.

Фазові рівноваги та кристалічна структура сполук у системах {Ti, V, Ag, Pd} – Li – {Si, Ge} та Cu – Li – Si: Автореф. дис… канд. хім. наук / Д.Г. Ке

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EUeA?ANUeEEE AeA?AEAAIEE OI?AA?NEOAO ?IAI? ?AAIA O?AIEA

EAAI?EIA AeIEO?I AAI?A?EIAE*

OAeE 546.736.4; 669.018

OACIA? ??AIIAAAE OA E?ENOAE?*IA NO?OEOO?A NIIEOE

O NENOAIAO {Ti,V,Ag,Pd}-Li-{Si,Ge} OA Cu-Li-Si.

02.00.01 – iai?aai?/ia o?i?y

AAOI?AOA?AO

aeena?oaoe?? ia caeiaoooy iaoeiaiai nooiaiy

eaiaeeaeaoa o?i?/ieo iaoe

Euea?a – 1999

Aeena?oaoe??th ? ?oeiien.

?iaioa aeeiiaia a Euea?anueeiio aea?aeaaiiio oi?aa?neoao? ?iai? ?aaia
O?aiea ia eaoaae?? iai?aai?/ii? o?i??.

Iaoeiaee ea??aiee: aeieoi? o?i?/ieo iaoe, aeioeaio Iaaethe
Aieiaeeie? Aaneeueiae/, Euea?anueeee aea?aeaaiee oi?aa?neoao ?iai? ?aaia
O?aiea, i?ioani? eaoaae?e iai?aai?/ii? o?i??.

Io?oe?ei? iiiiaioe: aeieoi? o?i?/ieo iaoe, i?ioani?, Ia?ao ?aaai
THe?eiae/, Oaeai?iaenueeee aea?aeaaiee oi?aa?neoao, caa?aeoaa/ eaoaae?e
iai?aai?/ii? o?i??

eaiaeeaeao o?i?/ieo iaoe, aeioeaio, Ee?/?a Aaeeia ?aai?aia, Euea?anueea
aeaaeai?y aaoa?eia?ii? iaaeeoeeie, aeioeaio eaoaae?e o?i??

I?ia?aeia onoaiiaa -?inoeooo caaaeueii? oa iai?aai?/ii? o?i?? IAI
Oe?a?ie, i. Ee?a

Caoeno aeena?oaoe?? a?aeaoaeaoueny 12 n?/iy 1999?. i 15:00 aiae. ia
can?aeaii? niaoe?ae?ciaaii? a/aii? ?aaee Ae 35.051.10 o Euea?anueeiio
aea?aeaaiiio oi?aa?neoao? ?iai? ?aaia O?aiea ca aae?anith: 290005,
Euea?a, aoe. Ee?eea ? Iaoiae?y, 6, o?i?/iee oaeoeueoao, aoaeeoi??y ?2.

C aeena?oaoe??th iiaeia iciaeiieoeny o iaoeia?e a?ae?ioaoe?
Euea?anueeiai aea?aeaaiiai oi?aa?neoaoo ?i. ?.O?aiea (290002, Euea?a,
aoe. Ae?aaiiaiiaa, 5)

Aaoi?aoa?ao ?ic?neaii 11 a?oaeiy 1998 ?.

A/aiee nae?aoa?

niaoe?ae?ciaaii? a/aii? ?aaee i?io.
ss?aiei C.I.

CAAAEUeIA OA?AEOA?ENOEEA ?IAIOE

Aeooaeuei?noue i?iaeaie. Oaeaeeee ?icaeoie no/anii? iaoee oa oaoi?ee
aeiaaa? i?iaaaeaiiy aenia?eiaioaeueieo aeine?aeaeaiue ana a?eueo
neeaaeieo aaaaoieiiiiiaioieo iaoae?/ieo nenoai. Iniiaith oaeiai iiooeo ?
aea/aiiy oaciaeo ae?aa?ai noaio, ye? a?aeia?aaeathoue aca?iiae?th
eiiiiiaio?a o iaoae?/ieo nenoaiao, oa e?enoae?/ii? no?oeoo?e niieoe.

