CHAPTER32

EXPLOSIVES
L. F. LIVINGSTON and W. C. HOLMES
E. I. du Pont de Nemours& Co., Inc.

INTRODUCTION

An explosive is material
a which,on proper initiation,becomesrapidlycon_
verted intoproductsof greatly increasedvolume. Ordinarilythe originalmate_
in form,whethera singlechemicalcompoundor a mixture
rial is solid or liquid
and becomesgasifiedduring the explosionreaction. The conversionto gaseous
form is accompaniedby intenseheat, whichincreasesthe volumeof gasesstill
more. The rapid expansiontaking place at the time of explosiongivesthe accom-
panying disruptiveor propellingeffect.
Explosivesare destructivein action when they decomposewithin a com-
pletely confined spaceor in closeproximityto other objects. If this decomposi-
tion takes placeinadvertently,the results may bedisastrous. When,however,
predeterminedamounts of explosivesare used under controlledconditionsof
time and place, theymay becomeconstructiveagents for accomplishing definite
objectives. By such control oftheir disruptive power, explosivesfunctionin
blasting ores ofiron and other metals,breaking clowncoal,miningsalt, quarrying
limestonefor use in road construction,and in performinga multitudeof useful
tasks.
POTENTIALENERGY OFEXPLOSIVES
Explosives areso disruptivein effect that theyare commonly reputed tobe
highly superiorreservoirsof energy. The fact is that, poundfor pound,com-
mercial blasting explosives contain considerably less potential energythan,for
example,liquid fuels. The shattering actionof explosivescomesfromthe ex-
tremely rapid conversionof solids or liquids togaseousproducts; in otherwords
from theoxidationof carbon and hydrogen tocarbon dioxideand watervapor.
In the case ofexplosives, the oxygen for this combustion is a chemically com-
bined portionof the material, whilewith fuels the oxygen of the air is utilized,
With most explosivesalso,there is a considerable content of inert materialnot
convertibleinto gaseousproducts.
The explanationof the effectiveness of explosivescomesin the almostin-
stantaneousrelease ofthe pent-up energy. While the combustionof fuelsis a
relativelyslow procedure,the progressof which canbe followedby the eye,the
decompositionof explosivestakes place at tremendous speed.Black powderis
considered aslow explosive,but even this has a velocityof combustion, when
shot in longcylindricalcolumns,upwardof around 1000feet per second.The
 EXPLOSIVES 1227
veloci0
„ dynamites,on the other hand, detonatent, rates of between5000
higher feet per second.
d 20000are givenin Table 1 to show eotnpnrntivelythe temperatures attained
in the eon)bustionof fuels and explosives,the volumeof gag pro-
theoretica at the ma.x•imllli)
tetnperature,and whencooledto 00,and the energy
d both of nunterinl mnployed. Because of various assumptiong
per pound
deased calculatedvaluesnntst be taken as only approximate.
Inade, the gasesis greaterthan that of the cold gasesboth because
Thevolumeof hotand because of the fact that, water, whichis in liquid state
f thermalexpansion
is in vapor form in the hot, gases and has been assumedto
gases,
in the cold
follow the gas laws.
TABLE, I—ENERGYVALVESOF' EXPLOSIVES
Thcorctical
Temp. Com- Volume of Gases Potential
Afatoial
buslion 0 C. cu. fl. /10()lbs. Energu
Cold 110t Ft. lbs./lb.
3900 '2500 83,000
Gasoline 3150 750 14,400
Nitroglycerin 2620
Straightdynamite 560 9,100
2350 514 5,200 958,000
Blackpowder

PROPERTIESOF EXPLOSIVES

In peacetimes the explosivesindustry ischieflyconcernedwith commercial

blastingexplosives,and the standardization and controlof their properties are
ofprimeimportance. This is particularly true ofdynamites. Since these must
beappliedto all kinds of blastingwork, a greatmany different types must be
and their propertiesmust be varied widely, to adapt them to do their
designed
workeffectively.
Strengthand Velocity—The two properties which are most important in
the proper execution of an explosive
assuring in blasting work are strength and
velocity.Probablyit is a combination of the two properties which determines
sometimes been termed "brisance."
effect. Thiscombined effect has
the shattering
explosives aregraded primarily, and
Strengthis the property on which this may
be consideredto depend on thegas pressure developedfrom a givenweight or
volume of material. Velocitydenotesthe rate at which the effectivestrength
is developed.Obviously,very hardrock can beblasted down onlyby a high
strengthexplosiveand by one whichpossesseshigh velocity ofdetonation. For
softerrockand material offeringless resistance,lower strengths andparticularly
lowervelocitiesgive more satisfactoryresults.
Sensitiveness—Sensitiveness to propagationis a property which mustbe
accuratelycontrolledand maintained,as failure to propagate will mean the
Presenceof a certain amount of unexplodedmaterialin the borehole, a very
hazardouscondition. Other properties,such as fumesand water resistance, are
likewise
importantand arematters of routinetest by manufacturers of explosives.
Tests—The be based
finaljudgmentas to the efficiencyof an explosive must
onits executionin actual blastingwork. Laboratoryand proving
122S INDUSTRIALCHEMISTRY
have been developed,however,which allow a good preliminary evaluation
Propellentexplosivessuch as smokelesspowder, aregiven very extensivetests
particularly withrespectto ballisticproperties and stability under storageCondi
tions.t It iseeecntinlthat the explosivegive the desired
velocity _
to the projectile
but that this shallnot be developed so rapidly as to burst,the
barrel. necauseof the fact that sniokelesspowder may bo stored for Years,
importantthat therebe no deteriorationin quality and propertiesoveritthis is
period.
Militaryexplosivesof the disruptivetype usedfor shellfillingand like
poses, TNT for example,are tested mainly for purity and freedomfrom Comami_
nation. Meltingpoint,tests and detenninntionsof percentagesinsolublein Cer.
tain solvents,acidity,nitrogencontent,amountof ash are theimportantcriteria
for suchcompounds. s
Role of Nitrogenin Explosives4—Thechemistryof explosives is closely
bound up with that, of nitrogen compounds. The alkali nitrates are the oxidiz_
ing agentsused in blackpowdercompositions, while ammonium nitrate is per.
haps the mostimportantingredientof dynamites,functioningboth as a strength
producer and as oxygensupplier. Practicallyall the high explosivecompounds
important in thecommercialand militaryfieldscontainnitrogen.
The explanationfor the adaptabilityof the nitrogen compounds as explosives
seemsto lie in their degreeof instabilityand sensitiveness to shock. A practical
explosivecompoundmust be sufficiently stableto permit safe handlingand stor-
age, yet mustbe capableof almostinstantaneousdecomposition whensubjected
to impact of definiteintensity. In certainnitrogencompounds,the strengthof
the bond linkingthe nitrogenatomsto adjacentatomsis suchas to givea prac-
tical sensitiveness. Since explosivedecompositionis essentiallya combustion
process,the organicnitrates and nitro-compounds fit well intothe requirements.
Nitrogenitself isusuallyfoundin elementalform in the productsof explosion,
while the attached oxygenis availablefor the combustionof the carbonand
hydrogenpresent. As additionalN02 groups areintroducedinto organicformu-
las, the sensitivenessof the nitrated compoundincreases.

