century and they are assigned to the Chinese (Mark, 2003). The rocket red glare from Spangled Banner of Francis Scott. Key was initially used in 1812 in a war ...
GRLMDWP
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$HURQiXWLFD6mR-RVpGRV&DPSRV63%UD]LO Abstract: 7KH FRPEXVWLRQ VLPXODWLRQ RI DPPRQLXP SHUFKORUDWH ZDV FDUULHG RXW ZLWK WKH VRIWZDUH &KHPNLQ LQ WZRVWHSVWKHEXUQLQJEHKDYLRURISXUHDPPRQLXPSHUFKORUDWHDQGWKHRQHRIIRUPXODWHGDPPRQLXPSHUFKORUDWH ZLWK K\GUR[\O WHUPLQDWHG SRO\EXWDGLHQH ELQGHU ,Q ERWK FDVHV WKH URRP SUHVVXUH YDULHG LQ RUGHU WR YHULI\ LWV LQÀXHQFH LQ WKH V\VWHP 7KH EXUQLQJ HQYLURQPHQW FRQGLWLRQV ZHUH GLYHUVH 'XULQJ WKH FRPEXVWLRQ SURFHVV WKH GDWDREWDLQHGIURPWKHNLQHWLFFKHPLVWU\VLPXODWLRQVRIWZDUHZHUHFRPSLOHG7KHÀDPHVWUXFWXUHFDQEHGHVFULEHG E\ WKH PRODU IUDFWLRQ RI WKH EXUQLQJ SURGXFWV DQG WKH WHPSHUDWXUH HYROXWLRQ IURP WKH VXUIDFH RI WKH PDWHULDO Keywords:$PPRQLXP3HUFKORUDWH$PPRQLXP3HUFKORUDWH+\GUR[\O7HUPLQDWHG3RO\EXWDGLHQH+\GUR[\O7HUPLQDWHG 3RO\EXWDGLHQH%LQGHU&KHPNLQ
INTRODUCTION 7KH ¿UVW VROLG SURSXOVLRQ URFNHW PRWRUV GDWH IURP th FHQWXU\DQGWKH\DUHDVVLJQHGWRWKH&KLQHVH0DUN 7KHURFNHWUHGJODUHIURP6SDQJOHG%DQQHURI)UDQFLV6FRWW .H\ZDVLQLWLDOO\XVHGLQLQDZDULQYROYLQJWKH8QLWHG 6WDWHVRI$PHULFDDQG(QJODQG6LJQL¿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
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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¿FLPSXOVHRIWKHSURSHOODQWXVXDOO\DOXPLQXPIURP WRRIR[LGL]HUOLNHDPPRQLXPSHUFKORUDWH±$3 DQG IURPWRRIWKHELQGHUPDWUL[PDLQVRXUFHRIFDUERQ ZKLFK DFWV DV IXHO (YHQWXDOO\ IURP WR RI SODVWLFL]HU FDQEHDGGHGWRLPSURYHWKHÀH[LELOLW\DQGWRKHOSGXULQJWKH SURSHOODQW SURFHVVLQJ ZKHQ LW LV VWLOO LQ WKH OLTXLG SKDVH3LVDFDQH
-$HURVS7HFKQRO0DQDJ6mR-RVpGRV&DPSRV9RO1RSS-DQ0DU
33
*RQoDOYHV5)%et al.
