hydrocarbon molecules are ârearranged/rebuildedâ into high octane gasoline .... reduce the vapor pressure of gasoline primarily strained some refiner's octane.
! "#$%&'
( ( %
)*+) #),-'
+ * $
. /
0
),- $%& 1
1
% 2 "
)
3 +4 5 5 #3455 +- 3'
! "
! " # $ !% ! & $ ' ' ($ ' # % % ) %* %' $ ' + " % & ' ! # $, ( $ - . ! "- ( %
. % % % % $ $ $ - -
- - // $$$ 0 1"1"#23."
4& )*5/ +) * !6 !& 7!8%779:9& % ) 2 ; ! * & /- 4& )*5/ +) "3 " & :=9>
$SURVSHFWLYHRQSURGXFWLRQRISHWUROHXPOLTXLGWUDQVSRUWDWLRQIXHOVUHFHQW DGYDQFHVLQKHWHURJHQHRXVFDWDO\VWVFKHPLVWU\WHFKQRORJLFDOVWDWXVDQG FKDOOHQJHV )$:=,0(/)*+, (QYLURPHQWDO(QJLQHHULQJDQG*UHHQ7HFKQRORJ\((*7 0DOD\VLD-DSDQ,QWHUQDWLRQDO,QVWLWXWHRI7HFKQRORJ\0-,,7 8QLYHUVLWL7HNQRORJL0DOD\VLD870 0$5&+
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
ii
7$%/(2)&217(176 &+$37(5 7,7/(
3$*(
$%675$&7
LL
7$%/(2)&217(176
LLL
/,672)7$%/(6
YL
/,672)),*85(6
YLLL
/,672)$%%5(9,$7,216
[
,1752'8&7,21
2LO3URSHUWLHV'HPDQGVDQG&RQVXPSWLRQV
3HWUROHXPDQGWKH(QHUJ\
3UREOHP6WDWHPHQW
+\SRWKHVHV
/,7(5$785(5(9,(:
7UDQVSRUWDWLRQ)XHOVDQGWKH1HZ7UHQGV
&DWDO\WLF1DSKWKD5HIRUPLQJ&15
5HVHDUFK2FWDQH1XPEHU521
iii
*DVROLQH3URGXFWLRQDQG
&RQVXPSWLRQ
0DMRU5HIRUPLQJ5HDFWLRQV
*DVROLQHDQGWKH(QYLURQPHQW
5HIRUPLQJ&DWDO\VWV
5HIRUPLQJ&DWDO\VW6XSSRUWV
'HYHORSPHQWRI5HIRUPLQJ&DWDO\VWV
+\GURWUHDWPHQW3URFHVVHV
+\GURGHVXOIXUL]DWLRQ3URFHVV+'6
6XOIXUDQGWKH(QYLURQPHQW
7\SHVRI6XOIXU&RPSRXQGV
+'65HDFWLYLW\RI6XOIXU&RPSRXQGV
+'65HDFWLRQ3DWKZD\VRI'LIIHUHQW
7LQ6Q
(IIHFWRI2SHUDWLQJ&RQGLWLRQV
6XOIXU&RPSRXQGV
7KLRSKHQHV
'LEHQ]RWKLRSKHQH'%7
DQG7KHLU$ON\O'HULYDWLYHV
(IIHFWRIVXOSKLGDWLRQSURFHVV
(IIHFWRI2SHUDWLQJ&RQGLWLRQV
(IIHFWRI)HHGVWRFN
+\GURGHVXOIXUL]DWLRQ&DWDO\VWV
iv
&R1L0R%LPHWDOOLF+'6 6XSSRUWHG&DWDO\VWV
$YDLODEOH5RXWHVIRU8/6'
9DU\LQJRI+'66XSSRUW
0L[HGRI'LIIHUHQW2[LGHV
=HROLWHV
0L[HG
'HYHORSLQJRI$OWHUQDWLYH
DQG
=HROLWHV
0HWKRGVDQG
7HFKQRORJLHV
7ULPHWDOOLF+'6&DWDO\VW
+'61(%8/$&DWDO\VW
2SWLPL]DWLRQRI2SHUDWLQJ
&RQGLWLRQVRI+'6
3URFHVV
+\SRWKHVHVLQILQGLQJVROXWLRQV
&21&/86,216$1'5(&20(1'$7,216
&RQFOXVLRQV
5HFRPPHQGDWLRQVDQG)XWXUH:RUN
5()(5(1&(6 v
