Hydrazine Nitrate Research Articles

Heat transfer to a single explosive particle injected into SCB plasma

This paper is concerned on the interaction of SCB plasma with Lead Azide, Lead Styphnate (LTNR) and Nickel Hydrazine Nitrate (NHN) primary explosive particles, with emphasis on the effects which the heat of explosive imposes on heat transfer from SCB plasma. The heat transfer from SCB plasma to a single spherical particle is calculated by simple calculation method. The effect of the ion and electron recombine reaction at particle’s surface and a spot of explosive reaction during the heating process was discussed. The results with a relatively simple analysis showed that the effect of particle charging on the heat transport to a particle from SCB plasma is not significant especially for the small particles. The effect of the heat of explosive on heat transfer to a particle is stronger for explosive materials with lower activation energy and larger heat of explosive or higher density.

A Dually Effective Inorganic Salt at Inducing Obvious Viscoelastic Behavior of both Cationic and Anionic Surfactant Solutions

Hydrazine nitrate (HN), an inorganic salt, was first found to have dual effects on inducing obvious viscoelasticity of both cationic and anionic surfactant solutions. It was interesting that the surfactant solutions exhibited characteristic wormlike micelle features with strong viscoelastic properties upon the addition of this inorganic salt. The rheological properties of the surfactant solutions have been measured and discussed. The apparent viscosity of the solutions showed a volcano change with an increase of the HN concentration. Correspondingly, the microstructures of the micelles in the solutions changed with the apparent viscosity. First, wormlike micelles began to form and grew with an increase of the HN concentration. Subsequently, the systems exhibited linear viscoelasticity with characteristics of a Maxwell fluid in the intermediate mass fraction range, which originated from a 3D entangled network of wormlike micelles. Finally, a transition from linear micelles to branched ones probably took place at higher HN contents. In addition, the origin of the dual effects brought by HN addition on inducing viscoelasticity in both cationic and anionic surfactant solutions was investigated.

Effect of some reducing and complexing agents on the extraction behavior of technetium in the TBP-HNO3 system

The effect of a series of complexing and reducing agents on the extraction-chemical behavior of technetium as applied to extraction splitting of uranium and plutonium in the Purex process was examined. Kinetic parameters of the catalytic decomposition of N2H5NO3 under the action of Tc in the presence of these agents were evaluated. Variation of the ratio of the oxidized and reduced Tc species in the course of the process and in the hydrazine-free systems was determined. Reagents preventing oxidation of the reduced technetium and decomposition of N2H5NO3 in nitric acid solutions (acetohydroxamic acid, hydroxylamine, ascorbic acid, etc.), inhibiting the reduction of Tc with hydrazine nitrate (H2O2, HN3, etc.), and known as complexing agents toward quadrivalent actinides but indifferent to Tc were considered. The possibilities of using these reagents for modifying the Tc behavior in the course of SNF extraction reprocessing with the aim to direct this element to different process streams were discussed.

Controlled Pertraction of Plutonium(III) Under Reducing Conditions From Acidic Feeds Using TODGA as the Carrier Extractant

Transport of Pu3+ across PTFE flat sheet supported liquid membranes (SLM) using N,N,N′,N′-tetraoctyl-3-oxapentanediamide (TODGA) in n-dodecane as the carrier extractant was investigated. The feed solution was usually 3.0 M HNO3 while the receiver phase contained 0.1 M HNO3. In order to model the transport data, the two-phase liquid-liquid extraction experiments are also reported. A series of reducing agents viz. hydrazinium nitrate (HN), phenyl hydrazine (PH), hydroxyl ammonium nitrate (HAN), and ascorbic acid (AA) were evaluated to maintain plutonium in the +3 state in the feed, out of which phenyl hydrazine was found to be the most effective. Effectiveness of various strippants for quantitative and rapid transport of Pu was also evaluated. Additionally, the effects of feed acidity, carrier concentration, membrane thickness, effect of Pu carrier concentration, etc. were investigated. Membrane diffusion co-efficients were calculated and found to be 1.47 × 10−6 cm2/s for Pu(III). The stability of the SLM, investigated as a function of contact time, was found to be reasonably good even after 20 days of continuous operation.

