Chapter

P^W^F

e ChmrmclrrUtic* Chmp. 22 Efplottrft, ProprllmnU, and Toxic 390 "91 Chfmic*! Agenlm

T a b l e 2 2 . 1 U S . I n d u s t r i a l C o n s u m p t i o n o f E x p l o s i v e s ( i n t h o u s a n d

s o f m e t r i c t o n s
1979 1977 ) 1978 Coal mining #etal mining %uarr&ing and nonmetal mining Construction 'or( and other uses )otal industrial
*+,-CE.

952 2!" 2"8 29$ 1 87

98 2 1 275 2 $ 178

1!17 279 297 2 7 18 !

11"8 25$ 28$ 2 7 19$"

Minerals Yearbook, V . Bureau of Mines, 1982/

sives differ 'idel& in their sensitivi t& and po'er/ +nl& those of a compar ativel& insensiti ve nature0 capa1le of 1eing controll ed and having a high energ& content are of

importa nce industri all& or militaril &/ )here are three fundam ental t&pes of explosiv es. mechan ical0 atomic0 and chemical / )his chapter is a1out chemical explosiv es/ 2or purposes of classifica tion it is conveni ent to place chemica l explosi ves in t'o division s in accorda nce 'ith their 1ehavior / 1/ 3etonati ng0 or high0 explosiv es0 (a) 4rimar&0 or initiatin g0 explosiv es (detonat

ors)5 (1) 1ooster and seconda r& explosiv es/ 2/ 3efla gratin g0 or lo'0 explo sives/ )here exists a ver& great differen ce 1et'ee n the detonati ng and deflagra ting explosi ve t&pes/ 6igh explosi ves detonat e at ver& high rates0 from 2 to 9 7 1!s m8s0 and the reaction front is a shoc( phenom enon moving activel& through out the material / 9o' explosi ves0 or propell ants0 1urn in

la&ers parallel to the surface at lo' rates0 around 1!:; m8s0 and the reaction front is a flame/ Coo( 1 lists the ma<or explosiv e chemica ls accordin g to militar& or commer cial use/ =aria> tions in their 1lasting characte ristics are o1tained 1& (1) altering ph&sical conditio ns such as densit& and granulat ion and (2) com1ini ng ingredie nts? paraffin0 aluminu m0 and 'axes0 for example / @ ta1le of nonexpl

osive additive s appears in the same referenc e/

INITIATI NG, OR PRIMARY

,
EXPLOSI VES.

Initiatin g0 or primar&0 explosiv es are material s that are Auite shoc( and heB t sensitiv e and that can 1e made to explode 1& the applicat ion of a spar(0 flame0 friction0 or heat source of appropr iate magnit ude/ )he& are ver& dangero us to handle and are used in compar ativel& small Auantiti es to

start the explosio n of larger Auan> tities of less sensitive explosiv es/ Initiating explosiv es are generall & used in primers0 detonato rs0 and percussi on caps/ )he& are usuall& inorgani c salts0 'hereas 1ooster and other high explo> sives and man& conventi onal propella nts are largel& organic material s/ 4rima r& explosiv es used include mercur& fulminat e C6g(+D C)iE0 lead aFide 4r7D<E< 0 1asic lead st&phnat

e (trinitro resorcin ate)0 diaFodi nitroph enol0 and tetraFin e (a comple x con<uga ted nitroge n compou nd)/ #ost priming compos itions consist of mixture s of primar& explosi ves0 fuels0 and oxidant s/ @n exampl e is 15G antimo n& sulfide0 2!G lead aFide0 $!G 1asic lead st&phna te0 2!G 1arium nitrate0 and 5G tetraFin e/ Hlue0 'hich acts as a 1inder0 and ground

glass0 'hich increase s internal friction0 ma& 1e added/ ICoo (0 Science of High Exp o!i "e,, @C* #onogr aph 1"90 Jeinhol d0 De' Kor(0 19580 p/ $/5 also Jiegel0 In#$!%&i ' (he)i! %&*, 7th ed/0 Jeinhol d0 De' Kor(0 197$0 pp/ 7 > 8"0 this contains an extensiv e list0 together 'ith characte ristics and uses/

-++*) EJ HIGH EXPLO SIVES. -ooster high explosiv es are materials that are insensiti ve to 1oth mechani cal shoc( and flame 1ut that explode 'ith great violence 'hen set off 1& an explosiv e shoc(0 such as that o1tained 1& detonati ng a small amount of a primar& explosiv e in contact 'ith the high explosiv e/ )he& are thus energ& amplifie rs/ 3ecomp osition proceeds 1& means of detonati

on0 'hich is rapid chemical rupturin g of 1onds progressi ng directl& through the mass of the explosiv e/ 3etonati on is thought to 1e a chain reaction and proceeds at rates of around !!! m8s/ It is this high rate of energ& release0 rather than the total energ& given off0 that ma(es a product an explosiv e/ Ditrogl& cerine has onl& one> eighth the energ& of an eAuivale nt 'eight of gasoline/ +n the other

hand0 most explosiv es0 'hen unconfin ed and unshoc( ed0 'ill merel& 1urn if ignited/ Impor tant 1oosters are J37 (c&clotri meth&le netrinitr amine)/ 4E)D (pentaer &thritol> tetranitr ate)0 and )etr&l (20$0 > trinitrop hen&l meth&l nitramin e)/ )here are also some heat> resistant 1oosters 0 e/g/0 6#7 (c&clotet rameth&l enetetra nitramin e)/
+LASTIN G AGENTS.

-lasting agents are po'erfu l explosiv e agents that meet the

criterion that the& cannot 1e detonate d 1& means of a Do/ 8 1lasting cap 'hen unconfin ed/ )he& are0 therefore 0 ver& safe to handle/ @ po'erful 1ooster is needed to start detonati on/
SLURRY EXPLOSIV ES.

E!P" # $V E C%A& ACTE &$ T$ C

*ome ver& interesti ng technolo g& has 1een used to determin e the characte ristics of explosiv es/ #uch is empiric al0 1ut measure ments of heat values0 rates of com1ust ion and detonati on0 shatterin g a1ilit&0 sensitivit &0 etc/0 reflect modern instrume ntal applicati on to high> speed phe> nomena0 and the results are a tri1ute to the s(ill and technolo g& of explosiv

