Ammonium Perchlorate and Ammonium Perchlorate
Hydroxyl Terminated Polybutadiene Simulated Combustion
Rene Francisco Boschi Gonçalves*, Koshun Iha, Francisco Bolivar Correto Machado, José Atílio Fritz Fidel Rocco
,QVWLWXWR7HFQROyJLFRGH$HURQiXWLFD6mR-RVpGRV&DPSRV63%UD]LO
Abstract:7KHFRPEXVWLRQVLPXODWLRQRIDPPRQLXPSHUFKORUDWHZDVFDUULHGRXWZLWKWKHVRIWZDUH&KHPNLQLQ WZRVWHSVWKHEXUQLQJEHKDYLRURISXUHDPPRQLXPSHUFKORUDWHDQGWKHRQHRIIRUPXODWHGDPPRQLXPSHUFKORUDWH ZLWK K\GUR[\O WHUPLQDWHG SRO\EXWDGLHQH ELQGHU ,Q ERWK FDVHV WKH URRP SUHVVXUH YDULHG LQ RUGHU WR YHULI\ LWV LQÀXHQFHLQWKHV\VWHP7KHEXUQLQJHQYLURQPHQWFRQGLWLRQVZHUHGLYHUVH'XULQJWKHFRPEXVWLRQSURFHVVWKH GDWDREWDLQHGIURPWKHNLQHWLFFKHPLVWU\VLPXODWLRQVRIWZDUHZHUHFRPSLOHG7KHÀDPHVWUXFWXUHFDQEHGHVFULEHG E\ WKH PRODU IUDFWLRQ RI WKH EXUQLQJ SURGXFWV DQG WKH WHPSHUDWXUH HYROXWLRQ IURP WKH VXUIDFH RI WKH PDWHULDO Keywords:$PPRQLXP3HUFKORUDWH+\GUR[\O7HUPLQDWHG3RO\EXWDGLHQH+\GUR[\O7HUPLQDWHG
3RO\EXWDGLHQH%LQGHU&KHPNLQ
INTRODUCTION
7KH ¿UVW VROLG SURSXOVLRQ URFNHW PRWRUV GDWH IURP th FHQWXU\DQGWKH\DUHDVVLJQHGWRWKH&KLQHVH0DUN 7KHURFNHWUHGJODUHIURP6SDQJOHG%DQQHURI)UDQFLV6FRWW .H\ZDVLQLWLDOO\XVHGLQLQDZDULQYROYLQJWKH8QLWHG 6WDWHVRI$PHULFDDQG(QJODQG6LJQL¿FDQWDGYDQFHVLQVROLG SURSHOODQWVWHFKQRORJ\RFFXUUHGGXULQJWKH:RUOG:DU,,DQG FRQWLQXHXQWLOWRGD\1RZDGD\VVROLGSURSHOODQWVDUHXVHGLQ VDWHOOLWHODXQFKHUYHKLFOHVERRVWHUVDQGVXVWDLQHUPRWRUVLQ PLOLWDU\DUWLIDFWVSURSXOVLRQDOWHUDWLRQDQGFRUUHFWLRQHQJLQHV RIJHRVWDWLRQDU\VDWHOOLWHVRUELWVDPRQJRWKHUV
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
5HFHLYHG$FFHSWHG
DXWKRUIRUFRUUHVSRQGHQFHUHQHIEJ#JPDLOFRP3o0DO(GXDUGR *RPHV&(36mR-RVpGRV&DPSRV63%UD]LO
R[LGL]LQJ FKHPLFDO VSHFLHV LQ D VROLG EORFN FDOOHG VROLG SURSHOODQWJUDLQ
7KHVH PDWHULDOV DUH FODVVL¿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
