Thermal Decomposition and Combustion of Ammonium Dinitramide (Review)

A comprehensive review of thermal decomposition and combustion of ammonium dinitramide (ADN) has been conducted. The basic thermal properties, chemical pathways, and reaction products in both the condensed and gas phases are analyzed over a broad range of ambient conditions. Detailed combustion-wave structures and burning-rate characteristics are discussed. Prominent features of ADN combustion are identified and compared with other types of energetic materials. In particular, the influence of various condensed- and gas-phase processes in dictating the pressure and temperature sensitivities of the burning rate is examined. In the condensed phase, decomposition proceeds through the mechanisms ADN → NH₄NO₃ + N₂O and ADN → NH₃ + HNO₃ + N₂O, the former mechanism being the basic one. In the gas phase, the mechanisms ADN → NH₃ + HDN and ADN → NH₃ + HNO₃ + N₂O are prevalent. The gas-phase combustion-wave structure in the range of 5–20 atm consists of a near-surface primary flame followed by a dark-zone temperature plateau at 600–1000°C and a secondary flame followed by another dark-zone temperature plateau at 1000–1400°C. At higher pressures (60 atm and above), a final flame is observed at about 1800°C without the existence of any dark-zone temperature plateau. ADN combustion is stable in the range of 5–20 atm and the pressure sensitivity of the burning rate has the form r _b = 20.72p ^0.604 [mm/sec] (p = 0.5–2.0 MPa). The burning characteristics are controlled by exothermic decomposition in the condensed phase. Above 100 atm, the burning rate is well correlated with pressure as r _b = 8.50p ^0.608 [mm/sec] (p = 10–36 MPa). Combustion is stable, and intensive heat feedback from the gas phase dictates the burning rate. The pressure dependence of the burning rate, however, becomes irregular in the range of 20–100 atm. This phenomenon may be attributed to the competing influence of the condensed-phase and gas-phase exothermic reactions in determining the propellant surface conditions and the associated burning rate. __________ Translated from Fizika Goreniya i Vzryva, Vol. 41, No. 6, pp. 54–79, November–December, 2005.     

Condensed Phase Behavior in the Combustion of Ammonium Dinitramide

This paper reports on the thermal and combustion behaviors of ammonium dinitramide (ADN). The thermal behavior is measured by a pressure thermogravimetric analysis (TGA) at pressures below 8 MPa. The burning rates of pure ADN and ADN/ammonium nitrate (AN) mixtures are measured in the range 0.2–12 MPa, and the burning temperature profiles are obtained using thermocouples with diameters of 5 and 25 μm. This report mainly focuses on the condensed‐phase behavior in the vicinity of a burning surface. The temperature profiles are complicated because the ADN decomposition and AN dissociation compete during the condensed phase, and the bubbles of the decomposition gas and gas‐phase flame also affect the surface temperature. AN addition helps to understand the effects of AN during the condensed phase, and it was shown that the burning temperature rises to the critical temperature of AN. Based on these experimental results, the pressure dependency of the burning rates is also discussed.     

Ultra-high temperature ablation behavior of MoAlB ceramics under an oxyacetylene flame

The ultra-high temperature ablation of a polycrystalline, fully dense, predominantly single phase MoAlB ceramic discs under an oxyacetylene flame is examined. The linear ablation rate decreases from 1.3 μm/s during the first 30 s to - 0.7 μm/s after 60 s when the surface temperature reached about 2050 °C (with a flame temperature around 3000 °C). Up to 60 s, the MoAlB is ablation resistant due to the formation of a protective and viscous surface Al₂O₃ layer. As the ablation time is prolonged, the protective Al₂O₃ scale becomes porous and is almost fully destroyed at the central ablation region after 120 s. This accelerates the formation of large amounts of volatile species (mainly B and Mo oxides), resulting in a reduction in the ablation resistance.     

