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.     

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

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

Combustion Effects of Nitrofulleropyrrolidine on RDX‐CMDB Propellants

The effect of N‐methyl‐2‐(3‐nitrophenyl)pyrrolidino[3′,4′:1,2]fullerene (mNPF) on the decomposition characteristics of hexogen (RDX) was investigated using differential scanning calorimetry (DSC). The results show that mNPF can accelerate the decomposition of RDX, the peak temperature (T_p) of the exothermal decomposition is reduced by 6.4 K, and the corresponding apparent activation energy (E_a) is decreased by 8.7 kJ mol⁻¹. N‐methyl‐2‐(3‐nitrophenyl)pyrrolidino[3′,4′:1,2]fullerene (mNPF), carbon black (CB), and C₆₀ were used as combustion catalysts to improve the combustion performance of a composite modified double‐base propellant containing RDX (RDX‐CMDB). The burning rate experimental results show that mNPF has a stronger catalytic effect than C₆₀ and CB. The magnitude of the effect of the three carbon substances on the enhancement of the burning rate is as follows: mNPF>C₆₀>CB. The catalytic effects of different contents of mNPF on the burning rates of RDX‐CMDB propellants were also studied, and the results show that the burning rates of RDX‐CMDB propellants are improved with increasing mNPF content. The plateau burning rate of a RDX‐CMDB propellant can be increased to 19.6 mm s⁻¹ when 1.0 % mNPF is added, and the corresponding plateau combustion region occurs at 8–22 MPa.     

Development of Polyurethane‐Based Solid Propellants Using Nanocomposite Materials

Mechanically‐activated nanocomposites (MANCs) of nano‐aluminum (nAl)/X (X=Cu, Ni, Zn, Mg, and graphite) were used as replacements for reference nAl powder and as catalytic ingredients in polyurethane (PU) propellants. The effects of their use on combustion heat, burning rate, and thermal decomposition were investigated. It was found that MANCs have catalytic effects and the modified propellants have enhanced the released heat, burning rate, and thermal decomposition properties. MANCs‐based propellants have improved the processing and the mechanical properties with acceptable safety aspects. They can be used for catalytic applications in solid propellants to improve their energetic, burning rate, and thermal decomposition characteristics.     

Research on Titanium‐Containing Micro‐Porous Propellants with Rapid Burning Rate

Micro‐porous propellants containing titanium powder were obtained by supercritical CO₂ (SC CO₂) foaming technique. The morphologies of the micro‐porous propellants were characterized by scanning electron microscopy (SEM) and energy‐dispersive X‐ray spectroscopy (EDS) measurement. The burning rate, the impetus, and the heat of explosion of the micro‐porous propellants were measured by the closed vessel test and the calorimetric bomb test. The results show that the porosity increased with increasing titanium powder content; compared with Benite, the burning rate was substantially improved, and the maximum values of the impetus and the isochoric heat of explosion increased by 51.4 % and 6.5 %, respectively. The Ti‐containing micro‐porous propellants with rapid burning rate and better energetic properties described in this paper may have the potential to replace Benite as igniter material in a flame igniter of a gun propellant charge.     

Evaluation of 4‐(Dimethylsilyl) Butyl Ferrocene Grafted HTPB as a Burning Rate Modifier in Composite Propellant Formulation using Bicurative System

High burning rate composite propellants are achieved by incorporation of fine particles of oxidizer, transition metal oxides, and liquid ballistic modifiers. However, they pose processing problems, inertness to the composition and migration related issues. To overcome such problems, an attempt was made to incorporate ferrocenyl grafted HTPB as a burning rate modifier by partly replacing HTPB from 10 % to 50 % using TDI/ IPDI bicurative system and to study their processability in terms of viscosity, mechanical, thermal, sensitivity, and ballistic properties. The data on viscosity reveal that there is a marginal enhancement in end of mix viscosity as percentage of ferrocenyl grafted HTPB increases. The mechanical data reveal that tensile strength and elastic modulus increases, whereas percentage elongation decreases compared to base composition. The results on thermal properties infer that, as the percentage of ferrocenyl grafted HTPB increases, onset decomposition temperature decreases. The impact and friction sensitivity data also envisage that sensitivity increases in comparison to base composition. The data on ballistic properties revealed that there is ca. 53 % increase in burning rate, while decrease in “n” value from 0.39 to 0.2 was obtained compared to base composition.     

