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AD503916

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CONFIDENTIAL

Approved for public release; distribution isunlimited.

Distribution authorized to U.S. Gov't. agenciesand their contractors; Critical Technology; MAY1969. Other requests shall be referred to AirForce Rocket Propulsion Laboratory, Attn:RPORT-STINFO, Edwards AFB, CA 93523. Thisdocument contains export-controlled technicaldata.

AFRPL LTR 31 JAN 1972, per TAB NO 72-7 dtd 1Apr 1972 AFRPL LTR 31 JAN 1972

AFRPL.TR-69.1o9

fJTHERIMAL DE COM P'OSTION10STUIE OF AAREPERCIORAE OIDIZER-

R. E.-FOSCANTE, CAT.SAF'101B. B. GOSHGARIAN iaowowA

f 0. ROBERTO ~ T D NO..72 -7

I APRIL 1972-

TECHNICAL lREPORT AFRPL TRO

MAY 1969'

I I

-~ iNADDITION TO SECURIT Y REQUIREMEN4TS WHICHMUST BE MET,, THIS DOCUMENT IS SUBJECT TOSF ICIAL EXPORT-CONTROLS AND- EACH TRANSMITTAL TO FOREIGN GOVERNMENTS-OR FOREIGNNATIONALS MAY BE MADE ONLY WITH PRIOR AP P ROYAL OF-AFRPL (RPORT-ST INFO), EDWARDS,

~ -ICALIFORNIA 93523.

'AIR FORCE ROCKET-PROPULSIQN OUTORY'AlP FOR1CE.SYSTEMSCOMMAND'

U UIT~fp STATESAIR FORCEEDARDS, CAIFORNIA.Ak ~

~ ~ * -DECLASSIFIED :AFTER 12 YEARS.

DOD 'DIR 5200.40-THISwtum COWiNS-IWOWITHhIN H MIAN INO, THE IN SPICtdAGI LAWS,

THI~s fOU* t olTI$No" MTO Tl Miuu~lNZoD r ASON';SpOISITtO ly IAW.

Ic IM - -j ---- ---- - - -_

{I

When U. S. Government drawings, specifications, or other data are usedfor any purpose other than a definitely related Government procurementoperation, the Government thereby incurs no responsibility nor any obliga-tion whatsoever, and the fact that the Government may have formulated,furnished, or in any way supplied the said drawings, specifications, orother d-ta, is not to be regarded by implication or otherwise, or in anymanner licensing the holder or any other person or corporation, or con-veying any rights or permission to manufacture, use, or sell any patentedinvention that may in any way be related thereto.

UN

U~~ATIA

21 fI 7

J..

AFRPL-TR-69- 109

(U) THERMAL DECOMPOSITION STUDIES OFA NEW PERCHLORATE OXIDIZER

Raymond E. Foscante, Capt, USAF

Berge B. Goshgarian

Francisco Q. Roberto

Ut

I!

ii

In addition to security requirements which must be met, this document issubject to special export controls and each transmittal to foreign govern-ments or foreign nationals may be made only with prior approval of AFRPL(RPORT-STINFO), Edwards, California 93523.

OW AT 3 YEA9 iNERALS;I IFIED A rER. 12 YEARS.

DDDIR 5200.10

neilSOCUUIIC~2?AtN ,NeM~lOI4 1t 116~ iii YSII5 1 WINI NI MANINO Of fill IPIOWACE IAWS.

Tll II a, U S.C. SKI1OH P93 AND 79, Tt99 ANSMI5SIOH VF WHMg# IN ANY MANNEE 1O AN UA OIIIOZI 'ItION I$ PIONIIITI Y ST LW.

II

Ft

FOREWORD

(C) This is a phase report of work done at the Air Force Rocket Pro-pulsion Laboratory to determine the results of thermal decomposition onmethylenedioxyamine diperchlorate (DOAP). This work was accomplishedunder Project 314804ACP during the period July through October 1968 byCapt Raymond E. Foscante and Mr. Berge B. Goshgarian. Dr. FranciscoQ. Roberto served as overall Program Manager for DOAP synthesis andevaluation.

(U) This report has been reviewed and approved.

NORMAN J. VANDERHYDEChief, Solid Propellant BranchPropellant DivisionAir Force Rocket Propulsion Laboratory

IL

ii

J M9 , S9 maCoH NAY STATO AN We M" IS PK0 6a11 o hIT LAWS

imi S. UC.. CI1WWi4

I a

ABSTRACT

(C) The initial step in the thermal decomposition of methylenedioxya-0mine diperchlorate occurs at 60 C with the loss of a perchloric acid group

to form the monoacid salt as an intermediate. As the temperature increases,the latter undergoes a concerted cyclization - cleavage reaction to formformamide and hydroxylammonium perchlorate.

(U) Mass spectrometry was used to formulate a working hypothesis for"~Ithe decomposition. The existence of each of the postulated intermediates

in the reaction was verified by independent experiments.

iii/iv

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i UNIlIiA

Section Page

(U) I INTRODUCTION ...... ................. I

(U) II MASS SPECTROMETRIC DECOMPOSITION STUDIES. 2

(U) III VERIFICATION OF INTERMEDIATES ........... .13

(C) IV DECOMPOSITION OF METHYLENEDIOXYAMINEMONOPERCHLCRATE ....... .............. 26

(U) V SIDE REACTIONS DURING DECOMPOSITION ... ...... 29

(U) VI MECHANISTIC HYPOTHESIS .... .......... 31

(U) VII COMPARISON WITH OTHER AMINEPERCHLORATES ...... .............. 33

(U) VIII EXPERIMENTAL PROCEDURE .... ......... 35

A. Sample Preparation ..... ............. 36

B. Thermal Analysis ...... .............. 36

(U) REFERENCES ....... .................... 37

(U) DISTRIBUTION ....... .................. . 39

(U) FORM 1473 .......... ..................... 45

I-

vTIS| ON T*AIN ggeo4ATION NOSN Of THE UNITED STATU WITHIN THE MEANING Of THE USPIOHAG LAWS,

inTI .I U.S.C., ISI 'O M Me 794, WHICH 114 ANT MANNE TO AN UNAUTNOIlZIO ESlON IS PFOWISITIO IV LAW.