([DPSOHVRIW\SLFDOFRQVWLWXHQWVRIVROLGSURSHOODQWVDUH SUHVHQWHGLQ7DEOH,WLVSRVVLEOHWRPDNHWKHV\QWKHVLVRI PDQ\VROLGSURSHOODQWIRUPXODWLRQVIURPWKHFRPELQDWLRQRI WKHVHFRPSRXQGV 7KH SRO\PHULF PDWUL[ QDPHG ELQGHU SOD\V WKH UROH RI ELQGHURIDOOWKHUDZPDWHULDOVWKDWFRPSRVHWKHFRPSRVLWH VROLG SURSHOODQW JUDLQ 0ROGHG LQ WKH URFNHW PRWRU FDVH LW 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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¿QHG GXH WR FKHPLFDO UHDFWLRQV EXEEOHV DQG FRQGHQVHG PDWHULDOEHLQJFRQYHFWHGDZD\IURPWKHVXUIDFH,QWKHJDV SKDVH UHJLRQ RI D PRQRSURSHOODQW WKH ÀDPH LV HVVHQWLDOO\ 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 RFFXUV LQ WKH JDV ÀDPH XQWLO HTXLOLEULXP LV UHDFKHG LQ WKH ¿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
7DEOH([DPSOHVRIW\SLFDOFRQVWLWXHQWVRIVROLGSURSHOODQWIRUPXODWLRQV 0HWDOOLF QRQPHWDOOLFIXHOV $OXPLQXP %HU\OOLXP
2[LGL]HUV $PPRQLXP3HUFKORUDWH1+&O2) /LWKLXP3HUFKORUDWH/L&O2)
0DJQHVLXP
3RWDVVLXP3HUFKORUDWH.&O2)
6RGLXP
$PPRQLXP1LWUDWH1+NO3)
+\GURFDUERQV
3RWDVVLXP1LWUDWH.123)
%LQGHUV
&XULQJ$JHQWV
3ODVWLFL]HUV
&DUER[\O7HUPLQDWHG
,VRF\DQDWHV
'2$'%7
3RO\EXWDGLHQH&73% (SR[\GHV
$PLQHV$PLGHV
7ULHWK\OHQHJOLFRO GLQLWUDWH
+\GUR[\OWHUPLQDWHG
7ULPHWK\OHWKDQH
SRO\EXWDGLHQH+73%
WULQLWUDWH
1LWURFHOOXORVH 3RO\EXWDGLHQHDFU\OLF DFLG3%$& 3RO\EXWDGLHQH
3RO\PHUV
6RGLXP1LWUDWH1D123)
3ODVWLFV
&\FORWHWUDPHWK\OHQHWHWUDQLWUDPLQH+0;
$VSKDOW
5XEEHUV
&\FORWHWUDPHWK\OHQHWULQLWUDPLQH5';
39&
DFU\ORQLWULOH3%$1
-$HURVS7HFKQRO0DQDJ6mR-RVpGRV&DPSRV9RO1RSS-DQ0DU
$PPRQLXPSHUFKORUDWHDQGDPPRQLXPSHUFKORUDWHK\GUR[\OWHUPLQDWHGSRO\EXWDGLHQHVLPXODWHGFRPEXVWLRQ 7DEOH 'HFRPSRVLWLRQUHDFWLRQVRIDPPRQLXPSHUFKORUDWHa
)LJXUH 6FKHPHRIWKHDPPRQLXPSHUFKORUDWHFU\VWDOFRPEXVWLRQ SURFHVV ZLWK HYROXWLRQ RI WKH WHPSHUDWXUHV IURP WKH PDWHULDOVXUIDFH
