S c i .a n dT e c h .E n e r g e t i cNa t e r i a l s .Vo I . 6 4 ,No . 2 ,2 0 0 3 61
T Y I e r m a l I ) e ha v i o ro fv ar io usme t a l c ompl e xni t r a t e s( V)
‑ Coc o mpl e xni t r at e s ‑
Mi y a k o A by o s h i ● , Na oYa ma g u c h i y a, a n dHi d ct s ug uNa k a mu m
net h e ml a Hxh a v i o ro f a) c o mp ] C xn i t r at e so fGI T b o h y d r a z i d ea n da mmi n c( h e r e a 什 e r ,C o CDHa n dCo AM ,
T CS F d i v c L y )wa si n v es L i g a t c dwh c nm iX c dwi t ht w ok i n d so f d l eO X i d i z i n ga g e n t , s o t ) n t i u mn i t r a t e ( he T mA c r , S ‑ N) a nd
c o p p e r n i t r a t eb a s i c( h e r e a A c r , C ND) .
¶ l ed l C n n aJ 由b i l i t yo f Q) C DHwa ss l i g ht ) yl o wc r t h a J l t h a t o fC bAM, wh i l ei t st h e T ma l陀 a Ct i v i 吋Wa Sh l ' g h e r , a s d e mo n 加 I e db yd l e陀S u ] t so rd i qe r e n t i a ld l e n l l a la n a l y s i s .Bo t hc o mp l e x e st mc t e dmo r e s 加n g T yt oCNB i n 0
0mp a h s o nwi t hS r N・
Ne i L h c ri gn i t i o nn o rb u mi n g m rr e di nt h ea) AMI S T N mi x t t m d l 血 gt h ec o mb u s t i o n e x p enme n t . T he
( bCDH ・ C NBmi x t L J T eWa sd t cm os te a s i l yi g r l i t e do fa l l 血em i xt ur t S.T k F X Xhi vee ne r g yn e c e s s a r y f ori gn軸 gd l e m
ix t uTCSex c e p t f o r t he( bCDH・ CNBw as t h o u 91 t t Ob eo 伝氾t b ymc ) l i n ga n de n d o t h e m i CT C a C t i o n ・
h T t : ga T dL oc o mb t J S t i o nmc t i v i ( y , t h e O} C DH ‑ C NDmi x t u r ewa sd l O u dl t t Ot X d l emo s t e 触 i v ea sag a sg e n e t a n t
be c a l m O fi t ss ma ll p
陀S S u r ee X t XI n e n t a n dl o wb t J mi n gt e m p e r a t t J J Y . TT I eCo A M c o mpl e xd i dT t O t e a s i l yr e a c t wi d l d l e
t w ok i n d so fo x i d 出n ga g e n tt d h t h i se x p enm c n L ,n 肥 S S i t a t i n g t h ea d d i t i o no fa T L O t h e r c o m 叩 n ti no 血 t o i mp 1 0 V Ct h er c a c t j v i t y ・
I nd l eC o CDHc o mp l e xm ix t t J J t S , d l et J S eO f CNBa sa no x i di z i n g喝印t C O n S i d e r a b l yr e d u c e d d l eg e n e mt j o nor 山e N Ox g a s ,dl i l et h eg e n e t 7 L d o no rCOg a si n c T 血 d u et o d l Ct e mp em t t J r er du c t i o n .F o rd l eCo AM mi x t t J J T,a
T t ! hd v e ] yh i g h a mo u n t o f N Ox g a s e swe T eg e n e mt e d , becaL J S et hec o mb L L S t i o nt e mF m t t J T e Wa sh i g h. C hd l eO t h e rh a n4
C O田SWa sn o t g e n e T a t e d . .
