$QQDOHVGHOD)RQGDWLRQ/RXLVGH%URJOLH9ROXPHQR
/RZ(QHUJ\7UDQVPXWDWLRQRI$WRPLF1XFOHLRI&KHPLFDO
(OHPHQWV
9'.8=1(7629*90,6+,16.<)03(1.299,$5%8=29
9,=+(0(1,.
'XEQD 0RVFRZUHJLRQ5&$33URPLVKOHQQD\DVW5XVVLD
P\VK#QUPDLOMLQUUX
$%675$&7$VKRUWUHYLHZRIH[SHULPHQWDOUHVXOWVLQGLFDWLYHRIWKHH[LV
WHQFH RI D IRUELGGHQ SK\VLFDO SKHQRPHQRQ ± D WUDQVIRUPDWLRQ RI VRPH
DWRPLF QXFOHL LQWR RWKHU DWRPLF QXFOHL DW ORZ HQHUJLHV LV JLYHQ $V WKLV
WDNHVSODFHQRJDPPDUD\TXDQWDQHXWURQVDQGEHWDSDUWLFOHVDFFRPSDQ\
LQJVXFKQXFOHDUWUDQVIRUPDWLRQVZHUHIRXQG7KHDPSOLWXGHRIWKHLPSDFW
RIVXFKWUDQVPXWDWLRQDFKLHYHV DYDOXHRIa7KHUHVXOWVRIRXUFKHFN
H[SHULPHQWVRQORZHQHUJ\HOHPHQWWUDQVPXWDWLRQDQGDFDOFXODWLRQRISRV
VLEOHHQGSURGXFWVWKDWDUH\LHOGHGLQWKLVSURFHVVXQGHUFRQVLGHUDWLRQRIHQ
HUJ\EDODQFHVRIQXFOHDUUHDFWLRQVDUHVKRZQ7KUHHPHFKDQLVPVRISURKLEL
WLRQRIWUDQVPXWDWLRQSKHQRPHQRQZLWKLQPRGHUQSK\VLFDOFRQFHSWLRQVDUH
LQGLFDWHG 7KH FRQFOXVLRQ LV GUDZQ WKDW D VROH SRVVLELOLW\ WR PDWFK WKHVH
SURKLELWLRQVZLWKWKHREVHUYHGWUDQVPXWDWLRQSURFHVVHVFRQVLVWVLQLQFUHDV
LQJWKHUHDFWLRQGRPDLQXSWRDWRPLFGLPHQVLRQV
5(680( 2QGRQQHXQEUHIDSHUoXGHVUpVXOWDWVH[SpULPHQWDX[LQGLTXDQW
O
H[LVWHQFHG¶XQSKpQRPqQHSK\VLTXHLQWHUGLW ODWUDQVIRUPDWLRQGHVQR\DX[
DWRPLTXHV G
XQV pOpPHQWV FKLPLTXHV HQ G¶DXWUHV VRXV O
DFWLRQ GHV EDVVHV
pQHUJLHV'DQVFHVWUDQVIRUPDWLRQVLOQ¶DSSDUDvWSDVGHUD\RQ;JDPPDGH
QHXWURQV HW GH SDUWLFXOHV ErWD /
DPSOLWXGH GH O
HIIHW G¶XQH WHOOH
WUDQVPXWDWLRQHVWGHO¶RUGUHGHJUDQGHXUGH2QGRQQHOHVUpVXOWDWVGH
QRV H[SpULHQFHV GH FRQWU{OH GH OD WUDQVPXWDWLRQ GH EDVVH pQHUJpWLTXH GHV
pOpPHQWV HW OH GpFRPSWH GHV SURGXLWV SRVVLEOHV ILQDX[ UpVXOWDQW GDQV FH
SURFHVVXVTXLGRQQHODEDODQFHpQHUJpWLTXHGHVUpDFWLRQVQXFOpDLUHV7URLV
PpFDQLVPHV GH OD WUDQVPXWDWLRQ DFWXHOOHPHQW VXSSRVpH LQWHUGLWH VRQW
SURSRVpV 2Q HQ WLUH OD FRQFOXVLRQ TXH OD VHXOH SRVVLELOLWp SRXU UHQGUH
FRPSWHGHFHVLQWHUGLFWLRQVHWGHVWUDQVPXWDWLRQVREVHUYpHVHVWG¶pWHQGUHOH
GRPDLQHGHUpDFWLRQMXVTX
DX[GLPHQVLRQVDWRPLTXHV
9'.X]QHWVRYHWDO
,QWURGXFWLRQ
$W WKH SUHVHQW WLPH LQIRUPDWLRQ DERXW QHZ SK\VLFDO SKHQRPHQRQ ± ORZ
HQHUJ\ WUDQVPXWDWLRQ RI DWRPLF QXFOHL RI FKHPLFDO HOHPHQWV KDV DSSHDUHG
LQ OLWHUDWXUH DQG SULYDWH FRPPXQLFDWLRQV ,Q SDUWLFXODU ORZ HQHUJ\ HOHPHQW
WUDQVPXWDWLRQ /((7LVVHHQDWHOHFWULFH[SORVLRQRIPHWDOIRLOVLQDOLTXLG
GLHOHFWULF PHGLXP DW HOHFWURQEHDP PHOWLQJ RI ]LUFRQLXP LQJRWV LQ D
YDFXXPIXUQDFHDQGDWXOWUDVRXQGSURFHVVLQJRIDTXHRXVVDOWVROXWLRQV
7KHSXUSRVHRIWKHSUHVHQWZRUNLVWRFDUU\RXWDWWKH-,15'XEQD5XV
VLDDFRPSDUDWLYHDQDO\VLVRIOLWHUDWXUHGDWDRQ/((7SKHQRPHQRQWRUHS
UHVHQWUHVXOWVRIRXUFKHFNH[SHULPHQWVRQIRLOVHOHFWULFH[SORVLRQWRFDOFX
ODWH SRVVLEOH ILQDO SURGXFWV RI WUDQVPXWDWLRQ XQGHU FRQVLGHUDWLRQ RI HQHUJ\
EDODQFHVRIQXFOHDUUHDFWLRQV
6KRUWVXPPDU\
,Q WKLV UHYLHZ ZH UHSUHVHQWWKHDOUHDG\SXEOLVKHGZRUNVRQH[SHULPHQWDO
REVHUYLQJ RI WKH SKHQRPHQRQ RI ORZ HQHUJ\ HOHPHQW WUDQVPXWDWLRQ OHDYLQJ
ZLWKRXWFRQVLGHUDWLRQWKRVHZRUNVZKLFKPD\EHNQRZQWRXVEXWZKLFKDUH
QRWSXEOLVKHG\HW)XUWKHUPRUHZHUHSUHVHQWH[SHULPHQWDOGDWDZKLFKKDYH
EHHQMXVWREWDLQHGE\WKHDXWKRUVUHDVRQLQJWKDWDXWKRUV¶LQWHUSUHWDWLRQDQG
GHVFULSWLRQ RI SK\VLFDO SURFHVVHV FDXVLQJ WKH SKHQRPHQRQ RI ORZ HQHUJ\
HOHPHQWWUDQVPXWDWLRQVKRXOGDOVRQRWEHLQFOXGHGLQWKHSUHVHQWSDSHU5HDO
L]LQJWKDWSXEOLFDWLRQVRQWKHWRSLFXQGHUGLVFXVVLRQDUHQRWHDVLO\DFFHVVLEOH
IRU D EURDG FLUFOH RI UHDGHUV ZH JLYH VKRUW GHVFULSWLRQV RI H[SHULPHQWDO LQ
VWDOODWLRQVDWZKLFKWKHWUDQVPXWDWLRQSKHQRPHQRQZDVGLVFRYHUHG
([SHULPHQWVRQHOHFWULFH[SORVLRQRIPHWDOOLFIRLOVLQOLTXLGPHGLD
7KRVHH[SHULPHQWVZHUHFDUULHGRXWDWWKH5XVVLDQ5HVHDUFK&HQWHU³.XU
FKDWRY,QVWLWXWH´XQGHUWKHGLUHFWLRQRI/,8UXWVNRHY>@7KHH[SHULPHQWDO
LQVWDOODWLRQ UHSUHVHQWV DQ H[SORVLRQ FHOO PDGH LQ WKH IRUP RI SRO\HWK\OHQH
WRUXV ZLWK HLJKW KROHV ZKLFK DUH XQLIRUPO\ GULOOHG DORQJ WKH FLUFOH 3RO\H
WK\OHQH FXSV ILOOHG ZLWK GLVWLOOHG ZDWHU DUH LQVHUW LQWR WKH KROHV 7LWDQLXP
HOHFWURGHV DUH SXW LQWR WKH FXSV PHWDOOLF IRLOV ZKLFK DUH D ORDG ZHUH FRQ
QHFWHGE\FRQWDFWHOHFWULFZHOGLQJWRWKHHOHFWURGHV7KHFXSGLDJUDPRIWKH
H[SORVLRQ FHOO LV JLYHQ LQ )LJ 0HWDOOLF IRLOV RI WLWDQLXP DQG ]LUFRQLXP
ZHUH XVHG DV ORDGV (OHFWURGHV ZLWKORDGVZHUHORFDWHGRQWKHSRO\HWK\OHQH
FDSZKLFKVHDOVWKHH[SORVLRQFHOO(OHFWURGHVOHDGRXWRQWKHH[WHUQDOVXU
IDFHRIWKHFDSZHUHFRQQHFWHGWRFDSDFLWRUEDQN(QHUJ\VWRUDJHRIWKHEDQN
DWGLVFKDUJHYROWDJH8aN9ZDVHTXDOWR:aN-$WSXOVHVXSSO\RIWKH
YROWDJH WR H[SORVLRQ FHOO PHWDOOLF IRLOV ZHUH GHVWUR\HG HOHFWULF H[SORVLRQ
/RZ(QHUJ\7UDQVPXWDWLRQRI$WRPLF1XFOHLRI&KHPLFDO(OHPHQWV
7KHGXUDWLRQRIFXUUHQWSXOVHLQH[SHULPHQWVZDVPVZLWKFKDUDFWHULVWLF
FXUUHQW SXOVH JURZWK WLPHV a PV 7KH DXWKRUV RI WKH SDSHU DIILUP WKDW
EHVLGHV D PDLQ HOHPHQW DQG LWV DGPL[WXUHV DWRPV RI RWKHU HOHPHQWV DUH
IRUPHG LQ WKH SURGXFWV RI HOHFWULF H[SORVLRQ ZKLFK ZHUH QRW SUHVHQW LQ WKH
H[SORVLRQ YROXPH SULRU WR EHJLQQLQJ RI WKH SURFHVV 7KH FRQWHQW RI IRUHLJQ
HOHPHQWV LQ WKH HOHFWULF H[SORVLRQ SURGXFWV DWWDLQV VHYHUDO SHUFHQW RI WKH
GLVFKDUJHU
VHDOLQJ
HOHFWURGH
FDSDFLWRUV
SRO\HWK\OHQH
FRYHU
H[SORVLRQ
FKDPEHU
IRLO
OLTXLGGL
HOHFWULF
PHGLXP
)LJ 'LDJUDPRIH[SHULPHQWDOLQVWDOODWLRQ
DPRXQW RI DWRPV RI WKH PDLQ IRLO HOHPHQW ZKDW FRUUHVSRQGV WRay
DWRPV 7KH OLVW RI IRUHLJQ HOHPHQWV LQFOXGHV % 1D 0J $O 6L &D9&U
)H1L&X=Q%D3E7KHDXWKRUVQRWHWKDWDSDUWLFXODUVSHFWUXPRIIRUHLJQ
FKHPLFDO HOHPHQWV FRUUHVSRQGV WR YDULRXV LQLWLDO ORDGV 7L =U (OHPHQW
FRPSRVLWLRQRIDOOSDUWVRIH[SORVLRQFHOOVZDVLQYHVWLJDWHGE\YDULRXVWHFK
QLTXHVEHIRUHWKHH[SORVLRQ7KHDXWKRUVDOVRUHSRUWDFKDQJHLQWKHLVRWRSH
FRPSRVLWLRQRIWLWDQLXPLQSDUWLFXODUDGLPLQLVKHGVSHFLILFTXDQWLW\RI7L
([SHULPHQWV VKRZ D FRUUHODWLRQ EHWZHHQ D SHUFHQWDJH RI IRUHLJQ HOHPHQWV
DQGDGHFUHDVHGSURSRUWLRQRI 7L7KHSDSHUZDVEDVHGRQUHVXOWVRIPRUH
WKDQH[SHULPHQWV$WWKLVSRLQWRYHUVXFKH[SHULPHQWVKDYHEHHQ
FDUULHG RXW 7KHUHLQ WKH HOHPHQW WUDQVPXWDWLRQ SKHQRPHQRQ LV REVHUYHG
VWHDGLO\)XUWKHUPRUHWKHDXWKRUVUHJLVWHUHGVRPH³VWUDQJH´SDUWLFOHVLQWKHLU
H[SHULPHQWV DFFRPSDQ\LQJ WKH WUDQVPXWDWLRQ HIIHFW DQG K\SRWKHVL]HG WKH
SUHVHQFHRIPDJQHWLFFKDUJHLQWKRVHSDUWLFOHV
([SHULPHQWVRQHOHFWURQEHDPPHOWLQJRI]LUFRQLXPLQYDFXXP
7KH SDSHU E\ 0,6ROLQ >@ GHVFULEHV WKH UHVXOWV RI H[SHULPHQWV RQ HOHF
WURQEHDPPHOWLQJRI]LUFRQLXPLQJRWV6WDQGDUGLQGXVWULDOYDFXXPIXUQDFHV
9'.X]QHWVRYHWDO
Counts, 1/s
ZLWKHOHFWURQEHDPKHDWLQJRIWKHLQJRWZHUHXVHGIRUWKHWHVWV(OHFWURQJXQ
DFFHOHUDWLQJ YROWDJH ZDV NHSW DW D OHYHO NH9 7KH GHQVLW\ RI SRZHU DS
SOLHGWRWKHVXUIDFHRIOLTXLGEDWKRQ]LUFRQLXPVXUIDFHDPRXQWHGWR±
N:FP 7KHSDSHUGHVFULEHVVRPHSKHQRPHQDWKDWDSSHDULQWKHSURF
HVV RI HOHFWURQEHDP YDFXXP PHOWLQJ RI ]LUFRQLXP :H MXVW PHQWLRQ WKDW
PHOWLQJ RI ]LUFRQLXP ZDV DFFRPSDQLHG LQ WKRVH H[SHULPHQWV E\ LQWHQVH
RVFLOODWLRQ K\GURG\QDPLF SURFHVVHV DQG ZH GZHOO RQ WKH GDWD RQ IRUHLJQ
HOHPHQWV IRUPDWLRQ LQ ]LUFRQLXP LQJRWV GXULQJ WKH PHOWLQJ $IWHU PHOWLQJ
WKH]LUFRQLXPLQJRWVVKRZPLFURVWUXFWXUHVRUDVWKHDXWKRUFDOOVWKHPQXJ
JHW SURGXFWV ZKRVH HOHPHQW FRPSRVLWLRQ GLIIHUV VXEVWDQWLDOO\ IURP LQLWLDO
PDWHULDO )LJ $V\RXFDQVHHWKHQXJJHWSURGXFWVKRZVWKHIRUPDWLRQRI
/L %H % %D DQG UDUH HDUWK PHWDOV LH HOHPHQWV WKDW ZHUH DEVHQW LQ WKH
LQLWLDOLQJRW)XUWKHUPRUHWKHFRQWHQWRIVXFKHOHPHQWVDV1D0J$O6L.
&D 7L &U 0Q )H LQ WKH REWDLQHG QXJJHW SURGXFW KDV LQFUHDVHG E\ RUGHUVRIPDJQLWXGH7KHFRQWHQWRIWKHVHHOHPHQWVLQVRPH]RQHVDPRXQWV
WRWRPDVVSHUFHQW
7KHDXWKRUUHSRUWHGDVLJQLILFDQWWLPHVLQFUHDVLQJRIWKHUDWHRILQJRW
PHOWLQJ DWDFRQVWDQWDSSOLHGHQHUJ\RIHOHFWURQEHDPDQGIRUVRPHPRGHV
RI LQJRW KHDWLQJ WKLV YDOXH KDV LQFUHDVHGE\ WLPHV $V WKLV WDNHV SODFH
WKHLQJRWPDVVLVDFULWLFDOSDUDPHWHUIRULQLWLDWLQJDEQRUPDOSURFHVVHV
10
6
10
5
10
4
10
3
10
2
Zr-ZrH
ZrO
a)
O
H
ZrO 2
Zr2
O2
K
AL
C
Na
Ti
Si Cl Ca
Cr Fe
10
TiO
1
0
20
40
60
80
100
Counts, 1/s
Zr-ZrH
10
6
10
5
b)
10
4
10
3
10
Si
K
O
160
180
200
ZrO 2
Ca
Ti
O2
Li
140
Mg AL
Na
H
120
ZrO
Fe
Ce - Lu
C
2
Cl
B
Zr2
Cs Ba
La
10
1
0
20
40
60
80
100
120
140
160
180
200
À, a.m.u.