Inoaii?i /anii oe?iei aeine?aeaeothoueny iiaeeeaino? ai?iaaaeaeaiiy
?ioa?iaoae?/ieo niieoe ia?ao?aeieo iaoae?a. Nieaae oeoaio oa aaiaae?th
caaaeyee aenie?e iaoai?/i?e i?oeiino?, eaaeino?, ooaiieaaeino?,
no?eeino? aei ei?ic?? oe?iei aeei?enoiaothoueny ye eiino?oeoe?ei?
iaoa??aee . I?aeue oa ?? nieaae ca ?aooiie iaaecae/aeii oe?iieo
o?ceei-o?i?/ieo aeanoeainoae ciaeoee canoinoaaiiy a on?o aaeocyo
i?iieneiaino?. ?o aeei?enoiaothoue a aeaeo?ioaoi?oe?, oaieiiai?iieo
nenoaiao, ye eaaoth/? aeiaaaee ? eaoae?caoi?e. Nieaae iaeaae?th oa
n??aea aiane?aeie nai?? iaei? o?i?/ii? aeoeaiino? ai?iaaaeaeai? a
iaaeeoeei? aeey aeaioiaeaiiy aioo??oi?o i?ioac?a. A aeaeo?ioaoi?oe? ?o
aeei?enoiaothoue a oa?iiaeaiaioao oa ye aeaeo?e/i? eiioaeoe. Oaeiae
iaeaae?e ? n??aei canoiniaothoueny a o?i?/i?e i?iieneiaino? ye
eaoae?caoi?e.

O no/aniiio ae?iaieoeoa? ii/eiathoue oe?iei ai?iaaaeaeoaaoeny nieaae
e?o?th. Aiie aeei?enoiaothoueny a aoiii?e, aa?aoe?ei?e, aaoiiia?euei?e,
iaoaeo?a?ei?e i?iieneiainoyo. E?o?e oaeiae canoiniao?oueny ye eaaoth/a
aeii?oea aei ??cieo iaoa??ae?a aeey iie?auaiiy ?o iaoai?/ieo
oa?aeoa?enoee, i?aeaeuaiiy ei?ic?eii? no?eeino? oa aeey noai?aiiy
iaaeeaaeeo nieaa?a.

Oi?eaeuei? aeaeo?e/i?, iaai?oi? oa iioe/i? aeanoeaino? nieaa?a
aeaiaio?a aieiaii? i?aea?oie /aoaa?oi? a?oie ia??iaee/ii? nenoaie ?
iaaecae/aeii aaaeeea? aeey noai?aiiy aeaeo?iiieo oaoiieia?e,
i?eeaaeiaoaeoaaiiy.

Iaeiae, aei oaia??oiueiai /ano o?ueioeiiiiiaioi? nenoaie c ia?ao?aeieie
iaoaeaie, E?o??i oa ?-aeaiaioaie IV-a?oie caeeoathoueny iaei aea/aieie.
E?oa?aoo?i? aeai? i?i ae?aa?aie noaio oa e?enoae?/i? no?oeoo?e
?ioa?iaoae?/ieo niieoe o?ueioeiiiiiaioieo nenoai c ia?ao?aeieie
iaoaeaie, ye? ciaoiaeyoueny ia ii/aoeo ia??iae?a ia??iaee/ii? nenoaie,
i?aeoe/ii a?aenooi?. E?oa?aoo?i? a?aeiiino? i?i o?ueioeiiiiiaioi?
nenoaie c o/anoth iaoae?a, ui ciaoiaeyoueny o e?ioe? ia??iae?a ? iaiiai?
? /anoi noia?a/eea?.

Oiio, aeey ocaaaeueiaiiy oei?a aca?iiae?? eiiiiiaio?a o aeaieo
nenoaiao, aoei iaiao?aeii i?iaanoe aeine?aeaeaiiy ye iiaeo nenoai, oae ?
oaeeo, ye? aoee ?ai?oa aea/ai? /anoeiai. Oea noaei iniiaith aeey aeai?o
nenoai, ye? aoee aeine?aeaeai? a i?ioean? aeeiiaiiy aeaii?
aeena?oaoe?eii? ?iaioe.

Aea/aiiy nenoai {Ag,Pd}-Li-{Si,Ge} oa Cu-Li-Si aeicaieeei aeiiiaieoe oa
aei?aaeoe e?oa?aoo?i? aeai?, a aeine?aeaeaiiy iiaeo nenoai
{Ti,V}-Li-{Si,Ge} aeaei iiaeeea?noue ii??aiyoe oa?aeoa? aca?iiae?? o
o?ueioeiiiiiaioieo nenoaiao c ia?ao?aeieie aeaiaioaie ii/aoeo oa e?ioey
ia??iae?a.

Oaia ?iaioe a?aeiia?aea? iniiaiiio iaoeiaiio iai?yieo eaoaae?e
iai?aai?/ii? o?i?? Euea?anueeiai aea?aeaaiiai oi?aa?neoaoo ?i. ?.O?aiea.
?iaioa aeeiiaia o a?aeiia?aeiino? aei Eii?aeeiaoe?eiiai ieaio 70
I?i?noa?naa ina?oe Oe?a?ie “Iaoeia? iniiae o?i?/ii? oaoiieia?? noai?aiiy
iiaeo iai?aai?/ieo ?a/iaei oa iaoa??ae?a, eiiieaenii?
o?i?ei-oaoiieia?/ii? ia?a?iaee i?ia?aeueii? ne?iaeie Oe?a?ie” ca oaiith
“Neioac iiaeo ?ioa?iaoae?/ieo niieoe, aeine?aeaeaiiy ?o no?oeoo?e ?
aeanoeainoae c iaoith iiooeo iiaeo iai?aai?/ieo iaoa??ae?a”.