1.I n t r o d u c t i o n
R cc e n t l y ,a u l o mo bi l c s s o ) di nJ a p a na J t e q t J i p F d wi t h a i r b a gs y s t c msf or s af c Td血血 g . An o n , a z i d eg a sg e n c r a J l t a S as u t di t def o rd i u ma z i d eh a s t mns t u d i d , a n dt c b 7 L Z O l e d c r i v a
tiv c s l ) , t J T W I c : )a n da z o d i c a r b o a m id e D ,wc r cl b e s u b j e c t so f t hi ss t u d y ・
T T I ca u t h o r se v a l u a t e dt h em ct a] c omp l e x e so fo 喝a n l C 0
0m f Dund s , wh i dl a r c C O m叫 o f ma n y ni t r o g e na t o m s , a s t h en e wg a sg e n e mn t ・l np r e v i o us r c poT b 4 トL : ) , t h et h c ml a ] d ∝o m押S i t i o nkh a v i o r o f meL a l c o mp l c x c so f c a J t X ) h y d J I L Z i d e wa si n v e s l i g a t c d .
l nd l i s T eT X) r L t h e0 )0 0 T n P l e x ni t ml c s
ofc a T t X d l y d l a Z i d e ( Q) ( NH! N HCON HNH ! ) 1
加o)2 , ∝ DW we r es y nt hc s お4
a n dt h et h e r ma l b e h a vi o r wa si n v e s l i g a L c di nami x e ds y s t e m v n ' t ht wok i n d so ft h eo x i di z i n ga g e n t :S t r o n t i u m n i t r a t e
Rc c c i v e d: No v e ml xI 2 0 ,2 0 0 2 . ^∝ q p t ed: Ma r c h1 9 ・2 0 0 3
叫 n t o f A p p l ) ' c dC h c mj 叫 F a c L J l け O r E n g i n c c 血&
Ky u du l 瓜i t u t c o r l t dl n O l o g y , 卜 I ,Sc T t S u i ‑ T T d , T j t x l t a ・ k u .
Kj L a k y us y u ・ s h i , S D 4 ‑ 8 5 5 0 , J Af T A N
TEL十 8 1 ‑ 0 9 3 ‑ 8 8 4 ‑ 3 3 3 4
F j u 十 8 卜0 9 3 ‑ S S ト3 3 1 9
( s r ( NO3 ) 2 , S r N)a n dc o p p e rn ] ' t r a t eb a s i c( Cu( OH)( N O B ) ,
CNB) .T T t eL h e ml a Ib c h a v i o ro fd t e s c mi x t l l 陀 S W
eTC0
0mp a T e d wi l ht ha t o f l h cmi x t t mo f d l eQ) a mm in e0 0mp l c x
nj t r a t c( a) ( N H J 6
加oJ, , chAM)a b e a d yi n
LJSC.2. Ex p e r i me n t
2.1Re a e e n t s
Cb O Hwa ss y n t h e s i z d b a s e do n t h em ct h d d e s cn M b yl v a n o vc ta l . ) 3 ) F o rt h e C h AM ,Q" mmi n ec o mp l e x c h l o r i d ewa ss ynt J I C S i z c dbmc o b a ) Ic h l o r i d ea n da q u e o t J S a mmo n i a , a n dt h eh y d
rc cMo r i d ewa st h e n0 0n v c佃 di n t oL h c n i t T a t C 川 . ¶e obt ai ne d c o mp l e x e s
w er ei d c n d f i e du s i n g e l c mc n t a la n ? 1 y s i s a n d F X ) l a 血 e d l i dl tZ C ma n a t o mi c a b s o r p t i o ns p e ct r o mc t r yd u et ot h e i ri n s o l u bi l i t yi nwa t e r .
¶l CSTn i t r a t eo ft h eo x i d ki n ga g e n twa s Wa k op u
rec h e mi c a lT t ng e n tg r a d e . lbe 0 0耶 rn i t r a l Cb a s i cwa s
s yn L h c si z e d r c f t r r i n gt ot h eme t h d d c s c n M i nGe mc ) i n ' S h a n d b wk J S ) ・ R e a g c n t s s c T e e n C dt oul d c r6 3p mw
er emi x e d f u rs i x t ymi n u t e su s l n gS P l i u a b L ec h o p s t i c k so np a T C h me r t t
pa p er . S c v e T a Jk i n d so r s a mp l e swe r e Pn P a T C db ym ix i n g : a
62 Sci.andTech.EnerleticMaterials,VoJ.64.No.2,2003 stoichiometr
k
compositionandarcw00mpositionseach wi
t
hFXBiLiveandnegativeoxygcJlbaJanccsba s
edoncq
s.1to 4.TableIshowsL hc s c
00mpositions.
