Ef fe c to fme t a lc o mpl e xc a t a l ys i so ft e t r aaz a‑ ( 1 4 ) ‑ anur e ne o nt het he r ma lde c o mpo s i t i o no fammo ni um ni t r a t e

研 究 姶 文

‖‖‖‖l‖lll‖‖‖川II

Ef fe c to fme t a lc o mpl e xc a t a l ys i so ft e t r aaz a‑ ( 1 4 ) ‑ anur e ne o nt het he r ma lde c o mpo s i t i o no fammo ni um ni t r a t e

andammo 山umpe r c uo r a t e

Hidet8u即 NAK如けURA●,MiyakoAXⅣ OSHl●,Ⅹ且2:unOriSAKATA●

andYa8utakeH瓜

Thee血ctofvariotJBmetdcomplex cataly8t80ftetraaZa･(14)･8Jlu用neOnthethermalde00mp ‑

8itionofammoTdumnitrate,Ammomium perchlorateandaSolidpropelbntoontai血ngamEnOnitn perchlorateaBanOXidizerw88Studiedl吋thermalazdySiSandburningratemea8urement8.The f

ouowingreOultSWereObtained̲

Ametaloomplex,wtdchhdironorvanadium a8aOentralmetAmciorL8howedhigh activity duringthethem aldecompositionofammoniu皿 nitrate.E8peCiAuy,thiBactivitybecamehigh whenchlorideandperchlorateionswerecx)mbinedwithironorvanadiumionB.

Ironandvanadium catalyさt88180lmdhigh activityduringthethermaldeoDmpO8itionofammo･

niumperchlorateandit880hdprqpenant.Forthe801idpropelhnt8WhichoontaimedinnoryAna‑

diumcotnplexe888CablyBtB,theburmingrateincrea8edby1.6time8andtheirniJldexdeqeaBed to80%comparedtotheburningexperinentSwithoutacatalystatapr朗BureOf5.0MPA.

1.lntro血ction

TherehiLVebeenawidevarietyof8tudie80nde‑

compo8itioncataly8t80fammordum perchlorate (NH4CIO一;AP)andburningcataly8t80rAPcontain･

i

ngoompoBitepropelhnt8,eventhough ba8icorprac･ ticAltheywere.Forexample8,JacobBetal.zmd SolymoSiSummarizedtheactionofmetalhcoxide8,

oxyacidB,haLide8and800mり12).withreprdtothe decompositionc8talyBt80f且mmOnium nitrate (NH‑N08;AN),wtdchAreextensivelytI8eda80Xi‑

diZerBOrindu8trialexplo8iveBandpropeuant8,there hvebeenmanyreportsWhichwere8ummad五ed

hyUrbanBki3).

Iti8Wellknownthttheactivityof80lidcatdyBtB

are8i宅れ追払ntb,innuencedbytheirmethodofprepか rationorrawm8teriAlB,because Catdyticactivities arecontrolledby8ur血00propertie88udlaB8u血ce Area,8ur血cO8truCtureAndinpuritie8.ESpeCiauy,

ReceivedonNoyenberll,1999

'DeprttnentorAppliedChemi BtZy,FAcultyofEngi‑ neering.Kyq8htJIn8tittlteOfTbchJ)Ology,SenBui, 1bbatA,KitAkyu8htI,804‑8550JAPAN

でEL098‑884‑3319 FAX093‑884‑3300

ametallicoxideiJlBtrOndyaffected.becauseitmay becalCinedorgrounddtwingpreparation.Inthe caeeOfthecatalyticACtivitie80rmetallicoxide80n t

hethermaldecompo8itionofAP,Solymo8ireported 8discrepancyintheorderofactivitieBOfmeblhc oxide82).

Inthi8paper,theeLrectofvariou8metalcomplex

catalyBt80ftetraAZA･(14)･anureneOnthethermal decompo8itionofammonium nitrate,AmmOmitlm perchlorateand80lidpr叩euAntCOntmi gAnmO‑ niumpelt:hloratea8anOXidizerwa且Btudiedbyther‑ malanaly8i8andburningratemeaBurement8.

