В.В. Вольхин, Д.А. Казаков, Г.В. Леонтьева, А.Л. Жарныльская

!" 546.62+546.831-31: 542.913-148+666.7:661.862`022.091.3-911.48
. .
!"#$%&, '.(. )*+*,!-, .. . /0!&1#0-*,
(./. 2*3&4"#5,*6
!"#$%&' ()$*+,"$-.!//0' -!1/&2!$%&' */&.!"$&-!-
789:':/:;<: =>/7 <? .<'97/<@( ZROCL2
89< 87/=A:;<< 89:)=9>79( B(C:9<(/7
><>C:BD AL2O3–ZRO2 B:C7'7B @7/E-.:/E-><;C:@(
!""#$%&'() &'*+,-%!%) ."",'/$0!(.1 2./&$,.*! "$,.
ZrOCl2 3&. 3$,+4'(.. 3&'5+&"$&! #!%'&.!,$0 "."%'#) Al2O3–ZrO2.
6!7/'() +",$0.1 3&$8'""! 2./&$,.*!, 5$%$&)' $9'"3'4.0!:% ;$&#.&$0!(.' (!($&!*#'&()< 4!"%.8 t-ZrO2 0 "$"%!0' 5$#3$*.%! 3&.
'2$ %'&#.4'"5$7 $9&!9$%5'. =$/%0'&>/'(! 0$*#$>($"%- "%!9.,.*!8.. 4!"%.8 ;!*) t-ZrO2, &!"3&'/','(()< 0 #!%&.8', $9&!*$0!(($7 ;!*$7 -Al2O3.
#$%&'($)* +$ ,-+,.& -(-%&/* Al2O3–ZrO2 (-0,)1234%-5 . 6$7&-%.& %,+6,8 6&'$/(6( %(0$ ZTA [1, 2], 6$%$)(2$%,',. ( +,-(%&)&8 6$%$)(2$%,',. [3]. 9.&:&+(& . /$%'(;3 -Al2O3 +$+,7$-%(; t-ZrO2 ,<&-0&7(.$&% 6,/0,2(;(,++*/ /$%&'($)$/ %'&=(+,-%,86,-%1, 7%, -.52*.$4%
- >$2,.*/ 0&'&?,:,/ t-ZrO2 ! m-ZrO2 (>$2,.*8 0&'&?,: /$'%&+-(%,.,@, %(0$), 6,%,'*8 @$-(% /(6',%'&=(+*, ,<'$234=(&-5 0,: +$@'326,8 [4, 5]. A:+$6, 0'(@,%,.)&+(& 6,/0,2(;(,++*? /$%&'($),. -(-%&/*
Al2O3–ZrO2 -.52$+, - ,0'&:&)&++*/( %'3:+,-%5/(. B$2$ t-ZrO2 +&3-%,87(.$ 0'( %&/0&'$%3'$? +(C& 1170 "D [6], $ 0'( <,)&& .*-,6(? %&/0&'$%3'$? ,6-(: $)4/(+(5 ,<'$23&% >$23 -Al2O3, -%'36%3'$ 6,%,',8
?$'$6%&'(23&%-5 .*-,6,8 0),%+,-%14, +(26,8 )$<()1+,-%14, 7%, 2$%'3:+5&% >,'/(',.$+(& +$ && ,-+,.& 6,/0,2(%,.. E,F%,/3 0'&:-%$.)5&%-5 ;&)&-,,<'$2+*/ -(+%&2(',.$%1 t-ZrO2 . /&%$-%$<()1+,/ -,-%,5+((
0'( +(26(? %&/0&'$%3'$? ( ..,:(%1 &@, . -,-%$. $)4/,,6-(:+,8 /$%'(;* :, && 0&'&?,:$ . >$23 -Al2O3.
G$+&& [7] <*), 0,6$2$+,, 7%, +$ ,-+,.& 2,)&8 #-AlOOH ( ZrO2,
0'(/&+(. 2,)1-@&)1--(+%&2, /,C+, 0,)37(%1 .*-,6,@,/,@&++*& 6,/0,2(;(,++*& @&)(. 9 :$++,8 '$<,%& 0,-%$.)&+$ 2$:$7$ ,0'&:&)(%1 3-),.(5 -(+%&2$ (-?,:+,8 >$2*, 6,%,'*& 0'&:,0'&:&)54% 0&'&?,: :(,6-(:$
15
;('6,+(5 (2 $/,'>+,@, -,-%,5+(5 . 6'(-%$))(7&-6(& - ,<'$2,.$+(&/
0'&(/3=&-%.&++, >$2* t-ZrO2 +&0,-'&:-%.&++, . -,-%$.& 6,/0,2(%$
. ?,:& &@, %&'/(7&-6,8 ,<'$<,%6(.