Kinetics of the CaO  quartz  H2O reaction at 120° to 180°C in suspensions

Kinetics of hydrothermal reactions have been studied for mixtures of CaO and quartz (<10 μm 10–20 μm) with Ca/Si = 0.8 and 1.0 in stirred suspensions at 120 – 180°C. Reaction proceeds through the sequence: Ca(OH)₂ + SiO₂ → Ca-rich C-S-H + SiO₂ (at 120°C) → poorly crystalline tobermorite (at 140°C)→ highly crystalline tobermorite (at 180°C) → xonotlite at 180°C and Ca/Si = 1.0 and 180°C and Ca/Si = 0.8 if 10–20 μm quartz is used. Reaction is controlled by dissolution of the quartz. For both Ca/Si ratios the radius of the 10–20 μm quartz decreases at a constant rate, viz 0.85 μm/h at 180°C, 0.13 μm/h at 140°C, 0.04 μm/h at 120°C.     

DOPO-based curing flame retardant of epoxy composite material for char formation and intumescent flame retardance

Phosphorus-containing flame retardant (HBAEA-DOPO) for epoxy resin was synthesized by addition reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) with bis[2-(4-hydroxybenzylideneamino)ethyl]amine (HBAEA) that was synthesized via 4-hydroxybenzaldehyde with diethylenetriamine. HBAEA-DOPO was mixed with 4,4′-diaminodiphenyl sulfone to co-cure the epoxy resin of diglycidyl ether bisphenol A. The silane modified nano-silica (nano-SiO₂) was used to reinforce the epoxy resin. Thermal stability and dynamic mechanical properties of the cured epoxy materials were studied with the use of thermogravimetric analysis and dynamic mechanical thermal analysis. Flame retardance and burning behavior were evaluated by the limiting oxygen index (LOI), vertical burning test, and the cone calorimetry. The cured epoxy materials have excellent thermal stability, and the temperatures at the maximum weight loss rate are over 384.0°C. The characteristic temperature corresponding to 5.00 wt% of thermal decomposition reaches 341.5°C as 1.00 wt% of phosphorus content is loaded. Flame retardant grade meets the V-0 level. The fire residue mass gradually increases with HBAEA-DOPO and nano-SiO₂. The characteristics of high flame retardance and smoke suppression of HBAEA-DOPO and nano-SiO₂ on the cured epoxy composites have been demonstrated to be related to char formation and intumescent flame retardance in the condensed phase.     

Ablation behavior and mechanism of bulk MoAlB ceramic at ∼1670–2550 °C in air plasma flame

In this work, MoAlB samples for plasma exposure test were condensed by spark plasma sintering at 1200 °C for 10 min. Ablation resistance of MoAlB ceramic was investigated in a plasma torch facility for about 30 s at high temperature range of ～1670?2550 °C, which provided a quasi-real hypersonic service environment. The results showed that the linear ablation rate was increased from 0 μm/s at ～1670 °C to 86.4 μm/s at ～2550 °C. At ～1670 °C, the ablated surface of MoAlB ceramic was covered by Al₂O₃ layer, presenting excellent ablation resistance. At ～2220 °C, the macroscopic cracks were induced by thermal stress, which opened up channels for the inward diffusion of oxygen and deteriorated the ablation resistance of the substrate. Above ～2400 °C, the volatile MoO₃ and B₂O₃ and the erosion of viscous oxides by the high shearing force of plasma stream were the main ablation mechanisms.     

A temperature-profile Study of the Combustion of Black Powder and its constituent binary mixtures

An earlier thermo-analytical study of black powder, using small sample masses and slow heating rates, has been extended to an examination of the behaviour of black powder under the less-controlled conditions of ignition and combustion, by simultaneous measurement of temperature profiles and burning rates. Burning-rate against composition curves for various charcoal/KNO₃, mixtures (sulphurless black powder) and for charcoal/KNO₃, mixtures with various proportions of sulphur, were concave-down-type curves. The compositions of mixtures with maximum burning rates did not correspond with the compositions of mixtures with maximum enthalpy-of-reaction. Maximum temperatures of ∼1400°C were recorded. Burning rates were found to decrease with increasing particle size of the constituents: with increasing compaction of the mixtures, or when inert diluents or subsidiary fuels were added to the mixtures. Burning rates were also affected by moisture contents above 276, and failure of burning occurred at >15% moisture.     

