Preparation and Properties of Boron‐Based Nano‐B/NiO Thermite

Boron particles have several major burning problems, such as incomplete combustion, poor ignitability, and a complex burning process in solid propellants. It is documented that the low ignitability and combustion efficiency of boron are caused by the oxidation of its surface. In order to improve the combustion efficiency of boron particles, a precipitation method was employed to prepare nanometer‐sized NiO and coat it on boron particles. The morphology and coating results of the B/NiO nanocomposite thermite were characterized using different approaches such as SEM, X‐ray Diffraction (XRD), and EDS. The results indicated that the boron particles were well distributed and coated completely by nanocomposite NiO. The B/NiO nanocomposite thermite reaction process was tested by TG‐DTA. The results showed that the reaction temperature of B/NiO particles is about 30 °C lower than that of boron particles. The B/NiO thermite and boron powder were added to Mg/PTFE propellant to be measured for their respective combustion performance. The results showed that the burning rate of the B/NiO‐Mg/PTFE propellant increased by 22.8–25.2 %, mass burning rate by 26.7–30.8 %, and combustion temperature increased by 8–56 °C compared to the B‐Mg/PTFE propellant. The above results indicate that NiO coating of boron particles has a significant effect on the combustion behavior and increases the combustion performance of the propellant compared with uncoated particles.     

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

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

Condition monitoring of a thermally aged hydroxy‐terminated polybutadiene (HTPB)/isophorone diisocyanate (IPDI) elastomer by nuclear magnetic resonance cross‐polarization recovery times

A hydroxy‐terminated polybutadiene (HTPB)/isophorone diisocyanate (IPDI) elastomer is commonly used as propellant binder material. The thermal degradation of the binder is believed to be an important parameter governing the performance of the propellant. The aging of these binders can be monitored by mechanical property measurements, such as modulus or tensile elongation. These techniques, however, are not easily adapted to binder agents that are dispersed throughout a propellant. In this paper we investigated solid‐state nuclear magnetic resonance (NMR) relaxation times as a means to predict the mechanical properties of the binder as a function of aging time. Proton (¹H) spin–lattice and spin–spin relaxation times were insensitive to the degree of thermal degradation of the elastomer. Apparently, these relaxation times depend on localized motions that are only weakly correlated with mechanical properties. A strong correlation was found between the ¹³C cross‐polarization (CP) NMR time constant, T_cp, and the tensile elongation at break of the elastomer as a function of aging time. A ramped‐amplitude CP experiment was less sensitive to imperfections in setting critical instrumental parameters for this mobile material. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 453–459, 2001     

Chemical Imaging of Explosions – Mapping BO2 Light Emission

This work describes chemical imaging of BO₂ formed during ballistic initiation of 1 : 1 by weight powder‐mixtures of boron (B) and potassium nitrate (KNO₃) contained within a polyethylene spherical projectile (25 mm diameter). Initiation was achieved by impact of the gas‐gun‐launched B/KNO₃‐filled projectile with an anvil in a windowed, air‐filled chamber. To monitor the subsequent chemical reaction, a two‐camera, optically‐filtered method to map discrete chemical emission from the BO₂ molecule was used. This technique distinguishes incandescence of hot particles produced during the event from discrete chemical emission by BO₂ near a wavelength of 546 nanometers (nm). The dependence of delay in BO₂ chemical emission (that exceeded particle incandescence) with impact velocity was investigated and chemical emission movies which ratio the intensity of discrete to thermal emission are discussed. Emission spectra (300–1000 nm wavelength) were recorded during the impact event, and used to determine a grey‐body temperature of the hot particles during the time when BO₂ emission was most intense.     