'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 7KLV VRIWZDUH FRQVLGHUV WKH HTXDWLRQV RI PDVV DQG HQHUJ\ FRQVHUYDWLRQFKHPLFDOVSHFLHVLQYROYHGDQGOLQHDUPRPHQWXP DQGLWHQDEOHVWKHDQDO\VLVWKURXJKWHPSHUDWXUHDQGFKHPLFDO VSHFLHVPRODUIUDFWLRQVYDULDWLRQLQIXQFWLRQRIWKHGLVWDQFH IURPWKHPDWHULDOVXUIDFHDPRQJRWKHUV 7KHSUHVHQWSDSHUWUHDWVWKHFRPEXVWLRQVWXG\RISXUH$3 DQGIRUPXODWHGLQDVROLGFRPSRVLWHSURSHOODQWJUDLQIRFXVLQJ LQWKHVWUXFWXUHRIWKHÀDPHIRUPHGLQWKLVSURFHVV
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+
(
NH3&O 1++&O
(
NH32+ 1++O
(
NH2 +122+
(
NH12 +21
(
+122+ 12+O
(
+122 122+
(
+12+ +12
(
12+0 +120
(
HO1 +1212
(
12+2 122+
(
+12 122+
(
H2+ +2+
(
N $7EH[S(57 8QLWV$PROFPV. (-PRO a
NLQHWLFGDWDFRPSRVHGIURP.RUREHLQLFKHYet al
EXPERIMENTAL PART 7KH HOHPHQWDU\ UHDFWLRQV WKDW FRPSRVH WKH EXUQLQJ PHFKDQLVPRI$3DUHOLVWHGRQ7DEOH7KLVPHFKDQLVPZDV SURSRVHGE\*URVV DFFRUGLQJWRGDWDREWDLQHGIURP WKHOLWHUDWXUH ,QWKHXVHGVLPXODWLRQPRGXOHLWLVQHFHVVDU\WKHLQVHUWLRQ RI D WHPSHUDWXUH SUR¿OH 7KLV SUR¿OH OLVWV WKH GHYHORSHG WHPSHUDWXUH LQ WKH PDWHULDO EXUQLQJ LQ IXQFWLRQ RI WKH GLVWDQFH IURP WKH VROLG VXUIDFH 7KH GDWD FDQ EH REVHUYHG LQ )LJ 7KH SUHVHQW SUR¿OH ZDV REWDLQHG IURP WKH VRIWZDUH¶V GDWDEDVH DQG LW LV D JRRG DSSURDFK WR WKH VROLG IXHO XVHG LQ WKH VWXG\ $V WKLV SUR¿OH ZDV GHYHORSHG IRU DWP WHPSHUDWXUHV IURP WR . DUH H[SHFWHG IRUWKHVLPXODWLRQV
)LJXUH 7HPSHUDWXUHSUR¿OHXVHGLQWKHVLPXODWLRQV
)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 $3 GHFRPSRVLWLRQ SXUH ZLWK FRPSRVLWLRQ DQG
-$HURVS7HFKQRO0DQDJ6mR-RVpGRV&DPSRV9RO1RSS-DQ0DU
*RQoDOYHV5)%et al.
FRQFHQWUDWLRQ REWDLQHG IURP OLWHUDWXUH %HFNVWHDG DQG 3XGXSSDNNDP $ VWXG\ RI $3 IRUPXODWHG ZLWK K\GUR[\O WHUPLQDWHG SRO\EXWDGLHQH +73% ELQGHU ZDV DOVR FDUULHG RXW ZKRVH PHFKDQLVPFDQEHREVHUYHGLQ7DEOH7KLVPHFKDQLVPZDV EDVHGRQ*URVV ZRUN.RUREHLQLFKHYet al DFFRUGLQJ WRGDWDREWDLQHGIURPWKHOLWHUDWXUH7KHLQLWLDOFRQFHQWUDWLRQ RI WKH VSHFLHV LQVLGH WKH FKDPEHU ZDV VHW DFFRUGLQJ WR DQ $3+73%UDWHRI 7DEOH 'HFRPSRVLWLRQUHDFWLRQVRIDPPRQLXPSHUFKORUDWHa
Reaction
A
E
Ea
&O+2 &O22+ &O22 &O2
( (
++&O &O+
(
+&O2 &O2+
(
&O2 &O&O2
(
N20 120
(