E'( .*0,)+&+(( F6-0&'(/&+%$)1+,8 7$-%( '$<,%* . 6$7&-%.& (-?,:+*? '&$@&+%,. <*)( (-0,)12,.$+* -,)( AlCl3 ( ZrOCl2. H(:',)(2
-,)&8 ,-3=&-%.)5)( - 0,/,=14 .,:+,@, '$-%.,'$ NH3. 9*:&)(.I(&-5
0',:36%* @(:',)(2$ ,%:&)5)( ,% C(:6,8 >$2* - 0,/,=14 ;&+%'(>3@(',.$+(5. !)5 0'(@,%,.)&+(5 2,)&8 AlCl3 ( ZrOCl2 (-0,)12,.$)( /&%,:
0&0%(2$;(( $2,%+,8 6(-),%,8. D%$<()1+*& 2,)( 0,)37$)(-1 0'( /,)1+*? -,,%+,I&+(5? NA3/Al ( NA3/Zr, '$.+*? 0,33 ( 1,00 -,,%.&%-%.&++,. D'&:+(8 '$2/&' 7$-%(; 2,)&8 #-AlOOH -,-%$.)5) ~ 7 +/ (/&%,:
3)1%'$;&+%'(>3@(',.$+(5) ( 7$-%(;* 2,)&8 ZrO2 – 0'(/&'+, 26 +/
(/&%,: /$),3@),.,@, '$--&5+(5 '&+%@&+,.-6(? )37&8).
J,)1-@&)1--(+%&2 6,/0,2(;(,++,@, @&)5 ,-3=&-%.)5)( . -,,%.&%-%.(( - /&%,:(6,8, (2),C&++,8 . '$<,%& [7]. ",/0,2(;(,++*8 @&)1 .*-3I(.$)( 0'( 105$5 "D . %&7&+(& 48 7 . 6$/&'+,8 0&7( DKAL1,6.2.5·1/9-MJ ( 2$%&/ 0',6$)(.$)( . /$),(+&';(,++,8 0&7( 9NE 0'(
2$:$++*? %&/0&'$%3'$? .0),%1 :, 1250 "D. E'( %&/0&'$%3'& 400 "D
0',:,)C(%&)1+,-%1 %&'/(7&-6,8 ,<'$<,%6( -,-%$.)5)$ 12 7, 0'( 600
( 900 "D – 6 7 ( 0'( 1250 "D – 2 7.
B$2,.*8 -,-%$. 0,)37&++*? ,<'$2;,. ,0'&:&)5)( /&%,:,/ '&+%@&+,.-6,8 :(>'$6;(( 0,',I6,. +$ :(>'$6%,/&%'& !GAK-2 (CuK (2)37&+(&). DO&/6$ 0',.,:()$-1 - /,+,?',/$%,',/ +$ 0&'.(7+,/ 0376& 0'( -6,',-%( '$2.,',%$ -7&%7(6$ 2 @'$://(+. E,:@,%,.63 ,<'$2;,.
:)5 -O&/6( ( ,<'$<,%63 0,)37&++*? '&23)1%$%,. .*0,)+5)( 0, /&%,:(6$/, (2),C&++*/ . /,+,@'$>(( [8].
D,,%+,I&+(& >$2 t-ZrO2 ( m-ZrO2 . -,-%$.& :(,6-(:$ ;('6,+(5
. %&'/(7&-6( ,<'$<,%$++*? ,<'$2;$? 6,/0,2(%,. ,0'&:&)5)( 6$6 ,%+,I&+(& (+%&+-(.+,-%&8 ,%'$C&+(8 ,% 0),-6,-%&8 (111), 2 P = 30,5",
:)5 t-ZrO2 ( (111), 2 P = 28,4", ( (11Q), 2 P = 31,6", :)5 m-ZrO2 [9]. !,)4
>$2* t-ZrO2, ?t, . -,-%$.& ZrO2 .*7(-)5)( 6$6 ,%+,I&+(& (+%&+-(.+,-%&8 ,%'$C&+(8 0, >,'/3)& [10]
Xt = It(III)/(Im(III) + Im(IIQ) + It(III)),
@:& It – (+%&+-(.+,-%1 ,%'$C&+(8 >$2* t-ZrO2; Im – (+%&+-(.+,-%1 ,%'$C&+(8 >$2* m-ZrO2.