"NUIULNH I IALILLUSTRATIONS

Figure Page

(U) 1 Plot of Ion Intensity versus Temperature forFormamide and Related Species from DOAPDecomposition ...... ................. 3

(U) 2 Plot of Ion Intensity versus Temperature forHydroxylamine and Related Species from Dr'APDecomposition ...... ................. 7

(U) 3 Plot of Ion Intensity versus Temperature forPerchloric Acid and Related Species from DOAPDecomposition ........ ................. 9

(U) 4 Comparative Plot of Pressure versus Temperaturefor the Decomposition of DOAP and HAP .......... . 10

(U) 5 DTA Thermogram for DOAP .... ....... ... 14

(U) 6 DTA Thermogram for 80 0 C Vacuum-TreatedDOAP ....... ................... .. 15

(C) 7 DTA Thermogram for HydroxylammoniumPerchlorate ....... .................. 16

(U) 8 Plot of Weight Loss versus Time for 60 0 C andVacuum-Treated DOAP ..... .............. 19

(U) 9 DTA Thermogram for 60 0 C Vacuum-Treated DOAP 20

0(U) 10 DTA Thermogram for 70 C Vacuum-Treated DOAP 21

(U) 11 X-Ray Diffraction Pattern for HydroxylammoniumPerchlorate ....... .................. 23

(C) 12 X-Ray Diffraction Pattern for MethylenedioxyamineDiperchlorate ......... .................. 24

(U) 13 X-Ray Diffraction Pattern for 70°C Vacuum-TreatedDOAP ........... .................... 25

vi

C0 IDENt ALI" eCoOM ? CNTMAINM IWOATIMM MHCTING T"I NATIONAL HPINN OF THI UNITO STATIS WITHIN THI MIAMINO 01' TWI rSPIONAO LAWS.

11Ttl IV, U.S.C.. S ETION 712 AND 794. TE TAMMISICN Of WHICH IN ANY 2ANNIM TO AN UNAUTM IZI I PSON IS POIOISNTSO 1Y LAW.

Table Page

(U) I Mass Spectrum of Thermal DecompositionProducts from DOAP ...... .............. 4

(C) H Comparative Mass Spectra of Formamide,Methylene Dioxyamine, and SelectedDecomposition Species from DOAP .. ........... 5

(U) III Mass Spectral Ion Ratios for HAP and DOAP ........ 1

(U) IV Elemental Analysis of 80 C Vacuum-Treated DOAP . . . 18

(U) V Comparative Mass Spectra for Do-MonoperchlorateDecomposition and Selected Species from Do,Formamide, I-AP ..... ............... .. 28

IM IETHIS SCUMI NT CONAIPdb htl4OIIMAIO9 ADIKIIO f 1 ATIONAt 015Of Of THE UNITED STATlS WITHIN INC MIANING Of T91 ISPIONAGO LAWS.

tits Is. U.S.C., SCTION M92 AND 794, TIN T@ANMISSION Of WHICH IN ANY MANNIN TO AN UHAUTNOIIZIO 11%9ON 1 OHtIIT0 BY LAW.

~SECTION I

INTRODUCTION

(C) Methylenedioxyamine diperchlorate (DOAP) is a new material

synthesized and characterized within recent months at AFRPL (1). As

part of its evaluation as a potential s::!.Ad propellant oxidizer, studies were

initiated to determine the mechanism by which this compound undergoes

thermal decomposition. Knowledge of this mechanism was sought to pro-

vide a sound basis for predictions and conclusions concerning the stability

of DOAP in various thermal and chemical environments. To this end, the

thermal behavior of the oxidizer was studied over a broad temperature

range to detect endothermic and exothermic transformations, to establish

the initial step in the decomposition reaction, and to identify, anc, where

possible, to isolate intermediate species. Various analytical and experi-

mental techniques were employed, including mass spectrometry, differ-

ential thermal analysis (DTA), differential scanning calorimetry (DSC),

thermogravimetric analysis (TGA), infrared spectroscopy, and X-ray and

elemental analysis.

I,

I" DOCUMi CoiTAINS INPOWMATiON A MTI , DIPINS1 O THO UNITI0 STATES WITHIN THI MiANING OF THE UI# 4A0 WAWS,TITL IS, U.S.C., $WIO 7M AND 7#4, THE IAUIt ION Of W HICH IN ANY MANNE

RTO AN UJAUTHORIZEO 1110H4 IS "4014111) IT LAW.

jCONFIDENTIALSECTION II

MASS SPECTROMETRIC DECOMPOSITION STUDIES

(C) Studies of recrystallized DOAP (see Section VIII) were used as the

b- sis for mechanistic conclusions concerning the decomposition behavior

of the material. Tle data obtained for key ian species over the tempera-

ture range of 60 to 95 0 C (0. 5°C/min heating rate) for recrystallized DOAP

are listed in Table I. These data have been corrected for pressure and

the time required to collect a constant quantity of ions on the mass spectro-

meter photoplate at a given temperature.