Combustion characterization of hydrazinium nitrate/energetic binder/Alex based model propellants

The hydrazinium nitrate (N 2H 4∗HNO 3 HN) can be considered as a candidate for using instead of ammonium perchlorate (AP) in eco-friendly solid propellant formulations. In combination with energetic binder it provides reasonably high energetic parameters of solid propellant. In addition, the substitution of AP by HN leads to decrease in the combustion temperature. The combustion of the HN based metallized propellants containing energetic binder has been investigated. The effect of partial substitution of commercial Al powder by Alex on the propellant combustion characteristics has been examined. The burning law was measured in the pressure range 20–80 atm, the ignition delay time and temperature profile were measured at atmospheric pressure. Some qualitative observations on the combustion behavior of the propellants under study have been made by analyzing the video camera and recoil force transducer records.

Thermal hazard analysis of mixed system of hydrazine and nitric acid

In order to obtain a better understanding of the thermal hazard of hydrazine and nitric acid mixtures which are used in plutonium and uranium recovery by extraction (PUREX) process during recycling of spent fuel in nuclear plant, DSC was carried out for the mixed system made by the small scale reaction calorimeter super-CRC in various conditions. It was found that the concentration of the nitric acid has a strong influence on the thermal behavior of the mixed system, and hydrazine nitrate which is formed in the reaction in the mixture was determined by DSC with FTIR analysis.

English

Nickel hydrazine nitrate is an energetic coordination compound having explosive properties in between that of primary and secondary. This compound was used to develop a new type of detonator by replacing the sensitive primary explosive, lead azide in conventional detonators and keeping RDX (cyclotrimethylenetrinitramine) as the output secondary explosive. The detonator consists of three regions, viz., initiation, deflagration-to-detonation transition (DDT), and output. The initiation and the electrical rating of 1A/1W no-fire were achieved using a suitable squib. The DDT and the output were taken care of, by pressing requisite quantities of Nickel hydrazine nitrate and RDX, respectively at required densities in a stainless steel stem channel. The detonator assembly involves crimping the squib and the stem channel in a stainless steel housing and applying a suitable resin at the crimped-end for leak tightness. The output was assessed from the dent depth on aluminium plate, volume expansion on lead block, and by achieving veloctiy of detonation of 8200 m/s in mild detonating cords, containing 0.95 g/m of RDX, which indicates full-order detonation. The detonators were tested at system level and found to perform satisfactorily.

Primary explosives: Electrostatic discharge initiation, additive effect and its relation to thermal and explosive characteristics

All explosives, under all conditions must be considered vulnerable to generation, accumulation and discharge of static charge. The low energy static hazards of the order as low as 2–3 mJ need to be guarded against in case of highly sensitive compounds namely primary explosives. The hazard is normally associated with manufacturing and filling operations due to discharge of static charge accumulated on a person supplying energy up to 20 mJ. To reduce the risk associated with static initiation hazard in the processing and handling of the explosives, the electrostatic sensitivity tests can provide an important input regarding electrostatic hazards. This paper presents electrostatic sensitivity data in terms of zero ignition probability data ( E SE0) of some of the initiatory explosives such as nickel/cobalt hydrazinium nitrate, silver azide, lead azide and mercury salt of 5-nitro tetrazole. Similar data has also been presented for samples coated with polyvinyl pyrrolidone to study its effect on electrostatic sensitivity. The electrostatic spark sensitivity of some conventional and novel made to explain the increased spark sensitivity behavior on the basis of the possible primary explosives has been studied. The electrostatic spark sensitivity of primary explosives decreased in the order of AgN 3 = NHN > PbN 6 > MNT > CoHN > BNCP. A possible correlation of spark energy with approximation and assumption has been drawn with thermal, detonation and mechanical properties. The polyvinyl pyrrolidone coated samples followed the same order but interestingly with increased spark sensitivity. An attempt has been reasoning of dielectric nature of the materials or exothermic effects of decomposition products of PVP. The present work also reports the electrostatic spark sensitivity of cap compositions.