Moreover,theorderofcahlyticActivitie8withre･ 富ardtometal8pCCie8WerealsodiBCuBBed.Cata‑

1y8tSusedarethecomplexesWhichcoordinateme･

taJJicBPeCie80ntheoentralp8rtOrthetetraam･(14)I anurenhgand.The8eCatAly8t8takethefom ofa powder.Themostimportant8dvantaP8forusing thesetypes0fcataly8tBarethAt(1)compatibility amongphyBicalpropertieoJluCh88partide8i加,mOl lecularweightandmeltingpointwitheachother

beCau8eOftheBtrOTlgeqeCtOfAhrgeligand丘eld and(2)acapabilityofthchpnd'8action88anOXy‑

K.yakLJGBkbishi.Vol.61.No.3.2000 ‑101‑

Tab一e1Propenantcomp08itionStC8tedinthisStudy Comple又

prop

･

A l

1 4 8 4rI l l

8 4:1

8 4】

M n ･ N

genCarrier. 2.Experhenta1 2.1Maten'als

Ammonium nitrateandammo血u皿 perChlorate werepreparedby^recry8talli2ntionofcommerdalre‑

agent8b mpurewater.CompositepropenantBfor bumingratemeaBu柁mentSCOJ旭iBtedofammonium perchloratehavinganaveragepartideBiZX!Of200

LLm andhydroxyl‑terminatedpolybutadiene (HTPB)aBabinder.

Theformulation80fammonium perchlorateoom‑

poSitepropellantsareShowninTable1andthe 8truCtural formulaofthecomplexandtheligand usedinthisexperimentareShowninFig.1.The hpnd,nickelcomplex,iron00mplexanda)baitcom‑

plexwere8ynthe8i乞edbyapreviou81yreported method415)andtheothercomplexesWereprepared byAmethod8imihrtothatpreviouBlyさtated.

2.2TherTnalanalysisandburningcharacteristicmea‑ Surements

Them al anabr8飴 WereCarriedoutusingaRigaku Simultaneou8DTA‑TGAm ly班randaRiga

k n q h

Pre88ureDTAAndyzerwhichcanbeoperatedun ･ derpre88uri2iedconditions.Smallcylindrically さh pedaluminum cruciblesWereuSedin thiBeX‑

perimentSWhichhadanintemaldianeterof4mm めandaheightof5mm,andwere8ealedwith aalu‑

minum ODVerWhichhadanpin･holeatthecentezT̲ HeatingratesWere20℃/mi nfortheanaly8i80f ammonium nitratemixture8and10℃/hh forazn･

moniumperchloratemixtufe8.

1gmitiontempemturewasmeasuredbytheXn岬p methodunderanatmosphereofargon,u8inga 8ampleofabout30mgwhichhasadimensionof1

C 2 H 5

L i g a n d l C 2 2 n 2 2 N 4 H 2 ,

5 1 1 4 1 d i h y d

0 ‑

be

n z o 【 b . i H l , 4

cyc

l o t

e t

a d e ^$ c i

敬 : Y ) M く N

: 3

conplextC22t!2

2N4M''RM) M= Cu, Co.NilMn･NCSIM

n･CIO41 Fe･Cl, Fe･CIO4,V=O

Fig.1Structural formu180fligandandit8metal

complexe8te8tCdinthi卓Study mmthidkn e88and3mmX3mmw

idth.

Theburningratetn

ea8urement8WereCami edout tJBingachimneytypeSt.r

andbumerpre881血 dwith nitrogen.

3.ResuksandDiscussion 3.1Effectofme

tzLlliccomplexesonthethermalde‑ composh'ono

fammoniurTlnitrate Thermalanaly8iBe)申eri

nentBforammOniumni‑ trateanditsmktureBW

ereCarriedoutunderpre81

8urizedconditionsb

ecauseAmmOnium mitrate evaporatesWithoutd

ecompo8itionunderatm0‑

8phericoDnditionB.Fig.2andFig.3ChowDm ctm

ofammo血um 血trate,lipnd,metanc00mplexcata‑

1mebmcyBtBandammonium nitrateaddedwi th10wt% complexeatAly8tS.

L

igandBShowanendothernic

peakatabout230

℃ corre8POndingtoitsmelting(melti叩 pOi

.〇X3｢ILV‑1･.OpU3

0

10Te0mperat200ure toC)300 400

‑ I,T4Ll.NO,(1),Ml.t10'tJlth10;llSaTtd(2 ) allJNtIJ10,vlthlo‡cdEalySt9(3〜5

‑‑一一一;(2)u88nd.(3)RCU, (/･)1tCo.(5)抑I) Fig2DTAcurvt580fNHINOa,租talyBt8andNH‑NO

B w

ithcata

ly8t8underapreBBureOf5.0MPa puge(1)