)LJDPDVVVSHFWUXPRI]LUFRQLXPLQJRWSULRUWRHOHFWURQPHOWLQJEPDVVVSHF
WUXPRIPLFURVWUXFWXUH LQ]LUFRQLXPLQJRWDIWHUHOHFWURQPHOWLQJ
/RZ(QHUJ\7UDQVPXWDWLRQRI$WRPLF1XFOHLRI&KHPLFDO(OHPHQWV
8OWUDVRXQGHOHPHQWWUDQVPXWDWLRQ
C o n c e n tra tio n C o n c e n tra tio n C o n c e n tra tio n C o n c e n tra tio n
'HVWUXFWLRQ WUDQVPXWDWLRQ RI DWRPLF QXFOHL RI FKHPLFDO FRPSRXQGV LV
QRWHG LQ WKH ZRUNV E\ $.ODGRY >@ LQFOXGLQJ UDGLRDFWLYH LVRWRSHV DIWHU
XOWUDVRXQG WUHDWPHQW RI WKHLU DTXHRXV VROXWLRQV 0DLQ UHVXOWV RI WKHVH H[
SHULPHQWV ZHUH WDNHQ IURP >@ 7KH H[SHULPHQWDO LQVWDOODWLRQ UHSUHVHQWV DQ
XOWUDVRQLFK\GURG\QDPLFJHQHUDWRURIURWRUW\SH7KHDFWLYDWRULVPDGHIURP
VWDLQOHVV VWHHO 7KH LQVWDOODWLRQ KDV WKH IROORZLQJ PDLQ SDUDPHWHUV VRXQG
LQWHQVLW\ ! :P IUHTXHQF\ IXQGDPHQWDO WRQH Â +] RSHUDWLQJ
SUHVVXUH LQ DFWLYDWRU ± 3D ZRUNLQJ YROXPH ± Â P DFWLYH ]RQH
YROXPH± Â P
7KH DXWKRU GHDOW ZLWK VWDEOH DQG UDGLRDFWLYH LVRWRSHV ,Q FDVH RI VWDEOH
HOHPHQWV LQLWLDO VROXWLRQV ZHUH WUHDWHG GXULQJ KRXUV IRU /L&O DQG
KRXUVIRU&V&O(OHPHQWVSHFWUDREWDLQHGIRUYDULRXVVROXWLRQWUHDWPHQW
WLPHVRIVWDEOHHOHPHQWVDUHSUHVHQWHGLQ)LJ<RXFDQVHHIURPWKHILJXUH
WKDW D TXDQWLW\ RI IRUHLJQ HOHPHQWV IURP ERURQ WR OHDG )LJF DFWXDOO\
0
10
-1
10
-2
10
-3
10
-4
10
-5
10
-6
10
Na
Si
C
a ) L iC l 2 h
Cl
O
Li
Ca
Fe
Cu
0
10
20
30
40
50
60
70
80
0
10
-1
10
-2
10
-3
10
-4
10
-5
10
-6
10
O
Li
C
Cl
Na
Ca
Si
b ) L iC l 8 h
Fe
Cu
Zn
0
10
20
30
40
50
60
70
80
0
10
-1
10
-2
10
-3
10
-4
10
-5
10
-6
10
S i C l C a F eC u
O
Cs
Na
Rb
B
0
10
20
30
40
c ) L iC l 2 4 h
Sn
Pb
50
60
70
80
0
10
-1
10
-2
10
-3
10
-4
10
-5
10
-6
10
Cl
O
Zn
Na
d) C sC l 360h
Mo
Cd
Ge
0
10
20
30
Ba
Eu
Pr
40
50
60
Er
70
W
Pb
80
)LJ (OHPHQW FRPSRVLWLRQ RI OLWKLXP FKORULGH VROXWLRQ DIWHU XOWUDVRQLFDFWLYD
WLRQDKRXUEKRXUFKRXU GHOHPHQWFRPSRVLWLRQRIFDHVLXPFKORULGH
VROXWLRQDIWHUKRXUXOWUDVRQLFDFWLYDWLRQ
Z e le m e n ts
9'.X]QHWVRYHWDO
LQFUHDVHVLQVROXWLRQDVWLPHJRHVRQ8QIRUWXQDWHO\WKHDXWKRUGLGQRWVKRZ
LQKLVSDSHUWKHHOHPHQWFRPSRVLWLRQRI/L&ODQG&V&OVDOWVROXWLRQVSULRUWR
XOWUDVRQLFDFWLYDWLRQ+RZHYHUZHFDQGRDQLQGLUHFWEDFNJURXQGHYDOXDWLRQ
E\ VSHFWUD FRPSDULVRQ RI /L&O DIWHU DQG KRXU WUHDWPHQW ,W VKRXOG EH
QRWHG WKDW DW WKH HOHPHQW VROXWLRQ DQDO\VLV WKH VDWXUDWLRQ LV REVHUYHG IRU
PDQ\HOHPHQWVDWDFRQFHQWUDWLRQRILWLVOLNHO\WREHFRQQHFWHGWRWHFK
QLTXH OLPLWDWLRQV RI PDVVVSHFWURPHWHU PHDVXUHPHQWV 7KLV PDWWHU VWURQJO\
FRPSOLFDWHVDTXDQWLWDWLYHHYDOXDWLRQRIWKHUHVXOW
2QH FDQ DIILUP WKDW WKH H[SHULPHQWDO GDWD EURXJKW E\ $.ODGRY DUH DQ
HYLGHQFHRIDGPL[WXUHDFFXPXODWLRQRIIRUHLJQHOHPHQWV
([SHULPHQWVZLWKUDGLRDFWLYHLVRWRSHV&V &R +J 3W 6Q .
DUH DOVR GHVFULEHG LQ WKLV SDSHU 7KH DXWKRU LQVLVWV WKDW KLV LQVWDOODWLRQ
FKDQJHVWKHTXDQWLW\RIUDGLRDFWLYHQXFOHLLHDWUDQVPXWDWLRQRIUDGLRDFWLYH
LVRWRSHVLQWRVWDEOHLVRWRSHVRFFXUV)XUWKHUPRUHWKHDXWKRUQRWHVDYROXPH
GHFUHDVH RI UDGLRDFWLYH VROXWLRQ LQ WKH DFWLYDWRU GHVSLWH WKH JXDUDQWHHG LP
SHUPHDELOLW\RIWKHGHYLFH7KHDYHUDJHUDWHRIVROXWLRQUHGXFWLRQLVPOK
6HSDUDWHO\WKHDXWKRUHVWDEOLVKHVDIDFWRIUHJLVWUDWLRQRIVRPHUDGLDWLRQDQG
RI FRUUHODWLRQ RI LWV LQWHQVLW\ ZLWK D FKDQJH RI DFWLYDWRU RSHUDWLRQ PRGH $
VXEVWDQWLDODFWLYLW\GHFUHDVHRISOXWRQLXPEHU\OOLXPQHXWURQVRXUFHDIWHUWKH
RSHUDWLRQRIDFWLYDWRULVVSHFLDOO\VWUHVVHG7KHVRXUFHZDVORFDWHGDWDGLV
WDQFH RI P IURP WKH DFWLYDWRU 7KH DXWKRU DVVXPHV FDYLWDWLRQ WR EH D
PDLQDFWLQJIDFWRULQWKHUHSUHVHQWHGWHFKQRORJLFDOSURFHVVHV
7R FRQFOXGH WKH VHFWLRQ ZH QRWH WKDW GLIIHUHQW DXWKRUV LQ WKH DERYH
ZRUNV LQGHSHQGHQWO\ IURP HDFK RWKHU DQG XVLQJ YDULRXV SK\VLFDO LQVWDOOD
WLRQV FRXOG REVHUYH WKH ORZ HQHUJ\ HOHPHQW WUDQVPXWDWLRQ (OHPHQW
FRPSRVLWLRQ RI HQG SURGXFWV LQ WKHVH H[SHULPHQWV KDV FRPPRQ IHDWXUHV
IRUHLJQ HOHPHQWV WKDW ZHUH DEVHQW LQ WKH LQLWLDO PDWHULDO DSSHDU WKH FRQWHQW
RI OLJKW HOHPHQWV IURP 1D WR =Q VXEVWDQWLDOO\ LQFUHDVHV 1R UDGLRDFWLYH
UDGLDWLRQZDVUHJLVWHUHGGXULQJWKHWHVWV7KHHQGSURGXFWLVQRWUDGLRDFWLYH
&KHFNH[SHULPHQWVRQHOHPHQWWUDQVPXWDWLRQDWHOHFWULFH[SORVLRQ
7HFKQLTXHRIH[SHULPHQWV
7KH VXEMHFW RI RXU LQYHVWLJDWLRQ ZDV EDUHO\ DQ DQDO\VLV RI HOHPHQW DQG
LVRWRSH FRPSRVLWLRQ RI WKH VXEVWDQFH WKDW ZDV LQ WKH ZRUNLQJ FHOOV RI WKH
LQVWDOODWLRQSULRUWRDQGDIWHUHOHFWULFH[SORVLRQ )RLOHOHFWULF H[SORVLRQVZHUH
FDUULHG RXW E\ XV WRJHWKHU ZLWK WKH JURXS RI /,8UXWVNRHY DW WKHLU LQVWDOOD
WLRQ>@7KUHHWHFKQLTXHVRIDQDO\VLVZHUHXVHGIRUWKDWSXUSRVHPDVVVSHF
WURPHWULF DQDO\VLV 06$ [UD\ IOXRUHVFHQFH DQDO\VLV ;)$ JDPPD DQG
QHXWURQDFWLYDWLRQDQDO\VLV*$$DQG1$$
/RZ(QHUJ\7UDQVPXWDWLRQRI$WRPLF1XFOHLRI&KHPLFDO(OHPHQWV
7KHVDPSOHVWREHDQDO\]HGFDQEHFRQGLWLRQDOO\GLYLGHGLQWRWZRJURXSV
7KH ILUVW JURXSLQFOXGHGWKHVDPSOHVZKLFKZHUHREWDLQHGLQRXUSUHVHQFH
XQGHU RXU VXSHUYLVLRQ 7DEOH D 2XU GLVWLOOHG ZDWHUZDVXVHGLQWKRVHH[
SHULPHQWVWKHFKDUJLQJSURFHGXUHRIH[SORVLRQFHOOVWKHH[SORVLRQLWVHOIDQG
ZDWHU PDQDJHPHQW LQWR JODVV FRQWDLQHUV FRQWDLQLQJ VXVSHQGHG SURGXFWV RI
IRLO HOHFWULF H[SORVLRQ ZDV YLVXDOO\ FRQWUROOHG LQ RXU SUHVHQFH 7KH VHFRQG
JURXS LQFOXGHG DVVD\V REWDLQHG ZLWKRXW RXU FRQWURO 7DEOH E 7KH FRQGL
WLRQVIRUWKHH[SHULPHQW± ORDGPDWHULDOOLTXLGGLHOHFWULFPHGLXPZKHUHWKH
HOHFWULF H[SORVLRQ RFFXUV HOHFWULF IHDWXUHV RI GLVFKDUJH ZHUH FKRVHQ LQ D
ZD\ WKDW ZRXOG JXDUDQWHH WKH PD[LPXP RXWSXW RI IRUHLJQ HOHPHQWV DQG LW
ZDV EDVHG RQ D EURDG VHOHFWLRQ RI H[SHULPHQWDO GDWD RQ HOHFWULF H[SORVLRQV
FDUULHGRXWE\WKHJURXSRI/,8UXWVNRHY
7DEOHZ 7KHOLVWRIWKHLQYHVWLJDWHGVDPSOHVUHFHLYHGXQGHURXUFRQWURO
VDPSOH
ORDGIRLO
7D
7L
7D)H1L7D
7D3E7D
PHGLXP
+2
+2
+2 +2 1XPEHURIVDPSOHV
7DEOHE7KHOLVWRIWKHLQYHVWLJDWHGVDPSOHVUHFHLYHGZLWKRXWRXUFRQWURO
VDPSOH
ORDGIRLO
7D3E7D
7D3E7D
7D3E7D
7L
7L
7L
1L
PHGLXP
+2 +2 +2 JO\FHULQ
+2
+2 +2
1XPEHURIVDPSOHV
:HVWHDPHGWKHVDPSOHVREWDLQHGLQWKLVZD\ZLWKVXVSHQGHGSURGXFWVRI
IRLOHOHFWULFH[SORVLRQLQZDWHU SKDVHLQJODVVFRQWDLQHUVXQGHUGU\LQJODPSV
DWDWHPSHUDWXUHayqK DQGWKHQSRXUHGWKHPLQWRFDVVHWWHVPDGHIURP
SOH[LJODVV DQG PP WKLFN P\ODU IRLO DQG WKHQ WKH\ ZHUH GULHG XQGHU WKH
VDPHFRQGLWLRQV7KHJO\FHULQEDVHDVVD\VZHUHVWHDPHGRQHOHFWULFUDQJHDW
D WHPSHUDWXUHa qK XS WR WKH PRPHQW ZKHQ D YLVLEOH OLTXLGUHVLGXHUH
PDLQHG RQ WKH ERWWRP RI JODVV FRQWDLQHUV 7KDW UHVLGXH ZDV SRXUHG LQWR
FDVVHWWHV DQG ZDV GULHG XQGHU GU\LQJ ODPSV DW D WHPSHUDWXUH aqK ,Q
ERWKFDVHVWKHWHPSHUDWXUH ZDVFRQWUROOHGE\DWKHUPRFRXSOH7KHGU\VDP
SOHVZHUHVXEPLWWHGIRUIXUWKHUDQDO\VLV
9'.X]QHWVRYHWDO
7KHUHVXOWVRIDQDO\VHVDUHVXPPDUL]HGLQWDEOHVDQGSDUWO\UHSUHVHQWHGDV
EDUFKDUWV$IROORZLQJUHPDUNVKRXOGEHGRQHIRUDEHWWHUXQGHUVWDQGLQJRI
WKH PDWHULDO SUHVHQWHG )URP DOO WHFKQLTXHV XVHG WKH YROXPH DFWLYDWLRQ
WHFKQLTXHE\QHXWURQVRUJDPPDTXDQWDLVWKHPRVWVHQVLWLYHRQHDQGIUHHRI
LQDFFXUDFLHVLIFRPSDUHGZLWK;)$DQG06$WHFKQLTXHV+RZHYHULQRUGHU
WRGHWHUPLQHWKHFRQWHQWRIDSDUWLFXODUHOHPHQWE\DFWLYDWLRQWHFKQLTXHWKH
VDPSOH VKRXOG EH LUUDGLDWHG DQG LWV DFWLYLW\ VKRXOG EH PHDVXUHG GXULQJ D
WLPH ZKLFK LV WKH PRVW VXLWDEOH IRU WKLV HOHPHQW 7KHUHIRUH WKH IROORZLQJ
VWUDWHJ\ WR DQDO\]H VDPSOHV KDV EHHQ DGRSWHG $W WKH ILUVW VWDJH HOHPHQW
VDPSOH DQDO\VLV ZDV FDUULHG RXW E\ PHDQV RI [UD\ IOXRUHVFHQFH DQG PDVV
VSHFWURPHWHU DQDO\VLV 7KHVH PHDVXUHPHQWV VLQJOHG RXW HOHPHQWV ZKLFK
VDPSOHFRQWHQWGLIIHUHGIURPWKHLUFRQWHQWLQLQLWLDOPDWHULDOV$WWKHVHFRQG
VWDJHH[SHULPHQWVRQJQ RUQJDFWLYDWLRQRIVDPSOHVZHUHUXQLQRUGHU
WRFRQILUPWKHUHVXOWVREWDLQHGE\SUHYLRXVWHFKQLTXHV)RUWKLVSXUSRVHWKH
VDPSOHVZHUHLUUDGLDWHGDQGPHDVXUHGLQFRQGLWLRQVZKLFKZHUHWKHRSWLPDO
RQHV IRU D SDUWLFXODU HOHPHQW 5HIHUHQFH VDPSOHV FRQWDLQLQJ D NQRZQTXDQ
WLW\RIWKHHOHPHQWLQTXHVWLRQZHUHLUUDGLDWHGVLPXOWDQHRXVO\ZLWKVDPSOHV
7KH PHDVXUHPHQWV RI JDPPDUDGLDWLRQ RI DFWLYDWHG VDPSOHV DQG UHIHUHQFH
VDPSOHV ZHUH FDUULHG RXW DW WZR *H/LGHWHFWRUV ,I QHHG EH WKH DFWLYDWHG
VDPSOHV ZHUH PHDVXUHG VHYHUDO WLPHV 7KLV WHFKQLTXH DOORZHG WR LPSURYH
WKHFRQWHQWGHWHUPLQDWLRQSUHFLVLRQIRUHOHPHQWVLQTXHVWLRQLQVDPSOHV
;UD\ VDPSOH VSHFWUD RI [UD\IOXRUHVFHQFHDQDO\VLVZHUHREWDLQHGDWWKH
6L/LVSHFWURPHWHU ZLWK D UHVROXWLRQ H9 7KH VSHFWURPHWHU HQDEOHG WR
ILQG RXW HOHPHQWV VWDUWLQJ IURP VFDQGLXP (OHFWURQ VKHOO H[FLWDWLRQ RI WKH
DWRPV LQ VDPSOHV ZDV SHUIRUPHG E\ UDGLRDFWLYH VRXUFHV &G DQG $P
6HQVLWLYLW\OHYHORIWKHVSHFWURPHWHUHTXDOHGIRUYDULRXVHOHPHQWVDQGVDP
SOHVXSWR
/DVHUPDVVVSHFWURPHWHU06ZDVXVHGWRIXOILOOPDVVVSHFWURPHWULF
PHDVXUHPHQWV ,RQV ZHUH UHJLVWHUHG RQ SKRWRJUDSKLF ILOP 7KH GHQVLW\ RI
ILOP EODFNHQLQJ ZDV PHDVXUHG E\ DXWRPDWHG VSHFWUXP PHDVXUHU 6DPSOHV
ZHUHSUHSDUHGE\WKHWHFKQLTXHRISUHVVXUHWHVWRIGU\PDWHULDORQDQDOXPL
QXP VXEVWUDWH $WRP LRQL]DWLRQ RI VDPSOH VXEVWDQFH RFFXUUHG LQ WKH ODVHU
UDGLDWLRQIRFXVUDQJHWKDWZDVXVHGWRVFDQWKHVDPSOHVXUIDFH7KHGLDPHWHU
RI LRQL]DWLRQ ]RQH ZDV a PP (OHPHQWV WR EH GHWHUPLQHG UDQJHG IURP
OLWKLXPWRXUDQLXP5HODWLYHOLPLWRIHOHPHQWGHWHFWLRQZDVHTXDOXSWR
7KH JDPPD DQG QHXWURQ DFWLYDWLRQ RI VDPSOHV ZDV FDUULHG RXW DW WKH
HOHFWURQDFFHOHUDWRUZLWKDPD[LPXPHOHFWURQHQHUJ\0H9DQGDFXUUHQW
P$ 'HSHQGLQJ RQ DQ HOHPHQW WR EH DQDO\]HG WKHVDPSOHV ZHUH OR
