Ozawa and Kissinger methods. The calculated activation energies for the low and high temperature exothermic reactions were 91 and 229 kJ/mol for pure AP, 90 and 112 kJ/mol for 80 wt% AP/20 wt% Al particles. When zinc was incorporated, activation energy of 56 kJ/mol was determined for the only exothermic peak observed for 90 wt% AP/10 wt% Zn and 44 kJ/mol for 78.4 wt% AP/19.6 wt% Al/2 wt% Zn propellant composition.展开更多
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 formulat...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%.展开更多
To improve the performance of solid composite propellants(SCPs)supplemented with ammonium nitrate(AN)as an oxidizer,the incorporation of energetic ingredients such as explosives,energetic binders or catalysts is a com...To improve the performance of solid composite propellants(SCPs)supplemented with ammonium nitrate(AN)as an oxidizer,the incorporation of energetic ingredients such as explosives,energetic binders or catalysts is a common effective approach.For this purpose,polyurethane(PU),a typical inert binder,was mixed with nitrocellulose(NC)as an energetic polymer.Numerous composite solid propellant compositions based on AN and NC-modified polyurethane binder with different NC ratios were prepared.The prepared formulations were characterized using Fourier transform infrared spectroscopy(FTIR),RAMAN spectroscopy,X-ray diffraction(XRD),electron densimetry,thermogravimetric(TG)analysis,and differential scanning calorimetry(DSC).A kinetic study was then performed using the iterative KissingerAkahira-Sunose(It-KAS),Flynn-Wall-Ozawa(It-FWO),and non-linear Vyazovkin integral with compensation effect(VYA/CE)methods.The theoretical performances,such as theoretical specific impulse,adiabatic flame temperature,and ideal exhaust gaseous species,were also determined using the NASA Lewis Code,Chemical Equilibrium with Application(CEA).Spectroscopic examinations revealed the existence of NC and full polymerization of PU in the prepared propellants.According to density tests,the density of the propellant increases as the nitrocellulose component increases.According to the thermal analysis and kinetics study,the increase in NC content catalyzed the thermal decomposition of the AN-based composite solid propellants.Based on the theoretical study,increasing the amount of NC in the propellant increased the specific impulse and,as a result,the overall performance.展开更多
Ammonium dinitramide [NH4 N(NO_2)2, ADN] is considered as a possible replacement for ammonium perchlorate(AP) in nearly all kind of solid rocket propulsions in the coming future. The reason to use ADN instead of AP in...Ammonium dinitramide [NH4 N(NO_2)2, ADN] is considered as a possible replacement for ammonium perchlorate(AP) in nearly all kind of solid rocket propulsions in the coming future. The reason to use ADN instead of AP in solid rocket propulsion is because of its harmless combustion products, along with its capacity to generate high specific impulse(Isp). ADN is fairly a new member in the solid oxidizer community and is considered under green energetic material(GEM). Application and feasible utilization of ADN as an oxidizer for composite solid propellants(CSP's) requires complete knowledge of its thermal decomposition processes along with its combustion behavior. A detailed overview on the physical and chemical properties, thermal decomposition, and combustion behavior of ADN and ADN based propellants has been discussed in this paper. Catalytic effect on thermal decomposition, combustion wave structure, and burning rate of ADN is also discussed.展开更多
Based on the dynamic loading(1-100 s^(-1)) experiments under different temperatures(223-298 K) and stress states, uniaxial and biaxial strength criterion of a Hydroxyl-terminated polybutadiene(HTPB)based composite sol...Based on the dynamic loading(1-100 s^(-1)) experiments under different temperatures(223-298 K) and stress states, uniaxial and biaxial strength criterion of a Hydroxyl-terminated polybutadiene(HTPB)based composite solid propellant were further investigated. These experiments were conducted through the use of a new uniaxial INSTRON testing machine, different new designed gripping apparatus and samples with different configurations. According to the test results, dynamic uniaxial tensile strength criterion of the propellant was directly constructed with the master curve of the uniaxial maximum tensile stress. Whereas, a new method was proposed to determine the dynamic uniaxial compressive strength of the propellant in this study. Then uniaxial compressive strength criterion of the propellant was constructed based on the related master curve. Moreover, it found that the uniaxial tensilecompressive strength ratio of the propellant is more sensitive to loading temperature under the test conditions. The value of this parameter is about 0.4 at room temperature, and it reduces to 0.2-0.3 at low temperatures. Finally, the theoretical biaxial strength criterion of HTPB propellant under dynamic loading was constructed with the unified strength theory, the uniaxial strength and the typical biaxial tensile strength. In addition, the theoretical limit lines of the principal stress plane for the propellant under dynamic loading at different temperatures were further plotted, and the scope of the limit line increases with decreasing temperature.展开更多