N22+ 1+2
(
N22 1212
(
N22 12
(
N2+ 12+
(
+0 !+0
(
Reaction
A
E
Ea
++ !+
(
&O20 &O2&O0 &O212 &O12
( (
++2 !++O
(
(
+&2 !+&2
(
+&O2+ &O+O
(
&O+ +&O&O
(
&O212 &O212
(
&O&O2 &O2&O2
(
NH3&O 1++&O
(
NH32+ 1++O
(
&O2&O2 &O2
NH2 +122+
(
NH12 +21
(
+122+ 12+O
(
+122 122+
(
+12+ +12
(
12+0 +120
(
HO1 +1212
(
12+2 122+
(
+12 122+
(
H2+ +2+
(
CH&O &+3+&O
(
CH+ &+3+
(
CH2+ &+3+O
(
CH3+0 &+0
(
&22+ &2+
(
&2&O2 &2&O
(
&2&O2 &2&O2
(
+2 22+
(
CH+ &+3+
(
CH+0 &+30
(
CH2 &+32+
(
2+&+3 &++O
(
CH2 &2+
(
NH12 +12
(
NH&O2 +12+&O
(
O+12 12+2
(
+&O0 +&O0
(
&O&O0 &O0
(
&O+2 +&O2
(
&O20 &O20
(
NO2 122
(
+12+12 +21O
(
NO12 12122
(
&O12 &O21
(
2+2+ +22
(
NH12 +21O
(
+121+ 1+312
(
&O2+12 +&O12
(
+&O+2 &O2+O
(
NH12 +12+
(
NH2+ +21+
(
NH1+ 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
(
N $7EH[S(57 8QLWV$PROFPV. (-PRO 0DQ\PHWDO VXUIDFHRUPHWDOOLFDGGLWLYHXVHGRQO\DVVXSSRUWRUFDWDO\VW a
NLQHWLFGDWDFRPSRVHGE\.RUREHLQLFKHYet al
-$HURVS7HFKQRO0DQDJ6mR-RVpGRV&DPSRV9RO1RSS-DQ0DU
$PPRQLXPSHUFKORUDWHDQGDPPRQLXPSHUFKORUDWHK\GUR[\OWHUPLQDWHGSRO\EXWDGLHQHVLPXODWHGFRPEXVWLRQ
6LPLODUO\ LQ$3+73% VLPXODWLRQ WKH SUHVVXUH RI WKH FRPEXVWLRQFKDPEHUZDVYDULHGLQRUGHUWRVWXG\LWVLQÀXHQFH LQWKHÀDPHVWUXFWXUH7KHDWPRVSKHUHRIWKHFKDPEHUZDV FRPSRVHG E\ WKH LQLWLDO SURGXFWV RI$3 DQG +73% ELQGHU GHFRPSRVLWLRQ
QRWLFHG )LJXUH VKRZV WKH FRPEXVWLRQ VLPXODWLRQ RI WKH PDWHULDODWDWPSUHVVXUH
RESULTS AND DISCUSSION ,Q$3FRPEXVWLRQVLPXODWLRQSURFHVVDWSUHVVXUHRIDWP )LJ LWFDQEHQRWLFHGWKDWWKHFXUYHVKDYHH[SRQHQWLDO SUR¿OHVDFFRUGLQJWRWKHHTXDWLRQSURSRVHGE\$UUKHQLXVDQG DOVRWKHÀDPHPXVWEHSUHVHQWHGLQWKHUHJLRQIURPWRPP RIWKHEXUQLQJPDWHULDOVXUIDFH7KHUHLVDVLJQL¿FDQWGHFD\ RIWKHPRODUIUDFWLRQVRIZDWHUDQGFKORULQHZKLOHWKHUHLVDQ LQFUHDVHRQWKHPROHIUDFWLRQVRIFKORULGULFDFLGQLWURJHQDQG R[\JHQ)URPWKLVUHVXOWLWZDVSRVVLEOHWRREVHUYHWKDWWKH FRPEXVWLRQRI$3LQDFRPEXVWLRQFKDPEHULVQRWFRPSOHWH GXH WR WKH UHGXFHG SHUPDQHQFH WLPH RQ LW WKHUHIRUH WKHUH LV WKH IRUPDWLRQ RI D JUHDW TXDQWLW\ RI FKORULGULF DFLG DQG WKHUHLVQRFRPSOHWHFRQVXPHRIWKHR[\JHQ$FFRUGLQJWR Cai et al GXULQJ WKH GHFRPSRVLWLRQ RI $3 WKH IRUPDWLRQRIQLWURJHQLVH[SHFWHG