Iaoa ?iaioe. Aeine?aeaeaiiy aca?iiae?? eiiiiiaio?a o iio??eieo nenoaiao
{Ti,V,Ag,Pd}-Li-{Si,Ge} oa Cu-Li-Si. Iiaoaeiaa ?cioa?i?/ieo ia?a??c?a
ae?aa?ai noaio. Aecia/aiiy e?enoae?/ii? no?oeoo?e niieoe, ye?
ooai?ththoueny, oa ?o e?enoaeio?i?/iee aiae?c.

Iaoeiaa iiaecia ?iaioe. Aia?oa iiaoaeiaai? ?cioa?i?/i? ia?a??ce
ae?aa?ai noaio nenoai {Ti,V}-Li-{Si,Ge} oa Cu-Li-Si i?e 570E a iiaiiio
eiioeaio?aoe?eiiio ?ioa?aae?. Caaa?oaii aeine?aeaeaiiy nenoai
Pd-Li-{Si,Ge}, ye? aoee ?ai?oa aea/ai? /anoeiai. Aeey nenoai
Ag-Li-{Si,Ge} iiaoaeiaai? ?cioa?i?/i? ia?a??ce ae?aa?ai noaio i?e 470E a
iiaiiio eiioeaio?aoe?eiiio ?ioa?aae?, ooi/iai?, aeiiiaiai? oa aei?aaeai?
e?oa?aoo?i? aeai?.

Aeyaeaii ?nioaaiiy 38 oa?ia?ieo niieoe, na?aae ieo – 29 aia?oa. Aeey 21
niieoee iiai?noth aecia/aia e?enoae?/ia no?oeoo?a, aeey 3 – /anoeiai.
?icoeo?iaaii oa iienaii 5 iiaeo no?oeoo?ieo oei?a.

Iaoeiaa oa i?aeoe/ia oe?ii?noue. Ia iniia? i?iaaaeaieo aeine?aeaeaiue
anoaiiaeai? aeaye? caeiiii??iino? aca?iiae?? ia?ao?aeieo aeaiaio?a c
E?o??i oa ?-aeaiaioaie IV-a?oie: c?iaeaii aeniiaee i?i oa?aeoa?
aca?iiae?? aeaiaio?a o aeine?aeaeaieo oa nii??aeiaieo aei ieo iio??eieo
nenoaiao, ?iia??i?noue ooai?aiiy ?ioa?iaoae?/ieo niieoe oa ?o
e?enoae?/io no?oeoo?o. Io?eiai? aeai? iiaeooue aooe aeei?enoai?: aeey
?aeaioeo?eaoe?? oac i?ae /an neioaco iiaeo iaoa??ae?a, aeey i?iaaaeaiiy
oa?iiaeeiai?/ieo ?ic?aooie?a ? aeey i?iaiicoaaiiy oa?aeoa?o aca?iiae??
eiiiiiaio?a o nii??aeiaieo iio??eieo oa aaaaoieiiiiiaioieo nenoaiao.

Iniaenoee aianie aeena?oaioa. I?ae /an i?iaaaeaiiy aeine?aeaeaiue oa
i?aeaioiaee aeena?oaoe?eii? ?iaioe aeena?oaioii aoei:

neioaciaaii nieaae nenoai {Ti,V}-Li-{Si,Ge} (naiino?eii),
{Ag,Pd}-Li-{Si,Ge} oa Cu-Li-Si (ni?eueii c iaoeiaei ea??aieeii);

i?iaaaeaii oa?i?/io ia?iaeo c?ace?a;

c?iaeaii ?aioaaiioaciaee oa ?aioaaiino?oeoo?iee aiae?c nieaa?a nenoai
{Ti,V}-Li-{Si,Ge} (naiino?eii) oa {Ag,Pd}-Li-{Si,Ge} (ni?eueii c
iaoeiaei ea??aieeii), ?aioaaiioaciaee (naiino?eii) oa
?aioaaiino?oeoo?iee (ni?eueii c iaoeiaei ea??aieeii) aiae?c c?ace?a
nenoaie Cu-Li-Si;

aia?oa iiaoaeiaaii ?cioa?i?/i? ia?a??ce ae?aa?ai noaio nenoai
{Ti,V}-Li-{Si,Ge} oa Cu-Li-Si i?e 570E a iiaiiio eiioeaio?aoe?eiiio
?ioa?aae?, ? aeey nenoai {Ag,Pd}-Li-{Si,Ge} caaa?oaii ?icii/ao? ?ai?oa
aeine?aeaeaiiy;