po

8ition.Thethermalbehavior80fmetalliccom･

plex

e8are8trOnglydependentona(治ntralmetauic ion

andarecla88i丘edintotwocAtegorie8.Onei8

thecomplexwhichpvcrisetOanendothemi cde･ compo8itionSuch88thevanadiumcomplexShown inFi

g.3,andtheotheri8theoomplexe8Whichgave r

isetOtheexothermicdecomposition8howninFig.2 and3.E叩eCi811y,both mAngane8eCOmplexe8and ironcomplexesWhichcoordinateperchlorateion Showedcharacteri8ticfeature8inthem albehavior. Thati8,theformerhadaLargeheatevolutionand thelatterhadalowd∝ompoBitiontemperature.

Ammoniummitrateundergoesphasetran8itionB, meltingat169℃ andexothermi cdecompoeitio

n aboveapproximately265℃ uponheatingunder pr

e88uri雄dcondition8.Additionoftheaboveme･ ta

lhccomplexcatalyStStOammOmiumnitratemade it8decompositiontemperaturelowerandit8eXOther･ micitylarger.Wh entheorganiccompoundBWere

addedtoammomium mitrate,aviolentexothermic. ox3｢1‑LV‑Jl.OpUZ0 100200300でemperature(

oC)

‑ ;Nll.NO'tJithlo∑cJ)talysts(6〜10) 400

‑‑‑一一;(6)RHn･NCS, (7)Wtt

･C10..(8)RFC･Cl,

(9)RFe･C10.. (10)TtV･, 0

Fi83DTAcuzve80fNR4NOa,Catalystsand

NH4NOa w

ith

cataly8t8underapreSeureOf5.0MPa gauge(2)

reactionoccurredatabout220℃ accordingtoa mutualredoxreaction.Therefore,itCanbeunde

r‑ 8tOOdthattheligandact8Similartoorga血c

com‑

poundsiftheyareaddedtoammomium nitrate.

Metaniccomplexcataly8tBhavingCu,Co,NiorMn

‑ NCSa8aCentrdmetahcionshowedthe8ame

ther一 malbelmvioraBtheligand.Although theMn‑Cl complexit8elfun dez･wentanexothermicdeoompo d0

8itionatabouttheSametemperatureatWhich ‑

am‑

monium nitratecommencedmelting,itcouldn ot cau8eSuchaviolentexothem icreactionjudging f

rom theamoun

toflowleveladditiona8inthese experiment

･8.

BothironandvanadiumcomplexesShowedare‑ marknblecatalyticeLrectduringthethermal reac･ lion.Theoxide80fironorvarLadiumSuchasF

e203 andV205areknowntohaveaSligh tcataly

tic effectonthethermaldecompo8itionofammonium nitrate6).Therefore,thecatabrticeqect80fironand vanadillmincomplex軸WereODn8ideredtobeeauBed

K

.ox3･LLV‑J･.

OptJ H

0 10300Tem 0per atu re200 (O c)

‑;IM.NO'ulth RFe'C1

‑‑‑‑ ‑;Nlt､NO}vlth RVoO

cAtAlyBt$levels;(1日 ‡,(2日王,(3)

5王byt'e1811亡 Fig.4瓦Efecto

fcataly8tSlevelさOnDTAcurve80f NtI‑N03wi

thCataly8t8 hyeitherthereactionprodu

ctsformingduringthe thernald

c

fthecomplexe80rthemu･

tualreactionoftheme

tallicionwithaliganda8a f

uel.Ftlrthermore,hviJ

qb*nknownthatthecata･ lyticeffectofchlo

r

ideiononthethermaldecompo･ 8itionofam

monium mitrate,iti8COn8ideredthat twotype80fcAta

ly8tBWhich00ntainchlorideorper‑ chlorateion

88howedthecatalyticeLrectbecause chlorideion

i8formedbyitsthermaldecompo8ition.

Inordert

ochri&thecablyticeqectofcomplexes indetai

l,the1,3,5wt%additionofcatalyStWas te8te

dintheaboveexperiment8.Fig.48how8the eLrectof

theamountofadditionofFe･ClorV主O^cata‑

1y8t

80nthethermalreACtionofAmmOniumnitrate.

Itwa8foundfromthe8Cre8ult8thattheadditio nof 3wt%租taly8t8gaveanadequateeLrect.

3.2Effectofmetalliccomplexesonthetherma lde‑ compositionofammoniumperchlorate

A8in theca8eOfammoniumnitrate,theeqectof HOX.

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