Study of Some Low Temperature Gas‐Generating Compositions

Some low temperature gas‐generating compositions, comprised of guanidine nitrate (GN), basic cupric nitrate (BCN), and ferric oxide (Fe₂O₃), were studied herein. The thermal decomposition properties and burning characteristics of GN/BCN/Fe₂O₃ mixtures were investigated by thermogravimetry/differential scanning calorimetry (TG/DSC), burning temperature measurements, automatic calorimetry, and X‐ray diffraction (XRD). This study showed that the maximum burning temperature of GN/BCN/Fe₂O₃ mixture (613 °C) was 31 % lower than that of GN/BCN mixture and the corresponding heat of combustion (2647 J g⁻¹) decreased by 15 %. When the GN/BCN/Fe₂O₃ mixtures were burning, Fe₂O₃ did not directly react with GN but with Cu (or CuO), which was produced by reaction between GN and BCN. The combustion process of GN/BCN/Fe₂O₃ grains could be divided into four stages: pre‐heated, condensed, combustion, and cooling.     

In Situ Neutron Powder Diffraction Study of Ti3SiC2 Synthesis

The synthesis of Ti₃SiC₂ by pressureless reactive sintering of Ti/SiC/C mixtures under an Ar atmosphere has been studied using in situ neutron diffraction. The intermediate phases TiC_x and Ti₅Si₃C_x (x≤ 1) form first at ∼800–1400°C. These phases are consumed in the formation of Ti₃SiC₂, at ∼1500°C. After sintering, Ti₅Si₃C_x disappears but an amount of TiC_x remains in the sample primarily as a surface layer. The studies appear to support a suggestion that the intermediate phases react to form Ti₃SiC₂ through a diffusion-controlled process. Prolonged stepwise heating under argon in some experiments resulted in decomposition of Ti₃SiC₂ above ∼1400°C and significant disproportionation of the sample.     

Role of Additives in the Combustion of Ammonium Dinitramide

The thermal decomposition behavior and combustion characteristics of mixtures of ammonium dinitramide (ADN) with additives were studied. Micrometer‐sized particles of Al, Fe₂O₃, TiO₂, NiO, Cu(OH)NO₃, copper, CuO, and nanometer‐sized particles of aluminum (Alex) and CuO (nano‐CuO) were employed. The thermal decomposition was measured by TG‐DTA and DSC. The copper compounds and NiO lowered the onset temperature of ADN decomposition. The heat value of ADN with Alex was larger than that of pure ADN in closed conditions. The burning rates and temperature of the pure ADN and ADN/additives mixtures were measured. CuO and NiO enhance the burning rate, particularly at pressures lower than 1 MPa, because of the catalyzed decomposition in the condensed phase; the other additives lower the burning rate. This negative effect on the burning rate is explained based on the surface temperature measurements by a physicochemical mechanism, which involves a chemical reaction, a phase change of the ammonium nitrate, and the blown‐off droplets of the condensed phase.     

Conducting nanocomposites of polyacrylamide with acetylene black and polyaniline

A conducting nanocomposite of polyacrylamide (PAA) with acetylene black was prepared via Na₂AsO₃‐K₂CrO₄ redox initiated polymerization of acrylamide in water containing a suspension of acetylene black. FTIR analyses confirmed the presence of PAA in the nanocomposites. The composite possessed lower thermal stability than AB and exhibited three stages of decomposition upto 430°C. DSC thermogram revealed three endotherms due to minor thermal degradation (at ∼100°C), melting and decomposition (at ∼230°C) and major decomposition (at ∼430°C). TEM analyses indicated the formation of globular composite particles with sizes in 30–70 nm range. In contrast to the very low conductivity of the base polymer the composite showed a dramatic increase in conductivity (0.19–6.0 S/cm) depending upon AB loading. Log (conductivity) –1/T plot showed a change in slope at ∼127°C indicating the manifestation of an intrinsic conductivity region and an impurity conductivity region. The activation energy for conduction as estimated from the slope of region I was 0.008 eV/mol. The C–V plot was linear showing a metallic behavior. For comparison in conductivity PAA‐polyaniline composite was also prepared which however displayed much lower conductivity values. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Decomposition of burning polytetrafluoroethylene