aeine?aeaeaii e?enoae?/io no?oeoo?o 24 oa?ia?ieo niieoe, c ieo 18
-naiino?eii oa 6 ?ioa?iaoae?ae?a c? neeaaeiith e?enoae?/iith no?oeoo?ith
– ni?eueii c iaoeiaei ea??aieeii;

c?a?aii, nenoaiaoeciaaii oa e?eoe/ii i?iaiae?ciaaii e?oa?aoo?i? aeai?;

ia iniia? e?oa?aoo?ieo aeaieo oa ?acoeueoao?a aeanieo aeine?aeaeaiue
c?iaeaii aeniiaee i?i oa?aeoa? aca?iiae?? aeaiaio?a o aeine?aeaeaieo oa
nii??aeiaieo aei ieo iio??eieo nenoaiao.

Ai?iaaoe?y ?iaioe. Iniiai? ?acoeueoaoe aeena?oaoe?eii? ?iaioe aoee
aeeeaaeai? ia: VI ia?aae? c e?enoaeio?i?? iai?aai?/ieo ?
eii?aeeiaoe?eieo niieoe (Euea?a, 1992); Iaoeiai-i?aeoe/i?e eiioa?aioe??
“Euea?anuee? o?i?/i? /eoaiiy” (Euea?a, 1992); Oino?e i?aeia?iaei?e
eiioa?aioe?? c e?enoaeio?i?? iai?aai?/ieo niieoe (Euea?a, 1995);
O?ueionoi?iii?e oeie? “?ioa?iaoae?aee. Neioac, no?oeoo?a ? aeanoeaino?”
(Euea?a, 1996); ?? Oe?a?inueei-iieuenueeiio nai?ia?? c ieoaiue o?ceee oa
o?i?? iaoa??ae?a (Euea?a-Oaoeuee, 1996); I’yo?e i?aeia?iaei?e oeie?
“Oacia? ae?aa?aie o iaoa??aeiciaanoa?” (Eaoeeaae?, 1996).

Ioae?eaoe??. Ca iaoa??aeaie aeena?oaoe?? iioae?eiaaii 14 ?ia?o, na?aae
ieo 8 iaoeiaeo noaoae oa 6 oac eiioa?aioe?e.

Ia’?i oa no?oeoo?a aeena?oaoe??. Aeena?oaoe?eia ?iaioa neeaaea?oueny c
anooio, /ioe?ueio ?icae?e?a, aeniiae?a oa nieneo aeei?enoaieo o ?iaio?
e?oa?aoo?ieo aeaea?ae. Ia’?i aeena?oaoe?eii? ?iaioe 148 noi??iie, aiia
i?noeoue 78 oaaeeoeue oa 77 ?enoie?a. Nienie e?oa?aoo?e aeeth/a? 176
aeei?enoaieo aeaea?ae.

INIIAIEE CI?NO ?IAIOE

ANOOI

O anooi? iaaiai?th?oueny aeooaeuei?noue oaie aeena?oaoe?eii? ?iaioe,
aecia/athoueny iaoa oa iniiai? iai?yiee aeine?aeaeaiue, iaoeiaa iiaecia,
iaoeiaa oa i?aeoe/ia oe?ii?noue ?iaioe.

?ICAe?E 1

IAEssAe E?OA?AOO?E

Ia?oee ?icae?e aeeth/a? e?oa?aoo?i? aeai? i?i ae?aa?aie noaio
iiaea?eieo nenoai, ye? iaiaaeothoue aeine?aeaeai? iio??ei? nenoaie
{Ti,V,Ag,Pd}-Li-{Si,Ge} oa Cu-Li-Si, ? e?enoaeia?ao?/i? oa?aeoa?enoeee
a?ia?ieo niieoe oeeo nenoai. Aeai? i?i ?cioa?i?/i? ia?a??ce ae?aa?ai
noaio nii??aeiaieo iio??eieo nenoai ? e?enoae?/io no?oeoo?o oa?ia?ieo
niieoe, ye? a ieo ooai?ththoueny. Ia iniia? aiae?co e?oa?aoo?ieo aeaieo
c?iaeaii aeniiaee i?i iniaeeaino? aca?iiae?? eiiiiiaio?a o iiaea?eieo oa
iio??eieo nenoaiao. C?iaeaii i?iaiic i?i oa?aeoa? ooai?aiiy oa
e?enoae?/i? no?oeoo?e oa?ia?ieo ?ioa?iaoae?/ieo niieoe.

?ICAe?E 2

IAOIAeEEA AENIA?EIAIOAEUeIIAI AeINE?AeAEAIIss

O ae?oaiio ?icae?e? iienaii iaoiaeeeo aenia?eiaioaeueiiai
aeine?aeaeaiiy.