Hot‐Wire Ignition of AN‐Based Emulsions

Emulsions based on ammonium nitrate (AN) and water locally ignited by a heat source do not undergo sustained combustion when the pressure is lower than some threshold value usually called the Minimum Burning Pressure (MBP). This concept is now being used by some manufacturers as a basis of safety. However, before a technique to reliably measure MBP values can be designed, one must have a better understanding of the ignition mechanism. Clearly, this is required to avoid under ignitions which could lead to the erroneous interpretation of failures to ignite as failures to propagate. In the present work, facilities to prepare and characterize emulsions were implemented at the Canadian Explosives Research Laboratory. A calibrated hot‐wire ignition system operated in a high‐pressure vessel was also built. The system was used to study the ignition characteristics of five emulsion formulations as a function of pressure and ignition source current. It was found that these mixtures exhibit complicated pre‐ignition stages and that the appearance of endotherms when the pressure is lowered below some threshold value correlates with the MBP. Thermal conductivity measurements using this hot‐wire system are also reported.     

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.     

A Pressurized Vessel Test to Measure the Minimum Burning Pressure of Water‐Based Explosives

It is well known that water‐based commercial explosives locally ignited in closed vessels do not undergo self‐sustained combustion when the pressure is lower than some threshold value. The latter is usually referred to as the Minimum Burning Pressure (MBP) of the explosive and is now being used by some manufacturers as a basis of safety for many associated manufacture, transport, and handling processes. In the present work, both an apparatus based on hot‐wire ignition and an associated methodology were developed to measure the MBP of water‐based explosives. Typical results for various emulsion and water‐gel explosives are also reported and discussed. It is also shown that the technique could be used to characterize very insensitive explosive substances normally used as explosive precursors.     

Burning Characteristics of Ammonium Nitrate‐Based Composite Propellants Supplemented with Fe2O3

Ammonium nitrate (AN)‐based composite propellants have attracted a considerable amount of attention because of the clean burning nature of AN as an oxidizer. However, such propellants have several disadvantages such as poor ignition and a low burning rate. In this study, the burning characteristics of AN‐based propellants supplemented with Fe₂O₃ as a burning catalyst were investigated. The addition of Fe₂O₃ is known to improve the ignitability at low pressure. Fe₂O₃ addition also increases the burning rate, while the pressure exponent generally decreases. The increasing ratio (R) of the burning rate of the AN/Fe₂O₃ propellant to that of the corresponding AN propellant vs. the amount of Fe₂O₃ added (ξ) depends on the burning pressure and AN content. R decreases at threshold value of ξ. The most effective value of ξ for increasing the burning rate was found to be 4 % for the propellant at 80 % AN, and the value generally decreased with decreasing AN content. According to thermal decomposition kinetics, Fe₂O₃ accelerates the reactions of AN and binder decomposition gases in the condensed‐ and/or gas‐phase reaction zones. The burning characteristics of the AN‐based propellant were improved by combining catalysts with differing catalytic mechanisms instead of supplementing the propellant with a single catalyst owing to the multiplicative effect of the former.     

Productions of Ultra‐Fine Powders and Their Use in High Energetic Compositions

Fine and ultra‐fine powders are actively studied in pyrotechnics, explosives and propellants. The important questions are how to produce a powder with specified characteristics and how to use the powder produced.     

