Diazodinitrophenol A Detonating Explosive

8/7/2019 Diazodinitrophenol A Detonating Explosive

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Diazod.initropheno1, a Detonating ExplosiveL. T. CLARK

B u r e a u of M i n e s E x p e r i m e n t S t a t i o n , P i tt s b u r g h , Pa.HE 4,6-dinitrobenzene-2-diazo-l-oxide,more com-monly knonm as diazodinitrophenol, and hereafterT referred to as D D N P, is a detonating compound, theman ufactu re and use of which for charges in percussion capsand in d etonators has been th e subject of se ieral patents

(2, 5 , 0 , 12-14) issued in the United States, Germany, andGreat Britain.The so-called diazophenols, to which DDKP belongs,are in reality internal diazooxides, formed from the truediazophenols by a process of dehyd ration. Th e diazooxidesare of g reat historical interes t inasmuch a s the prepar ationof o ne member (D D S P ) of the class from picramic acid in1858 by Griess (9, 10) led him to undertake his classicalresearches on the diazo compounds.N or e recently these compounds have acquired considerableindustrial importance because the o-diazooxides furnishnumerous azo dyes which form valuable lakes with suitableacid mord ants ( 2 $ ) .

PREPARATIOXO F D D K PThe epochal discovery of the diazo reaction x a s mad e byGriess (9 ) when he prepared 4,6-dinitrobenzene-2-diazo-l-oxide (D DN P) by passing nitrous acid as a gas into an alco-holic solution of pieramic acid, He a lso obta ined DDNPfrom both ether and aqueous nitr ic acid solutions, but foundth at th e product from nitr ic acid solutions was contaminatedwith picric acid and oth er by-products. T he best resultswere obtain ed when working w ith alcoholic solutions.Schmit t ( 2 2 ) , Knoevenagel

(2) to ai d in th e rete nti on of oxides of nitrog en, an d (3) toelimina te the ha zard of explosion of t he charg e, particularlyduring the later stages of th e process.This process does not appear to be one th at can f ind readyapplication to commercial use, largely because of th e extremeprecaution which must be exercised to complete a run satis-factorily. hloreo ver, th e unused nitric acid cannot be re-covered and therefore constitu tes an appreciable loss. Severala t t e m pt s by the a u tho r t o p r epar e D D N P by th is m e thodme t with only mediocre success; hence, it was abandonedin favor of m ethods t o be described later.Some of t he numerous a nd interesting means availablefor the preparation of some of t he ot her diazooxides are asfollows: hIorg an and Porter (19) obtained 2-nitrobenzene-4-diazo-I-oxide in quantitative yield by hydrolysis in acidsolution of 4-chloro-3-nitrobenzenediazonium chloride. Thisdiazooxide was produced by a similar method by hleldolaand S tevens ( I ) , and b y Klemenec (17) from 4-methoxy-3-nitrobenzenediazonium chloride, by which means the forma-tion of a diazooxide by t he dem ethylation of a nitroanisidinederivative is brought about. Morgan and Porter (19) pre-pared 2-nitrobenzene-4-diazo-1-oxide from the 3-nitro-phenylazoimide of Friedlander and Zeitlin ( 7 ) by convertingth e azoimide into 2-nitro-4-aminophenol sulfate and trea tingthis compound in ice-cold, dilute sulfuric acid solution withsodium nit rite . T h e 3-nitrobenzene-4-diazo-I-oxide wa sobtained by Morgan and Porter (19) by the action of ethylnitrite on 3-nitro-4-aminophenol in acetic acid solution.Likewise. t h e comlnound w a s

( I h ) , and Hantzsch and David- o b t a i n e d b y t h e * a c t i o n ofAn investigation is made to determine certain nitrous acid gas on the amino-son ( 1 1 ) recommended the addi-tion of amyl nitrite t o an acidj- of the chemical, physical, and explosii>eproper- phenol. The last two methodsfied a n h y d r o u s s o l u t i o n of ties of diazodinitrophenol. Tests show that it are similar to those of Griess,picramic acid in abso lute alcohol, can be used f o r the iniliation of detonation of S c h m it t, K n o e v e n a g e l , a n dH a n t z s c h a n d D a v i d s o n .and thus the generation Of th e high explosives such as the dynamites, T-VT, Tile 2-nitrobenzene-4-diazo-l-nitrous acid in situ.D D S P by pouring boi ling n i t ric in Place Of certain Of the more COmmOnb used by diazotization of 4-chloro-3-acid on picramic acid. Accord- initiating tzgents, particularly mercury fulmi- n i t r a n i l i n e , w i t h s u b s e q u e n ting to Cain ( 3 ) the preparation nate, or nliztures of mercury fulminate 2Cith diminution of the acidity, com-ple te neutra l iza tion , o r ad d i-tion of sodium acetate to theOf diazo compoullds m ay oxidizing salts such as potassium chlorate.b e a c c o m p l i s h e d b y causing

S t e n h o u s e ( 2 : ) p r e p a r e d etc*,fo r which purpose it may be o xid e m a y a l s o b e p r e p a r e d

fuming nitr ic acid to act directlyon an amine. In either case the required nitrous acid is pro-duced in statu nascendi by the reducing action of the picramicacid according to th e equation:

At least 25 per cen t of t he picramic acid is lost throughoxidation to picr ic acid when D D K P is prepared in thismanner .De hn (6) developed a method fo r preparing DDSPwherein the use of organic solvents and gaseous nitrous acidis avoided. Dehns significant contribution lay in the addi-tion of reducing agents such as methyl or ethyl alcohol, orcarbohydrates, to replace and conserve the picramic acidpreviously lost by oxidation. De hn also introduced the useof a floating layer of a high-boiling paraffin oil, which serves( 1 ) t o reduce th e liability of spon taneo us surface combustion,

diazo solution.Pa tent l i te ra ture show tha t dye manufac ture rs pr ior to1899 were making D D S P in a very different way from theabove metho ds, p:eparing it as an in terme diate by diazo-tizing picramic acid m-ith sodium nitrite in a manner similarto th at used in the preparation of th e diazonium compounds.Abel (1) stated that picramic acid may be diazotized byth e addition of 6.9 kg. of sodium nitrite to 22.1 kg. of picramicacid in 20 kg. of h ydroch loric acid (sp. gr. 1.16). In 1899S e wdon (21) referred to a similar method as the knownmanner of preparing D D S P . Th is method of preparationis of distinct a dvan tage to dyers because D D K P is solublein hydrochloric acid of sp . gr. 1.16, and may be run directlyto th e coupling tanks.Preliminary tests showed that diazotization may also beeffected in hydrochloric acid of 5 to 10 per cent strength

1 The diazooxides so far discussed are either of the ortho or the paraconfiguration Morgan and Porter, J C h e m .Soc , 107, 64 5 (1915), havedemonstrated the nonexistence of a m-d~aeooxide

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of the series of physical tdMETHODli. One pa r sodium picraniate (100 per cent)is rnpidly agitstcrl i n 12.5 parts of 5.5 prr cent Irydrochloric acidat a temperatwo of 15" C. A slight excess of sodium nit,ritrdissolvod in 150 to 200 cc. of water is 8ddr.d d l at once. Atthis stage th e temprraturc rises to 1s" o r 20' C . T h e colorchanges repidly from t,he chnrneteristic brown of sodium piora-mate solutions to a bright yellow which i s slightly mnskcd by a

ljelirr ( i )rcpnrts 1JIJSl' t o be SOIUJJIP in ~ i i t n h e ~ r s e n e ,acetone, aiiilitie, Iiyriiline, acetic acid, strong liyilrocliloricacid, acetyl cliloridr, and glyceryl tr initrnte at room tmipcra-ture. IIe says that UUSP is stablc in l!Old minerd acids but,is decomposed by h o t concentrated sulfuric acid and by coldalkali solutions.Recrystallization may he made from iiitrdx:naene or fromacetone solut,ion by addition of tlie solution to cold ether.DDNP niay be purificd by addition of ice water in con-siderable excess t,o a rapidly agitated hot acetone solution.Th i s ha tn ie n t p roduces a brilliant yellow amorphous powder.

EXPLOSIVECH.4l%ACTEBI8TiCS OF I>I>KI'IVENES'S TO IYPACT .4ND F R I C T I O N . DUSP deto-nates when strui,k a sharp blow, but, when ignited (uncon-fined) by fuse, it flashes like nitrocellulose, even in quantitiesof several grains.Several samples of UDSI' were tested for serisitireiressto impact on the Bureau of Xines small impact device ($0)(J'igiires 2 and 3), and for sensitiveness to friction on it stype U pendulum friction device (SO) (Figure 4 ) . It \\-asfound that DDSI' requires tlic drop of a 500-gram m i g h ttlirouph 22.5 em . to produce detonat ion. Table I1 s h o m tlieresults of impact tests on UDXP, eoiiipared with similartests on mercury fulminate, lead azide, arid lead stypiinate.

Cm.I JDNP 2 2 . 5Lead azide 17 .5Meroury l"Irnia*ls i ILead stmhnate 2Uu.uz-grsm aampla tmed fo r *&(ill teat.

Residts of tes ts wit l r th e type 13 pendii lum friction deviceare s h o w i i ll Table 111.TAB1.E 11s. SI;NSITI"ENESS TO Fnlcrrora

Cm. GWrn.9DDNP 50 >5000 2 8 - 8 2Lead azide 50 1u00 13-15Merciiry iiirininaie SO 25 8Lend stgptinate SO >5uuu 30-330.02-grnm ahinpie used i o r ear12 lest.

Tire results of these tests sliow that the sa~nplesof U U S Pprepared according to method R are no more s e i d i v e toimpact than tlie ot.her detona nts tcsted, an d are markedlyless seiisitiw to friction than either the lead azide or mercuryfulminate. Su rn e ro u s at tempts to detonate DDKP underwat er wit,liKO.8 electric detonators rnet with failure.DDKI', eitherloose or when compressed under hi& pressures, is easilyignited by the spit of a fuse. Und er tlic first. condition itmerely ouffs off like nit.rocellulose; under th e second condi-

EFFECTOF PRESSUREON EXPLOSIBIIJTY.. .k y 0.27. i Y l m r i,oinpres&!d in a detonator slieil' a t a tion i t may burn with explosive vihleiice or detonate, hut can