OF EXPLOSIVES
MANUFACTURE

Black Powder5—Thestory of black powder goes backmany centuries,so

far back that its originis a matter of tradition. While someof the very early
investigatorsmay have experiencedthe explosively violent action of intimate
mixturesof ingredientssimilarto those in blackpowder, its authentichistory
appears to havebegunin the 14th century, whenit was first usedin firearms.
1 Munroe, C. E.and Tiffany,J. E., "Physical Testing of Explosives at the Bureau
of Mines ExplosivesExperiment Station," U. S. of
Bureau Mines, Bulletin 346(1931)
;
Gillie,B. A., J. Chem.Education5, 1213-1223 (1928).
2Tschappat, W.ll., "Textbookof Ordnance and Gunnery,"Wiley(1917);Mar-
shall, A., "Explosives," second edition, Vol.pp.
1, 289-335,Blakiston (1917).
Taylor,C, A.and Rinkenbach, W. fl.,"Explosives:Their Materials,Constitu-
lion and Analysis," U,S. Bureau of Mines, Bulletin 219 (1923).
4 Sidgwick,N. V., "Organic Chemistry of Nitrogen," second edition, Clarendon
Press (1937).
Vol. 1, p. 24 Whittaker& Co.
5 Guttmann, 0., "Manufacture of Explosives,"
Vol. 1, p.53, 'Blakiston
(1895); Marshall, A., "Explosives," second edition,
 1229
frequentlygiven credit,for the inventionof firearmg nnd
holdSchwartzis powder or gunpowderas the propellent,charge.
the of black out as gunpowderand is snid to hnvebeen first
powderstarted for
purposTS at the I of Crécyin 1346. It wasnot until 1627that
q.dcfis known to have been used in mininc,in Hungary. Gunpowder
nilitary
this the,accepted for black powderdown prnctienllyto the end of
century, regardless of the methodof use.
the19thpowderis an excellentexplosivefor the blastingdown of coal, as its
ives it,n slow,heavingaction that does not shatter the coal un-
velocityg
For safety reasons,however,black powdercannot be used in minesin
duly, inflammable gases are present or suspected,as its long flame ofconsider-
which it more hazardousthan the highervelocity safety dynamites
abledurationmakes
"permissible" explosives.
designated as
composition.The compositionof black powderhas changedvery little
overthe courseof many of
centuries. An Englishpowderof the year 1350 is
66.6%
the composition saltpeter, 11.1%sulfur, and 22.3% charcoal,
While a French powder of 1650 had these ingredientspresent in the respective
of 75.6%, 10.8%, and 13.6%. This latter compositionwouldbe satis-
amounts
factoryfor a present-daypowder. Wherepotassiumnitrate was formerly used
exclusivelyas oxidizingagent, it has beenreplacedin American blackblasting
powders by sodiumnitrate. Becauseof the higherweightpercentageof oxygen
in the latter, about 2% less of the sodiumsalt may be desirablyused than of
thepotassium,for comparable results.
Blackpowder,therefore, is essentiallyan intimate mixture of (1) sodium
orpotassiumnitrate, (2) sulfur and (3) charcoal,in the approximatecomposi-
tionsgivenabove. The replacement ofpotassiumnitrate took place in Ameri-
canpowdersabout the middleof the 19thcentury. At the presenttime, all
American blackblasting powders containsodiumnitrate, whichis considerably
cheaper as an ingredientthan potassiumnitrate and possessesgreater potential
strength.It has the disadvantageof beinghygroscopic,hence potassiumnitrate
is retainedin black sporting powders andin fusepowders,where uniformity of
burningand of moisturecontent is essential.
RawMaterialsfor Black Powder. Sodiumnitrate is the ingredientused
inmuchthe largestamount inAmerican black powder. Until the last fewyears,
thismaterialwas obtained almost entirely by importation from Chile. Now
synthetic sodium nitrate has largely replaced the
natural product,and is avail-
ablefreefrom impurities.
Charcoal is one of themost importantingredientsand one thatrequiresmost
carefulcontrolas to uniformity,freedom from undesirable impuritiesand gen-
eralexcellence.Any markeddeviationfrom the standard in the propertiesof
thecharcoalwill affect the properties of the finished powder,Charcoal maybe
obtained from various non-resinouswoods, for example, maple, and resultsfrom
a charringand a dry distillation process, (See Chapter 17, Wood Distillation
Industry.)
Sulfur is availablein the UnitedStates in a high state of purity, the only
specifications it shall befree from grit and acidity,
generally being that
DecompositionReactions of Black Powder, Black powder comprises a
Combustion
mixtureof oxidizing andreducingagents.
1230 INDUSTRIALCHEMISTRY
eotnposition of 73% sulfur, and 14%charcoal,Thefollowing
the approxitnatemolecular proportions
tion would represent present:
2NaN03+ S + 3C = N[12S + N2+ 3C02
is muchmore complex. Someformationof sodiumsulfate
Actually the reaction
and sodium carbonatewill take place. Those familiar with black powderblast_
ing know also thatsome carbon monoxideis always formed.Under Conditions
it is notedthat, thereis substantiallyno formation
operations,
of use in mining
of free hydrogensulfide,this gas beingfixed by the alkali
elementpresent. Black
powder is notcompletelygasifiedon explosion,and in the, reaction shownthe
solid residuein the reactionproductsrepresentsabout % of the total by weight.
The sulfur in theblackpowdercompositionis not simplyan alternativecorns
bustible material. It appearsto have a characteristicaction in facilitatingigni_
tion of the powderand promotingcombustion.
ManufacturingOperations. The manufacture of blackpowder comprises
a number of steps ormechanicaloperationswhichare carriedout in separated
buildingsfor safetyreasons. Theseoperationsbrieflyare as follows:
1. Preliminary pulverizingof ingredients
2. Incorporationunder wheels
3. Pressing
4. Cutting ofpress cake
5. Granulation,or "corning"
6. Drying and glazing
7. Packing
Pulverizing. Theingredientsare preparedinitially in astate of finesubdivi-
and charcoal are firstgroundtogetherin a drum
sion. Ordinarily the sulfur
while thenitrate is disintegrated eitherin a ball millor
containing steel balls,
under steelcrusher rolls. Care is taken at theend of this preliminarygrinding
that the materials are free from foreignparticles of matter, particularlyof a
metallicnature, and this is accomplished
by screeningor passingover a magnetic
separator.
Wheeling. The finely divided ingredientsare given a more intimate and
thorough incorporation in the "wheeling"operation. The materials are intro-
duced into a cylindricalbowl,havingordinarilya metal bed plate and wooden
side walls. Within this bowl
two heavybroad-edgedrunners or wheelsconnected
by a shorthorizontalaxis rotate continuously. (See Crushing andGrindingin
Chapter 2,The Unit Operations.) Thesewheelsmay be over 7 feet in diameter
and around2 feet inwidthof rim. At the sametime the wheelsrevolveslowly
about their own axes.The wheelsare preferablydriven from belowand havea
certain amount ofclearanceabovethe bed plate. Metal plowsare arrangedin
front of each wheel tomovethe mixturefrom the sidesand centersof the bowl
under thepath of thewheels. Water is addedto the charge toensurethe proper
final moisturecontent. The operationis continuedfor severalhours,at which
time veryintimateincorporation is
has resulted. The productof this operation
designated"wheelcake."
Pressing. The wheeledand incorporatedmixture is subjectedto the action
of crusherrolls orother devicesfor breakingup the lumps andis then
 EXPLOSIVES 1231
presseswhere pressures of over 1200pounds por square inoh may
intohvdrnulic
The pressing operation gives a hard mass, designated ('presg cake,"
begpplied.
whichthere is no longer any tendencyfor segregationof the separate
in
ingredients.
cuttingand Granulation. The pressed cake is broken up into pieces of
in diameterand passesto the "corning"or granulating opera-
gbout1 to 2 inchesfragmentsof powder are caused to go through consecutive
tion,in whichthe rolls, provided with teeth. The powderis gradually reduced
setsof steelcrusher size, and screensbeneaththe rolls separatethe material
tograinsof the desired
desired
intothe various granulations. The corningoperationis one ofthe most
hazardoUS of blackpowdersteps, but in all stagesof blackpowder manufacture
careis takenthat no workersare presentin the buildingswhile the powder is in
courseof treatment.and
Drying,Glazing Packing. If granularblack powderis to be produced,
the"greengrain" powderfrom the corningoperationis run into therevolving
dryingandglazingdrums,whichmay have a length of 12 feet and a diameterof
4 feet. The powderis in these drums for severalhours,during whichtime the
grainshavetheir edges roundedoff. Heated air is blownin and the moisture
contentis reducedto about0.5%. A smallamountof graphite isadded during
thelatterpart of the rotationof the drum to glaze theparticlesand givethe
grainsa polishedsurface. The finishedpowderis sorted by means of screens
intothe desiredgranulations and ispacked in metal kegs, usually holding 25
poundseach.
PelletPowder. Black powder is now prepared in two commercialforms,
(1)in the formof free-flowinggrains and (2)in the formof pelletsor cylindrical
columns enclosedin a paper wrapper. The preparationof the granularpowder
hasbeendescribedin the preceding paragraph.
Pellet powder originated inEurope and wasintroducedby Americanmanu-
facturersabout 1925. In its usual form, it consists ofcylindricalagglomerated
pellets
2 inchesin length and of diameters up to 21/2 inches, eachpellet havinga
longitudinalcenterhole. Ordinarily four suchpelletsare placedend to end and
enclosedin a paper wrapperto form a cartridge 8 inches in length.
In the manufactureof pellet powder,the same materials aretaken as for
granular powder. The "green grain"powder resultingfrom the "corning"step
iscommonly usedand is fed froma hopper into a die or hole in a chargingblock
ofthediameterdesired for thepellet. A center pin isintroducedpreviousto
messing of the powderand two plungers compress the powderfrom aboveand
belowrespectively, until the desired density has been obtained. About 4.5%
Ofwateris present in the powder being compressed. The pressed pellets are
transferredfrom the press houseto another building, where theyare dried on
traysby meansof hot air, toa moisturecontent of about 0.5%. The finished
pelletsare wrappedin paper, waterproofedby dippingin paraffin, and packed
in 25-or 50-pound boxes.
Pelletpowderis in a formvery convenientfor use and very adaptable for
aCCUrate
measurementof the desiredexplosivecharge. It is safer tohandlethan
granular
powderbecauseno pouringof the powderis necessaryand spilling is
unlikely.
In the presenceof inflammable
gases,however,it is no safer
1232 INDUSTRIALCHEMISTRY'
in coalmining thnn the granular forth, since it possessesthe gamelong-flame
characteristicson combustion.
PotassiumNitrate Powders. The blasting powdersalready describedhave
containedsodiumnitrate as oxidizingingredient. For certaintypes of use,fuse
powder forexample,it is desirableto use potassiumnitrate as the oxidizing
agent.
Black propellent powder for use in firearms, though largely displacedby
smokelesspowder, islikewisea potassiumnitrate composition,since uniformity
of pressuredevelopmentis an absoluterequirementhere,

THE ROLEOF NITRATION

In black powderthe nitrogenof the explosiveis suppliedas an intimate
mechanicalmixture. With the developmentof the studiesof chemicalreactions
it wasfound that many explosivescouldadvantageouslybe madeby the incor-
porationof nitrogenin organicmolecules.Hence,nitrationhas assumeda role
of paramountimportancein this field (see Chapter 3, The OrganicUnit Proc-
esses.)
Nitrates and Nitro-Compounds—Twotypes of organic highexplosive com-
pounds are obtainedby the action of nitric acid on organic materials,
i.e., by
nitration. Theseare (1) the organic nitrates or nitric esters and (2) the nitro-
compounds. Both of these types containone ormoreN02 groupsreplacinghydro-
gen atoms of theunnitratedcompounds.In the case of the nitricesters,the
N02 group is attachedto an oxygenatom, whilein the nitro-compounds it is
linkedto a carbonatom. The nitric estersare obtainedby the nitricesterifica-
tion of alcohols,whilethe nitro-compounds are ordinarilyprepared by thenitra-
tion of hydrocarbonsor their derivatives. Nitroglycerinis an exampleof the
nitric esters,
CH2—ON02
CH—ON02
CHEON02
AEis apparent from the aboveformula, the name nitroglycerinis a misnomer,
the correct designationbeing glyceryltrinitrate. Trinitrotoluene(TNT),on
the other hand,is a true nitro-compound:

C—N02

N02
In additionto the abovetypes of nitratedproducts,the primarydetonating
compounds,commonly usedin blasting caps asinitiating explosives,
 EXPLOSIVLS
1233
nRontainingcompounds. Mercuryfulminatehas the formula(CNO)2iIg,
leadazide is PING.
q•bile
NitrationProcesseO---Nitration is the term commonlyemployedto desig-
the actionof nitric acid on organiccompoundswherebythe
nitro group
is introduced,usuallyin place of a hydrogenatom. Thus it includesboth
thepreparation of the true nitro-compounds, wherethe N02 group is attached
carbon atom,and esterificationby meansof nitric acid.
a
Thenitrationagent in commercialoperationsis ordinarilyone of the follow-
ingforms:
1. Mixedacid, comprisingnitric acid associated with a dehydrating agent
acid:
suchas sulfuric nitric acid,
2. Concentrated for example,around 95%.8
3. Nitrogentetroxide, preferably in vapor form.9
Nitrationproducts are important, in organic industries generallyand par-
as dye intermediates. (See Chapter 28, Manufactureof Intermediates
ticularly
ondDyes.) Many of suchnitro-compoundsare not explosivecompounds,having
perhaps oneor two nitro groupsin their formulas. Generallyit is the com-
pounds havingthree or more nitro groupsthat are important as explosives,though
glycoldinitrateis a conspicuous
ethylene exception.Thusthe mononitrophenols
andmononitrotoluenes are lacking in explosiveproperties,but are useful as
dyeintermediates.The correspondingdinitro-compounds are relativelyinsensi-
compounds,while trinitrophenol (picric acid) and trinitrotoluene
t.iveexplosive
areoutstandingexplosivecompounds. The lower nitro-compoundsare readily
obtainedby treatment ofthe starting materialwith low strengthnitric acid,
whilethe compoundscontainingthree or more nitro groups require a higher
in the nitration acid, or highertemperaturetreatment. The
nitricconcentration
replacementof hydrogenby a nitro group resultsin the formationof water as a
reactionproduct:
R —H + HO—N02+ R - N02+
Hence
the presenceof sulfuricacid or other dehydratingagent in the mixedacid
helpsmaintaina high concentration of nitric acid.