D'&:+(8 '$2/&' 6'(-%$))(%,. >$2* t-ZrO2, Dt, . ,<'$2;$? ZrO2
( 6,/0,2(%,. ,0'&:&)5)( +$ ,-+,.& 3I('&+(5 )(+((, -,,%.&%-%.34=&8
,%'$C&+(4 (111), '$-7&%* 0',.,:()( 0, >,'/3)& R&''&'$ [11].
16
G&23)1%$%* (--)&:,.$+(5 0,6$2*.$4%, 7%, @(:',)(2 0,1 # AlCl3
0,: :&8-%.(&/ 6,+;&+%'(',.$++,@, .,:+,@, '$-%.,'$ NH3 0'( %&/0&'$%3'& 90–100 "D ( 0'( .*:&'C(.$+(( 'K . 6,+;& @(:',)(2$ . 0'&:&)$? 9,6–10,2 0'(.,:(% 6 ,<'$2,.$+(4 0'&(/3=&-%.&++, 0-&.:,<&/(%$
#-AlOOH. A:+$6, 0'( 0,+(C&+(( %&/0&'$%3'* '$-%.,'$ ( 3.&)(7&+((
'K .*I& 10 0',(-?,:(% ,<'$2,.$+(& <$8&'(%$, %-Al(OH)3. E'(/&-1
<$8&'(%$ (/&&%-5 ., /+,@(? ,<'$2;$? #-AlOOH. J,)(, 0,)37&++*& 0&0%(2$;(&8 0',:36%,. @(:',)(2$ AlCl3, ,<*7+, ,<,2+$7$4%-5 -(/.,),/
«#-AlOOH» +&2$.(-(/, ,% :,)( 0-&.:,<&/(%$ . (? -,-%$.&.
D,-%$. 0',:36%,. @(:',)(2$ ZrOCl2 6,)&<)&%-5 /&C:3
Zr(OH)4·xH2O ( ZrO(OH)2·xH2A. E, '&23)1%$%$/ '&+%@&+,>$2,.,@, $+$)(2$ 0',:36%* @(:',)(2$ +$?,:5%-5 . $/,'>+,/ -,-%,5+((. "'(-%$))(2$;(5 (? 0',(-?,:(% 0'( 0,-)&:34=&/ +$@'&.$+((. E'( +(26(? %&/0&'$%3'$? %&'/,:(+$/(7&-6( <,)&& -%$<()1+$ >$2$ m-ZrO2. K, .,2/,C+,
%$6C& ,<'$2,.$+(& /&%$-%$<()1+,8 >$2* t-ZrO2, 7%, 0'&:,0'&:&)5&%-5
3-),.(5/( @(:',)(2$ -,)( ZrOCl2, 6,@:$ >,'/('34%-5 2$',:*I( %,8
()( (+,8 /,:(>(6$;(( ZrO2. 9$C+, +$8%( 3-),.(5, 0'( 6,%,'*? . -,-%$.& 2$',:*I&8 +& 0',(-?,:(), <* /,+,6)(++,& (-6$C&+(& 6'(-%$))(7&-6,8 '&I&%6( :(,6-(:$ ;('6,+(5.
E'( .*<,'& 3-),.(8 -(+%&2$ ,<'$2;,. ,6-(@(:',6-(:$ ;('6,+(5
<*)( .*<'$+* '$2+*& 6,+;&+%'$;(( '$-%.,',. NH3, (-0,)123&/*? 0'(
,-3=&-%.)&+(( @(:',)(2$: 6,+;&+%'(',.$++*8 .,:+*8 NH3 ( '$-%.,'
1 # NH3. D3=&-%.&++,& '$2)(7(& 6,+;&+%'$;(8 .,:+,@, '$-%.,'$
NH3 /,@), 0,.)(5%1 +$ 0&'&-*=&+(& '$-%.,'$ 0'( .*:&)&+(( %.&':,>$2+*? 0',:36%,. @(:',)(2$. 9%,',8 .$'1('3&/*8 0$'$/&%' – 'K C(:6,8 >$2* . 6,+;& 0',;&--$ @(:',)(2$ ( 0'( 0,-)&:34=&/ -%$'&+((
,-$:6$ ,6-(@(:',6-(:$ ;('6,+(5, (? 2+$7&+(5 .*<'$+* 4 ( 9. AC(:$),-1, 7%, F%,% 0$'$/&%' ,6$C&% .)(5+(& +$ -,-%$. ,6-(@(:',6-(:$
;('6,+(5, 6,%,',/3 -.,8-%.&+&+ +&-%&?(,/&%'(7&-6(8 ?$'$6%&',
Zr(OH)4-<·O</2, @:& 0 & < & 2.