15
C
bCDH + 22Sr(
MOS)2‑5払10.+22S
I O+
127N!+45CO!+135H:0 (1) 270)CDH + 44cN3‑9Cb30.+88a+211N..+81
C
O2+309H:0( 2 )
300)AM + Ssr(NOB)2‑10Cb30.+
8 s r o+
132N!+270H:0( 3 )
270
1AM + 8CNB‑9q Ol+16Cu+(251/2)N!+255H:0
( 4 )
2.2Apparatusandmethod 2.2.1ThemalanaJysis
「mediqcrentialtJlennaIanalysisand theTTICmla) graviJ
T K
bica J t a l y s i
sweT eC a J T i
cdouttJSingaRi Ba kt l
TbcTTrn]A
nalyz
c
rTTlemlOPltJS
.neSamPI c
00ntainerw
asannlumina∝ltaJld
t he
sampleamountw a s
lhrcemg.The
samp]cwa s
he a
tedto且oo℃ atahe a
tingmtcof20K
/manundcrAL
2.2.21gnitiontest
TTleignilioTlt
e S Iw as c
ardedotJIa∝
odingtothcc
71)uP mcth∝ l t
̀'・8m
gofthesampleoftheFX:1)ctw
asputingr
ass vessclof250mlcapady.Tlleignitiondclaypcr i
dwa s
meas
ured.2.2.3Combustionreactivity
heheatofthereaction
w
asme a s ud
LJSingaShimadzu CA14Type ALltOmaticBombcatodmctcrina喝on.TllC TCSultsofthei nv
estigationatambientpzcssuTeShoweda vadationintheme a s ur e
dvaluesof3% to4% Overtbc prcssuT eT a J l
geOfI .
IMPato3. 1 M P a .A c a s ee x
is l
cdin which no 00mbuslion∝血
deFX:nding on the comp
sitionat0.IMPa.¶1cmeaStJTementOfthebtlmingratewascarriedotJtunder thcfollowtn
s
00nditior
LS.ApI Cl i m
in
aJytnVCStiBadonshowd
thatt
J
leli
nearbumingrateint hedl C OZ Cd
caJde
nsitymn
geof 0.65100.70de cr e as e da st hedl
eOTCぬ Idensityinqcascd,whiletheweidltbumingratewasindcpendettLofthe
t h
coTt:tjcaldensity
.J h
.whendlCdiameteroft
hebLming tubewas6mm.d
lebtJmingTaleShoweditsma x
imumvaltJe.Table1 CbmpositionSOfmi
xhr e s
C b
00mplex/oxidizingagent Oxyg(genblooa且hJ
)1t CC
mot′mol wL
∽ H STN 0.441′0.559 0.628
′WL
/0.372‑ 2.66 0.417′0.5&3 0.605′0.
395 ‑ 0.85 0.405′0.595 0
.594′0.407 0 0.395′0.604 0.
583′0.417 + 0.82 0.375′0.625
0.562′0.438 + 2.38 C"B i 0.397′0
.603 0.554′0.446 ‑ 0.98 0.386′0.614 0.542′0.458 ‑ 0.32 0.380′0.620 0.536′0.463 0 0.375′0.625 0.531′0.469 + 0.3
1 0.365′0.635 0.520′0.480 + 0.92
C h J M
S rNトCNB 0.857′0.l43 0.908′0.0
92 ‑ 2.51 0.811′0.189 0
.876′0.25 ‑ 0.87 0.790′0.21
0 0.860′0.40 0 0.769′0.23
l 0.845′0.55 + 0.78 0.732′
0.268 0.817′0.83 + 2.26 0.844′0.156 0.887′0.13 ‑ 2.74 0.818′0.182 0.867′0.33
‑
I.78 0.794′0.206 0.848′0.152
‑ 0.87 0.77l′0.229 0.830′0
Sc i .a n dTe c h .E n e r g e t i cMa t e r i a 一 s ,Vo I . 6 4 .No . 2 .2 0 0 3 6 3 Q) n
se q u e n d y , L b
c sa mp l ew
asl o a d da t O ・ 60 f t h et h c oT t : t k a l
d e T t S i t yi na6mm i . d .a l u m iJ l u m t u t X.¶l CP
ressu r e d e p en d e m ∝
w asme a s u d o v e rap T e S S uモT a n g eO f O ・ lt o4 ・ l MPaa n dt h ei nf lt l e t t c e of t h e c o mpdL i D nO nt h eb u ml n gr a t e