Aeey aeaioiaeaiiy nieaa?a aeei?enoiaoaaee iaoaee ianooiii? /enoioe: O?
– 0,9991, V – 0,999, Cu – 0,995, Ag – 0,9999, Pd – 0,9998, Li – 0,982,
Si – 0,9999, Ge – 0,9999 ianiaeo /anoie iniiaiiai eiiiiiaioo.

C?acee aeaioiaeyee oeyoii nieaaeaiiy oeooe a aeaeo?iaeoaia?e ia/? c
aieueo?aiiaei aeaeo?iaeii ia i?aeiiio aiaeiioieiaeaeoaaiiio iiae? a
aoiinoa?? i/euaiiai a?aiio (ye aaoa? aeei?enoiaoaaee aoa/aoee oeoai)
i?ae oeneii ~1,1·105 Ia.

Oa?i?/ia ia?iaea nieaa?a iieyaaea o aiiiaai?coth/iio a?aeiae? i?e
oaiia?aoo?? 570E aeey nenoai {Ti,V}-Li-{Si,Ge} oa Cu-Li-Si ? aeey nenoai
{Ag,Pd}-Li-{Si,Ge} 470E i?ioyaii 400-600 aiaeei. Nieaae ciaoiaeeeenue o
oaioaeiaeo eiioaeia?ao, caiayieo o eaa?oeaa? aiioee c iiia?aaeiueith
aaaeoaoe??th iia?o?y. A?aeiae i?iaiaeeee o iooaeueieo ia/ao oeio II-2O c
aaoiiaoe/iei ?aaoethaaiiyi oaiia?aoo?e c oi/i?noth (10 E. A?aeiaeai?
nieaae aa?ooaaeenue o oieiaeiiio ?iaeeoa?aioiiio iane?.

?aioaai?anueeee oaciaee aiae?c aoa iniiaiei iaoiaeii, yeee
aeei?enoiaoaaee i?e iiaoaeia? ?cioa?i?/ieo ia?a??c?a ae?aa?ai noaio
aeine?aeaeaieo nenoai (eaia?e Aeaaay, aeeo?aeoiiao?e Ae?II-2.0 oa STOE).

Ooi/iaiiy ia??iae?a ?ao?oie ? e?enoae?/ii? no?oeoo?e niieoe i?iaiaeeee
iaoiaeaie ii?ioeo, ia iniia? aeaieo, iaea?aeaieo ia ii?ioeiaeo
aeeo?aeoiiao?ao Ae?II-2.0 (FeKa- aei?ii?ithaaiiy) oa Ae?II-4.07 (CuK(-
aei?ii?ithaaiiy), oa iiiie?enoaeo, ca aeiiiiiaith iaoiae?a Eaoa,
iaa?oaiiy (eaia?e ?EA-86, ?EA-86I, MoK- oa CuK-aei?ii?ithaaiiy) oa
Aaenaiaa?aa (?AIN-2 CuK-aei?ii?ithaaiiy).

Aeey ?icoeo?iaee no?oeoo?e niieoe iaoiaeii iiiie?enoaeo
aeei?enoiaoaaeenue aenia?eiaioaeuei? ianeae ?ioaineaiinoae a?aeaeoue,
ye? iaea?aeoaaee ia aaoiiaoe/ieo iiiie?enoaeueieo aeeo?aeoiiao?ao EI-4
oa AeA?*-1 c MoK(-aei?ii?ithaaiiyi. An? iaiao?aei? ?ic?aooiee
cae?enithaaee ca aeiiiiiaith eiiieaeno i?ia?ai CSD oa SHELX93.

Aeey aecia/aiiy oi/iiai neeaaeo aeayeeo niieoe, cie?aia c nenoai
Ti-Li-{Si,Ge} ? Nu-Li-Si, aeei?enoiaoaaany aeaeo?iiiiciiaeiaee
i?e?iaiae?c. Eieaeueiee ?aioaaii-niaeo?aeueiee aiae?c i?iaiaeeee ia
i?e?iaiae?caoi?? “CAMEBAX” oa neaioth/iio aeaeo?iiiiio i?e?ineii?
“LEITZ-AMR 1600O” c i?e?iaiae?caoi?ii “Robinson Detector RBA-1600 5MC“.

?ICAe?E 3

AENIA?EIAIOAEUeIA *ANOEIA

O o?aoueiio ?icae?e? i?aaenoaaeai? ?acoeueoaoe aenia?eiaioaeueieo
aeine?aeaeaiue iio??eieo nenoai {Ti,V,Ag,Pd}-Li-{Si,Ge} oa Cu-Li-Si ?
aeai? i?i aecia/ai? e?enoae?/i? no?oeoo?e oa?ia?ieo niieoe, ye? a ieo
ooai?ththoueny.