*lurr& explosiv es are ammoni um nitrate mixtures 'hich freAuentl & contain another oxidiFer as 'ell as a fuel disperse d in a fluid medium 'hich0 among other functions 0 controls the rheolog& of the gel> slurr&/

es scientists and technicia ns/ )ests for sensitivit & to impact and heat0 sta1ilit& on storage0 shatterin g a1ilit& (1risance )0 explosiv e strength per unit 'eight0 volatilit&0 solu1ilit& 0 densit&0 h&grosco picit&0 compati1 ilit& 'ith other explosive s0 additives and possi1le metals used for enclosure s0 resistanc e to h&drol> &sis0 and toxicit& must all 1e run in a standard manner and ta(en into consider ation/ )he 1risance of an

explosiv e is measure d 1& explodin g a measure d Auantit& of it in a sand 1om10 a heav& 'alled vessel filled 'ith a standard coarse sand 'hich is crushed 1& the explo> sion/ *creenin g measure s the sand crushed0 and from this the explosiv e force/ @nother test of a some'h at similar nature is the )rauFl 1loc( test/ )his test measure s the strength of the explosiv e 1& measurin g the 1alloonin g of a soft lead c&linder

in 'hich the explosive is inserted and exploded / Jesults are reported in terms of the increase in volume0 expresse d in cu1ic centimet ers0 caused 1& the detonatio n of the explosive / -risance is pro1a1l& a com1inat ion of strength and velocit&/ Coo( states that there is no reason to 1elieve that 1risance is po'er5 it seems to 1e directl& related to

detonati on pressure/
1

)he sensitivit & of an explosiv e to impact" is determin ed 1& finding the height from 'hich a standard 'eight must 1e allo'ed to fall in order to detonate the explosiv e/ ICoo(0 op/ cit0 p/ 271/ I#ace (0 *ensiti vit& of Explo sives0 (he). Re". 20 $1 (19 2) (1$! refere nces)/

393

392 Chmp. 22

Effl#fi'em, Propfllmnt*, mn( Tonic Chemlcml Agent*

It is important that explosives for use in mines0 particularl& coal mines0 1e of such a t&pe that on explosion the& evolve less than the specified amount of allo'a1le toxic gases0 as deter> mined or specified 1& federal or state regulating agencies0 and produce a minimum of flame/ )his latter reAuirement assures that the explosive is incapa1le of igniting mixtures of air and coal dust0 or air and methane (the so>called fire damp)0 'hich inevita1l& occur in coal mines/

Explosives for mine use are tested and their properties specified 1& the -ureau of #ines5 the& are commonl& (no'n as permissi1leL0 4ermissi1le. differ from other explosives0 particularl& 1lac( po'der0 most mar(edl& in the fact that the& produce a flame of small siFe and extremel& short duration/ 4ermissi1le; contain coolants to regulate the temperature of their flame0 further reducing the possi1ilit& of igniting several t&pes of com1usti1le mixtures/ )a1le 22/2 sho's the characteristics of explosives/

$)*U T&$A" E!P"# $VE

Cost per unit of 'or( done (shattering of material or displacement 'ithout shattering) is almost as important as safet& for industrial explosives/ 4resent agents are less expensive and far safer than their predecessors/ HISTORI(AL. -lac( po'der has 1een the preferred 1lasting agent 1ecause it is less shattering in its effects/ It is an intimate mixture of MD+<0 sulfur0 and charcoal in the approximate proportions of 75.15.1!/ @1out 5! percent of the products of com1ustion are solids0 giving its flames great igniting po'er0 'hich is undesira1le 'here com1usti1le gases or solids are present 1ut useful for igniting propellants/ *tarting in 18 !0 d&namite dominated the 1lasting industr& for a centur&0 1ut its current use is small and diminishing/ SLURRY EXPLOSIVES. -lasting agents and slurr& explosives have 1ecome the principal industrial explosives 1ecause the& ma& 1e handled 1& simple machiner& almost completel& 'ithout danger and 1ecause their cost is ver& lo'/ )hese are usuall& ammonium nitrate mixtures sensitiFed 'ith nonexplosive fuels such as oil or 'ax/ 4roperl& initiated0 such mixtures produce energies surpassing thai of d&namite and are far cheaper/ @mmonium nitrate is the 'orldIs most 'idel& used explosive su1stance/ Coo( lists the t&pes and compositions of present>da& industrial explosives (see also )a1le 22/")/ Explosives pla& such a vital part in the nationIs econom& that their consumption has 1een suggested as a relia1le index of the general scientific and technical atmosphere/ *ee )a1le 22/$ for ,/*/ consumption of explosives in the mineral industr&/ )he current energ& crisis ma& 'ell stimulate the use of explosives0 particularl& in mining coal and lo'>grade domestic ores/
+LASTING AGENTS AN, NITROGLY(EHIN AN, ,YNAMITE.

Ditrogl&cerin 'as the first high explosive to 1e emplo&ed on a large scale/ Ditration is effected 1& slo'l& adding gl&cerol of high purit& (99/9G N) to a mixture having the approximate composition. 6<*+; 59.-.. 6D+</ $!G0 and 6<+0 !/5G/ Ditration is accomplished in ! to 9! min in agitated nitrators eAuipped 'ith steel cooling coils carr&ing 1rine$ at 5OC to maintain the temperature 1elo' 1!OC @fter nitration0 the
$ -rine can 1e a little cooler than 5OC0 1ut pure nitrogl&cerin freeFes at 12/8OC/ 2reeFing 'ould 1e haFardous0 since it might interfere 'ith the temperature control

>/*omite8 froft#moi*, )ocftete, i 39(

In order to produce 1 t of nitrogl cerine, the follo!ing materials and utilities are re"uired#

6D+"(1!!G) 6<*+0 (1!!G) Hl&cerin

1!!!(g (1!G recovered) 1!!!(g (9 G recovered) $"!(g

Jefrigeration 3irect la1or

1/5 t ice eAuivalent 5 'or(>h

$ig. 22.1. $lo!chart for the manufacture of nitrogl cerin and d namites. %suall an e&aporator is needed bet!een the ammonium nitrate reactor and the cr stalli'er.

394

Chap. 22 Efplo*t'e+, Propfltant*, an( Tm(c Chemical AgenU

Table 23.3 Classes of Pell>CharacteriFed *lurr& Explosives and *lurr& -lasting @gents
Pater0 . 3esignation; Q *E>)D) *E>C*E>*4 *E>6**4 *E>)D)8@l *E>*48@l *-@>@l *-@>fuel G *ensitiFer 17> ! )D) 15>"5 C2!> ! *4 2!> ! 6**4 5>258!/5>$! )D)8@l 1!>2581>$! *48@1 !/1>$! @l !>12 fuel $/!>15 solid fuel +xidiFert @D0 *D0 -D0 *C0 Da40 C @D0 *D0 C @D0 *D0 -D0 *C Da4/ C @D0 *D0 C @D/ *D/ Da40 C @D0 *D/ C @D0 @D8*D0 @D8Da40 Da4 @D0 @D8*D/ Da40 *C Dominal 15 15 15 15 15 15 15 15 Jange R8>$! 12>1 2>2!) 2>2!S 1!>"! 12>"! >"!) ">1 t

safer and easier to handle0 it is usuall& manufactured into d&namite 3&namite 'as originall& made 1& a1sor1ing nitrogl&cerin into (ieselguhr0 a (ind of cla&/ #odem d&namites generall& use 'ood flour0 ammonium nitrate0 or sodium nitrate to a1sor1 the nitrogl&cerin/ *uch a mixture is eas& to handle and can 1e made to contain as much as 75G nitrogl&cerin and &et retain its solid form/ -ecause of the demand for a nonfreeFing d&namite for use in cold 'eather0 d&namites containing other materials designed to lo'er the freeFing point of the mixture are used0 for example0 gl&col dinitrate/ *uch nonfreeFing d&namites have potentials as great as QstraightQ d&namite/ Ditrocellulose can 1e gelatiniFed 1& nitrogl&cerin0 and the resultant firm gel Ts commonl& (no'n as gelatin d&namite/ )he a1ilit& to act as a com1ination plasticiFer and explosive ma(es nitrugl8cerin and the similar dieth&lene gl&col dinitrate (3EHD) useful in plastic explosives and smo(eless po'der manufacture/ @lmost 'ithout exception the nitro compounds and nitric acid esters used as explosives are toxic/ )he degree of toxicit& varies 'idel& 'ith the material in Auestion0 1ut most are capa1le of causing acute distress if ta(en orall&/ Ditrogl&cerin has a small medical use as a vasodilator/ Extremel& toxic properties 'ould 'eigh heavil& against an& ne' explosive that might 1e introduced/