Modified DB propellants, based on energetic nitramine(RDX) were manufactured by solventless extrusion process. Thermal stability and shelf life assessment of modified DB propellant were investigated. Shelf life assess...Modified DB propellants, based on energetic nitramine(RDX) were manufactured by solventless extrusion process. Thermal stability and shelf life assessment of modified DB propellant were investigated. Shelf life assessment was evaluated using Van’t Hoff’s formula and artificial aging at 70℃ up to120 days. Quantification of total heat released and heat flow with aging time was conducted using differential scanning calorimetry(DSC) and thermal activity monitoring(TAMIII) respectively. Modified DB formulation based on 20 wt % RDX demonstrated enhanced thermal stability in terms of controlled heat flow, and slow decomposition reactions at elevated temperature. This formulation demonstrated extended service life up to 56 years compared with reference formulation. These novel finding was ascribed to the high thermal stability of RDX and its compatibility with DB constituents. This manuscript shaded the light on novel and effective approach for thermal stability via monitoring thermal activity with aging.展开更多
In a quest of search for a new burning rate modifier for composite propellant, strontium titanate (SrTiO3), a perovskite oxide has been chosen for evaluation in a composite propellant formulation based on its other ca...In a quest of search for a new burning rate modifier for composite propellant, strontium titanate (SrTiO3), a perovskite oxide has been chosen for evaluation in a composite propellant formulation based on its other catalytic applications. Initially, SrTiO3 was characterized for particle size, morphology and material/ phase identification (using XRD). By varying SrTiO3 content in a standard composite propellant, different compositions were prepared and their performance and processing parameters like the end of mix (EOM) viscosity, mechanical properties, density, burning rate, pressure exponent (n-value), etc. were measured. The results reveal that 2% SrTiO3 causes more than 12% enhancement in propellant burning rate (at 70 ksc pressure) in comparison to the standard propellant composition. The pressure exponent also increases to 0.46, whereas the standard composition was having its value as 0.35.展开更多
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 start...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.展开更多
To prepare the porous NC-based(nitrocellulose-based) gun propellants,the batch foaming process of using supercritical CO_2 as the physical blowing agent is used.The solubilities of CO_2 in the single-base propellants ...To prepare the porous NC-based(nitrocellulose-based) gun propellants,the batch foaming process of using supercritical CO_2 as the physical blowing agent is used.The solubilities of CO_2 in the single-base propellants and TEGDN(trimethyleneglycol dinitrate) propellants are measured by the gravimetric method,and SEM(scanning electron microscope) is used to observe the morphology of foamed propellants.The result shows that a large amount of CO_2 could be dissolved in NC-based propellants.The experimental results also reveal that the energetic plasticizer TEGDN exerts an important influence on the pore structure.The triaxial tensile failure mechanism for solid-state nucleation is used to explain the nucleation of NC-based propellants in the sol id state.Since some specific foaming behaviors of NC-based propellants can not be explained by the failure mechanism,a solid-state nucleation mechanism which revises the triaxial tensile failure mechanism is proposed and discussed.展开更多