Sol–Gel Synthesis and Formation Mechanism of Ultrahigh Temperature Ceramic: HfB2

Hafnium diboride (HfB₂) powder has been synthesized via a sol–gel‐based route using phenolic resin, hafnium chloride, and boric acid as the source of carbon, hafnium, and boron, respectively, though a small number of comparative experiments involved amorphous boron as boron source. The effects of heat‐treatment dwell time and hafnium:carbon (Hf:C) and hafnium:boron (Hf:B) molar ratio on the purity and morphology of the final powder have been studied and the mechanism of HfB₂ formation investigated using several techniques. The results showed that while temperatures as low as 1300°C could be used to produce HfB₂ particles, the heat treatment needed to last for about 25 h. This in turn resulted in anisotropic particle growth along the c‐axis of the HfB₂ crystals yielding tube‐like structures of about 10 μm long. Equiaxed particles 1–2 μm in size were obtained when the precursor was heat treated at 1600°C for 2 h. The reaction mechanism involved boro/carbothermal reduction and the indications were that the formation of HfB₂ at 1300°C is through the intermediate formation of an amorphous B or boron suboxides, although at higher temperatures more than one reaction mechanism may be active.     

Mathematical modeling of rheological properties of hydroxyl‐terminated polybutadiene binder and dioctyl adipate plasticizer

Solid composite propellants contain 80–90% of a crystalline oxidizer like ammonium perchlorate and powdery metallic fuel like aluminum with 10 to 15% organic binders like HTPB or CTPB, to bind the solids together and maintain the shape under severe stress and strain environment. Also, the propellant must not crack or become brittle at subzero temperatures. Formulating and processing of the highly filled composite propellants are difficult tasks and need a thorough understanding of rheology, even apart from a knowledge of propellant chemistry, particulate technology, manufacturing methods, and safe handling of explosives and hazardous materials. The flow behavior or rheology of the propellant slurry determines the ingredients and some of the abnormalities of the motor during firing. The propellant viscosity and mechanical properties are determined by the binder system, and the unloading viscosity of the propellant slurry is dependent on the initial viscosity of the binder system, solid loading, particle size, and its distribution, shape, temperature, and pressure. In the present report an attempt is made to study the dependency of viscosity of the HTPB binder system on temperature, plasticizer level (composition), and torque (angular velocity of spindle). The viscosity measurements were made using a Brookfield viscometer model DV III at different plasticizer levels (10–50%), temperatures (30–65°C), and torques (50–100%). The data indicate that the viscosity of HTPB, DOA, and their mixture decreases with increasing temperature and is constant with torque. The Arrhenius equation gives the energy for viscous flow to be ?35 kcal/mol for HTPB. The variation of viscosity with temperature of HTPB/DOA and their mixture follows a mathematical model expressed as where T is the temperature and a₁, a₂, a₃, a₄, and a₅ are the constants. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1002–1007, 2002     

Terminal functionalized hydroxyl‐terminated polybutadiene: An energetic binder for propellant

We report the functionalization of hydroxyl terminated polybutadiene (HTPB) backbone by covalently attaching 1‐chloro‐2, 4‐dinitrobenzene (DNCB) at the terminal carbon atoms of the HTPB. The modification of the HTPB by the DNCB does not alter the unique physico–chemical properties and the microstructure of the parent HTPB. IR, ¹H‐NMR, ¹³C‐NMR, size exclusion chromatography (SEC) and absorption spectroscopy studies prove that the DNCB molecules are covalently attached to the terminal carbon atoms of the HTPB. The π electron delocalization owing to long polymer chain, strong electron withdrawing effect of the DNCB molecule are the major driving forces for the covalent attachment of the DNCB at the terminal carbon atom of the HTPB. We are the first to observe the existence of intermolecular hydrogen bonding between the terminal hydroxyl groups of the HTPB. IR study shows that the attached DNCB molecules at the terminal carbon atoms of the HTPB breaks the intermolecular hydrogen bonding between the HTPB chains and forms a hydrogen bonding between the NO₂ groups of the DNCB and the OH groups of the HTPB. Absorption spectral study of the modified HTPB indicates the better delocalization of π electron of butadiene due to the strong electron withdrawing effect of the DNCB molecules. Theoretical calculation also supports the existence of hydrogen bonding between the OH and NO₂ groups. Theoretical calculation shows that the detonation performance of both the DNCB and the HTPB‐DNCB are promising. HTPB‐DNCB is the new generation energetic binder which has potential to replace the use of HTPB as binder for propellant.© 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of Different Metal Fuels on the Characteristics for HTPB‐based Fuel Rich Solid Propellants