FDWHG HLWKHU LQ WKH JDPPDTXDQWXP EHDP RU LQ WKH WKHUPDO QHXWURQ ILHOG
*DPPDUDGLDWLRQ RI LUUDGLDWHG VDPSOHV DQG UHIHUHQFH VDPSOHV ZHUH PHD
/RZ(QHUJ\7UDQVPXWDWLRQRI$WRPLF1XFOHLRI&KHPLFDO(OHPHQWV
VXUHG DW WZR *H/LGHWHFWRUVZLWKDYROXPHFP7KHHQHUJ\UHVROXWLRQ
RIVSHFWURPHWHUVZDVNH97KHVHQVLWLYLW\OHYHORIWKHWHFKQLTXHIRUWKH
HOHPHQWVXQGHUDQDO\VLVDPRXQWHGWR JJ
7KH VDPH *H/LGHWHFWRUV ZHUH XVHG ILUVW WR FKHFN WKH GU\ VDPSOHV LQ
RUGHUWRGHWHFWLQWKHPWKHJDPPDDFWLYLW\7KHEHWDDFWLYLW\RIVDPSOHVZDV
FKHFNHG E\ PHDQV RI WKH GRVLPHWHU '.6% ZLWK D PP JDV FRXQWHU ,W
VKRXOGEHQRWHGULJKWDZD\WKDWQRJDPPD RUEHWDDFWLYLW\ZDVGHWHFWHGLQ
DQ\VDPSOH
0HDVXUHPHQWUHVXOWVDQGWKHLUGLVFXVVLRQ
7RWDOO\ZHKDYHDQDO\]HGWKHUHVXOWVRIH[SHULPHQWV)XUWKHUPRUHZH
KDYH WDNHQ WR DQDO\VLV VDPSOHV RI FXUUHQW VXSSO\ HOHFWURGH DQG IRLOV WKDW
ZHUH XVHG DV HOHFWULF ORDG &RPSRVLWLRQ RI DGPL[WXUHV FRQWDLQHG LQ ZDWHU
DQGSRO\HWK\OHQHZDVDOVRDQDO\]HG&RPSRVLWLRQRIDGPL[WXUHVLQJO\FHULQ
ZDV WDNHQ IURP WKH WHFKQLFDO SDVVSRUW 7KH TXDQWLW\ RI VDPSOHV DQG IRLO
VDPSOHVWRWDOHG;)$VSHFWUDPDVVVSHFWUDDQGJDPPDVSHFWUD
DIWHU*$$DQG1$$ZHUHREWDLQHG
'XH WR D VLJQLILFDQW YROXPH RI WKH IDFWV ZH VLQJOHG RXW WKH REWDLQHG
PHDVXUHPHQW UHVXOWV DQG FRUUHVSRQGLQJ FRPPHQWV DV $SSHQGL[ 0HDVXUH
PHQWGDWDDUHJLYHQLQ7DEOHVDQGSDUWO\DUHGHSLFWHGLQEDUFKDUWV7KH
SUHVHQWVHFWLRQGHVFULEHVWKHUHVXOWVRIVDPSOHDQDO\VHVDVDJJUHJDWHGGDWDRI
DOOH[SHULPHQWV
$V D UHVXOW RI HOHFWULF H[SORVLRQ RI WDQWDOXP IRLO LQ GLVWLOOHG ZDWHU PDVV
VSHFWURPHWU\ VKRZHG DQ LQFUHDVHG FRQWHQW LQ DVVD\V RI WKH IROORZLQJ HOH
PHQWV 1D $O . &D 0Q )H DQG 1L 7KH [UD\ IOXRUHVFHQFH DQDO\VLV
GHPRQVWUDWHGWKHSUHVHQFHRIQLFNHOPRO\EGHQXPDQGOHDG:HUHPLQG\RX
WKDW WKH ;)$ DOORZHG WR GHWHFW HOHPHQWV VWDUWLQJ IURP VFDQGLXP 7KH VDPH
DVVD\V VKRZHG D VXEVWDQWLDO TXDQWLW\ RI WLWDQLXP WKDW JHWV WR WKH VROXWLRQ DV
ZHVXSSRVHDVDUHVXOWRIVXEVWDQFHVHSDUDWLRQIURPWKHFHQWUDOFXUUHQWVXS
SO\ HOHFWURGH PDGH RI WLWDQLXP ,W LV LQWHUHVWLQJ WR QRWH WKDW RQO\ LQ WKLV
H[SHULPHQW DQG LQ RQH RI WKH H[SHULPHQWV ZKHUH WDQWDOXP DQG OHDG ZHUH
XVHGDVDORDGDQGDRQHSHUFHQWK\GURJHQSHUR[LGH+2DVXVHGDVOLTXLG
GLHOHFWULF PHGLXP /'0 ZH IRXQG D VXEVWDQWLDO FKDQJH LQ WKH LVRWRSLF
DEXQGDQFHUDWLRRIWLWDQLXP,WVKRXOGEHQRWHGWKDWRXUH[SHULPHQWVGLGQRW
VKRZ DQ\ ULJLG FRUUHODWLRQ EHWZHHQ WKH DSSHDUDQFH RI IRUHLJQ HOHPHQWV DQG
WKH FKDQJH RI WKH LVRWRSLFDEXQGDQFH UDWLR RI WLWDQLXP DV ZDV REVHUYHG LQ
KLV H[SHULPHQWV E\ /,8UXWVNRHY >@ 7KLV LV OLNHO\ WR EH FRQQHFWHG WR WKH
IDFW WKDW WKH OHYHO RI IRUHLJQ HOHPHQWV LQ WKH PDMRULW\ RI RXU H[SHULPHQWV
GRHV QRW H[FHHG SHUFHQW ZKLOH WKLV OHYHO LQ WKH H[SHULPHQWV E\
/,8UXWVNRHY DYHUDJHG IRXU SHUFHQW 7KXV LQ WKH PDMRULW\ RI RXU H[SHUL
9'.X]QHWVRYHWDO
PHQWV LVRWRSLF VKLIW LV ZLWKLQ WKH HUURUVDGPLVVLEOHIRUWKH06$WHFKQLTXH
+RZHYHULWVKRXOGEHVWUHVVHGWKDWLQWZRRXWRIWKUHHFDVHVWKHOHYHORIIRU
HLJQ HOHPHQWV H[FHHGHG SHUFHQW 7DEOH $SSHQGL[HV $V ZH OLQN WKH
DSSHDUDQFH RI WLWDQLXP LQ WKHVH DVVD\V WR WKH VXEVWDQFH VHSDUDWLRQ IURP WKH
WLWDQLXP FXUUHQW VXSSO\ HOHFWURGH WKH FKDQJH RI LVRWRSLF FRPSRVLWLRQ RI
WLWDQLXPHYLGHQFHVLWVSDUWLFLSDWLRQLQWUDQVPXWDWLRQUHDFWLRQV
,QFDVHVZKHQVLPXOWDQHRXVO\WDQWDOXPDQGOHDGIRLOVVHUYHGDVORDGDQG
K\GURJHQ SHUR[LGH VROXWLRQ VHUYHG DV OLTXLG GLHOHFWULF PHGLXP PDVV VSHF
WURPHWU\ DOVR VKRZHG DQ LQFUHDVHG FRQWHQW RI DGPL[WXUH HOHPHQWV LQ DVVD\V
DQGDSSHDUDQFHRIIRUHLJQHOHPHQWVVXFKDV1D$O6L3.&D)H1L&X
7KH[UD\IOXRUHVFHQFHDQDO\VLVGHPRQVWUDWHVDQLQFUHDVHGFRQWHQWRI0Q1L
LQDVVD\VDQGDGGLWLRQDOO\LWGHWHFWVWKHSUHVHQFHRIDQWLPRQ\
:KHQ WDQWDOXP DQG LURQQLFNHO IRLOV ZHUH VLPXOWDQHRXVO\ XVHG DV ORDG
DQGRQHSHUFHQWK\GURJHQSHUR[LGHZDVXVHGDVPHGLXPWKHPDVVVSHFWURV
FRS\ DQDO\VLV GHWHFWHG LQ WKH DVVD\V GHYLDWLRQV LQ WKH FRQWHQW RI HOHPHQWV
1D 6L . &D &X 1E 7KH [UD\ IOXRUHVFHQFH DQDO\VLV GHPRQVWUDWHG WKH
SUHVHQFHRIDQWLPRQ\LQDVVD\V
:KHQWLWDQLXPIRLOZDVXVHGDVORDGDQGZDWHURURQHSHUFHQWK\GURJHQ
SHUR[LGHZDVXVHGDVPHGLXPWKH06DQDO\VLVGHWHFWHGLQWKHDVVD\VGHYLD
WLRQVLQWKHFRQWHQWRIHOHPHQWV1D$O6L.&D0Q1L&X$J6Q6E
%D 7D 3E 7KH [UD\ IOXRUHVFHQFH DQDO\VLV GHWHFWHG WKH SUHVHQFH RI HOH
PHQWV 0Q 1L &X =Q < =U 0R ,Q 6Q 6E 3E $UHODWLYHJURZWKRIDG
PL[WXUHHOHPHQWVDQGDOHYHORIIRUHLJQHOHPHQWVFRPSDUDEOHWRWKHVHQVLWLY
LW\ OHYHO RI H[SHULPHQWWHFKQLTXHZKHUHWLWDQLXPIRLOXQGHUZHQWDQHOHFWULF
H[SORVLRQ LQ RQHSHUFHQW K\GURJHQ SHUR[LGH LV VKRZQ LQ GHPRQVWUDWLRQDO
ILJXUH D ,QWKHFDVHWKDWJO\FHULQ&+2ZDVXVHGDVDPHGLXPWKH[
UD\ IOXRUHVFHQFH DQDO\VLV VKRZHG D VWDEOH IURP RQH DVVD\ WR DQRWKHU LQ
FUHDVHRIVXFKDGPL[WXUHHOHPHQWVDV0Q)H1L&X=Q,QRQHH[SHULPHQW
ZKHUH WKH FRQGLWLRQV RI GLVFKDUJH IORZ ZHUH FKDQJHG QR PDQJDQHVH ZDV
IRXQGEXWLQVWHDGRILWDQLQFUHDVHGFRQWHQWRIOHDGZDVUHJLVWHUHG)LJE
)LJ F UHSUHVHQWV WKH UHVXOWV RI PDVV VSHFWURPHWULF DQDO\VLV RI DQ DVVD\
REWDLQHG WKURXJK HOHFWULF H[SORVLRQ RI QLFNHO IRLO LQ GLVWLOOHG ZDWHU 7KH
06$ DQDO\VLV VKRZHG DQ LQFUHDVHG FRQWHQW RI DGPL[WXUH HOHPHQWV LQ WKH
DVVD\ 1D 6L . &D DQG DSSHDUDQFH RI QHZ IRUHLJQ HOHPHQWV =U 1E$J
6Q 6E %D 7D 7KH DSSHDUDQFH RI $J DQG 6E ZDV QRWHG LQ DOO W\SHV RI
DQDO\VLV0RUHRYHUWKH[UD\IOXRUHVFHQFHDQDO\VLVVKRZHGDSUHVHQFHRI<
=UDQG3ELQWKDWDVVD\
7KH*$$DQG1$$FRQILUPHGWKHDSSHDUDQFHRIIRUHLJQHOHPHQWVLQWKH
DVVD\VVXFKDV1D0Q6EDQGGLVSOD\HGFKORULQHLQWKHDVVD\VLHDQHOH
PHQWWKDWGRHVQRWJHWUHJLVWHUHGE\RWKHUW\SHVRIDQDO\VLVDYDLODEOH
/RZ(QHUJ\7UDQVPXWDWLRQRI$WRPLF1XFOHLRI&KHPLFDO(OHPHQWV
Al
b) XFA
titanium in glycerin
a) MSA
titanium in H2O2 (1%)
10
100
3
10
3
10
2
Si
Mn
Sn
Ta
Sb
10
Ni Cu
Zn
2
Enhancement
Sb
Ag Sn Ba
Enhancement
Na K
10
Zr Ag
Na
Pb
Ca
Enhancement
c) MSA
nickel in
water
Pb
Fe
Ta
Ba
Ca
K
10
10
Ni
Nb
1
1
0
10
20
30
40
50
60
70
80
1
0
10
20
30
40
50
60
70
80
0
10
20
30
40
50
60
70
80
)LJ5HODWLYHJURZWKRIDGPL[WXUHHOHPHQWVDQGIRUHLJQHOHPHQWVRXWSXWLQDVVD\V
DIWHU HOHFWULF H[SORVLRQ IRU WKH PRVW H[SOLFLW H[SHULPHQWV $QDO\VLV WHFKQLTXH ORDG
PDWHULDO DQG GLHOHFWULF PHGLXP DUH VKRZQ LQ )LJXUHV (OHPHQWV ZKLFK SUHVHQFH LV
VXUHEXWWKHDEVROXWHYDOXHRIDGPL[WXUHKDVDQXSSHUOLPLWDUHVKRZQZLWKDGRWWHG
OLQHVHH$SSHQGL[
Z elements
Z elements
Z elements
+HUHLWLVQHFHVVDU\WRGLVFXVVDOOSRVVLEOHVRXUFHVRIEULQJLQJLQRILPSX
ULWLHV WKDW DUH SUHVHQW LQ WKH H[SHULPHQW WKH LQIOXHQFH RI DVVD\ SUHSDUDWLRQ
WHFKQLTXHVDQGVRXUFHVRIV\VWHPDWLFHUURUVRIWKHDQDO\VHVDSSOLHG
$WHOHFWULFH[SORVLRQDSDUWLDOGHSUHVVXUL]DWLRQRFFXUVGXHWRDSRZHUIXO
K\GUDXOLFVKRFNDQGWKLVFDXVHVDQHPLVVLRQRIyRIVXEVWDQFHLQWKH
VXUURXQGLQJ VSDFH DORQJ WKH VXUIDFH RI FXUUHQW VXSSO\ HOHFWURGHV 7KDW LV
ZK\LWLVQRWDSSURSULDWHWRWDONDERXWDEVROXWHDGPL[WXUHFRQWHQWRIIRUHLJQ
HOHPHQWVDQGZHTXRWHKHUHDOOGDWDLQUHODWLYHFRQFHQWUDWLRQV
)RXU W\SHV RI VRXUFHV RI HOHPHQW DGPL[WXUHV DUH SUHVHQW LQ WKH H[SHUL
PHQWV GHVFULEHG ZKLFK FDQ LQIOXHQFH WKH HQG UHVXOW OLTXLG GLHOHFWULF PH
GLXP ± GRXEOHGLVWLOOHG ZDWHU JO\FHULQ K\GURJHQ SHUR[LGH SRO\HWK\OHQH
ZDOOVRI H[SORVLRQFHOOVWLWDQLXPURGRIWKHFHQWUDOFXUUHQWVXSSO\HOHFWURGH
PDWHULDO RI IRLOV WR EH H[SORGHG ORDG $GPL[WXUH SHUFHQWDJH DQDO\VLV LQ
FHQWUDO HOHFWURGH DQG GLVSRVDEOH ORDG IRLOV ZDV UXQ VLPXOWDQHRXVO\ ZLWK
HOHFWULF H[SORVLRQ DVVD\ DQDO\VLV 2QRQH KDQG LW DOORZHG WR GLUHFWO\ FRP
SDUH WKH HOHPHQW SHUFHQWDJH RQ WKH RWKHU KDQG WR UHGXFH PD[LPDOO\ DQ
DEVROXWHYDOXHRIV\VWHPDWLFHUURU7KHUHIRUHWKHVHGDWDDUHLQFOXGHGLQWKH
VDPH7DEOHVDVWKHDVVD\GDWD
$GPL[WXUH GDWD LQ OLTXLG GLHOHFWULF PHGLD DQG SRO\HWK\OHQH DUH JLYHQ LQ
WKH $SSHQGL[ 7KH YROXPH RI OLTXLGV LQ H[SORVLRQ FHOOV DPRXQWHG WR FP+HQFHLWLVHDV\WRHYDOXDWHWKDWWKHDVVD\DGPL[WXUHFRQWULEXWLRQIURP
WKHOLTXLGGLHOHFWULFPHGLDWDNLQJLQWRDFFRXQWWKHLUYROXPHVLVVXEVWDQWLDOO\
OHVV WKDQ WKH DGPL[WXUH YDOXH LQ IRLOV DQG FHQWUDO WLWDQLXP HOHFWURGH 7KH
9'.X]QHWVRYHWDO
TXHVWLRQ RI SRO\HWK\OHQH VHHPV WR EH PRUH FRPSOLFDWHG (OHFWULF H[SORVLRQ
LQOLTXLGPHGLXPLVDFFRPSDQLHGE\DEODVWZDYHZKHUHWKHSUHVVXUHRQFHOO
ZDOOV PD\ DFKLHYH YDOXHV WKDW DUH FDSDEOH WR GHVWUR\ WKH VXUIDFH SRO\HWK\
OHQHOD\HU,WLVREYLRXVWKDWWRJHWKHUZLWKSRO\HWK\OHQHWKHDGPL[WXUHVGLV
VROYHG LQ SRO\HWK\OHQH JHW LQWR WKH OLTXLG 0DVV VSHFWURPHWULF DQDO\VLV
VKRZHG QR FDUERQ LQ WKH DVVD\V XQGHU LQYHVWLJDWLRQ +RZHYHU LQ SULYDWH
FRPPXQLFDWLRQV /,8UXWVNRHY UHSRUWV D SUHVHQFH RI FDUERQ LQ WKH DPRXQW
XS WR LQ VRPH H[SHULPHQWV DQG KH EHOLHYHV WKDW LWV DSSHDUDQFH LV FRP
SOHWHO\ UHODWHG WR WKH GHVWUXFWLRQ RI SRO\HWK\OHQH ZDOO RI H[SORVLRQ FHOO
7KHUHIRUHZHQRUPDOL]HGWKHSUHVHQFHRIRWKHUDGPL[WXUHHOHPHQWVHPLWWHG
IURPSRO\HWK\OHQHYVRQHSHUFHQWFDUERQDGPL[WXUH
7KH H[SHULPHQWV ZLWK HOHFWULF H[SORVLRQV RI IRLOV PDGH IURP 7D )H 3E
1L RU WKHLU FRPELQDWLRQV VKRZHG WKH SUHVHQFH RI WLWDQLXP LQ DVVD\V WKH
FRQWHQW RI WLWDQLXP UXQV XS WR GR]HQV SHUFHQW :H DVVRFLDWH DV VKRZQ
DERYH WKH DSSHDUDQFH RI WLWDQLXP LQ DVVD\V ZLWK D GHVWUXFWLRQ RI FHQWUDO
FXUUHQW VXSSO\ HOHFWURGH GXULQJ WKH IORZ RI FXUUHQW SXOVH 2WKHU HOHPHQW
LPSXULW\ FRQWULEXWLRQ IURP WKH HOHFWURGH ZDV HYDOXDWHG E\ WKH VDPH WHFK