w a
si n v e s t i g a t e d a tL ・ lMPa .Th eb u m] n g r a t ewa s d e t e r mi n e di nt e r mso fl h ct i met h a t w a sn e e d e dbrt h e
c o mb t J S t i o nwa v el oI ‑ 肥 e d1 0 T T t m・
¶l eb t J ml n gt e mF X : mt u r C
W asa l s omc a s u p xlt J S i n gt h e s a me t h e o 柁t i c a J d e t t s i t ya r t dt u t xd i a me t e r
ast h a t u s e dbr t h e me
asure m
en t o f t h eb u mi n gT a t s . A0 . 2 5mmd i a mc t c r W/ Rc t h e T T n CN 3 ) u P I cw
asv e r I 血l l y i ns ede di n t ot h ebu ml ● n Bt u b e a g a in s tt hec o mb
LJ S d o nd i r e c t i o na n d
was 0 0n n c c t e d t oa
Yo k o g a wa h o k u s i n nA n a ly z i n gR e0 0 f de L
l l c 0 0mb t di o n r e s i d u ew
asa血y z e db yX‑ r a yd i L hc t i o n
L J Si n ga R i g a k uT t ) t a r ) e xRU‑2 0 0 ・
2.2.4Th ee v o l v e de a s
¶l ee v ol v e d Ba s es ,P r D d u c c dwh e nt h eh e a lo fr e a di o n
w a
sme a s u血 , we r e c o l l ∝t c di na 0 0
lIec t i o nb 喝 ( l l dhr b 喝
3 5 0 ml叩 C i t y ) . T T t ea mo u nt sO fN : ,CO ,Cola n dN: 0 g a
se se v o l v e dw肌 qL J a n t i f i c dt J S hgaSh i ma d z uGC‑ 4 CG as
ch T t ) ma k) gr a p h ( h cr c a Ae r ,GC) . Th bl C 2 s h o w s l h c T T l e a S L J r e me n t C O n d i t i o n sf oTt h eGC ・刀l eNOa J l dNOZ B
as es
WC T Cq
tlan t i t a t i v e l ya n a l y z e
d us i n ga b s t e cg a sd c t ccbr t t J b e , T l l e W 3 a n dN2 H 4 g a s e sWe 陀q L J a n d f i e
d us i n gt h ei n d o p h e n o l ' S
' T d d l D ( A‑6 3 0 n m) a ' d 触 pa m i r K kr d d e h y 血 mc t ho dJ B ) ( A‑4 5 8 m m) . T C S p eC t i v c l y .
3.Re s u l t sa n dd i s c L I S S i o n
3.1 Th e r ma l a n a l y s i s
Fi B ・ ls h o wst h er e s u l t so ft h et h e r ma l a n a l y s i so f n I CDH a t l d C bAM. TT l e0 ) C DHs t a T t C dt ome l ta t2L 0 ℃ , a n dt h e n
血0 0m
押e de x o t h e r ma l L ya t2 5 0 ℃ a R e rt h ec n d o t h e r m i亡 d c c omp o s i t i o n ・ ¶cc bA Mc o mp l e xwa ss ] i dl d yr n o T CS t a b l e t h a nt h eC b C DH be c a u s eoramde r a t e l yh i g he rmc l t i n B
pi n t( 2 2 0 ℃ ) a n d i n i 血It e mp er a t u r eo fe x o t h e r mJ ・ c d c 0 0m 四 S i t i o n ( 2 7 5℃) .¶et he r d 陀a C t i v j t yo f t he
C b C DHw
as guess e dt ob ch j dl C rt h a nt h a to ft h e C bAM
0
0n s i d c 血g t h e we i dl ll
ossd u r i ng t h e e n d o l h c m i c d c c o mps j L i o n ・Th eha lr c s t ' d u c wa sC b3 0 4 ,WMc hw
asc o n 6 r me
du s J ' n gt h eF X ) Wd e rX‑ r a yd i h c t i o na n dt h eG n a I we i 9 1 L l os .
