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Chapter-1 Introduction Chapter-1 CHAPTER-1 INTRODUCTION CHAPTER-1 INTRODUCTION It has always been the aim of explosives technologists to achieve higher performance leading to enhanced lethality of system. Increase in oxygen balance (OB) and heat of formation (AHf) are the most sought after features to augment the performance of explosives. Most of the approaches to increase performance involve introduction of a large number of nitro / nitramino groups into a stable carbocylic or heterocyclic parent molecule. However, an increase in performance level is often accompanied by increase in sensitivity of the explosives. An increase in density offers an option to improve the performance of an explosive without increasing the sensitivity. Although gunpowder developed by Roger Bacon finds first mention as an explosive, it was the discovery of TNT in 1863, which led to tremendous development in the area of high explosives.The attractive feature of TNT is large gap between its melting point (80.8°C) and decomposition temperature (250°C) rendering it castable in wide range of munitions. TNT was used as a major explosive during World War I. Insatiable demand for high-energy potential brought nitramine class of explosives into focus ' . Cyclotrimethylene trinitramine (RDX) also referred as cyclonite / T4 / hexogen offered much higher velocity of detonation (VOD) compared to TNT due to its superior heat of formation and oxygen balance combination as well as higher density (Table-1). The cyclotetramethylene tetranitramine (HMX) also known as octogen provided still superior alternative. However, both RDX and HMX have melting points close to their decomposition temperature rendering them unsuitable for melt casting unlike TNT. As D (mixture) = I (^i Di [where D (mixture) is the VOD of mixture, D\ is the VOD of i•i h component and (j)i is the volume fraction of mixture of i" component of mixture], a combination of RDX/HMX with TNT in the form of castable slun-y (at 80-85"C) emerged as practical solution to meet the demand of high lethality for modern projectiles and warheads. RDX/HMX occupied prominent position as components of powerful new high explosives developed during World War II. Cyclotols and octols are the most sought after explosive formulations even today. Composition B comprising ~ 60% RDX and ~ 40 % TNT finds wide applications due to ease in casting (Table- 2). Innovative approaches leading to improved casting technologies render it possible to increase the percentage of RDX/HMX in TNT based compositions resulting in improved performance . Table -1: Characteristics of Widely used High Explosives', ^ Compound *MP Structure Density AHf OB YOD Detonation (°C) ig/cm') (kj/mol) (%) (m/s) Pressure (GPa) TNT 80.8 1.65 -63 -74 6950 18.9 NO, -22 8700 34.3 RDX 204 1 " 1.82 61.78 NO, 1 • 75.30 -22 9100 39.5 HMX 286 CH, N^GH, 1.91 1 r O^N N N — NO^ CH.. N CH,. 'MP- Meltinsi Point Table -2: Performance Potential of Selected Explosive Compositions' Composition Density VOD *Impact *Friction (g/cm^) (m/s) Sensitivity Sensitivity (hso. cm) for 2 kg (Insensitive up to fall weight load of kg) RDX/TNT 1.72 7900 106 24.0 (60/40) RDX/TNT 1.77 8250 95 14.8 (75/25) HMX/TNT 1.73 8150 96 19.2 (60/40) HMX/TNT 1.81 8640 61 16.8 (75/25) * Determined at HEMRL Applications demanding air blast effect for long duration led to the introduction of aluminium (Al) metal powder as a component of explosive formulation. A large amount of energy is liberated by aluminized explosives beyond the C-J plane as a result of reaction of Al with primary detonation products of high explosives. The basic chemical processes involving Al in this phenomenon can be summarized as 2A1 + 3H.0 AI2O3 +3H2 +866kJ/mol 2A1 + 3C0. AI2O34-3CO +741kJ/mol 2A1 + 3C0 Al.O, + 3C +1251 kJ/mol The well-known aluminized TNT based explosive is tritonal which is reported to produce impulse of the order of 115 kbar. However, aluminized RDX/TNT compositions like dentex and toipex acquired a great significance in modem projectiles and warheads aimed at producing blast effect^ (Table-3). Table -3: Performance Potential of Widely reported Aluminized Explosive Compositions'* Composition Density VOD *Peak *Impulse (g/cm') (m/s) pressure (kg ms/ (kg/ cm') cm') H-6 (RDX/TNT/AlAVax 1.76 