QLTXHDVWKDWIRUSRO\HWK\OHQH+\SRWKHWLFDOPHFKDQLVPVRIVHOHFWLYHH[WUDF
WLRQ RI RQH RU DQRWKHU HOHPHQW IURP WKH HOHFWURGH RU IURP SRO\HWK\OHQH DW
HOHFWULFH[SORVLRQZHUHQRWWDNHQLQWRFRQVLGHUDWLRQ
7KHDGPL[WXUHDQDO\VLVDFFRUGLQJWRWKHDERYHWHFKQLTXHVKRZHGWKDWWKH
DSSHDUDQFHRIVRPHFKHPLFDOHOHPHQWVLQDVVD\VLVLQQRZD\FRQQHFWHGZLWK
WKHGHVWUXFWLRQRIWLWDQLXPHOHFWURGHRUHYHQPRUHVRRISRO\HWK\OHQH
7KHGDWDJLYHQLQ7DEOHVGHPRQVWUDWHWKDWWKHHOHPHQWSHUFHQWDJHLQ
RQH DQG WKH VDPH DVVD\ GLIIHUV VLJQLILFDQWO\ GHSHQGLQJ RQ DQ DQDO\VLV WHFK
QLTXH 6XFK VXEVWDQWLDO GLIIHUHQFHV DUH FDXVHG E\ V\VWHPDWLF PHDVXUHPHQWV
HUURUVKDYLQJGLIIHUHQWQDWXUHWKH[UD\IOXRUHVFHQFHDQGPDVVVSHFWURPHWULF
DQDO\VHV
7KH VRXUFH RI HUURUV DW [UD\ IOXRUHVFHQFH DQDO\VLV LV WKDW WKH JDPPD
TXDQWDRIYDULRXVHQHUJ\SDVVWKHYROXPHWKLFNQHVVLQGLIIHUHQWZD\V6RIWHU
JDPPDTXDQWD DUH DGVRUEHG E\ WKH DVVD\ VXEVWDQFH 7KHUHIRUH GHSHQGLQJ
RQ DVVD\ FRPSRVLWLRQ LWV PDLQ HOHPHQW DQGWKLFNQHVVWKHUHODWLYHHOHPHQW
FRQWHQW YDULHV )XUWKHUPRUH DQ DVVD\ LV SUHGRPLQDQWO\ FRPSRVHG RI WKH
HOHPHQW ZKLFK ZDV D ORDG DW HOHFWULF H[SORVLRQ 7KLV PDNHV WKH [UD\ OLQHV
RIVRPHHOHPHQWVWREHVXSHULPSRVHGRQWKH³SRZHUIXO´SHDNVRIPDLQHOH
PHQW,QVRPHFDVHVWKLVFDXVHVDQLQFUHDVHGHUURULQTXDQWLW\GHWHUPLQDWLRQ
RIHOHPHQWVDQDO\]HGLQDQDVVD\LQRWKHUFDVHVWKLVPDNHVLWLPSRVVLEOHWR
GRVXFKDQDO\VLVIRUVRPHHOHPHQWV
7KH V\VWHPDWLF PDVV VSHFWURPHWU\ HUURU LV GHWHUPLQHG E\ WKH ZD\ RI LRQ
EHDPSURGXFWLRQDQGSKRWRJUDSKLFILOPDQDO\VLVWHFKQLTXH$WDVVD\LRQL]D
/RZ(QHUJ\7UDQVPXWDWLRQRI$WRPLF1XFOHLRI&KHPLFDO(OHPHQWV
WLRQWKHODVHUEHDPEXUQVRXWDWVDPSOHVXUIDFHVWKHVSRWVRIaPP&KD
UDFWHULVWLFORFDOIRUPDWLRQVRIPPDQGPRUHWKDWDSSHDUDWHOHFWULFH[SOR
VLRQPDNHWKHDVVD\FRQWHQWYDU\JUHDWO\GHSHQGLQJRQZKDWSODFHRIVDPSOH
VXUIDFHWKHODVHUEHDPKDVJRWWR
7KH LRQ TXDQWLW\ RI RQH RU DQRWKHU HOHPHQW LV GHWHUPLQHG E\ EODFNHQLQJ
GHQVLW\RIWKHSKRWRJUDSKLFILOPWKDWLVORFDWHGLQWKHIRFDOSODQHRIPDJQHWLF
DQDO\]HU 7KH UHODWLYH HOHPHQW FRQWHQWLQDQDVVD\LVGHWHUPLQHGE\UHODWLYH
EODFNHQLQJRIWKHSKRWRJUDSKLFILOPIRUWKLVHOHPHQWDQGIRUWKHPDLQDVVD\
HOHPHQWPD[LPDOEODFNHQLQJ7KHG\QDPLFUDQJHRIPLFURGHQVHPHWHUZDV
VPDOOHU WKDQ TXDQWLW\ UDWLR RI DGPL[WXUHV DQG PDLQ HOHPHQW 7KHUHIRUH D
FDVFDGH FDOLEUDWLRQ RI WKHLQVWUXPHQWKDGEHHQFDUULHGRXWLQWKHSURFHVVRI
PHDVXUHPHQWV ZKDW LQHYLWDEO\ LQGXFHV DQ DGGLWLRQDO VSUHDG RI WKH GDWD $
WKRURXJK ILOP DQDO\VLV E\ PHDQV RI PLFURSKRWRPHWHU VKRZHG WKDW GXULQJ
ILOP SUHSDUDWLRQ GHIHFWV DUH IRUPHG DW WKH SODFHV RI EODFNHQLQJ ZKLFK GH
FUHDVH WKH EODFNHQLQJ GHQVLW\ 7KLV IDFW GRHV DOVR FRQWULEXWH LWV V\VWHPDWLF
HUURU WR D ILQDO UHVXOW )RU DERYH UHDVRQV WKH UHVXOWV REWDLQHG E\ PHDQV RI
;)$ DQG 06$ DQDO\VHV DUH IRU ORZ DGPL[WXUH OHYHOV LQ VDPSOHV UDWKHURI
TXDOLWDWLYH WKDQ RI TXDQWLWDWLYH QDWXUH $V DOUHDG\ QRWHG WKH VWUXFWXUH RI D
GU\DVVD\FRQWDLQVH[SOLFLWKHWHURJHQLRXVLQFOXVLRQVZHGLGQRWKRPRJHQL]H
WKHPWRDYRLGDQXQFRQWUROOHGEULQJLQJLQRIIRUHLJQHOHPHQWV)RUWKLVUHD
VRQ ERWK ;)$ DQG 06$ WHFKQLTXHV \LHOG D ORFDO HOHPHQW FRQFHQWUDWLRQ
ZKDWUHVXOWVLQDVXEVWDQWLDOGLIIHUHQFHRIDGPL[WXUHFRPSRVLWLRQZLWKLQRQH
DVVD\DQGLQWKHIDFWWKDWFRPSRVLWLRQGDWDGLIIHUIURPWKHDYHUDJHYDOXHVRI
HOHPHQWFRQFHQWUDWLRQLQDQDVVD\
7KH YROXPH DFWLYDWLRQ DQDO\VLV KDV SUDFWLFDOO\ QR VRXUFHV RI V\VWHPDWLF
HUURUV 7KH GLVDGYDQWDJH RI WKH WHFKQLTXH LV WKDW QRW DOO VWDEOH LVRWRSHV FDQ
EHDFWLYDWHGLQRUGHUWRDQDO\]HWKHLUFRQWHQWLQVDPSOHV
7R FRQFOXGH WKH FKHFN H[SHULPHQWV FDUULHG RXW PRVW VXEVWDQWLDO H[SHUL
PHQW IHDWXUHV VKRXOG EH QRWHG 2XU LQYHVWLJDWLRQV FRQILUPHG LQ JHQHUDO
WHUPVWKHUHVXOWVRIH[SHULPHQWVRQHOHPHQWWUDQVPXWDWLRQDWHOHFWULFH[SOR
VLRQRIIRLOVLQGLHOHFWULFPHGLXPREWDLQHGE\WKHJURXSRI/,8UXWVNRHY$V
D UHVXOW RI HOHFWULF H[SORVLRQV WKH DVVD\V VKRZ IRUHLJQ HOHPHQWV DQG D VXE
VWDQWLDOO\ LQFUHDVHG DGPL[WXUH FRQWHQW RI VRPH HOHPHQWV ZKLFK DUH SUHVHQW
LQLQLWLDOIRLOVDQGWLWDQLXPHOHFWURGHURG
:HKDYHUHFRUGHGWKHDSSHDUDQFHRIIRUHLJQHOHPHQWVLQDVVD\VDQGDQLQ
FUHDVHG FRQWHQW RI DGPL[WXUH HOHPHQWV 7KHVH HOHPHQWV LQFOXGH 1D $O 6L
3 . &D &O 0Q )H 1L &X =Q < =U 0R $J ,Q 6Q 6E %D 7D 3E
'HFUHDVHGHOHPHQWDGPL[WXUHVWKDWDUHSUHVHQWLQIRLOVDUHREVHUYHGLQVRPH
DVVD\V$EVROXWHTXDQWLW\RIQHZ HOHPHQWDWRPVZKLFKDSSHDUHGDIWHUHOHF
WULFH[SORVLRQVDUHLQWKHUDQJHy
9'.X]QHWVRYHWDO
$FKDQJHLQWLWDQLXPLVRWRSLFDEXQGDQFHUDWLRLVVHHQLQVRPHDVVD\V
7KH FRPSRVLWLRQ DQG TXDQWLW\ RI DGPL[WXUHV DIWHU HOHFWULF H[SORVLRQ GH
SHQGVERWKRQORDGFRPSRVLWLRQ DQGOLTXLGGLHOHFWULFPHGLXP
*DPPDDQGEHWDDFWLYLW\ZHUHQRWIRXQGLQDQ\DVVD\
$QDO\VLVRIORZHQHUJ\HOHPHQWWUDQVPXWDWLRQ
,QSUHYLRXVVHFWLRQVGHYRWHGWRH[SHULPHQWDOFKHFNRIHOHPHQWFRPSRVL
WLRQFKDQJHDVDUHVXOWRIWUDQVPXWDWLRQDUHOLDEOHLQFUHDVHRIFRQWHQWRIRQH
JURXS RI HOHPHQWV DQG WKH DSSHDUDQFH RI RWKHU IRUHLJQ HOHPHQWV KDV EHHQ
QRWHG )XUWKHUPRUH HOHFWULF H[SORVLRQ H[SHULPHQWV UHYHDOHG D YLRODWLRQ RI
LVRWRSHFRPSRVLWLRQRI7L,WVKRXOGEHQRWHGVWUDLJKWDZD\WKDWVXFKHOHPHQW
WUDQVIRUPDWLRQV FDQQRW EH H[SODLQHG IURP WKH SRLQW RI YLHZ RI PRGHUQ
SK\VLFDO QRWLRQV ERWK EHFDXVH RI LPSRVVLELOLW\ IRU QXFOHL WR RYHUFRPH WKH
&RXORPE EDUULHU DQG EHFDXVH RI LPSRVVLELOLW\ WR FRQVWUXFW HOHPHQWV RE
VHUYHGZKLOHWKHQXPEHURISURWRQVLVFRQVHUYHG7RHOLPLQDWHWKHODVWFRQ
WUDGLFWLRQ ZH KDYH WR LQFOXGH HOHFWURQV LQWR LQSXW RU RXWSXW FKDQQHOV WKXV
VXSSRVLQJDSRVVLELOLW\RIZHDNUHDFWLRQVZLWK l HOHFWURQVLHWRDFFRXQWIRU
LPSUREDEOHUHDFWLRQVIRUFKDUJHWUDQVIRUPDWLRQV
Q
] $ OH
o
Q
Q
] O $ OQ H ] $
o
Q
] O $ OH OQH ZKHUH ] $ LVDQXFOLGHZLWKDFKDUJH=DQGDQDWRPLFQXPEHUQ
$QRWKHU SUREDELOLW\ SURKLELWLRQ RI WUDQVPXWDWLRQ SURFHVVHV LV NLQHWLFV ,W
DSSHDUV EHFDXVH WKH QXFOHLFDQQRWFROOLGHGXULQJHOHFWULFH[SORVLRQDVRIWHQ
DVWRSURYLGHIRUWKHTXDQWLW\RIQHZHOHPHQWVXSWR%HORZZHGLVFXVV
QXPHULFDO VFDOHV RI WKHVHWKUHHSURKLELWLRQV6LQFHDOOWKHVHSURKLELWLRQVIRU
WUDQVPXWDWLRQ SURFHVVHV WKH IRUP RI H[WUHPHO\ ORZ SUREDELOLW\ RI WKH SUR
FHVV ZHVKDOOXVHIRUVLPSOLFLW\SXUSRVHVWKHWHUPSUREDELOLW\SURKLELWLRQV
+RZHYHU LW LV FRPSOHWHO\ QRW HYLGHQW WKDW FRQVHUYDWLRQ ODZV OLQNHG ZLWK
VSDFHDQGWLPHSURSHUW\DUHREVHUYHG8QIRUWXQDWHO\ZHDUHODFNLQJH[SHUL
PHQWDO GDWD WR FKHFN WKH DQJXODU PRPHQWXP FRQVHUYDWLRQ ODZ +RZHYHU LW
LV SRVVLEOH WR FKHFN WKH HQHUJ\ FRQVHUYDWLRQ ODZ 2XU SUREOHP GHILQLWLRQ
UHGXFHVVXFKDFKHFNWRWKHWDVNWRVHHH[RWKHUPLFQXFOHDUUHDFWLRQVOHDGLQJ
WR IRUHLJQ HOHPHQWV ZKLFK FDQ EH REVHUYHG H[SHULPHQWDOO\ (QHUJ\ UHOHDVH
LQWKHVHUHDFWLRQVRFFXUVRZLQJWRDGLIIHUHQFHLQWKHVXPVRIDWRPLFQXFOHL
PDVVHV LQ WKH LQSXW DQG RXWSXW UHDFWLRQ FKDQQHOV $W WKH VDPH WLPH LW LV
PHDQWWKDWWKHHQHUJ\EDODQFHVKRXOGDFFRXQWQRWIRUWKHQXFOHXVPDVVRQO\
EXW IRU WKH l PDVV RI HOHFWURQV 0RUHRYHU WR SURYLGH IRU WKH SXULW\ RI WKH
FKHFNEHORZZHWRRNLQWRDFFRXQWWKHHOHFWURQELQGLQJHQHUJ\LQDWRPVWRR
Q
/RZ(QHUJ\7UDQVPXWDWLRQRI$WRPLF1XFOHLRI&KHPLFDO(OHPHQWV
5HIHUHQFHERRN>@ZDVXVHGWRDQDO\]HSRVVLEOHUHDFWLRQV7KH7DEOHLQ
FOXGHGVWDEOHDQGUDGLRDFWLYHLVRWRSHVZLWKKDOIOLYHVPRUHWKDQ\HDUVRU
LQ FDVH RI WKH DEVHQFH RI VWDEOH LVRWRSHV DQ LVRWRSH ZLWK PD[LPDO SRVVLEOH
OLIHWLPH ZDV WDNHQ 7KH ELQGLQJ HQHUJ\ RI HOHFWURQV RI DQ DWRP ZDV WDNHQ
LQWR DFFRXQW DFFRUGLQJ WR IRUPXOD ( $ = ZLWKLQ WKH 7KRPDV)HUPL
PRGHO>@
5HDFWLRQVRIORDGHOHPHQWV7LDQG1L
7L DQG 1L UHDFWLRQV KDYH EHHQ FRQVLGHUHG IRU WKH DQDO\VLV %HFDXVH RI
OLPLWHG WHFKQLFDO SRVVLELOLWLHV ZH DFFRXQWHG IRU QRW PRUH WKDQ WKUHH RXWSXW
QXFOLGHVLHDOOUHDFWLRQVZHUHFRQVLGHUHG
/ ]Q $
Q
] $
/ ]Q $ OH Q
] $
OH OQH 4 / ]Q $
Q
Q
] $ ] $
OQ 4 Q
] $
/ ]Q $ OH Q
] $
Q
] $
Q
Q
] $ ] $
OH OQH 4 Q
] $
OQ 4 XQGHU DGGLWLRQDO FRQGLWLRQV QXFOHRQ QXPEHU FRQVHUYDWLRQQ Q /Q DQG
QQQ /Q WRWDO FKDUJH FRQVHUYDWLRQ ]] /] r O DQG ]]] /] r O
DQG SRVLWLYH EDODQFH RI HQHUJ\ 4t $ SUHOLPLQDU\ FRQFOXVLRQ DERXW WKH
SRVVLELOLWLHV RI VXFK UHDFWLRQV IROORZV IURPFRQVLGHUDWLRQRIELQGLQJHQHUJ\
SHU QXFOHRQ LQ WKH QXFOHL RI LQLWLDO VXEVWDQFH )LJ 7KXV WKH PDLQLVRWRSH
1LaZKLFKKDVDPLQLPDOIURPDOOQLFNHOLVRWRSHVELQGLQJHQHUJ\
)LJ%LQGLQJHQHUJ\SHUQXFOHRQLQDWRPLFQXFOHL
9'.X]QHWVRYHWDO
SHU QXFOHRQ Fw< FDQ JHQHUDWH LQ UHDFWLRQV ZLWK WKUHH RXWSXW QX
FOLGHV D PD[LPDO KHDY\ HOHPHQW ZLWK = VWURQWLXP 7KH FDOFXODWLRQV
VKRZ WKDW VXFK IXVLRQ LV SRVVLEOH LQ UHDFWLRQV ZLWK WHQ ZHDN LQWHUDFWLRQV LQ
WKHUHDFWLRQ
1L H )H 6U
Q H 0H9 $W WKH VDPH WLPH WKH PRVW OLJKW SURGXFW RI UHDFWLRQV ± FDOFLXP LV RE
WDLQHGLQIRXUUHDFWLRQV
1L H 1L H 1L H 1L H &D 1L &D 1L &D 1L &D 1L =Q Q H 0H9
=Q Q H 0H9
1L Q H 0H9
1L Q H 0H9
5HDFWLRQV ZLWK SURWRQ QXPEHU FRQVHUYDWLRQ GR QRW H[LVW 7KH PD[LPDO
TXDQWLW\RIHOHPHQWVDWWKHRXWSXWIDOOVRQRWKHULVRWRSHVRIQLFNHODQGLURQ
7LWDQLXPKDVDEURDGHUVSHFWUXPRIRXWSXWHOHPHQWV7KXVWKHPDLQLVR
WRSH 7L a ZLWK ELQGLQJ HQHUJ\ SHU QXFOHRQ 0H9 FDQ EH
\LHOGHG E\ ]LUFRQLXP WKH PD[LPDO KHDY\ HOHPHQW LQ PDQ\ UHDFWLRQV :H
ZLOOTXRWHDVLQJOHUHDFWLRQZLWKWZRRXWSXWIUDJPHQWV
7L H
&U
=U Q H 0H9 6LOLFRQ LV WKHPRVWOLJKWHOHPHQWREWDLQHGLQUHDFWLRQV7LEHWZHHQHDFK
RWKHU7KHUHDUHPDQ\UHDFWLRQVDQGZHZRQ¶WTXRWHWKHP
7KH PRVW OLJKW WLWDQLXP LVRWRSH 7L ZLWK D UHODWLYH FRQWHQW a KDV D
PLQLPDOELQGLQJHQHUJ\SHUQXFOHRQ0H9DQGFDQJHQHUDWHFDGPLXP