The microstructures and granularity distribution of different metal particles were investigated and the energy, sensitivity, and combustion properties of fuel rich solid propellants with different metal particles were studied in detail. It was found that the magnesium particles are more uniform than other metal powders, the mean diameter of the magnesium particles d₅₀=67.6 μm is much higher than those of the other ones, which are in the range of 7.1 μm<d₅₀<20.5 μm. Additionally, the preparation process of the Mg‐based propellant is easier than those of the other ones. The experimental results showed that the propellant containing magnesium powder was less sensitive to friction and impact (165.1 NM and 21.9 NM, respectively), whereas, the burning rates of propellants with Zr and ZrH₂ particles increased, and the pressure exponents decreased.     

Synthesis of GAP-PB-GAP Triblock Copolymer and Application as Modifier in AP/HTPB Composite Propellant

A new triblock copolymer polyglycidylazide-block-polybutadiene-block-polyglycidylazide (GAP-PB-GAP) has been synthesized. The synthesis was done by cationic ring opening polymerization of epichlorohydrin (ECH) with HTPB as the alcohol and boron trifluoride etherate as the catalyst followed by the conversion of the -CH₂Cl group into -CH₂N₃ group. The presence of the azido groups in the GAP polymer chain makes it more energetic and the triblock copolymer can be used as an energetic binder/additive for propellant energy modification. Since the triblock copolymer has polybutadiene (PB) as the central block, which is from HTPB itself, it can be used as an additive in HTPB based polymeric formulations to improve their properties. In the present work, a part of HTPB, the propellant binder in ammonium perchlorate (AP)/HTPB propellant was removed and replaced with the GAP-PB-GAP copolymer. Burn rate, mechanical properties, and heat of combustion properties of these propellants were measured and compared with the unmodified HTPB/AP propellant. The results show that the burn rate of the HTPB/AP solid propellant could be enhanced by the addition of the triblock copolymer.     

Characterization of BPN Pyrotechnic Composition Containing Micro‐ and Nanometer‐Sized Boron Particles

The effect of micro‐ and nanometer‐sized boron particles on boron‐potassium nitrate (BPN) ignition composition was investigated in this paper. As a starting point, thermochemical calculations were made to determine the most promising ignition compositions. Both stoichiometric and fuel‐rich formulations of BPN were produced to observe the performance variation due to boron content. Particle morphology of boron particles and the surface structure of the ignition compositions were investigated by SEM. The influence of micro‐ and nanometer‐sized boron particles on the calorific value, sensitivity properties, and pressure buildup of compositions were investigated. Sensitivity tests showed that all compositions were safe enough for handling. It was seen that although nanometer‐sized boron particles enhanced calorific value and pressurization rate, they did not have a contribution on the maximum pressure level. The maximum adiabatic flame temperature was attained by the stoichiometric composition, but in practice, the stoichiometric composition resulted in much lower performance than the fuel rich composition. Possible reasons for these behaviors of the compositions were discussed in the paper.     

团聚硼颗粒在HTPB富燃料推进剂中的流变特性

为了探索球形团聚硼颗粒的制备效果,对端羟基聚丁二烯(HTPB)黏合剂、不同类型的团聚硼颗粒与HTPB黏合剂以一定质量配比形成的悬浮液,以及含团聚硼颗粒HTPB富燃料推进剂流变特性进行了对比研究。结果表明,HTPB黏合剂的表观黏度随温度的升高而降低,最终趋于某一定值;在一定温度下,无定形硼粉经团聚改性后,团聚硼颗粒与HTPB形成悬浮液的表观黏度和屈服值较团聚前降低,且两者均随时间的增加而增加;采用含团聚硼颗粒的富燃料推进剂药浆的流变特性大大改善,有利于含硼富燃料推进剂能量的提高和燃烧性能的改善。     

含团聚硼富燃料推进剂的能量特性及燃烧性能

用最小自由能计算程序计算了含硼富燃料推进剂的能量性能,探讨了不同压力时硼粉的质量分数对富燃料推进剂能量性能的影响,采用靶线法和化学滴定法研究了富燃料推进剂的燃烧特性和燃烧残渣中硼粉的燃烧效率。结果表明,随着硼粉含量的增加,推进剂的能量增大;大粒径的团聚硼对富燃料推进剂的燃速和压强指数影响较大,随着团聚硼含量的增加,推进剂的燃速提高;含硼富燃料推进剂中的硼粉燃烧后单质硼和硼化物的摩尔比发生了明显的变化,无定形硼粉经团聚后燃烧效率明显提高。     