/,672)7$%/(6 7$%/(12
7,7/(
3$*(
:RUOGHQHUJ\FRQVXPSWLRQE\IXHOW\SHFXUUHQWDQG
IRUHFDVW 4XDGULOOLRQ
&KDUDFWHULVWLFVRI3HWUROHXP7UDQVSRUWDWLRQ)XHOV
2LOV
5HJLRQDO0DUNHWVIRU*DVROLQH
0DLQ([KDXVW*DV&RQWDPLQDQWVDQG7KHLU(IIHFWV
5RVVLQL
'LIIHUHQW+\GURWUHDWPHQW8QLW2SHUDWLRQV([LVWLQWKH
2LO5HILQHU\6RQJet al.,
&RPPHUFLDO7HFKQRORJLHVRI+'62SHUDWLRQ$QWDOII\ et al
7\SLFDO +\GURGHVXOIXUL]DWLRQ 2SHUDWLQJ &RQGLWLRQV 8VHGLQ,QGXVWU\
86(3$VXOIXUUXOHVIRUKLJKZD\DQGQRQURDGGLHVHO
6WDQGDUGVVSHFLILFDWLRQIRU'LHVHOIXHOIRUWKH/DVW
7\SHVRI2UJDQLF6XOIXU&RQWDLQLQJ&RPSRXQGVLQ
DQG&RPLQJ'%7@GW
40
K1KDBTKH2PDBTPH2
(1+KDBTPDBT+KprodPprod)(1+KH2P H2)
%URGHULFN et al. ZHUH DOVR SURSRVHG WKH UHDFWLRQ UDWH HTXDWLRQV 7KH UDWH HTXDWLRQIRUK\GURJHQRO\VLVUHDFWLRQFRUUHVSRQGWRD/DQJPXLU±+LQVKHOZRRGPHFKDQLVP WKHOLPLWLQJVWHSRIUHDFWLRQUDWHEHLQJWKHVXUIDFHUHDFWLRQEHWZHHQDGVRUEHGK\GURJHQRQ RQHWKHFDWDO\VWVLWHZLWK'%7DGVRUEHGRQDQRWKHUVLWH,QDVLPLODUZD\WRWKLRSKHQHDQG EHQ]RWKLRSKHQHUDWHVKRZHYHUWKHUDWHRIGLEHQ]RWKLRSKHQH+'6UHDFWLRQLVLQKLELWHGE\ WKHUHDFWDQWVFRPSRQHQWVDQGE\+67KHUDWHHTXDWLRQVVWDWHGDV(TXDWLRQDQG DUHVLPLODUWRWKRVHIRUWKLRSKHQHDQGEHQ]RWKLRSKHQHDQGWKHVHFDQEHVHHQEHORZ 'LEHQ]RWKLRSKHQHK\GURJHQRO\VLV
(2.3)
'LEHQ]RWKLRSKHQHK\GURJHQDWLRQ
(2.4)
ZKHUH '%7 UHSUHVHQWV GLEHQ]RWKLRSKHQH DV D PRGHO FRPSRXQG N LV WKH UDWH FRQVWDQW IRU GLEHQ]RWKLRSKHQH K\GURJHQRO\VLV UHDFWLRQ PROJ RI FDWDO\VW Ví .'%7 UHSUHVHQWV WKH DGVRUSWLRQ SDUDPHWHU IRU '%7 DWPí &'%7 LV WKH FRYHUDJH RI '%7 RQ FDWDO\VWVXUIDFH&+WKHFRYHUDJHRI+RQWKHVXUIDFHRIWKHFDWDO\VW.+6WKHDGVRUSWLRQ SDUDPHWHU IRU +6 DWPí &+6 WKH FRYHUDJH RI +6 RQ WKH FDWDO\VW VXUIDFH N WKH UDWH FRQVWDQWIRU'%7K\GURJHQDWLRQPROJRIFDWDO\VWVí . '%7WKHDGVRUSWLRQSDUDPHWHUIRU '%7 LQ '%7 K\GURJHQDWLRQ DWPí DQG . + WKH DGVRUSWLRQ SDUDPHWHU IRU + LQ '%7 K\GURJHQDWLRQDWPí
41
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et al. ,QDFRPSDULVRQVWXG\EHWZHHQWZRIRUPVRIOLTXLGSKDVHVXOILGLQJSURFHGXUHVWKH REWDLQHGK\GURWUHDWLQJFDWDO\VWZKLFKVXOSKLGLHGZLWKWKHVSLNHGDJHQWRQHKDVUHYHDOHGWR DWWDLQ PD[LPXP DFWLYLW\ ±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et al.