PTFE rods, 0.6–3.8 cm diameter, were burnt from the top downwards in a gently rising atmosphere of oxygen. The burning was only possible in concentrated oxygen, or at elevated temperature or pressure. At its surface temperature of 920 ± 25°K, the polymer evolved monomeric C₂F₄ which oxidized in a surrounding gas flame; 15–35% of all the carbon in the gas was found present as monomer just above the larger rods. Depolymerization of the solid was not its only mode of decomposition, however. The heat radiated and conducted from the flame into the condensed phase was too little to depolymerize it completely, and heterogeneous reactions with species from the gas phase must also have contributed to the decomposition. Overall, the polymer burnt in O₂, but the gaseous reactant which attacked the surface need not have been O₂ or O in all cases, for these rare species just above the larger rods. Elemental fluorine was present in the gas even when elemental oxygen was absent, and calculations indicate that F atoms would be a major flame species at equilibrium. It is possible that heterogeneous attack by flame generated F atoms consumed part of the polymer and also supplied energy to help depolymerize the rest.     

Improving the flame retardance and melt dripping of poly(lactic acid) with a novel polymeric flame retardant of high thermal stability

A polymeric flame retardant containing phosphorus and nitrogen (PCNFR) was synthesized and characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance and gel permeation chromatography. The thermal decomposition temperatures at 10% weight loss (T_{10 wt%}) of PCNFR were around 358 °C, and the char yield at 600 °C reached about 60 wt% both in nitrogen and air by thermogravimetric analysis. The flame retarded poly(lactic acid) (PLA) composites with PCNFR were prepared. The thermogravimetric analysis results showed that PCNFR could improve the thermal stability of the flame retarded PLA composites with low loading (≤10 wt%) and at high temperature zone (≥390 °C). The condensed products from the decomposition of the flame retarded composites at 380 °C and 450 °C for different intervals were analyzed by Raman spectroscopy, and the results showed that time and temperature influenced the structure of the char residue evidently. When incorporating 30 wt% PCNFR into PLA, the limited oxygen index of the flame retarded composites reached 25.0%, and V‐0 rating was achieved. The char residues were analyzed by scanning electron microscopy, Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy in detail. Copyright © 2016 John Wiley & Sons, Ltd.     

Combustion of Nanoaluminum and Water Propellants: Effect of Equivalence Ratio and Safety/Aging Characterization

The deflagration and combustion efficiency of 80 nm aluminum/ice (ALICE) mixtures with equivalence ratios of ϕ=1.0, 0.75, and 0.67 were experimentally investigated. We find that pressure exponent and burning rate vary little between these three mixtures, with the exponent varying only from 0.42 to 0.50 and burning rate at 6.9 MPa varying from 2.05 to 2.10 cm s⁻¹. However, reducing the equivalence ratio from 1.0 to 0.67 surprisingly increases combustion efficiency from 70 % to 95 % with unburned aluminum agglomerates visible in electron microscopy photographs of 70 % combustion efficiency (ϕ=1.0) products. Our findings suggest that nanoaluminum/water combustion is diffusionally limited for all conditions considered. Aging tests on the propellant show that storage at −30 °C essentially stops the Al/H₂O reaction such that little nanoaluminum degradation occurs after 200 days. Electrostatic discharge (ESD), shock initiation, and impact sensitivity tests indicate that the propellant is insensitive to ignition by these stimuli. Specifically, while neat nanoaluminum powders are highly ESD sensitive (ignition threshold 0.3–14 mJ), nAl/H₂O mixtures are insensitive to ESD and have ignition thresholds in excess of 400 mJ. Likewise, nAl/H₂O mixtures are insensitive to impact ignition, having an ignition threshold in excess of 2.2 m. Propellants containing 80 nm or larger average particle size aluminum were also found to be insensitive to shock initiation.     