(C) The mass spectrum of the decomposition species from DOAP canbe grouped according to three main parent species: formamide, hydroxyl-

amine, and perchlocic acid. There is also a minor contribution to the

spectrum by impurities and species resulting from reaction of the contami-

nants with perchloric acid.

(U) The effect of these impurities is to reduce the temperature at which

decomposition begins. The reaction occurring between the organic impuri-

ties and perchloric acid in the solid or on its surface will be exothermic

and thereby add thermal energy to the system. This self-heating effect

enhances the decomposition rate of impure samples as compared to recrys-

tallized DOAP.

(C) The presence of formamide as an intermediate in the decomposition

of methylenedioxyamine diperchlorate was demonstrated by high-resolution

mass spectrometry and by comparison with the cracking pattern for a known

sample of formamide (Table II). Figure 1 shows a plot of the ion intensities

for key species from the cracking pattern of formamide as obtained from

DOAP. From Figure 1 it can be seen that the formamide-forming reaction

* reaches its peak at 85°C (0. 3x10 " torr) and is ebbnLiaiiy complete by0

90GC.

CONFIDENTIALIM.4 OM I TAIWS Wok"11TIO APPIANG INC NATIONAL 81FINU OF 1 40 STATU W175T'TiIVS M[Ah) _%t 11 MIONA01 EAWS.titIs. I, .S.C.. SgcION 793 AND 794. INC tiANSMISION OF WHIC14 IN ANY 1AS*4110 TO AM UXAL'I 2 -&OHT IS 79f-.ISIMt SY LAW.

A CONFIDENTIAL

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CONFIDENTIALTABLE I MASS SPECTRUM OF THERMALDECOMPOSITION PRODUCTS FROM DOAP

Relative Intensity

AMU ION 4xl7nm 9xIoT7 mm zxlO "5 2.5x106 mm 3.4x10 " 6- m67 0 C 80LC 850C 910 C 970 C

27 HCN . z. 6 4.0 1.4 0.85

28 CO ..2 4.0 2.1 1.1 2.0

28.1 N 0.6 0.7 0.5 0.6 0.6

28.2 CH.N 2._6 1.5 5.0 0.8 0.4

29 CHO 0.5 0.5 1.9 0.7 o.6

30 NO 0.9 3.4 4.2 1.8 5.6

30. 1 CH.O 0.2 0.9 0.9 0.5 0.3

31. 1 CH30 0.2 0. z 0.3 0.04 0.03

32 02 0.5 1.4 1.2 1.4 2.7

33 NH 2OH - 0.1 0.08 0.15 0.4

36 HCI 2. 1 5.4 2.3 3.1 3.9

44 CO . 1.9 5.3 2. 1 Z. 4 2.3

44.1 0.02 0.4 0.2 0.4 1.0

45. 1 CHz ONH 0.7 2.1 10.6 1.4 0.6

46 NO 2 0.03 0.1 0.15 0.14 0.22

51 CIO 0.4 1.7. 3.6 1.7 z. 6

58 C2H4NO 0. 2 0.1 0.4 - -

63 COCi - 0.09 - - -

V. -sa67 "iG2 0.45 3. 6. 2. I

83 CIO3 0.2 0.26 4.4 0.6 1.0

100 HCIO 0.1 0. 2 Z. 6 0.4 0.54

, CONFIDENTIALItol is, U.S.C., HOW"'t~ M AND Y94, tW Wv4M'l,%IlSSO

NOf WNICH 100 ANYr OAW, IltO A;A U04AUTMXIXVD MWHK~ IS VlWN16l11O SY tAW.

TABLEIL COMPARATIVE MASS SPECTRA OF FORMAMIDE,DO, AND SELECTED DECOMPOSITION SPECIES FROM DOAP

Relative Intensity Relative Intensity Relative IntengityIon Specie DOA D.OAP Formamide (1)

CH 2 1.9 4.2

NH2 52.5 8.2 -

CF N 70.0 44.3

2H 0 22.4 5.6.

NH OH 105.0 2.7

cHoN 6.0 16.0 16.0

CHONH 45.1 20.7 22.0

CHONH z 12.3 100.0 100.0

'CH 2 ONH2 100.0 1.6

HCN z2. 5 55.0

(1) Only peaks at m/e 43.0, 44. 2, and 45. 1 can be correlated since thereis a contribution of ion fragments from other compounds in DOAPspectrum.

5

S VIH S

No bockW, =WA" W06" a MOM is ""11"M Gl".SC.omtuw m 's

(C) Further insight into the mechanism by which formamide is formed

in the decomposition of DOAP was obtained from a comparison of the crack-

ing pattern for the free amine methylenedioxyamine (DO), CHz(ONHz) 2 ,

and the C-H-N-O decomposition products of DOAP. These are shown in

Table II. The DO cracking pattern contains a species at m/e 46

(CH z ONH 2) whichi'is the largest in the spectrum. In the DOAP spectrum

the m/e 46 peak is extrerrely small and is due to the naturally occurring13 and not C+ N 2 CosqetyC isotope of formamide (C1 3 HONH 2 +) and not CH ONH2 . Consequently,

the decomposition of DOAP does not occur through dissociation of the salt

to the free amine (DO) and perchloric acid. A condensed-phase rearrange-

ment and cleavage is required to give formamide as one of the intermediates.