Double-base(DB) propellant is vulnerable to auto-catalytic decomposition reactions during storing with the evolution of nitrogen oxides. Modified DB propellant based on energetic nitramines(RDX) can offer enhanced thr...Double-base(DB) propellant is vulnerable to auto-catalytic decomposition reactions during storing with the evolution of nitrogen oxides. Modified DB propellant based on energetic nitramines(RDX) can offer enhanced thrust and action time. This study is devoted to evaluate the impact of RDX on chemical stability and shelf life of DB propellant. Extruded modified DB propellant based on RDX was manufactured by solventless extrusion process. Shelf life assessment was performed using an artificial aging at70 ℃ up to 120 days and employing Van't Hoffs formula. Quantification of evolved NOx gases and stabilizer depletion with aging time was conducted using Bergmann-Junk test and HPLC respectively.Modified DB formulation based on RDX 20 wt % demonstrated enhanced chemical stability and extended service life up to 46 years compared with reference formulation. This finding was ascribed to the high chemical and thermal stability of RDX as well as its compatibility with DB constituents; no side chemical reactions could take place during storing. This manuscript shaded the light on RDX as effective energetic constituent that offered DB propellants with enhanced performance, good chemical stability, and extended service life.展开更多
Microcellular propellants show a vast applicable prospect due to their special shell-pore structure. The effects of saturation pressure and desorption time on skin thickness are studied. The skin thickness is observed...Microcellular propellants show a vast applicable prospect due to their special shell-pore structure. The effects of saturation pressure and desorption time on skin thickness are studied. The skin thickness is observed and measured using scanning electron microscope (SEM). The results show that the skin thickness decreases when saturation pressure increases from 15 MPa to 30 MPa. In contrast, the skin thickness increases as the desorption time changes from 2 min to 20 min.Therefore, the microcellular propellants with adjustable skin thickness can be obtained under the variable process conditions such as saturation pressure and desorption time.展开更多
基金the support of this research from the Serbian Ministry of Education,Science and Technological Development(Grant No.451-03-68/2023-14/200325)Ministry of Defense(Grant No.VA-TT/1/22-24)。
文摘Conventional plasticizers deteriorate mechanical and viscoelastic properties of the propellants due to their migration upon aging and long-term storage,which affects reliability and safety properties during exploitation.To address this issue,conventional plasticizer,dioctyl adipate(DOA),is replaced by reactive one,castor oil(CO).In addition,three different types of HTPB were used to obtain propellants with designed viscoelastic and mechanical properties.The CO increased propellants viscosity,without a significant impact on the propellant processability,regardless to the type of prepolymer.Conversely,mechanical properties were different depending on the type of resin,which were further analyzed by gel permeation chromatography(GPC).Addition of CO formed a denser polymer network and shifted T_(g) to higher values,compared to the compositions with DOA.The tensile strength of CO-containing propellants was lower at +20℃ and +50℃ compared to the reference compositions,while the strain at maximum load and strain at break were significantly increased with pronounced plastic deformation,especially for samples at -30℃.The inclusion of CO in the propellants composition gives more room for adjusting a wide range of mechanical properties.
基金the National Natural Science Foundation of China(Grant No.22075146).
文摘Appropriate drying process with optimized controlling of drying parameters plays a vital role in the improvement of the quality and performance of propellant products.However,few research on solvent transport dynamics within NC-based propellants was reported,and its effect on the evolution of mechanical properties was not interpreted yet.This study is conducted to gain a comprehensive understanding of hot-air drying for NC-based propellants and clarify the effect of temperature on solvent transport behavior and further the change of mechanical properties during drying.The drying kinetic curves show the drying time required is decreased but the steady solvent content is increased and the drying rate is obviously increased with the increase of hot-air temperatures,indicating hot-air temperatures have a significant effect on drying kinetics.A modified drying model was established,and results show it is more appropriate to describe solvent transport behavior within NC-based propellants.Moreover,two linear equations were established to exhibit the relationship between solvent content and its effect on the change of tensile properties,and the decrease of residual solvent content causes an obvious increase of tensile strength and tensile modulus of propellant products,indicating its mechanical properties can be partly improved by adjustment of residual solvent content.The outcomes can be used to clarify solvent transport mechanisms and optimize drying process parameters of double-based gun propellants.
