The r ma lde c o mpo 8 i t i o no fmu lt i pl e･ baB e dm it r ami nepr o pe nant 8

研 究 鼓 文 Illllllll‖‖‖川川‖‖‖川

The r ma lde c o mpo 8 i t i o no fmu lt i pl e･ baB e dm it r ami nepr o pe nant 8

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A

8Z lm u l ^{t i pl e ‑ bas e dpr o pe nant ,n i t r am i ne ' 8de c ompo s i t i o nat t r i but e st Ot h0 8 eO fc o mpo ne n}

butno tt ot he i rB i mpl epl us .

r e et y pi c a lpr e 8 C r ipt i on80fmul t i pl e ‑ ba令 e dpr o pe l l a

t , Whi c har e RNG ( c ont a im ingm it r o g um i d i ne,NGu) ,RHN ( c ont a im inghe xan托r o 8 t i l be ne,HNS)andRNO

( nano ･ o x i de 8Z l dde d) ,ar et e 8 t e d.He r eO2 nWame t ho di 8us e dt ode a lw it ht hedat ag a ine df ro m t he r no g r av imet r y( TG)andt oAna ly2 K Bi t st he r ma l de c ot npo 8 i t i onme c hani s m andac t i vat i o n e ne r g i e 8 .

8ar e s u l t , i ti Be v identt hatn i t r am i nede c ompo 8 i t i onma in lyunder g ot woS t ag e 8 . Co mpa r e d t oRNGwho 8 eme e han i S mf unc t i o nBa l eF J ( r a ndomnuc l e at i o n)a ndD 3 ( t hやe

me n･

B i o na ld i m1 8 i o n)f ore ad1S t a g e , RHNma int a inst he各 a meme C hr d8 mf unc t i o n, bute x hi bi t 8l o we r ac t i vat iO ne ne r g i e s .

hi l ei ti Sr a t he rpe c u li a rt hatnano･ o x i de 8i nRNOc anno ton lyl o we rac t i v a‑

t i o nener g ie 8 , butA1 8 0C hang et heme c hani S mf unc t i o nwhi c hbe c o me

( i nt e r f ac er e z I C t i on)a nd Dl( t w o ‑ d i menB i o na l di 艮1 8 i on)r e s pe c t i ve l y .I tB ho w8t hatnano･ O X i de 8LabAC e r t a ine L r e c tt o

c at a ly次 t het he r ma lde t o mpo 8 i t i o nandc o mb us t i o nofni t r ami ne8 i g n i B 租nt l y . Ke ywo r d s:n i t r ami nepr o pe uant , t he r ma lde c o mpo s i t i on, nan〇 ･ 0 7 dde S

1 .I n t r du c t i o n

Con8 i 8 t i ngo fmul t i pl ei ng r e di e n t 8 ,ni t r ami ne ' 8 t he r ma l de c ompo 8 i t i o n i 8r e l e vantt ot ho s eO f c oT npO ne n

8 , butno tt ot he i r8 i mpl epl u合 .Combu8 1 一 i one x pe r i me nt 88 ho w8t hatHNSandman〇 ･ 〇 X i de B ma yc hng ebum i ngr at eof pr o pe uant H . Ho we Wr

t

her e a c t i o nme c hani B mi Bf a rbe yo ndmadec l ear . U8 ua ll yi nAuenc edb y8 0meC 0 0r di nat i nge qe c to r e ve n ca kI y 8 i BO faαr t a inormo r ec omponent s, t he t he r ma lde c ompo S i t i o npr e B en t B C O mp l i ca t e dm u l‑

t i pl e ･ 8 t a g eC hr AC t e r i8 t i

f ore x ampl e , t hema xi m e x ot he r ma l pe akoni t sDSCc t m ei 8anO V er l a p･

pi ngone .I t ' 8di mc u l tt odi 8 t i n印i 8 hi t st woma in S peci f i cpeak

,Whi chr es pe c t i vel ySt andr or e x o t he m a l BO fNNC 2 andRDX 2 ･ 3) . Fo rt hi sr e a8 0 n

08 8Wamet hodi 8e mpl o ye dt oc l ar i秒 t heki net i c c hr a C t e r iS ti c 80 f e ac h8 t ag e.

2 .Ex p e r i me n t a l 2 ,1

de s

Thr e epr o pe l hnt ' 88 8mpl e 8 ,Whos ei ng r e di ent s Re c e i y e d: Aug qB t31 . 2 0 01

Ac c e p t e d: Se pt e T n b er6 , 2 0 01

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sc ho o lo fChe m ic a lEnB i J l e e r i J

g, Nan j i ngUni y e r ･ 8 i t yo f

c i e n

b c hno l o w , Na n j i ng21 0 0 9 4P . R.