)D)0 trinitrotoluene0 C-0 composition -/ *40 smo(eless po'der5 6**40 high>strength smo(eless po'der5 fuel0 various t&pes?sulfur0 gilsonite0 other solid h&drocar1ons0 D6c>lignosulfonate0 others/ (@D0 ammonium nitrate5 *D/ sodium nitrate5 -D0 1arium nitrate5 Da40 sodium perchlorate5 *C/ sodium chlorate5 C0 com1inations (@D8*C incompati1le)/ (9o' percent reAuires 'ater extenders0 such as lormamide0 eth&lene gl&col0 sugar0 molasses0 scxmcc In#. Eng. (he) !(7) $$ (19 8)/ Jeprinted 'ith permission of the @merican Chemical *ociet&/

1977 1978 1979 @mmonium nitrate>fuel oil0 mixed and unprocessed/ G Pater gels and slurries0 . +ther high explosives0 . 4ermissi1le explosives . )otal0 thousands of metric tons QCalculated from data in the Mine&' ! Ye'&1oo2. 1345.

mixture of nitrogl&cerin and spent acid is allo'ed to flo' through a trough (a trough is easier to clean completel& than a pipe) into separating and settling tan(s some distance from the nitrator/ )he nitrogl&cerin is carefull& separated from the acid and sent to the 'ash tan(0 'here it is 'ashed t'ice 'ith 'arm 'ater and 'ith a 2G sodium car1onate solution to ensure the complete removal of an& remaining acid/ @dditional 'ashes 'ith 'arm 'ater are continued until no trace of al(alinit& remains/ *ee 2ig/ 22/1/ 'here the Auantities of ra' material are also listed/ )he product is reall& gl&cer&l trinitrate0 and the reaction is an esterification/ *mall continuous stirred stainless>steel nitrators (-iaFFi and other t&pes) give higher &ields0 lo'er operating costs0 and greater safet& than the 1atch process illustrated in 2ig/ 22/1 1ecause much less material is in process at an& given time and control is easier/ #ost of the streams are in the form of emulsions0 an inherentl& safer stale/ +ther gl&col nitrates are also made in continuous nitrators/ Dilrogl&ceriii is a liAuid similar in appearance to the original gl&cerol/ It is sensitive to 1lo's and freeFes at 1"OC5 'hen solid it is less sensitive/ )he solid tends to explode incom> pletel&0 so froFen nitrogl&cerin must al'a&s 1e tha'ed 1efore using/ )o ma(e nitrogl&cerin

P & # P E " " A ) T , & # C , E T , A ) *

)a1le 22/$ ,/*/ 3istri1ution of Consumption of Explosives in the #ineral Industr&; /Inc $#e! (o' Mining, Me%' Mining, %uarr&ing0 and Non)ine&' Mining0

propellant (no'n is 1lac( po'der0 1ut its use toda& is trivial/ It 1urns 1adl& and far too fast for

Cellulose

Dry* H.O ('fOc7 394steps# ing

Cot ton Lingers Wood Pulp Tissue Paper Cotton

Ma OH i Sf to n

Kier Boilin g > _J

$ig. 22.2. $lo!chart for cellulose of nitrate 2nitrocellulose3 manufacture. 5itrogen content of cellulose The commercial manufacture cellulose nitrate is illustrated in 56T7 $ig. # 22.2 !ith the follo!, ' stem# nitrate is controlled b the composition of nitration mi+ed acid. 8ualit product depends on the grade of cellulose used and the care de&oted to manufacturing procedures. .teps sho!n are for the militar product. In use, !et product is dried b alcohol displacement

39*

Chap. 22 Explo.i'e*, Proptllmnt*, mo( Tofte Chemical Agentm

$ " E
PROPELLAffTS GUNS. )he 6OR oldest

propellant use if the ingredients are left in finel& divided form/ #erel& stirring the ingredients together produces useless material/ 9arger

grains are produced b intimate, intensi&e mi+ing, the mi+ actuall being made into a dense colloid in a hea& ,dut mi+er. Blac- po!der remains the best igniter.a&ailable. .mo-eless po!der replaced blac- po!der for se&eral reasons/ its smo-elessness, its superior po!er, and its better storage characteristics, but principall because it can be formed into stable grains !hose si'e and shape go&erns the burning characteristics. This ma-es possible the construction of large roc-ets and guns. .mo-eless po!der is colloided cellulose nitrate, usuall containing a plast-i'er, such as nitrogl cerin or nitrogl col. .ometimes a none+plosi&e plastici'er such as dibut iphthalate is added and usuall about 10 of diphen lamine or similar amine designed to impro&e its storage life. 1hen the onl e+plosi&e used is nitrocellulose of o&er /01 nitrogen content, it is -no!n as single,base po!der/ !hen t!o or more e+plosi&e ingredients are used 2nitrocellulose and nitrogl cerin3, the grains are less brittle and the product is -no!n as a double,base po!der. Most sporting ammunition uses double,base po!der. Militar po!ders !ith grains o&er 22 mm in diameter are used in large rifles. Combustion of smo-eless po!der proceeds at a relati&el constant rate in la ers parallel to the ignited surface, so the speed of gas e&olution 2hence ma+imum bore pressure3 is controlled b the geometr of the grain. Most rifle grains ha&e internal perforations to control burning rates so as to be progressi&e bore pressure 2increasing !ith time3, neutral 2constant !ith time3, or degressi&e 2decreasing !ith time3. )$T&#CE""U"# E.3 The e+plosi&e properties of nitrated cotton !ere recogni'ed at an earl date. The disco&er of methods for con&erting the material into a dense uniform colloidal mass reduced the surface and the rapidit of the e+plosion. 1ith the disco&er of suitable stabili'ation methods to prolong its storage life, nitrocellulose soon put blac- po!der out of use as a propellant. Most nitrocellulose is no! made from !ood fibers rather than cotton. )he cellulose molecule is a complicated one0 'ith a molecular 'eight freAuentl& as high as "!!0!!!/ @n& given sample of cellulose contains a 'ide distri1ution of molecules0 all having the empirical formula CC<6)+U+6E<V00/ )here are thus three h&drox&l groups per fundamental (glucose) unit that ma& 1e esterified 'ith nitric acid to &ield a theoretical nitrogen content of 1$G0 'hich is higher than an& commerciall& used product/ )he reaction is. 3),6 9 2):.6;3 "6+D+0 N (6<*+0) >