0RGHUQ VROLG URFNHW PRWRUV DUH PRVWO\ FKDUJHG E\ FRPSRVLWH SURSHOODQWV 7KH PDVV GLVWULEXWLRQ RI WKHLU FRQVWLWXHQWVLVIURPWRRIPHWDOOLFIXHOWRLQFUHDVH VSHFL¿FLPSXOVHRIWKHSURSHOODQWXVXDOO\DOXPLQXPIURP WRRIR[LGL]HUOLNHDPPRQLXPSHUFKORUDWH±$3DQG IURPWRRIWKHELQGHUPDWUL[PDLQVRXUFHRIFDUERQ ZKLFKDFWVDVIXHO(YHQWXDOO\IURPWRRISODVWLFL]HU FDQEHDGGHGWRLPSURYHWKHÀH[LELOLW\DQGWRKHOSGXULQJWKH SURSHOODQW SURFHVVLQJ ZKHQ LW LV VWLOO LQ WKH OLTXLG SKDVH3LVDFDQH
([DPSOHVRIW\SLFDOFRQVWLWXHQWVRIVROLGSURSHOODQWVDUH SUHVHQWHGLQ7DEOH,WLVSRVVLEOHWRPDNHWKHV\QWKHVLVRI PDQ\VROLGSURSHOODQWIRUPXODWLRQVIURPWKHFRPELQDWLRQRI WKHVHFRPSRXQGV
7KH SRO\PHULF PDWUL[ QDPHG ELQGHU SOD\V WKH UROH RI ELQGHURIDOOWKHUDZPDWHULDOVWKDWFRPSRVHWKHFRPSRVLWH VROLGSURSHOODQWJUDLQ0ROGHGLQWKHURFNHWPRWRUFDVHLW SDVVHVWKURXJKDFXULQJSURFHVVZKHUHPHFKDQLFDODQGEDOOLVWLF SURSHUWLHVDUHGHYHORSHGZKLFKDUHQHHGHGWRWKHSURMHFWHG SHUIRUPDQFH RI WKH PRWRU URFNHWPRWRU LQ WKH KDQGOLQJ WUDQVSRUWÀLJKWDQGVWRUDJHSKDVHV0RQWHLUR et al 7KH PHWDOOLF DGGLWLYHV KDYH WKH IXQFWLRQ RI VWDELOL]LQJ WKHEXUQLQJSURFHVVDJDLQVWLQVWDELOLWLHVDQGRILQFUHDVLQJWKH LQYROYHGHQHUJ\GXULQJVROLGJUDLQFRPEXVWLRQ
AP (NH&O2 LV D SRZHUIXO VDOW R[LGL]HU ODUJHO\ XVHG LQ VROLGSURSHOODQW IRUPXODWLRQV IRU DSSOLFDWLRQ LQ DLUVSDFH DQGIRUGHIHQVHRIPDWHULDOVLQGXVWULHV,WLVREWDLQHGE\WKH UHDFWLRQEHWZHHQDPPRQLDDQGSHUFKORULFDFLGRUE\GRXEOH GHFRPSRVLWLRQ EHWZHHQ DQ DPPRQLXP VDOW DQG VRGLXP SHUFKORUDWHDQGLWLVFU\VWDOOL]HGZLWKURPERHGULFVWUXFWXUHLQ URRPWHPSHUDWXUHDQGSUHVVXUHZLWKUHODWLYHGHQVLW\RI %HFNVWHDGet al
6LPLODUO\ WR PRVW DPPRQLXP VDOWV $3 WKHUPDO GHFRPSRVLWLRQRFFXUVEHIRUHLWVIXVLRQ:KHQVXEPLWWHGWRD ORZKHDWLQJUDWHLWGHFRPSRVHVE\UHOHDVLQJJDVHVFKORULQH QLWURJHQDQGR[\JHQDQGZDWHULQWKHYDSRUVWDWHZKLOHZLWKD KLJKKHDWLQJUDWHVWLPXOXVWKHUHDUHLQVWDQWUHDFWLRQVZLWKKLJK HQHUJ\UHOHDVH7KHWKHUPDOGHFRPSRVLWLRQPHFKDQLVPRIWKLV
NLQGRIPDWHULDOKDVQRWEHHQWRWDOO\HOXFLGDWHG\HWEHFDXVHRI LWVHOHYDWHGSK\VLFDOFKHPLFDOFRPSOH[LW\+RZHYHUVHYHUDO VWXGLHVKDYHEHHQSXEOLVKHG.RUREHLQLFKHYet al%RJJV %HFNVWHDGDQG3XGXSSDNNDP-HSSVRQ et al 'XULQJ WKH FRPEXVWLRQ SURFHVV RI$3 FU\VWDOV DW KLJK SUHVVXUHVLWLVSRVVLEOHWRREVHUYHWKHIRUPDWLRQRIDWLQ\OD\HU RI$3LQWKHOLTXLGSKDVHDWWKHJUDLQVXUIDFH%RJJV IROORZHGE\DUHJLRQZKHUHJDVHRXV$3LVSUHVHQWHG