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June. 1933 I N D U S T R I A L A N 1) I i N G I N Ls E II 1 N G C H Pi &I I S ' l It Y 665be depended upon to detona te with cer tainty The average weight of tlie saud crushed inouly vlien confined by a re&nforcing ca p su le . these nine experiments was but 2.4 grams more.4ccordingly, a reenforcing capsule was used in t ha n the lowest, result in experirnent 1, an d 2.06making up all th e e x p e r i m e n t a l d e t o n a t o r s . q a m s less tlian the higliest result in experim ent 5 .S e v e ra l a t t e m p t s were m a de t o d e a d - p r e s s It is fair to assume t.liat UI)SI' is not nffectedU D S P . Pressures u p to 100,000 pounds per in its devdopnrent of energy by any s ta t ic pres-square incli (7030 kg . per sq. cm.) failed to pre- sure t o wliicli it has been siihjected.ven t detonation when ignition was by fuse. T w o Tinder l.he same conditioris with a 0.50-grmla t t e m p t s were macle to use greater pressures. charge of niercury fiilinitinte 11In the first case, explos ion occur red it i t,lie jeet,cd i,o a pressure of 31M pounds per squarepress at ll(i,000 and in tile second at 1:10,0100 inch. 2 5 g r a m of s:ind 1wro criidicd; r i t h a nj i ( i i i n i I s per s q u a r e in c h (51% and 9139 kg. equal w i g l i t of lii~iilazide c x p w e d lo s i m i l a rpressure, 20 grams of s an d w r e criislicil: 1)UKl'TESTS. I n IS10 S~icll ing($3) (le- iimlcr 3400 p imi ids pressure c!nisl~cd45.0 grams.t rnetiiod fo r tcsting t i l e strength of I3y these tests it w o u l ~ ldetonators. Tliis rnctliod depends upon tlie es - s:tn(l-crusliing st,riingtli of I)tent to wiiich a hard br i i t ie suhtancc , s l i c i i ns that of rriercury fulininnte aquartz smd, is pulverized by firing a detona- t h a t of lead azide. To ascertaiii wliether t l i eto r emliedded in i t . To carry out this test , a strengtli of l>IlS P is enliariced by the use of acontainer later known as th e Iiurenu of M i i r e s priniing charge of rnercilry fulrniiiatc, tests veri!sand-test liomb Xo. 1 was designed. Specifica- i na t l e i i r i l i e So . 2 sand-test bomb with detona-t.ions fo r this bomb, in o t l iod s f o r i t s use, an d tors coritaiiiing 0.50 grain of 1 ) U N P as tlie bases p e c i f i c a t i o n s for 6lre quartz sand have been charge. 'Fhe fuiininate in t h e priming chargesd i sc us se d in de ta il by Storm and Cope ( $6 ) . varied From 0.15 to 0.30 gram. A reihiforciigTaylor and hI imroe (27) niade a furtlier s tudy caprille was supcrim~iosedon the prirrriiig charge,of this itrothod slid recommemicd t i l e use of a aiid the base and priming charges \\-ere then com-bomb of larger diameter, knoivn as the Bureau pressed under the capsule at pressures varyingof Mines sand-test bomb No. 2, which differen- from 500 to 4000 p o u n d s per s q u a r e i n c htiates more exactly betweeii tlie different grades (Table V).of detonators in commercial use. The results indicate tliat an increase in tireI'I~OCEDURE.E i g h t y g a m s of sand, weighed weight of fulmina te a t n given pressiiro does noton a prescr ipt . ion balance, are placed in the increase the sand crusliing strength of DDKP,bottom of t l i e boiiib which is jarred to level th e wlrerea~fo r a given weight of priming chargesurface of th e s m d . T he detona tor is rested o n FmunE 2. S M A L L the strength increases somewhat with increasingth e center of this, 120grams more of tile saird arcpoured around it, and the bomb is rocked or tapped No efforts were made t o ascertain tlie effectonto l e w l th e surface. The cover is placed aird the detonator IIDSP of using a priming eliarge of lead aside. Tlie mixingfired. The m i g h t of sand crushed f iner than 30 mesh is of lead azide with DDXP is definitely to be avoided becausetaken as a nieasure of th e strength of the detonator . This such a mixture dacomposes promptly and destroys t.lie proper-method of testing, using the No. 2 sand-test bomh, was t,ies of both explosives. Moreover, sensitiveness to impa ct offollowed thro ugh out th is investigation. Dehn (4)studied th e tlie mixture is greater t h a n that of either of the constituents.effect of greater confinement of th e sand by placing a weight Using a mixtu re of equal rreiglrts of D D N P and lead azide,on i t , and stated t h a t "Tlie inass of meta.1 suparimposed tlia ~ r i x n i i i i u ml i r igl i t of drop of a 500-gram weight fo r ('noon th e sand x I I ca n be increased with accornpanying in- explosion" in five trials is 7. 5 ern. Values for lead azide andcrease iri t,he weight of sand crushed." Taylor and Munroe 1)IlSP alone are 17.5 and 22.5 cm., respectively.($7') slrowt~Ithat th e results obtained by this riietliod aremore erratic than wlien the sand is sin lpl y tcsettledx in TABLEV. S A N DTESTSOF 0.50-Gltau CH ARG EOF D D N PPRI ME DWITH ME RCU RYFULXIXATEbomb by jarr ing. wmatm Or S*nn CS"SXEU F I X E R TU*N 30 &lean

lb'p*~T D E ~ ~ Epressure.

TABLE I V .E X P T

CIarns43.146.545.94 5 . 64 7 . 84 3 . 04 5 . 344.943.:

TbY DDxI'hI.oxr*0.0 0.16 0.20 0 . 2 5 0 .30pram prnin Pram m n i n gramW El R l T ox S*ao Cllisnlro P i l r .anar t f >lI.F.b AI . P . 6 L 1. F . b M.F.6 X F . 6*'"IN 30 alruri 1.b.i~y in . [ k g . / nq . i r r c . ) G r a m a i;iiims Giarns C ~ a n i r Orilma