E'(@,%,.)&+* 05%1 ,<'$2;,. ,6-(@(:',6-(:,. ;('6,+(5: Z1
(6,+;. NH3, 'K 4), Z2 (6,+;. NH3, 'K 9), Z3 (6,+;. NH3, 'K 9, -%$'&+(&
0'( 95 "D), Z4 (1# NH3, 'K 9), Z5 (1# NH3, 'K 9, -%$'&+(& 0'( 95 "D).
N& ,<'$2;*, :)5 6,%,'*? -%$'&+(& 0'( 95 "D +& 36$2$+,, ,-%$.$)(-1
. /$%,7+,/ '$-%.,'& 0'( 6,/+$%+,8 %&/0&'$%3'&. E,-)& 0&'&.,:$ 36$2$++*? ,<'$2;,. ,6-(@(:'$%,. ;('6,+(5 . -,-%,5+(& 2,)&8 ,+( <*)(
..&:&+* . -,-%$. 6,/0,2(;(,++*? @&)&8 -(-%&/* Al2O3–ZrO2, 6,%,'*/
17
-,,%.&%-%.&++, 0'(-.,&+* -(/.,)*: AZ1…AZ5. D,-%$. 6,/0,2(;((
?$'$6%&'(23&%-5 -,:&'C$+(&/ 75 % Al2O3 ( 25 % ZrO2 0, /$--&, 7%, -,,%.&%-%.3&% '&6,/&+:$;(5/ [12].
K$@'&.$+(& ,<'$2;,. 6,/0,2(;(,++,@, @&)5 (SZ) 0'(.,:(% 6 >$2,.*/ 0&'&?,:$/. K$<)4:$&/*& 0'&.'$=&+(5 ,6-(@(:',6-(:$ $)4/(+(5 . '$2+*? ,<'$2;$? 0'(/&'+, ,:(+$6,.*. N$6, +$@'&.$+(& (--)&:,.$++*? ,<'$2;,. :, 250 "D 3-()(.$&% 6'(-%$))(2$;(4 . +(? <$8&'(%$
(%-Al(OH)3). E'( :$)1+&8I&/ 0,.*I&+(( %&/0&'$%3'* 0',(-?,:(%
:&@(:',6-()(',.$+(& @(:',6-(:$ ( ,6-(@(:',6-(:$ $)4/(+(5: Al(OH)3 !
! AlOOH ! Al2O3. A<'$2;* -&'(( SZ, 0',6$)&++*& 0'( 400 "D, -,:&'C$% . ,-+,.+,/ -)$<, ->,'/(',.$++34 >$23 #-Al2O3 ('(-. 1).
" 600 "D >$2$ #-Al2O3 0'(,<'&%$&% <,)&& ,>,'/)&++34 6'(-%$))(7&-634 -%'36%3'3, +, . -,-%$.& ,<'$2;,. .,2/,C+$ 0'(/&-1 '-Al2O3.
K$@'&.$+(& ,<'$2;,. -&'(( SZ 0'( <,)&& .*-,6(? %&/0&'$%3'$? 0'(.,:(% 6 2$.&'I&+(4 >$2,.,@, 0&'&?,:$ #-Al2O3 ! '-Al2O3 ( :$)&& 0',(-?,:(% 0&'&?,: '-Al2O3 ! P-Al2O3. 9 ,<'$2;$?, 0',6$)&++*? 0'(
900 "D, >$2* '-Al2O3 ( P-Al2O3 -,-3=&-%.34%. B$2,.*8 0&'&?,:
P-Al2O3 ! -Al2O3 . 6,/0,2(;(,++*? ,<'$2;$? 2$.&'I$&%-5 6 1200 "D,
( 0'( 1250 "D $)4/,,6-(:+*8 6,/0,+&+% 0,)+,-%14 0'&:-%$.)&+ >$2,8 -Al2O3.
