Synthesis of Poly(1,4-Divinylbenzene Peroxide)

Polymeric peroxides have received renewed attention in the recent past, in view of some significant explorations of their physical and chemical properties. The potential of polymeric peroxides as a class, as specialized fuel, and the need to synthesize such new materials have been reported in the literature. So far, this class of polymers is constituted only by a dozen or so polyperoxides. From the point of view of their use in propellant applications, the importance lies in making materials which are easy to handle etc., unlike the earlier reported poly(styrene peroxide) (PSP), a sticky semi-solid mass. However, judging from the better combustion characteristics, exploring aromatic monomers was thought worthwhile. In this preliminary communication, the synthesis of a new polymeric peroxide made from 1,4-divinylbenzene is reported. The polymer obtained was in powder form and had an exothermic heat of degradation approximately equal to that of PSP. 4 ref.--AA

Modeling of heat and mass transfer for solid state fermentation process in tray bioreactor

A mathematical model is developed to simulate oxygen consumption, heat generation and cell growth in solid state fermentation (SSF). The fungal growth on the solid substrate particles results in the increase of the cell film thickness around the particles. The model incorporates this increase in the biofilm size which leads to decrease in the porosity of the substrate bed and diffusivity of oxygen in the bed. The model also takes into account the effect of steric hindrance limitations in SSF. The growth of cells around single particle and resulting expansion of biofilm around the particle is analyzed for simplified zero and first order oxygen consumption kinetics. Under conditions of zero order kinetics, the model predicts upper limit on cell density. The model simulations for packed bed of solid particles in tray bioreactor show distinct limitations on growth due to simultaneous heat and mass transport phenomena accompanying solid state fermentation process. The extent of limitation due to heat and/or mass transport phenomena is analyzed during different stages of fermentation. It is expected that the model will lead to better understanding of the transport processes in SSF, and therefore, will assist in optimal design of bioreactors for SSF.

Mass spectrometric and electrochemical studies of thermodynamic properties of liquid and solid phases in the CaO Al2O3 system

The activities of CaO and Al2O3 in lime-alumina melts were studied by Knudsen cell-mass spectrometry at 2060 K. Emf of solid state cells, with CaF2 as the electrolyte, was measured from 923 to 1223 K to obtain the free energies of formation of the interoxide compounds. The results are critically evaluated in the light of data reported in the literature on phase equilibria, activities in melts, and stabilities of compounds. A coherent set of data is presented, including the previously unknown free energy of formation of CaO.6Al2O3 and the temperature dependence of activities in the liquid phase.

Condensed phase reactions in solid propellants

The paper investigates the cause for the difference between differential scanning calorimetric results and mass spectrometric studies on polystyrene (PS) ammonium perchlorate (AP) propellants as related to the method of preparation of the propellant and the difference in experimental conditions by the use of mass spectrometry. Sufficient time is given for the product sublimates to interact with each other and attain equilibrium. It is shown that the propellant decomposition is a nonadditive phenomenon and that even a physical mixture of AP and PS does not yield additive decomposition products of its components. Results on the identification of a yellow compound containing chlorine in the bulk of the propellant suggest a condensed phase reaction. The occurrence of the reaction in the porous condensed phase of the propellant may explain the larger exothermicity of the propellant compared to the additive heats of decomposition of its components.

Thermal Decomposition of hydrazinium monoperchlorate in the solid state

Hydrazinium monoperchlorate (HP-1) has been shown to decompose thermally in the solid state according to the chemical equation: 5N2H5CIO4 = 4NH4CIO4+1HCI+3N2+4H2O The activation energy for the evolution of HCl as determined mass spectrometrically is 8.05 kcal mol−1 in the temperature range of 80 to 120°C. The rate of decomposition is seen to be altered by doping HP-1 with small concentrations of SO2−4, Ca2+ and Al3+.

Effect of surface radiation on conjugate natural convection in a horizontal annulus driven by inner heat generating solid cylinder

This paper reports a numerical study of the laminar conjugate natural convection heat transfer with and without the interaction of the surface radiation in a horizontal cylindrical annulus formed between an inner heat generating solid circular cylinder and an outer isothermal circular boundary. Numerical solutions are obtained by solving the governing equations with a pressure correction method on a collocated (non-staggered) mesh. Steady-state results are presented for the flow and temperature distributions and Nusselt numbers for the heat generation based Grashof number ranging from 10(7) to 10(10), solid-to-fluid thermal conductivity ratios of 1, 5, 10, 50 and 100, radius ratios of 0.226 and 0.452 and surface emissivities of 0-0.8 with air as the working medium. It is observed that surface radiation reduces the convective heat transfer in the annulus compared to the pure natural convection case and enhances the overall Nusselt number.

Thermogravimetric and mass-spectrometric study of the thermal decomposition of PBCT resins

The thermal decomposition of three commercial samples of carboxy-terminated polybutadiene (PBCT) resins was studied by thermogravimetric analysis (TGA) at heating rates varying from 2° to 100°C/min. Kinetic parameters of the decomposition process at different heating rates were evaluated by means of the Fuoss method.1 The decomposition process and the activation energy values are found to be dependent on heating rate. Mass-spectrometric analysis of the decomposition products shows that the pyrolysis products of PBCT resins are mainly low molecular weight hydrocarbons: ethylene, acetylene, butadiene, propadiene, vinylcyclohexene, etc. The rates of evolution of these hydrocarbon products vary with the carboxy content of the PBCT resin. Based on this, a carbonium ion mechanism has been suggested for the thermal decomposition. The data generated from this work are of importance for a consideration of the mechanism of combustion of composite solid propellants based on PBCT binders.