500 ( 35.2) . . . . 4 i . 4 4 5 4 44 1 46.91160 ( 8 1 . 5 ) 43.3 45.2 4R.7 48.4 44.61750 ( l X . 0 ) 46.1 48 .2 50.9 49.3 48.6232o ( 1 6 3 . 1 ) 44.9 F3.8 4 8 . 9 52.1 49.63400 (239.0) 45.6 51.9 51.1 52 .2 50.84000 (281.2) 47.8 52.0 54.1 61.7 5 4 . 5Obtained by subtraotiog weight of sand oiushed by iulrninate fromt b n t e r u h e d by rvliole rhsrge.b .\leieuiy iulininrte.hverhre 4 i . 1 4 Dehn's patent (6)states that a a rea t advsn taae in th e useof I I D N P - I ~ ~ ~in 'its ability, in ehplosive compositions con-taining oxidants, to utilize tlie available oxygen and thusadd to its own nojver. Tliis natent eivrs tlic follon+,a eoitn-

Preliminary t es i s i n th e s o . 2 sand-test bomb to determiiletire strength of DDSP indicated that it ha d a greater sand- ~,~~ ~ ~ ~~~~ ~~~--- '--~crushing strength, gram for gram, than niercury fulminatewhen bot.li were tested under the same conditions.To test the effect of compression on the str eng th of DUSI',0.5O-gram charges were placed in KO . S detona tor shells,

pressed under reenforcing eapsulcs at various pressures, andfired in tile N o . 2 sand-test bomb by means of a fuse (TableIV) . nitrat.e)

tions fo r t.he d&olrlposition hf ~ n ~ paioneand also whenmised with an oxidant such as ammonium nitrate:C J I I N I O ~+4CO + 2C + Hz O + ZNzC,Ii,N,Osnitrate) + 2NIirNOI+ CjCO + 5 H 2 0 + 1X (43.5%C,EI,N',O~+ ~ N ~ I , N O ~+ 0 ~ 0 ~+ 1 7 ~ ~ 0+ (75.3%


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666 I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y Vol. 25 , No. 6To compare the strength of D D N P with mixtures of D D N Pand o xidants by the sand tests, mixtures in various propor-tions of D D K P with potassium chlorate or with potassiumperchlorate were prepa red. A 0.50-gram charge of themixture was weighed into a No . 8 deton ator shell, a 0.2-grampriming charge of fulm inate added, a reenforcing capsulesuperimposed on the fulminate, and the whole system

subjected to a pressure of 3400 pounds per square inch.This method of loading was first used by Wohler and M atte r(28). The detonators so made were fired in the No . 2 sand-test bomb (Table VI) .

TABLEVI. SANDTESTWITH DDNP-OXIDANTMIXTURESWEIGHTOF SAND CRUSHEDFINERTHANCOMPOSITIONOF BASECHARGE 30 MESHDDNP Oxidant BYtotal chareea Bv DDNP-oxida nt% % Grams Grams

WITH P O T A S S I U M C H L O R A T E100959 08 58 06 55 0352 010 09 59 0858 065

0510152 03550658 0

5 8 . 75 7 . 65 8 . 85 7 . 35 7 . 75 4 . 15 1 . 14 7 . 53 0 . 2W I T H POTASSIUM PERCXLORl TE0510152 035

5 8 . 75 5 . 25 4 . 85 5 . 95 4 . 95 4 . 3

5 2 . 25 1 . 15 2 . 35 0 . 85 1 . 24 7 . 64 4 . 64 1 . 02 3 . 75 2 . 24 8 . 74 8 . 34 9 . 44 8 . 44 7 . 84 5 5 5 4 9 . 9 4 3 . 43 0 7 0 4 1 . 9 3 5 . 415 85 25 . 0 18 5

a Total charge consisting o,f base charge of 0.50 gram,of DDNP-oxidantmixture plus ti 0.2-gramgriming charge of mercury fulminate.

It has been sta ted tha t method A produces DDNP inthe form of a free-flowing granu lar powder. Inasm uch asthese physical characterist ics are those which make a materialmost easily adaptable in detonator loading, sample A wastested in the N o. 2 sand-tes t bom b in a series of te sts similarto the above, in order to compare the explosive propertiesof samples A an d B. Tests were made to determine (1) th erelative strength of sample A and of mixtures of it withoxidants, and (2) whether th e stre ngth of these mixturesof sample A with ox idants is enhanced by the use of a m ercuryfulminate priming charge (Table VII).

T A B L EVII. SANDTEST OF DDNP (SAMPLEA)WEIGHT O F SAND CRUSHED FI NERTHAN3 0 MESH

F I R E D W I T H 0.2-GM.MERCERY FULMIXATE.~P R I M I N G C H A R G ECOMPOSITIONO F BASE CHARGEBy total BY DDN P- F I R F D T I T H O E TDD NP KClOa charge5 KClOs PRIMING C H A R G E% % Grams Grams Grama0 5 6 . 1 4 9 . 6 4 4 . 64 4 . 4100 1 0 5 4 . 9 4 8 . 4 4 4 . 59 08 0 2 0 5 5 . 5 4 9 . 04 0 5 5 . 5 4 9 . 0 4 4 . 32 9 . 6605 0 5 0 5 7 . 2 5 0 . 7mixture plus 0.2-gram prlmlng charge of mercury fulminate.

a Tota l charge consist ing of base charge of 0.50 gram of DDNP-KCl Os

These tests show no appreciable difference in the s treng thdeveloped by the bright yellow, amorphous DDNP and thebrown, granular , free-flowing modification. Com paringTables IV and VI1 (where no fulminate priming charge wasused) with Tables V and VI (where a priming was used), it isappa rent th at, w eight for weight, the stre ngth of m ixturesof D D X P with oxidants i s of th e same order as DD N Palone. Hence th e addition of oxidizing salts would seem ofconsiderable value from the economic viewpo int. Th est rength of mixtures of DDXP with potassium chlora teor potassium perchlorate is increased to the same slightextent as tha t of DDNP alone by the use of a 0.2-grampriming cha rge of fulmina te.