EXPLOSIVESMADE BY NITRATION
Manufactureof Nitroglycerin10—Nitroglycerin is the ingredient which,
fromthe beginningof the dynamite industry,has given such explosives their
characteristic
high velocity, as distinguished from low-velocityblack powder,
thecommercial blastingpowder previouslyin use. Nitroglycerinis obtainedby
theactionof nitric acid on glycerin :
gGroggins,P, ll., "Unit Processesin OrganicSynthesis,"secondedition, p. I,
McGraw-HillBook co. (1938).
7Naoum,P„ "Nitroglycerinand NitroglycerinExplosives,"Americantranslation
byE. M. Symmes,
p, 51, Williams & Wilkins Co, (1928),
8Naourn,P., ibid.,
9Wilhelm, 244 (PETN),
Pounds), R. H., S. Patent 2,109,873(March 1, 1938)(Aromatic Nitro-Com-

InOrganic
Synthesis,"
1234 ISDUSTIUALCHEMISTRY
C1120N02

+ CllON02 + 31-120
CH2011 CH20N02
it willthus be seen that nitroglycerinis not a true nitro-compound, but actually
is a nitric ester,glyceryltrinitrate.
Nitroglycerinresemblesglycerinin appearance,and is white to yellowish
viscousliquid,having aspecificgravityof 1.6.
The raw materials employedin the manufactureof nitroglycerinare glycerin
acid. So-calleddynamiteglycerinis a high-gradeproduct
sulfuric acid, and nitric
of around 99% purity, having a specificgravity of about 1.262and a high
viscosity. The mixedacid usedin the nitration has a compositionof aboutequal
parts of sulfuric acidand nitric acid, with possiblya slight excessof the former,
and is substantially free fromwater. For informationon the manufacture of
these raw materials see Chapters 7, S and 42.
In carrying outthe nitration,the proper amountof mixedacid is introduced
into thesteel nitratingvessel,in whichbrine coilsserve to coolthe acid. (See
Chapter 2, The Unit Operation.) After agitationhas been started, glycerinis
added at such a ratethat the temperaturerise isonly moderate. The tempera-
ture rangeis maintainedgenerallybetween500 and 370 F. (10-30 C.). Nitro-
glycerinitself mayfreeze at about 550 F. (12.80C.) and its freezingin the
nitrator wouldconstitutea hazard, but variousconditionspresent make opera-
tion safe at somewhatlowertemperatures. Actually itis the practiceto make
low freezing ordifficultlyfreezablenitroglycerinby nitrating, instead of glycerin
alone, a solutionin glycerinof ethylene glycol, diglycerin orother similarni-
tratable material. The nitratedproduct then isa solution innitroglycerin of
ethyleneglycoldinitrate,tetranitrodiglycerin or other freezingpoint depressant.
In additionto the formationof glyceryl trinitrate, therefore,one of the following
reactionsmay be proceedingsimultaneously in the nitrator:
CH20H CH20N02
+ 2HN03= + '21120
CH20T1 CH20N02
EthyleneGlycol Ethylene Glycol
Dinitrates
C1120J1 C1120N02
CHOJI CHON02

C112

11011 CllON02
CH20N02
Diglycerin Diglyceryl
(polymerizedglycerin)
 EXPLOSIVES 1235
resultingnitroglycerinand spent,acid, having a compositionof about
760/0IJ2S04,70/oIINO.g,and 17%1120,are run fromthe nitratorinto a separat-
In the courseof about •Y'of an hour, the nitroglycerinand spent
layers, with the nitroglycerinon top and with a clear
acidformseparate line
the two layers,whichmay be observedthrougha sight,glass. Usually
into layers is hastenedby the additionto the nitrationmixture
theseparation material such as a mixture
of a facilitating is drawnoff from of sodiumfluorideand kieselguhr.
The nitroglycerin the separator, given a preliminarywater
wash,and treated in the neutralizer with a weak solutionof sodiumcarbonate
duringvigorousagitation to removethe last traces of acidity from thenitro-
glycerin. to be stronglyemphasized
It needs that the manufactureof nitroglycerin is a
hazardoUS operation, and one that, shouldnever be attemptedby inexperienced
persons. Such care is taken, however, in commercialproductionin the control of
temperature, the purity of materials and the avoidanceof dangerouspractices
that explosions are uncommon. If there is an undulyrapid rise oftemperature in
thenitrator, or if, for any reason, a nitration must be interruptedbefore com-
pletion,the entire charge is drowned,that is, droppedinto an excessof water
directlybeneaththe nitrator.
The yieldis commonlycalculatedon the basis of glycerinas 100,and the
theoreticalyield would be 245; in practice, yields of around 230 are commonly
obtainedunderbest operatingconditions. Chargesof around 3000pounds nitro-
glycerin and over are frequentlyobtainedin one nitration.
In recentyears,continuousprocessesfor the nitration,separation,and washing
ofnitroglycerin have beenadopted in a number of Europeanplants.ll These have
replacedthe formerbatch processes.
Nitrocellulose12—The nitration of cellulosefollowsthe same principlesas
in the case ofglycerin,namelythe treatment of cellulosewith nitric acid and
theintroductionof nitro groupsin place of hydrogenatoms. Nitrocellulose,like
is misnamedand actuallyis a nitric ester,cellulosenitrate. Its
nitroglycerin,
formation is shown by the
followingreaction:
+ 3HN03 + 31120
In reality,the nitration reactionis muchmore complicatedthan this, as the size
ofthe cellulosemoleculeis doubtlessvery much larger than indicated and should
be written (C6H1005)n.In the caseof nitroglycerin,a single relativelypure
productis formed. In the nitration ofcellulose,on the other hand, a mixture of
cellulose
nitratesmay be obtained,varyingin nitrogencontent and solubilityin
organicsolvents,dependingon the compositionof the mixedacids and the condi-
tionsof nitration.
Priorto nitration,the cotton linters are
purifiedby digestionunder pressure
witha dilute solutionof causticsoda. This serves to reduce the content of
vegetableoils, resins,and other removable
impurities.
In onemethodof nitration, the purifiedcelluloseis immersedin a mixedacid,
having,for example,the approximatecomposition63% H2S04,22% HN03,
Il Gassner,0., Chem. Ztg. 57, 201-2 (1933)
; Schmid,A. U. S. Patents 1,893,447,
1,939,634, 1,946,414-5.
Marshall,A., "Explosives," second edition, Vol.
1, p. 168,Blakiston
1236 INDUSTRIALCHEMISTRY
1120. It iscommonto nitrate 30 pounds ofcotton as one chargefor about
30 minutes, withagitation,using about 1500pounds of mixed acid and main.
taining a temperature of 30-350C.
When nitration iscomplete,the nitrocellulose and thespent acid are run
into a centrifugal wringer, whichrevolvesslowlynt first and then at a highspeed
of around 1100 RPM. This causesthe separation of the acid, whichcan be
sent to mixingtanks for fortificationand subsequentre-utilization, or to the
denitrator. The centrifugednitrocotton,with its acid content,is drownedin an
excessof water.
The purificationtreatment consistsof a prolonged boiling in water, slightly
acidifiedwith sulfuricacid in order to break downunstable esters, a mechanical
pulping treatment to reducethe length of the fibers, and an alkalineboiling
(poacher) treatment to neutralizeacid products,followed byseveralboilingsin
fresh water and finallya numberof coldwater washings.
Trinitrotoluene 13---lnthe case of nitroglycerinand nitrocellulose,nitration
is a one-stepprocess,all the acid and the material fornitration beingintroduced
during oneoperation. With trinitrotoluene(TNT), either a two-stepor a
three-step processis used, the formerseparatingout the mono-nitrocompound
first, then going throughthe bi-and tri-stagesin onestep. The three-step
process obtains in separatenitration stages, the mono-, di-, and trinitro-com-
pounds, by successiveaction of onemolecule of nitric acid on one moleculeof
toluene, or its nitrationcompounds, with simultaneous
splitting off of water:
CH3 CH3

C—N02
HC
c

Toluene Mononitrotoluene

TIC C—N02 02N—C C—N02

TIC TIC

N02 N02
Dinitrotoluene Trinitrotoluene
The preparation ofTNT is not as simpleas the outlineshownaboveindi-
cafes. Three isomericformsof the mono-compound exist and all are formedin
Smith, G. C., "Trinitrotoluenesand Mono-and Dinitrotoluenes,"D. VanNos•
co. (1918); Cower,E. de W. S., "Iligh Explosives,"p. 170,D. van Nostrand
(1918); Marshall, "Explosives,"secondedition, p. 260,Blakiston
 EXPLOSIVES 1237
the Ortho,meta- and para-cornpoun(18,
tnono-nitration, having meltingpoints
160, and 580 C., respectively. Six isomers are possible and known
trinitro-compound. It is the formationof undesirable impurities,both
for the and oxidationproducts,that makes the preparationof pure TNT a
isomeric operation. CommercialTNT
complicated consistsprincipallyof the 2-4-6-igorner,
purified material melts at 80.80C.
andthe completely of
In the preparation TNT in severalnitration steps, stronger acids and
highertemperatures are used during the contact of mixedacid and nitratable
materialas the higher stages of nitration are carried out. Accordingto one
process,the acid compositionfor the finalnitration step is approximately79.5%
H2s04,17.8% TINO$,and 2.7% 1120.14
Other Nitration Procedures—Inthe three examplesof nitration described,
mixturesof sulfuricand nitric (mixedacids)have beenemployedas the nitration
medium. While nitric acid is always the active reactant, various other pro-
ceduresare frequentlyfollowed. In the preparationof picricacid from phenol,15
the latter is commonly firsttreated with strong sulfuricacid to form phenol
sulfonicacid, whichis then convertedto picric acid by treatment with strong
nitricacid. In the case of pentaerythritoltetranitrate,Naoum16 states that
mixedacidis not suitable forthe nitration,and he treats the pentaerythritolwith
acidhavinga contentof around99% I-IN03.