Design and fabrication of an automated thermal desorption gas-solid reaction system: Oxidation of ammonia and methanol over YBa2Cu3O7−δ(123) oxide systems

A fully automated, versatile Temperature Programmed Desorption (TDP), Temperature Programmed Reaction (TPR) and Evolved Gas Analysis (EGA) system has been designed and fabricated. The system consists of a micro-reactor which can be evacuated to 10−6 torr and can be heated from 30 to 750°C at a rate of 5 to 30°C per minute. The gas evolved from the reactor is analysed by a quadrupole mass spectrometer (1–300 amu). Data on each of the mass scans and the temperature at a given time are acquired by a PC/AT system to generate thermograms. The functioning of the system is exemplified by the temperature programmed desorption (TPD) of oxygen from YBa2Cu3−xCoxO7 ± δ, catalytic ammonia oxidation to NO over YBa2Cu3O7−δ and anaerobic oxidation of methanol to CO2, CO and H2O over YBa2Cu3O7−δ (Y123) and PrBa2Cu3O7−δ (Pr123) systems.

Investigations Of Iron Adducts Of C-60 - Novel Fec60 In The Solid-State With Fe Inside The C-60 Cage

By carrying out contact-arc vaporization of graphite in a partial atmosphere of Fe(CO)5, an iron-adduct with C60 has been obtained. The adduct has been characterized by various techniques including mass spectrometry, Fe-57 Mossbauer spectroscopy and Fe K-EXAFS. Properties of this adduct are compared with those of an adduct prepared by solution method where Fe is clearly outside the cage. Results suggest that FeC60 obtained from the gas phase reaction has the Fe atom in the cage.

Evaluation of relative growth limitation due to depletion of glucose and oxygen during fungal growth on a spherical solid particle

A mathematical model for glucose and oxygen consumption, and cell growth during fungal growth on a single solid particle is developed. A moving biofilm is assumed to be present on the surface of the solid particle. Initially only glucose is assumed to be growth limiting and later oxygen transferred from the gas phase on to the biofilm is also assumed to be growth limiting. Glucose is found to be severely growth limiting when assumed to be the only growth limiting factor and its limiting levels far less severe when oxygen limitation is also included. The objective of the model is to gain a better understanding of the mass transfer and relative growth limiting characteristics of glucose and oxygen in fungal growth systems. The results obtained from the model proposed here will be the subject of future work.

Some observations on the ignition of composite solid propellants

Heat-up times derived from studies on the ignition characteristics of a few model composite solid propellants, containing polystyrene, carboxy-terminated polybutadiene, plasticised polyvinyl chloride and polyphenol formaldehyde as binders, show that they are directly proportional to the mass of the sample and inversely proportional to the hear flux. Propellant weight-loss prior to ignition and high pressure ignition temperature data on the propellants, ammonium per chlorate, and binders show that the ignition is governed by the gasification of the binder pyrolysis products. The activation energy for the gasification of the pyrolysed polymer products corresponds to their ignition behaviour suggesting that propellant ignition is controlled by the binder.

Sensors based on the dissipation characteristics of n-BaTiO3 ceramics and its solid solutions

The humidity, heat flux and mass flow sensing capability of n-BaTiO3 and its solid solutions were evaluated based on their dissipation characteristics. The cubic/tetragonal phase content of the ceramics seem to play an important role in their sensitivity towards the measurand. The humidity-sensitive characteristics of these perovskites were studied with respect to different moisture sensitive coating materials. The sensor was also used to determine the heat of hydration during the curing process of cements and the mass flow rate of the gases. For all these applications, suitable operating points have been fixed from the highly non-linear I-V characteristics with the retention of good stability and high sensitivity. (C) 1997 Elsevier Science S.A.

Universal behaviour in erosive burning of solid propellants

This paper considers the extensive data and correlations on the erosive burning of solid propellants. A relatively simple nondimensional relationship between the ratio of the actual to nonerosive burn rate (eta) and a quantity g, which is the product of g(0)-the ratio of free stream mass flux to the mass flux from the surface for nonerosive condition-and Re-0(m), where Re-0 is the Reynolds number based on the nonerosive mass flux of the propellant and port diameter, is shown to correlate most data within the accuracies of the experiments with m = -0.125. This shows the above relationship to account for the effects of pressure, aluminum, even up to a proportion of 17%, burn rate catalysts, and motor size. It is concluded that the suggested correlation between eta and g may be adopted universally for most practical propellants. (C) 1997 by The Combustion Institute.

Modeling re-ignition and chuffing in solid rocket motors

A nonlinear model is developed to numerically simulate dynamic combustion inside a solid rocket motor chamber. Using this model, the phenomena of re-ignition and chuffing are investigated under low-L* conditions. The model consists of two separate submodels (coupled to each other), one for unsteady burning of propellant and the other for unsteady conservation of mass and energy within the chamber. The latter yields instantaneous pressure and temperature within the chamber. The instantaneous burning rate is calculated using a one-dimensional, nonlinear, transient gas-phase model previously developed by the authors. The results presented in this paper show that the model predicts not only the critical L*, but also the various regimes of L*-instabihty. Specifically, the results exhibit (1) amplifying pressure oscillations leading to extinction, and (2) re-ignition after a dormant period following extinction. The re-ignition could be observed only when a radiation heat flux (from the combustion chamber to the propellant surface) was included. Certain high-frequency oscillations, possibly due to intrinsic instability, are observed when the pressure overshoots during re-ignition. At very low values of initial L*, successive cycles of extinction/reignition displaying typical characteristics of chuffing are predicted. Variations of the chuffing frequency and the thickness of propellant burned off during a chuff with L* are found to be qualitatively the same as that reported from experimental observations.