)LJXUH $PPRQLXPSHUFKORUDWHGHFRPSRVLWLRQXQGHUSUHVVXUHRI DWPRVSKHUH
7KH QLWURJHQ XVXDOO\ SUHVHQWV DV DQ LQHUW JDV DOWKRXJK LQ WKH V\VWHP WHPSHUDWXUH a. LW SDUWLFLSDWHV DV WKH PHFKDQLVP LQ UHDFWLRQV ZLWK$3 GHFRPSRVLWLRQ SURGXFWV +RZHYHUWKHGHFRPSRVLWLRQRIDPPRQLDLQJDVHRXVQLWURJHQ LVIDVWHUWKDQWKHUHDFWLRQVRI1ZLWKRWKHUVSHFLHVWKHUHIRUH DQLQFUHDVHRQWKHPRODUIUDFWLRQLVREVHUYHG $V WKH SUHVVXUH RQ WKH FRPEXVWLRQ FKDPEHU ULVHV VLJQL¿FDQWGLIIHUHQFHVRQWKHFRPEXVWLRQSURFHVVRI$3ZHUH
)LJXUH $PPRQLXPSHUFKORUDWHGHFRPSRVLWLRQXQGHUSUHVVXUHRI DWPRVSKHUHV
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 LQWKHÀDPHUHJLRQSUHVHQFHRIHOERZV LQZKLFKWKHUHLV GHFUHDVHDQGSRVWHULRULQFUHDVHRIWKHPRODUIUDFWLRQIRU+&O DQGLQFUHDVHDQGSRVWHULRUGHFUHDVHRIWKHPRODUIUDFWLRQIRU ZDWHUDQG&O $VWKH$3DFWVDVDQR[LGL]HUWKHLQFUHDVHRI R[\JHQFRQFHQWUDWLRQLVH[SHFWHG7KHPDVVEDODQFHRIWKH VSHFLHVLVPDLQWDLQHGIURPWKHEHJLQQLQJWRWKHHQGRIWKH VLPXODWLRQ 7KH³HOERZV´DSSHDUGXHWRWKHLQFUHDVHRIWKHRFFXUUHQFH RILQWHUPHGLDWHUHDFWLRQVLQWKHÀDPH]RQH7KLVSKHQRPHQRQ JHQHUDWHVDJUHDWYDULDWLRQRILQWHUPHGLDWHVPROHIUDFWLRQV ZKLFKPRGLI\WKHFRQFHQWUDWLRQRIWKHPDLQVSHFLHVHVSHFLDOO\ LQWKHÀDPH]RQH VRWKHGLIIHUHQWVORSHLVREVHUYHG )LJXUHVDQGSUHVHQWQHZ$3GHFRPSRVLWLRQVLPXODWLRQV IRUSUHVVXUHVRIDQGDWPRVSKHUHVUHVSHFWLYHO\ ,W LV REVHUYHG WKDW DV WKH SUHVVXUH LQ WKH FRPEXVWLRQ FKDPEHULQFUHDVHVWKHUHLVDQDSSUR[LPDWLRQRIWKHÀDPHWR WKHVXUIDFHRIWKHPDWHULDODQGDQDFFHQWXDWLRQRIWKHHOERZV SUHVHQWHGRQWKHÀDPHUHJLRQLQGLFDWLQJWKHLQÀXHQFHRIWKH VSHHGLQFUHDVHRIHOHPHQWDU\UHDFWLRQVLQWKHGHFRPSRVLWLRQ SURFHVVRIWKHPDWHULDOLQVWXG\6XFKJDLQLQFKHPLFDOVSHHG UHDFWLRQVPD\EHFRQYHUWHGLQWKUXVWRIURFNHWPRWRUDQGVSHFL¿F LPSXOVHRIVROLGSURSHOODQWJUDLQ6RWKLVNLQGRIVLPXODWLRQ LVLQWHUHVWLQJLQRUGHUWRNQRZWKHEHKDYLRURIRQHRUPRUH
-$HURVS7HFKQRO0DQDJ6mR-RVpGRV&DPSRV9RO1RSS-DQ0DU
*RQoDOYHV5)%et al.