Snc&'f%) inf %&e'%)en%!

ifteoi,
3456aiting freofmrnf. 7.Co- +ta4

In order to produce 2.2 -g of dr cellulose nitrate 2<.4( -g ra! cotton furnishes about <.* -g of purified cotton fibers3, the follo!ing materials and utilities are re"uired# Iariable but small Chlorine >irect labor <.<3 !or-,h 224 J Cotton 2inters < 4( -g 1ater )56, 1.<-g 21<<973 );.<4 <.( -g

(1!!G) Da0C+"

! !!2 (g

Celluloses that ha&e not beep nitrated completel to the trinitrate are used as &arious industrial cellulose nitrates as sho!n in $ig. 22.2. In addition to nitrate esters, some sulfate esters are formed b sulfuric acid, !hich must be used to tie up the !ater resulting from the nitration reaction and to permit the reaction to progress to the right. These sulfate esters are unstable, and their decomposition !ould gi&e rise to a dangerous acid condition in the stored po!der if not remo&ed/ the are decomposed in the poaching process. The finished nitrocellulose should not be allo!ed to become acid in use or in storage, since this catal 'es its further decomposition. = stabili'er is therefore added !hich reacts !ith an trace of nitrous, nitric, or sulfuric acid that ma be released because of the decomposition of the nitrocellulose and thus stop further decomposition. >iphen lamine is used for smo-eless po!der 2diphen lurea in ?reat Britain3, and for celluloid, urea. The diphen lamine forms a series of innocuous compounds !ith the e&ol&ed gases. @=lthough the !ord AnitrocelluloseA is commonl used for

nitrated cellulose fiber, the material is not a nitro compound but a true ester of nitric acid. The name cellulose nitrate is therefore chemicall more proper, but nitrocellulose is more !idel emplo ed in the industr .

Cotton 2inters, or !ood pulp high in a,cellulose, are purified b boiling in Biers 2&ats3 !ith dilute caustic soda solution. B l e a c h i n g i s e f f e c t e d ! i t h C a C l 6 C l , 5 a 6 C l , o r C a 2 6 C l 3 C . T h

e c o t t o n i s d r i e d , f l u f f e d , a n d ! e i g h e d . Mi+ed acid is made up from fortif ing acid and spent acid, brought to proper temperature and run into the nitrator. 5itration 2esterification3 is usuall conducted under carefull controlled conditions in a Amechanical dipperA nitrator. 6ne nitrator charge is formed b 14.( -g of purified cellulose. The cellulose @s agitated !ith appro+imatel *D2 -g of mi+ed acid at 3<EC for about 2( min. The composition of the acid used a&erages# )56:, 21;/ )F6F *3G/ 5.6G <.(;/ ):6, 1(.(H.

The entire nitrator charge is dropped into a centrifuge, !here the spent acid is centrifuged from the nitrated cellulose. The spent acid is partl fortified for reuse and partl sold or other!ise

disposed of, e,g., b denitration and concentration of the ):.6G The nitrated cellulose is dro!ned !ith !ater, !ashed b boiling, and again !ashed in a beater.

$ig. 22.3. $lo!chart for single,base smo-eless po!der manufacture. $or a Bo! sheet for nitrocellulose manufacture, see $ig. 22.2. 56T7 =steris-s denote e"uipment connected to sol&ent reco&er s stem.

399

Propellxnlmfor &ocket*

to gi&e small spheres, and the sol&ent is dri&en off !ith heat. These spheres are sie&ed to gi&e uniform si'e and can ha&e nitrogl cerine added to them to gi&e double,base plastici'ed balls Treatment !ith burning,rate regulators, such as dinitrotoluene, can cause the rate of burning to increase as the surface area for burning decreases. = sphere is the most degressi&e,burning shape possible. Kroper treatment results in a progressi&e burning ball. Balls much abo&e 3 mm are not practical, so onl ammunition up to (< caliber 2<.( in L 12.4 mm bullet diameter3 is made. Much sporting ammunition is ball po!der.

398

Chap. 22

Efftlomlve*, PropellanC*, and Toxic Chemical Agento

P&#PE""A)T 8#& &#C,ET

There are a great &ariet of choices in the design of efficient propulsion s stems/ li"uids, solids, and castable solid units are all in use. Moc-et propulsion s stems deri&e their energ from chemical sources.
Joc(et propellants are lo' explosives 'hich consist of fuel; 'hieh include their o'n oxi>dant or other reactant necessar& to cause the planned reaction/ )he thrust of the escaping hot gases pushes the device for'ard0 according to the principle that forces act eAuall& in opposite directions/ 6igh>performance s&stems under fine control are used for the launching of missiles and spacecraft for explorator& and scientific missions and for militar& offense and/ defense/ Careful selection of the propellant ingredients is important to give high cham1er temperature and pressure/ )he gases produced should 1e of lo' molecular 'eight/ )he reaction temperature ma& 1e so high that resistant structural materials are not availa1le0 in 'hich case the temperature must 1e reduced/ )he fuel should 1e one 'hich provides the greatest amount of heat for the smallest amount of 'eight/ )he foregoing factors are the most important ones in the eAuation defining !pecific i)p$ !e, or pounds of thrust per pound of 'eight of propellant 1urned per second0 'herein the sAuare root of the a1solute temperature T divided 1& the sAuare root of the average molecular 'eight M of the exhaust gases determines the value of the specific impulse. */ I/ W 78)878#/ 2igure 22/$ sho's the characteristics of ma<or roc(et propellants/

In order to produce a smo-eless po!der that is more stable on storage, the follo!ing puri, fication is emplo ed to destro unstable sulfate esters and to remo&e free acid completel . 2This is a militar procedure/ commerciall , the nitrated cellulose is dissol&ed in a sol&ent and neutrali'ed chemicall / this procedure !or-s !ell and@gi&es a stable product.3 $ort hours of boiling !ith at least four changes of !ater is follo!ed b pulping, of the fiber b means of a beater. Koaching of the !ashed nitrated cotton b boiling first !ith a dilute 5a:C6: solution 22.( -g of soda ash per metric ton of cellulose nitrate3 and then man !ashes of boiling !ater. The poached nitrocellulose is freed of most of its !ater b centrifugation. The !ater content is no! appro+imatel 2D0. =t this point the nitrocellulose is usuall stored and a laborator e+amination made. The !ater content of the nitrated cotton is reduced to a lo! figure b alcohol displacement of the !ater. The nitrated cellulose is bro-en up and made into a dense colloid b mi+ing !ith alcohol, ether, diphen lamine, and other modif ing agents. ?rains are formed b e+trusion through dies, and these are dried and blended to form smo-eless po!der grains. The commonest shape is a pierced c linder 2macaroni3 for small arms and a multipl pierced c linder or rosette for larger guns. The cellulose produced in this manner contains about 12.*0 nitrogen and is -no!n as p ro, cotton. B using a stronger acid, the nitrogen content ma be made as high as 13.*0. Cotton nitrated to contain 13.20 nitrogen or greater is -no!n as guncotton. Modern militar smo-eless po!der contains about 13.1(0 nitrogen and is made from a blend of p ro, and guncotton.
*mo(eless po'der is dense colloidal nitrocellulose containing a1out 1G diphen&lamine and a small amount of a plasticiFer such as di1ut&l phthalate/ )he manufacture is sho'n in 2ig/
-Blockin pre* DouHe-arm mixer 'tiedsolvents and wattr