LQUHDFWLRQVZLWKILYHLVRWRSHV7LDQGVL[HOHFWURQV
5HDFWLRQVZLWKPHGLXPHOHPHQWV
:H VWDUW IURP D WULYLDO VWDWHPHQW WKDW DQ\ HOHPHQWV RI SHULRGLF WDEOH FDQ
EH REWDLQHG IURP SURWRQV WDNLQJ LQWR DFFRXQW ZHDN LQWHUDFWLRQ 1RW JLYLQJ
KHUH FDOFXODWLRQV ZH LQGLFDWH WKDW HOHPHQWV IURP 2 WR 8 FDQ EH EXLOW
IURP WKH JURXS 2+ :DWHU H[WHQGV WKLV URZ LQWR WKH VSKHUH RI VXSHUKHDY\
HOHPHQWVLQWHUSRODWLRQRIFXUYHV\LHOGVDFURVVLQJDUHDDW=|
5HDFWLRQVRIPHGLXPHOHPHQWVZLWKORDGHOHPHQWVDUHRIPXFKJUHDWHULQ
WHUHVW $V DQ H[DPSOH ZH FRQVLGHU UHDFWLRQV 1L DQG 7L ZLWK /HOHPHQWV
2 (QHUJ\ RXWSXWV LQ WKH UHDFWLRQV 1L ZLWK /HOHPHQWV 2 DUH JLYHQ LQ
/RZ(QHUJ\7UDQVPXWDWLRQRI$WRPLF1XFOHLRI&KHPLFDO(OHPHQWV
)LJ%7KHHOHPHQWQXPEHU=ZKLFKLVFRQVWUXFWHGRIVXFKFRPELQDWLRQV
LVSORWWHGDORQJWKHD[LVRIDEVFLVVD$UHDFWLRQZLWKSXUHR[\JHQLVJLYHQIRU
FRPSDULVRQ6LQFHWKHUHDUHPDQ\ DVDUXOHRXWSXWFKDQQHOVZLWKDQRXWSXW
RI D JLYHQ HOHPHQW ZH VKRUWO\ LQGLFDWH WKH FRQVWUXFWLRQ WHFKQLTXH RI WKHVH
FXUYHV7KHIROORZLQJVFKHPHKDVEHHQFKRVHQIRUUHDFWLRQVZLWKSXUHR[\
JHQ (OHPHQW ZLWK QXPEHU = ZDV FKRVHQ IURP UHDFWLRQV ZLWK WZR RXWSXW
HOHPHQWVDQGDPLQLPDOYDOXH/
/ 2 OH / Q
Q
] $ / ] O $
OQ H 4 ] d ,Q FDVHV ZKHQ D JLYHQ HOHPHQW GRHV QRW H[LVW LQ WKH LQGLFDWHG UHDFWLRQ
WKHHOHPHQWZDVSUHVHQWLQUHDFWLRQVZLWKWKUHHRXWSXWHOHPHQWV,Q)LJXUHD
GRWWHG OLQH FRUUHVSRQGV WRVXFKHOHPHQWV :ZLWKELQGLQJHQHUJ\SHUQX
FOHRQ0H9DW/ LVWKHKHDYLHVWHOHPHQWWKDWFDQEHREWDLQHGIURP
WKLV R[\JHQ LVRWRSH ZLWK ELQGLQJ HQHUJ\ SHU QXFOHRQ 0H9 )RU R[\
JHQUHDFWLRQVZLWKQLFNHODQRXWSXWFKDQQHOZLWKDPLQLPDOYDOXHRI/DQGD
PD[LPDOYDOXHRIHQHUJ\UHOHDVH4ZDVFKRVHQ
/ 2 1L OH / Q
Q
] $ / ] O $
OQ H 4
)LJ 1HZ HOHPHQWV DGPL[WXUH LQ WKH DVVD\ 1L +2SHUFHQWDJHZLVH
$ DQG HQHUJ\ UHOHDVH LQ UHDFWLRQV 1L DQG 2 DV D IXQFWLRQ RI FKDUJH RI DQ
HOHPHQWWREHV\QWKHVL]HG%
9'.X]QHWVRYHWDO
$W WKDW DOO RXWSXW FKDQQHOV ZHUH WZRHOHPHQW FKDQQHOV /HW XV QRWH WKDW
KLJK ³EURFNHQQHVV´ RI WKH HQHUJ\ UHOHDVH FXUYH LQ WKHVH UHDFWLRQV LV ODUJHO\
GHWHUPLQHG E\ WKH DOWHUQDWLRQ RI WKH TXDQWLW\ / WKDQ E\ WKH GLIIHUHQFH RI
ELQGLQJ HQHUJ\ RI RXWSXW HOHPHQWV 1HRG\PLXP ZKLFK UHTXLUHV DWRPV RI
R[\JHQLVWKHKHDYLHVWHOHPHQWREWDLQHGLQWKHVHUHDFWLRQV
2 1L H &
1G Q H 0H9 7KHPRVWEULJKWGDWDRIWKHDVVD\DUHJLYHQLQ)LJ$IRUFRPSDULVRQ
$WWKDWHOHPHQWVZKLFKSUHVHQFHLVFHUWDLQDUHPDUNHGZLWKILOOHGVTXDUHV
EXW DQ DEVROXWH YDOXH RI WKH DGPL[WXUH SOD\V WKH UROH RI XSSHU OLPLW VHH
$SSHQGL[ ,W LV VHHQ WKDW LQ UHDFWLRQV EHWZHHQ 1L DQG 2 ZH FDQ REWDLQ
PRUH DQG PRUH QHZ HOHPHQWV ZLWK WKH H[FHSWLRQ RI WDQWDOXP $ SRVVLEOH
FRQILJXUDWLRQ RI LQLWLDO VDPSOH FRQWDLQLQJ ERWK QLFNHO DQG R[\JHQ FDQ EH
R[LGH ILOP ,Q WKLV FDVH QLFNHO R[LGH ,, KDV D ODWWLFH ZKLFK LV VLPLODU WR
1D&OLHRQHQLFNHOLRQKDVFORVHVWQHLJKERUVR[\JHQDWRPV7KHDSSHD
UDQFH RI WDQWDOXP FDQ EH H[SODLQHG E\ UHDFWLRQV EHWZHHQ HOHPHQWV RI WKH
PHGLXPRQO\,QSDUWLFXODULWFDQEHEXLOWIURPR[\JHQ5HDFWLRQVRIR[\JHQ
ZLWK WLWDQLXP JHQHUDWH HOHPHQWV IURP K\GURJHQ WR 6P ,Q RUGHU QRW WR
UHSHDW WKH ILJXUH VLPLODU WR )LJ ZH JLYH )LJ ZKHUH DQ H[SHULPHQWDO
HOHPHQW GLVWULEXWLRQ DQG WZR GLVWULEXWLRQV FDOFXODWHG QRW E\ HQHUJ\ UHOHDVH
EXW E\ WKH FRPELQDWLRQ TXDQWLW\ RI RXWSXW HOHPHQWV LQ UHDFWLRQV EHWZHHQ
WLWDQLXP DQG WLWDQLXP ZLWK R[\JHQ DUH FRPSDUHG ,W LV VHOIHYLGHQW WKDW
GLVWULEXWLRQVERXQGDULHVRQO\FDQEHFRPSDUHG
:H GRQ¶W TXRWH KHUH ILJXUHV ZLWK FDUERQ SDUWLFLSDWLRQ :H MXVW PHQWLRQ
WKDW LQ UHDFWLRQV ZLWK WZR RXWSXW HOHPHQWV ZH FDQ REWDLQ IURP FDUERQ DOO
HOHPHQWVGRZQWRDVWDWLQH
& H /L
$W Q H 0H9 5HDVRQLQJ IURP DVVXPSWLRQ WKDW D SUREDELOLW\ RI SURGXFWLRQ RI QHZ HOH
PHQWV GHFUHDVHV DV WKH TXDQWLW\ RI QXFOHL LQ LQSXW DQG RXWSXW FKDQQHOV GH
FUHDVHVRQHFDQFRQFOXGHWKDWWKHIROORZLQJJURXSRIHOHPHQWV 1D$O6L
. &D &O 0Q )H 1L &X =Q ± LV JHQHUDWHG E\ WKH HOHPHQWV RI ORDG DQG
ORDGPHGLXP $QRWKHU JURXS RI HOHPHQWV 0R $J ,Q 6Q 6E ± LV JHQH
UDWHGLQFRPELQDWLRQRIHOHPHQWVRIORDGDQGPHGLXP7KHKHDYLHUHOHPHQWV
3E7D± FDQEHJHQHUDWHGE\PHGLXPHOHPHQWVRQO\ ,QWKLVFDVHWKHPH
GLXPVKRXOGFRQWDLQHLWKHUFDUERQRUWKHJURXS2+/HWXVUHPLQG\RXWKDW
WKHVHFDOFXODWLRQVZHUHIRUDOLPLWHGTXDQWLW\RIRXWSXWQXFOLGHVWKHLUQXP
EHUVKRXOGQRWH[FHHGWKUHH
/RZ(QHUJ\7UDQVPXWDWLRQRI$WRPLF1XFOHLRI&KHPLFDO(OHPHQWV
Concentration
7KXV DQ DQDO\VLV FDUULHG RXW WR FKHFN WKH HQHUJ\ FRQVHUYDWLRQ ODZ IRU
QHZHOHPHQWVREWDLQHGLQH[SHULPHQWVZLWKHOHFWULFH[SORVLRQRIORDGVKRZV
WKDW DOO DGPL[WXUH HOHPHQWV FDQ EH REWDLQHG IURP LQLWLDOQXFOHLDWDSRVLWLYH
HQHUJ\ RXWSXW +RZHYHU WKH H[SHULPHQW RQ FKDQJLQJ WKH HOHPHQW FRPSRVL
WLRQRISXUH]LUFRQLXPWKDWKDVEHHQGLVFXVVHGLQWKHILUVWSDUWRIWKHSDSHU
VKRXOG EH DQDO\]HG DGGLWLRQDOO\ EHFDXVH WKH ]LUFRQLXPPHOWLQJRFFXUUHGLQ
D YDFXXP ,H QDWXUDO LVRWRSH FRPSRVLWLRQ RI =U LV WKHRQO\LQLWLDOHOHPHQW
IRUWKHSURGXFWLRQRIDOOHOHPHQWVVKRZQLQ)LJGRZQWR/XZKLFKELQG
LQJHQHUJ\SHUQXFOHRQLVVXEVWDQWLDOO\OHVVWKDQLQDOO]LUFRQLXPLVRWRSHV
Ti
1
-1
10
-2
10
-3
10
-4
10
-5
10
-6
10
-7
10
Na
Si Ca
Fe
Ni
Mn
K
Cu
Zn
Ag Sn Sb Ba
Ta TaO Pb
Zr Nb
Mo In
0
Probability, a.u.
Al
a) MSA. Sample 415
Ti in H2O2 (1%)
10
20
30
40
50
60
70
80
70
80
70
80
300
250
200
150
100
50
0
Ni
b) 4 * Ti
Zn
Zr
Ca
0
10
20
30
40
50
60
Probability, a.u.
Ca
600
c) 6 * O + Ti
H
400
Ne
Zn
Zr
200
Sn
Ba
0
0
10
20
30
40
50
Z elements
60
)LJ&RPSDULVRQRIH[SHULPHQWDOHOHPHQWFRPSRVLWLRQRIVDPSOHDIWHUHOHF
WULF H[SORVLRQ ZLWK FDOFXODWHG UHODWLYH SUREDELOLWLHV RI FUHDWLRQ RI HOHPHQWV D
VDPSOHORDG± 7LPHGLXP +2 EFDOFXODWLRQPDGHIRUIRXUQXFOHLRI
7LLQWKHLQSXWUHDFWLRQFKDQQHOFFDOFXODWLRQPDGHIRUVL[QXFOHLRI 2DQG7L
LQWKHLQSXWUHDFWLRQFKDQQHO
9'.X]QHWVRYHWDO
5HDFWLRQVZLWK=U
$ VSHFWUXP RI HOHPHQWV REWDLQHG DIWHU ]LUFRQLXP PHOWLQJ LV VKRZQ LQ
)LJ :H REWDLQHG WKLV VSHFWUXP E\ WUDQVIRUPDWLRQ RI PDVV VSHFWUD )LJ
=U a SURFHHG WR GHFD\ VLGH DQG
5HDFWLRQV RI WZR PDLQ LVRWRSHV \LHOG HOHPHQWV IURP VLOLFRQ WR VWURQWLXP 7KH UHDFWLRQ VSHFWUXP RIWZRLVR
=U a LV PXFK PRUH UHDFK DQG LQFOXGHV GHXWHULXP DQG WKHQ
WRSHV VSUHDGV FRQWLQXRXVO\ IURP FDUERQ WR SDOODGLXP :H FDQ REWDLQ IURPGHXWH
ULXP KHDYLHU DQG KHDYLHU HOHPHQWV +RZHYHU WR UHPRYH DOO GRXEWV DERXW
OLJKWJDVSDUWLFLSDWLRQLQIXUWKHUUHDFWLRQVZHQRWHWKDWFDUERQDOVR\LHOGVDOO
HOHPHQWV VKRZQ LQ )LJ 7KHUH DUH VL[ UHDFWLRQV ZLWK FDUERQ RXWSXW IURP
=U ZKLFKZHGRQRWTXRWHKHUHEHFDXVHRIWKHLUREYLRXVQHVV
WZRDWRPV 5HDFWLRQV WKDW UHVXOWV LQ KHDY\ HOHPHQWV DUH VXSSRVHG WR KDYH WZR PHFKD
QLVPV 7KH\ DUH HLWKHU D VXFFHVVLYH SURGXFWLRQ RI FDUERQ DQG RWKHU OLJKW
HOHPHQWVZKLFKKDYHDELQGLQJHQHUJ\SHUQXFOHRQWKDWLVFORVHWKDWRIFDU
ERQ DQG WKHLU IXUWKHU SDUWLFLSDWLRQ LQ WKH IRUPDWLRQ RI QHZ HOHPHQWV RU D
SDUWLFLSDWLRQRIDJUHDWHUTXDQWLW\RI]LUFRQLXPDWRPVLQWKHUHDFWLRQVLPXO
10
Concentration
10
0
Zr
-1
Mg
10
-2
10
-3
10
-4
Na
H
Al
Si KCa
Ti Fe
Cr
Sr
Li
Ni
10
10
-6
10
-7
Se
La
Hf
Rb
B
0
Ce - Lu
Ge
P
-5
Sn
Cd Te
Cs
10
20
30
40
50
60
70
80
Z Elements
)LJ (OHPHQW FRPSRVLWLRQ RI ]LUFRQLXP LQJRW )LOOHG EDU JUDSKV VWDQG IRU DIWHU
HOHFWULFH[SORVLRQXQILOOHGEDUJUDSKVVWDQGIRUEHIRUHHOHFWULFH[SORVLRQ
/RZ(QHUJ\7UDQVPXWDWLRQRI$WRPLF1XFOHLRI&KHPLFDO(OHPHQWV
WDQHRXVO\ 7KH ODWWHU GRHV QRW VHHP REYLRXV DQG ZH TXRWH KHUH D UHDFWLRQ
WKDWJHQHUDWHVSODWLQXPDQHOHPHQWWKDWLVKHDYLHUWKDQ/X)LJ
=U o 7L 3W H QH Fw< *HQHUDOO\VSHDNLQJWKHJHQHUDOIRUPXODRIWKLVUHDFWLRQ
/ =U o / 7L 3W / H / QH 4 DW / ! KDV D SRVLWLYH HQHUJ\ RXWSXW4 'HVSLWH WKH DSSHDUDQFH RI SODWL
QXP WKH FKDUJH EDODQFH RI WKLV UHDFWLRQ LQGLFDWHV D SUHGRPLQDQFH RI OLJKW
HOHPHQWV /HW XV WHOO IRU LQIRUPDWLRQ WKDW DW / WKH HQHUJ\ RXWSXW RI WKH
UHDFWLRQLV0H9
3HUIRUPHGFDOFXODWLRQVVKRZWKDWWKHSURGXFWLRQRIIRUHLJQHOHPHQWVLQD
ORZ HQHUJ\ WUDQVPXWDWLRQ UHDFWLRQ GRHV QRW FRQWUDGLFW WR HQHUJ\ FRQVHUYD
WLRQ ODZ 0RUHRYHU VRPH UHDFWLRQV KDYH VXFK D VLJQLILFDQW HQHUJ\ RXWSXW
WKDW WKH\ FRXOG EH D EDVH IRU HQHUJ\ JHQHUDWLQJ LQVWDOODWLRQV ,W LV VHOI
HYLGHQWDWDPXFKJUHDWHUSRUWLRQRIQXFOHLWREHWUDQVIRUPHGDQGDWXQGHU
VWDQGLQJRISK\VLFDOUHDVRQVFDXVLQJWKHORZHQHUJ\WUDQVPXWDWLRQ
'LVFXVVLRQRIWKHRUHWLFDOSURKLELWLRQVRIORZHQHUJ\WUDQVPXWDWLRQ
$VZHKDYHDOUHDG\PHQWLRQHGDERYHWUDQVPXWDWLRQVDWORZHQHUJLHVFDQ
QRW EH H[SODLQHG ZLWKLQ PRGHUQ SK\VLFDO FRQFHSWLRQV 7R EH PRUH SUHFLVH
WKHSRUWLRQRIFKDQJLQJQXFOHLPXVWEHVRWLQ\WKDWLWFDQQRWEHGHWHFWHG:H
VHHWKUHHWKHRUHWLFDOSURKLELWLRQVIRUWUDQVPXWDWLRQSKHQRPHQRQWKHLPSRV
VLELOLW\WRSDVVWKH&RXORPEEDUULHUVPDOOWRWKHOLPLWSUREDELOLWLHVRIZHDN
SURFHVVHV DQG VPDOO SUREDELOLWLHV RI PXOWLSDUWLFOH FROOLVLRQV HYHQ LI WKH
&RXORPE EDUULHU LV DEVHQW ,Q RUGHU WR UHO\ RQ QXPHULFDO YDOXHV RI WKHVH
VPDOOSUREDELOLWLHVZHTXRWHWKHLUHVWLPDWHGYDOXHV
7KH&RXORPEEDUULHUFDQEHDFFRXQWHGIRUIURPWKHHYDOXDWLRQRIQXFOHDU
UHDFWLRQFURVVVHFWLRQDWORZHQHUJLHV
VU
V _ < & _ ZKHUH _ < & U _ LVDVTXDUHG&RXORPEZDYHIXQFWLRQRIWKHUHODWLYHPRWLRQ
RI QXFOHL GHWHUPLQLQJ WKH SUREDELOLW\ RI SDVVLQJ WKH &RXORPE EDUULHU V LV
QXFOHDUUHDFWLRQFURVVVHFWLRQDWWKH³VZLWFKHGRII´&RXORPEEDUULHU%HORZ
ZH VKDOO XVH LWV JHRJUDSKLFDO VFDOH HTXDO WR RQH EDUQ kf 7KHQ D