42
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et al.,6RQJet al.,
43
,Q DGGLWLRQV DQRWKHU FULWLFDO VLWXDWLRQ ZLOO EH H[LVW LI QHZ SK\VLFDO SURSHUWLHV VSHFLILFDWLRQV OLNH GHQVLW\ SRO\DURPDWLF FRQWHQW DQG &HWDQH QXPEHU IRU WKH GLHVHO SURGXFWV DUH LQWURGXFHG DQ\ RI WKHVH FRXOG PDNH LW PRUH GLIILFXOW IRU WKH UHILQHULHV WR DFKLHYH OHVV WKDQ WKH SSPZW VXOIXU VSHFLILFDWLRQ *HQHUDOO\ LW LV RSWLPDO WR DWWDLQ WKH QHZ IXHO VSHFLILFDWLRQV E\ WDNLQJ LQWR FRQVLGHUDWLRQ ERWK FDWDO\VW DQG SURFHVV LVVXHV 7RSV¡H et al :KLWHKXUVW et al., $FFRUGLQJ WR WKH DERYH IDFW GHHS XQGHUVWDQGLQJ RI +'6 UHDFWLRQ PHFKDQLVP LV H[WUHPHO\ UHTXLUHG DQG LW ZLOO EH YHU\ LQIRUPDWLYHUHJDUGLQJWKHLPSURYHPHQWRI+'6FDWDO\WLFSHUIRUPDQFH 7DEOH5HTXLUHG,QFUHDVHLQ&DWDO\VW$FWLYLW\DQG5HDFWRU7HPSHUDWXUHIRU8/+'6 &RQFHQWUDWLRQRIVXOIXULQ
&DWDO\VWDFWLYLW\
LQFUHDVHLQUHDFWRU
3URGXFWSSPZW
WHPSHUDWXUHR&
D
SSPZWLVFKRVHQDVWKHEDVHFDVHDQG/+69LVNHSWFRQVWDQW7KHGDWDDUHIRUD
W\SLFDO&R±0RFDWDO\VW
44
)LJXUH5HODWLYH9ROXPHRI&DWDO\VW%HG5HTXLUHGIRU$WWDLQLQJ/RZ/HYHOVRI'LHVHO 6XOIXU8VLQJ&RQYHQWLRQDO+'6FDWDO\VW6RQJDQG;0D (IIHFWRI)HHGVWRFN 2QHRIWKHPRVWHIIHFWLYHYDULDEOHVXSRQWKH+'6UHDFWLRQUDWHLVWKHQDWXUHRIWKH PRGHO UHDFWDQW FRPSRXQG VROYHQW 'LIIHUHQW W\SHV RI PRGHO K\GURFDUERQ FRPSRXQGV 6ROYHQWV\VWHPV KDYHEHHQIRXQGWRDIIHFWWKHUDWHRIUHDFWLRQ.DEHet al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
+RZHYHU WKLV SKHQRPHQRQ OHDGV WR WKH IDFW WKDW FRPSDUDWLYH VWXGLHV RI +'6 RI %7 DQG '%7FDUULHGRXWLQGLIIHUHQWPRGHOK\GURFDUERQFRPSRXQGVFDQQRWEHGLUHFWO\FRPSDUHG XQOHVVWKHHIIHFWRIWKHVXOIXUPRGHOFRPSRXQGW\SHPXVWEHWDNHQLQWRDFFRXQW.DEHet al. SHUIRUPHG D VXEVHTXHQW VWXG\ RI +'6 RI KLQGHUHG '%7V ,Q WKLV VWXG\ &R 0R$O2 FDWDO\VWV ZHUH DOVR HPSOR\HG YLD D FRPSOH[ UHDO FRPSRXQG UDZ OLJKW RLO IHHGVWRFN KRZHYHUWKHUHDFWLRQRSHUDWLQJFRQGLWLRQVZDVVLPLODUWRLQGXVWU\H[SORLWDWLRQ LH EDU ± R& +RZHYHU LW LV REYLRXV WKDW VRPH FRPSRXQGV DUH SDUWLFXODUO\ IOH[LEOHZLWKUHVSHFWWR+'62QWKHRWKHUKDQGVRPHRIWKHPDUHQRWUHVLOLHQWSDUWLFXODUO\ XQUHDFWLYH DUH 0'%7 DQG '0'%7 VXEVWLWXWHG '%7V +RZHYHU +LV LQVSHFWLRQ ZDVOHGWKDWWKH+'6UHDFWLYLW\GHFUHDVHVLQWKHRUGHU'%7!0'%7!'0'%7