In the last column of Table VI1 a marked decrease in thestrength of DDNP-po tassium chlorate mixtures containingmore than 40 per cent of potassium perchlorate is noted whenno fulminate priming charge is used.To compare fur ther the s t rength of D D X P wi th mercuryfulmin ate and lead azide, various weigh ts of the explosivet o be tested were put in No. 8 deto nator shells,pressed und era reenforcing capsule at 3400 pounds per square inch, and firedin the No. 2 sand-test bomb (Table VIII).TABLEVIII. COMPARISONOF SANDTESTS UBINGD D N P ,MERCURYFULMINATE,AND LEADAZIDE

WEIQHTOF SANDCRTVHEDFINERTHAN 3 0 MESHWEIGHTOF CHARGE DD NP Mercury fulminate Lead azideGrams Grams Grams Grams0 . 1 0 9 . 1 3 . 1 3 . 50 . 2 0 1 9 . 3 6 . 5 7 . 20 . 4 0 3 6 . 2 17.0 1 4 . 20 . 6 0 5 4 . 3 2 7 . 5 2 1 . 50 . 8 0 7 2 . 1 3 8 . 0 2 8 . 71 . 0 0 9 0 . 6 4 8 . 4 3 6 . 0

Resul ts show tha t DDNP is much more powerful thaneither mercury fulminate or lead azide.Additional tests were made in th e No. 2 sand-test bomb tocompare the strength of D D N P with other nitroaromaticexplosives. I n the prep aration of th e charges, 0.50 gram ofthe n itroaromatic explosive to be tested w as placed in a No. 8detonator shell, a priming charge of 0.3 gram of mercuryfulminate added, a reenforcing capsule superimposed on thefulminate, and the whole system compressed at a pressureof 3400 pounds per square inch (Table IX).TABLEIx. COMPARISOX OF SANDTESTSUSINGD D N P ANDOTHERNITROAROMATICEXPLOSIVES

WEIQHTO F SANDCRUSHEDFINERTHAN 30 MESHEXPLOSIVE By total charge" By nitroaromatic explosiveGrams GramaTrinitrotoluenePicric acidTrinitroresorcinTetranitranilineHexanitrodiphenylamineTrinitrobenzaldeh ydeTetryl

6 3 . 95 5 . 35 7 . 05 2 . 95 6 . 36 0 . 26 2 . 86 5 . 9

5 2 . 24 3 . 64 5 . 34 1 . 24 4 . 64 9 . 56 1 . 15 4 . 2a Using 0.3-gram mercury fulminate rimer.b Weight of sand crushed by DDNf: when no priming charge warn used= 45.7 grama.

STRENGTHIN SMALLTRAUZLBLOCK. A 1.00-gram chargeof D D N P, mercury fulminate, or lead azide was weighedinto a No . 8 detonator shell, compressed under a reenforcingcapsule at a pressure of 3400 pounds per square inch, andfired in the small Trauzl block by means of a fuse (Table X).TABLEX. COMPARISONOF TESTSIN SMALLT R A U Z LBLOCK

EXPLOSIVEDDNPMercury fulminateLead azide

EXPANSIONOF LEADBLOCKcc.2 5 . 08 . 17 . 2INITIATINGPOWEROF DD XP . The ini tia ting power of adeton ant is expressed in term s of t he m inimum weightwhich will cause maximum detonation as shown by no fu r therincrease of sand crushed w ith an increased weight of initiator,except tha t resulting from the addition al weight of initiator.To compare the va lue of D D N P wi th mercury fulminateor lead azide as an initiator of detonatio n of various nitro-arom atic explosives, a 0.50-gram charg e of t he explosive to betested was weighed into a No. 8 detonator shell, and a de -sired weight of the priming charge was placed as a top layer.Th e charge was then compressed under a reenforcing capsulea t a pressure of 3400 pounds per square inch. The detonatorwas fired in the No . 2 sand-test bomb, and th e weight of sandcrushed noted (Table XI).


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June, 1933 I N D U S T R I A L A4N D E N G I N E E R I N G C H E M I S T R Y 66 7T A B L EXI. INITIATINGPO WE ROF D D S P C O M P A R E DWITHM E R C U R YFULMINATEAND LEADAZIDE

MINIMUMDETONATISQCHARGEGr a m Gr a m Gr a mEXPLOSIVE Fulminate DD NP Lead azide

Picric acidTrinitrotolueneTetrylTrinitroresorcinTrinitrohenzaldehydeTetranitranilineHexanitrodiphenylamine

0,2250.2400.1650,2250.1650.175

0.1150.1630.0750.1100 ,0750,0850.075

0.120.160.030.0750.050.050.05

Results show that approximately only one-half as muchD D K P as mercury fulminate is required to cause the com-plete detonation of the explosives in the left-hand column ofTable XI. D D S P is , however, shown to be a s l ightly lesseffective initiator of detonation than is lead azide.The true diazo compoundsare readily affected by light. Those containing negativegroups such as OH, SO s ,COOH, etc., in the para position aremore sensitive than those containing similarly situatedpositive groups; the influence of the nitro group is greatest.Ortho-substi tuted groups behave in the same manner assimilar para -subs tituted groups. Th e sensitizing effect isgreatest for a meta group (19). Meldola, Woolcott , andWray (18) found that the diazooxide, 3-bromo-&nitro-benzene-l-diazo-2-oxide, is more s table to l ight than the true

, diazo compounds, the stability being due in all probabilityto its peculiar diazoijxide ring structu re.I n the case of D D N P it seemed possible th at t he sensitizingeffect of th e two m-nitro group s mig ht more th an ove rshadowth e stabilizing effect of th e diazooxide ring struc ture .DDKP has been found to be stable for long periods of t imein diffused light. Samples s tanding in the laboratory andprotected from direct sunlight have shown no signs of dis-coloration after 6 months. I n direct sunlight, however,DDYP darkens rapidly, eventually acquir ing a dark browncolor.To determine t he effect of direct sunlight on its explosivestrength, D D S P was exposed for var ious periods of time.A 0.50-gram portion of the exposed materia l was then placedin a X o . 8 deton ator shell and compressed under a reenforcingcapsule at 3400 pounds per square inch. The detonato r s soprepared were fired in the No. 2 sand- test bomb, and theweight of sand crushed was noted (Table XII).