SUREDELOLW\ RI QXFOHDU UHDFWLRQ SHU WLPH XQLW UHODWHG WR RQH DWRP ZLOO EH
GHWHUPLQHGE\DVLPSOHIRUPXOD
9'.X]QHWVRYHWDO
:Q | QYV U ZKHUHQ LVDWRPLFGHQVLW\RIPDWWHUDQGY LVDUDWHRIQXFOHDUFROOLVLRQVDWD
FHUWDLQ HQHUJ\ ( 7DNLQJ LQWR DFFRXQW WKH H[SUHVVLRQ IRU WKH YDOXH RI &RX
ORPE ZDYH IXQFWLRQ LQ ]HUR DW VPDOO HQHUJLHV _ < & _ H S ND S ND
VHHIRULQVWDQFH>@ZKHUHN LVDZDYHQXPEHUFRUUHVSRQGLQJWRQXFOHDU
FROOLVLRQV HQHUJ\DQGD LV%RKUUDGLXVIRU&RXORPESDUDPHWHUVRIFROOLGLQJ
QXFOHL ZH FDQ REWDLQ DQ HYDOXDWLRQ RI SUREDELOLW\ RI WLWDQLXP QXFOHL UHDF
WLRQVSHURQHVHFRQG
:Q | H (
+HUHWKHHQHUJ\(VKRXOGEHVXEVWLWXWHGLQH9XQLWV,HDSUREDELOLW\RI
QXFOHDU UHDFWLRQ DW D W\SLFDO HQHUJ\ RI RQH HOHFWURQYROW LV GHWHUPLQHG E\ D
GHFLPDO GHJUHH a 7KXV QR QXFOHDU UHDFWLRQ ZLWK WLWDQLXP ZLOO WDNH
SODFHGXULQJWKHOLIHWLPHRIWKH8QLYHUVHDWWKHVHHQHUJLHV,QRUGHUWRDYRLG
K\SRWKHVLVRQFXPXODWLYHSURFHVVHVOHWXVQRWHWKDWHYHQLIWKHQXFOHLKDGDQ
HQHUJ\RIWKHYROWDJHDSSOLHGWRHOHFWURGHVRINH9WKHQLQWKLVFDVHDSUR
EDELOLW\ ZRXOG EH GHWHUPLQHG E\ D GHFLPDO RUGHU a DQG ZRXOG EH DV
EHIRUH LQFUHGLEOH LQ WKH 8QLYHUVH 2QH FDQ VD\ WKDW WKH &RXORPE EDUULHU
IRUELGVSUDFWLFDOO\DEVROXWHO\UHDFWLRQVREVHUYHGLQWKHH[SHULPHQW
/HWXVQRZGLVFXVVWKHPDJQLWXGHRIYHORFLWLHVRIZHDNWUDQVLWLRQV,QRU
GHU WR DYRLG WKH FRPSOH[LW\ RI PRGHO SUHVHQWDWLRQV ZH VKDOO SURFHHG IURP
GLPHQVLRQV FRQVLGHUDWLRQV DQG H[SHULPHQWDO YDOXHV RI OLIHWLPHV RI UDGLRDF
WLYHQXFOHLWKDWFDSWXUHDQHOHFWURQ6XFKQXFOHLFDQOLYHIRU\HDUV+RZHYHU
WKHUHH[LVWVXFKUDGLRDFWLYHQXFOHLZKLFKOLIHWLPHLVGHWHUPLQHGE\PLQXWHV
)RU H[DPSOH WKH QXFOHXV RI WXQJVWHQ : FDSWXUHV DQ HOHFWURQ LQ WKH
FRXUVHRIPLQXWHV)RUHYDOXDWLRQOHWXVWDNHDQRYHUVWDWHGYHORFLW\RI
HOHFWURQFDSWXUHE\DQXFOHXV± RQHWUDQVLWLRQSHUVHFRQG'LPHQVLRQDOFRQ
VLGHUDWLRQV DOORZ WR ZULWH GRZQ DQ H[SUHVVLRQ IRU WKH YHORFLWLHV RI ZHDN
WUDQVLWLRQVLQWKHIRUP
:Z a
'(
D
!
ZKHUH '( LV HQHUJ\ UHOHDVHG DW ZHDN LQWHUDFWLRQ DQG TXDQWLW\ D LV GLPHQ
VLRQOHVV FRQVWDQW 'RXEOH DQG WULSOH EHWD WUDQVLWLRQV ZLOO EH GHWHUPLQHG MXVW
E\ WKH GHJUHH LH D DQG D FRUUHVSRQGLQJO\ /HW XV HYDOXDWH WKLV TXDQ
WLW\)RU : Z k_d DQG ' ( Fw< ZHREWDLQ D a 7KHW\SLFDOWLPH
RIGXUDWLRQRIFXUUHQWIORZDWHOHFWULFH[SORVLRQLVPV,WPHDQVWKDWHYHQ
/RZ(QHUJ\7UDQVPXWDWLRQRI$WRPLF1XFOHLRI&KHPLFDO(OHPHQWV
DW VXFK RYHUVWDWHG YHORFLWLHVRIZHDNWUDQVLWLRQVZHZRXOGQRWREWDLQPRUH
WKDQ WKRXVDQGWK SHUFHQW RI WUDQVIRUPHG QXFOHL,IZHWDNHLQWRDFFRXQWWKDW
DV D UXOH WZR ZHDN WUDQVLWLRQV SHU QXFOHXV RFFXU LQ JLYHQ IRUPXODV WKHQ D
YHORFLW\ RI GRXEOH ZHDN WUDQVLWLRQV ZLOO EH a VHF D TXDQWLW\ ZKLFK
GHWHUPLQHV RQH GRXEOH WUDQVLWLRQ SHU KXQGUHG PROHV RI VXEVWDQFH GXULQJ
H[SHULPHQWWLPH
7KHODVWSUREDELOLW\SURKLELWLRQLVNLQHPDWLFVLWLVGHWHUPLQHGE\GLPHQ
VLRQVRIQXFOHLZKLFKDUHWRRVPDOOHYHQIRUWKUHHSDUWLFOHFROOLVLRQV5HDOO\
DSUREDELOLW\RIDSDUWLFOHSDLUWRJHWLQWRWKHYROXPH9RFFXSLHGE\DWKUHH
SDUWLFOH LV 9 97RW
ZKHUH 97RW LV D IXOO YROXPH RFFXSLHG E\ 1 SDUWLFOHV
7KH TXDQWLW\ RI GRXEOH FRPELQDWLRQV IURP 1 SDUWLFOHV ZLOO EH HTXDO WR
1 7KXV YROXPH 9 DOZD\V FRQWDLQV 9 Q WKUHHSLHFH VHWV RI SDU
WLFOHV )RU YHORFLW\ HYDOXDWLRQ RI SUREDELOLW\ RI WKUHHSDUWLFOH FROOLVLRQ
IRUPDWLRQWKHODVWTXDQWLW\VKRXOGEHGLYLGHGRYHUWKHWLPHRIW\SLFDOVWD\LQ
WKLVYROXPH
:. a 9 Q W :H KDYH WZR OHQJWK SDUDPHWHUV 5 GHWHUPLQLQJ WKH YROXPH 9 DQG D
PHDQ GLVWDQFH EHWZHHQ SDUWLFOHV Q WKDW LV ZK\ WKH W\SLFDO WLPH W LV
GHWHUPLQHG E\ DQ LQWHUYDO IURP Q Y WR 5 Y /HW XV WDNHDQRYHUVWDWHG
YHORFLW\ RI IRUPDWLRQ RI WKUHHSDUWLFOH FROOLVLRQ IRUPDWLRQ DFFRUGLQJ WR WKH
VKRUWHVW WLPH W 5 Y (YDOXDWLQJ WKH VL]H RI QXFOHXV 5 DV FP WKH
PRWLRQHQHUJ\RIWLWDQLXPQXFOHLDVH9DQGWDNLQJWKHGHQVLW\RIPHWDOOLF
WLWDQLXP ZH UHFHLYH :. a VHF 7KXV D SUREDELOLW\ RI WKUHHSDUWLFOH
FROOLVLRQVUHODWHGWRRQHDWRPZLOOKDYHDVFDOHa GXULQJWKHWLPHRI
H[SHULPHQWZKLOHWKHREVHUYHGYDOXHLVa,HWKUHHSDUWLFOHDQGPRUH
FROOLVLRQVDUHFOHDUO\QRWVXIILFLHQWIRUWKHSURGXFWLRQRIWKHREVHUYHGTXDQ
WLW\RIHOHPHQWV
7KH FRQVLGHUHG SUREDELOLW\ SURKLELWLRQV IRU QXFOHDU WUDQVPXWDWLRQ DW WKH
HQHUJ\ VFDOH RI H9 FDQQRW EH RYHUSDVVHG ZLWKLQ WUDGLWLRQDO SK\VLFDO FRQ
FHSWLRQV ,W HVSHFLDOO\ FRQFHUQV WKH NLQHWLF SURKLELWLRQ ZKLFK FDQQRW EH
RYHUSDVVHG HYHQ E\ LQWURGXFWLRQ RI K\SRWKHWLF SDUWLFOHV ZKLFKDUHLQWHUPH
GLDULHVWREULQJWKHQXFOHLFORVHUWRHDFKRWKHU+RZHYHUH[SHULPHQWDOGDWD
VKRZ WKH H[LVWHQFH RI WUDQVPXWDWLRQ $V NLQHWLF SURKLELWLRQ LV EDVHG RQ GL
PHQVLRQVRIDQXFOHXVOHWXVHYDOXDWHZKDWVKRXOGEHWKHVL]HRILQWHUDFWLRQ
DUHD 5 VXIILFLHQW WR REWDLQ RQH SHUFHQW RI WUDQVPXWHG QXFOHL GXULQJ PV
6LPSOH FDOFXODWLRQV \LHOG D VXUSULVLQJ YDOXHa FP ,I ZH WDNH PD[LPDO
9'.X]QHWVRYHWDO
WLPH W Q Y ZH REWDLQ 5 a FP ,H ERWK HYDOXDWLRQV JLYH D VL]H
FORVHWRWKHVL]HRIDQDWRP/HWXVQRWHWKDWLIDQXPEHURISDUWLFOHVSDUWLFL
SDWLQJ LQ WKH UHDFWLRQ LQFUHDVHV WKHQ WKH TXLFNO\ DWWDLQDEOH OLPLW 5a Q GRHV QRW GHSHQG RQ UHDFWLRQ YHORFLWLHVFKRVHQRURQW\SLFDOFROOLVLRQWLPHV
/HWXVQRWHWKDWDWVXFKGLPHQVLRQVRILQWHUDFWLRQDUHDQRWRQO\UHPRYHGDUH
SURKLELWLRQVLPSRVHGE\WKH &RXORPEEDUULHUWKH&RXORPEEDUULHULWVHOIMXVW
GLVDSSHDUVEXWZHDNLQWHUDFWLRQLVVXEVWDQWLDOO\DFFHOHUDWHV7KLVWDNHVSODFH
EHFDXVH WKH TXDQWLW\ D FRQWDLQV D PXOWLSOLHU HTXDO WR YROXPH UDWLR RI D
QXFOHXVDQGDQDWRP,IZHVXEVWLWXWHWKHTXDQWLW\ D5 LQWKHH[SUHVVLRQ
IRUGRXEOHEHWDSURFHVVLQVWHDGRID DQGVHWWLPHRIPVDQGSUREDELOLW\RI
ZHFDQGHILQHWKHTXDQWLW\5,WDOVRSURYHVWREHHTXDOWRWKHVL]HRIDQ
DWRP 5 a FP 7KHUHIRUH ZH FDQ RYHUSDVV DOO DERYH SURKLELWLRQV IRU
QXFOHL ZKLFK VL]H LV HTXDO WR WKDW RI DQ DWRP :H FDQQRW LQGLFDWH PHFKD
QLVPV FDXVLQJ VXFK ELJ GLPHQVLRQV RI DWRPLF QXFOHL LQ FRQGLWLRQV RI DQ
H[SHULPHQW:HMXVWVWDWHWKHRQO\ WRRXUPLQGSRVVLELOLW\RIWUDQVPXWDWLRQ
$V D K\SRWKHVLV ZH FDQ H[SUHVV DQ RSLQLRQ RQ WKH FKDQJH RI IXQGDPHQWDO
SK\VLFDO FRQVWDQWV XQGHU FRQGLWLRQV RI D SK\VLFDO H[SHULPHQW RQ HOHPHQW
WUDQVPXWDWLRQ
&RQFOXVLRQ
,I \RX FRPSDUH HOHFWULF H[SORVLRQ H[SHULPHQWV ZLWK ]LUFRQLXP PHOWLQJ
DQG XOWUDVRQLF DFWLYDWLRQ H[SHULPHQWV 86$ DWWHQWLRQ VKRXOG EH GUDZQ WR
WKHWLPHGLIIHUHQFHRIWKHORZHQHUJ\WUDQVPXWDWLRQSURFHVVLQWKHVHWHVWV,I
LQWKHILUVWFDVHWKHSURFHVVWDNHVWHQVPLFURVHFRQGVLQRWKHUFDVHVLWWDNHV
WHQV PLQXWHV DQG HYHQ VRPH GD\V 7KRXJK ZH NQRZ QHLWKHU ZKDW WLPH LV
QHFHVVDU\ IRU WKH WUDQVPXWDWLRQ SURFHVV WR WDNH SODFH QRU ZKDW WLPH WKH
FRQGLWLRQV IRU WKLV UHDFWLRQ WR EH LQLWLDWHG DUHDYDLODEOHLQWKHPHGLXPLWLV
SODXVLEOH WR DVVXPH WKDW WUDQVPXWDWLRQ UHDFWLRQ GHQVLW\ SHU PHGLXP XQLW LV
PXFK JUHDWHU DW ]LUFRQLXP PHOWLQJ DQG XOWUDVRQLF DFWLYDWLRQ WKDQ DW HOHFWULF
H[SORVLRQ 'XH WR WKH DERYH ZH FDQ DVVXPH WKDW WUDQVPXWDWLRQ UHDFWLRQ DW
HOHFWULF H[SORVLRQ SURFHHGV WR D VXEVWDQWLDO GHJUHH XQGHU SDUWLFLSDWLRQ RI
LQLWLDO PDWHULDO RQO\ ZKLOH VHFRQGDU\ HOHPHQWV UHSUHVHQWLQJ SURGXFWV RI
SUHYLRXV WUDQVPXWDWLRQV FDQ EH LQYROYHG LQ WKH UHDFWLRQ DW ]LUFRQLXP PHO
WLQJ DQG XOWUDVRQLF DFWLYDWLRQ 7KLV FDQ KDYH D UDGLFDO LPSDFW RQ WKH VSHF
WUXP RI ILQDO SURGXFWV LQ WKH ORZ HQHUJ\ HOHPHQW WUDQVPXWDWLRQ UHDFWLRQ
0RVW SUREDEO\ WKLV H[SODLQV DQ LUUHJXODULW\ RI DSSHDUDQFH RI HOHPHQWV ZLWK
=!DWHOHFWULFH[SORVLRQ)LJDQGDQDSSHDUDQFHRIDEURDGVSHF
WUXP RI FKHPLFDO HOHPHQWV )LJ DW ]LUFRQLXPHOHFWURQ EHDP PHOWLQJ DQG
XOWUDVRQLFDFWLYDWLRQ)LJG
/RZ(QHUJ\7UDQVPXWDWLRQRI$WRPLF1XFOHLRI&KHPLFDO(OHPHQWV
7KH DERYH H[SHULPHQWDO GDWD RQ WUDQVPXWDWLRQ SURFHVVHV RI FKHPLFDO
HOHPHQWV GHVSLWH DOO WKHLU IUDJPHQWDULQHVV KDYH D UHJXODULW\ FRPPRQ IRU
YDULRXV H[SHULPHQWV 0RUHRYHU D VLPSOH FDOFXODWLRQ RI HQHUJ\ EDODQFH UH
YHDOVSRVVLEOHSDUWLFLSDQWVRIQXFOHDUUHDFWLRQV,QSDUWLFXODUWKUHHDQGPRUH
DWRPV VKRXOG EH DWWUDFWHG LQWR WKH LQSXW FKDQQHO WR H[SODLQ DOO HOHPHQWV
ZKLFKDUHREVHUYHG7KLVQHFHVVDULO\UHTXLUHVWRH[WHQGWKHUHDFWLRQVSKHUHV
XSWRDWRPLFDQGJUHDWHUGLPHQVLRQV7KHQDWXUHRIDSSHDUDQFHRIVXFKFRQ
GLWLRQV LV XQNQRZQ /HW XV QRWH WKDW WKH FRUUHFWQHVV RI WKH EDODQFH WKDW KDV
EHHQ FRQVLGHUHG ZKHQ WKH OHSWRQ QXPEHU LV FRQVHUYHG FDQ EH FKHFNHG E\
PHDQVRIUHJLVWUDWLRQRIQHXWULQRDQWLQHXWULQREXUVW
7KHDXWKRUVZLVKWRH[SUHVVWKHLUDSSUHFLDWLRQWR/,8UXWVNRHYIRUJUDQ
WLQJ D SRVVLELOLW\ WR UXQ FKHFN H[SHULPHQWV WR 90'XERYLN IRU LQLWLDWLQJ
GLVFXVVLRQVDQG993DYOHQNRIRULQIRUPDWLRQDOVXSSRUW
$SSHQGL[
,QYLHZRIH[WUDRUGLQDU\UHVXOWVRIWKHSUHVHQWSDSHUZHKDYHFRQVLGHUHG
LW QHFHVVDU\ WR SUHSDUH FRPPHQWV RQHDFKFKHFNH[SHULPHQWUHSUHVHQWHGLQ
7DEOHVDQGWRUHSUHVHQWIRUREYLRXVQHVVWKHFRQWHQWRIVRPH7DEOHVDVEDU
FKDUWV
'DWD RQ PDVV VSHFWURPHWULF PHDVXUHPHQWV DUH JLYHQ LQ 7DEOHV ± GDWD
RQ [UD\ IOXRUHVFHQFHDQDO\VLVDUHGHPRQVWUDWHGLQ7DEOHV±DQGGDWDRQ
DFWLYDWLRQ DQDO\VLV DUH VKRZQ LQ 7DEOH 'DWD RQ VDPSOH DUH EURXJKW
WRJHWKHU LQ 7DEOH $GPL[WXUH FRPSRVLWLRQV FRQWDLQHG LQ ZDWHU JO\FHULQ
DQG SRO\HWK\OHQH DUH JLYHQ LQ 7DEOHV (OHPHQWV WKDW DSSHDUHG DIWHU
HOHFWULFH[SORVLRQEXWQRWUHJLVWHUHGLQLQLWLDOPDWHULDOVIRLOVWLWDQLXPHOHF
WURGH DV ZHOO DV HOHPHQWV ZKLFK FRQWHQW LQ WKH DVVD\V LQFUHDVHG DUH EROG
W\SHG LQ 7DEOHV $V WKLV WDNHV SODFH D VWDWLVWLFDO UHTXLUHPHQW RQ H[FHHGLQJ
WZRVWDQGDUGHUURUVLVPHW0DUNHGZLWKFLUFOHVDUHHOHPHQWVZKLFKZHUHQRW