"$6 ( 0'&:0,)$@$),-1, 6,/0,2(;(,++*& ,<'$2;* AZ1…AZ5, '$2)(7$4=(&-5 3-),.(5/( 0'(@,%,.)&+(5 ;('6,+(&.,@, 6,/0,+&+%$, 0,6$2$)( '$2)(7(& . &@, >$2,.*? 0&'&?,:$? ,-,<&++, 0'( 0,.*I&++*?
%&/0&'$%3'$?. 9 -,-%$.& 6,/0,2(;(,++*? ,<'$2;,., 0',6$)&++*? 0'(
250 "D, ,6-(@(:',6-(: ;('6,+(5 ,-%$&%-5 . '&+%@&+,$/,'>+,/ -,-%,5+(( (-/. '(-. 1). M2.&-%+, [10], 7%, 6'(-%$))(2$;(5 (+:(.(:3$)1+,@,
:(,6-(:$ ;('6,+(5 0',%&6$&% 0'( 380–450 "D. A:+$6, . 6,/0,2(%&
ZrO2 ,-%$&%-5 . '&+%@&+,$/,'>+,/ -,-%,5+((, am-ZrO2, .0),%1 :, 600 "D.
"'(-%$))(7&-6$5 >$2$ t-ZrO2 ,<+$'3C(.$&%-5 . ,<'$2;$?, %&'/(7&-6(
,<'$<,%$++*? 0'( 900 "D. K, 0'( F%,/ ,%/&7$&%-5 '$2)(7(& >$2,.,@,
-,-%$.$ /&C:3 ,<'$2;$/(. 9 ,<'$2;$? AZ1, AZ2 ( AZ3 ,<+$'3C&+, ,:+,.'&/&++,& ,<'$2,.$+(& >$2 t-ZrO2 ( m-ZrO2, . %, .'&/5 6$6 ,<'$2;*
AZ4 ( AZ5 -,:&'C$% 0,7%( 7(-%34 >$23 t-ZrO2 (?t > 90 %). N$6(/ ,<'$2,/, (-0,)12,.$+(& 6,+;&+%'(',.$++,@, .,:+,@, NH3 0'( @(:',)(2&
ZrOCl2 0'(.&), 6 +&<)$@,0'(5%+*/ '&23)1%$%$/, 7%, /,C&% <*%1 -.52$+, - (-6$C&+(&/ -%'36%3'* 2$',:*I&8 >$2* ZrO2, >,'/('34=(?-5
. 3-),.(5? -()1+,@, 0&'&-*=&+(5 '$-%.,'$. 9,2/,C+,, 7%, .&',5%18
+,-%1 ,<'$2,.$+(5 -%$<()1+*? 2$',:*I&8 >$2* t-ZrO2 . F%(? 3-),.(5?
0,+(C&+$, $ 0'( 0,-)&:34=&/ +$@'&.$+(( 0',(-?,:(% >,'/(',.$+(&
%&'/,:(+$/(7&-6( <,)&& -%$<()1+,8 >$2* m-ZrO2.
23 (4uK5), (",+
G(-. 1. !(>'$6%,@'$//* ,<'$2;,.: AZ4, 250 "D (1), AZ4, 400 "D (2), AZ4,
600 "D (3), AZ4, 900 "D (4), AZ4, 1250 "D (5). A<,2+$7&+(5 0(6,.: t – t-ZrO2;
m – m-ZrO2; T – T-Al2O3; P – P-Al2O3; U – U-Al2O3; V – V-Al2O3; b – <&/(%
E,),C(%&)1+*& '&23)1%$%* 0,)37&+* 0'( (-0,)12,.$+(( '$-%.,'$ 1# NH3. G&23)1%$%* %$6C& 3)37I$4%-5, &-)( @(:',)(2 ZrOCl2
2$.&'I$&%-5 0'( 'K 9, +, +& 4. 9&)(7(+$ 'K .)(5&% +$ 0',;&--* ,)5;((
( ,6-,)5;((, 6,%,'*& (@'$4% ',)1 0'( 2$',:*I&,<'$2,.$+((.
