Degree of conversion of dual cure resins light cured ...

BBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBB

5HVHDUFK$UWLFOH

BBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBB

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

'U )UDQFHVFD &HUXWWL 'HSDUWPHQW RI 0DWHULDOV IRU (QJLQHHULQJ 8QLYHUVLW\ RI %UHVFLD ,WDO\ ( IF#IUDQFHVFDFHUXWWLLW

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

$PHULFDQ-RXUQDORI'HQWLVWU\9RO1R)HEUXDU\

'HJUHHRIFRQYHUVLRQRIGXDOFXUHFHPHQWV

7DEOH 0DWHULDOV WHVWHG LQ WKLV VWXG\ 7KHLU FRPSRVLWLRQ LV TXLWH VLPLODU LQ SHUFHQWDJHVWKHVKDGHLVFRPSDUDEOH BBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBB

0DWHULDO

0RQRPHU

)LOOHU

&RORU

&DOLEUD

%LV*0$

*ODVVSDUWLFOHVVLOLFDERURQ 7UDQVSDUHQW IOXRULGHDOXPLQXPWLWDQLXP GLR[LGH

0XOWLOLQN $XWRPL[

+(0$

%DULXPJODVV\WWHUELXPWUL IOXRULGHPL[HGVSKHURLGDO R[LGHV

7UDQVSDUHQW

9DULROLQN,,

%LV*0$ XUHWKDQH GLPHWKDFU\ODWH WULHWK\OHQJO\FRO GLPHWKDFU\ODWH

%DULXPJODVV\WWHUELXPWUL IOXRULGHEDULXPVLOLFDWHV DOXPLQXPIOXRULGHPL[HG VSKHURLGDOR[LGHV

7UDQVSDUHQW

BBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBB


0DWHULDOVDQG0HWKRGV 6HWXS RI WKH VLPXODWHG URRW FDQDO 7KUHH FXVWRP WHPSODWHV PDGH IURP PLUURUILQLVKHG %|KOHU 0,VRSODVWD VWHHO ZHUH SURGXFHG HDFK FRQVLVWLQJ RI WZR VOLGHV îî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

)LJ5DPDQ PHDVXUHPHQWVZHUHSHUIRUPHGDWLQFUHDVLQJGLVWDQFHVIURP WKH FRURQDOPRVWSRUWLRQRIWKHJODVVILEHUSRVWLQWZRSRVLWLRQVRQLWVVXUIDFH 7DEOH 0HDQ '& LQ SHUFHQWDJH DQG VWDQGDUG GHYLDWLRQ RI WKH VDPSOHV SRO\PHUL]HG DFFRUGLQJ WR 6 P:FP IRU VHFRQGV DQG + P:FPIRUVHFRQGV PRGH BBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBB

&DOLEUD

BBBBBBBBBBBBBBBBBBB

&XULQJ PRGDOLW\

6

0XOWLOLQN $XWRPL[

BBBBBBBBBBBBBBBBBB

+

6

+

9DULROLQN,,

BBBBBBBBBBBBBBBBBBBBBBBBB

6

+


3RVLWLRQ

PP

PP

PP

PP


DFU\ODWH +(0$ 9DULROLQN ,, LV D GXDOFXULQJ FRPSRVLWH ZKRVHRUJDQLFPDWUL[FRQVLVWVRI%LV*0$XUHWKDQHGLPHWKD FU\ODWHDQGHWK\OHQHJO\FROGLPHWKDFU\ODWH /XWLQJSURFHGXUH7KHSRVWZDVOD\HUHGZLWKDGKHVLYHDQGWKH YRODWLOH FRPSRQHQW ZDV UHPRYHG E\ JHQWOH DLU EORZLQJ 7KH VHOI DQG OLJKWFXULQJ DGKHVLYH V\VWHPV XVHG ZHUH ;3 %RQG 6&$GIRU&DOLEUDDQG([FLWH'6&EIRU0XOWLOLQN$XWRPL[DQG 9DULROLQN,,7KHVHOHFWHGOXWLQJFRPSRVLWHZDVPL[HGDFFRUG LQJ WR WKH PDQXIDFWXUHUV¶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