文摘To simplify the composite propellant formulation and address the current issue of the single-functionality present in existing additives,the multi-cyano,amine-based polybutadiene(AEHTPB-CN)was prepared based on AEHTPB by adopting appropriate synthesis strategies.By replacing 10% of HTPB binder in the propellant formulation,it can effectively enhance the interfacial bond strength between the propellant binder matrix and solid fillers(AP(ammonium perchlorate)and RDX(cyclotrimethylene-trinitramine)),the mechanical properties of the HTPB/AP/RDX/Al propellant were superior to blank control propellant with an improvement of 35.4% in tensile strength,62.0% enhancement in elongation at break,and reduce the propellant burn rate by 10.7% with any energy loss.The function mechanism of AEHTPB-CN was systematically elucidated through experiments and computer simulation techniques.The results show that the tertiary amine group in AEHTPB-CN can react with AP to form ammonium ionic bonds,and the hydroxyl and cyano groups can form hydrogen bonding interactions with AP,which enables AEHTPB-CN to be firmly adsorbed on the AP surface through chemical and physical interactions.For RDX,the interfacial bonding effect of AEHTPB-CN is attributed to their ability to form C-H···N≡C weak hydrogen bonding interaction between the cyano group and RDX methylene group.
基金the support of the instrument and equipment fund of the Key Laboratory of Special Energy,Ministry of Education,Nanjing University of Science and Technology,China.
文摘The severe erosion and inadequate mechanical strength are prominent challenges for high-energy gun propellants.To address it,novel PTW@PDA composites was prepared by polydopamine(PDA)-modifying onto potassium titanate whisker(PTW,K_(2)Ti_(6)O_(13)),and after was incorporated into gun propellant as erosion-reducing and mechanical-reinforcing fillers.The interfacial characterizations results indicated that as-prepared PTW@PDA composites exhibits an enhanced surface compatible with propellant matrix,thereby facilitating their dispersion into propellants more effectively than raw PTW materials.Compared to original propellants,PTW@PDA-modified propellants exhibited significant less erosion,with a Ti-Kbased protective coating being detected on the eroded steel.And 0.5 wt%and 1.0 wt%addition of PTW@PDA significantly improved impact,compressive and tensile strength of propellants.Despite the inevitably reduction in relative force,PTW@PDA slightly increase propellant burning rate while exerting little adverse impact on propellant dynamic activity.This strategy can provide a promising alternative to develop high-energy gun propellant with less erosion and more mechanical strength.
基金supported by the National Natural Science Foundation of China(Grant No.22075146)。
文摘Drying is a complicated physical process which involves simultaneous heat and mass transfer in the removal of solvents inside propellants.Inappropriate drying techniques may result in the formation of a hard skin layer near the surface to block the free access of most solvent through for long stick propellants with large web thickness,which lead to lower drying efficiency and worse drying quality.This study aims to gain a comprehensive understanding of drying process and clarify the mechanism of the blocked layer near the propellant surface.A new three-dimensional coupled heat and mass transfer(3D-CHMT)model was successfully developed under transient conditions.The drying experiment results show that the 3DCHMT model could be applied to describe the drying process well since the relative error of the content of solvent between simulation and experiment values is only 5.5%.The solvent behavior simulation demonstrates that the mass transfer process can be divided into super-fast(SF)and subsequent minorfast(MF)stages,and the SF stage is vital to the prevention of the blocked layer against the free access for solvent molecules inside propellant grains.The effective solvent diffusion coefficient(Deff)of the propellant surface initially increases from 3.4×10^(-6)to 5.3×10^(-6)m^(2)/s as the temperature increases,and then decreases to 4.1×10^(-8)m^(2)/s at 60-100 min.The value of Deffof surface between 0-1.4 mm has a unique trend of change compared with other regions,and it is much lower than that of the internal at100 min under simulation conditions.Meanwhile,the temperature of the propellant surface increases rapidly at the SF stage(0-100 min)and then very slowly thereafter.Both the evolution of Deffand temperature distribution demonstrate that the blocked layer near the propellant surface has been formed in the time period of approximately 0-100 min and its thickness is about 1.4 mm.To mitigate the formation of blocked layer and improve its drying quality of finial propellant products effectively,it should be initially dried at lower drying temperature(30-40℃)in 0-100 min and then dried at higher drying temperature(50-60℃)to reduce drying time for later drying process in double base gun propellants.The present results can provide theoretical guidance for drying process and optimization of drying parameters for long stick propellants with large web thickness.