Nenoaia Ti-Li-Si aeine?aeaeaia ia 50 c?aceao i?e 570 K (?en. 1).

Aeyaeaia iaeanoue iaci?ooaaiino? e?o?th ? oeoaio, yea i?inoyaa?oueny o
iio??eio iaeanoue aei (8 ao.% O?.

Aeey i?aaenoaaeaii? nenoaie oa?aeoa?ia iayai?noue oaa?aeeo ?ic/ei?a
cai?uaiiy ia iniia? a?ia?ieo oac cenoaie Li-Si ((5 ao. %) oa aeeth/aiiy
? cai?uaiiy ia iniia? niieoee Ti5Si3.

Ciaeaeaii 3 niieoee: ~Ti25Li65Si10, ~Ti50Li40Si10, Ti2LiSi, ye? iathoue
aocuee? iaeano? aiiiaaiiino?. E?enoaeia?ao?/i? oa?aeoa?enoeee niieoe
nenoaie Ti-Li-Si i?aaenoaaeai? a oaaeeoe? 1.

Nenoaia Ti-Li-Ge aeine?aeaeaia ia 54 c?aceao i?e 570 K (?en. 2).

Aeyaeaia iaeanoue iaci?ooaaiino? e?o?th ? oeoaio, yea i?inoyaa?oueny o
iio??eio iaeanoue aei (8 ao.% Ti.

I?e aeai?e oaiia?aoo?? ?nio? 5 niieoe: TiLi2Ge3, Ti4Li11Ge6, Ti4Li3Ge4,
~Ti15Li65Ge20, ~Ti50Li40Ge10 (oaae.1). Niinoa??aa?oueny ooai?aiiy
oaa?aeiai ?ic/eio aeeth/aiiy oa cai?uaiiy ia iniia? a?ia?ii? oace
Ti5Ge3, a oaeiae oaa?ae? ?ic/eie cai?uaiiy ((5 ao. %) ia iniia? a?ia?ieo
oac nenoai Ti-Ge oa Li-Ge.

Aeey niieoe TiLi2Ge3, Ti4Li11Ge6 oa Ti4Li3Ge4 iiai?noth aecia/aia
e?enoae?/ia no?oeoo?a, a aeey niieoee ~Ti50Li40Ge10 anoaiiaeai? ia??iaee
?ao?oee oa neiaii?y.

Oaaeeoey 1

E?enoaeia?ao?/i? oa?aeoa?enoeee niieoe nenoai Ti-Li-{Si,Ge}

Niieoea No?oeoo?iee oei I?.a?. aai neiaii?y Ia??iaee ?ao?oee, ii

3m 0.7603(4)

~Ti15Li65Ge20 no?oeoo?a ia aecia/aia

~Ti50Li40Ge10

aaen. 0.5096(3)

1.204(6)

Nenoaia V-Li-Si aeine?aeaeaia ia 48 c?aceao i?e 570 K (?en. 3).
Oa?ia?ieo niieoe ia aeyaeaii. Ciaeaeaii iaiaaeai? oaa?ae? ?ic/eie ia
iniia? a?ia?ieo oac cenoai Li-Si oa V-Si.

Aeyaeaia iaeanoue iaci?ooaaiino? e?o?th ? aaiaae?th, yea i?inoyaa?oueny
o iio??eio iaeanoue aei (11 ao.% V.

Nenoaia V-Li-Ge aeine?aeaeaia ia 52 c?aceao i?e 570 K (?en. 4).
Oa?ia?ieo niieoe ia aeyaeaii. Ciaeaeaii iaiaaeai? oaa?ae? ?ic/eie ia
iniia? a?ia?ieo oac cenoai Li-Ge oa V-Ge

Aeyaeaia iaeanoue iaci?ooaaiino? e?o?th ? aaiaae?th, yea i?inoyaa?oueny
o iio??eio iaeanoue aei (8 ao.% V.

Nenoaia Cu-Li-Si aeine?aeaeaia ia 125 c?aceao i?e 570 K (?en. 5).

I?aeoaa?aeaeaii ?nioaaiiy 2 ? ciaeaeaii 11 iiaeo oa?ia?ieo
?ioa?iaoae?ae?a (oaae. 2).

Oaaeeoey 2

E?enoaeia?ao?/i? oa?aeoa?enoeee niieoe nenoaie Cu-Li-Si

Niieoea No?oeoo?iee oei I?.a?. aai neiaii?y Ia??iaee ?ao?oee, ii

m 0.4297(3)

1.3765(7)

~Cu7Li40Si3 no?oeoo?a ia aecia/aia

An? niieoee iathoue aocuee? iaeano? aiiiaaiiino?. Oaa?ae? ?ic/eie ia
iniia? a?ia?ieo oac ia niinoa??aathoueny.