Designing Starch‐Based Nanospheres to Make Hydrogels with High Mechanical Strength

A robust method to prepare hydrogels with high mechanical strength is presented. Core/shell nanospheres with derivatizable allyl groups in the shell were first prepared. Starch‐based nanospheres were used as crosslinker to prepare polyacrylamide hydrogels. The starch‐based nanospheres were bridged by acrylamide to form crosslink points in the hydrogel network. They possess an extremely high mechanical strength. The results show that starch‐based nanosphere hydrogels can sustain strengths of 10.34 MPa, which is 60 times greater than for a normal hydrogel. The mechanical properties of SNH can be tailored by varying the content of SN. This approach offered a new way of making functional hydrogel with biodegradable component as a substitute for tissue.

     

Physicochemical Characterization of Chrysin‐Derivative‐Loaded Nanostructured Lipid Carriers with Special Reference to Anticancer Activity

Homologues long‐chain chrysin derivatives (LCD, C _n: 8–18) were synthesized and incorporated into nanostructured lipid carriers (NLC) with the aim to treat human neuroblastoma. Mutual miscibility and attractive interactions among the NLC components, namely tripalmitin (TP), cetyl palmitate (CP), oleic acid (OA), and the chrysin (CHR) derivatives (LCD) at the air–water interface were assessed by the Langmuir monolayer approach. Optimum combination for the NLC formulations was found to be 2:2:1 (M/M/M) for TP/CP/OA, respectively. NLC formulations, both in the absence and presence of LCD, were characterized by combined dynamic light scattering, electron microscopy, atomic force microscopy, and differential scanning calorimetry. The size and zeta potential of the NLC formulations were found in the range 200–350 nm and ?12 to ?18 mV, respectively. Encapsulation efficiency and release kinetics of CHR and LCD when loaded into NLC were also evaluated. LCD exhibited maximum incorporation, drug‐loading capacity, and sustained release because of its enhanced hydrophobicity. Superior incorporation efficiency and sustained‐release profile of LCD were able to enhance their anticancer activity against human neuroblastoma cell lines, compared to CHR, making them promising agents in combating cancer.     

γ‐FOX‐7: Structure of a High Energy Density Material Immediately Prior to Decomposition

1,1‐Diamino‐2,2‐dinitroethene, C₂H₄N₄O₄ (FOX‐7), is a novel high energy density material with low friction and impact sensitivity and a high activation barrier to detonation. In this study, the previously unknown crystal structure of the γ‐polymorph of trimorphic FOX‐7 is reported. γ‐FOX‐7 is stable from ∼435 K until the compound decomposes just above 504 K. A single crystal of α‐FOX‐7 (P2₁/n, Z=4, a=694.67(7) pm, b=668.87(9) pm, c=1135.1(1) pm, β=90.14(1)°, T=373 K) was first transformed into a single crystal of β‐FOX‐7 (P2₁2₁2₁, Z=4, a=698.6(1) pm, b=668.6(2) pm, c=1168.7(3) pm, T=423 K) and then into a single crystal of γ‐FOX‐7 at 450 K. The γ‐FOX‐7 crystal was then subsequently quenched to 200 K. The structure of γ‐FOX‐7 (P2₁/n, Z=8, a=1335.4(3) pm, b=689.5(1) pm, c=1205.0(2) pm, β=111.102(8)°, T=200 K) consists of four planar layers, each containing two crystallographically independent FOX‐7 molecules found in the asymmetric unit.     

Surface Modification of Polycarbonate Urethane with Zwitterionic Polynorbornene via Thiol‐ene Click‐Reaction to Facilitate Cell Growth and Proliferation

Herein, we grafted the zwitterionic polynorbornene onto polycarbonate urethane (PCU) film surface by a convenient route of thiol‐ene click‐chemistry. The PCU film surface was first treated with hexamethylene‐1,6‐diisocynate and subsequently with two different thiol agents (l ‐cysteine and β‐marcaptoethanol) in the presence of di‐n‐butyltin dilaurate (DBTDL) to immobilize sulfhydryl groups onto the surface. Here, DBTDL acted as selective catalyst for the reaction between surface‐tethered isocyanates and amine/hydroxyl groups in thiol agents over that of free thiol groups. In the next step, zwitterionic polynorbornene (poly(NSulfoZI)) having functionalizable double bonds was grafted onto these surfaces by photo‐initiated thiol‐ene click‐reaction. The modified surfaces were characterized by water contact angle and XPS analysis. Moreover, the cytocompatibility of these surfaces was investigated by model endothelial cells, EA.hy926, for 1, 3, and 7 d culture times, which showed enhanced cell adhesion and growth. Therefore, the poly(NSulfoZI) functionalized PCU surface using l‐cysteine as thiol agent could be a good candidate for tissue engineering material application.     

