Compositions, typical propellant

Table 1. Typical Components of Composite Rocket Propellants...

Modern composite solid propellant is a mechanical mixture of the powder-like chemicals and a binding resin. The propellant used for the Space Shuttle solid rocket boosters (SRBs) is a typical example of such mixture ... 

A Small but important daSS of fOi mUlatiOnS comprises the Composite Solid Rocket Propellants. Composites typically contain a major amount of an oxidizer such as AP or HMX, a metal powder such as Al, a binder which is one or another type of rubber (or double-base), and up to a dozen trace ingredients such as catalysts, stabilizers, etc. There are literally hundreds of formulations, all to a degree similar and the choice comes down to specific missions, economics, and special requirements Loading of End Items. The blends and formulations described above may be loaded into their hardware in the plant where they are made, or they may be shipped to another plant for Load/... 

A typical propellant composition in relation to the above was given as potassium perchlorate (72%), copper(II) oxide, burn rate enhancer (1.4%), potassium benzoate, fuel (10.9%), charcoal, fuel (5.4%) and epoxy resin (9.6%). 

The temperature and composition of propellant combustion products are of interest to those concerned with materials of construction and insulation for the combustion chamber and nozzle of the rocket motor. These values are readily computed from basic thermodynamic data for the specific propellant composition and operating pressure of interest with the aid of today s large-scale digital computers. By way of illustration, however, the products of combustion computed this way for the three typical plastisol propellants given in Table I are shown in Table III for a combustion pressure of 1000 p.s.i.a. Approximate propellant composition is also shown for convenient reference. 

Polymer-based rocket propellants are generally referred to as composite propellants, and often identified by the elastomer used, eg, urethane propellants or carboxy- (CTPB) or hydroxy- (HTPB) terrninated polybutadiene propellants. The cross-linked polymers act as a viscoelastic matrix to provide mechanical strength, and as a fuel to react with the oxidizers present. Ammonium perchlorate and ammonium nitrate are the most common oxidizers used nitramines such as HMX or RDX may be added to react with the fuels and increase the impulse produced. Many other substances may be added including metallic fuels, plasticizers, stabilizers, catalysts, ballistic modifiers, and bonding agents. Typical components are Hsted in Table 1. 

Solventless Extrusion Process. The solvendess process for making double-base propellants has been used ia the United States primarily for the manufacture of rocket propellant grains having web thickness from ca 1.35 to 15 cm and for thin-sheet mortar (M8) propellant. The process offers such advantages as minimal dimensional changes after extmsion, the elimination of the drying process, and better long-term baUistic uniformity because there is no loss of volatile solvent. The composition and properties of typical double-base solvent extmded rocket and mortar propellant are Hsted ia Table... 

Typical marine propellers are fixed pitch and small in diameter with veiy thin, but broad, blade sections. They are made from either cast metal, corrosion-resistant metal alloys such as copper, or composite materials. Marine propellers normally operate at 60 percent efficiency due to the proximity of the ship s hull, which limits the overall diameter of the propeller and disturbs the efficient flow of water through the blades. As a result, the blades have to be veiy wide to produce adequate thrust. Marine propeller designers use innovations such as overlapping blades and wheel vanes to offset those problems and improve efficiency. 

Inspection of the numerical solutions of the equations shows that, with the exception of Es= 0 kcal/mole, the rate of surface temperature increase with time is very large once the surface temperature reaches approximately 420°K—on the order of 108°K/sec. Because typical autoignition temperatures are of the order of 625°K for composite propellants, the particular value of the ignition temperature does not affect the computed numerical value of the ignition-delay time. 

When one considers the potential high-energy release on rupture of a carborane unit, together with the thermodynamic stability of combustion products, it is hardly surprising that there is a body of literature that reports on the use of carbo-ranes within propellant compositions. Their use in energetic applications is to be expected when the enthalpy of formation (AH/) data for the products of combustion for boron are compared to those of carbon. Thermodynamic data for the enthalpy of formation of o-carborane and of typical boron and carbon combustion products is shown in Table 4. Measurements of the standard enthalpy of combustion32 for crystalline samples of ortho-carborane show that complete combustion is a highly exothermic reaction, AH = — 8994 KJmol. ... 