Nenoaia Ag-Li-Si aeine?aeaeaia ia 29 c?aceao i?e 470 K (?en. 6). I?e
aeai?e oaiia?aoo?? ?nio? o?e niieoee: Ag2Li3Si3, AgLi2Si2 oa Ag2LiSi,
aeey yeeo iiai?noth aecia/aia e?enoae?/ia no?oeoo?a (oaae.3).

Nenoaia Ag-Li-Ge aeine?aeaeaia ia 32 c?aceao i?e 470 K (?en. 7). I?e
aeai?e oaiia?aoo?? ?nio? o?e niieoee: Ag2Li3Ge3, Ag3Li3Ge2 oa Ag2LiGe,
aeey yeeo iiai?noth aecia/aia e?enoae?/ia no?oeoo?a (oaae.3).

Oaaeeoey 3

E?enoaeia?ao?/i? oa?aeoa?enoeee niieoe nenoai Li-Ag-{Si,Ge}

Niieoea No?oeoo?iee oei I?inoi?iaa a?oia Ia??iaee ?ao?oee, ii

0.6326(3)

Nenoaia Pd-Li-Si aeine?aeaeaia i?e 470 K o iiaiiio eiioeaio?aoe?eiiio
?ioa?aae? (?en. 8). O oe?e nenoai? ooai?th?oueny 6 oa?ia?ieo niieoe
(oaae.4). Iiai?noth aecia/aia e?enoae?/ia no?oeoo?a /ioe?ueio niieoe:
Pd12Li13Si12, PdLiSi3, Pd2LiSi oa Pd40Li13Si31, a oaeiae i?aeoaa?aeaeai?
e?oa?aoo?i? aeai? aeey Pd15Li13Si12.

Nenoaia Pd-Li-Ge aeine?aeaeaia i?e 470 K o iiaiiio eiioeaio?aoe?eiiio
?ioa?aae? (?en. 9). O oe?e nenoai? ooai?th?oueny 6 oa?ia?ieo niieoe
(oaae.4). Aeey niieoe Pd2LiGe, Pd2.7Li2Ge2.3 oa PdLi2Ge

i?aeoaa?aeaeaii e?oa?aoo?i? aeai?, aeey ?ioa?iaoae?ae?a Pd40Li13Ge31 oa
Pd2Li5Ge2 aia?oa aecia/aii e?enoae?/io no?oeoo?o.

Oaaeeoey 4

E?enoaeia?ao?/i? oa?aeoa?enoeee niieoe nenoaie Pd-Li-Si

Niieoea No?oeoo?iee oei I?inoi?iaa a?oia Ia??iaee ?ao?oee, ii

m1 0.4327(1)

0.8271(5)

E?enoae?/ia no?oeoo?a niieoe

O aeine?aeaeaieo nenoaiao ciaeaeaii 38 oa?ia?ieo niieoe, na?aae ieo 29
niieoe – aia?oa. Iiai?noth anoaiiaeaia no?oeoo?a aeey 21 ?ioa?iaoae?aeo
? /anoeiai – aeey 3. E?enoae?/i? no?oeoo?e 5 niieoe a?aeiinyoueny aei
iiaeo no?oeoo?ieo oei?a.

On? aeyaeai? niieoee e?enoae?cothoueny o 21 no?oeoo?iiio oei?, na?aae
yeeo 8 a?aeiinyoueny aei eoa?/ii?, 7 – aei aaenaaiiaeueii?, 2 – aei
oao?aaiiaeueii?, 1 – aei ?iia?/ii? ? 3 – aei iiiiee?iii? neiaii??.

Niieoee c iiaeie no?oeoo?ieie oeiaie iathoue neeaaeio e?enoae?/io
no?oeoo?o ? i?noyoue a?ae 74 aei 441 aoii?a: Pd12Li13Si12 (oP74),
Cu7Li7Si5 (hP171), Cu3LiSi2 (hP179), Cu54Li113Si57 (mC224),
Cu119Li145Si177 (hR441).

E?enoae?/i? no?oeoo?e oeeo niieoe iiaeia iienaoe, ye neeaaei? oeeaaeee
oa??a aoii?a.

?ICAe?E 4

IAAIAI?AIIss ?ACOEUeOAO?A

O /aoaa?oiio ?icae?e? i?eaiaeeoueny iaaiai?aiiy io?eiaieo ?acoeueoao?a:
aiae?co?oueny oa?aeoa? aca?iiae?? eiiiiiaio?a o aeine?aeaeaieo nenoaiao,
?icaeyaeathoueny caeiiii??iino? ooai?aiiy oa?ia?ieo niieoe, iniaeeaino?
?o e?enoae?/ii? no?oeoo?e oa nii??aeiai?noue aei aaea a?aeiieo niieoe.