F J ' g ・ 2s h ows t h er cs uI L so ft h e r ma l a n a l y s i so ft J l e C b CDH
a
T t d I . t S m ix
ILJTCSa tt h e s t o i c h i o mc 什i c c o n l P O S i t i o n , T C P T C Sent a ( j v e l y ・F o rl h cmi x l t J r ew it hS r ( N o . . ) Io ft h e o x j d i z j n ga B e n Lt h e r ewa sa] j L d cd i f fe r c n c ci na p p a r e n t l h e r ma l t da v i o r 0 0mp a r e dwi t ht h a t o f o n lyt h e c o n l P ) e x( a s
Ta b l e2 G
asc h T O ma t O ga P h c o n d i t i o n s Ga s es N 2 , C O N2 0 , CO
qI l u mn mo kc u t a r s i e v c s5 A a 亡 l i v a l e d亡 h a r I
c o a l Pa r t i c l cs bc 6 0 ‑8 0me s h 6 0
‑8 Ome s h L
en g
t h 2m 1m
Te
mp . 4 0 ℃ 4 0 ℃
C h r r i c r ps He , 2 0m伽 in.He,60mJ/m
i n .
. O X H
LI
『 p 凹 1 O u .
l ‑‑‑‑
TG
ヽ l Co c°
I
P TA ‑‑‑ ‑‑‑‑‑
● l ‑ I ‑‑‑‑
t l ■
‑
‑‑‑̀ヽ Co AM
TG
DTA I
II ‑‑■‑‑1■‑ 一一■ ■■■■■‑I‑
■ l t l ■ 一 一 0 0 5 川 0 0 0 % J T も ! A
)s s o a
50 t
0 20 0 Te mp 40 e r a 0 山r e / 600 ℃ $ 00
Fig・lDTAITGcurvesfor theC bc omplexnit
rat es ㌔ \ ss o
Ttも!o A oo1 0 0 200400
600 8 00
Te mp e r a t u r e/℃
F i g l DT AI TGC uVC SG o r t h e a
c o mp l e xm ix t u r e s s e e ni nFi g ・ Ⅰ ) It h g h t h es e p a J a t C d
p e a kb e amet h es h a r p o n e .¶eu n r c a c l i v eS r ( N O B )
2
Wa Sf ou n dt od e 0 0m
叩党a 1 5 6 0 ℃.T T ) em ix t u 陀w it hm s t a nc dt o
T t nC ta t1 9 0 ℃
t x
b ret h emc l t i n g ・ Ont h eo t h e rh a n d
6 4 Sc i . a n dTe c h . E n e r g e t i cMa t e r i a l s . Vo L6 4 . No . 2 , 2 0 0 3 e x o t h e r mi cI C a C l i o nw a s 0 0n f m e db yt J S j n gl h eCNBa st h e o x i d i z i n ga g e n t T T t er e a c t i v 舌 l ywi t ht h eC NDwa se x p c c t c dt o b eh 砂e r t h a nt h a t wi t hSr ( N O3 ) ? i nb o t h c omp l e x e s . 3. 2He a to f c o mb s u t i D n
Fi g . 3s h o wst h ec o mJ X ) S i t i o nd e p en d e n c eo ft h eh e a to f T t n C d o n .T l l eC OmPS i t i o nd c F X ! n d e n c cwa ss ma l li na l l s y s t e m s . T l l eS m a ll 0 0mp o s i l i o nr a n g ew a sc o n s i d e r e dB ob c o n eo f t h er e asoT t S f or t h k, be au set h e 0 ) A Mm ix t t J r ed i d n ' t
es p ec i a l L yi g n i t ei nt h ew id e0 0 q x ) s i t i o nr a n g c ・ Fj g ・ 4s h o ws t h eX m p a u e mso ft h e c o mb t J S t i o n r e s i d u e a tt h e s t ∝h i o me t r i cc o m p o s i t i o n . h t hemi xt t J J Tw it hSr ( MOS ) 2 , v a r i o L J S 0 0b a J l o x i d e swe f e 0 0n 血mc da n dOゎ03f o r me dI k e c om F X ) S i t e o x i d e w i t h Sr O . Ont h eo t h e rh a r L d , a) 0wa s
0
0n f iml e do n l yh t h em ix t u r ew it hCNB.S r C O3 Wa s p r o d u c e db yt h er e a c t i o no f Sr Oa n dCol .
h t h e C hA M‑ m m ix l u J T, t h eh e a t o f 8 0 mbu s t i o nh a da ma xi mu mv a l u ea t ‑ 1 . 7 7 6 g( l o o s) l o f t h eo x y g e nb a l a J I C C .