$FFRUGLQJWR%HFNVWHDGDQG3XGXSSDNNDPWKH FRPEXVWLRQRIDPRQRSURSHOODQWFDQEHGLYLGHGLQWRWKUHH UHJLRQV FRQGHQVHG OLTXLGJDV WZRSKDVH DQG JDV 7KH WZRSKDVH UHJLRQ FRQVLVWV RI OLTXLG DQG JDVHRXV VSHFLHV UHVXOWLQJ IURP WKH PHOWLQJ DQGRU GHFRPSRVLWLRQ RI WKH VROLG SKDVH 7KH SUHFLVH GLYLVLRQ EHWZHHQ WKH WZRSKDVH DQGJDVSKDVHUHJLRQLHWKHEXUQLQJVXUIDFHLVQRWZHOO GH¿QHGGXHWRFKHPLFDOUHDFWLRQVEXEEOHVDQGFRQGHQVHG PDWHULDOEHLQJFRQYHFWHGDZD\IURPWKHVXUIDFH,QWKHJDV SKDVHUHJLRQRIDPRQRSURSHOODQWWKHÀDPHLVHVVHQWLDOO\ SUHPL[HG 7KH VSHFLHV HPDQDWLQJ IURP WKH VXUIDFH UHDFW ZLWK HDFK RWKHU DQGRU GHFRPSRVH WR IRUP RWKHU VSHFLHV $ ZLGH YDULHW\ RI UHDFWLRQV LQYROYLQJ PDQ\ VSHFLHV RFFXUVLQWKHJDVÀDPHXQWLOHTXLOLEULXPLVUHDFKHGLQWKH ¿QDO ÀDPH ]RQH$ VFKHPDWLF SUR¿OH RI WKH WHPSHUDWXUHV GHYHORSHGIURPWKHJUDLQVXUIDFHGXULQJWKHFRPEXVWLRQLV SUHVHQWHGLQ)LJ
7KLV FRQVLGHUDWLRQ LV EDVHG RQ D UHDFWRU PRGHO ZKLFK FDQEHIRXQGLQWKHFRPSXWDWLRQDOSDFNDJHQDPHG&KHPNLQ &KHPLFDO.LQHWLFVGHYHORSHGE\6DQGLD/DERUDWRULHV
0HWDOOLF
QRQPHWDOOLFIXHOV 2[LGL]HUV %LQGHUV &XULQJ$JHQWV 3ODVWLFL]HUV
$OXPLQXP $PPRQLXP3HUFKORUDWH1+&O2) &DUER[\O7HUPLQDWHG
3RO\EXWDGLHQH&73% ,VRF\DQDWHV '2$'%7 %HU\OOLXP /LWKLXP3HUFKORUDWH/L&O2) (SR[\GHV $PLQHV$PLGHV 7ULHWK\OHQHJOLFRO
GLQLWUDWH
0DJQHVLXP 3RWDVVLXP3HUFKORUDWH.&O2) +\GUR[\OWHUPLQDWHG
SRO\EXWDGLHQH+73%
7ULPHWK\OHWKDQH WULQLWUDWH
6RGLXP $PPRQLXP1LWUDWH1+NO3) 1LWURFHOOXORVH
+\GURFDUERQV 3RWDVVLXP1LWUDWH.123)
3RO\EXWDGLHQHDFU\OLF DFLG3%$&
3RO\PHUV 6RGLXP1LWUDWH1D123)
'XH WR WKH GLI¿FXOW\ RI SHUIRUPLQJ H[SHULPHQWV ZLWK WKHVHPDWHULDOVLQUHDOFRPEXVWLRQFRQGLWLRQVLWLVFRPPRQ WRHPSOR\FRPSXWDWLRQDOPRGHOLQJWHFKQLTXHVWRHVWLPDWHWKH EXUQLQJEHKDYLRURIVROLGSURSHOODQWV
$ ZLGHO\ XVHG VRIWZDUH IRU WKH VWXG\ RI WKH ÀDPH IRUPHGGXULQJHQHUJHWLFPDWHULDOVFRPEXVWLRQLV&KHPNLQ 7KLVVRIWZDUHFRQVLGHUVWKHHTXDWLRQVRIPDVVDQGHQHUJ\ FRQVHUYDWLRQFKHPLFDOVSHFLHVLQYROYHGDQGOLQHDUPRPHQWXP DQGLWHQDEOHVWKHDQDO\VLVWKURXJKWHPSHUDWXUHDQGFKHPLFDO VSHFLHVPRODUIUDFWLRQVYDULDWLRQLQIXQFWLRQRIWKHGLVWDQFH IURPWKHPDWHULDOVXUIDFHDPRQJRWKHUV