"$9U$* P&#PE""A)T .* Ji"uid propellants are those added to the combustion chamber as li"uids. This includes all li"uids used in a single propellant s stem, ser&ing as fuel, o+idi'er, and catal st. Ji"uid fuels are, for the most part, used in bipropellant s stems 2fuel and o+idi'er stored in t!o fuel tan-s and fed separatel to the combustion chamber3. Monopropel,lants combine the fuel and o+idi'er in one mi+ture. = fe! of the better,-no!n li"uid propellants are listed in Table 22.(, together !ith some of their characteristics. Ji"uid propulsion s stems are the means for achie&ing the propulsi&e energ re"uired for human space tra&el. Jarge high,performance roc-ets no! use J6H 2li"uid o+ gen3 and J): 2li"uid h drogen3 propellants, because of their high specific impulse and lo! cost. ?reater storage efficienc is achie&ed b catal tic con&ersion of nearl all the h drogen to the para form. Jarge solid units are used !here long storage time is re"uired.
Q)schin(el0 4ropellants for Joc(ets0 (he). Eng. Ne8! "2 (2 ) 2582 (195$) (excellent article 'ith eAuations and ta1les)5 EC)0 "d ed/ vol/ 90 198!0 p/ 2!5 4enner0 Com1ustion and 4ropulsion Jesearch0 (he). Eng. Ne8! $1 (2) 7$ (19 ")/ IMit0 Roc2e% P&ope 'n% H'n#1oo2, #acmillan0 De' Kor(0 19 !/
4ropellant )&pe 4ropellant s&stem Casta1le Composite +xidiFer>fuel0 Extruded 3ou1le>-ase; DC0 DC0 miscellaneous

22/"/ @n interesting variant on this manufacturing process produces spheres0 (no'n as 1all po'der/ )he nitrocellulose0 along 'ith the additives0 is dissolved in a solvent0 e/g/0 mixed (etones0 to form a lacAuer 'hich is then carefull& emulsified 'ith 'ater/ )he emulsion is then inverted

)&pical ingredient variation/ . @dia1alic flanif temperature/ CO )&pical sea>level specific impulse Characteristic velocit&0 (m8s 3ensit&0 g8cm" 9o'er com1ustion limit/ (4a 4ro1a1le allo'a1le operating> temperature limits/ CO *torage sta1ilit& *mo(e

D6UI+00(C067)X0 MCI+0 (5!>85)0 (%68))/ (5!>15) 15$!>2$8! 175>2$! >1 1 > 1/$ 1/52>1/7$
QQX 1 ;=i@ !9: liME,

DC (5!> !)0 DH ("!>$5)0 miscellaneous (1>1!) 21!!> 29!! 2!5>2"! 1/"7>1/52

propellant/ )he retro>roc(ets the #ercur& capsule used for atmospheric reentr& emplo&ed solids/ 2lo'charts and eAuipment have not 1een released0 1ut processing methods have 1een descri1ed/ @rtificial satellites are another t&pe of spacecraft that reAuire roc(et propulsion for launch> R*utton0 Roc2e% P&op$ !ion E e)en%!. "d ed/ Pile&/ De' Kor(0 19 "5 Mit0 op/ cit5 *olid Hround'or( for *olid Joc(ets0 6o&%$ne 710 11$(#aich 19 57excellent illustrations of case and noFFle fa1rication for Qmodern and fierce compounds that strain the pol&mer chemist s ne'found artQ)/ R#cCrau)>6Y# Enc*c ope#i' of Science 'n# Techno og*, vol/ 110 #cCra'>6ill0 De' Kor( 19820 p/ 72"/

>57 to 112 Hood #uch at lo' oxidiFer5 little at high oxidiFer/ mist at relative humidit& greater than 8!G/ *oft and resilient to hard and tough
)0*

avg/ 1/ 1 > 29 to 9 2air 9ittle

#echanical properties Com1ustion !"*i#$iito%or&a'$($

6ard and tough

2
4.OO 3."" #""

)emperature0 OC "11

4<< Ch-p.:! Efptott'f*, fropttlmm*, )'% T%trfc Chemicml Agent*

Of 59 -26

"$!!
! Li,uid -luorine ./00
LO% 23'4

27"!

$O% B&'e 29 !T*pi+al solid ( )."" 2955 P

1 0

! Li,uid -luorine Li,uid 4*drogen

5 29"! ".6" 8

"!9!

2&"4 6"96" :--iJB0

0
!
LO% 2'3 0

"11

. LO% Li,uid 4*drogen

27 ! ': '2O/ 2'3 o 2525 ; < 0 "."6 7 ! '2O3 JP ) 21

O.O)

>?

!LO% i
TO

=P 5
##6

) i i i #6" #@6 3OO 3#6 36O (pe+i-i+ iApulse /s ?eBpansion -roA 36"" to )OO CPoD

5 3@6

2ig/ 22/$/ Jelative cost and specific impulse of roc(et prope,ants/ Dote that the 1etter the performance of the propellant0 the higher the cost 9+70 liAuid ox&gen5 D<600 h&draFine5 -ir,0 1oroet1ane (di1orane)5 +2 fc ox&gen di-uoride5 J4>10 (erosene h&dro> car1on fuel5 E4>10 (et fuel ;(he). Eng/ Ne8%. $1 /<30 => /13?<0 /)o#ifie# 13=-,13450.@

SOLI, PROTELLANTS.A *olid propellants have advantages over liAuids in that the& are simple in design and more easil& stored0 handled0 and serviced/ )he& cost less and0 1ecause the ingredients are com1ined in a mold 'hich serves to confine the materials and impart the desired grain configuration0 the& can 1e launched expeditiousl&0 and predicted 1urning rates can 1e achieved/ +riginall&0 solids 'ere classified into t'o groups. he%e&ogeneo$!, o& co)po!i%e propellants (oxidiFer and reducer present in t'o distinct phases) and0 homogeneous0 or dou1le 1ased (oxidiFer and reducer present in a single or colloidal phase0 e/g// nitrocellulose dissolved in nitrogl&cerin)/ *mall percentages of additives are used to control the ph&sical and chemical properties of the solid propellant/ )he properties of solid propellants are sho'n in )a1le 22/ / *olid propellants have a variet& of applications. as propulsion units for missiles0 target drones0 and supersonic sleds Joc(ets used for the separation of stages during flight and for settling ullage .n the liAuid>propellant tan(s sre usuall& of the solid t&pe5 for example0 some details of the #inute #an IC-# sol id>propellant roc(et stages are availa1le/Q Hlass>filament 'ound casing for 1oth the first and second stages of the su1marine>launched 4olaris carr& a po'erful solid