文摘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.
文摘The monolithic foamed propellants with high densities were prepared by casting and two-step foaming processes.Glycidyl azide polymer(GAP)and isocyanate were used as the binder system and 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane(HNIW,CL-20)was employed as the energetic component.The newly designed formulation containing 60%CL-20 produced a force constant of 1077 J/g and low flame temperature of 2817 K.Two foamed propellants with densities of 1.32 g/cm^(3)and 1.53 g/cm^(3)were fabricated by a confined foaming process and examined by closed bomb tests.The results revealed that porosity significantly affects burning performance.A size effect on combustion behaviors was observed for the foamed propellant with 5.56%porosity,and a double-hump progressive dynamic vivacity curve was obtained.At last,the 30 mm gun test was carried out to demonstrate the interior ballistic performance,and the muzzle velocity increased by 120 m/s at the same maximum chamber pressure when monolithic propellant was added in the charge.
基金Ministry of Education and Science of the Russian Federation(14.613.21.0043)
文摘The experimental values of the enthalpy of formation of two isomeric 3,4-and 3,5-dinitro-1-(trinitromethyl)-1H-pyrazoles have been obtained(261.5±5.0and 246.4±6.7kJ/mol for crystalline 3,4-and 3,5-dinitro-1-(trinitromethyl)-1H-pyrazoles,respectively).The ballistic effectiveness of these potential oxidizers in composite solid propellants was studied.It is shown that these two oxidizers may be successfully applied in metal-free compositions or with a small content of metal.For the bottom stage 3,4-dinitro-1-(trinitromethyl)-1H-pyrazole is a bit better than 3,5-dinitro-1-(trinitromethyl)-1H-pyrazole,for the upper stage the both oxidizers show the equal ballistic parameters.These oxidizers allow to create metal-free solid composite propellants with the binder percentage not lower than 19%(volume fraction),with I3spequal to 256.5-257.0sat density equal to 1.72-1.74g/cm^3.
基金the National Natural Science Foundation of China(Grant No.22075146)to provide fund for conducting experiments。
文摘A kind of phase change material(PCM)-based nanocomposite was prepared and added into high energy propellants containing RDX as additives to investigate its effect on thermal decomposition and burning characteristic of high energy propellants.The effect of PCM-based nanocomposites on thermal decomposition of high energy propellants is investigated by TG/DSC-FTIR-MS technology.Due to the delayed protection effect(PCM-based nanocomposites can absorb lots of heat at the range of certain temperature when it undergoes structure change or phase transitions)of PCM-based nanocomposites under the thermal decomposition condition,the thermal stability of high energy propellants modified with PCMbased nanocomposites is improved.At the same time,the concentration of N2,NO2,H2O and CO_(2)is increased during thermal decomposition of high energy propellants whereas NO and CO is decreased.The burning gaseous products and burning characteristic of high energy propellants are studied by the combination of closed bomb test and Fourier transform infrared spectrum.The main burning gaseous products are N2,CO_(2),CO,H2O,CH4,etc.After the high energy propellant modified with PCM-based nanocomposites,the concentration of CH4is increased while CO,CO_(2) and H2O is decreased under the high-pressure burning condition.The progressivity factor of high energy propellants is increased by22.2%compared with the control sample while the maximum pressure is merely decreased 1.25%after the addition of the PCM-based nanocomposite,thus PCM-based nanocomposites can be used to adjust the burning process and improve the burning progressivity of high energy propellants.This study is expected to boost the practical application of PCM-based nanocomposite to the propellant formulation and effectively control the burning characteristic of high energy propellants.
文摘The thermal decomposition of ammonium perchlorate (AP) with Al and Zn metallic particles was studied at different heating rates in dry air atmosphere and the combustion behavior of AP/Al/Zn propellant was evaluated. The exothermic reaction kinetics was studied by differential thermal analysis (DTA) in non-isothermal conditions and compare with the thermal decomposition of pure AP and AP/aluminum particles analyzed in the same experimental conditions. The Arrhenius parameters were estimated according to the Ozawa and Kissinger methods. The calculated activation energies for the low and high temperature exothermic reactions were 91 and 229 kJ/mol for pure AP, 90 and 112 kJ/mol for 80 wt% AP/20 wt% Al particles. When zinc was incorporated, activation energy of 56 kJ/mol was determined for the only exothermic peak observed for 90 wt% AP/10 wt% Zn and 44 kJ/mol for 78.4 wt% AP/19.6 wt% Al/2 wt% Zn propellant composition.