Influence of Aluminium Alkyl Compounds on the High‐Pressure Polymerization of Ethylene with Ternary Metallocene‐Based Catalysts. Investigation of Chain Transfer to the Aluminium

The influence of aluminium alkyl compounds on metallocene‐catalyzed high pressure polymerizations of ethylene has been investigated at 150 MPa and 180°C in a continuously operated autoclave. The catalysts were based on the metallocenes bis(cyclopentadienyl)zirconium dichloride (Cp₂ZrCl₂) and diphenylmethylene (cyclopentadienylfluorenyl)zirconium dichloride (Ph₂C‐(CpFlu)ZrCl₂), which were preactivated outside the reactor with triisobutylaluminium (TiBA) and N,N‐dimethylanilinium tetrakis(pentafluorophenyl)borate (DMAP, [PhNHMe₂][B(C₆F₅)₄]). The concentrations of triisobutylaluminium (TiBA) and triethylaluminium (TEA) in the reactor were varied over a wide range, using a separate dosing for these two aluminium alkyl compounds. Productivity and polymer properties strongly depended on the type and the concentration of the aluminium alkyl compound used. Highest productivities and molecular weights were obtained with low concentrations of TiBA in the reactor. Up to a concentration of 30 molppm Al in the reactor, unimodal polymers were formed with M̄_w/M̄_n between 2 and 3. With higher aluminium concentrations the products formed contained small amounts of waxes, due to oligomerization catalyzed by the aluminium alkyl compounds. The molecular weight distributions (MWDs) of these products could be described as a superimposition of two Schulz‐Zimm distributions. All MWDs were analyzed with regard to the amount of waxes produced by ethylene oligomerization and with regard to the influence of chain transfer reactions to the aluminium. The rate constants of chain transfer to aluminium, in relation to the rate constants of insertion of ethylene, were estimated.     

Access to Both Enantiomers of α‐Chloro‐β‐keto Esters with a Single Chiral Ligand: Highly Efficient Enantioselective Chlorination of Cyclic β‐Keto Esters Catalyzed by Chiral Copper(II) and Zinc(II) Complexes of a Spiro‐2,2′‐bischroman‐Based Bisoxazoline Ligand

The spiro‐2,2′‐bichroman‐based chiral bisoxazoline ligands (SPANbox) were found to be highly efficient in copper(II)‐ and zinc(II)‐catalyzed asymmetric chlorinations of cyclic β‐keto esters with N‐chlorosuccinimide (NCS) as the chlorination reagent, to give the corresponding α‐chloro‐β‐keto esters in excellent yields in 5–30 min with ee values up to 97%. The copper(II) triflate and zinc(II) triflate complexes of a single SPANbox ligand demonstrated complementary results to each other with respect to the enantioselection, affording both antipodes of the chlorinated product enantiomers with good to excellent optical purities.     

The Decomposition of some RDX and HMX Based Materials in the One‐Dimensional Time to Explosion Apparatus. Part 1. Time to Explosion and Apparent Activation Energy

A One‐Dimensional Time to Explosion (ODTX) apparatus has been used to study the times to explosion of a number of compositions based on RDX and HMX over a range of contact temperatures. The times to explosion at any given temperature tend to increase from RDX to HMX and with the proportion of HMX in the composition. Thermal ignition theory has been applied to time to explosion data to calculate kinetic parameters. The apparent activation energy for all of the compositions lay between 127 kJ mol⁻¹ and 146 kJ mol⁻¹. There were big differences in the pre‐exponential factor and this controlled the time to explosion rather than the activation energy for the process.