T T t i sw as c a u s e db yt h ef b r m c do x i d ewa sn o t t x : i ng恥 04 b u t0) 0. nes t o i d血m c bi ce q u a t i o nwa ss e t u pa s s u mi n g t h a tl h c r e s i d u e wa s C b3 04 ,C O n 丘m d d u r i T t g t h e
d e 0 0mp o s i l i o r L a t t h eh e a t i n gr a t eo f2 0 K/ m in . ; e q s . 1t o4 . I n t h i ss y s t e r r L ,t h ec o mbL J S t i o nr c a c t i v i L yi nat u b ewa s i n v c s t i g a l e d f ort h e 0 0mp o s i t i o no f ‑ 1 . 7 7 6 g( 1 0 0 9‑ ‑ ,a s d e s c n M l a t e ri ns e c t i o n3 ・ 3 ・ I J la l ls y s t e n l Se X C e P tf ort h e D AM・ CN Bmi x t u r e ,i twa su n k T ) O wnWh e t h e rL h ch e a to f 0
0mb u s t i o nr e a c h e si t sma x i mu m v a l u ea ta n yo x y g e n b a la n c e
bec a u s eo fas ma l lc o mp o s i t i o nd e p er L d e n c c . T bc h e a to fc Dmb t J S t i o T ti nt h ebCDH ‑ m mi x t u t ch a dt h e s ma ) t e s t v a t u co f a l l t h emi x t u r e s .
叫
fP O ! )S n q u O9 30 7tZa H 4000 3500 3000
̲ 3
0x‑ 2 ‑
ygenb1
alan0
ce/g1 ( l
oo基)2 3
‑ 1
▲ cocDH/ Sr N ● coCDH/ CNB
△ COAM/ Sr N O CoAM/ CND
F i g 3 He a t o f 0 0mb u s t i o n触 ・ t h e ( b c o mp l e xmi x t u r e s F b d h e r no r
e, f orl h cG ) A M m i xt u r cs y s t e m,a ni n t e n s e a mr n o n i u ms mc uwa sd e t e de d
i n o p e n i n gt h ep
TCSStJTei) r ∞ f c o mbu s t i o nv e s s e la 触rt h e
e n do ft h ec x p enme T t t . l le s e s y s t e msd i d n p t s c c mL ob u mc o
mp l e t e l y . 3.31 F i g ・ 5 g n S j h t i o o wsl nt e mp h cr e c r a t u r e
L a d o n s h i pb e t we e nt h eJ ' g n i t i o nd e l a y
p
er i da J l dt h et e mp er a t t J r
ei nd l e C b C DH‑ C N Dmi x t u 托 , a Sa r e p r e s e n t a t i v ec x a mp l e . Tl l C
mhi mu ml g n i l i o nt e mp e
mt t
Jrea n dt h ei g n i t i o nt e mp e m
t u T ei na4 sd e l a yi sl i s l e di nTa b 一 e3 , i r L Wh i c ht h ea c (
i v cc n e 唱yO ft h ei g n i t i o ni sa l s os h o wnNo
l g n i t i o no c c u mdi nl h c bA M ST Nmi x t L J r C . T T ] em i nimum lgnilio nte m peratureT mj ni nt h e C bCDH・ Sr Nmi x t t J T e
h a sa h i dlV a l u e0 0mp a J d
wi t h t h e i n i 血Jt e mp e r a t t J T e O r 普 ● 亡 4 ■ > ■
己
ト = = = 1 工 . ・ 。 ・ ・ I. . . A
1
c x o t h e r ma l r e a c t i o n) ' nt h ePT AC U J VC ;2 5 0 ℃ Q ; j g . 2 ) . I nl h i s s y s t e m,t J l eS o u n dwi t ht h es a mp l eme l t i J l gWa sC t C a r ) y h e a db e f o r et h ei g n i t i o n . TT t cma t c 血 l i gl i t e sb ya p p l y I ' n gt h e
n e w e n e 唱y斤o m L b cou l s i d e ・ T l l e F K X S i t i v cc n e 喝y n
eq f ort h ei g n i t i o n
wa sa s s u me dt ot n o u tb yt h e me l t i n ga n dt h ee n d o t h c r mi cr t nc t i o n . As i m il a rp h e n o me n o n wa so b s e r v e da l s oi nt h e C bAM‑ CNBm i xt ur e.