D%$'&+(& 0',:36%,. @(:',)(2$ ZrOCl2 0'( 95 "D +& 0'(.&),
6 -3=&-%.&++,/3 (2/&+&+(4 -.,8-%. ,<'$2;$ AZ5 0, -'$.+&+(4 - ,<'$2;,/ AZ4, ,-%$.)&++*/ . /$%,7+,/ '$-%.,'& 0'( 6,/+$%+,8 %&/0&'$%3'&. K&6,%,'$5 ',)1 -%$'&+(5 ,<+$'3C&+$ . ,<'$2;& AZ5, %&'/(7&-6( ,<'$<,%$++,/ 0'( 1250 "D (2 7). G$2/&' 6'(-%$))(%,. >$2* t-ZrO2
. ,<'$2;& AZ5 -,-%$.() 26 +/, . %, .'&/5 6$6 . ,<'$2;& AZ4, 0'(@,%,.)&++,/ <&2 -%$'&+(5, '$2/&' 6'(-%$))(%,. 21 +/.
G&23)1%$%* 0',.&:&++,@, (--)&:,.$+(5 :)5 ,<'$2;,. AZ4 ( AZ5
,<,<=&+* . %$<)(;&.
19
!"#$%& '#'(!$ ) *!"+,* -*)'(!..)(#$ /!"% t-ZrO2
$ #0*!"1!2 AZ4 ) AZ5, 3*#-!.,44%2 3*) *!"4%2 (,+3,*!(5*!2
B$2,.*8 -,-%$. :)5 ZrO2: ?t,%; Dt, +/
A<'$2&;
400 "D, 12 7
ZrO2
Al2O3
600 "D, 6 7
ZrO2
Al2O3
AZ4
am-ZrO2 #-Al2O3 am-ZrO2 #-Al2O3
AZ5
am-ZrO2 #-Al2O3 am-ZrO2 #-Al2O3
900 "D, 6 7
ZrO2
t-ZrO2
>90; 12
t-ZrO2
>90; 12
Al2O3
1250 "D, 2 7
ZrO2
'-Al2O3, t-ZrO2
W-Al2O3 80,5; 21
'-Al2O3, t-ZRO2
W-Al2O3 82,0; 26
Al2O3
-Al2O3
-Al2O3
-),.(5 0'(@,%,.)&+(5 ,<'$2;,. AZ4 ( AZ5 ,<&-0&7(.$4% @,/,@&++,& '$-0'&:&)&+(& +$+,'$2/&'+*? 7$-%(; t-ZrO2 . /$%'(;&, ->,'/(',.$++,8 >$2,8 -Al2O3.
G$2/&' 6'(-%$))(%,. >$2* t-ZrO2 +& 0'&.*I$&% 26 +/. M/&++, F%,
,<&-0&7(.$&% -%$<()1+,-%1 >$2* t-ZrO2. D7(%$&%-5 [10], 7%, .&'?+(8 6'(%(7&-6(8 '$2/&' 6'(-%$))(%,. t-ZrO2 -,-%$.)5&% ,6,), 30 +/. E,-6,)163
'$2/&' 6'(-%$))(%,. t-ZrO2 . ,<'$2;$? AZ4 ( AZ5 +& 0'&.*I$&% 6'(%(7&-634 .&)(7(+3, /,C+, -:&)$%1 .*.,: , %,/, 7%, 0,)37&++*& ,<'$2;* 3:,.)&%.,'54% %'&<,.$+(5/ 6 0'&63'-,'3 /$%&'($),. -(-%&/* Al2O3–ZrO2.
D?&/$ ,-+,.+*? ,0&'$;(8 0',;&--$ 0,)37&+(5 0'&63'-,'$ /$%&'($),. -(-%&/* Al2O3–ZrO2 0'&:-%$.)&+$ +$ '(-. 2.
G(-. 2. D?&/$ ,0&'$;(8 0',;&--$ 0,)37&+(5 0'&63'-,'$
20
9 -,,%.&%-%.(( - '&23)1%$%$/( 0',.&:&++,@, (--)&:,.$+(5 0'(.&:&++*& ?$'$6%&'(-%(6( 0,)37&++*? ,<'$2;,. 0'&63'-,'$ ,<&-0&7(.$4%-5 -,<)4:&+(&/ -)&:34=(? 3-),.(8 @(:',)(2$ -,)( ;('6,+(5:
0,1 # ZrOCl2, ..&:&+(& . '$-%.,' -,)( 1 # NH3 0'( 6,/+$%+,8 %&/0&'$%3'& ( (+%&+-(.+,/ 0&'&/&I(.$+((, 'K C(:6,8 >$2* . 6,+;& @(:',)(2$ ,6,), 9, :,03-%(/, ,@'$+(7&++,& 0, .'&/&+( -%$'&+(& ,-$:6$.
63)'#- .)(,*!(5*%
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