(U) As the temperature is increased, the peak at m/e 33, identified

as NH OH+, also increases in concentration. Figure Z gives a plot of the

ion intensities/temperature relationship for the cracking fragments of

hydroxylamine and its oxidation products from DOAP decomposition. Small

amounts of hydroxylamine are being produced during the low-temperature

stages of the reaction. An initial maximum concentration of NO is reached

at 850C corresponding to the maximum DOAP decomposition. The NO

concentration "then decreases until the decomposition of HAP surpasses that,

for DOAP, at which time the NHzOH and its oxidation product concentrations

increase.

(C) Hydroxylamine is formed by the electron bombardment of methylene-

dioxyamine; however, since no free amine is detected in the DOAP decom-

position pattern under analogous conditions, the hydroxylamine must arise

from another source. Similarly, m/e 33 (NH OH+) does not originate from2the electron bombardment or fragmentation of formamide. The source of

m/e 33 in the DOAP mass spectrum must be another decomposition inter-

mediate more stable than DOAP itself, since the NH2 OH+ pattern does not

contribute appreciably to the overall spectra until relatively high tempera-

r tures are reached.

6'

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111 W 4

'CONFIDE4TiAL

(U) Perchloric acid is liberated over the entire temperature range

during the decomposition reaction (Figure 3). Removal of one perchloric

acid molecule and cleavage of formamide from the remaining mono-acid

salt w-l give hydroxylammonium perchlorate (HAP) as an accompanying

intermediate. HAP formation would occur simultaneously with formamide

generation; however, the former would remain intact and not contribute

substantially to Lhe spectra until an elevated temperature is reached. At

this temperature most of the DOAP would have been decomposed, as

evidenced from Figures 1 and 2.

(U) The spccies corresponding to HAP decomposition and fragmentation

of its intermediates, i. e. , NO, O , NH2 OH, N O, and HClO 4 (and its

fragments) continue to increase in intensity as the temperature rises

(Figures 2 and 3). Those species related to DOAP degradation, i. e.

CHONH 2 HCN, and other H-C-N-O fragments, decrease with increasing

temperature (Figure 1). The perchloric acid peak intensities observed in

the 900 to 1000C range are directly related to the hydroxylamine peak

intensities and not to formamide.

(U) In order to substantiate the existence of HAP in the DOAP decom-

position pattern, a samplc of HAP was heated in the direct inlet of the mass

spectrometer, using the identical conditions as in the DOAP runs. Figure 4

presents comparative plots for pressure-temperature data for DOAP and

HAP. The curve for HAP parallels that for the DOAP baseline up to the

temperature where HAP dissocia is accelerated. It appears from this

data that HAP is continually being rmed from the DOAP rearrangement

and dissociating at the same rate as the known HAP sample. Ion ratios

from both the HAP and DOAP data between 92.5 0 and 9500 are given in

Table III. The data correlate will within E10% experimental error encoun-

tered in photoplate data retrieval.

8

"" CONFIDENTIAL,(This page is unclasdbfied)

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20 ODOAP

OHAP I

109.08.0-7.0

6.0

5.0

' 3.0-

2.0-

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.4 ,

.2

-7o 75 80 85 90 95 100TEMPERATURE, 00C

Figure 4. Comparative Plot of Pressure versus Temperaturefor Decomposition of DOAP and HAP.

10

CONFIDENTIAL I1lh. do.tu.en, iomq.,nt .,fo-oton affecting the notional defense of she United ,Stote% withn, the rteoning of the (sponoge tows.

1.11e 18 U $ C Set,.on 793 od 794. Ihe IIon trisgson of which in ony monnet to on u.nouho,,ied pet-or is pvohihied by low

.all.

GOrniuMn AL(C) Based on the mass spectral data a preliminary working hypothesis

can be formed. The decomposition of m ethyle nedioxya mine diperchiorate

appears to be initiated by the loss of one perchioric acid group to form the

nionoperchiorate salt. Since no parent species other than m/e 45

(formamide), 100 (perchloric acid), and 33 (hydroxylamine) are observed

in the cracking pattern, a condensed-phase concerted rearrangement-

cleavage reaction must be postulated as leading to two major intermediates,

formamide and hydroxylammoniurn pe rchlorate.

Me DCIP~ CONAINSIMPOOMTION APKIING INS NATIONAL 0111014 OfTHEUNITED STATES WITHIN THE MEL'41N0 Of THE t5.tIONA61 IAWS.

TI IS. U.S.C.SCT MCI@ APO IN TEAN"MION OF WHICH I"4 ANY MANNEE TO AN UNAUTHORIZED PINVIN IS PONISITEO 21' tAW.

CONFIDENTIALTABLE III. MASS SPECTRAL ION RATIOS FOR HAP AND DOAP

HAP DOAP

Ion Ratio Ion Ratio

N 21.5 N2 2. z

NO 12.0 NO 11.8

02 5. Z 02 6.9

NH2OH 1.0 NH2OH 1.0

N O 3.4 NO 2.4

C10 2 10.3 C1Oz 9.3

Ci03 1.7 CiO3 3.0

NO Z 0.8 NO [ 0.7

Pressure 2. 5x10" 6mm Pressure 3x0 6 amm

Temperature 92. 5 - 95 C

a

CONFIDENTIAL"a C 0PCINi At MfIiNG ME HATI14L to 0O# 1100 1111R STATS WITi"N 1140 MEANING 0C *N A I4C4AOI LAWS.

titl Is. U.I.C. "ia"M ON UNO WI 194. 1 IMIIIOM 09 WOICH IN AN MAIYIH TO AN WNAUTNO4iZ0 9920 IS IOi 1iNTE BY LAW.