Separation of Trivalent Americium and Rare-Earth Elements from Iron Impurity Using Certain Coordination Compounds

A procedure was developed for separation of trivalent Am and rare-earth elements from iron, involving stabilization of iron in the Fe(II) state with hydrazine nitrate in weakly acidic solution in the presence of dimethylglyoxime or bipyridine, followed by precipitation of f elements as hydroxides. With bipyridine used as a complexone, the iron content in the recovered and washed 4f and 5f element hydroxides does not exceed 10−6 M.

Hydrazinium nitrate

The monoprotonated hydrazinium cation in the title compound, N2H5+·NO3−, forms several types of hydrogen bonds. Stronger ones, in which the H atoms attached to the protonated N atom take part, link cations and anions into layers. Less strong hydrogen bonds, with participation of H atoms attached to the non-protonated N atom, link the layers into a three-dimensional structure. In addition to hydrogen bonds, short contacts of 2.8607 (10) Å have been found between O and N atoms of neighbouring nitrate anions. Such contacts can correspond to a weak inter­molecular inter­action similar to that in organic compounds containing nitro groups.

Selective Removal of Uranium from High‐Level Waste Solution Employing Tri‐n‐Butyl Phosphate as the Extractant

Conditions for the selective removal of uranium from high‐level waste solution have been optimized using tri‐n‐butyl phosphate (TBP) as the extractant. Various aqueous soluble reducing agents viz. hydroxylamine nitrate (HAN), hydrazine nitrate (HN), and diethyl hydroxylamine nitrate (DEHAN) as well as n‐dodecane soluble reductant viz. tert‐butyl hydroquinone (TBH) have been evaluated for the separation of U with respect to Pu and Np. The combination of DEHAN and TBH has been found to be most promising for the selective extraction of U from HLW. Extraction data of a few other metal ions expected to be present in high‐level waste solutions viz. Am(III), Eu(III), Zr(IV), Sr(II), and Cs(I) are also obtained.

Di(2‐Ethylhexyl) Pivalamide (D2EHPVA): A Promising Extractant for Selective Removal of Uranium from High Level Nuclear Waste Solutions

High concentration of uranium present in high‐level waste is responsible for third phase formation during actinide partitioning either by TRUEX or DIAMEX process. Di(2‐ethylhexyl) pivalamide (D2EHPVA) has been found to be a promising extractant for the selective removal of U over Pu, Np, and Am from simulated PHWR high level waste (SHLW). Role of reducing agents viz. hydroxylamine nitrate (HAN) and hydrazine nitrate (HN) has been evaluated for the adjustment of oxidation states of Pu and Np to inextractable state. Multiple extraction from SHLW containing 0.3 M HAN + 0.8 M HN at 4 M HNO3 using 1 M D2EHPVA in n‐dodecane revealed that ∼98% of U could be extracted in five contacts with <1% cumulative Pu extraction.

Ion‐Exchange Separation of Pu from Macro Concentration of Th in HNO3 Medium

Sorption behavior of Th and Pu from anion‐ as well as cation‐exchange resin was investigated from nitric acid medium by both batch and column methods. The anion‐exchange studies involved anionic nitrate complexes of Pu4+ and Th4+ sorbed onto DOWEX 1x4 resin (50–100 mesh), and the cation‐exchange studies involved the sorption of Pu3+ and Th4+ onto BIORAD AG 50Wx8 (50–100 mesh) or DOWEX 50Wx4 (50–100 mesh) resin. The batch data gave a separation factor (K d,Pu/K d,Th) of 22 for the anion‐exchange method and 0.017 for the cation‐exchange method at 3 and 2 M HNO3, respectively. A two‐stage ion‐exchange separation method was developed for the quantitative separation of Pu (8 g/L) from a macro amount of Th (200 g/L) in nitric acid medium. The first step involved the quantitative sorption of plutonium from the mixture while about 90% of Th could be washed in 6 column volumes. The plutonium, eluted (as Pu3+) using 0.5 M HNO3 + 0.2 M hydrazinium nitrate (HN) + 0.2 M hydroxyl ammonium nitrate (HAN), and the residual (∼10%) Th were subsequently loaded onto a cation‐exchange column in the second step. Greater than 99% Pu was recovered with 2 M HNO3 (in ∼8 column volumes) containing 0.2 M HN + 0.2 M HAN. The final elution of thorium from the cation‐exchange column was achieved in about 6 column volumes of 1 M α‐hydroxy isobutyric acid. A (Pu, Th)O2 fuel scrap sample was dissolved in 16 M HNO3 containing 0.005 M HF and was used subsequently as the feed for the anion‐exchange column. The eluted Pu was subsequently loaded onto a cation‐exchange column for final purification. The recovery of plutonium and thorium was found to be >99% and >98%, respectively, while the respective decontamination factors were estimated to be 215 and 292.

