Thermodynamics |
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Piobert's law applies to the reaction of solid propellant grains to generate hot gas. It is stated: "Burning takes place by parallel layers where the surface of the grain regresses, layer by layer, normal to the surface at every point." [1]
The law was devised by French general Guillaume Piobert (in French) in 1839 to explain the behavior of gunpowder, but it has subsequently been applied to other solid propellants. Description of the reaction as burning may cause confusion with simple atmospheric combustion of solid materials where a similar reaction progression may be attributed to availability of the oxygen reactant only at the surface of the solid being consumed by the reaction. In the case of single-phase propellant grains, the progression is attributed to heat transfer from the surface of the solid of energy necessary to initiate the reaction. The heat transfer rate increases with pressure; and smokeless powder reaction rates vary with pressure as described by Paul Vieille in 1893. [1]
Studies of solid single- and double-base propellant reactions suggest a series of zones or phases as the reaction proceeds from the surface into the solid. The deepest portion of the solid experiencing heat transfer melts and begins phase transition from solid to gas in a foam zone. The gaseous propellant decomposes into simpler molecules in a surrounding fizz zone. Energy is released in a luminous outer flame zone where the simpler gas molecules react to form conventional combustion products like steam and carbon monoxide. Propellants designed for a minimum heat transfer pressure may fail to sustain the flame zone at lower pressures. [2]
Combustion, or burning, is a high-temperature exothermic redox chemical reaction between a fuel and an oxidant, usually atmospheric oxygen, that produces oxidized, often gaseous products, in a mixture termed as smoke. Combustion does not always result in fire, because a flame is only visible when substances undergoing combustion vaporize, but when it does, a flame is a characteristic indicator of the reaction. While the activation energy must be overcome to initiate combustion, the heat from a flame may provide enough energy to make the reaction self-sustaining.
Evaporation is a type of vaporization that occurs on the surface of a liquid as it changes into the gas phase. The surrounding gas must not be saturated with the evaporating substance. When the molecules of the liquid collide, they transfer energy to each other based on how they collide with each other. When a molecule near the surface absorbs enough energy to overcome the vapor pressure, it will escape and enter the surrounding air as a gas. When evaporation occurs, the energy removed from the vaporized liquid will reduce the temperature of the liquid, resulting in evaporative cooling.
A solid-propellant rocket or solid rocket is a rocket with a rocket engine that uses solid propellants (fuel/oxidizer). The earliest rockets were solid-fuel rockets powered by gunpowder; they were used in warfare by the Chinese, Persians, Mongols, and Indians as early as the 13th century.
Heat transfer is a discipline of thermal engineering that concerns the generation, use, conversion, and exchange of thermal energy (heat) between physical systems. Heat transfer is classified into various mechanisms, such as thermal conduction, thermal convection, thermal radiation, and transfer of energy by phase changes. Engineers also consider the transfer of mass of differing chemical species, either cold or hot, to achieve heat transfer. While these mechanisms have distinct characteristics, they often occur simultaneously in the same system.
Adsorption is the adhesion of atoms, ions or molecules from a gas, liquid or dissolved solid to a surface. This process creates a film of the adsorbate on the surface of the adsorbent. This process differs from absorption, in which a fluid is dissolved by or permeates a liquid or solid. Adsorption is a surface phenomenon, while absorption involves the whole volume of the material, although adsorption does often precede absorption. The term sorption encompasses both processes, while desorption is the reverse of it.
A rocket engine uses stored rocket propellants as the reaction mass for forming a high-speed propulsive jet of fluid, usually high-temperature gas. Rocket engines are reaction engines, producing thrust by ejecting mass rearward, in accordance with Newton's third law. Most rocket engines use the combustion of reactive chemicals to supply the necessary energy, but non-combusting forms such as cold gas thrusters and nuclear thermal rockets also exist. Vehicles propelled by rocket engines are commonly called rockets. Rocket vehicles carry their own oxidizer, unlike most combustion engines, so rocket engines can be used in a vacuum to propel spacecraft and ballistic missiles.
A propellant is a mass that is expelled or expanded in such a way as to create a thrust or other motive force in accordance with Newton's third law of motion, and "propel" a vehicle, projectile, or fluid payload. In vehicles, the engine that expels the propellant is called a reaction engine. Although technically a propellant is the reaction mass used to create thrust, the term "propellant" is often used to describe a substance which is contains both the reaction mass and the fuel that holds the energy used to accelerate the reaction mass. For example, the term "propellant" is often used in chemical rocket design to describe a combined fuel/propellant, although the propellants should not be confused with the fuel that is used by an engine to produce the energy that expels the propellant. Even though the byproducts of substances used as fuel are also often used as a reaction mass to create the thrust, such as with a chemical rocket engine, propellant and fuel are two distinct concepts.
Chemical kinetics, also known as reaction kinetics, is the branch of physical chemistry that is concerned with understanding the rates of chemical reactions. It is to be contrasted with thermodynamics, which deals with the direction in which a process occurs but in itself tells nothing about its rate. Chemical kinetics includes investigations of how experimental conditions influence the speed of a chemical reaction and yield information about the reaction's mechanism and transition states, as well as the construction of mathematical models that also can describe the characteristics of a chemical reaction.