The effect of red phosphorus on the flammability of poly(ethylene terephthalate)

Addition of red phosphorus in concentrations of about 4% to poly(ethylene terephthalate) (PET) reduces the flammability of that polymer. The rates of flame propagation and the ignitability are reduced, while the oxygen index (O.I.) is increased. The surface temperature of burning PET amounts to T_S ≈ 380°C; addition of 4% red phosphorus raises this value to T_S ≈ 450°C. An increase of the environmental temperature T_E enhances the flammability of PET and PET + phosphorus samples; the O.I. decreases and the rate of flame propagation increases with temperature. The flame-retardant effectiveness of red phosphorus is reduced if the sample is burned in a N₂O atmosphere. This indicates that part of the flame retardancy imparted by phosphorus involves gas-phase inhibition. The major flame-retardant action does, however, occur in the condensed phase, since the rate of pyrolysis of PET is affected by the presence of red phosphorus.     

Microstructural evolution in bone china

Abstract

Phase and microstructural evolution in model bone china bodies was determined by XRD and electron microscopy of quenched samples fired for 3 h at 600–1500°C. Unfired but shaped bone china comprised bone ash and clay agglomerates (≤70 μm) in a matrix of smaller (from submicron to 10 μm) mixed clay, feldspar, and bone ash particles. The unfired microstructure and subsequent phase evolution is believed to be strongly dependent on the extent of prior mixing. On firing, the clay component dehydroxylated to metakaolin at ～550°C. Metastable sanidine formed from decomposition of the feldspar component above 600°C and dissolved at 1100°C. The bone ash com ponent decomposed into β-TCP and lime (and/or Ca²⁺ and O^2- ions) beginning at ～800°C. CaO from the bone ash reacts with the clay decomposition products forming liquid and anorthite at ～900°C. Liquid formation is due to reaction of CaO with feldspar and clay relict grains and is discussed in terms of the CaO–P₂O₅–Al₂O₃ ternary phase diagram. Above 1200°C pure bone ash relicts contained small (5–10 μm) β-TCP crystals, CaO penetrated clay relicts contained anorthite, and mixed clay–bone–feldspar regions contained both anorthite and larger (>50 μm) β-TCP crystals in calcium aluminosilicate glass. The major phase in the clay relicts was anorthite although a few elongated (～100 nm) needles resembling mullite in composition and morphology also crystallised in samples fired to 1100°C and grew to ～30 μm in length at 1300°C.     

Condensed combustion products of aluminized propellants. IV. Effect of the nature of nitramines on aluminum agglomeration and combustion efficiency

The condensed combustion products of two model propellants consisting of ammonium perchlorate, aluminum, nitramine, and an energetic binder were studied by a sampling method. One of the propellants contained HMX with a particle size D ₁₀ ≈ 490 μm, and the other RDX with a particle size _{D 10} ≈ 380 μm. The particle-size distribution and the content of metallic aluminum in particles of condensed combustion products with a particle size of 1.2 μm to the maximum particle size in the pressure range of 0.1–6.5 MPa were determined with variation in the particle quenching distance from the burning surface to 100 mm. For agglomerates, dependences of the incompleteness of aluminum combustion on the residence time in the propellant flame were obtained. The RDX-based propellant is characterized by more severe agglomeration than the HMX-based propellant — the agglomerate size and mass are larger and the aluminum burnout proceeds more slowly. The ratio of the mass of the oxide accumulated on the agglomerates to the total mass of the oxide formed is determined. The agglomerate size is shown to be the main physical factor that governs the accumulation of the oxide on the burning agglomerate. __________ Translated from Fizika Goreniya i Vzryva, Vol. 42, No. 4, pp. 78–92, July–August, 2006.     