Retention time (min) )LJXUH*&3URILOHRI5HDO)HHG6WRFN/LJKW*DV2LO .DEHet al.,
46
Remaining Amount of Sulfur DBT % Temperature, oC
)LJXUH &KDQJHV ,Q 5HPDLQLQJ $PRXQW RI 6XOIXU ,Q 'LEHQ]RWKLRSKHQHV :LWK 7HPSHUDWXUH
0HWK\OGLEHQ]RWKLRSKHQH 2WKHU
'LPHWK\OGLEHQ]RWKLRSKHQH
&'LEHQ]RWKLRSKHQHV
2WKHU&'LEHQ]RWKLRSKHQHV6RQJ
,QGHHG WKLV IDFW LV LQ D JRRG DJUHHPHQW ZLWK WKH SUHYLRXV VWXGLHV SHUIRUPHG E\ +RXDOODet al,QDGGLWLRQ+'6UHDFWLRQVLQDEDWFKDXWRFODYHUHDFWRUIRUDYDULHW\RI VXOIXUFRQWDLQLQJFRPSRXQGVZHUHFDUULHGRXWE\0Det al.+RZHYHUWKHPDMRULW\RI WKH VXOIXU FRQWDLQLQJ FRPSRXQGV ZDV DON\O %7 RU DON\O '%7 +H DQG KLV FRZRUNHUV FRQFOXGHGWKDW0'%7DQG'0'%7ZHUHWKHPRVWGLIILFXOWUHIUDFWRU\FRPSRXQGVWR GHVXOIXUL]H +\GURGHVXOIXUL]DWLRQ&DWDO\VWV 7KH FDWDO\VW GHYHORSPHQW KDV EHHQ RQH RI WKH IRFXVHV RI LQGXVWULDO UHVHDUFK DQG GHYHORSPHQWIRUGHHS+'66KLIOHWWDQG.UHQ]NH )RUH[DPSOHQHZDQGLPSURYHG FDWDO\VWV KDYH EHHQ GHYHORSHG DQG PDUNHWHG E\ &ULWHULRQ $N]R 1REHO ,)3 +DOGRU 47
7RSVRH 8QLWHG &DWDO\VW6XG&KHPLH ([[RQ0RELO $GYDQFHG 5HILQLQJ 1LSSRQ .HWMHQ LQ -DSDQDQG5,33LQ&KLQD$N]R1REHOKDVGHYHORSHGDQGFRPPHUFLDOL]HGYDULRXVW\SHV RIFDWDO\VWVWKDWFDQEHXVHGIRU+'6RIGLHVHOIHHG.).)DQG.)DQG.) $N]R 1REHO .) FDQ EH FRQVLGHUHG WR EH W\SLFDO RI DQ $N]R 1REHO FDWDO\VW .) LV D &R±0R FDWDO\VW ZLWK KLJK +'6 DFWLYLW\ LW ZDV MRLQWO\ GHYHORSHG E\ $N]R 1REHO DQG ([[RQ 5HVHDUFK DQG (QJLQHHULQJ E\ DSSO\LQJ D QHZ DOXPLQDEDVHG FDUULHU WHFKQRORJ\ DQG D VSHFLDO SURPRWHU LPSUHJQDWLRQ WHFKQLTXH WR DOORZ KLJK DQG XQLIRUPGLVSHUVLRQRIPHWDOV 0RO\EGHQXPVXOILGH0R6 SURPRWHGZLWK&REDOWVXOILGH&R6 SURGXFLQJZKDWLV FDOOHGFREDOWPRO\EGHQXP&R0R WKLVELPHWDOOLFFDWDO\VWXVXDOO\VXSSRUWHGRQDOXPLQD LV WKH PRVW ZLGHO\ XVHG FDWDO\VW LQ K\GURWUHDWLQJ SURFHVV IRU K\GURGHVXOSKXUL]DWLRQ UHDFWLRQV+'6:KLWHKXUVWet al., 2QWKHRWKHUKDQG1LFNHOPRO\EGHQXP1L0R ELPHWDOOLF
FDWDO\VW
LV
XVHG
IRU
K\GURGHQLWURJHQDWLRQ
+'1
DV
ZHOO
DV