Table 2:.2

Curneot 4ropellan
.../..> EEEEEEEEEEEE . _____ =rdstonr :ppli+ation :tlas T4or. Jupiter. Titan )/ (aturn. F l -iiKine ?;rntaur. (aturn. J # engine. . J i ngirn (Aall air+ra-t engines :gK na. :Ll0 BKiAar+ : . #H@ 3") (pe+i-i+ 5Apulse;

EEEEEEEEEEEE iiiiiiin i^ Propellant O/9?*i sO' ?9#.6>1D ?G'P ) O39'. WF2:D9J5I 4 5=F2:59lIO.l5 5=F2:9J"9 JP 4 + 4m ?C'/D/2/55# 2^D496">K 2#554 t 6tr1 ?C'3l3G'3 23O.9-C'.5G .'/ 5KF2:9.:K(
9?O0 '3O1 JP 4

Fen si4

".99 )."# ".#H )33 ).#6 ).3) ).#) ).#) ).3) ).#9 ).39 ).")

-tM5 "7@N

#JH #@@

Titan 55. Tilall 555. Trails :pollo Kr-0niini Bullptip 5D (Aall air+ra-t engines .< r-ur*. Aan* K50QKT( .ariner. 'aligtT

#J9 #HH ! #HH #@" #JJ )6) )9)

.$P ItJ.), inK'KiQ>rupel$n? 2^'^ ii'iuotJrni.Illaiit

EEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEE EE E

! <gI<nEEEEEEE.EEEE

Q4mimi; of thrust per pout+l of 'eight of f<roprtlatil burned f BN .tecand. .ee te+t. tP2D@/ Phile fuming nitric acid EI62D@0 Inhi1ited rZl fuming nitric acid [#@M/ #uiil <initu> h%&B. =#tfux. C@i'/ 8R5Z\/ 68g. ! (7) 7" (Ittfrl)

T'1 e 55.? *olid 4ropellants for Joc(ets

-llltmr; Efploiir 4"3 $!2

Ch;p. 22

Efplotl'e*, PropeltonU, ;nd Tofic Chemical Agent*

Rn; *everal have 1een placed in the earthIs or1it0 some for communications ()elstar)0 for meteorological o1servations (]eros)0 for scientific measurement0 for human space fhght0 and to detect nuclear explosions/

E
)here are a num1er of industrial procedures 'hich ma(e use of small Auantities of explosives 'hich are highl& important/ Explosive rivets can 1e placed 'ithout 1aclang dev0ces/ Explo> sive thrustors0 pin pullers0 separators0 and release devices 'ere extremel& relia1le on the space missions and find use in industrial emergenc& devices/ 2orming0 shaping0 and claddmg metals 1& explosive 'elding have 1ecome important manufacturing techniAues/ Explosive 'eldmg is used to form plate heat exchangers/ *hearing and punching of metals 'or(s ver& 'ell E<ection seats are explosive po'ered/ Electrical ca1le and connectors are no' 1eing attached 1& firing explosive charges/ #etal po'ders are compacted into formed shapes 1& use of explo> sives/ Pherever a directed0 relia1le0 s'ift 1lo' can accomplish a tas(0 an explosive ma& 'ell 1e the preferred choice/ #uch remains to 1e discovered/

$ C E " " A ) E # U $ ) * U T & $ A " E ! P " # $ V E U

PY&#TEC%)$C
-ecause of antifire'or(s la's0 the p&rotechnics industr& has no' onl& a fraction of its former importance/ 4&rotechnic mixtures0 ho'ever0 still have a num1er of uses. illuminating flares0 marine signal roc(ets0 the red signal flare (fusee) used 1& truc(s and trains for signaling an emergenc&0 and colored light mixtures used for militar& purposes/ In general0 these products consist of mixtures

of strong oxidiFing agents0 easil& oxidiFa1le materials0 and various other materials 'hich act as 1inders and 'hich alter the character of the flame0 together 'ith the color>producing chemical itself/ @ t&pical composition used in the manufacture of illuminating flares contains the follo'ing materials. 1arium nitrate (oxidiFing agent)0 "$*5 magnesium (to give heat)0 " G5 aluminum po'der (to give strong light)0 4.C sodium oxalate (to give a &ello' tint)0 2!G5 and calcium stearate0 caster^oil/ andlinseed^oil (as 1inders)0 2G/ @s this formula does not fire readil&0 an igniter consisting of a mixture of 75G 1lac(Q po'der and 25G of the a1ove formula is al'a&s used to start the flame/ @ mechanical device starts the com1ustion of the formula/

-$"$TA& Y E!P"# $VE

Cost is less vital in the case of militar& explosives and the accent is on performance and good storage life #ore organic materials are used than in industrial 'or(0 1ut ammonium nitrate remains the ma<or explosive su1stance/ @ complete round of ammunition is ever&thing necessar& to fire a shot/ #ilitar& ammunition varies in siFe from cali1er "! (!/"! in RW 7/ mm 1ullet diameter) to 17 in W $"2 mm 'eapons )he essential ingredients for a complete round of high>explosive ammunition is sho'n in 2ig/ 22/5/ )he unit consists of a thin cartridge case holding the primer0 igniter0 and propellant charge/ )he case is designed to fit smoothl& into the gun and0 on explosion0 to expand0 sealing the lirm>li of the gun so that the escape of gases to the rear is prevented0 thus allo'ing the full efiZ>t of the propellant to 1e exerted on the pro<ectile half of the shell/ )he primer contains a small amount of a priming mixture Ce/g/0 MC1+" N 41(CD*)< N *1<*a D )D) >I> ground glass)/ )his mixture explodes under the impact of the firing pin and produces a flame 'hich Iignites the 1lac( po'der charge of the igniter 'hich in turn ignites the propellant charge of coarsr>graiiied smo(eless po'der/ )lie 1urning of the smo(eless po'der causes the rapid emission of lieated gas/ 'hich e<ects the pro<ectile from the gun/ @t the target0 upon impact or upon functioning of the time>fuFe mechanism0 a small Auantit& of a primar& explosive (the detonator) is set off5 this causes explosion of the 1ooster?an explosive of intermediate sensitivit& (1et'een that of a primar& explosive and the 1ursting charge)?'hich pic(s up the explosive shoc( from the detonator0 amplifies it0 and ensures

complete detonation of the 1ursting charge/ )he 1ursting charge of high explosive is usuall& )D) alone or mixed 'ith ammonium nitrate/ #ost 1ursting charges are mixtures0 for example amatol ()D) >I> D6$D+")0 compound - (J37 N )D))0 pentolite (4E)D N )D))0 tetratol (tetr&l N )D))0 and octol (aluminum N )D) N> D60D+<)/ @mmonium picrate is used for armor>piercing shells 1ecause of its extraordinar& resistance to shoc(/ Industrial and militar& explosives 1oth use the same chain initiator> primer (1lasting cap)0 1ooster (1ooster)0 1ursting charge (1lasting agent) pattern0 except for the fuFe0
Bursting 2uFe +4arge i