I nac o mp a n s o T IO ft h eo x i d i z i n ga g e r t b, t h em ix t u r ew it h C N
Dwa se a s i e rt o 暮 g n i t c舟o mt h a Lw it hS r N. T l l ea) AM mi x t u r e t J S C da l r e a d yi n a ct 血 l o p er a t i o nwa sdi f R c u ) It o i g n i t ei na t w o ・ 0 0mp o n c n ts y s I C m 0 0m P d s c do fs i mp t c r e d u c i n ga J l do x i d i z i n ga ee n t ・
3.4Co mb t J S t i o nr e a c t i v i t y
F i B . 6s h o ws t h ep
rcs s u T Cd c f X :
ndcnc co f t h eb u m in gr a t ei l l t h 柁 8mi x t t J J t Se X C C P lf ort h eC b J M , S T N m ix t ut t .No i gt i t i o na n dc omb t J S t i o n 0 0 m ¶ di nt h eQ) AMI S I Nm ix t u n.
T a b l e4 l i s t sl h c
叩S S u 柁 C X P O l 1 e n
Lc a l c u l a L c db a s e do n
Ⅵe i l l e l s e q t J a t i o n ( V dPn )a n dt h eb u m in gt e mp e T a t L m a t t h es t oi c h i o me t r i cc om p o s i t i o n ・ T h eb u mi n gr a l c a l1 ・ 0 1 MP a s h o we dt h eh i gI C S t V a l L ) Ci n t h eQ ) A M{m m ix t u T e , bl l 仇 柁db yt heC bCDH‑ Sr Nm ix t t J r C a n d t hea) C DH・ 0ヾ B m
i x t t J J C . ¶l CC bCDH一口ヾ Bm ix t t l r e
W ast hu dl HOb c a d v aJ l bg eoL J Sa Sl h c 伊Sg e n e r a J l tt m u S eO fi t ss ma l l
SP u J!一 u O S一 .己 叫Ⅰ
1 . 6 1 . 8 2 2. 2
20 1 0 0 ■ l ■ ー ● 一
●
○
&
. . 一
2 00 30 0
40 Te mp e r
a t u T d℃
Fi B S I g n i t i o nt e s t f o r L b e ( b CDH‑ m m ix t tJn 一 亡 t tJ
2 ‑ Sc i .a n dTe c h .E n e r g e t i cNa t e r i a l s .Vo l . 6 4 .No . 2 ,2 0 0 3
6 5 p T e S S t J T ee X Pn e n t a n dl o wb u mi n gt c mp c r a t t J r e . l l
ca) AM 0
0mp l e xd i dT t O t e a s i l yr e a c t wi t ht h et wok i n d so fo x i d i z i n g a g e n t u s e di nt J l i se x p e
nm c n t ・
AR o n ‑ s t o i dl i o me t r i c ( bOf on n c dd u r i n gt h e
de 0 0mF K Ei t i o n o ft h ec omp l e xmi g h tc a t J S ea t S Ot h ed i 飴 T C n C e
i nt h e c o mb t J S t i o nr e a c t i v i t y
t 9 ) ・
4.
Ga se v o l u t i o nb e h a v i o r .