-------------------------------------------------------------------------

1.. - -

IU'UrULrI DALSECTION II

VERIFICATION OF INTERMEDIATES

(C) Perchloric acid liberation and decomposition in general were noted

to begin at 650C in the mass spectral decomposition studies. Rapid-heating-

rate experiments at atmospheric pressure, such as DTA, TGA, DSC, show

decomposition occurring at 1400C after the sample has melted. These data,

taken under different heating-rate conditions, imply an induction period

prior to bulk decomposition. Several other experiments were run to clarify

this point and to verify the existence of the postulated intermediates in the

decomposition. Samples of DOAP were placed in an eva.-uated glass tube

and heated in a constant-temperature bath at 600C. In less than 2 days the

samples liquified. No gaseous decomposition products (or pressure rises)

were detected above the samples when the tubes were opened into a vacuum

rack. Infrared analysis of the residue gave absorbances for perchlorate

and amide groups. The characteristic absorbances for DOAP (Figure 5)

were missing, indicating decomposition of the starting material at a temper-

ature far below that determined by such conventional methods as DTA.

(C) The weight loss from DOAP was monitored at 60, 70, and 850C.

Samples (in this case unrecrystallized DOAP) were placed in a continuously

evacuated oven/(<100 microns) and weighed periodically. At 850C, both

samples liquified after 16 hours and resolidified when the temperature was

reduced below 800C. The average weight loss from the sample for the dur-

ation of the experiment was 39%. DTA of the treated sample gave a ther-

mogram (Figure 6) which very closely matches that for HAP (Figure 7).

The melting endotherm for DOAP is missing in the thermogram for the

thermally treated sample and only a minimal amount of starting material is

present, as indicated by the slight exotherm at 1500C. The DTA thermo-

arnm ~ ~ ~ ~ ~ ~ i fn- ngr ntr5. CofT'fNM11. r pre , 1 TiiA Figure 5. vieiting occurs at

1150C followed by exothermic decomposition of the melt over a range from00

140 to 1600C (peak at 1500C). A white solid forms after decomposition at

13

CONFIDENTIALThis doC.nilmI Cont."%il' in.,tt. olfecqtaq th ficional dAfense of Ot. to d t1s wd)n the meanog 4 O Espionoe Laws.

1.60. IS. US C Section 793 and 794. *h0 OoCSn"e.6,n OI who in any inacn"t Se an vPehlonied e i s ti plohbelud by low

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IT9 14 %.S...SWH MANSM4 ?WTOMWISI44 0 ml~ I AR M"M O N UA6 rjfo~AV~W SM'%ll l IW SV1.4W

'180 °C (visually obs ve in DSC experiments). The second exotherm,

occurring at 2600C corresponds to the HAP exotherm, thereby supporting

the premise that the latter cor,pound is formed as a stable decomposition

product.

(C) The presence of other decomposition species (formamide) in the

erstwhile DOAP sample act as contaminants, thereby lowering the melting

point of the HAP formed.

(C) Elemental analyses of the 80 0C vacuum-treated samples are given

in Table IV. The average elemental ratios in the samples are C1 H2 0 N5 . 2"

Since all the forma ,ie and perchloric acid formed during the vacuum

thermal treatment would be removed by vaporization, only HAP and unde-

composed DOAP remain. Based on this assumption and the average weight

loss of 39%, a HAP-DOAP ratio of 3 to I results from treatment under

these temperature, time, and pressure conditions.

(C) Another DOAP sample was subjected to similar treatment at 600C

for 600 hours. These data are plotted in Figure 8. There is a weight loss

for the first 2 hours amounting to 2% per hour. After 24 hours, the sample

has lost 5. 5% of its initial weight. The weight loss rate continued to

decrease to the end of the run, where the total change after 600 hours was

20%. This represents an average rate of 0. 03%/hour at 600C and of 100

microns. DTA of this sample showed no difference between the starting

material (DOAP) and the sample after vacuum thermal treatment (Figure 9).

(C) The remainder of the sample was reheated at 700C under vacuum

(100 micron) until 50% by weight of the remaining sample has been lost.

The DTA thermogram for this sample is shown in Figure (10). Once again,

the starting material (DOAP) was almost completely converted to HAP.

This sample did not melt n r liquify ,since the ielting point of HAP was not

reached. Elemental analysis of this material, assuming only HAP and

th.0 dwg fC m.e . 'Ale "F"tO09(.on Po w e tovP d,9.wiq of Ph. t.Pd States,tk.*.. Ow. ineowng of r* 14UbslGA tof.%

f..9. is. U SC c.* to *9 Ad Y94. A-0 e'-%&o.,ao of woch n. **I PGAAP Po on .snowthot.ie ptIOA rv ptok.bP~d by Pow

burnuwNM~r 0TABLE IV. ELEMENTAL ANALYSIS OF 80 C VACUUM- TREATED DOAP

IVac Heat Vac HeatOriginal Treated Treated Avg

Element Theoretical Sample 8ZPC 100 M 8500 100 i Treated

C 4.316 4.5% 1.7% 1.6%6 1.6576

H 2.9%0 2. 8% 2. 8% 2. 7% 2-75%6

N 10.1% 10.0%0 10. 1% 10. 0% 10.05%

Elemental Ratio

C 1 H 2 0 N 5 .2

18

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- CONFIDENTIALDOAP to be its components, gave a ratio of 6. 8 to 1 (HAP/DOAP) based on

an elemental ratio of C1 H3 5 2 N8 .8.