Involvement of apoptosis in hydrazine induced toxicity in rat primary hepatocytes

The current study was undertaken to investigate the role of apoptosis in hydrazine induced hepatotoxicity. Hepatocytes were exposed to hydrazinium nitrate (HzN) at two doses (50 and 75 mM) for 2 h then placed in fresh HzN-free media and cultured for an additional 24 h. Post-exposure, cell viability was evaluated at several time points by lactate dehydrogenase (LDH) leakage and 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) reduction. Markers of apoptosis (mitochondrial membrane potential, annexin binding, DNA fragmentation, caspase activation, and cytochrome c release) were measured 24 h post-exposure. The viability data showed time dependent increase in LDH leakage at 75 mM of HzN, with only a slight increase at 50 mM. MTT reduction showed a decrease in mitochondrial activity at both doses immediately after the 2 h continous exposure. However, MTT reduction returned to normal at 50 mM while at 75 mM, MTT reduction initially recovered but then deteriorated to approximately 50% of controls at 24 h post-exposure. Based on viability data, exposure to 50 mM HzN for 2 h is a marginally toxic dose while 75 mM is a significantly toxic dose. The results for apoptosis biomarkers showed a reduction in mitochondrial membrane potential, an increase in annexin binding, an increase in total caspase activity, moderate activation of caspase-3, and release of cytochrome c. However, the appearance of DNA fragmentation in HzN exposed cells was very low compared to positive controls (cadmium and cyclosporine). The possibility that HzN induces apoptosis without the involvement of DNA fragmentation can not be ruled out. The present results, overall, suggest that apoptosis may be a contributing factor in acute HzN toxicity.

Synthesis, characterization and thermal studies of (Ni/Co) metal salts of hydrazine: potential initiatory compounds

Nickel hydrazinium nitrate (NiHN) and cobalt hydrazinium nitrate (CoHN) were prepared by reacting their respective metal nitrates with hydrazine hydrate at 25 and 65 °C. The compounds were characterized by metal content and infrared (IR) spectroscopy. Differential thermal analysis (DTA) results suggest that the nickel complex is relatively more stable than the cobalt complex. The activation energy determined by DTA and ignition delay measurements corresponds to an energy of activation ( E a) of 80±4 kJ/mol for NiHN and that of 150±8 kJ/mol for CoHN. Thermo gravimetry (TG) also revealed more rapid decomposition of NiHN than that of CoHN in the temperature region of 215–235 °C. High temperature Fourier transform-infrared (FT-IR) studies indicated rupture of the NiN/CoN bond as the primary step in the thermolysis. As regards sensitivity to mechanical stimuli, NiHN was found to be less impact sensitive while CoHN exhibited less friction sensitivity. The study revealed that NiHN could be used alone as well as in combination with oxidizer/fuel as initiators depending upon the specific requirements. The effect of silver azide and glass on the sensitization of NiHN was also studied. CoHN appears to be an effective ballistic modifier in enhancing burning rates of composite propellants.

Calculated and Experimentally Obtained Heats of Combustion of Hydrazinium Nitrate, Monomethylhydrazinium Nitrate, and N, N-Dimethylhydrazinium Nitrate

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Determination of fictive binary data for uranium(IV) nitrate: preliminary results

The concept of simple solutions is applied to a quaternary system of U(NO3)4, HNO3, N2H5NO3 and H2O in order to determine fictive binary data for U(NO3)4. Hydrazinium nitrate solutions were used at low concentrations relative to the nitric acid and uranium(IV) nitrate concentrations, allowing this system to be considered as a ternary (U(NO3)4, HNO3, H2O) system. The simple behavior of the system allowed fictive binary data (osmotic coefficient and density) to be calculated from water activity and density measurements. The results were then used to calculate the coefficients related to Pitzer´s model and to specific interaction theory, used to model the deviation of the concentrated solution from ideality. The results were also used to calculate the activity coefficient of uranium(IV) nitrate in the presence of uranyl(VI) nitrate and nitric acid. The binary data obtained for uranium(IV) nitrate were found to differ significantly from the data for plutonium(IV) nitrate.