7KHSUHVHQWSDSHUWUHDWVWKHFRPEXVWLRQVWXG\RISXUH$3 DQGIRUPXODWHGLQDVROLGFRPSRVLWHSURSHOODQWJUDLQIRFXVLQJ LQWKHVWUXFWXUHRIWKHÀDPHIRUPHGLQWKLVSURFHVV
EXPERIMENTAL PART
7KH HOHPHQWDU\ UHDFWLRQV WKDW FRPSRVH WKH EXUQLQJ PHFKDQLVPRI$3DUHOLVWHGRQ7DEOH7KLVPHFKDQLVPZDV SURSRVHGE\*URVVDFFRUGLQJWRGDWDREWDLQHGIURP WKHOLWHUDWXUH
,QWKHXVHGVLPXODWLRQPRGXOHLWLVQHFHVVDU\WKHLQVHUWLRQ RI D WHPSHUDWXUH SUR¿OH 7KLV SUR¿OH OLVWV WKH GHYHORSHG WHPSHUDWXUH LQ WKH PDWHULDO EXUQLQJ LQ IXQFWLRQ RI WKH GLVWDQFHIURPWKHVROLGVXUIDFH7KHGDWDFDQEHREVHUYHG LQ )LJ 7KH SUHVHQW SUR¿OH ZDV REWDLQHG IURP WKH VRIWZDUH¶VGDWDEDVHDQGLWLVDJRRGDSSURDFKWRWKHVROLG IXHO XVHG LQ WKH VWXG\$V WKLV SUR¿OH ZDV GHYHORSHG IRU DWP WHPSHUDWXUHV IURP WR . DUH H[SHFWHG IRUWKHVLPXODWLRQV
)RUWKHH[SHULPHQWVWKHV\VWHPSUHVVXUHRIWKHFRPEXVWLRQ FKDPEHU YDULHG LQ RUGHU WR VWXG\ LWV LQÀXHQFH LQ WKH IODPH VWUXFWXUH LW ZDV VLPXODWHG WKH FRPEXVWLRQ LQ DWPRVSKHUH FRPSRVHG E\ WKH LQLWLDO SURGXFWV RI $3 GHFRPSRVLWLRQ SXUH ZLWK FRPSRVLWLRQ DQG )LJXUH 6FKHPHRIWKHDPPRQLXPSHUFKORUDWHFU\VWDOFRPEXVWLRQ
SURFHVV ZLWK HYROXWLRQ RI WKH WHPSHUDWXUHV IURP WKH PDWHULDOVXUIDFH
Reaction A E Ea
+&O2 &O232+ (
+&O2+12 &O23+212 (
&O23 &O22 (
&O20 &O2&O0 (
&O212 &O12 (
&O2&O2+ &O+2 (
&O2+2+ &O2+O (
+&O2+ &O+O (
&O+ +&O&O (
&O21+3 &O2+1+ (
NH
3&O 1++&O (
NH
32+ 1++O (
NH
2 +122+ (
NH
12 +21 (
+122+ 12+O (
+122 122+ (
+12+ +12 (
12+0 +120 (
HO
1 +1212 (
12+2 122+ (
+12 122+ (
H
2+ +2+ (
7DEOH 'HFRPSRVLWLRQUHDFWLRQVRIDPPRQLXPSHUFKORUDWHa
N $7EH[S(578QLWV$PROFPV.(-PRO
a
NLQHWLFGDWDFRPSRVHGIURP.RUREHLQLFKHYet al
)LJXUH 7HPSHUDWXUHSUR¿OHXVHGLQWKHVLPXODWLRQV
FRQFHQWUDWLRQ REWDLQHG IURP OLWHUDWXUH %HFNVWHDG DQG 3XGXSSDNNDP
$ VWXG\ RI $3 IRUPXODWHG ZLWK K\GUR[\O WHUPLQDWHG SRO\EXWDGLHQH+73%ELQGHUZDVDOVRFDUULHGRXWZKRVH PHFKDQLVPFDQEHREVHUYHGLQ7DEOH7KLVPHFKDQLVPZDV EDVHGRQ*URVVZRUN.RUREHLQLFKHYet alDFFRUGLQJ WRGDWDREWDLQHGIURPWKHOLWHUDWXUH7KHLQLWLDOFRQFHQWUDWLRQ RIWKHVSHFLHVLQVLGHWKHFKDPEHUZDVVHWDFFRUGLQJWRDQ $3+73%UDWHRI
Reaction A E Ea
&O+2 &O22+ (
&O22 &O2 (
++&O &O+ (
+&O2 &O2+ (