(C) X-ray analysis of the 70 0 C vacuum-treated sample confirms the

observation that the solid remaining after DOAP decomposition is HAP.

Recorded density values for the X-ray diffraction patterns for HAP, DOAP,

and thermal vacuum-treated (TVT) DOAP are given in Figures 11, 12, and

13. Every line corresponding to HAP is present in the TVT-DOAP sample

pattern, with the exception of one line noted in the TVT-DOAP pattern at

5. 28 inches. The lines for DOAP at 5. 54, 5. 91, and 6. 32 inches are

masked in the TVT-DOAP pattern by the intense HAP lines at 5. 6, 6. 1,

and 6. 3 inche3.

(C) Based on these data, it is concluded that the majority of the 70°C

vacuum-treated DOAP sample was converted to HAP; approximately 12%

of the original DOAP survived. Melting of the bulk sample is apparently

not required for decomposition and rearrangement. A solid-phase or

K surface reaction is implied.

*All measurements are made from a starting point on Ohe recorder curves

common to all three X-ray films.

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CONFIDENTIAL

SECTION IV

DECOMPOSITION OF METHYLENEDIOXYAMINEMONOPERCHLORATE

(C) In order to verify the proposed mechanism for thermal rearrange-

ment/decomposition of DOAP, a sample of methylenedioxamine mono-

perchlorate, H NOCH ONH - HC10 4 (DOAMP), was prepared (2) and decom-posed in the mass spectrometer under the same experimental conditions

used in the DOAP study. The ion source pressure during programmed

heating of the monoperchlorate reached maxima at two temperatures, 85

to 86°C and 90 C A third temperature-pressure rise began at 92 0C and

continued to the termination of the experiment at 970C.

(U) The initial pressure rise was accompanied by a cooling of the

sample (endothermic reaction). The second pressure increase occurred

simultaneously with sample self-heating (exothermic reaction). Table Vshows the key ion intensities appearing during the initial stages of each

pressure rise.

(U) The initial pressure rise may be attributed to the liberation of

occluded starting material, mostly the free amine (DO). Such a reaction

is endothermic (boiling). The mass spectrum observed in this region is

identical to the cracking pattern for DO (Table V). An excess of the free

amine was used in the preparation of the mono-acid salt; hence, occlusion

of residual starting material in the solid is a reasonable explanation for

the effects noted in the temperature range.

(U) The second pressure rise is attributable to the formation and

liberation of formamide from the salt. The majority of the spectrum at

this temperature correlates with the cracking pattern for formamide.

26

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(C) Initial liberation of perchloric acid does not occur until after the

maximum concentration of formamide (and its fragments) is achieved.

Perchloric acid liberation also parallels the pressure rise and the observed

exothermicity effects. Subsequently the hydroxylamine species, as well as

NO, 0 , NO, NO?, and perchlora.e fragments all increased in concentra-22 2

tion. The mass spectrum in this temperatre range can be attributed to the

thermal decomposition of HAP (Table V).

(U) These data support the segmental aspects of the mechanism pro-

posed for DOAP decomposition. After initial loss of perchloric acid from

the di-acid salt (DOAP), the monoperchlorate remains as a stable inter-

mediate. Degradation of the latter gives formarnide, which is not accom-

panied by perchloric acid formation, ar'd hydroxylammonium F.-rchlorate

as the temperature is increased.

(C) The mechanism for methylenedioxyamine monoperchlorate decom-

position can be formalized as follows:

ON -HC104

HaC "HClO4 s. H HZC+

ONH z

6ONH -HCl02 4

9H

HCNH + HONW H l 2 NH

2 2 H'4..

if hUEI Cl ?NE sAW M T O A AUT 621 M 1 04 I H MIbIOL W

cqIo a 0 0 ~ 00 0n 01000nenk n D 0V co N O C t 0' mi N

1 v N en 100 1 0 0 -0 00

-n N LI - 0 -

0 vU N. 0' OO'. v N 0 0n 0 LA 0N fl 00 ,LA U).t 0 00o - LA O 0 r- a m Ci V; cN 0' t C 0 0 ' ; V mN '.0" r-1

0 OC v- -L-- IN N

N 0

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P-1N

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mill -

SECTION V

SIDE REACTIONS DURING DECOMPOSITION

(U) The majority of the experiments described above were r'onducted

under conditions in which initial volatile decomposition products such as

perc.hloric acid and formamide were removed from contact with the solid

starting material and its residue. Several experiments were run to identify

the reactions and products of the decomposition intermediates which would

occur in a closed system.

(U) Mixing formamide and aqueous perchloric acid at room temperature

gave rise to instantaneous precipitate formation. The latter was identified

as ammun;urn perchiorate by infrared and DSC analyses. Infrared analysis

of the v. Liles from the reaction mixture showed the major product to be

formic acid. The formamide was hydrolyzed to the acid and ammonia. The

latter then reacted with perchloric acid to give the salt

0 H0/H4

it2

H - C - NH Z _- HCOzH + NH 3

NH 3 + HCIO 4 IN. NH 4CIO4

(C) Hydroxylammonium perchlorate is completely miscible with form-

amide. After 24 hours at 600C, appreciable amounts of ammonia and carbon

dioxide were detected when the volatiles from the mixture were expanded

into a vacuum rack and analyzed by infrared analysis. Some dissociationof HAP to hydroxylamine and perchloric acid will occur under these con-

ditions (60 C, vacuum). Water is formed among other products from theIHAP decomposition reaction. Hence, in a closed system, decomposition

of DOAP to HAP, formamide and free perchloric acid can give rise to

numerous side products, including ammonium perchlorate, formic acid,

29

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CONFIDENTIALammonia, carbon dioxide (from oxidation of formamide by perchloric acid

or one of its ozidizable decomposition species), water and the decomposition

products of hydroxylamine.