DYNAMITE
Dynamitemay be definedas a commercialhigh explosive. This distinguishes
it (1) fromthe solidorganichigh explosiveswhichare used for military purposes
and (2) from lowvelocity commercialexplosivesof the black powder type.
There is nosharp lineas to velocitywhichseparatesthe high from the low
explosives,
but thedistinctionis often made betweenthe two as detonatingand
deflagrating
compositions. The dynamitesor detonatingexplosivesare exploded
by meansof the violentimpulsefrom a blastingcap, whilethe deflagratingex-
plosives
are initiatedby meansof a flame. Sometimesthe term dynamitehas
beenlimitedto those commercialexplosiveswhich contain nitroglycerin,
is not necessarilythe distinguishingpoint in the United States. The but this
betweenthe varioustypes of dynamiteis shownby the diagramof Figurerelation
1.
The inventionof dynamite dates from 1866,when Alfred Nobel conceived
the idea of mixing liquid explosivenitroglycerinwith
a highly absorbent ma-
terial. In this way he obtained,in place of a liquiddangerousto transport
andto handle,a solid compositionrelativelyinsensitive to ordinaryshock,but
capableof completedetonationby means ofa blastingcap. Nitroglycerinhad
beendiscoveredby Sobrero in
beenof little practical 1846,
twenty years earlier,but prior to Nobelhad
value. The importanceof Nobel's discoveryto the ad-
Vancement of civilizednationscannotbe too strongly emphasized,
timeit shouldbe and at the same
realizedthat commercial dynamites are constructivetools. It
14''Thorpe's
& co.
(1940).
Dictionary of Applied Chemistry," Vol. 4, p. 468,
Longmans,Green
U. S. War Dept., ('MilitaryExplosives," Technical Manual No. 9—2900
(1940).
p.244,aoum P , ('Nitroglycerinand NitroglycerinExplosives,"American
Willia'mg•
& Wilkins (1928).
1238 INDUSTRIALCHEMISTRY
is this type of explosivewhichis the Inoscimportantand the one to whichthe
and efforts.
explosivecotnpaniesdevotethe bulk of their equipmentthere
Ingredients of Dynamites—Unlikeblack powder, is no standard
corns
position for dynamite.Nitroglycerin,probablythe most characteristicingredient
may vary in percentage, for example,from 5 to 90%, and otheringredientsmay
likewisevary widely,dependingupon the properties desired
but
in the finished
plosive. Not only arethere many rangesof composition, also many typesof
dynamites,owing to the differingfieldsof applicationfor such explosiveswhere
varied forms ofblastingaction are needed. A few of the most importantin.
gredients of dynamite compositionswill first be considered briefly.
INDUSTRIAL
EXPLOSIVES

OYNAMITE

EXTRA SEM)•GELATIN
NITROGLYCERIN (AMMONIA) GELATIN PERMISSIBLES
DYNAMITE DYNAMITE

HIGH LOW
DENSITY DENSITY
CARTRIDGE
I-owCARTRIDGE HIGH
COUNT COUNY

NITROGLYCERIN EXTRA
GELATINS (AMMONIN

FIG. 1. General Classes of Industrial Explosives.

Nitroglycerin. This has long been the most important explosiveingredient
of dynamite,thoughthe trend for many years has been continuouslytowardof a
reduction of the nitroglycerincontent. The preparation and properties
nitroglycerin have been discussedpreviously in connection with nitration
processes.
AmmoniumNitrate. Whilenitroglycerinholds its place in popular estima-
tion as the outstandingingredient ofdynamites,ammoniumnitrate pronitro- bably
should be given first place. It does notpossessthe explosiveproperties of ex-
glycerin,when used by itself and in small quantities, but it is a powerfulOf
plosive compound when once initiated byan external detonating impulsead-
sufficientmagnitudeand whenused in considerableamounts. It has thebeing
vantages of being absolutelysafe to handleunder ordinary conditions, of
universally
formedreadilyby the neutralizationof nitricacid with ammonia,two dis-
available raw materials, andbeing low in cost. As will be seen in a later usedas
cussionof types of dynamites, ammonium nitratehas been increasingly
an explosivesalt to replacea portion ofthe nitroglycerinformerlyused.composi-
CombustibleAbsorbents. Nitroglycerin isretained in dynamite used
tions by absorptionby combustibleingredients. The absorbent first that
adapted for
Nobel was kieselguhr,a siliceousmaterial, which was excellently it was
purpose but which reducedthe strength of the explosive,because
 EXPLOSIVES 12.39
action and could not beconvertedinto gaseous matter, Such combustible
inert in as woodpulp, starch, and variousmealsnnd lowdensityfibers arenow
n1aterials
The choiceof absorbentdependson variousfactors,such as nitroglycerin
dynamite,desireddensity,and sensitiveness,etc.
contentof the
sodiumNitrate.theSodium nitrate is used as an oxidizing agentin dynamite.
explosive
that be oxygen-balanced so that good fume properties
It is desirable execution can beobtained. The combustibleabsorbentsare
andgoodblastingoxygenand the presence of sodiumnitrate makes possiblea
in
verydeficient whereall the carbonand hydrogenpresent
balanced mixture, willbe burnt com-
carbon dioxide and water.
pletelyto
FreezingPoint Depressants. Nitroglycerinhas the disadvantnge of a rela-
tivclyhigh freezing point, about 550 F. (12.80 C.). Consequently dynamites
containing it will freeze at comparativelymild winter temperatures. When in
frozencondition,dynamite isunsatisfactoryfor usein blasting andmust be
thawed.Not only is the thawingoperationtime-consuming,
but it is also
extremelyhazardousunlessunusual precautions aretaken.
The hazard of frozen dynamitehas been removedby introductioninto the
nitroglycerinof materialswhichdepress thefreezingpoint sufficientlyto ensure
softdynamiteat the most extreme winter temperatures. At the same timethe
strengthof the explosive is maintained,
as the depressantused is itself a highly
nitratedexplosivecompound. The usual procedure is notto dissolve thenitrated
but to nitrate thesolutionof the startingmaterial
in nitroglycerin,
compound
in glycerin.
Theintroductionof ethyleneglycol dinitrate ortetranitrodiglycerin as freezing
pointdepressanthas been discussed in connection with the nitration of glycerin.
Theco-nitrationof glycerin with either ethylene
glycol or diglycerin (polymerized
glycerin)makesit possible to obtain a nitratedproduct of the desired extremely
low-freezing properties. The amount of nitroglycolor tetranitrodiglycerin present
in the nitroglycerincan be ascertained by determination of the nitrogencontent
of theproduct,as obtained onthe nitrometer,together with the specific gravity.
Many otherfreezing point depressants have been proposed andused, for ex-
ample,nitrochlorhydrins,nitrotoluenes, etc.No two such depressants are equiva-
lentsand, witha change ofdepressant, formulas must be adjustedthat so the
explosive properties of thefinished explosive remain unaffected.
Ant-Acids(Anti-Acids). The presence of even a small amount of nitric
acidhas a slightdecomposingeffecton nitroglycerin.For this reason,it is the
usualpracticeto include in the formulas of nitroglycerin dynamites asmall
amountof an acid-accepting material, or ant-acid. Calciumcarbonate iscom-
monlyusedfor this purpose,in the amount of 0.5to 1.0% of the total composi-
tion. The regulationsof the Interstate CommerceCommissionstate that, for
shipmentby freight,explosivescontainingnitroglycerin or other liquid explosive
ingredients,must containan ant-acidmaterial "in quantity sufficient to have the
acidneutralizing power of anamountof magnesium carbonate equal to 1 per cent
of the nitroglycerin."
Manufactureof Dynamite—Thevarioustypes ofdynamites require different
treatments,but the generalmanufacturingproceduredepends uponwhether the
explosive is (I) a gelatin dynamiteor (2) a non-gelatinousdynamite.
 1240 INDUSTRIALCHEMISTRY
operations will bedescribedbrieflyunder these twoclassifications,
and are illus.
trated on the accompanying flowsheet,Figure2.
Non-Gelatinous Dynamites—Themanufactureof thisclass of PUIVerulent
dYY1mitesfrom the raw materialsconsistsessentiallyof two operations,(1)
mixingand (2) cartridging.
Miring. The ingredientsto be mixedcome fromtwo differentsources. First
the nitroglycerin fromthe neutralizeris wheeledto the mixinghouse in rubber.
tired, hand-operated"buggies,"whichhave copper compartmentsadaptedto
hold weighed charges of nitroglycerin,in the amount desiredfor the dynamite
mixing. The secondingredientcomprisesa mixture ofmaterialand is designated

wom 21XQ_C2PC3
ctC

MIXING HO-ISC MIXING POJSt

CARTAIOGING
HOUSE

RtCOv•tRt

PACKING

HNO ANDGELATIN DYNAMITE

DYNAMITE MANUFACTURE

FIG. 2. Dynamite and GelatinDynamite Manufacture.