'hich is some t&pe of mechanical or electronic device to cause explosion on impact0 dela&ed on impact0 or 1& proximit&0 as desired/ #an& militar& explosives have at least some industrial use0 'hich is not surprising0 since man& militar& and industrial uses are similar/ *mo(eless po'der0 1lac( po'der0 and primers have all 1een discussed earlier/ #ilitar&1 units tend to 1e larger0 the performance demanded reAuire rXetter Aualit& control0 and the effects of reall& long>time storage under difficult conditions must 1e minimiFed/ *ome ma<or explosives used are listed 1elo'/

Piopetlont
_

Igniter?v

Cartridge cose>8 4ro<ectile>

M=TC)7.
)he manufacture of matches is an essential industr& that is highl& mechaniFed @t present0 practicall& all matches fall 'ithin t'o categories0 safet& matches and stri(e>an&'here matches/ )he match head composition of the latter consists essentiall& of a fuel 'ith a lo' (indling point0 usuall& phosphorus sesAuisulfide (4Z*<)0 an oxidiFing agent such as potassium or 1arium chlorate0 ground glass0 and glue/ *afet& matches are ignited 1& the generation of heat on the stri(ing surface of the 1ox0 the coating/of 'hich consists mainl& of red phosphorus0 ground glass0 and glue/ Do phosphorus sesAuisulfide is used in safet& matches0 1ut antimon& sulfide is used in the heads as a flame>producing agent/

`S(/ 22OJ Complete round of high,e+plosi&e ammunition.

Chmp. -ilitar; 22Efplomlr Efpl#flre-, Pi 4<( ml Agent* 4"4

T)T <Trinitrotol=ene>
In spite of other ne' explosives developed0 s&mmetrical )D) remains an important militar& explosive0 particularl& in mixtures 'ith ammonium nitrate/ Its lo' melting point (8!OC) permits loading into 1om1s and shei( in the molten state/ It does not have picric acidIs tendenc& to form shoc(>sensitive metallic salts/ )D) is made 1& multiple>stage nitration of toluene 'ith a mixture of nitric and sulfuric acids/ )hree>stage nitration to mono>0 di>0 and trinitrotoluene 'as formerl& used0 1ut continuous>flo' stirred>tan( reactors and tu1ular units using the coun>tercurrent flo' of strong acids and toluene permit 1etter &ields0 control0 and lo'er costs/1!

i bunti ng charg e.

I t i s u s i i t m u s t 1 e l o a d e d

Tetr;l
)etr&l C20$0 > trinitrophen&lmeth&lnitramine0 %6FfD+UDC6<D+<V is chiefl& used as a>1ase charge in 1lasting caps0 as the 1ooster explosive in high>explosive shells0 and as an ingredient of 1inar& explosives/ It is generall& prepared 1& the action of mixed sulfuric and nitric acid on dimeth&laniline in a multiple>stage nitration/

PET)
4E)/D0 pentaerUhnto tetr/mtrate %C6UD+U0 is one of the most 1risan0 and sensitive of R he m0htarv h/gh explores/ 2or use as a 1ooster explosive0 a 1ursting charge0 or a plastic demohuon charge00/ E desensitiFed 1& admixture 'ith )D) or 1& the addition of 'ax/ 4E)D ma& 1e made 1& the miration of pentaer&thritol 'ith strong (9 G) nitric acid at a1ou0 F( )he reaction of decomposition is pro1a1l&.

%C6<+DC&0 > "C!2 N 2C+ N $62+ >f 2D2

4E)D is used in ma(ing detonating fuses and commercial

1lasting caps0 and has Z tmall 260! C<6<DIC6<E<>D+0 D!2 C060D(C6")2 N 26D+0 ? D ?C6" C6" ?D ?C6"
+H,-

medicinal use/ R##,I i >I> "6D+" >

&*!

It ma& also 1e made 1& al(&lating 20$> dinitrochloro1enFene 'ith meth&lamtue %o# then nitrating/Q )etr&l is a po'erful high explosive 'ith intermediate sensitivit& and great shattering po'er/

Picric Aci(
4icric acid (20$/ >trinitrophenol) is not made 1& the direct nitration of phenol0 1ecause too man& oxidative 1&>products are formed/ It is manufactured instead 1& the nitration of mixed phenotsulfonaIes 'ith mixed arid 12 #ixed arids cut do'n the health haFard caused 1& fuming0 reduce the amount of acid reAuired0 and increase the &ield of desired products )he use of mixed acid is no' almost universal/ Its heav&>metal salts are dangerousl& sensitive0 and its ma<or use is for the manufacture of ammonium picrate/

J37/ c&clonite0 or s&m> trimeth&lenetrinitramineMC6<E<Dsf D+FE<V0 is one of the most po'> erful explosives (no'n at the present time/ J37 is used in a mixture 'ith )D) and aluminum0 (no'n as )orpex0 for mines0 depth charges0 and torpedo 'arheads/ It is also emplo&ed as an ingredient in explosives for shells and 1om1s and is desensitiFed 1& 'ax or oil& materials/ 4entolite/ made 1& casting slurries of 4E)D 'ith )D)0 has specialiFed uses5 for example0 5!.5! pentolite is used as a 1ooster for slurr& 1lasting agents and prilled ammonium nitrate>fuel oil mixtures and as the main charge in 4rocore 1oosters/ )he -ritish developed the first practical s&nthetic process0 'hich involved the destructive nitration of hexameth&lenetetra>mine 'ith concentrated nitric acid. > "6C6+ N D60 @ com1ination process 'as developed 1& -achman at the ,niversit& of #ichigan0 'ho uti> liFed the 1&>productf to o1tain a seccnd mole of J37/ )his method ;as developed on a continuous scale 1& )ennessee Eastman0 'hich manufactured it the most economicall& (&ields of 7! percent)/

Explo.i'e *
7+plosi&e >, or ammonium picrate, is made b the neutrali'ation of a hot a"ueous mint ion

12C6sC++6

of picric acid 'ith aAueous ammonia/

% 612D$ N $6D +" D D6T

D+" N (C 6"C +)2+ *om e 1&> prod ucts of this @l1right0 4rocesses for Ditration of @romatic 6&drocar1ons/ (he). Eng. 7" (1!) 1 1 (19 )5 4rime0 *even> *tage Ditration of )D)0 (he). Eng. 71 ( ) 12 (19 $)/ HMi i%'&* Exp o!i"e!, 3epts/ +f the @rm& and @ir 2orce0 )echnical #anual )#9>191!0 @pril 19550 p/ 157/ Q2ormerl&0 strong nitric acid alone 'as used/ //////// ./
1!