UHJLVWHUHG LQ DVVD\V EXW KDG EHHQ UHJLVWHUHG LQ LQLWLDO PDWHULDOV (OHPHQWV
ZKLFK FRQWHQW LQ DVVD\V GHFUHDVHG DUH XQGHUOLQHG $ V\PERO OHVVRU HTXDO
dLQ7DEOHVLQGLFDWHVLQFDVHVRI[UD\IOXRUHVFHQFHDQDO\VLVDVZHOODVLQ
WKRVHRIJDPPDDQGQHXWURQDFWLYDWLRQDQDO\VLVDWHFKQLTXHVHQVLWLYLW\OLPLW
IRUDJLYHQHOHPHQW
,QFDVHRIPDVVVSHFWURPHWULFDQDO\VLVWKHV\PEROOHVVPHDQVWKDWWKLV
HOHPHQWZLWKDOOLWVLVRWRSHVZDVUHJLVWHUHGDWDJLYHQOHYHORIVHQVLWLYLW\EXW
WKHVWDWLVWLFDOUHTXLUHPHQWRQH[FHHGLQJWZRVWDQGDUGHUURUVLVQRWPHWIRUDQ
LVRWRSH ZLWK WKH ORZHVWSHUFHQWDJH$WWKDWWKHPDLQHOHPHQWLVGHWHUPLQHG
UHOLDEO\ 'XH WR WKLV ZH FRQVLGHU WKH DSSHDUDQFH RIVXFKHOHPHQWVLQH[SH
ULPHQWDVUHOLDEOHDQGPDUNWKHPRQEDUFKDUWVZLWKVHSDUDWHVTXDUHV
9'.X]QHWVRYHWDO
0DQ\ PDVV VSHFWUD LQGLFDWH WKH DYDLODELOLW\ RI JROG LQ WKH DVVD\V +RZ
HYHUQHXWURQDFWLYDWLRQDQDO\VLVZLWKDJRRGVHQVLWLYLW\OHYHOd ÂKDV
QRW UHYHDOHG WKLV HOHPHQW LQ DQ\ DVVD\V 2XU DWWHQWLRQ LV GUDZQ WR WKH IDFW
WKDW WKH DSSHDUDQFH RI PDVV LQ VSHFWUD IDLUO\ ZHOO FRLQFLGHV ZLWK WKH
SUHVHQFHRIWDQWDOXPLQDVVD\V7KDWLVZK\ZHFRQVLGHUWDQWDOXPR[LGHWREH
UHVSRQVLEOHIRUWKHDSSHDUDQFHRIPDVVLQVSHFWUD
,QWKHH[SHULPHQW1RWDQWDOXPZDVXVHGDVDORDGDQGZDWHUVHUYHG
DVPHGLXP7KHUHVXOWVRI06DQDO\VLVRIVDPSOHV)LJFDUH
JLYHQLQ7DEOHE)XUWKHULQDOOILJXUHVILOOHGEDUJUDSKVVWDQGIRUWKHVWDWH
DIWHUHOHFWULFH[SORVLRQHIIHFWXQILOOHGEDUJUDSKVWDQGIRUWKHVWDWHEHIRUH
HOHFWULF H[SORVLRQ EDFNJURXQG )LOOHG DQG XQILOOHG VTXDUHV VKRZ WKH OHYHO
RIVHQVLWLYLW\IRUHIIHFWDQGEDFNJURXQGFRUUHVSRQGLQJO\7KHDVVD\FRPSR
VLWLRQ VKRXOG EH FRPSDUHG ZLWK FRPSRVLWLRQ RI 7D ZKLFK LV UHSUHVHQWHG LQ
7DEOHDQG,WLVVHHQWKDWHOHPHQWV1D$O.&D1LKDYHDSSHDUHG7KH
FRQWHQW RI 1D LV HVSHFLDOO\ JUHDW LQ WKHVH DVVD\V DQG ,W FDQ EH
VHHQ WKDW WKH DVVD\ DOVR FRQWDLQV 7L ,WV SUHVHQFH LV OLNHO\ WR KDYH D WULYLDO
H[SODQDWLRQ$VXEVWDQWLDOHQHUJ\UHOHDVHDWFRQWDFWVRIIRLODQGFHQWUDOHOHF
WURGHFDQEHUHOHDVHGDWHOHFWULFH[SORVLRQRZLQJWRWKLVDPDWWHUIURPWLWD
QLXP HOHFWURGH FDQ JHW LQWR VROXWLRQ DUFLQJ EUDNLQJ XS RI D VXEVWDQFH ,Q
WKLV FDVH WKH FRQWHQW RI FHQWUDO HOHFWURGHVXEVWDQFHLQDQDVVD\FDQDPRXQW
WR GR]HQV RI SHUFHQW 1DWXUDOO\ DOO DGPL[WXUHV SUHVHQW LQ WLWDQLXP FDQ JHW
LQWROLTXLGGLHOHFWULFPHGLXP,WVKRXOGEHQRWHGKHUHWKDWWKRXJK)HDQG0Q
DUHSUHVHQWLQWDQWDOXPIRLODQGLQWLWDQLXPHOHFWURGH7DEOHVDQGWKHLU
FRQFHQWUDWLRQ KRZHYHU KDVLQFUHDVHGVXEVWDQWLDOO\,WLVHVSHFLDOO\VHHQIRU
0Q ,W FDQQRW EH H[SODLQHG E\ WULYLDO UHDVRQV $V ZH VKDOO VHH LQ ZKDW IRO
ORZV WKLV LV D UHJXODU HIIHFW 7KHVH DVVD\V ZHUH DOVR LQYHVWLJDWHG E\ PHDQV
RI;)$7DEOH1LDVZHOODV0RDQG3EDUHUHYHDOHGLQWKHVHDVVD\VE\
;)$ WKRXJK LQ VPDOOHU TXDQWLWLHV 7LWDQLXP LVRWRSH FRPSRVLWLRQ LQ WKH
DVVD\LVJLYHQLQ7DEOHD,WFDQEHVHHQWKDWWLWDQLXP LVRWRSHUDWLRFKDQJHG
DQGEHFDPHGLIIHUHQWIURPWKHQDWXUDOLVRWRSHUDWLR 7L 7L 7L 7L
7L >@
,QWKHH[SHULPHQW1RWLWDQLXPZDVXVHGDVDORDGDQGZDWHUVHUYHG
DV PHGLXP 'DWD RQ WKH DVVD\V DQG VKRZ DQLQFUHDVHGFRQWHQW
RI1D6L$J 6Q6E%D7DDSSHDUDQFHRI.&DDQGDGHFUHDVHGFRQWHQW
RI1L7DEOHE7KHFRQWHQWRI1LLQLQLWLDOWLWDQLXPIRLOIRUPHGLQ
WKH DVVD\ ± DQG QR QLFNHO ZDV IRXQG LQ WKH DVVD\ 7KH
;)$ 7DEOH DQG 06DQDO\VLV7DEOHEVKRZDSLFWXUHZKLFKLVVRPH
ZKDWGLIIHUHQW7KHDSSHDUDQFHRI1LLQDVVD\VDQGYDULDWLRQVRILWVTXDQWLW\
FDQEHH[SODLQHGE\WKHLQJUHVVRIWLWDQLXPHOHFWURGHLQWKHDVVD\7KLVFDQ
QRWEHVDLGDERXW0QZKLFK SUHVHQFHLQWKHDVVD\GRHVVXEVWDQWLDOO\H[FHHGV
/RZ(QHUJ\7UDQVPXWDWLRQRI$WRPLF1XFOHLRI&KHPLFDO(OHPHQWV
WKH FRQWHQW RI 0Q LQ IRLO DQG WLWDQLXP HOHFWURGH =LUFRQLXP DQG QLRELXP
7DEOH DUH IRXQG LQ IRLO EXW QRW LQ WKH DVVD\V 7KH ;)$ 7DEOH FRQ
ILUPHG WKH DSSHDUDQFH RI 6Q 6E LQ DVVD\V DQG VKRZHG D SUHVHQFH RI RWKHU
IRUHLJQHOHPHQWVVXFKDV,Q3E7KHDSSHDUDQFHRI6EDQGFRQWHQWLQFUHDVH
RI1D0QLVFRQILUPHGE\DFWLYDWLRQDQDO\VLV7DEOH7KHJDPPDDFWLYD
WLRQDQDO\VLVVKRZHGDSUHVHQFHRIFKORULQHLQWKHDVVD\V
$ FRPSOLFDWHG HOHFWURGH ZLWK LURQ IRLO SODFHG EHWZHHQ WDQWDOXP IRLOV
ZDVXVHGDVORDGLQWKHH[SHULPHQW1R2QHSHUFHQWK\GURJHQSHUR[LGH
ZDWHU VROXWLRQ +2 VHUYHG DV PHGLXP 7KH GDWD RQ WKLV DVVD\ DUH UHSUH
VHQWHG LQ 7DEOHV D DQG $Q 06DQDO\VLV RI LURQ IRLO ZDV QRW FDUULHG RXW
DQGGDWDRQLWVFRPSRVLWLRQDUHWDNHQIURPWKH;)$'HYLDWLRQVLQWKHFRQ
WHQWRIVXFKHOHPHQWVDV&X1EZHUHIRXQGLQWKHDVVD\VE\06$WHFKQLTXH
7KH [UD\ IOXRUHVFHQFH DQDO\VLV VKRZHG D SUHVHQFH RI DQWLPRQ\ LQ DVVD\V
0RUHRYHUWKHDVVD\VDIWHUHOHFWULF H[SORVLRQUHYHDOHGDVXEVWDQWLDOFKDQJHLQ
WKHUDWLRRIQLFNHOLURQDQGPDQJDQHVH7DE
$ FRPSOLFDWHG HOHFWURGH ZLWK OHDG IRLO SODFHG EHWZHHQ WDQWDOXP IRLOV
ZDVXVHGDVORDGLQWKHH[SHULPHQW1R2QHSHUFHQWK\GURJHQSHUR[LGH
ZDWHUVROXWLRQ+2VHUYHGDVPHGLXP7KHUHVXOWVDUHJLYHQLQ7DEOHVD
)LJF )LJD DQG 0DVV VSHFWURPHWULF DQDO\VLV VKRZHG DQ LQ
FUHDVHG FRQWHQW RI 1D 6L . &D )H 1L &X LQ WKH DVVD\V DQG SKRVSKRUXV
ZDVIRXQGLQWKHDVVD\1R+HUHDVXEVWDQWLDOVKLIWLQWKHLVRWRSHUDWLR
IRU 7L XS WR r VKRXOG EH PHQWLRQHG ,W VKRXOG EH VWUHVVHG WKDW 7L
FRXOGDSSHDULQWKHDVVD\DVDUHVXOWRIWKHLQJUHVVRIWLWDQLXPHOHFWURGHLQWR
VXEVWDQFH VROXWLRQ 7KH ;)$ FRQILUPHG DQ LQFUHDVHG FRQWHQW RI 1L DQG UH
YHDOHG DQ LQFUHDVH RI 0Q 6E LQ WKH DVVD\ 7DEOH $FWLYDWLRQ DQDO\VLV
VKRZHG D SUHVHQFH RI FKORULQH DQG DQ LQFUHDVH RI 1D 0Q 6E LQ WKH DVVD\
1R7DEOH
1LFNHO ZDV XVHG DV ORDG LQ H[SHULPHQW 1R DQG ZDWHU VHUYHG DV PH
GLXP 7KH GDWD RQ WKLV H[SHULPHQW DUH VKRZQ LQ 7DEOHV E )LJD DQG )LJE 7KH 06DQDO\VLV VKRZHG DQ LQFUHDVHG FRQWHQW RI DGPL[WXUH HOH
PHQWVLQWKHDVVD\1D6L.&D DQGDSSHDUDQFHRIQHZ± IRUHLJQHOHPHQWV
=U1EDQG$J0RUHRYHUWKH06DQDO\VLVVKRZHGDSUHVHQFHRI 6Q6E%D
DQG7DLQWKLVDVVD\WKHSUHVHQFHRIWKHVHHOHPHQWVLQWKHDVVD\H[FHHGVE\
WZRRUGHUVRIPDJQLWXGHWKHLUSUHVHQFHLQIRLODQGFHQWUDOHOHFWURGHVDPSOHV
7KHDSSHDUDQFHRI$JDQG6EZDVQRWHGLQDOONLQGVRIDQDO\VLV7DEOH
)XUWKHUPRUHWKH;)$DQDO\VLVVKRZHGWKHSUHVHQFHRI<=UDQG3ELQWKH
DVVD\
7LWDQLXP ZDV XVHG DV ORDG LQ WKH H[SHULPHQW 1R DQG RQHSHUFHQW
K\GURJHQ SHUR[LGH ZDWHU VROXWLRQ ZKLFK ZDV SUHYLRXVO\ VDWXUDWHG ZLWK
K\GURJHQDQGKHOLXPVHUYHGDVPHGLXP7KHGDWDDUHFROOHFWHGLQ7DEOHVE
9'.X]QHWVRYHWDO
)LJE DQG 7KH 06DQDO\VLV VKRZHG DQ LQFUHDVHGFRQWHQWRIDGPL[WXUH
HOHPHQWV $O 6L . &D 0Q 1L DQGDSSHDUDQFHRIIRUHLJQHOHPHQWV7DDQG
3E LQ WKH DVVD\ :H KDYH WR QRWH WKDW 7D DQG 3E DUH DEVHQW LQ WKH WLWDQLXP
IRLO DQG HOHFWURGH )XUWKHUPRUH WKH 06DQDO\VLV VKRZHG D SUHVHQFH RI $J
6Q 6E %D LQ WKLV DVVD\ WKH SUHVHQFH RI WKHVH HOHPHQWV H[FHHGV E\ WKUHH
VHYHQ WLPHV WKHLU SUHVHQFH LQ IRLO DQG FHQWUDO HOHFWURGH VDPSOHV 7KH ;)$
DQDO\VLV7DEOHFRQILUPHGWKHDSSHDUDQFHRI6Q6E3EDQGIRXQGDQRWKHU
IRUHLJQ HOHPHQW± \WWULXP 7KH HOHPHQWV &X =Q =U DUH SUHVHQW LQ WLWDQLXP
HOHFWURGHDQGIRLO+RZHYHUWKHDVVD\VKRZHGDQLQFUHDVHGFRQWHQWRIWKHVH
HOHPHQW7DEOHZKDWFDQEHKDUGO\H[SODLQHGE\DQLQJUHVVRIPDWHULDORI
IRLO DQG HOHFWURGH LQ ZDWHU PHGLXP DW HOHFWULF H[SORVLRQ 7KH H[SORVLRQ RI
1D 0Q DQG6ELVFRQILUPHGE\DFWLYDWLRQDQDO\VLV7DEOH&KORULQHZDV
IRXQGLQWKHDVVD\
7LWDQLXP ZDV XVHG DV ORDG LQ H[SHULPHQW 1R DQG ZDWHU VHUYHG DV
PHGLXP 7KH UHVXOWV RI WKH ;)$ DUH JLYHQ LQ 7DEOH )LJF DQG WKH
UHVXOWV RQ DFWLYDWLRQ DUH JLYHQ LQ 7DEOH :H FDQ VHH IURP WKHVH GDWD WKDW
ERWK WHFKQLTXHV \LHOG D VXEVWDQWLDO LQFUHDVH RI 0Q FRQWHQW LQ WKH DVVD\ LI
FRPSDUHG ZLWK LWV SUHVHQFH LQ WLWDQLXP IRLO DQG WLWDQLXP HOHFWURGH $Q LQ
FUHDVHRI1D&X=QLVIRXQGLQWKLVDVVD\DQGDOVRIRUHLJQHOHPHQWVVXFKDV
0R 3E 7DEOH DQG &O DQG 6E 7DEOH DUH GHWHFWHG 7KH[UD\IOXRUHV
FHQFHDQDO\VLVLQWKHHOHPHQWUDQJH,Q± %DZDVQRWFDUULHGRXW
7LWDQLXPZDVXVHG DVORDGLQH[SHULPHQWV1RDQG
JO\FHULQ &+2 VHUYHG DV PHGLXP 7LWDQLXP IRLO 1R ZLWK RWKHU RXWSXW
GDWD GLIIHUHQW IURP WKRVH RI WLWDQLXP IRLO 1R IURP SUHYLRXV H[SHULPHQWV
ZDVXVHGLQWKHVHH[SHULPHQWV7KHGDWDRQWKHH[SHULPHQWVZHUHJDLQHGE\
WKH;)$DQDO\VLVRQO\VHH7DEOHDQG)LJDG7KRXJKVXFKHOHPHQWVDV
0Q)H1L&X=QDUHSUHVHQWLQWLWDQLXPIRLODQGWLWDQLXPHOHFWURGHWKHLU
UHODWLYH FRQWHQW DIWHU HOHFWULF H[SORVLRQ KDV SUDFWLFDOO\ LQFUHDVHG E\ WZR
RUGHUVRIPDJQLWXGH$OOWKHVHH[SHULPHQWVZHUHFDUULHGRXWXQGHUWKHVDPH
FRQGLWLRQVZLWKWKHH[FHSWLRQRIFXUUHQWSXOVHDPSOLWXGHVVXSSOLHGWRORDGV
7KH PD[LPDO FXUUHQW TXDQWLW\ ZDV UHDOL]HG LQ WKH H[SHULPHQW /HW XV
QRWHWKDW3EDSSHDUVDQG0QGLVDSSHDUVLQWKLVH[SHULPHQWVHH)LJD
,QWKHH[SHULPHQWV1RDQGDFRPSRVHGHOHFWURGHZLWKOHDG
IRLOEHWZHHQWDQWDOXPIRLOVZDVXVHGDVDORDG+\GURJHQSHUR[LGHDTXHRXV
VROXWLRQZLWKFRQFHQWUDWLRQVDQGFRUUHVSRQGLQJO\ZDVXVHGDV
PHGLXP7KH06$GDWDDUHJLYHQLQ7DEOHE)LJDQGGDWDJDLQHGE\
PHDQVRI;)$DQGDFWLYDWLRQDQDO\VLV± LQ7DEOHVDQG7KHVHWHVWVVKRZ
WKDW H[SHULPHQWV SURYLGH IRU D JRRG UHVXOWV UHSHWLWLRQ 0DVV VSHFWURPHWULF
DQDO\VLVVKRZHGDQLQFUHDVHGFRQWHQWRI1D$O6L.&D)H1L&XLQWKH
DVVD\V %RWK ;)$ 7DEOH DQG 1$$ VKRZDFRQVLGHUDEOHLQFUHDVHRI0Q
/RZ(QHUJ\7UDQVPXWDWLRQRI$WRPLF1XFOHLRI&KHPLFDO(OHPHQWV
LQWKHVHDVVD\V%HVLGHVWKDWIRUHLJQHOHPHQWV&O7DEOHDQG6E7DEOHV
DSSHDU LQ WKHVH DVVD\V 7KH DGPL[WXUH LQFUHDVH RI 1D DQG DSSHDUDQFH RI
6ELVFRQILUPHGE\DFWLYDWLRQDQDO\VLV
7DEOHZ,VRWRSHFRPSRVLWLRQRIWKHWLWDQSUHVHQWLQVDPSOHV06$PDVV
7L7L7L7L7L 6DPSOH ,VRWRSH
7L 7L 7L 7L 7L 7DEOHE(OHPHQWVFRPSRVLWLRQRIVDPSOHV06$PDVV
VDPSOH
HOHPHQW
1D
$O
6L
3
.