EFFECTOF LIGHTON D D N P .

TABLEXII . SANDTESTSWITH D D N P AFTER EXPOSURETODIRECTSUNLIGHTWEIGHT OF S.4ND WEIGHTOF SANDTIMEOF CRUBHEDFINERTHAN TIMEOF CRUSHEDFINERTHANEXPOSURE 30 M E SH EXPOBUR. 30 MESHHours Grama Hours Grams

012345.145.343.941.8

510152042.838.836.335.3

TABLEXII I . SANDTESTSON D D N P AFTER HEATINGAT 60" C.DURATION WEIGHTOF SAND DURATION WEIGHTOF SANDHEATING 30 MESH HEATING 30 MESHD a y s Grams Da y s Gr a ms0 45.8 7 44.22 44.5 14 45.44 45.5 2s 45.2

OF CRUSHED F I N E R T H A N O F CRUSHED FINERTHAN

These results show that DDNP undergoes no loss ofstreng th on exposure of on e hour to direct sun light and showsno marked decrease even after 3 t o 5 hours, despite a ma rkeddarkening in color. T h e D D K P w as s u bj ec t edto a temperature of 60" C., which is higher than is usuallyencountered under storage conditions; 0.5-gram charges ofthe test sample were weighed into No . 8 detonator shells,compressed under a reenforcing capsule with a pressure of

EFFECTOF H E A TON D D K P .

3400 pounds per squa re inch, and fired in the S o . 2 sand-testbomb. Results are shown in Table XIII.D D N P was also subjected to a tem perature of 75" C. fo r48 hours with a loss of only 0.3 per cent in weight. Afterthis period of heating, 0.50 gram of the test sample crushed45.60 grams of sand, whereas the original sample crushed45.80 grams.A similar sample of D D X P, heated a t 100" C. fo r 96 hours,lost only 1.25 per cent in weight. It is interesting to notethat diazobenzene nitrate, a true diazo compound, explodesviolently when heated t o 90" C.

FIGURE3. DETAILSOF SMALLIMPACTDEVICEAbove, impact block: below, plunger and plunger tip.

EFFECTOF D R Y A N D \$'ET STORAGE ON D D N P . A 0.50-gram charge of freshly made D D N P crushed 45.80 grams ofsand. This weight of D D N P preserved dry in a dark bottlefor 5 month s crushed 45.00 grams of sand. Th e difference iswithin experimental error. -4similar sample preserved in amoist state over the same period of time showed no lossin s trength as indicated by the sand test . Neither sampledeveloped any discoloration during storage.To ver ify fur ther the impassivity of D D N P to moisture, aquantity was stored under distilled water at room tempera-ture. After chosen periods of time, 0.50-gram samples werewithdrawn, dried, compressed in KO.8 detonator shellsunder a reenforcing capsule at a pressure of 3400 pounds persquare inch, and tested in the K O.2 sand-test bomb (TableXIST).T A B L EXIV. SASD TES T ON D D N P AFTER UNDERWATERSTORAGE

%'EIGHT OF S.4ND WEIGHTOF SANDSTOR.4GE CRUSHED FINERT H A N STORAGE CRUSHED FINERT H A NPERIOD 30 Mesh PERIOD 30 MESHD a y s Gr a ms Da y s Gr a ms0 45.6 2s 45.87 45.4 36 46.414 44.2 50 44.021 45.5

Results show tha t the sand-crushing strength of D D N Pis not affected b y storage unde r water for a 50-day period.-4s it seemed possible th at D D S P might undergo veryslow decomposition when immersed in water and to so


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668 I N D I . I S T I I I A I A A N D E N Gliinitrd an d e n t as to he iincletcotalile by the sand test,a sample was plec?ed under water at rooiii teinperat,ure,and means \\-ere provided to collect an y saws resulting fromi ts r locorn~wsit ion; liairevcr, none was libernteri during a45-day period.

F'isunc 4. TYPE33 I'ENDULUMFRICTIO~~I h W ZA modified gap test wa s iiseil by

of the disturbance sent out by th e esplosion of a sliielderidetonator to traiisfer detonation over an a ir gap l o a receivingcliargc of explosive. For these tests a 0.50-pam cliarge ofIIUSP mas plnced in a So. 8 detonator shell arid pressedunder a. reenforcing capsule a t 3400 pounds per square iiicli.In a similar inunncr detonators were prepared containing0.50- an d I .OO-gram (:haThe test detonator 1 ple,orrl centrally in a eylindricaloiiken shield, mitli its long axis parallel to aiid coincidingwith tire long axis of the shie ld an d xi tb its base flush withthe end of tho shield. The siiield eont.aining th e detonatorunder test an d th e cartridge of receiving explosive usTonaTone

1 ' 2 ~ ~ 1 ~ A O , , T l O NTc>&T,-t.llrop (8 ) an d rs t o deterniiiic th e relat ive al i l i ty

s of mercury fulminate.