Chi na

ar el iB t e di nTab l e1 , ar e8 e l c ct e d t o t e s t . T he B i 男 eO f NanO･ O X i dei 81 0nm.

2 .2 Ap p a r a t US

The r mo g mv ine t r yt e 且

s

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O2 i aWa,OneOfno n･ i 8 0 t he r ma l me t ho d8 ,i 8a d ynami co net oma idyde a lw it hTGc ur v e sunde r di L r e r enthe at ingr at e l ) iABS ho wni l lFi g. 1 ,o n8 t y pi c a lTGc ur v eci 8t hec o nve r J i i o nr at i oo rma8 8 f

rac t i o no fr ema i nde r , de丘ne dA BWN . , whe r eW i B t hema与 BO fr e ma inde randW.i 8t hemaB 80 ft ot a l r eaC t ant .Whent hepr ope l l antde c ompo 8 e8 ,t he ma8 8l o 8 8r at 8C anbee x pr e 8 8 edby

‑ i‑ ^{u( C )}

wher ef ( C )i Baf unc t i ono fma8 8de c ompo 8 i t i on

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Ta b l e1Che mi c alc ompo 8 i t i onBO ft hepr o pe l hnt st e 8 t e di nt h i s 8 t udy

NNC, RDX NGu HNS Nano l 0 X i de DBP RN G て5 6 . 5 % 2 7 . 0% 1 5 . 0 %

RHN 6 0 . 0 % 3 2 . 0 % RNO 6 0 , 5 % 3 2 . 5 %

でく K)

Fi

g .1De f ini t i ono fanal y S i Sf orTGc uve de 丘ne da

8

̀ ̀ me c hAJ d8 mf unc t i o n"andki Sr e a c t i o n r at ede丘n

e db y

A=Ae‑ A/ Rr ( 2)

whe r eEai BaC t i v at i o nener w , Ti 8t empe r a t uJ ･ e ,氏 i 8g8 8C On S t ant ,andAi 8p 柁 ‑ e X pO ne nt i a lc

o n 8 t ant . Subs t i t ut i ngEq. ( 1 )i nt oEq .( 2 ) , oneg et

普‑Ae一

^{助 ' W F( C)} s ^{( 3)} Sub8 t i t ut i ngt hehe at i ngr at e

, whi c hi 8de 丘ne d a

8dT/ ‑ i dt , i nt oEq.( 3 ) , o neg e t sane X pr e 8 8 i o nof

‑i e‑ A, w l( C) ( 4) Tr ans f or mi ngTGc ur ･ v e 88 t

d i f fer enthe a t i ngr at e 8 t oaS e r ie 80 fc ur v e 80 fl o

g ar it hmofhe at i ngr at eby r ec i pr oc a l oft emper at ur e,Lo

g O

ur ve 8at d i L r er e ntr e ma inde rpe r c e nt

ag ec anbepl ot t e d. I f a

llt he 白 eS t r a ig htl i ne 卓O b

t a in e dar epar al l e l , i tc an b ed r a w n

t btt heme c hnbmo f B a mpl ei 8unC hang e ･ a bl edur ingt hewho l et he r ma lde c

ompo s i t i o

The n t

her LogO = e g Lo r e gt 8 8 i AEJRf v ee quat (

i ) o i ni ‑2 B: . 31 4‑0 . 4 5 6 7EJRT ( 5 ) 5 . 0% 1 . 5 % 1 . 5 % 5 . Fr 0% o mt heS 0 . l o 5% peo f