&O2 &O&O2 (
N
20 120 (
N
22+ 1+2 (
N
22 1212 (
N
22 12 (
N
2+ 12+ (
+0 !+0 (
++ !+ (
++2 !++O (
+&2 !+&2 (
&O212 &O212 (
&O&O2 &O2&O2 (
&O2&O2 &O2 (
&O+2 +&O2 (
&O20 &O20 (
NO
2 122 (
+12+12 +21O (
NO
12 12122 (
&O12 &O21 (
2+2+ +22 (
NH
12 +21O (
+121+ 1+312 (
&O2+12 +&O12 (
+&O+2 &O2+O (
NH
12 +12+ (
NH
2+ +21+ (
NH
1+ 1+1+3 (
1+12 12+ (
1+12 +12 (
&O1+ +&O1+ (
&O21+ &O2+12 (
112 1212 (
112 112 (
1+2+ +21 (
1+2+ +12 (
1+1+ 11+3 (
HO
&+3 !2&+ (
CH
&+ !&+3 (
Reaction A E Ea
&O20 &O2&O0 (
&O212 &O12 (
+&O2+ &O+O (
&O+ +&O&O (
NH
3&O 1++&O (
NH
32+ 1++O (
NH
2 +122+ (
NH
12 +21 (
+122+ 12+O (
+122 122+ (
+12+ +12 (
12+0 +120 (
HO
1 +1212 (
12+2 122+ (
+12 122+ (
H
2+ +2+ (
CH
&O &+3+&O (
CH
+ &+3+ (
CH
2+ &+3+O (
CH
3+0 &+0 (
&22+ &2+ (
&2&O2 &2&O (
&2&O2 &2&O2 (
+2 22+ (
CH
+ &+3+ (
CH
+0 &+30 (
CH
2 &+32+ (
2+&+3 &++O (
C
H2 &2+ (
NH
12 +12 (
NH
&O2 +12+&O (
O
+12 12+2 (
+&O0 +&O0 (
&O&O0 &O0 (
7DEOH 'HFRPSRVLWLRQUHDFWLRQVRIDPPRQLXPSHUFKORUDWHa
N $7EH[S(578QLWV$PROFPV.(-PRO0DQ\PHWDO
VXUIDFHRUPHWDOOLFDGGLWLYHXVHGRQO\DVVXSSRUWRUFDWDO\VW a
6LPLODUO\ LQ$3+73% VLPXODWLRQ WKH SUHVVXUH RI WKH FRPEXVWLRQFKDPEHUZDVYDULHGLQRUGHUWRVWXG\LWVLQÀXHQFH LQWKHÀDPHVWUXFWXUH7KHDWPRVSKHUHRIWKHFKDPEHUZDV FRPSRVHG E\ WKH LQLWLDO SURGXFWV RI$3 DQG +73% ELQGHU GHFRPSRVLWLRQ
RESULTS AND DISCUSSION
,Q$3FRPEXVWLRQVLPXODWLRQSURFHVVDWSUHVVXUHRIDWP )LJLWFDQEHQRWLFHGWKDWWKHFXUYHVKDYHH[SRQHQWLDO SUR¿OHVDFFRUGLQJWRWKHHTXDWLRQSURSRVHGE\$UUKHQLXVDQG DOVRWKHÀDPHPXVWEHSUHVHQWHGLQWKHUHJLRQIURPWRPP RIWKHEXUQLQJPDWHULDOVXUIDFH7KHUHLVDVLJQL¿FDQWGHFD\ RIWKHPRODUIUDFWLRQVRIZDWHUDQGFKORULQHZKLOHWKHUHLVDQ LQFUHDVHRQWKHPROHIUDFWLRQVRIFKORULGULFDFLGQLWURJHQDQG R[\JHQ)URPWKLVUHVXOWLWZDVSRVVLEOHWRREVHUYHWKDWWKH FRPEXVWLRQRI$3LQDFRPEXVWLRQFKDPEHULVQRWFRPSOHWH GXHWRWKHUHGXFHGSHUPDQHQFHWLPHRQLWWKHUHIRUHWKHUH LV WKH IRUPDWLRQ RI D JUHDW TXDQWLW\ RI FKORULGULF DFLG DQG WKHUHLVQRFRPSOHWHFRQVXPHRIWKHR[\JHQ$FFRUGLQJWR
Cai et al GXULQJ WKH GHFRPSRVLWLRQ RI $3 WKH
IRUPDWLRQRIQLWURJHQLVH[SHFWHG