Hydroxy-terminated polyester (HTPS) is made from diethylene glycol and adipic acid, and hydroxy-terminated polyether (HTPE) is made from propylene glycol. Hydroxy-terminated polyacetylene (HTPA) is synthesized from butynediol and paraformaldehyde and is characterized by acetylenic triple bonds. The terminal OH groups of these polymers are cured with isophorone diisocyanate. Table 4.3 shows the chemical properties of typical polymers and prepolymers used in composite propellants and explosives.E4 All of these polymers are inert, but, with the exception of HTPB, contain relatively high oxygen contents in their molecular structures. 

Figure 4.5 shows the chemical processes and molecular structures of typical inert binders used in composite propellants and plastic-bonded explosives.Ph Polysulfides are characterized by sulfur atoms in their structures and produce H2O molecules during the polymerization process. These H2O molecules should be re-... 

Fig. 4.5 Chemical processes and molecular structures of typical binders used in composite propellants.

The physicochemical properties of explosives are fundamentally equivalent to those of propellants. Explosives are also made of energetic materials such as nitropolymers and composite materials composed of crystalline particles and polymeric materials. TNT, RDX, and HMX are typical energetic crystalline materials used as explosives. Furthermore, when ammonium nitrate (AN) particles are mixed with an oil, an energetic explosive named ANFO (ammonium nitrate fuel oil) is formed. AN with water is also an explosive, named slurry explosive, used in industrial and civil engineering. A difference between the materials used as explosives and propellants is not readily evident. Propellants can be detonated when they are subjected to excess heat energy or mechanical shock. Explosives can be deflagrated steadily without a detonation wave when they are gently heated without mechanical shock. 

Fig. 6.18 shows a typical comparative example of the burning rates of two propellants composed of NC-TMETN and NC-NG. The chemical compositions (% by mass) and thermochemical properhes are shown in Table 6.5. The energy densities of these two propellants are approximately equivalent. 

A typical super-rate burning of an HMX-GAP composite propellant is shown in Fig. 7.43. The lead catalyst is a mixture of lead citrate (LC PbCi), Pb3(C5H50y)2-x H20, and carbon black (CB). The composition of the catalyzed HMX-GAP propellant in terms of mass fractions is as follows gap(0.194), hmx(0-780), lg(0 020), and, q 0.00G). GAP is cured with 12.0% hexamethylene diisocyanate (HMDI) and then crossUnked with 3.2 % trimethylolpropane (TMP) to... 

In order to avoid the use of lead compounds on environmental grounds, lithium fluoride (liF) has been chosen to obtain super-rate burning of nitramine composite propellants.P7281 Typical chemical compositions of HMX composite propellants-with and without liF are shown in Table 7.4. The non-catalyzed HMX propellant is used as a reference pyrolant to evaluate the effect of super-rate burning. The HMX particles are of finely divided, crystalline (3-HMX with a bimodal size distribution. Hydroxy-terminated polyether (HTPE) is used as a binder, the OH groups of which are cured with isophorone diisocyanate. The chemical properties of the HTPE binder are summarized in Table 7.5. 

Like double-base propellants, CMDB propellants show super-rate and plateau burning when they are catalyzed with small amounts of lead compounds. Fig. 8.21 shows a typical plateau burning for a propellant composed of NC-NG and HMX.P I The chemical composition of the catalyzed propellant is shown in Table 8.1. 

Thus, AP is a valuable oxidizer for formulating smokeless propellants or smokeless gas generators. However, since the combustion products of AP composite propellants contain a relatively high concentration of hydrogen chloride (HCI), white smoke is generated when they are expelled from an exhaust nozzle into a humid atmosphere. When the HCI molecules diffuse into the air and collide with H2O molecules therein, an acid mist is formed which gives rise to visible white smoke. Typical examples are AP composite propellants used in rocket motors. Based on experimental observations, white smoke is formed when the relative humidity exceeds about 40 %. Thus, AP composite propellants without any metal particles are termed reduced-smoke propellants. On the other hand, a white smoke trail is always seen from the exhaust of a rocket projectile assisted by an aluminized AP composite propellant under any atmospheric conditions. Thus, aluminized AP composite propellants are termed smoke propellants. 

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