K\GURGHVXOSKXUL]DWLRQ SURFHVV 7KLV FDWDO\WLF V\VWHP LV YHU\ G\QDPLF DQG IOH[LEOH ,W GHYHORSV DQG UHVWUXFWXUHV GXULQJ LWV HQWLUH OLIH F\FOH LQLWLDOO\ IURP WKH R[LGH IRUP GXULQJ SUHSDUDWLRQ VWHS RYHU WKH VXOILGHV GXULQJ DFWLYDWLRQ SURFHGXUH DQG XQGHU UHDFWLRQ FRQGLWLRQV XS WR LWV UHWXUQ WR WKH R[LGH IRUP GXULQJ UHJHQHUDWLRQ SURFHVV 7RSV¡H et al., :KLWHKXUVWet al., +RZHYHU WKH HPSOR\PHQW RI &R±0R 1L±0R DQG 1L±&R±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
48
7KHDFWLYLW\DQGVHOHFWLYLW\RIWKHVHFDWDO\VWVKDYHEHHQLPSURYHGFRQVLGHUDEO\GXH
WR FRQWLQXRXV UHVHDUFK DQG GHYHORSPHQW LQ UHVHDUFK LQVWLWXWLRQV DQG FDWDO\VWV DQG SHWUROHXPUHILQHUFRPSDQLHVZRUOGZLGH+RZHYHU7KHSUHFLVHRIWKHDFWLYHVLWHVQDWXUHLQ &R±0RRU1L±0RFDWDO\VWVV\VWHPLVVWLOODVXEMHFWRIGLVFXVVEXWWKH&R0R6RU1L0R 6 PRGHO IRU 1L0R FDWDO\VW LV QRZ WKH PRVW ZLGHO\ XVHG ZLWK YDULRXV PRGLILFDWLRQV YLD GLIIHUHQWDGGLWLYHVVXFKDVERURQRUSKRVSKRUXVRUVLOLFDRUE\XVLQJPRUHSURPRWHUVHJ 1L±&R±0R$O2 RUE\HPSOR\LQJDQLPSURYHGSUHSDUDWLRQPHWKRGV7RSVRHet al., 3ULQV &R1L0R%LPHWDOOLF+'66XSSRUWHG&DWDO\VWV &RPSDULVRQ RI &R0R$O2 DQG 1L0R$O2 FDWDO\VWV ZKLFK LV WKH PRVW ZLGHO\ XVHG FDWDO\VW LQ WKH UHILQHU ZRUOGZLGH KDV EHHQ ZLGHO\ LQYHVWLJDWHG $ GLUHFW FRPSDULVRQ VWXG\ SHUIRUPHG E\ 0D et al. RQ WKH UHDFWLRQ SDWKZD\V RI WKH WZR FDWDO\VWV +RZHYHU'0'%7ZDVIRXQGWREHWKHOHDVWUHDFWLYHVXEVWUDWHRQERWKFDWDO\VWVEXW 1L0R$O2 H[KLELWHG KLJKHU +'6 DFWLYLW\ IRU '0'%7 WKDQ &R0R$O2 7KLV IDFW ZDV DWWULEXWHG WR WKH RZQLQJ RI KLJK K\GURJHQDWLRQ DFWLYLW\ RI 1L0R$O2 FDWDO\VWV 7KH +\GURJHQDWLRQ UHDFWLRQ RI WKH DURPDWLF ULQJV ZDV FRQVLGHUHG WR DVVXDJH WKH VWULFW KLQGUDQFH HQFRXQWHUHG LQ WKH +'6 RI '0'%7 WKLV SKHQRPHQRQ ZDV FRQVLGHUHG WR EH WKH UHDVRQ IRU LWV ORZ UHDFWLYLW\ ,VRGD et al., +RZHYHU ,W ZDV GHWHUPLQHG WKDW RI WKH +'6 UHDFWLRQV RI '0'%7 ZDV VKRZQ WR EH FDUULHG RXW E\ WKH K\GURJHQDWLRQURXWHRQWKHVHW\SHVRIFDWDO\VW ,Q WKH FDVH RI $O2VXSSRUWHG &R±0R VXOILGHG FDWDO\VWV V\VWHP KRZHYHU WKH VXOILGDWLRQ VWHS DW WHPSHUDWXUH KLJKHU WKDQ . UHVXOWHG LQ DQRWKHU W\SH RI &R0R6 LV FUHDWHGRZQLQJDERXWWZLFHKLJKHULQWULQVLFDFWLYLW\WKDQWKDWIRUPHGDWDW\SLFDOVXOILGDWLRQ WHPSHUDWXUH HJ . 