&D
7L
0Q
)H
1L
&X
=Q
=U
1E
0R
$J
6Q
6E
%D
7D
$X
3E
q
q
q
q
q
q
q
q
q
q
q
q
q
q
9'.X]QHWVRYHWDO
7DEOHZ,VRWRSHFRPSRVLWLRQRIWKHWLWDQSUHVHQWLQVDPSOHV06$PDVV
7L7L7L7L7L 6DPSOH
,VRWRSH
7L
7L
7L
7L
7L
7DEOHE(OHPHQWVFRPSRVLWLRQRIVDPSOHV06$PDVV
VDPSOH
HOHPHQW
1D
$O
6L
.
&D
7L
&U
0Q
)H
&R
1L
&X
=Q
=U
$V
1E
0R
$J
6Q
6E
%D
7D
:
$X
3E
IRLO
7L
/RZ(QHUJ\7UDQVPXWDWLRQRI$WRPLF1XFOHLRI&KHPLFDO(OHPHQWV
7DEOH(OHPHQWVFRPSRVLWLRQRIVDPSOHVRIIRLOV06$PDVV
VDPSOH
HOHPHQW
1D
$O
6L
.
&D
7L
9
&U
0Q
)H
&R
1L
&X
$V
1E
0R
$J
6Q
6E
%D
7D
:
$X
3E
7L
7D
3E
!
!
1L
9'.X]QHWVRYHWDO
7DEOH(OHPHQWVFRPSRVLWLRQRIVDPSOHV;)$PDVV7LLQ+2+H+DQG+2
PJo
7L
0Q
)H
1L
&X
=Q
<
=U
1E
0R
,Q
6Q
6E
3E
)RLO
7L
d
d
d
d
d
d
d
d
)RLO7L
PJo
7L
0Q
)H
1L
&X
=Q
<
=U
1E
,Q
6Q
6E
3E
d
d
d
d
d
d
d
7L
HOHFWURGH
d
d
d
d
d
d
d
7L
HOHFWURGH
d
d
d
d
d
d
+2
+H+
GLVWLOOHGZDWHU
GLVWLOOHGZDWHU
7KHUHVXOWUHFHLYHGE\WKHQHXWURQDFWLYDWLRQDQDO\VLV
/RZ(QHUJ\7UDQVPXWDWLRQRI$WRPLF1XFOHLRI&KHPLFDO(OHPHQWV
7DEOH(OHPHQWVFRPSRVLWLRQRIVDPSOHV;)$PDVV7LLQJO\FHULQ
VDPSOH )RLO7L 7LHOHF
HOHPHQW
WURGH
7L
0Q
d ¹ )H
1L
&X
=Q
=U
1E
3E
d d
&X=Q &X=Q
7KHUHVXOWUHFHLYHGE\WKHQHXWURQDFWLYDWLRQDQDO\VLV
&X=Q
7DEOH(OHPHQWVFRPSRVLWLRQRIVDPSOHV;)$PDVV7D)H1LLQ+2 7L
0Q
)H
1L
&X
=Q
=U
1E
0R
6E
7D
7DIRLO
)H1LIRLO
d
d
d
d
7L
HOHWURGH
d
d
7KHUHVXOWUHFHLYHGE\WKHQHXWURQDFWLYDWLRQDQDO\VLV
7KHUHVXOWUHFHLYHGE\WKHJDPPDDFWLYDWLRQDQDO\VLV
7KHUHVXOWUHFHLYHGE\PDVVVSHFWURPHWULFDQDO\VLV
9'.X]QHWVRYHWDO
7DEOH(OHPHQWVFRPSRVLWLRQRIVDPSOHV;)$PDVV7DLQ+2DQG7D3ELQ
+2
7D
IRLO
3E
IRLO
7L
0Q d d
)H 1L d
&X
=Q
=U
1E 0R d
d
6E d d
7D 3E
7D
IRLO
3E
IRLO
7L
0Q d d
)H 1L d
&X
=Q
=U
1E 0R d
d
6E d d
7D 3E
7L
HOHFWURGH
d
d
7L
HOHFWURGH
d
d
+2
QXPEHURIVDPSOHV
+2 LQ
+2
QXPEHURIVDPSOHV+2 LQ
7KHUHVXOWUHFHLYHGE\WKHQHXWURQDFWLYDWLRQDQDO\VLV
7KHUHVXOWUHFHLYHGE\WKHJDPPDDFWLYDWLRQDQDO\VLV
7KHUHVXOWUHFHLYHGE\PDVVVSHFWURPHWULFDQDO\VLV
/RZ(QHUJ\7UDQVPXWDWLRQRI$WRPLF1XFOHLRI&KHPLFDO(OHPHQWV
7DEOH (OHPHQWV FRPSRVLWLRQ RI VDPSOHV UHFHLYHG E\ WKH QHXWURQ DQG JDPPD
DFWLYDWLRQDQDO\VLVJJ
VDPSOH
PJo
$OQJ
7L 7L 7LHO
d
d
1DQJ
d
d
d
&OJQ d d d 0QQJ d 6EQJ
6EJQ
NH9
6EJQ
NH9
VDPSOH
PJo
$OQJ
d
d
d
d
7LHO
7D
3E
d d 1DQJ
d d d
&OJQ d d
0QQJ
d
d
6EQJ
d
d d
6EJQ
d d NH9
6EJQ
NH9
0HDVXUHPHQWVZHUHFDUULHGDIWHUPDVVVSHFWURPHWULFDQDO\VLVWKHVDPSOHZDV
FOHDQHGRIIIURPDQDOXPLQLXPVXEVWUDWH
9'.X]QHWVRYHWDO
7DEOH(OHPHQWVFRPSRVLWLRQRIVDPSOHUHFHLYHGE\WKHGLIIHUHQWPHWKRGV
RIDQDO\VLV1LLQGLVWLOOHGZDWHU
7L
;)$ 0&$ 1$$ *$$ 0Q
)H
1L
&X
<
=U
$J
6E
%D
3E
d DFWLYDWLRQZDVFDUULHGDIWHUF6:WKHVDPSOHZDVFOHDQHGRIIIURPDQ$OVXEVWUDWH
7DEOH7KHFRQWHQWRIDGPL[WXUHVLQ
ZDWHU
(OHPHQW
$O
6L
.
&D
7L
0Q
)H
&R
1L
&X
=Q
&G
3E
$EXQGDQFHJJ
7DEOH7KHFRQWHQWRIDGPL[WXUHV
LQJO\FHULQ&+2
(OHPHQW
&O
6
)H
$V
3E
$EXQGDQFH
JJ
7DEOH7KHFRQWHQWRIDGPL[WXUHV
LQSRO\HWK\OHQH
(OHPHQW
&
)
1D
0J
$O
6L
3
6
&O
.
&D
7L
9
&U
0Q
)H
&R
1L
&X
=Q
6U
%D
$EXQGDQFH
ZHLJKW
/RZ(QHUJ\7UDQVPXWDWLRQRI$WRPLF1XFOHLRI&KHPLFDO(OHPHQWV
Ni
Ti Fe
Concentration
0
10
-1
10
-2
10
-3
10
-4
10
-5
10
-6
10
-7
10
K
20
Concentration
Na Al Si
Concentration
Ca
K
40
30
Si
Ca
K
Nb
Mo
40
80
Ta
TaO Pb
In
50
60
70
80
Ta
Fe
Mn Ni
Ag
Zr
20
70
Ag SnSb Ba
Cu
Zn
10
60
c) Sample 662-7, Ta in H 2O
Ti
Na
Al
50
Pb
b) Sample 415, Ti in H 2O2 1%
Fe
Ni
Mn
Cu
Zn
20
Ta W TaO
In
Zr
0
10
-1
10
-2
10
-3
10
-4
10
-5
10
-6
10
-7
10
30
Ti
0
10
Sn
Sb Ba
Zr
As
Zn
10
10
-1
10
-2
10
-3
10
-4
10
-5
10
-6
10
-7
10
Cu
Ca
Na
a) Sample 453, Ni in H 2O
Mo
Ag
Nb
Mn
Si
Al
30
TaO
Sn
Sb Ba
Pb
Nb
In
Mo
40
50
Z elements
60
70
80
)LJ(OHPHQWFRPSRVLWLRQRIVDPSOHVPHDVXUHGE\06$WHFKQLTXHDVDP
SOHORDG± 1LGLVWLOOHGZDWHUDVPHGLXPEVDPSOHORDG±7LPHGLXP
± +2FVDPSOHORDG± 7DGLVWLOOHGZDWHUDVPHGLXP
Concentration
9'.X]QHWVRYHWDO
a) Sample 670-8, Ta+Pb in H2O2 10%
1
Ti
-1
10
-2
10
-3
10
-4
10
-5
10
-6
10
-7
10
AlSi
Na
Ca
Fe Ni
K
Mn
Ag
30
In
Nb
Zr
20
TaO
Sn Sb Ba
Cu
Zn
10
Pb
Ta
Mo
40
50
60
70
80
Concentration
b) Sample 669-4, Ta+Pb in H2O2 3%
1
10
-2
10
-3
10
-4
10
-5
10
-6
10
-7
10
Pb
Ta
Ti
-1
Si
Al
Na
Fe Ni
Ca
K
Mn
Ag
30
In
Nb
Zr
20
TaO
Sb Ba
Cu
Zn
10
Sn
Mo
40
50
60
70
80
Concentration
c) Sample 666-1, Ta+Pb in H2O2 1%
1
Na
Pb
Ta
Ti
-1
10
-2
10
-3
10
-4
10
-5
10
-6
10
-7
10
Al Si
Ca
K
Fe Ni
Cu
Mn
Ag Sn Sb Ba
Zn
Zr
10
20
30
Nb
Mo
40
TaO
In
50
Z elements
60
70
80
)LJ (OHPHQW FRPSRVLWLRQ RI VDPSOHV PHDVXUHG E\ 06$ WHFKQLTXH D
VDPSOHORDG±7D3EPHGLXP+2 EVDPSOHORDG± 7D3E
PHGLXP± +2FVDPSOHORDG± 7D3EPHGLXP +2
/RZ(QHUJ\7UDQVPXWDWLRQRI$WRPLF1XFOHLRI&KHPLFDO(OHPHQWV
Concentration
1
10
-1
10
-2
10
-3
10
-4
10
-5
10
-6
10
-7
Cu
Concentration
10
-2
10
-3
10
-4
10
-5
10
-6
10
-7
Sb
Concentration
10
-2
10
-3
10
-4
10
-5
10
-6
10
-7
20
30
Ti Fe
40
50
60
70
80
Ni
b)Sample 453 Ni in H2O
Mo
Cu
Ag
Zr
W
Sb Ba
As Y
Pb
Na
1
-1
Mo
Zr
10
10
Nb
Zn
1
-1
Ta Pb
Fe
10
10
a) Sample 666-1 Ta+Pb in H2O2 1%
Ti
20
30
40
50
60
70
80
Ti
c)Sample 414 Ti in H2O
Fe Cu
Zn
Mo
Pb
Sn
Sb
Zr
10
20
30
40
50
Z elements
60
70
80
)LJ (OHPHQW FRPSRVLWLRQ RI VDPSOHV PHDVXUHG E\ ;)$ WHFKQLTXH D VDPSOH
ORDG± 7D3EPHGLXP +2 EVDPSOHORDG± 1LGLVWLOOHGZDWHUDV
PHGLXP FVDPSOHORDG± 7LGLVWLOOHGZDWHUDVPHGLXP
9'.X]QHWVRYHWDO
Concentration
0
10
-1
10
-2
10
-3
10
-4
10
-5
10
-6
10
-7
10
Ti
Pb
Zr Nb
10
0
Concentration
a) Sample 660 Ti in glicerin
FeNi Cu
Zn
Mn
20
30
40
Ti
10
-1
10
-2
10
-3
10
-4
10
-5
10
-6
10
-7
10
50
60
70
b) Sample 661 Ti in glicerin
FeNi Cu
Mn
Zn
Zr Nb
10
20
30
80
40
Pb
50
60
70
80
Concentration
0
10
-1
10
-2
10
-3
10
-4
10
-5
10
-6
10
-7
10
Ti
Zr Nb
10
0
Concentration
c) Sample 664 Ti in glicerin
Fe
Mn Ni Cu
Zn
20
Ti
10
-1
10
-2
10
-3
10
-4
10
-5
10
-6
10
-7
10
30
40
Fe
Pb
50
60
70
80
d) Sample 671-7 Ti in glicerin
Mn Ni Cu
Zn
Zr Nb
Pb
10
20
30
40
50
Z elements
60
70
80
)LJ(OHPHQWFRPSRVLWLRQRIVDPSOHVPHDVXUHGE\;)$WHFKQLTXHPHGLXP ±
JO\FHULQORDG±7LDVDPSOHEVDPSOHFVDPSOHGVDPSOH
/RZ(QHUJ\7UDQVPXWDWLRQRI$WRPLF1XFOHLRI&KHPLFDO(OHPHQWV
5HIHUHQFHV
>@ Urutskoev L.I., Liksonov V.I., Tsinoev V.G., Applied physics (J.of Russia), 4,
>@ Solin M.I., Physical idea of Russia, 1, 43-58, (2001)
>@ Kladov •., Nuclear reactions in the cavitation bubble. 13th Radiochemical
83-100, (2000); Annales Fondation Louis de Broglie, v.27, 4, 701-726, (2002)
>@
>@
>@
>@
>@
>@
Conference. 19-24th April 1998, Marianske Lazne Jachymov, Czech Republic.
Booklet of Abstracts.
Kladov •., Cavitation destruction of a matter: energy balance during the
th
cavitation destruction of pentachlorophenol. 21 International Symposium
“Industrial Texicology-2001”.Proceedings,.May 30-June 1, 2001, Bratislava,
Slovak Republic
Kladov •., Destruction of radioactive wastes by using experimental highth
intensity ultrasonic technology. 5 International Conference on Nuclear and
Radiochemistry. Pontresina, Switzerland, September 3-8, (2000), Extended
Abstracts, Vol.1
Kladov •., Cavitation destruction of matter, KWWSURVORQDURGUXUDRUDRKWP
Nemets O.F., Gofman Yu.V., Reference book on nuclear physics. Kiev,
Naukova dumka, (1975)
Landau L.D., Lifshitz E.M.. Qauntum mechanics. Nonrelativistic theory,
Moscow, Science, (1974)
Babichev A.P. et al. Physical quantities. Reference book, Moscow.
Energoatomizdat, (1991)
0DQXVFULWUHoXOHDYULO
© Copyright 2026 Paperzz