as "mixeddope." This mixturecomes fromwhat is knownas the "dopehouse,"
whereall the dry non-explosiveingredients,called forby the dynamiteformula,
have been mixed and screened. This mixtureis likewisetransported to the
mixinghousesin the required amount.
The mixingvesselordinarilyconsists ofa circular woodenbowl or trough
The bottomof the bowlmay
about 7 feet in diameter and less than 2 feet deep.
be coveredwith hard rubber. The mixing device consists oftwo large wood en
wheels,preferablyrubber-covered, which operate on theedge-runnerprinciple.
Whena mixingis to be made,the "dopes"are emptiedinto the mixingbowl
and levelled,and the nitroglycerinis poured from the buggy over the top of the
dopes by meansof a rubberhose. The mixingwheels are thenstarted, two hard
rubber plowsfollowingthe wheels,one serving tomovematerial from the inside
of the bowlunder one wheelwhilethe other plowthrows the dynamitefromthe
outside edge of the bowl under the other wheel. Between5 and 10 minutesis
ordinarilysufficient mixingtime. Mixings of around 1,000 pounds of dynamite
are commonlymade at one time.
Cartridgino, The mixeddynamiteis usually ofa dry, powderynature and
is transportedin barrowsto the cartridgingor punching house.Here it is
 124t
cylindricalpaper shells,opennt one end of nny (legireddinmeter
intopreformed,
inch up, and ordinnrilyabout 8 inchegin length. monngof *peeinl
the dynatniteis packedto the desireddensityin the paper cartridge,
machines, end of the cartridge is crimped
nd the open down tightly. Whilen gtnnclnrtl
cartridge is 8 inches long by 1% inches in dinrnofer,the
site of (bmatnite
be as large ns 7 inchesin diameterby 24 inches inlength. The
cartridges may
packedin woodenboxesfor shipment.
sticksarecartridgcd
The dyn,nmitemay be protected from moisture penetration, if
necesary,by coating Mith pnrnmn.
Gelatin Dynamites—Themanufactureof gelatin dynamites includes both
operationsdescribed under the non-gelatinousdynamites, but, with different
and one additionaloperation: gelatinization.
ty1esof equipment,The
Gelatinization. essentialdifferencebetweengelatin dynnmites and the
non-gelatinouscomes in the introductionof nitrocottoninto the nitroglycerin in
thegelatins. This forms a viscousliquidwhichgivesa plasticrather thanpow-
deryproductwhenmixed with thedry, non-explosive ingredients.
The gelatinizationoften takes place in what is knownas a figure8 bowl,
theshapeof whichinsideis evidentfrom its name. Two sets of bronzepaddles
rotateat oppositeends of the vessel sothat thoroughincorporationof ingredients
take place. After introductionof the nitroglycerininto the bowl, the
weighed amount of nitrocotton isadded to the nitroglycerin.Dynamitenitro-
cottonordinarilyhas a nitrogencontent of around 12.25%. With the nitro-
glycerinand nitrocotton in the bowl, the agitationis started, while thebowl is
maintained at a slightlyelevatedtemperatureby water-jacketing control. Five
to eightminutes will ordinarily give a
satisfactorilygelatinizedproduct.
Miring. The mixingoperationfollowsgelatinizationimmediately inthe same
vessel.The "mixeddope," or mixtureof dry non-explosive ingredients,is intro-
ducedinto the bowl with the liquid mixture. After mixing forperhapsanother
fiveminutes,the gelatin isremoved from the bowl. Instead ofa powderymix-
ture, it is now a plastic putty-like
product, incapable
of free flow,but capable
of being pressed
into any desired form.
Cartridging Gelatin dynamite, like the non-gelatinous product, is packed
intopreformedcylindrical paper cartridges.Instead of beingpressedor tamped
intothe cartridges,however, itis packed in by means of a metal
worme.xtruding
device,operatingunder slightpressure. The open end of the shell is crimped
downafter the cartridging operation.
Types of Dynamites—Thereare two conditions which must be satisfiedif a
dynamiteis to prove satisfactoryin blasting service.First, it must have the
safetypropertiesthat allowit to be used without hazard, and, secondly,
it must
be adaptedto the type ofblastingin question. Becauseof the many and varied
kindsand hardnessesof materialto be blasted and the different uses to which
the explosivesare put, a great numberof types and brands of dynamite have
beendeveloped. See Figure 1,
StraightDynamites. The straight dynamitesare the simplest type of dyna-
miteand may be definedas high explosivescontainingnitroglycerinas the sole
explosive
ingredient, sufficientamount of absorbentmaterialbeing present to
preventexudationofathe
1242 INDUSTRIALCHEMISTRY
The straightdynamitesare the basis ofcomparison, as to strength,
Other dynamites.They are made in a series from 15 to 60%, each for
designated by itsnitroglycerincontent. For example,40% straight gradeb •
contains 40%nitroglycerin. Other types ofdynamitesare designated dynarnite
60%, etc., whenthey have the same strength by ballistic mortar determination

FIG. 3. Pipe Line CrossingDitch Blast in Orderto Lay Pipe Below Bed of River.
as the correspondingly
namedstraight dynamite. The standard 40%straight
com-
dynamiteused in testsby theU. S. Bureau of Mineshas the following
position :
Nitroglycerin 40%
Sodium Nitrate 44
Wood Pulp 15
Calcium Carbonate
The straight dynamitesare characterizedby high velocityof detonation(over
13,000 feetper secondfor 40% straight, for example) and a high degreeOf
sensitivenessto propagation.Becauseof this latter property,they are excel-
Jentlyadapted for usein submarinework and ditch blasting,wherethe explosionOf
from one stick of dynamiteis propagated successivelyto a large number See
other sticksseparatedfromone anotherby distancesof perhaps18 inches•
Figures3 and 4. Becauseof the relativelyhigh sensitivenessto friction,straight
where
dynamitesare not recommended for quarryingand generalblastingwork,
other types
 EXPLOSIVES 12
I)vnnmitcs. The nmmonindvnnmites Are dynamites in which
of the strnightdynamiteshas beenreplncerlby am-
of the nitroglvcerin
m nitrate.
nonill and their relativelylowprice. They are put out in the•amestrength
as the straight dynamitebut are lower in voloritythan tha strnichtg
grade. The mnmonindynamitesare attractive for use because ot
for a given

FIG.4. RemovingTemporaryDam in HydroelectricDevelopment.

theirinsensitivenessto shock and frictionand their lack of inflammabilityin
comparisonto the straight dynamites. They have one drawbackin that they are
low inwater resistanceso that they are not welladapted for use under
relatively
very wet conditions.
Gelatin Dynamites.The gelatin dynamitesare those in whichthe nitro-
glycerin has been at least partly gelatinizedby meansof nitrocotton. The
higheststrength gelatin is "blasting gelatin,"which is considered thestrongest
industrialexplosive known.It usuallyhas the approximatecomposition:91.5%
nitroglycerin;8% nitrocotton, 0.5% calciumcarbonate. Blasting gelatin is a
solid,light-colored,elasticmaterial,too adherentfor mixingwith other materials.
Thecomrnongelatin dynamitesare madeby the use of a lowerratio of nitro-
cottonin nitroglycerin, so that a thick, viscousliquidis obtainedrather than a
solidmass. The other usualingredientsof dynamitesare nxi.xed with this viscous
liquidor gel. Both straight and ammonia gelatins are made, depending on
Whether nitroglycerinaloneis the explosiveingredientor anuuoniutnnitrate has
replaceda part of the nitroglycerin.
Thegelatindynamitesare designatedby strengthmarkingsalso,as 40%,
1244 INDUSTRIALCHEMISTRY
etc. They are outstandinglyexcellentwith respect to four properties:
they possesshigh bulk density; (2) they are the most water-resistantof all
dynamites; (3) they excelfromthe point of viewof fumes; and (4) they donot
in holesinto whichthey have been loadedbecauseof their
flow, but stick well
plastic nature. These properties,in additionto their relative insensitiveness
to
shock, make the gelatin dynamites the preferred explosive for use under wet
conditionswhere a high loadingdensity is desired,as in hard rock blasting,in
blasting underground inconfinedworkingswheretoxic fumeswouldbe dangerous
and in boreholesdirectedupwardlyin hard rock. Becauseof their relativelyhigh
price, the gelatin dynamitesare replaced frequently by other explosivesof
slightly less efficiency.
Setni-Gelatins. The so-calledsemi-gelatinsare ammonia dynamiteswhich
are intermediatebetweenthe ammoniadynamitesand the gelatinsin the proper.
ties of density,plasticity,and water resistance.
Permissibles. The "permissible"dynamitesare high explosivesadaptedto
a specialuse, namely,in gassycoalmines,whereblack powderand the regular
dynamitesare not considered safe inthe presence ofthe inflammablegases.A
"permissible"may be defined as anexplosivesimilar inall respectsto a sample
passingcertain prescribed testsof the U. S.Bureau ofMines,when the explosive
is used under the conditionsand in the amounts prescribed bythe Bureau. The
Bureau of Minesissues periodically a list of active permissible
explosives,all of
which have passedthe official tests.The Bureauhas no authority to enforce
the sale and use of "permissibles,"but its stamp of permissibilitycarriesgreat
weight.
The firstpermissiblelist wasissuedin 1909by the technologic branch ofthe
U. S. Geological Survey, subsequentlythe Bureau of Mines. This list included
17 authorizedexplosives.The list of active permissibleexplosives published in
December 1937 included196 differentexplosivessold by 15 different explosive
companies.
The permissibility tests of the Bureauof Mines17include severalspecialde-
terminations of properties whichaffectthe suitabilityof the explosivefor usein
coal mines. One suchtest is the determinationof the "unit deflectivecharge/'
that is, the weight of
the explosiveunder test whichwill give a deflectionof the
ballistic mortar equal
to that producedby 1/4pound of the standard 40% straight
dynamite. Tests are alsomadein their specialtesting galleryto determinethe
degree ofsafety of theexplosivewhenfiredin the presenceof inflammable gases
and of coal dustrespectively.A specialtest is made for fumesalso,and per-
missiblesare classified accordingto the content of toxic gases (carbonmonoxide
and hydrogensulfide)in their gaseousdetonationproducts.
The most generally usedpermissibles today contain (1) a high percentageOf
ammonium nitrate, in the neighborhood of 80%; (2) a relativelylow percentage
of nitroglycerinas sensitizingagent; and (3) fibrous combustiblematerialfor
utilizing the excessoxygenof the ammoniumnitrate absorbingthe nitro-
glycerin. Black powderis admirablyadapted for use inand down coalas far
blasting
as its blasting actionis concerned,but it is not safe in gassy mines. Its blasting
action characteristically bringsdowncoalin largelumps rather than shatteringit
17Munroe,C. E. and Tiffany,J. E., "Physical
of Mines ExplosivesExperimentStation," Testing of Explosivesat the Bureau
U. S. Bureau of Mines, Bulletin 346
 EXPLOSIVES 1245
and detonating
fine fragments, in its heaving permissibleshave boon developedwhich
powder action by attainment of very low velocities
approachblack density by various expedients.
d very low type of permissiblehas been introducedwhich is more suitable
A gelatinous
wet conditionsof blasting. This type containsa highernitro-
for use under
glycerin contentthan the usual permissible,a smallpercentageof nitrocotton,and
lower contentof amtnonium nitrate.
a MiscellaneousDynamites—Inadditionto the importantgeneral typesof
dynamites, a great many special kinds have been developed,intended par-
kinds of work. The types of dynamiteare similarto those
ticularlyfor specialNo attempt has been madehere to describethe methodsof
alreadydescribed.blastingexplosives, in the pub-
as this is adequately covered
useof commercial'a
lishedliterature.l