Application of Nitramines Coated with Nitrocellulose in Minimum Signature Isocyanate‐Cured Propellants

Cyclotrimethylenetrinitramine (RDX) coated with nitrocellulose (NC‐RDX) is prepared by an internal solution method and applied in a minimum signature isocyanate‐cured propellant. It was found that RDX was coated or bonded by NC to form NC‐RDX particles; the median particle diameter (d₅₀) and specific surface area of NC‐RDX are in the range from 150 to 240 μm and 0.03 to 0.04 m²⋅g⁻¹, respectively. The NC‐RDX particles could swell in nitrate ester plasticizers with relatively low swelling rate compared with NC added directly in the plasticizers. Different types of ballistic modifiers can be effectively added to NC‐RDX. It was experimentally shown that NC‐RDX can increase the content of NC in the propellant with viscosities in the range from 371 to 394 Pa s and improve the mechanical characteristics of the propellant with maximum tensile strength (σ_m) between 0.48 MPa<σ_m<1.92 MPa, elongation at maximum tensile strength (ε_m) between 28.0%<ε_m<37.3%, and elastic modulus between 3.18 MPa<E<8.68 MPa in the temperature range from −40 to +50 °C.     

Single Step Synthesis of Nitro‐Functionalized Hydroxyl‐Terminated Polybutadiene

The paper reports the energization of Hydroxyl‐Terminated Polybutadiene (HTPB) by functionalizing explosophore  NO₂ over the HTPB backbone, resulting in the formation of conjugated nitro‐alkene derivative of HTPB. A convenient, inexpensive and efficient “one pot” procedure of synthesizing Nitro‐Functionalized Hydroxyl‐Terminated Polybutadiene (Nitro‐HTPB) is reported. The reaction was carried out with sodium nitrite and iodine. To retain the unique physico‐chemical properties of HTPB, functionalization by  NO₂ group was restricted to 10 to 15 % of double bonds. The Nitro‐HTPB was characterized by FTIR, ¹H NMR, VPO, DSC, TGA etc. The polymer has shown good thermal stability for practical applications. The kinetic parameters for the decomposition of Nitro‐HTPB at 150–300 °C were obtained from non‐isothermal DSC data.     

Burning Rate – Pressure Relationship of NG‐PE‐PCP‐based High Energy Propellants

Nitramines are known to produce lower burning rates and higher pressure exponent (η) values. Studies on the burning rate and combustion behavior of advanced high‐energy NG/PE‐PCP/HMX/AP/Al based solid propellant processed by slurry cast route were carried out using varying percentages of HMX and AP. It was observed that propellant compositions containing only AP and Al loaded (total solids 75 %) in NG plasticized PE‐PCP binder produce comparatively lower pressure exponent (η) values similar to AP‐Al filled HTPB based composite propellants. However, energetic propellants containing high level of nitramine (40–60 %) produce high pressure exponent (0.8–0.9) values in the same pressure range. Incorporation of fine particle size AP (ca. 6 μm) and change in its concentration in the propellant composition reduces η value marginally and influences the burning rate. However, such compositions have higher friction sensitivity.     

Development of Composite Solid Propellant Based on Nitro Functionalized Hydroxyl‐Terminated Polybutadiene

This paper presents an overview of a modified composite propellant formulation to meet future requirements. The composite propellant mixtures were prepared using nitro functionalized Hydroxyl‐Terminated Polybutadiene (Nitro‐HTPB) as a novel energetic binder and addition of energetic plasticizer. The new propellant formulation was characterized and tested. It was found that the Nitro‐HTPB propellant with and without energetic plasticizer exhibited high solid loading, high density, and reasonable mechanical properties over a wide range of temperatures. It was shown that the burning rate of Nitro‐HTPB propellant is up to 40% faster than that of the HTPB propellant. These results are encouraging and suggest that it should be possible to improve the ballistic performance of popular HTPB propellants through use of the studied Nitro‐HTPB binder.     