reacti on are also useful as explo sives/ Le' # AGi #e

Jead a'ide has largel replaced mercur fulminate as an1tiatingetplosi&e for blasting caps. The fulminate has less than desirable stabilit , has to be manufactured in small batches, and

4<*

,, an( Toxic Chtit )0. creening .mofceG

0nd poisonous mercur&/ 9ead aFide has remar(a1le sta1ilit&0 involves no stra>> ^//r?///?i.>large 1atches 1& treating sodium aFide 'ith lead le from sodium amide and nitrous oxide/

DaD60 N D0! > DaD" N 60+ 2DaDs N 41fC<6<+<)0 > 41(Ds)t N 2Da(%6<+i)

2lame 'eapons provide the fuel for a fire 'hir>h AIA /u / //t/ 9 0 / . >uIc'nicti destro&s the target 1& heat0 e/g// personnel0 'eapons0 or electronic eAuipment/ 2lame 'eannnc n / i i 'ea // I / ,J 0 ;/ 4Ons are usuall& massive 1om1s or armored vehicular>mounted flame thro'ers/ 2lame 'eanonc 0i R R; i/ 11 i 'ea , /u / ^ c>u 9 0 4Ons also ignite com1usti1le material present at the target/ 2lame thro'ers en<o& a limited use for a00Y n> < / 1>7 ZWu use lor controlling un'anted vegetation/

"ea( t;phnate
*tvohnic acid is trinitroresorcinol and forms t'o salts on reaction 'ith lead acetate or nitrate0 1ale lead st&phnate C%6UD+U+41+6V0 and lead st&phnate/ )he 1asic st&phnate is a favored primer ingredient/ *t&phnic acid can 1e prepared from dinitrochloro1enFene/ 1ut nitration of resorcinol gives ver& poor &ields/

$)CE)*$A&$E
2lamma1le mixtures are pro1a1l& the oldest chemical 'eapons (no'n to humans5 the destruction of man& ancient cities 'as due to the use of fire/ *amson tied fire1rands to the tails of foxes and ran them through the 4hilistineIs grain fields/ Incendiaries 'ere the largest single categor& of chemical supplies consumed during Porld Par II and 'ere vital factors in that victor&/ @n incendiar&0 strictl& spea(ing0 causes ignition of com1usti1le materials at the target0 e/g/0

'ooden 1uildings or petroleum products/ Incendiaries ta(e the form of 1om1s0 1om1lets0 artiller& shells0 and grenades/ Incendiaries fall into t'o classes0 metallic and petroleum> #etallic incendiaries provide intense sources of ignition0 petroleum units scatter less intense sources 'idel&/ #etallic incendiaries include 1om1s 'ith metallic cases0 usuall& made of a com1usti1le magnesium allo& filled 'ith a mixture of 1arium nitrate and aluminum 'ith thermite to ignite the case/ )hermite is a mixture of aluminum po'der and iron oxide 'hich0 'hen ignited0 1urns fiercel& at a high temperature and cannot 1e extinguished 1& means of 'ater/ H2es +0 N 8# ? $@12 +" >I> 92e @6 W >"/!1 #E *ome readil& ignita1le material0 such as 1lac( po'der0 is emplo&ed to ignite the thermite/

*ometimes 'hite phosphorus or a small amount of tetr&l is added as a deterrent to fire fighters/ 4etroleum incendiaries contain gasoline thic(ened 'ith various ingredients/ )he first satisfactor& thic(ener 'as ru11er0 1ut other thic(eners such as iso1ut&l methacr&late pol&mer0 'hich 'as dissolved in gasoline in com1ination 'ith calcium soap0 'ere discovered/ 4erhaps the most important thic(ener is napalm/ )his is a granular aluminum soap prepared 1& pre> cipitating aluminum sulfate in excess al(ali 'ith t'o parts of acids from coconut oil0 one part of naphthenic acid0 and one part of oleic acid/ )he soap is capa1le of 'ithstanding elevated temperatures and produces a gasoline <ell& at ordinar& temperatures 1& simple mixing/ Dapalm surpasses ru11er gels in effectiveness and is applica1le in

flame thro'ers 'here ru11er gels 'ould 1e too viscous/ It 'as 1ecause of napalm that the 3ame thro'er 1ecame such an important and formida1le 'eapon/

T#!$C C%E-$CA" ?EAP#)

#odern use of toxic chemicals in 'ar 1egan in 19150 'ith the release f chlorine0 a gas 'hich 'as rather ineffective 1ecause of its lo' molecular" Auent high diffusion rate 'hich made it difficult r concentrations in the areas desired/ Contact poisons such as Qre
li&e. .uch agents are persistent because of lo! &apor p P

produce sneeFing0 tears0 vomiting0 and8or nausea Has mas(s are rarel& effective and self> contained 1reathing apparatus is reAuired for adeAuate protection/ Common tear gases include chloroacetophenone0 1rom1enF&lc&anide and o>chtoro1enF&lmalonitrile/

C&EE)$)@ -#,E
*mo(es or persistent fogs are used to hide areas on a temporar& 1asis/ *mo(es 'n disperse>.L 1& mechanical0 thermal0 and chemical means/ #ost fogs are created 1& forming lo' volatile droplets of 'ater 'hich remain dispersed in air/ Phite phosphorus0 'hich 1ums to 4F+<5 hexachloroethane>Finc com1ustion0 'hich forms ]nCl<5 and sulfur trioxide0 and chlorosul> fonic acid0 'hich gives off 6C1 and 6<*Cv are used to create chemical nuclei for fog formation/ +il vapor mists are used in smo(e grenades/ Colored smo(es are made 1& 1urning p&rotechnic mixtures 'hich volatiliFe various heat>resistant orgapic d&es/

agents have 1een devised containing 1oth chemical and 1iological i to den& 5 unprepared enem&0 these agents are ver& effective/ ,sed . area to an enem&0 these agents might 1e useful0 1ut as an F.
difficult decontamination before ad&ancing troops can enter contained breathing apparatus hamper mo&ement and greatl AreduceAeffec)&e ness %se of

toxicants is universall& condemned0 1ut mutual fear and distrust (eeps interest in their devel> opment alive i temporar& incapacit& are of value m Utodling riots e/ *uch matemls ma&

E"ECTE* &E8E&E)CE
=lbright. J. $.# A5itration,A -cCraA4%iU Enc;clope(ia of cience an( Technolog;, &ol 1(, Mc?ra!, )ill, 5e! Nor-, 19D1, p. D41.

Barbour, M. T.# P;rotechnic. in $n(=.tr;. McCra!, )ill, 5e! Nor-, 19D1. Bo ars. C. and B. Blager 2eds.3#

Propellant. -an=fact=re, %aBar(. an( Te.ting, =C., Columbus, 6hio,

19*9/

$!8 Chap. 22
Agenlm

Effloatrf*, Propellent*, an( Tofic Chemical

5-0

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