DEToV.ATo1%CDMFREU WITB < h M E n C I A L ELECTRIC

Grams cm .350150?UO400"300"'30"100"50"

k I N E E H I N G C H E M I S T I< Y Vol. 25 , So. 6Tlicw: results show that the effectiveness oi the disturbanceart u p by a 0.50-grain charge of D D S P (in a reenforceddetonat ,or) in propagation of detonation across an air gapis greater than t.hat of any of tiie eonirnerical detonatorstrstod except tet,ryl.IONITIONTmmiiAwm. Ignit ion tem perature of DUNP

wa,s iletcrmined by droppiiig 0.02-gram charges of D D N Pon a molteii metal bath and noting tlie interval betweenth e iiioinent of c on ta c t of th e explosive n it h th e ho t moltenmass, an d tlie moment of explosion (Tab le XVIj.

. .... ,..explosior,S U M M A R Y

:I study of tlie inetiiod of preparation, and of tiie explosivemd certain of the chemical eh araeterist.ics of diaaodinitro-jheiio! has siiowi th e following:

The methods found in natent literature msv be niodifiedI .ta give a more satisfactory method of preparing DDNP.DDNP, prepared aocording to method B, is a brightyellow amorghouu powder having a true density of 1.63 (d iS) ,an a m n r e n t densitv of 0.27. and a densitv of 0.86 when orossed2.

m a'hetonator shill at 3400 pounds PO; 8quare inch (239 kg .

and a h in elvcervl trinitrnte

of lead azide.I'rrssure does not affect th e strength of D U X P ivhen it isfired without n priming charge of mercury fulminete. When apriming charge wm used, nn iiicreaso in the weight of primer at agiven gresr-ni'eappeared to have no bencficial effect on strength.Horvever, lo r u given weight of primer, the strength increased

5.

somewhat with increasing ~- r e s u r e .6 J)DXP crtnnot be ii)tdnated under water with a No. 8clect,ricdetonator.7. DDiYP is no t dead-pressed even by pressures up to130,000 murids per square inch (9139 kg.per sq. em.).8. The strength of mixtures o f DDNP with oxidaiits isiinrilnr t,o t,liut, of D DN P itself: hence. t,he addition of oxidantsis of value from the economic hewpoint.9. The strength of DDNP, int,erpreted in terms of th eweight of sand crushed in th e sand teat hounh, is about twricet,hiit of mercury fulminate or lead aside. By the same criterion,thc rtrength of DDNP is of the same order :is other nitro aromaticexplosives, soch xs tetryl a i d trinitmbenzaldehyde, and i s some-what stronger than TNT, picric acid, trinitroresorcin, tetra-iiitraniline, or hexanitrodipherrylamine.10. The strength of DDNP tested in the small Trauzl-blockis approximately three times t h s t of mercury fulminate or leadazide.11. The initiut.ing power 01 D D N P is greater than that ofmercury fulminate and similnr to tha t of lead azide.12. JIDNP is stable for lonrr ucriods of time in diffwed light

hmtrd'at 75" C f& 48 hours, and; loss of only 1 25 u& cent at100" C. for QG hours.14. The strength of D D N P is not aBected by storage underwater for 50 days.15. The effect of tha disturbance set up by a detonatorcontaining 0.50 Bram of D D N P is greater, &a shown by propage-t,iori tcsts, than t,hat of an y o f the commercial detonators testede nwpt , t,iiose contsiiiing tetry l as B base charge.D D N P explodes when heated to a tornperature of 180' C .IG.

100" (14.rvater15.containing 0.50 Bram of D D N P is greater, m.s ih&n by propitge-t.iori tcsts, than t,hat of an y of the commercial detonators testede nwpt , t,iiose contsiiiing tetry l as B base charge.D D N P explodes when heated to a tornperature of 180' C .IG.

ACKNO\VLEDGI\IEiYTThe author wishes to t h a n k CIiarIes E. Murrroe, chiefexplosives chemist, J. E. Tif fany, ex plo~ivestesting engineer,


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June, 1933 I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y 66 9

this paper .IiITERATURE CITED

(1) Abel, C. D., British Pa ten t 10,294 (1900).(2) Burns, J. E., U. S. Paten t 1,862,295 (June 7 , 1932).(3) Cain, "Ch emistry and Technology of Diazo Compounds,"(4) Dehn, 1%'. M., Chem. &. X e t . Eng., 27, 784-7 (1922).( 5 ) Dehn, W.M.,U. S Pat ent 1,428,011 (Sept. 5 , 1922)).(6) I b i d . , U. S.Paten t 1,460,708 (July 3, 1923).(7) Friedlander, P. , and Zeitlin, M., B e r . , 27, 192 (1894).(8) Gawthrop, D. B., J . F r a n k l i n I n s t . , 214, No. 6, 647 (1932).(9) Griess, J. P. , A n n , 106, 123 (1858).

p. 10, .Irnold, 1920.

(10) I b i d . , 113,205 (1860).(11) Hantzsch, *I.,and Daridson, W. B., B e r . , 29, 1832 (1896).(12) Hem, E. von, German Paten t 373,426 (May 24, 1923).(13) Howles, F., British Patent 125,600 (1917).(14) Kaiser, H. E. , U . S. Pat ent 1,852,064 (April 5 , 1932).

924 (1906):I b i d . , 69, 1327 (1896).(18) Meldola, Ra phae l, M'oolcott, G. H., and Wray, Edward,(19) Morgan, G. T., and Porter, J. W ,, I b i d . , 107, 645 (1915).(20) Alunroe, C. E.,and Tiffany, J. E., Bur. Mines, Bull. 346 (1931).(21) Kewdon, H. E., British Pat ent 13,213 (1899).