Effect of Boron Particle Surface Coating on combustion of solid propellants for ducted rockets

Combustion behavior of B/MA/AP/HTPB fuel rich propellants containing different coated boron particles was studied with several diagnostic facilities such as windowed strand burner, CO₂ laser ignition facility, rapid depressurization quenched device, thermal analyzer and micromotor static test. Materials selected for boron coating include LiF, Viton A and silane. Baseline propellant containing uncoated boron was also studied for comparison Results from windowed strand burner and static test show that LiF-propellant exhibits the most remarkable overall behavior. Ignition study indicates that LiF-propellant gives the shortest while Viton A-propellant gives the longest ignition time under the same heat flux. Moreover, mechanisms were proposed to elucidate the experimental results and the observed combustion phenomena.     

Radiative Ignition of Fine‐Ammonium Perchlorate Composite Propellants

Radiative ignition of quasi‐homogeneous mixtures of ammonium perchlorate (AP) and hydroxyterminated polybutadiene (HTPB) binder has been investigated experimentally. Solid propellants consisting of fine AP (2 μm) and HTPB binder (~ 76/24% by mass) were ignited by CO₂ laser radiation. The lower boundary of a go/no‐go ignition map (minimum ignition time vs. heat flux) was obtained. Opacity was varied by adding carbon black up to 1% by mass. Ignition times ranged from 0.78 s to 0.076 s for incident fluxes ranging from 60 W/cm² to 400 W/cm². It was found that AP and HTPB are sufficiently strongly absorbing of 10.6 μm CO₂ laser radiation (absorption coefficient ≈250 cm⁻¹) so that the addition of carbon black in amounts typical of catalysts or opacitymodifying agents (up to 1%) would have only a small influence on radiative ignition times at 10.6 μm. A simple theoretical analysis indicated that the ignition time‐flux data are consistent with in‐depth absorption effects. Furthermore, this analysis showed that the assumption of surface absorption is not appropriate, even for this relatively opaque system. For broadband visible/near‐infrared radiation, such as from burning metal/oxide particle systems, the effects of in‐depth absorption would probably be even stronger.     

Preliminary Characterization of Propellants Based on p(GA/BAMO) and pAMMO Binders

In previous papers, the synthesis and characterization of OH‐terminated glycidyl azide‐r‐(3,3‐bis(azidomethyl)oxetane) copolymers (GA/BAMO) and poly‐3‐azidomethyl‐3‐methyl oxetane (pAMMO) by azidation of their respective polymeric substrates were described. The main objective was the preparation of amorphous azido‐polymers, as substitutes of hydroxy‐terminated polybutadiene (HTPB) in new formulations of energetic propellants. Here, the subsequent characterization of both the binders is presented. First of all, several isocyanates were checked in order to optimize the curing reaction, and then two small‐scale formulations of a propellant, based on aluminium and ammonium perchlorate, were prepared and characterized. Finally, the mechanical properties and burning rate were compared to those of a similar propellant based on HTPB as binder.     

Boron‐dependent microstructural evolution,thermal stability,and crystallization of mechanical alloying derived SiBCN

Amorphous boron‐rich SiBCN were prepared by high‐energy ball‐milling of the mixtures of Si, graphite, h‐BN, and inorganic boron, which acted as extra boron source. The solid‐state amorphization, thermal stability, and crystallization of the boron‐rich SiBCN were studied in detail. It was suggested that mechanical alloying can drive solid‐state amorphization but also can be an initiation step for the nucleation of nanocrystals. The amorphous networks of Si‐C, C‐B, C‐C, C‐N, B‐N, and C‐B‐N bonds are detected by XPS; however, solid‐state NMR further confirms the formation of a new chemical environment around B atoms, BC₃. The increases in boron content improve the thermal stability of SiBCN ceramics but weaken their oxidation resistance. Nano‐SiC crystallizes first while BN(C) forms subsequently. Boron promoting SiC crystallization may result from the reduced hindering effects of B‐N‐C nanodomains that retard SiC crystallization.