7490 5.03 1.51 45.1/29.2/21/4.7) HTA (HMX/TNT/Al 1.90 7866 5.29 1.97 /CaCl. 49/29/22/0.5 added) Dentex (RDX/TNT/Al/Wax 1.81 7780 5.27 1.45 48.5/33.5/18/1 added) Torpex -4B 1.76 6700 4.25 1.47 (RDX/TNT/Al/Wax 40.5/37.5/18/4) *(Experimentally determined at HEMRL for charge weight 1 kg at a distance of 1.5 m) 1.1 Low Vulnerable Explosives (LOVEXs) Although TNT-based explosives have enormous advantages such as cost effectiveness and ease of large-scale manufacturing as well as possibility of demilitarization of filled munitions by remelting of explosive charges, their disadvantages cannot be overlooked. The most glaring drawback of TNT based formulations is their high vulnerability to mechanical and shock stimuli. Thus, TNT based explosives are susceptible to sympathetic detonation in magazines and storage areas as well as can undergo premature initiation upon impact with hard targets. Shrinkage after casting resulting in large internal voids as well as lack of structural integrity and possibility of exudation of TNT during extended storage due to temperature cycling, particularly in tropical countries as well as due to the shock encountered in supersonic systems mainly due to its low melting point are other areas of concern. Moreover, like most of the other aromatics, TNT is toxic. The issue of safety assumed great significance with the signature of STANAG 4439, which provided thrust to the implementation of Insensitive Munitions (IM) policy all over the world. For certain applications, low vulnerability even at the cost of power (VOD) is of utmost importance. Introduction of IM with added feature of superior structural integrity has been identified as major goal since last decade^. These developments have led to the emergence of plastic bonded explosives (PBXs) on global arena ' . Polymer matrix introducing flexibility (rubbery material) can absorb shocks, rendering the PBXs less prone to accidental detonation. Further, PBX can be cast into even a geometrically complicated shape as a liquid at near room temperature, unlike TNT based compositions rendering the processing less hazardous. The systems requiring large quantum of explosive formulation are preferably based on cast PBXs. PBXN-106, PBXN-107 and PBXN-110 based on such flexible binders are widely used particularly in Naval Ordnance^ Hydroxyl terminated polybutadiene (HTPB) is the preferred choice as binder for cast compositions due to its high filler loading capability Q and clean curing reaction . Rowanex range of PBX compositions containing nitramine loaded in HTPB matrix were the first entrant to this class^. Aluminized castable compositions are being pursued for underwater applications. In order to enhance bubble energy and to achieve complete oxidation of Al, AP is also incorporated in these formulations (PBXN-IU / PBXW-115). Royal Ordnance (RO) Defence has planned spending of £ 2 million to establish the facility of filling of Rowanex-1100 in 105 mm projectiles'^. Filling of 155 mm shells/projectile is also envisaged. Table - 4 and 5 include properties of widely studied castable PBXs"^''. The polymers have also made in-roads into the field of pressed explosives conventionally comprising of 90-97% RDX/HMX coated with 10-3% wax. PBX based pressed explosives offer superior mechanical properties and retain their structural integrity even at higher temperatures comp£ired to wax based compositions. PBXN series of pressed compositions based on Laminac-Styrene binder found application in early stages. However, they became obsolete due to brittle nature resulting in low load bearing capabilities as well as high sensitivity. Polyethylene glycol (PEG) binder also evinced interest. Plastisol grade nitrocellulose emerged as moderately energetic alternative. However, its sensitivity to thermal inputs from impact, friction and electrostatic stimulations resulted in fewer applications. Thermoplastic Elastomers (TPEs) particularly, ethylene vinyl acetate (EVA) and Estane have acquired great significance as binder for pressed PBXs'l LX-14 comprising of 95.5% HMX and 4.5% Estane binder is under production for application in anti-tank weapons. Viton is also emerging as a promising binder for futuristic explosives demanding higher thermal resistance (Table- 6). 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