Kinetics of hydrazinium nitrate decomposition in nitric acid solutions under the effect of power ultrasound

The effect of ultrasound ( f=20 kHz) on the decomposition of hydrazinium nitrate was investigated in a nitric acid medium. The kinetics of N 2H 5 + decomposition and initial HN 3 formation increase in a linear manner with the HNO 3 concentration (from 1 to 6 M) and with the ultrasonic intensity (from 0.5 to 3.1 W cm −2). Both rates were equal to that of HNO 2 formation in the absence of N 2H 5 +, indicating that the N 2H 5 + decomposition mechanism is the same as observed without ultrasound between HNO 2 and N 2H 5 +. The variation of the steady-state HN 3 concentration with the HNO 3 concentration and the ultrasonic intensity suggests the existence of a nonexplosive HN 3 thermal decomposition mechanism in the cavitation bubble under the effect of ultrasound. It was also observed at ultrasonic intensities exceeding 3.5 W cm −2 that the decomposition of HN 3 led to the accumulation of NH 4 + in solution.

In vitro toxicity assessment of a new series of high energy compounds

Hydrazine is an aircraft fuel and propellant used by the US Air Force. Due to its toxicity the Propulsion Directorate of the Air Force Research Laboratory (AFRL/PR) has investigated alternative chemicals to replace hydrazine. AFRL/PR has synthesized a series of high energy chemicals (HECs), primarily hydrazine derivatives and amino containing compounds such as hydrazinium nitrate (HZN), 2-hydroxyethyl-hydrazine nitrate (HEHN), diethyl hydrazine nitrate (DEHN), ethanolamine nitrate (EAN), histamine dinitrate (HDN) and methoxylamine nitrate (MAN) to study as alternative chemical candidates. Although HECs are reliable constituents of powered propellant systems, they constitute an important class of toxic agents to which military and civilian personnel can be exposed. The current study was undertaken to examine the toxicity of HECs in primary hepatocytes in vitro. The effects of short-term exposure (4 h) of hepatocytes to HECs were investigated with reference to viability, mitochondrial function and oxidative stress markers. The results showed a decrease in mitochondrial activity, increase in lactate dehydrogenase (LDH) leakage and depletion of reduced glutathione (GSH) levels. The levels of reactive oxygen species (ROS) increased dose dependently in HZN, MAN and HDN exposed cells. However, there was no induction of ROS generation in EAN, DEHN and HEHN exposed cells. Depletion of GSH in hepatocytes by buthionine sulfoximine (BSO) prior to exposure to HZN increased its toxicity. The results suggest that at least one mechanism of HEC toxicity is mediated through oxidative stress.

Contribution of the concept of simple solutions to calculation of the stoichiometric activity coefficients and density of ternary mixtures of hydroxylammonium or hydrazinium nitrate with nitric acid and water

Binary data (water activity as a function of the molal concentration) at 25°C for the principal anti-nitrous compounds used in nitric acid aqueous media—hydrazinium nitrate (HDZN) and hydroxylammonium nitrate (HAN)—are determined by direct water activity measurements. Density variations at 25°C are also established. Ternary systems involving these nitrate salts and nitric acid are studied from the standpoint of simple solution theory. It is observed that the system HDZN–HNO3–H2O does not exhibit simple behaviour, which is due to the acid–base equilibrium involving HDZN and HNO3 (i.e., N2H62+ formation). On the other hand, the system HAN–HNO3–H2O which does not undergo major chemical interactions follows satisfactorily the simple solution rule as long as the water activity is higher than 0.84. For ternary simple solutions it is possible to predict activity coefficients for each component by applying the Zdanovskii–Stokes–Robinson rule and the Mikulin relationship.