7KHQLWURJHQXVXDOO\SUHVHQWVDVDQLQHUWJDVDOWKRXJK LQWKHV\VWHPWHPSHUDWXUHa.LWSDUWLFLSDWHVDVWKH PHFKDQLVP LQ UHDFWLRQV ZLWK$3 GHFRPSRVLWLRQ SURGXFWV +RZHYHUWKHGHFRPSRVLWLRQRIDPPRQLDLQJDVHRXVQLWURJHQ
LVIDVWHUWKDQWKHUHDFWLRQVRI1ZLWKRWKHUVSHFLHVWKHUHIRUH
DQLQFUHDVHRQWKHPRODUIUDFWLRQLVREVHUYHG
$V WKH SUHVVXUH RQ WKH FRPEXVWLRQ FKDPEHU ULVHV VLJQL¿FDQWGLIIHUHQFHVRQWKHFRPEXVWLRQSURFHVVRI$3ZHUH
QRWLFHG )LJXUH VKRZV WKH FRPEXVWLRQ VLPXODWLRQ RI WKH PDWHULDODWDWPSUHVVXUH
7KH FXUYHV DUH SUHVHQWHG ZLWK H[SRQHQWLDO SUR¿OHV DOWKRXJKWKHUHZDVDGLVSODFHPHQWRIWKHÀDPHUHJLRQQRZ SUHVHQWHG DW WR PP IURP WKH EXUQLQJ VXUIDFH $V WKH SUHVVXUH LQFUHDVHV WKH VSHHG RI WKH HOHPHQWDU\ UHDFWLRQV SUHVHQWHGLQ$3GHFRPSRVLWLRQPHFKDQLVPULVHVWKHUHIRUH WKLVPD\EHWKHPDLQFDXVHRIWKHDSSUR[LPDWLRQRIWKHÀDPH WRWKHPDWHULDO,WZDVDOVRREVHUYHGEHKDYLRUWRWKHVSHFLHV LQWKHÀDPHUHJLRQSUHVHQFHRIHOERZVLQZKLFKWKHUHLV GHFUHDVHDQGSRVWHULRULQFUHDVHRIWKHPRODUIUDFWLRQIRU+&O DQGLQFUHDVHDQGSRVWHULRUGHFUHDVHRIWKHPRODUIUDFWLRQIRU
ZDWHUDQG&O$VWKH$3DFWVDVDQR[LGL]HUWKHLQFUHDVHRI
R[\JHQFRQFHQWUDWLRQLVH[SHFWHG7KHPDVVEDODQFHRIWKH VSHFLHVLVPDLQWDLQHGIURPWKHEHJLQQLQJWRWKHHQGRIWKH VLPXODWLRQ
7KH³HOERZV´DSSHDUGXHWRWKHLQFUHDVHRIWKHRFFXUUHQFH RILQWHUPHGLDWHUHDFWLRQVLQWKHÀDPH]RQH7KLVSKHQRPHQRQ JHQHUDWHVDJUHDWYDULDWLRQRILQWHUPHGLDWHVPROHIUDFWLRQV ZKLFKPRGLI\WKHFRQFHQWUDWLRQRIWKHPDLQVSHFLHVHVSHFLDOO\ LQWKHÀDPH]RQHVRWKHGLIIHUHQWVORSHLVREVHUYHG
)LJXUHVDQGSUHVHQWQHZ$3GHFRPSRVLWLRQVLPXODWLRQV IRUSUHVVXUHVRIDQGDWPRVSKHUHVUHVSHFWLYHO\
,W LV REVHUYHG WKDW DV WKH SUHVVXUH LQ WKH FRPEXVWLRQ FKDPEHULQFUHDVHVWKHUHLVDQDSSUR[LPDWLRQRIWKHÀDPHWR WKHVXUIDFHRIWKHPDWHULDODQGDQDFFHQWXDWLRQRIWKHHOERZV SUHVHQWHGRQWKHÀDPHUHJLRQLQGLFDWLQJWKHLQÀXHQFHRIWKH VSHHGLQFUHDVHRIHOHPHQWDU\UHDFWLRQVLQWKHGHFRPSRVLWLRQ SURFHVVRIWKHPDWHULDOLQVWXG\6XFKJDLQLQFKHPLFDOVSHHG UHDFWLRQVPD\EHFRQYHUWHGLQWKUXVWRIURFNHWPRWRUDQGVSHFL¿F LPSXOVHRIVROLGSURSHOODQWJUDLQ6RWKLVNLQGRIVLPXODWLRQ LVLQWHUHVWLQJLQRUGHUWRNQRZWKHEHKDYLRURIRQHRUPRUH
)LJXUH $PPRQLXPSHUFKORUDWHGHFRPSRVLWLRQXQGHUSUHVVXUHRI DWPRVSKHUH