Sublimation is the transition of a substance directly from the solid to the gas state, without passing through the liquid state. Sublimation is an endothermic process that occurs at temperatures and pressures below a substance's triple point in its phase diagram, which corresponds to the lowest pressure at which the substance can exist as a liquid. The reverse process of sublimation is deposition or desublimation, in which a substance passes directly from a gas to a solid phase. Sublimation has also been used as a generic term to describe a solid-to-gas transition (sublimation) followed by a gas-to-solid transition (deposition). While vaporization from liquid to gas occurs as evaporation from the surface if it occurs below the boiling point of the liquid, and as boiling with formation of bubbles in the interior of the liquid if it occurs at the boiling point, there is no such distinction for the solid-to-gas transition which always occurs as sublimation from the surface.
Internal ballistics, a subfield of ballistics, is the study of the propulsion of a projectile.
Smokeless powder is a type of propellant used in firearms and artillery that produces less smoke and less fouling when fired compared to gunpowder. The combustion products are mainly gaseous, compared to around 55% solid products for black powder. In addition, smokeless powder does not leave the thick, heavy fouling of hygroscopic material associated with black powder that causes rusting of the barrel. Despite its name, smokeless powder is not completely free of smoke; while there may be little noticeable smoke from small-arms ammunition, smoke from artillery fire can be substantial.
The fire triangle or combustion triangle is a simple model for understanding the necessary ingredients for most fires.
A pyrotechnic composition is a substance or mixture of substances designed to produce an effect by heat, light, sound, gas/smoke or a combination of these, as a result of non-detonative self-sustaining exothermic chemical reactions. Pyrotechnic substances do not rely on oxygen from external sources to sustain the reaction.
Ammonium perchlorate composite propellant (APCP) is a modern fuel used in solid-propellant rocket vehicles. It differs from many traditional solid rocket propellants such as black powder or zinc-sulfur, not only in chemical composition and overall performance but also by the nature of how it is processed. APCP is cast into shape, as opposed to powder pressing as with black powder. This provides manufacturing regularity and repeatability, which are necessary requirements for use in the aerospace industry.
This glossary of chemistry terms is a list of terms and definitions relevant to chemistry, including chemical laws, diagrams and formulae, laboratory tools, glassware, and equipment. Chemistry is a physical science concerned with the composition, structure, and properties of matter, as well as the changes it undergoes during chemical reactions; it features an extensive vocabulary and a significant amount of jargon.
Improved military rifle propellants are tubular nitrocellulose propellants evolved from World War I through World War II for loading military and commercial ammunition and sold to civilians for reloading rifle ammunition for hunting and target shooting. These propellants were DuPont modifications of United States artillery propellants. DuPont miniaturized the large artillery grains to form military rifle propellants suitable for use in small arms. These were improved during the first world war to be more efficient in rimless military cartridges replacing earlier rimmed rifle cartridges. Four-digit numbers identified experimental propellants, and a few successful varieties warranted extensive production by several manufacturers. Some were used almost exclusively for military contracts, or commercial ammunition production, but a few have been distributed for civilian use in handloading. Improved military rifle propellants are coated with dinitrotoluene (DNT) to slow initial burning and graphite to minimize static electricity during blending and loading. They contain 0.6% diphenylamine as a stabilizer and 1% potassium sulfate to reduce muzzle flash.
Ultra-high-purity steam, also called the clean steam, UHP steam or high purity water vapor, is used in a variety of industrial manufacturing processes that require oxidation or annealing. These processes include the growth of oxide layers on silicon wafers for the semiconductor industry, originally described by the Deal-Grove model, and for the formation of passivation layers used to improve the light capture ability of crystalline photovoltaic cells. Several methods and technologies can be employed to generate ultra high purity steam, including pyrolysis, bubbling, direct liquid injection and purified steam generation. The level of purity, or the relative lack of contamination, affects the quality of the oxide layer or annealed surface. The method of delivery affects growth rate, uniformity and electrical performance. Oxidation and annealing are common steps in the manufacture of such devices as microelectronics and solar cells.
Rocket propellant is the reaction mass of a rocket. This reaction mass is ejected at the highest achievable velocity from a rocket engine to produce thrust. The energy required can either come from the propellants themselves, as with a chemical rocket, or from an external source, as with ion engines.
Heterogeneous combustion, otherwise known as combustion in porous media, is a type of combustion in which a solid and gas phase interact to promote the complete transfer of reactants to their lower energy potential products. In this type of combustion a high surface area solid is immersed into a gaseous reacting flow, additional fluid phases may or may not be present. Chemical reactions and heat transfer occur locally on each phase and between both phases. Heterogeneous Combustion differs from catalysis as there is no focus to either phase individually but rather both examined simultaneously. In some materials, such as silicon carbide (SiC), oxide layers, SiO and SiO2, which form on the surface enable the adsorption of water vapor from the gas phase onto the solid lowering partial pressures. In this regime of combustion, thermal heat released from the combustion byproducts are transferred into the solid phase by convection; conduction and radiation both then conduct heat upstream (along with adverse convection within the gas phase). Heat is then convectively transferred to the unburnt reactants.
A pool fire is a type of diffusion flame where a layer of volatile liquid fuel is evaporating and burning. The fuel layer can be either on a horizontal solid substrate or floating on a higher-density liquid, usually water. Pool fires are an important scenario in fire safety science, as large amounts of liquid fuels are stored and transported by different industries.
G. Piobert, Mémoire sur les poudres de guerre, des différents procédés de frabrication (1844)