増 1 . 中 5 ‑1 % / T (

e

alt 0‑0 . 4 5 6 7E J R) ,t heac t i v at i one ne r g y c a

nbede t e r mi ne d.Ot h‑

e r w i8 e

i ft heS l o pedo e 8

no ta ppe a r a8 t m i g htl ine

t

heS ampl e ' Bt he r ma lde c

o mpo 8 i t i o ni sno tas i ng l e 8 t e Pr ea c t i on,andLog o

‑I / Tc ur v e sappe armo r e t hno neB etO f pa ra ne ll in

e

8 , i nwhi c ho n lypa r a ll e l one 8ata d j ac e ntr ema i nde r

m a88 f ra c t i o nBS t a ndf or onet y peo fme c bads m

.By8 1 q p eo fdi qe r entpa r a l‑

1 e ll ine S , Eao fe a

c hs t ag ec ana l8 0bedet er mi ne d̲

3.2 Ni t

r a mi ne ' sThe r ･ ma l De c or T I P O S i t i o n l nt hedi B mB S i

o n, RNGi Sar e f e r e nc e8 a 皿 pl ea nd t heo t he rt w

oar emo di 丘e d,amongwhdlRHN i nc l ude sHNS8 ub8 t

i t ut i ngf orNGu, whe r e B L 8RNO i sadde dby0. 5% nano

l 0X i de.Thei

Log o ‑1 /T G um sa tdi J r e 柁nt r e ma inde r

pe me nt ag e 8a l e8 ho wn i nFi g s. 2‑4 .Fr o mt he丘g ur e

S , WeC anS e et hatal l t

he 8 eC u r v e s0 f t het hr e es a m

p le sa柁di v i de dbyt wo g r o up8 .W h e nci 8l a r g

r , t he

c ur v e 8pr e s e ntO neB et o fpara ll e l sWho 母 e8 1 o pe Ba柁

8malJer,whereascis Smaller,thectme8pre8ent anotherBetOfpara lIelS ▲ ｢ 2 0 tB 1

1 . 1 . 0 4 ) 3 0 1 T ti:00180 . 00200 . 00220 .00240.0028

a‑I) Fig.2

.og 0 ‑1/Tctme80

fRNG (Note:numbers1to10corre8pOndtocurvesunder di f ‑ ferentavalue s , s u c h

0 . 0 0 1 8 0 . 0 0 2 0 0 . 0 0 2 2 0 . 0 0 2 4 0 . 0 0 2 8

1/T(K‑I)

g.3

.0g

(Note:number81to 10correspondtocuryesunderdif

･ fereTltCValue8.8uCh88from0.95to0.80.intervalofO.05 fortheEirStfour,andfrom0.70to0.20,intervalofO.10 fortheother8)

4 ' ■ 0 8 ▲T 1 l ■U o Bo.I Td:00180.0020 0 .00220.0024 0 . 0026 1/T(K 1) Fig.4

Ag 0 ‑I/Tcurve80fRN O (Note:numbersIto10correspondtocurvesunderdif‑ ferentcvalu

8,8uCha8from0.95to0.80,intervalofO.05 fortheEir8tfour.andfrom0.70to0.20,intervalofO.10 fortheotherさ)

w ho8e8lope8a sSug官eSt･ ingthtmitramine'8thermaldecomp sitionunder‑ pe8two8tage8.By r e bigger.It8uggeBtSthi Eq. ( 5 ) ,Onec o

anc a l c u lat et he a c t i v at i one ne r g i e Bf ore a c h8t a g e , a81 i B t e di nTa

b l e 2 ,whi c h8 ho w8t h上t heva l ue 80fE.f o rt h

et hr e e B ampl e Sc onei nt oade c r e as i ngS e quenc eb y

RドG

RHNandRNO.

3 .3 Me Theme c h a n i s mF un c t i o n

c ham i8 mf unc t i o ni 8g i v e nb yO祖WaaS

l n( AEJR￠) = h ど ( e )‑1 nP(

( 6) Ta b l e2Ac t i v at i o nener g i e s0r

t hepr o ･

pe uant 9 5 8t e 8 t e d I

E A( KJ/mo

‑7 5 4 9.1 0 7 5‑1 0 1 1 3 4 21 4 7 . . 6 7 4 0

. 5 8 4 4 . 3 4 9 7.1 8 whe r el n( AEJRO)i 8aC O n8 t an

ti r r e l e vantt o t e mpe r at ur ef orac e r t ai n 0 .w

he r e as1 nP( Y)i 8a l

ine arf unc t i o no fI / Tf ora

pr o pe rr e ac t i onme c ha‑

ni 8 m, S Ol nf ( C )

Ba l s obo und t o b eal

i ne arf unc t i on ofl / T.Ther ear e3 0t y pe80rt hef ( C )

f

or m8 ,t he c ommonni neandt hei rc or r eB pOndi ngr eac t

i on me c ha ni 8 mamo ngt he mb e i ngh8 t edi nTa bl e3 .

Se l e c t i ng0b yt o ℃/ m i n,l nf ( C )

ur v e 80r e a c hf

uJ I C t i o nf orRNG,RHNandRNOAr epl ot t ed i nFi 野.5‑

7 ,andme anwhi l el nP( Y) l l / Tc ur v e s ar eo bt a i

ne dbyt hef oI l o w inge quat i o n' ･

Imp(Y)

=

1 . 0 5 2

) Th ti B , i fl nf ( C ) ll / Ti Bpar al l e lt ol nP(

Y) ll / T

t l l ent hi sf ( C )i 8j us tt het her malr e ac t i o

nme c ha･

ni S m f unc t i onf ort t t eS ampl e.I nFi

g 8.5‑7,1 n f ( C ) ‑1 / Tc ur ve 8f ort het hr e eB Ampl e 8ar eal l

made upo ft wo8 e 即t l e nt 80 rl i ne 8 , C O r r e 8 pOnd i ng

t ot he i r t wot her ma l dec ompo8 i t i onB t ag e8r es pec t i vel y

,

i nd i c t i ngt hatt he s ef ( C ) 8S t andf o rt he i rt h

er ma l r eac t i o nmec hani 8 m f unc t i on.Fr om t her es u lt S ho wni nTa bl e4 , i tc a nb e c onc l ude dt hatRN

Ga nd RHNha v et heS ameme C hami 8 mf unc t i on

f orbo t

h 8 t ag

B , Whi l eRNOi 8q ui t e di dT e r e ntf romt he m.