COMMERCIALHIGH EXPLOSIVESCONTAININGNO NITROGLYCERIN

AmmoniumNitrate Explosives—The logical extensionof the trend toward
the replacement of nitroglycerin dynamites by ammonium nitrate wouldbe to
replacethe nitroglycerinentirely. This idea is not new in the industry;
explosives
manyformulashave been prepared over a long period of years embodyingthe
combination of ammonium nitrate having an excess of oxygen, with an oxygen
deficientbut non-explosivesensitizing agent.However, ammoniumnitrate is a
highlydeliquescentsalt, and mixturescontaining it tend tobecome hardand
and incapable of propagating theexplosion afterexposureto
insensitive,
moisture.
Anewtype of blastingagent of thisnature wasintroduced in1935 designated
"Nitramon,"which possessesa degreeof insensitivenesssuch that itis incapableof
detonatingunder the influenceof a blasting cap. When onceinitiated by a
suffcientlystrong booster charge,however, thematerial is capableof propagating
theexplosion indefinitelyat highand undiminishing velocitywhen usedin large
diameters.The disadvantagesof moistureeffectare overcomeby having the
materialenclosedin a waterproofmetal container. A numberof suchcans of the
material,for example, 7inchesin diameterby 24incheslong, are loaded into
large-diametervertical quarry holes. (SeeFigure5.) The explosion propagates
throughthe metalends of the cansat velocitiesaround16,000feet per second.
to impact,friction,and shock,it is the safest high
Becauseof its insensitiveness
velocityagent yet introduced.
Nitrostarch Explosives—Nitrostarchis a solid, white explosive material
by nitration ofcornstarchor cassavastarchby means of practically
Obtained
anhydrous mixedacid. The nitrated productis drownedin an excess of water,
washedthoroughly,neutralizedwith dilute sodiumcarbonate solution, and dried,
firstby wringing,then in hot-air driers. The commercialnitrostarchis mainly
starchtrinitrate and ordinarilycontainsslightlybelow13.0%nitrogen,as against
a theoreticalcontent
of about 13.3%.
Nitrostarchis used in commercialhigh explosivesin Americato a limited
extent. Sinceit is a solidexplosivematerial, no freezingcan take place. Am-
LaMotte, A., editor, "Blasters' Handbook," describingpractical methods of
usingexplosives
for variouspurposes,E. I. du Pont de Nemours& Co.
 1246 INDUSTRIALCHEMISTRY
monium nitrate is commonlyincluded in considerableamounts in nitrostarch
explosivecompositions.Nitrostarchhas had some applicationin military
plosives.
Chlorate Explosives—Explosivescontainingsodium or potassium chlorate
have been made for wellovera centuryand periodicallyattract, renewedatten_
tion. The earlierchloratepowdersweredry mixturesof chloratewith oxidizable
materialssuch assugar, charcoal,sulfur,etc. These mixtures were all highly
to frictionalilnpact. Sooneror later their manufacture
inflammable and sensitive
usually ledto disastrousresults. More recently,chlorate explosiveshave in.

FIG.5. QuarryBlast at Instant ofExplosionof a Chargeof Nitramon.

material,and suchmixturesare less
eludeda liquidingredient, ora desensitizing
chlorateexplosives
sensitive. In spite of thecheapnessof raw materials, however,
have not provedvery attractive.
Liquid Oxygen Explosives 18—Liquid oxygenexplosivescomprisecarbona-
ceous absorbent materials saturated with liquid oxygen. Theoretically,such
to carbondioxidecompletely,
explosivesappear very attractive, as carbon burns
if sufficientoxygenfor combustionbe present,and the explosiveis entirely
consistingusually
gasified. In making liquid oxygen explosives, the cartridge,
of lampblackor other carbonblackpacked ina porouscontainer,is first pre-
pared. This cartridge isdipped into abath of liquidoxygenand allowedto
becornesaturated.
explosivesare of high strengthand velocitybecause
Potentially,liquid oxygen
of the composition,and this is actuallythe caseunder favorableconditions
There is the disadvantagethat liquidoxygenevaporatesvery rapidly, so that
Of
Perrott, G. St. J. and Tolch,N. A.,"Liquid OxygenExplosives,"U. S. Bureatl
Mineg,Bulletin 349
 EXPLOSIVES 1247
an explosive cartridgeis relativelyshort. Also,thn strengthis not
thelifeof
because of the steady loss of oxygen. A further disadvantagecomes in
cons•tant
sensitivenessto shock of liquid oxygenexplosives,a serious considera-
the high operations.
in quarrying Explosive Devices—Mention
tionMiscellaneous shouldbe made of a type of
devicewhich has had some popularity, and which does not depend
blasting effectivenesson the oxidationof combustible materials to
primarilyfor its One such device, whichhas been applied in the mining of
gaseousproducts. the use of a confined
coal,is basedon supply of liquidcarbon dioxide,19 together
composition, adapted to be ignited at the proper time andto exert
witha heating effect by converting
the desiredblasting the carbon dioxide to the gaseousstate.
Thereal novelty comes inthe use of a specially designed cartridge constructed
a closingdisc which will rupture when the pressure exceeds apredetermined
amount. A later development uses the same general type cartridge,but brings
aboutthe rupture of the disc and the release of pressureby the use of compressed
air froma portable compressor.
A blastingdevice for use in coal has also been introduced, consisting
of an
tube of particular,designoperatingunder hydraulicpressure.20
expansible
Allthesemechanicaldevicesyield a goodgrade of lump coal, but theirultimate
valuemust still be determined.

INITIATINGDEVICES
After nitroglycerinbecame available as anexplosive compound, itshigh
explosiveenergycould not be utilized satisfactorily until Nobel had devised and
introduced into practice a form of blasting cap. . It was then realized that,
whereasa simple flame was sufficient to the
initiate explosionof black powder, the
effcientdevelopmentof the strength of nitroglycerinexplosivesresulted only
wheninitiationwas from thepowerful influenceof a detonatingmaterial.
A group ofcompoundshas been developedwhichare peculiarly adapted for
explosivesof the dynamitetype. Suchmaterialsare
usein initiating detonating
as primarydetonatingcompounds.The secretof their effectiveness
designated
comesnot in their high temperature of explosion,or the volume of gasproduced,
butin the fact that theyattain their high velocityof explosionwith extreme
rapidityafter initiationby a flame. As a matter of fact, the most effective
primarydetonatingcompoundsare characterizedby small volume ofgas forma-
as are most of theexplosive
tion,andare not nitrates or nitrated compounds,
materials.
MercuryFulminate—Mercuryfulminate,(CNO)2Hg,has long been a very
primary detonatingcompound.It is commonlyused witha smaller
satisfactory
amountof an oxidizingagent such as potassiumchlorate. It is made by dis-
solvingmercuryin a large excessof 68% nitric acid and addingthe solutionto
95%alcohol,with arrangementsfor controllingthe temperature. The reaction
sooncausesthe solution to boil spontaneouslyand vigorouslyand mercury
fulminateprecipitatesin the boilingflaskas a finewhite powderof high density.
Tiffany,J. E., "A New PermissibleBlastingDevice,"U.
Portof
S. Bureau of Mines,Re-
Investigations 2920 (1929); Hart, E., Colliery Eng. 15, 373-377(1938).
20Mining Congr. J. 26,39-41
1248 INDUSTRIALCHEMISTRY
One economicdisadvantageof mercury fulminatecomes in the high price
mercury and thefluctuafionsin pricebecauseof the uncertainsupplies. Spain
is the principalsourceof mercuryores. has becomefully as
Lead cotnpound,l'bNd, importantas
compound in the last few Years. Tth
fulminateas n prinnry detonating top charge because
disadvantageof requiringn stnallignition of its relative
insensitivenessto fimne,in contrastto mercury fulminate. Ilowever,it picks
more rapidly than fulminate, hence a smallerweight
to its maximumhigh heavier fulminate charge.
charge have the detonatingeffectof a raw materials.
An addi«
tional advantageliesin the ready availabilityof the It is madeby
W'RC

SHCU

bR/DGe w,'RZ

CHAMece

capsvzz ..cowæe
DELAY
oa,4YmwotR
BASC CHA
CHARGE

czarcrR/C
REGULAR ORDINARY
a,4S7/N5 CAP BLASTINGCAP

DELAYELECTRIC
CAP
BLASTING
FIG.6. Three Types of BlastingCaps.
the reaction of sodiumazidewith a solublelead salt. Sodium azidein turnis
derivedfrom sodamide(frommetallicsodiumand ammonia)and nitrousoxide.
Other Primary Detonating Compounds—While mercuryfulminateandlead
azideare the two most widelyused compoundsof this nature, other materials
are also employed;for example,diazodinitrophenol, obtainedby reacting concen-
traced nitric acid with picramicacid or a picramate in the presence of alcohol,and
mannitolhexanitrate,a nitrationproduct of the polyhydricalcohol,mannitol(see
compound106,Chapter 27).
Blasting Caps—blastingcaps are smallcylindricalmetal shells,usually about
% inch in diameter by 2 inches long. These shellsare of copperor aluminumand
containa detonatingchargeof explosive. Mostblastingcaps are of the com-
pound type and contain a fraction of a gram of a base charge at the closedend
of the shell, a charge of a primary detonating explosive upon the base charge'
followedby a more readilyignitabletop charge if necessary.Mercury fulminate
and lead azideare the most commonly used primarydetonatingcharges,while
tetranitromethylanjline(tetryl) js an excellentbase charge. Blastingcaps are
usedfor initiatingthe explosion of dynamitesand are insertedinto the explosive
at thetime of use,
Three typesof blastingcaps are employed,the first twodifferingby the method
of firing, Sce Figure 6, In the caseof ordinaryor fuse caps,a length of
 EXPLOSIVES 1249
inserted into the open end of the cap and the metalwallig crimpodAbout
fuse is In use, the end of fuse away froth the cap is lighted,nnd the epitof
fromthe fuse wit,hinthe cap fires the ignitionchargeand brings about
The secondtype of cap is firedelectrically,21 the two lending wireg
detonation. within the cap by a fine wire of high electricalresistance. When
beingconnected
current, passes through the wires, the finebridgewire becomesheated
electric and fires the ignition charge. A third type, designatedas a
to incandescence
is ordinarily fired electrically, but contains a delay chargeof a slow
delaycap, which is inserted in
burningcomposition the cap so that the detonation of the cap
take place after a definite time interval. By the useof delays,the
chargewill a cap will fire,
timeinterval before after application of the current, canbe varied
from0 to 15 or 20 seconds. Recently, delays have been improved by the use as
delay compositions of charges which give off practically no gas on combustion;
for example, mixtures of a combustible metal with an oxidizingagent. This
permitsthe employment of ventless caps, so that moisture penetration is pre-
vented, as well as excessive gas pressure variation in the cap previous to firing.
squibs—Whendeflagratingexplosivessuch as black powder are used, the
simpleapplicationof flame issufficientfor firing. This is done by using devices
similarto blastingcaps, exceptthat theycontainno detonatingexplosive,hence
explodelessviolently. Preferably, electricsquibsare used and the construction of
theseis similarto that of electric blasting caps,exceptfor the nature of the ex-
plosive charge. Squibsmay be in metal orcardboardtubes, and may be either
openor closedat the firing ends.
Fuse—Twotypes of fuse are in general use in blasting. Safety fuse is em-
ployedfor initiating caps or squibs where electrical firingis not used. Safety fuse
consistsof a small-diametercore of black powder, enclosed in a covering wrapper
of various waterproofed fabrics. It is made to have an approximate burning
speedof 30or 40 secondsper foot. When fuse is used to fire a shot in blasting, a
suffcient length isused so that ampletime is allowed for the shot firer to reach
a point of safety.
Detonatingfuse, on theother hand, has a velocityof detonation of over 5000
meters persecond (16,500feet). It is used principallyfor explodingcharges of
explosivesin deep holes. The usual detonatingfuse, calledCordeau,consistsof a
chargeof high velocity explosivesuch as trinitrotoluenecontained in a small-
diameter leadtube. The line of Cordeauis in contactwith the chargethroughout
its length,and thus causespractically instantaneousdetonation of the whole
charge,regardlessof its velocity. A more recent type of detonatingfuse com-
prisespentaerythritoltetranitrate containedin a non-metallicwrapping. The
velocityof this fuse is about 7000metersper second(23,000ft.).