&HUXWWLHWDO 6WDWLVWLFDO DQDO\VLV 7KH GDWD ZHUH DQDO\]HG XVLQJ $129$ 3 WRWHVWWKHQXOOK\SRWKHVLVZKLFKVWDWHGWKDWWKHUHVXOW ZRXOG QRW YDU\ DFFRUGLQJ WR WKH WUHDWPHQWV SHUIRUPHG $IWHU WKLV D SRVWKRF DQDO\VLV ZDV SHUIRUPHG WR GHWHUPLQH ZKLFK VSHFLILF JURXSV RI PHDVXUHPHQWV ZHUH VLJQLILFDQWO\ GLIIHUHQW 6WXGHQW1HXPDQ.HXOVWWHVW3

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

)LJ3HUFHQWDJHGHJUHHRIFRQYHUVLRQUHDFKHGE\WKHWHVWHGPDWHULDOVZKHQ FXUHGDFFRUGLQJWRWKH+P:FPIRUVHFRQGV DQGWKH6PRGH P:FP IRUVHFRQGV ,QFUHDVLQJWKHGLVWDQFHIURPWKHOLJKWWLSEULQJVWR DGUDZEDFNLQWKH PDWHULDOSHUIRUPDQFHVLQDOOWKHWHVWHGFRPSRVLWHVH[FHSW IRU&DOLEUD

PL[6PRGHP:FPIRUVHFRQGV LVDGYLVDEOH 7KH GHFUHDVH LQ OLJKW LQWHQVLW\ ZLWK LQFUHDVLQJ GLVWDQFH RI WKH OLJKW WLS IURP WKH FRPSRVLWH VXUIDFH GHVSLWH XVLQJ D WUDQVOXFHQW OLJKWFRQGXFWLYH SRVW RFFXUV 2Q WKLV EDVLV GXDO FXULQJ PDWHULDOV ZHUH WHVWHG WR UHGXFH WKH LQIOXHQFH RI WKLV YDULDEOHRQ'& $ SUHYLRXV VWXG\ HYDOXDWHG WKH '& LQ FRPSRVLWHV XVLQJ OLJKWWUDQVPLWWLQJ SRVWV EXW LW KDG OLPLWDWLRQV EDVHG RQ WKH VSHFLPHQV¶ VL]H ORQJHU DQG JUHDWHU LQ GLDPHWHU WKDQ D URRW FDQDO DQGWKHXVHRIPDWHULDOVWKDWFDQQRWEHXVHGFOLQLFDOO\ 7KLV VWXG\ VKRZHG KRZ D OLJKWWUDQVPLWWLQJ SRVW LQFUHDVHV WKH .QRRSKDUGQHVVQXPEHUDWJUHDWHUGHSWKVQHDUWKHSRVWEXWWKH UHVXOWV GLG QRW FOHDUO\ GHPRQVWUDWH ZKHWKHU WKLV GHYLFH LPSURYHGFXUHGHSWK 7KH SUHVHQW VWXG\ ZDV GHVLJQHG WR UHSURGXFH WKH FOLQLFDO FRQGLWLRQVRIFHPHQWDWLRQ7KHSRVWSURWUXGHG IURPWKHFDQDO


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

%|KOHU8GGHKROP6SD0LODQ,WDO\ ,YRFODU9LYDGHQW6FKDDQ/LHFKWHQVWHLQ (061\RQ6ZLW]HUODQG 'HQWVSO\%DLOODJXHV6ZLW]HUODQG

$FNQRZOHGJHPHQWV 7R WKH VWDII RI WKH /DERUDWRU\ RI &KHPLVWU\ IRU 7HFKQRORJLHVRIWKH8QLYHUVLW\RI%UHVFLDIRUWKHLUNLQGKHOSLQWKHXVHRIWKH 0LFUR5DPDQ 'LVFORVXUHVWDWHPHQW7KHDXWKRUVKDYHQRFRQIOLFWRILQWHUHVW

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l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