30

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CONFIDENTIALSECTION VI

MECHANISTIC HYPOTHESIS

(C) Based on the evidence cited, the mechanism proposed for the

primary decomposition route of methylenedioxyamine diperchlorate is:

ONH "HCIO4 ONH "HCO 460°C

CH 60 C CE + HCO 4

ONH "HCO ONH

rapid

GONE HECIO H 1 .NH 2EClO( 2 4 rapid H. H 4

H + H ONH2

H-C-NH + HONH HCIO110 2 2 4

(C) Loss of one perchloric acid group leaves the mono-acid salt in a

configuration which is sterically unfavorable. The crystal structure of the

dipe. -hlorate has been destroyed. The mobile free oxyamine group lies

adjacent to the oxyammonium perchlorate group, an equally electron-rich

group. This electronically repulsive situation contributes to the driving

force for the rearrangement. The oxyamine nitrogen is in position relative

to the electrophilic methylene carbon to attack the latter and initiate a con-

certed cyclization-cleavage reaction. Such a mechanism is reasonable in

light of the weakness of the C-O bond and the known existence of three-

membered heterocycles of analogous structure (3) to the postulated proton-

ated oxazirane transition state. Electronic charge balance leads to

31

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CONFIDENTIALformation of formamide and hydroxylammonium perchlorate. The driving

force, once again, is conversion to more stable products. In essence, the

overall driving force for the reaction is the transition from an unstable

intermediate (sterically distorted monoperchlorate) to a more stable

product.

CONFIDENTIALj TNI6 C N6 I~~~t OWJTC) TING ?"I NAT*ONA DHOiM Ot Tod MHINDO TAIU WITIN t 41ACM|ING OF "M 1UMOM I AWS,

T1IM Y".U e, APOI M . 1141 11A M I ONq Of W IC IM ANY MA N# 10 AN W~qAUM 0l 11102 M 16 N 0 16 Itt*__ .. .IT tAW .

SECTION VII

COMPARISON WITH OTHER AMINE PERCHLORATES

(C) The decomposition of methylenedioxyamine diperchlorate is

reminiscent of the thermal behavior of hydrazinium diperchlorate (HP-2)

(References 4 through 7). Both are strong acids; one perchlorate group

is lost relatively easily. Both give more stable solid intermediates, though

in the case of HP-2 the first step in the decomposition is less complex and

cleaner. That is, loss of one perchloric acid group gives only the stable

monoperchlorate as product. Loss of perchloric acid from DOAP gives

rise to a thermally unstable form of its mono-acid salt which continues to

degrade to hydroxylammonium perchlorate, a stable intermediate, plus

formamide. The latter is incompatible with its environment under these

conditions and will react to give volatile products (NH 3 , CO, CO 2 , HCO 2 H)

and possibly some AP.

(C) The key difference between the two oxidizers lies in the hazardous

nature of their composition products. HP-2 continually degrades to a more

hazardous material, i. e. , HP-i, while DOAP does not. In terms of per-

chloric acid liberation, the temperature threshold for this occurrence in

the HP-2 decomposition is considerably lower, i. e. , 400 C compared to

65 0 C for DOAP. This implies better compatibility behavior for DOAP than

HP-2 under processing and storage conditions.

(C) The temperature threshold for decomposition of DOAP is lower

than that for HAP, the latter being a stable product of DOAP degradation.

The rate at which perchloric acid is evolved form DOAP is greater than

that for HAP.

(C) Compatibility behavior dependunt only on these factors (thermal

stability and perchloric acid evolution) should be better in the HAP system.

th.4 dv.,,e omq S .54I 0",IV 4 0..0 A W t hE. on" *1 f tEs s U fd 1 . Koo A f o h tao m4 tows,I@~I. U S C., Sfthaft ?93 efd 794. *4 of E .Wh ~ aA 40-ftt ft SA .0VO~4A.d PO 6po'w.IH~ by low

CONFIDENTIALThis would be especially true for those effects attributable only to per-

chloric acid reactions under long-term aging conditions. i. e. , HAP pro-

pellants should age better at room temperature than propellants containing

DOAP. This is an oversimplification, however, since factors such as

hydrcscopicity and crystalline phase changes also appear to effect HAP

reactivity (4, 5). The endothermic transition undergone by HAP at 55 0 C

is also accompanied by a marked increase in reactivity. DOAP is less

hydroscopic than HAP and it does not undergo any phase changes below its

melting point. A comparison of the reactivities of these oxidizers is pre-

sently underway at AFRPL. Conclusions concerning DOAP and HAP

compatibility will have to await the results of this study.

(C) For the sake of completeness, the obvious should be stated:

ammonium perchlorate is significantly more stable than DOAP.

AY

34

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UNCLASSIFIEDSECTION VIII

EXPERIMENTAL PROCEDURE

(U) DOAP samples of 0. 01 mg were packed into 2mm OD glass capillary

" tube and placed on the end of a direct-inlet mass spectrometer probe. The

probe consisted of a nichrome wire heater wrapped around a ceramic mm

* ID tube. The sample-containing capillary tube was placed in the ceramic

tube and rested on a thermocouple.