Ta b ] e5l i s t st h ea n a l y t i c a )mu l t so ft h ec v o l v c d g as es du 血g0 0mb t J S l i o n . T T t cQ ) A M ・ SI Nmi x t u r edi dn o t ]
g n i t e . T he C bAM<m m ix t u r c di d n o t g c T t C r a
l e t h e c a J t K
)n
.0 0n t a in i n gCo lg a s , a sp I C d i c t e dbmt h emo l
c cul a T
f o ml u ho f 0) AM. Ho wevc T . i t i sn cc c s s a J Yt Oa d da t a J T D d l e r 0
0mpT t e n td u et ot h edi mc dt i c so fi gl i t i o n a n db u m i n g , a s
al r e a d y
d esm M .
N
2a n d C O: g a s e sa c mt ntf ora b o u t
99%o fa ll e v o l v e d
ga s e si nt h e C b CDH mi x t w c s .Us i n gt h eC ND o fd l e o x i d i z i n ga B e n t 0 0n S i d e r a b l y l du c c dt h eg c n c T a t i o n
o fNOR
Ba S・Tt t ee v o l u t i o no rNOg a si nt h e C bCDH・ CNもm i xttJJt
川
5
㌔ut
uJa lC J g
u
! u l n
中
1Pr es s ur
2e n n a
3 4● ▲ Co co CD cD H
H// 伽 ,
Sr即Q3 k
O Co A M / CN D ,
F i g B l k bm l 血 唱
d 打 a C t Fb t i c sf o r ぬ C o c o mp ) e x
m i
x t
tJrCSTa b l e3 Ⅶ d o u sc h a r a
c t e d s t i c sj nt h ei g n i t i o nt e s t
T , n h/ ℃ ( S e e . ) I T I J ℃ AE/ kT ( mo ] ) ‑ ) a) C D H
/ Sr N 3 2 4( 2 4 . 1 ) 3 7 2 . 3 7 5 . 6
a) C DH / CNt i 1 8 2( 2 6 . 3 ) 2 6 6 . 8 3 8 . 3
c
6 6 Sc i . a n dTe c h . E n e r g e t i cMa t e r i a l s , Vo † . 6 4 , No . 2 . 2 0 0 3
Ta b l e4 Q) n s t a n L so f t h eb t J mi n g柑L L C
a) mp l c x Ox i d i z i n ga g e n t ー a ∩ Bu mi n gt e mp er a t t J r e/ ℃ Co CDH Sr N l . 7 2 9 0 . 4
1 0 1 3 0 0 CND 0 . 8 8 4
0 . 3 0 5 1 1 7 0 C o AM CNB
0 .1 9 7 0 . 41 0 1 3 6 0 Ta b l eS ¶l ea mo u n t
O f t h ec v o l v c d
gas e s ( u n i t : m o Vmo I ‑ c
omp kx ) Co CD
H C o j M S r N
CNB CNB N2 8 . 3
8 . 3 7 . 4 NH3 ≒0 . 0
≒0 . 0 ≒0 . 0 N 2 H 4 ≒0 . 0 ≒0 . 0 ≒
0 . 0 NO 41 2 . 0×1 0 ー 4 8 . 7×1 0 4 61 . 9×1 0 ‑ 4
NO2 I . 2X
lO ‑ 2 ≒0 . 0 ≒ 0 . 0 N2 0 0 . 0 ≒
0 . 0 ≒0 . 0 HCN 1
. 4×
10 3 ≒0 . 0 ≒0 . 0 Col 1 . 8 2 . 6 0 . 0 CO 0 . 0 8 0 . 2 6 0 .
0 NT l u mb e r
1 6 . 7 1 4 . 8 9 . 0
%
9 8 . 4 9 4 . 7 9 6 . 9 Cn u mb c r 1 . 9 )
. 3 8 ‑
%
6 2 . 7 9 5 . 3 ‑
Ⅵ 伯SS l i d l t0 0m Pa J d w i t h t h a ti
nl h ca ) A M‑ C NDmi x t t J r e.
Ho we v e r , t h eB C n C r a l i o no fCOg a shc T
e a S e dd u el ot h e T du c t i o ni nt e mp c r at t J r e . Ar e d u c t i o ni nC O
g a si sr e q u i J d i n t h e f ut ur c. T T l et o wm a s sb a ) a n c eo f Cmo l e c u l e s w a sd t J Ct O t h ef oT ma t i o n
o f S r CO3 b yl h cT e a C t i o no f S r O a n dCol i nt J I C mi
x t u r ew it hSr N.
5.