(22) Schmitt, R., B e r . , I , 67 (1868).(23) Snelling,W. O ., Proc. E n g r s . ' SOC.West. Penn., 28, 673 (1912).(24) Soc. Dyers and Colourists, Colour Index, Kos. 101-8 (1924).(25) Stenhouse, J. J. , J . Chem. SOC.,21, 150 (1868).(26) Storm, C. G. , and Cope, W.C. , Bur. Mines, T e c h . P a p e r 125(27) Taylor, C. A , , and Munroe, C. E. , I b i d . , Rep t . I n v e s t i g a t i o n s(28) Wohler, L., and Matter, O. , Z . ges . S c h i e s s - S p r e n g s t o f w . ,

(1916).2558 (1923).2, 181,203, 214, 265 (1907).

R E C E I V E DDecember 15 , 1932.U.S. Bureau of Mines. Published by permission of the Director,(Not subject to copyright.)

Gelation of Frozen Egg MagmaARTHURW. THOMASAND M. IHENEBAILEY,Columbia University, New York, N . Y.S A DD IT IO S to the co ld sto rage of hens' eggs in the shell,millions of poun ds of he ns' eggs ar e commercially frozenI each year. Such frozen egg ma tte r is consumed chiefly bythe baking industry. Frozen yolk magma is prepared inlarge quantities principally for mayonnaise manufacturers.Eggs to be frozen are carefully selected before the candle.Those which ap pear sat isfactory are broken into cups by ex-pert egg breake rs. Before th e conten ts of a given i:gg is add edto the bulk container , it is critically examined for appearanc eand odor . If unsatisfactory, the egg is discarded, the cup

containing it sterilized, and the hands of the operator arethoroughly cleansed before breaking another egg.The edible portions of th e eggs are churned in order to breakthe yolks and to mix thorou ghly the ma terials of the yo lks andthe whites to form a uniform egg magma. It is obviouslynecessary t o exclude even one egg of do ubtful qua lity und ersuch a system. This churned whole-egg magma is thenplaced in 30-pound (13.6-kg.) containers which are im-mediately s tored at - -5" t o 0" F. ( -21" to -18" C.) .TT7hen such frozen egg m agm a is stored for a few w eeks a ndthen thaw ed, it is generally very thick in consistency. Th ethickness, or stat e of gelation, has been found quite variable.Heretofore there has been no knowledge concerning the con-trol of the s tat e of gelation other tha n tha t the addition ofcommon sal t or sugar , etc. , prevents this phenomenon.M o r an (9) found that, when eggs in the shell were frozenbelow -6 " C. and then thawed, the normal fluidity of theyolk was lost, an d there resulted a stiff pas ty mass. An ir-reversible change in volume also occurred, as indicated bydilatometric measuremen ts which he made . Moran's publi-cation is the first scientific study of th e changes in the n atu reof the egg as a result of freezing.The present investigation was undertaken with the hopeof developing a method fo r the study of the gelation phe-nomenon an d of discovering the controlling factors.

hf.4TERIALS USEDTh e eggs used in these experim ents were fresh eggs of com-merce shipped from various pa rts of the United States. The ywere taken f rom car load lots received a t an egg breaking andfreezing establishm ent in Jersey City ; expert employees care-

fully selected the eggs and broke the m ou t of the shells, plac-ing the contents in pails. Th is was done under the super-vision of the authors, one of whom then churned the eggsand stored the egg magma in a room at -21 " to - 18" C.Since it was foreseen tha t as constant conditions as possiblewere essential to a study of the influence of mechanicaltrea tme nt of t he eggs, one commercial churn provided witha direct-drire motor n.as obtained and used throughout theinvestigation. When em pty, the motor shaf t was found torevolve 1750 revolutions per minute. The construction ofthe ap par atu s was such th at me asurements of the speed ofthe shaft while churning eggs mere impracticable.Through experience with egg churning in 1929, it was dis-covered that, if the churn was allowed to operate until allof th e yolks or all bu t three or four resistant yo lks were dis-rup ted, a highest possible viscosity of uniform egg magm a wasobtained. Conse quently, this end point was used as a guidewhen egg mag ma of high viscosity was desired. Wh enlower viscosities were desired, the churning was continuedbeyond this end point. Through out the investigation theamounts of egg matter churned consisted of 45 or of 90 kg.After churning, the whole-egg magma was passed througha screen (seven holes per cm.) and approximately 800 gramsof it were placed in 2-pound (0 9-kg.) capacity tin c ans whichwere immediately closed and pu t in a storage room a t -5 " to0 " F. (-21" to -18" C.) until removed for experimentaluse. These cans were taken out a t intervals , the contentswere tha wed under comparable conditions, and th e degree ofgelation was measured. Most of the other measuremen tswere carried ou t on the unfrozen whole-egg magm a on th e da ythe samples were prepared.In th e course of th e investigation, determinations of p H,total solids, and ether extract (fat) were made upon a seriesof 45 to 90 kg. mixtures of fresh eggs of comm erce. Since nosuch data l are available in th e l i terature, they are set down

1 In commercial egg breaking (as also in household practice) a smal lamount of ahi te is left adhering to the shells. The whole egg matt er thusobtained contains a slightly higher ratio of yolk to white than would be thecase if the edible matter ue re quantitatively removed from the shell. Unlessstated otherwise, all analytical data reported in this paper uere obtainedfrom this sort of egg matter consisting of a homogeneous mixture of about1000 or about 2000 eggs.

Diazodinitrophenol A Detonating Explosive

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