(U) The probe was placed into the ion-source housing of a CEC 21-110

double-focusing mass spectrometer, such that the sample tube exit was

within 1/2 inch of the perpendicular electron ionizing beam. The ion source

housing was evacuated to 2 x 10- 7 torr and warmed to 40 C overnight prior

to a run. Heating rates were regulated to 0. 5°C/minute with a temperature

programmer for 40 C to 100 C. Ions produced from the ionization of gases

being liberated from the sample were collected on an ion-sensitive photo-

graphic plate.

(U) The ion exposure energy transmitted to the plate was kept constant

while the time required for a constant-energy-exposure value varied. Data

was collected at each degree sample temperature. Pressure measurements

were obtained from the ion-source ionization pressure gage.

(U) A total of 30 spectra were recorded on the plate for each experi-

mental run. After plate development, the data was reduced by measuring

the ion line positions, for accurate mass measurements, and density for

relative quantitative measurements. No ion sensitivity corrections were

made since only relative quantitative and qualitative data were desired.

(U) Weight-loss measurements were made on 0. 2 gram samples of

DOAP. Samples were weighed to 0. 1 mg and placed in a vacuum oven pre-

sent at the desired temperature. Continuous evacuation was conducted v ith

35

UNCLASSIFIED

I -

UNCLASSIFIEDan effeccive oven vacuum of less than 100 microns. Samples were periodi-

cally removed and cooled in an inert atmosphere dessicator prior to weight-

loss measurements.

A. SAMPLE PREPARATION

'U) The samples of DOAP employed in this study were purified by

reczystallization from ethanol. Elemental and perchlorate analyses

indicated this material to be 98% pure DOAP.

B. THERMAL ANALYSIS

(U) The thermal behavior of various materials was studied on a

Perkin-Elmer Model lB Differential Scanning Calorimeter and a Dupont

Model 900 Differential Thermal Analyzer.

36

UNCLASSIFIED

UNCLASSIFIEDREFERENCES

I. C. S. McDowell, AFRPL, unpublished results.

2. C. S. McDowell, AFRPL, unpublished results.

3. W. D. Emmons, J. Am. Chem. Soc., 79, 5339 (1957).

4. I. Smith, J. Nebgen, and T. Lapp; "Compatibility of Selected BinderPrepolymers and Curing Agents with Oxidizers"; Midwest ResearchInstitute; AFRPL-TR-68-183, AD 393426, August 1968. ConfidentialReport.

5. A. D. McElroy and J. W. Nebgen; "Studies of Stability Problems inAdvanced Propellants"; Midwest Research Institute, -MRI-3006-C;AFRPL-TR-67-304, AD 386008, November 1967. ConfidentialReport.

6. Y. Tajima, J. Hammond, and G. Stapleton; "Kinetics of Decomposition

of Solid Oxidizers"; Lockheed Propulsion Company, 7Z0-F;AFRPL-TR-68-76, AD 390481, March 1968. Confidential Report.

7. C. J. Grelecki and W. Cruice, Advances in Chemistry Series, 54,73(1966).

37/38

UNCLASSIFIED

VV

Ie__

-~C N

'~ ~i~utty ego sDOCUMENT o CONTROL DATA. R Dt & D nt0 t~ t clasiied)

1. ORIGINA TING AC TIVITY 7C0?P0N~iO -utho')

Air Force Rocket Propulsion LaboratoryEdwards, California 93523Gru4

3 REPORT TITLE

Thermal Decomposition Studies of a New Perchlorate Oxidizer (U)

C OESCRIPTIVE NOTES (TY~Pofreportand Ilcl r da I**)

Phase Report July-October 1968S. AU THOR(S) (FItSt name, middle initil. last name)

R. E. Foscante, Capt, USAF; B. B. Goshgarian; F. Q. Roberto

6. REPORT O~kTE 7a TOTAL NO. OF PAGE; 7b NO. OF, REFS

May 1969 46 7

ISa. CONTRACT OR GRANT NO 9a. ORIGINATOR'S REPORT NUM8Cr.(S)

b. PROJECT NO 3148 AFRPL-TR-69-109

c. St. OTH R REPORT NO(S) (Any other numbers that may be aa 014idVe

C. this report)

d.

to 015-RIBUTION STATEMENT Inadto o security requirements which must be met, thit

document is subject to special export controls and each transmittal to foreign

governmetts or foreign nationals may be made only with prior approval of AFRPL

(RPORT-STINFO), Edwards, California 93523. -,

It UPEETR NOTES 12. SPONSORING MILITARY ACTIVITY

SUPPEMENARYAir Force Rocket Propulsion Laboratory

Air Force Systems Command, USAF

Edwards, California

(C) The initial step in the thermal decomposition of methylenedioxyamfine

diperchlorate occurs at 60 0 C with the loss of a perchloric acid group to form the

monoacild salt as an intermediate. As the temperature increases, the latter

undergoes a concerted cyclizatioi - cleavage reaction to form formamide and

hydroxyimm--irn perchiorate.

()Mass spectromnetry was used to formulate a working hypothesis for the

d~crnposition. The existence of 2ach of the postulated intermediates in the

reaction was verified byr independent experiments.

DD ,-0" 1473 45 Secutity IlosiSiaigtnf -.

KEY WORDS LINK A LINK 0 LINK CROLE WT ROLE WT OLEr WT

(U) Oxidizer decomposition(U) Perchlorate oxidizer(C) Methylenedioxyamine diperchlorate

- 46 1 Ay-EM