7KLV XQXVXDO &R0R6 LV QDPHG &R0R6 7\SH ,, ZKLOH WKH W\SLFDOODWWHU&R0R6LVFDOOHG7\SH,&DQGLDet al., 7DEOHJLYHVWKH6XPPDU\ RI,QWHQVLYHO\8VHG&DWDO\VWBi-metallic DWYDULRXVRSHUDWLQJFRQGLWLRQVDQGUHDFWRUVIRU WKH/DVW'HFDGHV
49
$PRQJ WKH &R0R6 FDWDO\VWV VWUXFWXUH VXSSRUWHG RYHU DOXPLQD HVVHQWLDOO\ WKH PRVWDFWLYHZDVUHIHUUHGWRWKHSKDVHRIW\SH,,&R0R6,, DQGOHVVDFWLYHZDVUHIHUUHG WR SKDVH RI W\SH , &R0R 6, W\SH , VWUXFWXUH LV DVVXPHG WR EH OLQNHG WR WKH VXSSRUW WKURXJK0R2$OOLQNDJHVDQGOHVVVWDFNLQJZKLOHWKHVWUXFWXUHRIW\SH,,LVKLJKHUDQGIHZ VWDFNLQJ OLQNV ZLWK WKH VXSSRUW +RZHYHU WKH VXSSRUWHG FDWDO\VW OLQNDJHV LQ &R±0R±6 , W\SHSUREDEO\KLQGHUWKHUHDFWDQWPROHFXOHVIURPDSSURDFKLQJWKHDFWLYHSKDVHVLWHVRIWKH FDWDO\VW)RUWKLVVWULFWUHDVRQLWKDVEHHQFRQFOXGHGWKDW&R0R±6,,LVPRUHDFWLYHWKDQ &R±0R±6,DOWKRXJK0RVVEDXHUWHFKQLTXHDQG(;$)6VLJQDOVRIW\SHV,DQG,,VWUXFWXUHV DUHWKHVDPH3ULQV'DDJHDQG&KLDQHOOL
50
*
(Ma al 1996) (Maet etal., al et 1996) (Ma 1996)
(Zhang et al., 1997)
(Isoda et al., 1996) )
51 (Isoda et al., 1996) ) (Isoda et al., 1997) )
(Ma et al.,1995)
Sakanashi et al.,1992
(Sakanashi et
(Sakanashi et al.,1993)
(Sakanashi et al.,1991)
(Mochida et al.,1996)
(Isoda et al., 1996)
(Ma et al., 1996)
(Zhang et al., 1996)
(Landau et al., 1996)
(Lamuremeille et al., 1995)
(Ma et al 1994)
(Kabe et al., 1993)
(Kabe et al., 1992)
(Kilanowski et al., 1978)
(Houalla et al., 1980)
7DEOH6XPPDU\RI,QWHQVLYHO\8VHG&DWDO\VWBi-metallic DWYDULRXVRSHUDWLQJFRQGLWLRQVIRUWKH/DVW'HFDGH
56
$YDLODEOH5RXWHVIRU8/6' &RPPHUFLDO+'6FDWDO\VWVDUHVXOILGHVEDVHGRQ0RRU:DQGSURPRWHGZLWK1LRU &R7KHWRSLFKDVEHHQFRYHUHGLQVHYHUDODUWLFOHVDQGGHHS+'6 LQRWKHUPDQXVFULSWV 0RUHUHFHQWUHSRUWLQJRQGHHSGHVXOIXUL]DWLRQKDVEHHQPDGHLQUHYLHZVE\0RFKLGDDQG &KLR DQG %DELFK DQG 0RXOLMQ DQG KDV EHHQ D SULQFLSDO WRSLF LQ UHFHQW FRQIHUHQFHV DQG KDV EHHQ D SULQFLSDO WRSLF LQ UHFHQW FRQIHUHQFHV DQG WKH VXEMHFW RI GHGLFDWHG MRXUQDO YROXPHV DQG ERRNV 6SULQJHU 1HZ