SPORTINGAND MILITARYEXPLOSIVES
The explosivesdiscussedin the precedingparagraphshave been almosten-
tirelythoseintendedfor use in commercialblasting. In additionto such ex-
plosives,
the explosivesutilized for sporting and military purposesconstitute a
21
in Mines,
Tunn\kl'th'J
 1250 INDUSTRIALCHEMISTRY
though normallyof less
group whichis of very great interestchemically,
portancethan the blastingexplosives.
propellentexplosivesare meant the explosives
Propellent Explosives—By as well as propellantsfor
used in firearms,both rifleand shotgunpowders,
well be used in designatingsuch
tary use. The ternl gunpowdertnight
pellants,but this word has been too long identifiedwith black powdertoprosb
other meaning. The here
propellants discussedwill be what are corns
given any a nitrocellulosebase.
monly known as smokelesspowdershaving Nitrocellulosewas sug_
Smokelesspowderhas had a gradual development. until the work of Vieillein
at an early
gestedfor use in explosives date, but not
France, about ISS6,when he showedthat the formation of nitrocelluloseinto
densecolloidalformallowedcontrolof the rate of burning, was there any marked
successin its promotion. Two reasonsexisted for displacing the older black
powderby a propellantsuch as a nitrocellulose powder. First, the densecloud
of smokeresultingfrom the explosionof black powderwas very objectionable
particularlyin militaryuse. Secondly,there was a demandfor increasedenergy
per unit volumeof propellant. The utilizationof nitrocellulosein simplefibrous
or compressedform was impractical,however,becausethe highrate of pressure
developmentwouldburst the gun. Nitrocellulosehas the advantageof raw
materialsthat are of widedistributionand highavailability. Cotton is the most
suitablesourceof cellulosefor use, and the ordinaryform employedis cotton
linters,obtainedfrom the cottonseedsas a secondcut, after removalof the long-
fiberedcotton and the first cut of lint. Woodpulp is another possiblesourceof
cellulosefor nitration,and has beenwidelyusedfor militarypurposesby coun-
tries shut off fromcottonsupplies. The nitration procedurefor nitrocellulose
has
been outlinedpreviously.
Smokeless Powder22—Nitrocellulose may vary rather widelyin composi-
tion, as shownby the nitrogencontent. This in turn means a variation in poten-
tial, whichis an importantconsideration in smokelesspowdermanufacture.
Assumingthe simplified,but hypotheticalformula CGI-11005 for cellulose,the
trinitrate wouldcontain14.14%nitrogen. The nitrocottonsof interest in con-
nection with smokelesspowdercontain between 12 and 13.4% nitrogen. Pyro-
celluloseor pyrocotton, an important type forsmokeless powder,contains between
12.5 and 12.7%nitrogenand is solublein a 2 to 1 ether-alcoholsolution;gun-
of 13.0 to13.4%, isinsolublein the ether-alcohol
cotton,with a nitrogen content
mixture; dynamitenitrocotton, witha 12.25%content, isused in gelatindyna-
ts
mites whereit isgelatinizedby nitroglycerin;nitrocelluloseof nitrogenconten
such as lacquers, plastics, fabrics,etc•
below 12.3%is used for non-explosive outlets
Manufacture of Single-BasePowders—Theterm "single-basepowder"
is the sole nitric
designatesa type of smokelesspowder in which nitrocellulose
ester. This is the typeof powderused by the UnitedStatesArmyand Navy,
The processinvolvedin the manufactureof single-basenitrocellulosepowders
may be considered under(1) dehydration,(2) mixingand colloiding,(3) pressing
and graining,and (4) solventrecoveryand drying.
; S'
22Marshall,A., "Explosives,"secondedition, Vol. 1,p. 289,Blakiston (1917)Storm'
War Dept., "Military Explosives,"TechnicalManual No.9—2900(1940);
C. G., "SmokelessPowder,"in Alexander,J., "Colloid Chemistry,"Vol. 4, P'
ChemicalCatalog Co.
 EXPLOSIVES 1251
After the wringingof the purifiednitrocotton,the material
Dehydration.
content of '25to 30%, in whichwet,condition it isentirely safe
stillhasa water
Thedryingof this materialby warmair currents ontrays wouldbe
tohandle. on a largescale,becauseof the static susceptibilityof dry nitrocotton.
hazardous therefore,dehydration takes place by displacingthe water with
In practice, followingstep in the process treating the nitrocotton
alcohol.Sincethe solution,the presenceof theinvolves alcohol brings in nodifficulties.
withan ether-alcohol
1.25 pounds of 95% alcoholare used per poundof dry nitro-
Approximately
of the aleoholbeingby meansof a hydraulicpress.
cotton,the introduction
Colloiding. The dehydrationoperationleavesthe nitrocotton in
Mixingand
theformof a compressed block wet with alcohol. This isbrokenup and intro-
ducedintoa mixing machine, where the materialis kneadedby two sets of agita-
tionbladesrotating in opposite directions. The nitrocotton hereis to be col-
loided by the ether-alcohol solution containingtwo parts of etherto one of alco-
1101,the total weight of solvent being approximatelyequal to the weightof the
drynitrocotton.Before additionof the ether, diphenylamineis dissolvedtherein
in an amountsuch that about 1% will be present in thefinishedpowder. The
etheris quicklypoured into the mixer,whereit blendswith the alcoholpresent
andthe contentsare agitated for aboutan hour.
Thediphenylamine is added to the ether duringthe mixingoperation inorder
thatit may be intimately distributed throughout the blend, so that nitrogen
any
oxidedecomposition products which may be developed during years ofstorage
wilreactwith this stabilizer and thus be removed.
Pressingand Graining. The colloidalsmokelesspowder is now ready for its
finaltreatment. A dense cylindrical mass is formed first by compression of the
material in a cylinder by means of a hydraulic pressexerting a of
pressure around
3000 poundsper square inch. The blocks arethen grainedby forcing thematerial
through diesprovidedwith pins undera pressure ofseveral tonsper square inch.
Thestrandsof powderare perforatedas they passthrough the dieand then are
guided to mechanicalcutters. Cannonpowdersin the United Stateshave seven
longitudinal perforations,one in the center surroundedby six others. Powders
forsmallarmshave only one smallcenterperforation. The object of the per-
in the powder isto obtain a progressiveincreasein the area of burning
forations
duringcombustion. The smokelesspowderin its final form is actually a
surface
of variablesize,dependingon the type of weaponin which it is to be
cylinder
used.Cannonpowders inthe UnitedStateshave a lengthabout 21/4 times their
diameter
and are of considerablesize, whilevarious powders for smallarms are
ofverysmall diameter.
SolventRecoveryand Drying. The solventrecoveryprocess is adapted for
Partialdryingof the "green" powder,with recovery ofwhatever alcoholand ether
aregivenoff. The dryingis a continuationof the solventrecovery step except
thatin the secondstep, solventis removedbeyondthe point where its recovery
ISjustified.Precautions aretaken that the removalof solvent is not rapid
enough to causedistortion of the powder grains.
RecentImprovementsin Nitrocellulose—Thelast fewyears haveseen the
rmProvementof the nitrocellulosetype of propellentpowder as used by the
UnitedStates,particularly in two respects. First, the hygroscopicity of the
Powderhas been reduced byusing nitrocelluloseof higher nitrogen
 1252 INDUSTRIALCHEMISTRY
by non-volatileand non-hygroscopic
replacinga portionof the nitrocellulose
in many
solvents. Secondly,flashlessnesshas been obtained guns by the
of compositionsof suitable potential which are in themselves flashlessor b
the use ofsupplementalflash suppressingsalts. This means that muzzle flash,due
to the icnition of highly combustiblegaseousproducts issuingfrom
the gun,has beenpreventedfrom taking place,thus eliminatingthe usuallarge
luminousmuzzle flashwhich is visible for many miles. This is an important
consideration inmilitary operations.
Manufacture of Double-Base Powders—Thesepowdersdifferbecauseof
the fact that, instead of containingnitrocellulose alone as explosiveester,they
contain both nitrocelluloseand nitroglycerin. A well-known exampleof this type
powder is the BritishCordite. M. D. Cordite contains30% nitroglycerin,657
guncotton,and 5% vaseline. The nitrocottonhas a nitrogencontentof at least
13%, hence is difficultly solublein an ether-alcoholmixture. Consequently,ace.
tone is usedas solvent. The vaselineacts as stabilizerand coolingagentin the
powder, as it has atendencyto lowerthe temperatureof explosion.
The Italian Ballistite is anotherpowderof this double-base type, but contains
a nitrocelluloseof about12%nitrogencontent,solublenot only in an ether-alcohol
solvent, but also innitroglycerin. This type of powder, which containsequal
parts of nitrocelluloseand nitroglycerinplus 1% of diphenylamine(see com_
pound 239, Chapter27), is made on rollswithout the use of acetoneor any other
volatile solvent.
The nitrocellulosetype of smokelesspowderpropellanthas been usedby the
United States, Russia,England,and France. The nitroglycerintype of propellant
is used byGreat Britainand Italy. Germanyis said to have used to a largeex-
type in their army and the nitroglycerin
tent the nitrocellulose type in their
navy.
DISRUPTIVEEXPLOSIVESFOR MILITARY USE