基金Ministry of Education and Science of the Russian Federation(14.613.21.0043)
文摘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%.
文摘To improve the performance of solid composite propellants(SCPs)supplemented with ammonium nitrate(AN)as an oxidizer,the incorporation of energetic ingredients such as explosives,energetic binders or catalysts is a common effective approach.For this purpose,polyurethane(PU),a typical inert binder,was mixed with nitrocellulose(NC)as an energetic polymer.Numerous composite solid propellant compositions based on AN and NC-modified polyurethane binder with different NC ratios were prepared.The prepared formulations were characterized using Fourier transform infrared spectroscopy(FTIR),RAMAN spectroscopy,X-ray diffraction(XRD),electron densimetry,thermogravimetric(TG)analysis,and differential scanning calorimetry(DSC).A kinetic study was then performed using the iterative KissingerAkahira-Sunose(It-KAS),Flynn-Wall-Ozawa(It-FWO),and non-linear Vyazovkin integral with compensation effect(VYA/CE)methods.The theoretical performances,such as theoretical specific impulse,adiabatic flame temperature,and ideal exhaust gaseous species,were also determined using the NASA Lewis Code,Chemical Equilibrium with Application(CEA).Spectroscopic examinations revealed the existence of NC and full polymerization of PU in the prepared propellants.According to density tests,the density of the propellant increases as the nitrocellulose component increases.According to the thermal analysis and kinetics study,the increase in NC content catalyzed the thermal decomposition of the AN-based composite solid propellants.Based on the theoretical study,increasing the amount of NC in the propellant increased the specific impulse and,as a result,the overall performance.
文摘Ammonium dinitramide [NH4 N(NO_2)2, ADN] is considered as a possible replacement for ammonium perchlorate(AP) in nearly all kind of solid rocket propulsions in the coming future. The reason to use ADN instead of AP in solid rocket propulsion is because of its harmless combustion products, along with its capacity to generate high specific impulse(Isp). ADN is fairly a new member in the solid oxidizer community and is considered under green energetic material(GEM). Application and feasible utilization of ADN as an oxidizer for composite solid propellants(CSP's) requires complete knowledge of its thermal decomposition processes along with its combustion behavior. A detailed overview on the physical and chemical properties, thermal decomposition, and combustion behavior of ADN and ADN based propellants has been discussed in this paper. Catalytic effect on thermal decomposition, combustion wave structure, and burning rate of ADN is also discussed.
基金financial support of the National 973 Program in China (No. 61338)the National Funds in China (Nos.11772352, 61407200203 and 51328050101)
文摘Based on the dynamic loading(1-100 s^(-1)) experiments under different temperatures(223-298 K) and stress states, uniaxial and biaxial strength criterion of a Hydroxyl-terminated polybutadiene(HTPB)based composite solid propellant were further investigated. These experiments were conducted through the use of a new uniaxial INSTRON testing machine, different new designed gripping apparatus and samples with different configurations. According to the test results, dynamic uniaxial tensile strength criterion of the propellant was directly constructed with the master curve of the uniaxial maximum tensile stress. Whereas, a new method was proposed to determine the dynamic uniaxial compressive strength of the propellant in this study. Then uniaxial compressive strength criterion of the propellant was constructed based on the related master curve. Moreover, it found that the uniaxial tensilecompressive strength ratio of the propellant is more sensitive to loading temperature under the test conditions. The value of this parameter is about 0.4 at room temperature, and it reduces to 0.2-0.3 at low temperatures. Finally, the theoretical biaxial strength criterion of HTPB propellant under dynamic loading was constructed with the unified strength theory, the uniaxial strength and the typical biaxial tensile strength. In addition, the theoretical limit lines of the principal stress plane for the propellant under dynamic loading at different temperatures were further plotted, and the scope of the limit line increases with decreasing temperature.