4.Re Ni t r s a u l t s

mi ne ' St he r mdde c o mpo e i t i o nunde rg o 飴t WO 8 t a

労,

an df ore a dhS t ag eEAa ndF( C )a r ed i J r e 柁nt .

m e 8 e

Ta b一 e3Commo nt y pe s0 ft hef ( C ) 竹peof r e a c t i o n

me c han i 8 mf unc t i o n

D , = (llC)2

〇

･2 .4 ( 台 .｡

. 5 . 8 . 1 0

･ 1 2

Pr o 伐dur ec o nt r o ungr e ac t i o nr at e o ne ‑ d i me n B i o na ldi m1 8 i o n

D 2 = C l nc

( 1 ‑C ) it wo ･ d i me n8 i o na ld i J Rl B i o n. c yl ind r iC a l8 ymme t r y

D 3 ‑( 1 ‑c l ′ 3)2 号 e d e 芸 ::h ! : n mld i L Rui o n･ B Phe r iC a l8 y m e t r y

D 4‑ (

･2 C ) '31C2 ′ ･ 工 芸 :B e t ‑ l i e . e imm i = a l諾 票 : n u ･ a B t : . h n e 血 IS ymme t r y

F l ≡‑1 n c irandom nucl eatio n , o n e n u c ^l e a r ^{f orapar t i c ul a r}

A: =( ‑ 1n c )' ' 2

A, =( ‑ 1 n c )レ3

R, =卜c l / 2 A , = l l CI n

random nu c l ea t i o n , A 汀 a m ie q u a t i o n I

random nu c ^l e a t i o n , A mm ie q u a t i o n 皿

i nter払 ce re a c t i o T L C y l i n d r i C a l8 y mm e t r y

inter払 ce r e a c t i o n , 8 p h e r i C a ls y m m e t r y

0 . 0 02 0 0 ^{. 0 0 22 0. 0024 0. 0 0 2 0}

1 / T( K ‑ I

)

F i g . 0 5 Me c ham i8 mf unc t i onof RNG

‑2

.4

等 ･･g .一8

‑1

⁰

̲ 0. 1 2 00 20 0. 0 0 22

0. 0 024 0 . 0 021

1 /T ( K l l ) ■

1 ■ 0 (3

) J t ani8mfunctionofRNO T t t T( rl) Fi g.7Mech 1 /

a b l e4Re t hepr a c t i o o pe nme c h an i S mf unc t i o nf or

l hnt 8t e8 t e d

C( %) Func t i o nf ( C ) RNG 9 7 5 5 ‑7 ‑1 5 0 I 払 R D D .

E E ← N . l 3

va luebu ta l s o

Edi 8t he8 ma ll e 8 ti n t het hr e e8 8mpl e

,and c o mpar e dt oRNGandRHN, i t 8me C han i 8 m f unc ‑ t i onf ( C )f ore ac hS t ag eC h ng e 8f rom F.( r andom nuc l e at i o n)a ndD 3 ( t hr e e･ d i me n8 i o na l d i 鮎 i o n)t o R

( i nt e r f ac er eac t i on)andDl( t wo･ di men8 i onAl di h 8 i o n) , r e さ pe C t i v e l y .I t8 ho w8t hatnanO ･ O X i de 8 c anc At a ly Z i et het he r na 1de c ompo 8 i t i onandc om･

bu8 t i ono fni t r am i ne S i gn追 払n tly.

F t e f e r en oe s

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)Ba

a ng

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Ka y i b k uQa k k a i s h i ,Vo L6 2 .No. 5 .2 0 01 ‑207‑

pub ^li c at i o n, 2 0 0 0 .

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,Naq' i ng

1 9 9 7

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Fo 8 t e r ," L e ng ‑ t e r mCo mpat i bi l i t y l b8 tO f RDXw it hHNSPe r io d : ' m sMp‑ 7 4 ‑3 5 J,1 9 7 4 4 )T. 02 aWa," E8 t imat i ono f Ac t i v at i onEne r 召 yby I 8 0 0 0nV e r 8 i onMe t ho

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