)LJXUH $PPRQLXPSHUFKORUDWHGHFRPSRVLWLRQXQGHUSUHVVXUHRI DWPRVSKHUHV
PDWHULDOVLQWHUQDOO\WRDURFNHWPRWRUFRPEXVWLRQFKDPEHUWR GHYHORSWKHRSWLPXPSURSHOODQWIRUPXODWLRQLHWKHRQHWKDW JHQHUDWHVKLJKHUWKUXVWVSHFL¿FLPSXOVHDQGIHZHUUHVLGXHV
%H\RQG WKH VLPXODWLRQV RI SXUH $3 VLPXODWLRQV ZHUH FDUULHGRXWZLWK$3IRUPXODWHGZLWK+73%WRDSSUR[LPDWH WKHPD[LPXPSRVVLEOHWRDUHDOVROLGSURSHOODQWIRUPXODWLRQ EHFDXVH+73%SRO\PHUPDWUL[LVDELQGHUODUJHO\XVHGLQ IRUPXODWLRQV)LJXUHSUHVHQWV$3+73%GHFRPSRVLWLRQ 7KHFRPEXVWLRQSURFHVVRI$3+73%KDVEHHQLQYDULDEOH ZLWK SUHVVXUH 7KLV EHKDYLRU VKRXOG EH DWWULEXWHG WR WKH KRPRJHQHRXVGLVSHUVLRQRI$3DPLGVWWKHELQGHULQWKHVROLG SKDVHDQGWRWKHODFNRIWKLVVSHFLHVLQUHODWLRQWRWKHELQGHU JHQHUDWLQJORZHUFRQFHQWUDWLRQVRI2WKDQQHFHVVDU\$OVR LQWKHJDVSKDVHVLWLVDVVXPHGWKDWDOORIWKHOLTXLG$3DQG +73%SUHVHQWRQWKHFRQGHQVHGSKDVHGHFRPSRVHWRIRUP JDVHRXV VSHFLHV HYDSRUDWLRQ LV QRW LQFOXGHG $FFRUGLQJ WR -HSSVRQ %HFNVWHDG DQG -LQJ WKH NLQHWLF PRGHO DFFXUDWHO\FDOFXODWHVWKHÀDPHVWUXFWXUHXSWRDERXWWR
DWPLQZKLFKDVHSDUDWLRQEHWZHHQWKHPRGHOFDOFXODWLRQV DQGH[SHULPHQWDOGDWDEHFRPHVLQFUHDVLQJO\DSSDUHQW$WORZ SUHVVXUHVWRDWPWKHSURSHOODQWLVPRUHOLNHO\WREXUQDV DSUHPL[HGÀDPHZLWKWKHR[LGL]HUDQGELQGHUGHFRPSRVLWLRQ SURGXFWVIURPWKHFRQGHQVHGSKDVHPL[LQJFRPSOHWHO\EHIRUH WKHJDVSKDVHUHDFWLRQVRFFXU$VWKHSUHVVXUHLQFUHDVHVWKH GLIIXVLRQRIWKHIXHOSURGXFWVLQWRWKHUHDFWLQJVWUHDPDERYH WKHR[LGL]HULVGLVUXSWHGDQGWKHJDVSKDVHÀDPHEHFRPHV LQFUHDVLQJO\ GLIIXVLRQOLPLWHG 7KXV DW SUHVVXUHV DERYH WRDWPWKHNLQHWLFPRGHOZKLFKDVVXPHVFRPSOHWHO\ SUHPL[HGFRPEXVWLRQZRXOGEHH[SHFWHGWREHJLQWR\LHOG FDOFXODWLRQVLQH[FHVVRIWKHPHDVXUHGEXUQUDWH,QGHSHQGHQWO\ RIWKHSUHVVXUHLQWKHFKDPEHUWKHSDFNLQJDQGWKHPROHFXODU GLVWULEXWLRQRIWKHPDWHULDODUHQRWJRLQJWRVXIIHUDOWHUDWLRQ DQG DUH QRW JRLQJ WR OHDG WR SUHVVXUH YDULDWLRQV LQ WKHLU EHKDYLRUSURYLQJWKHOLPLWDWLRQVRIWKHPRGHO
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
CONCLUSIONS
7KH$3GHFRPSRVLWLRQSURFHVVZDVVLPXODWHGLQGLIIHUHQW VLWXDWLRQV XVLQJ WKH FRPSXWDWLRQDO SDFNDJH &KHPNLQ
)LJXUH $PPRQLXPSHUFKORUDWHGHFRPSRVLWLRQXQGHUSUHVVXUHRI DWPRVSKHUHV