文摘Modified DB propellants, based on energetic nitramine(RDX) were manufactured by solventless extrusion process. Thermal stability and shelf life assessment of modified DB propellant were investigated. Shelf life assessment was evaluated using Van’t Hoff’s formula and artificial aging at 70℃ up to120 days. Quantification of total heat released and heat flow with aging time was conducted using differential scanning calorimetry(DSC) and thermal activity monitoring(TAMIII) respectively. Modified DB formulation based on 20 wt % RDX demonstrated enhanced thermal stability in terms of controlled heat flow, and slow decomposition reactions at elevated temperature. This formulation demonstrated extended service life up to 56 years compared with reference formulation. These novel finding was ascribed to the high thermal stability of RDX and its compatibility with DB constituents. This manuscript shaded the light on novel and effective approach for thermal stability via monitoring thermal activity with aging.
文摘In a quest of search for a new burning rate modifier for composite propellant, strontium titanate (SrTiO3), a perovskite oxide has been chosen for evaluation in a composite propellant formulation based on its other catalytic applications. Initially, SrTiO3 was characterized for particle size, morphology and material/ phase identification (using XRD). By varying SrTiO3 content in a standard composite propellant, different compositions were prepared and their performance and processing parameters like the end of mix (EOM) viscosity, mechanical properties, density, burning rate, pressure exponent (n-value), etc. were measured. The results reveal that 2% SrTiO3 causes more than 12% enhancement in propellant burning rate (at 70 ksc pressure) in comparison to the standard propellant composition. The pressure exponent also increases to 0.46, whereas the standard composition was having its value as 0.35.
文摘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.
基金funded by the priority academic program development of Jiangsu Higher Education Institutions
文摘To prepare the porous NC-based(nitrocellulose-based) gun propellants,the batch foaming process of using supercritical CO_2 as the physical blowing agent is used.The solubilities of CO_2 in the single-base propellants and TEGDN(trimethyleneglycol dinitrate) propellants are measured by the gravimetric method,and SEM(scanning electron microscope) is used to observe the morphology of foamed propellants.The result shows that a large amount of CO_2 could be dissolved in NC-based propellants.The experimental results also reveal that the energetic plasticizer TEGDN exerts an important influence on the pore structure.The triaxial tensile failure mechanism for solid-state nucleation is used to explain the nucleation of NC-based propellants in the sol id state.Since some specific foaming behaviors of NC-based propellants can not be explained by the failure mechanism,a solid-state nucleation mechanism which revises the triaxial tensile failure mechanism is proposed and discussed.
文摘Double-base(DB) propellant is vulnerable to auto-catalytic decomposition reactions during storing with the evolution of nitrogen oxides. Modified DB propellant based on energetic nitramines(RDX) can offer enhanced thrust and action time. This study is devoted to evaluate the impact of RDX on chemical stability and shelf life of DB propellant. Extruded modified DB propellant based on RDX was manufactured by solventless extrusion process. Shelf life assessment was performed using an artificial aging at70 ℃ up to 120 days and employing Van't Hoffs formula. Quantification of evolved NOx gases and stabilizer depletion with aging time was conducted using Bergmann-Junk test and HPLC respectively.Modified DB formulation based on RDX 20 wt % demonstrated enhanced chemical stability and extended service life up to 46 years compared with reference formulation. This finding was ascribed to the high chemical and thermal stability of RDX as well as its compatibility with DB constituents; no side chemical reactions could take place during storing. This manuscript shaded the light on RDX as effective energetic constituent that offered DB propellants with enhanced performance, good chemical stability, and extended service life.
文摘Microcellular propellants show a vast applicable prospect due to their special shell-pore structure. The effects of saturation pressure and desorption time on skin thickness are studied. The skin thickness is observed and measured using scanning electron microscope (SEM). The results show that the skin thickness decreases when saturation pressure increases from 15 MPa to 30 MPa. In contrast, the skin thickness increases as the desorption time changes from 2 min to 20 min.Therefore, the microcellular propellants with adjustable skin thickness can be obtained under the variable process conditions such as saturation pressure and desorption time.