PDWHULDOVLQWHUQDOO\WRDURFNHWPRWRUFRPEXVWLRQFKDPEHUWR GHYHORSWKHRSWLPXPSURSHOODQWIRUPXODWLRQLHWKHRQHWKDW JHQHUDWHVKLJKHUWKUXVWVSHFL¿FLPSXOVHDQGIHZHUUHVLGXHV
)LJXUH $PPRQLXPSHUFKORUDWHGHFRPSRVLWLRQXQGHUSUHVVXUHRI
DWPLQZKLFKDVHSDUDWLRQEHWZHHQWKHPRGHOFDOFXODWLRQV DQGH[SHULPHQWDOGDWDEHFRPHVLQFUHDVLQJO\DSSDUHQW$WORZ SUHVVXUHVWRDWP WKHSURSHOODQWLVPRUHOLNHO\WREXUQDV DSUHPL[HGÀDPHZLWKWKHR[LGL]HUDQGELQGHUGHFRPSRVLWLRQ SURGXFWVIURPWKHFRQGHQVHGSKDVHPL[LQJFRPSOHWHO\EHIRUH WKHJDVSKDVHUHDFWLRQVRFFXU$VWKHSUHVVXUHLQFUHDVHVWKH GLIIXVLRQRIWKHIXHOSURGXFWVLQWRWKHUHDFWLQJVWUHDPDERYH WKH R[LGL]HU LV GLVUXSWHG DQG WKH JDV SKDVH ÀDPH EHFRPHV 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
DWPRVSKHUHV
)LJXUH $PPRQLXPSHUFKORUDWH+73%ELQGHUGHFRPSRVLWLRQ )LJXUH $PPRQLXPSHUFKORUDWHGHFRPSRVLWLRQXQGHUSUHVVXUHRI DWPRVSKHUHV
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ÀDPH VWUXFWXUH XS WR DERXW WR
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
CONCLUSIONS 7KH$3GHFRPSRVLWLRQSURFHVVZDVVLPXODWHGLQGLIIHUHQW VLWXDWLRQV XVLQJ WKH FRPSXWDWLRQDO SDFNDJH &KHPNLQ
-$HURVS7HFKQRO0DQDJ6mR-RVpGRV&DPSRV9RO1RSS-DQ0DU
$PPRQLXPSHUFKORUDWHDQGDPPRQLXPSHUFKORUDWHK\GUR[\OWHUPLQDWHGSRO\EXWDGLHQHVLPXODWHGFRPEXVWLRQ
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 DQG 7HFKQRORJ\ 9RO SS *URVV0/³7ZRGLPHQVLRQDOPRGHOLQJRI$3+73% XWLOL]LQJDYRUWLFLW\IRUPXODWLRQDQGRQHGLPHQVLRQDOPRGHOLQJ RI$3 DQG$'17KHVLV SUHVHQWHG DW %ULJKDP 8QLYHUVLW\ -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 2 et al $,$$6$($60($6(( WK-RLQW3URSXOVLRQ&RQIHUHQFH2UODQGR86$ 0DUN + ³(QF\FORSHGLD RI 6SDFH 6FLHQFH DQG 7HFKQRORJ\´9RO:LOH\,QWHUVFLHQFHS 0RQWHLUR 55 et al ³9XOQHUDELOLGDGH GH PRWRU IRJXHWH D SURSHOHQWH VyOLGR HP UHODomR DR LPSDFWR EDOtVWLFR $UPD GH )RJR ´ ± ,; 6LPSyVLR ,QWHUQR GH *XHUUD (OHWU{QLFD 6,*( 6mR -RVp GRV &DPSRV 6mR3DXOR%UD]LO 3LVDFDQH9/³)XQGDPHQWDOVRI6SDFH6\VWHPV´WK HG2[IRUG8QLYHUVLW\3UHVVS
-$HURVS7HFKQRO0DQDJ6mR-RVpGRV&DPSRV9RO1RSS-DQ0DU