)LJXUH $PPRQLXPSHUFKORUDWHGHFRPSRVLWLRQXQGHUSUHVVXUHRI DWPRVSKHUHV
3UHPL[PRGXOH:LWKWKHUHDFWLRQVLQYROYHGLQWKHSURSRVHG PHFKDQLVPV WKH YDULDWLRQ RI WKH$3 FRPEXVWLRQ EHKDYLRU ZDV REVHUYHG DV WKH SUHVVXUH RI WKH FRPEXVWLRQ FKDPEHU RI D VROLG SURSHOODQW URFNHW PRWRU ZDV YDULHG %DVHG RQ WKH UHVXOWV WKH SUR¿OHV RI WKH ÀDPHV RULJLQDWHG IURP WKH $3 DQG $3+73% FRPEXVWLRQ ZHUH PRGHOHG SUHVHQWLQJ WKH GLIIHUHQW WHPSHUDWXUH UHJLRQV DQG WKH PRODU IUDFWLRQ YDULDWLRQRIFKHPLFDOVSHFLHVJHQHUDWHGE\WKHGHFRPSRVLWLRQ RI WKH PDWHULDOV 7KLV VWXG\ FRQWULEXWHV WR XQGHUVWDQG WKH GHFRPSRVLWLRQSURFHVVLHKRZWKHVSHFLHVLQYROYHGEHKDYHV GXULQJ WKH FRPEXVWLRQ DQG ZLWK YDULDWLRQV RI GLIIHUHQW SDUDPHWHUV7KHSURFHGXUHDGRSWHGPD\EHRIXVHZLWKQHZ IRUPXODWLRQVRISURSHOODQWVDYRLGLQJFRVWO\DQGORQJWHVWV
REFERENCES
%HFNVWHDG0:DQG3XGXSSDNNDP.9³0RGHOLQJ DQG6LPXODWLRQRI&RPEXVWLRQRI6ROLG3URSHOODQW,QJUHGLHQWV 8VLQJ 'HWDLOHG &KHPLFDO .LQHWLFV´ WK $,$$$60( 6$($6(( -RLQW 3URSXOVLRQ &RQIHUHQFH DQG ([KLELW
%HFNVWHDG 0:et al ³3URJUHVV LQ (QHUJ\ DQG
&RPEXVWLRQ6FLHQFH´9ROSS
%RJJV7/³'HÀDJUDWLRQ5DWH6XUIDFH6WUXFWXUHDQG 6XEVXUIDFH 3UR¿OH RI 6HOI'HÀDJUDWLQJ 6LQJOH &U\VWDOV RI $PPRQLXP3HUFKORUDWH´$,$$-RXUQDO9RO1RSS
&DL :et al ³$ 0RGHO RI $3+73% &RPSRVLWH
3URSHOODQW &RPEXVWLRQ LQ 5RFNHW 0RWRU (QYLURQPHQWV´ &RPEXVWLRQ 6FLHQFH DQG7HFKQRORJ\9RO SS
*URVV0/³7ZRGLPHQVLRQDOPRGHOLQJRI$3+73% XWLOL]LQJDYRUWLFLW\IRUPXODWLRQDQGRQHGLPHQVLRQDOPRGHOLQJ RI$3DQG$'17KHVLVSUHVHQWHGDW%ULJKDP8QLYHUVLW\
-HSSVRQ 0 %et al ³$ .LQHWLF 0RGHO IRU WKH
3UHPL[HG &RPEXVWLRQ RI D )LQH $3+73% &RPSRVLWH 3URSHOODQW´ $PHULFDQ ,QVWLWXWH RI $HURQDXWLFV DQG$VWURQDXWLFV
.RUREHLQLFKHY 2et al $,$$6$($60($6((
WK-RLQW3URSXOVLRQ&RQIHUHQFH2UODQGR86$
0DUN + ³(QF\FORSHGLD RI 6SDFH 6FLHQFH DQG 7HFKQRORJ\´9RO:LOH\,QWHUVFLHQFHS
0RQWHLUR 55et al ³9XOQHUDELOLGDGH GH PRWRU
IRJXHWH D SURSHOHQWH VyOLGR HP UHODomR DR LPSDFWR EDOtVWLFR $UPD GH )RJR´ ± ,; 6LPSyVLR ,QWHUQR GH *XHUUD (OHWU{QLFD 6,*( 6mR -RVp GRV &DPSRV 6mR3DXOR%UD]LO
3LVDFDQH9/³)XQGDPHQWDOVRI6SDFH6\VWHPV´WK HG2[IRUG8QLYHUVLW\3UHVVS