The explosivecompoundsup to this point have beenmainly nitricesters of

aliphatic alcoholsand carbohydrates. These compoundsare not ordinarily suit-
able as burstingchargesfor firingshellsand other military devicesbecauseof
too great a sensitiveness to shock. The aromaticnitro-compounds are generally
better adaptedfor this purpose.
Trinitrotoluene—Thisexplosivecompoundis prepared by the nitrationof
toluene,an aromatichydrocarbonderivedfrom coaltar, or obtainedsynthetically
from petroleumproducts. The nitrationprocedurehas been discussedpreviously.
TNT, as it is called,is the most widely usedshell-firingexplosive,and is well
suited for loadinginto containersbecause ofits lowmeltingpoint of 80.80 C. Its
importancefor military usecomes from itscomparativeexcellencein the follow-
ing respects: (1) it is a safeexplosive inmanufacture,transportation, and storage,
(2) it is non-hygroscopic, (3) it has notendencyto form unstablecompounds
withmetals,yet (4)it is a violent, disruptive explosive.
Amatol—Amatol is an explosive mixtureof TNT with ammonium nitrate'
developedduring the First WorldWar. A 50-50mixture ofthe respective ingredi-
ents is sufficientlyfluid to allowcasting,but an 80-20ammoniumnitrate-TNT
mixturewas subsequently found suitable for loadinginto shellsby an extrusion
process. It was developed becauseof the imminentshortageof toluenefor
 V,XPLOSIVF.S 1253
yenrs of the war. Actually,such mixturesare, in some
duringthe early on TNT by itself. TNT is deficientin
an on explosion
is not and black The
products tnay include,enrbon, carbon monoxide,hydrogen and
detonation of further
methane,all TN"I' assuresalmost nn evenlybalanced compositionwith re-
nitratewith '20% resultingincreasedstrengthand improvedfumes. Compared
ct to oxygenwith
TNT, amatolhas the disadvantageof beinghygroscopic.
to Tetryl—-Tetrylis the name commonlyapplied to tetranitromethylaniline (see
328, Chapter 27), or more properly, trinitrophenylmethylnitramine.
compound nitration of dimethylaniline(see compound 231,Chapter 27),
It is madeby the point of around 1300C.
melting
andhas a

I N02
I xcH3
cyl 02N—C C—N02
NC)3
I + '261-1 + 5C02 + 281-120+ 3N2
TIC

11 N02
Dimethylaniline Tetryl
(5 mols)
(5 mols)

Tetrylhas a very importantuse in commercial explosivesas a base chargefor

blastingcaps. In militaryexplosives, it is too sensitivefor use as a main shell
fillingcharge,but is well suited for use as a •boostercharge,intermediatebetween
the sensitiveignitionchargeand the main burstingcharge.
Picric Acid—Chemically,picric acid is trinitrophenol(see compound330,
explosive.
Chapter27). It has had considerableuse as a shell-filling
OH

ON—C C—N02
I + 3HN03 + 3H20
Il—c CAI

N02
Phenol PicrioAcid
It hasa meltingpoint ofabout 1220C. Oneobjectionablecharacteristicof pierie
acidigits tendency,as an acid,to formmetallicsalts or picrates,whichsalts are
unfortunatelydangerously sensitive.
AmmoniumPicrate—Ammonium picrate is the salt formedby neutralizing
picricacidwith ammonia. Its relativelack of marked tendencyto form sensitive
metallicpicrateswhen in contact with metalsgivesit an advantageover
 INDUSTRIALCIIF,MISTRY
acid. It is not altogetherfree from thig tendency, however. Ammoniumpierate
is claimedto be the least,sensitiveto shockof all explosivesused as shellbursting
charges. However,it is inferiorto TNT in strength.
Pentaerythritol Tetranitrate—Thisexplosivecompoundhas cometo be
portant since the FirstWorldWar, and owesits ntffr,qetivcness partly to the fact
that it is obtainedfrom raw materials of altnost universtll
occurrence. Thismakes
the compoundof particular interest to those nations whichwish to becomeself.
contained. Pentaerythritoltetranitrate, or PETN, Inelts at oround 1410C. It
is obtained by thenitration of the irregulartetrahydric nlcohol,pentaerythritol
which inturn is prepared by the condensationof formaldehydewith acetaldehyde.
(For a description of such condensationreactions see Chapter 2, The Unit
Operations.)
C112011 CT120N02
CT12011 —C1120N02 + 41120
c + 411N03 C CH20N02
CH20T1 \CT120N02
Pentaerythritol Pentaerythritol
Tetranitrate
Trimethylene Trinitramine—Thisis another post-war highexplosivecom-
pound, frequentlydesignatedHexogenin the literature. Like the precedingex-
plosive,it is attractivebecauseof the widely-occurring raw materials. In this
case, theexplosive isobtainedby the nitrationof hexamethylenetetramine,com-a
pound obtained fromformaldehydeand ammonia. Theraw materialsin thiscase
give Hexogengreater promisethan PETN, but the yields obtainedare said to be
suffcientlylowto offsetthat apparentadvantage. Hexogenhas a melting point
of 200-201 0C.

N02
C112
H2C I CT12

CH2 + -+ + 61120+ 3C02+ 2N2

02N—N N—N02

c 112
112
Hexamethylene Hexogen
Tetramine
HANDLING
ANDSTORAGE
OF EXPLOSIVES
Becauseof the potentialhazard when explosivesare present,some generally
accepted rules are observedin their handling andstorage. The basic principles
underlyingthese rulesare that (1) explosivesshould be treatedwith respect,(2)
they should be handledonly by those experienced orproperly instructedin their
positions
use, and (3) they shouldbe storedunder favorableconditionsand at endanger
sufficientlyisolated that accidentalor malicious explosionwill not
personsnot directly concerned with their
 EXPLOSIVES 1255
In the case of nitroglycerinexplosives,the unwrappedexplosiveshouldnot
unnecessarily,sincethe
behandled contact with nitroglycerinor nitroglycerinheadachemay result
from
bodily other liquid nitric esters, or from
vapors. This does not occur with ammoniumnitrate, nitro-
breathingtheir or other solid
nitrostarch,
cellulose, explosive nitrates. The aromaticnitrocom-
a certain
poundspossess either in degree of toxicityand continuedcontact with them
shouldbe avoided, handling or inhalingtheir vapors or dust.23
For the storage of explosives in magazines there are definitelaws andregula-
tionsin the various states. A so-called"AmericanTable of Distances24has
beenpreparedwhich specifiesminimumdistancesat which magazinescontaining
explosivesshould be spaced from inhabited buildings,railroads, and public
highways, the distances increasing with increasedamountof explosivesstored.
Becauseof the care exercised in the observanceof safety rules,it wasstated
in 1937that "duringthe last 14 yearsmorethan three billionpounds ofdynamite
havebeenshipped over millionsof miles ofAmericanrailroads," and"this move-
mentof dynamitehas been accomplished withoutinjury to a person, andwith no
practicaldamageto property."

ECONOMICTREND OF COMMERCIAL
EXPLOSIVES

The accompanyinggraph shows the annualproduction figures for dynamite

andblackpowder,along with those for coal andiron ore. From this it willbe

oaaoonooaaaaoo
600
700

nmnnnunauuuzn
o

- 500
z 0400

naaunuannza—n
0 300
200

IRO
1875lago 188518901895190019051910191519201925193019351940
FIG.7. Productionof Dynamite,Black Powder,Coal, and Iron Ore in the
U.s. A. from 1875-1939.
seenthat the dynamiteindustryis a rather reliableindexto the prosperityof
thecountry. The curve for dynamiteproductionfollowscloselythat of coal and
Hamilton,A., "IndustrialPoisonsin the United Slates," p. 497,Maernillan
(1925).
&
LaMotte,A., "Blasters'Handbook,"p. 34, E. I. du Pont de Nemotlits
(1939).
1256

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 EXPLOSIVES 1257
the pulseof businessactivity; more80 than iron ore. The
is quickto registerfact
explanation of this comesin the variedUsesof dynamitein connectionwith
construction activities.
nearlyall
Theproportionof productionof the differentcommercial explosives is given
in Table 2.
inmoredetail
READINGLIST
womcs
GENERAL
Marshall,A., ' 'Explosives,"secondedition,3 vols.,Blakiston (1917-1932).
Brunswig, H., "Explosives,"Americantranslationby Munroeand Kibler,Wiley
(1912)(Second Germanedition, 1923).
'"Thorpe'sDictionaryof AppliedChemistry,"fourth edition,Vol. 4,"Explosives,"
pp. 453-562, Longmans,Green & Co. (1940).
A.,
Marshall, ' 'Dictionary of Explosives,"Blakiston (1920).
Taylor,C. A. and Rinkenbach,"Explosives:Their Materials,Constitutionand
Analysis,"U. S. Bureau of Mines,Bulletin 219(1923).
Beyling,C. and Drekopf,K., "Sprengstoffe und Zundmittel,"Julius Springer
(1936).
Stettbacher,A., "Schiess-und Sprengstoffe,"second edition,Barth, Leipzig (1932).
DYNAMITES
Naoum,P., "Nitroglycerin andNitroglycerinExplosives,"
American translation
by E. M. Symmes,Williams andWilkins Co.(1928).
LaMotte,A., editor, "Blasters'Handbook,"describingpractical methods of using
explosivesfor variouspurposes,E. I. du Pont de Nemours & Co. (1939).
Sohlman,R. and Schuck, H.,"Nobel : Dynamite and Peace," translation,
Cosmo-
politan Book Corp. (1929).
BLACKPOWDER
Guttmann,0., "Manufacture of Explosives,"
2 vols., Whittaker & Co. (1895).
MILITARYEXPLOSIVES
UnitedStates War Dept.,"Military Explosives,"
Technical Manual No. 9—2900
(1940).
Colver,E. de W. S., "High Explosives," D.
Van Nostrand Co. (1918).
Storm,C. G., "SmokelessPowder,"in Alexander, J., "Colloid Chemistry,
Theo-
retical andApplied,"Vol. 4, pp.101-116,
Chemical Catalog Co. (1932).
HISTORICAL
Van Gelder,A. P. and Schlatter,H., "History of the Explosives
Industry in
America,"ColumbiaUniversityPress (1927).
TESTING
Munroe, C.E. and Tiffany,J. E., "Physical Testing of Explosivesthe
at Bureau
Of MinesExplosivesExperimentStation," U. S. Bureau of Mines, Bulletin
346