Kinetics and crystal structure of isothermal crystallization of poly(lactic acid) plasticized with triphenyl phosphate

In this article, the spherulitic growth rate of neat and plasticized poly(lactic acid) (PLA) with triphenyl phosphate (TPP) was measured and analyzed in the temperature range of 104–142°C by polarizing optical microscopy. Neat PLA had the maximum value of 0.28 μm/s at 132°C, whereas plasticized PLA had higher value than that of neat PLA, but the temperature corresponding to the maximum value was shifted toward lower one with increasing TPP content. The isothermal crystallization kinetics of neat and plasticized PLA was also analyzed by differential scanning calorimetry and described by the Avrami equation. The results showed for neat PLA and its blends with various TPP contents, the average value of Avrami exponents n were close to around 2.5 at two crystallization temperatures of 113 and 128°C, the crystallization rate constant k was decreased, and the half‐life crystallization time t_1/2 was increased with TPP content. For neat PLA and its blend with 15 wt % TPP content, the average value of n was 2.0 and 2.3, respectively, the value of k was decreased, and the value of t_1/2 was increased with crystallization temperature (T_c). Further investigation into crystallization activation energy ΔE_a of neat PLA and its blend with 15 wt % TPP showed that ΔE_a of plasticized PLA was increased compared to neat PLA. It was verified by wide‐angle X‐ray diffraction that neat PLA and its blends containing various TPP contents crystallized isothermally in the temperature range of 113–128°C all form the α‐form crystal. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Fouling tendency of ash resulting from burning mixtures of biofuels. Part 3. Influence of probe surface temperature

Mixtures of peat with bark and peat with straw were burned in a large lab-scale entrained flow reactor under controlled conditions, and deposits were collected on an air-cooled probe controlled at four to six different probe surface temperatures between 475 and 625 °C. The results show that the probe surface temperature has no effect on the deposition rate when peat is burned. When burning bark, either alone or in mixtures with peat, the deposition rate decreases with increasing probe surface temperature. When burning straw, either alone or in mixtures with peat, the deposition rate increases with increasing probe surface temperature up to 550 °C and remains constant at higher temperatures. The Cl content in the deposits decreases with increasing probe surface temperature, regardless of the mixture composition. In deposits obtained from burning peat–bark mixtures, K appears as K₂SO₄ when the deposition rate is low and as KCl when the deposition rate is high. In deposits obtained from burning peat–straw mixtures, no clear relationship is found between the deposition rate and the contents of Cl, S and K in the deposits.     

Combustion Mechanism of Azide Polymer

The combustion wave structure and thermal decomposition process of azide polymer were studied to determine the parameters which control the burning rate. The azide polymer studied was glycidyl azide polymer (GAP) which contains energetic – N₃ groups. GAP was cured with hexamethylene diisocyanate (HMDI) and crosslinked with trimethylolpropane (TMP) to formulate GAP propellant. From the experiments, it was found that the burning rate of GAP propellant is significantly high even though the adiabatic flame temperature of GAP propellant is lower than that of conventional solid propellants. The energy released at the burning surface of GAP propellant is caused by the scission of N N₂ bond which produces gaseous N₂. The heat flux transferred back from the gas phase to the burning surface is very small compared with the heat generated at the burning surface. The activation energy of the decomposition of the burning surface of GAP propellant, E_s, is determined to be 87 kJ/mol. The burning rate is represented by r = 9.16 × 10³ exp(–E_s/RT_s) where r (m/s) is burning rate, T_s (K) is the burning surface temperature, and R is the universal gas constant. The observed high temperature sensitivity of burning rate is correlated to the relationship of (∂T_s/∂T₀)_p = 0.481 at 5 MPa, where T₀ is the initial propellant temperature.