Iine?aeiaia cai?ia 3-d aeaiaio?a a 4 ia??iae? i?eaiaeeoue aei nooo?aeo
a?aei?iiinoae a oa?aeoa?? aca?iiae?? eiiiiiaio?a o iio??eieo nenoaiao.
Niinoa??aa?oueny ooai?aiiy oa?ia?ieo niieoe c iaoaeaie, ye? ii/eiathoue
ia??iae (Sc,Ti), ?o a?aenooi?noue aeey nenoai c V (c Cr nenoaie ua ia
aeine?aeaeai?) ? iiiioiiiee c??no e?eueeino? niieoe a ?yaeo a?ae Mn aei
Cu. I?e ia?aoiae? aei Zn e?euee?noue niieoe ciaioo?oueny a?ae 13 (aeey
Cu-Li-Si) aei 1 (aeey Zn-Li-Si) ? a?ae 9 (aeey Cu-Li-Ge) aei 4 (aeey
Zn-Li-Ge).

Iiae?aiee oa?aeoa?, aea c? ci?uaiiyi iaeneioio ooai?aiiy oa?ia?ieo
niieoe ia Pd, iiaeia i?ine?aeeoaaoe ? aeey ?yaeo nenoai c 4-d iaoaeaie.

Aiae?c caeiiii??iinoae ooai?aiiy oa?ia?ieo niieoe oa iniaeeainoae ?o
e?enoae?/ii? no?oeoo?e iieaco?, ui ooai?aiiy oa?ia?ieo niieoe o
aeine?aeaeaieo nenoaiao caeaaeeoue a?ae oa?iiaeeiai?/ieo, ?ici??ieo oa
no?oeoo?ieo oaeoi??a aca?iiae?th/eo aeaiaio?a. Iaea?eueo ni?eyoeeaeie
oiiae aeey ooai?aiiy ? noaa?eueiiai ?nioaaiiy oa?ia?ieo ?ioa?iaoae?ae?a
o nenoaiao I-Li-{Si,Ge} (I-ia?ao?aeiee iaoae) ?:

ianoaa?eueia aeaeo?iiia eiio?ao?aoe?y d-??aiy ia?ao?aeiiai iaoaeo;

??cieoey i?ae ?aae?onaie aoii?a ia?ao?aeiiai aeaiaioo ? Li;

??ci? e?enoae?/i? no?oeoo?e aca?iiae?th/eo aeaiaio?a (?en.10).

Na?aae 38 oa?ia?ieo niieoe, ye? ?niothoue o nenoaiao
{Ti,V,Ag,Pd}-Li-{Si,Ge} iiai?noth a?aeii? e?enoae?/i? no?oeoo?e 29
niieoe, ye? e?enoae?cothoueny o 21 no?oeoo?iiio oei?.

Aeey niieoe c? neeaaeieie e?enoae?/ieie no?oeoo?aie oa?aeoa?ia oa?iaa
aoaeiaa (?en.11). A caeaaeiino? a?ae neeaaeiino?, no?oeoo?e iiaeooue
i?noeoe a?ae 2 aei 6 ??cieo aeae?a oa??a.

Aeey niieoe, ye? e?enoae?cothoueny o eoa?/i?e neiaii?? oa?aeoa?ia
?einaaae?e/ia oa eoaieoaaae?e/ia eii?aeeiaoe?y aoii?a. Aaenaaiiaeuei?
niieoee c ianeeaaeiith e?enoae?/iith no?oeoo?ith iathoue
?iiaiaeiaeaeaaae?e/io eii?aeeiaoe?th aoii?a (?en.12). Aeey iiiiee?iieo
niieoe niinoa??aathoueny oeeaaeee aeaoi?iiaaieo ?iiaiaeiaeaeaaae??a.

?ICAe?E 5

AENIIAEE

O aeniiaeao noi?ioeueiaai? iniiai? ?acoeueoaoe aeena?oaoe?eii? ?iaioe:

Ca aeiiiiiaith iaoiae?a ?aioaaiioaciaiai oa ?aioaaiino?oeoo?iiai aiae?co
aecia/aii oa?aeoa? o?ceei-o?i?/ii? aca?iiae?? eiiiiiaio?a o iio??eieo
nenoaiao {Ti,V,Ag,Pd}-Li-{Si,Ge} oa Cu-Li-Si. Aia?oa aeine?aeaeai? ?
iiaoaeiaai? ?cioa?i?/i? ia?a??ce ae?aa?ai noaio nenoai {Ti,V}-Li-{Si,Ge}
oa Cu-Li-Si i?e 570E, caaa?oaii aeine?aeaeaiiy, aeiiiaiai? ? aei?aaeai?
e?oa?aoo?i? aeai? oa iiaoaeiaai? ?cioa?i?/i? ia?a??ce ae?aa?ai noaio
nenoai {Ag,Pd}-Li-{Si,Ge} i?e 470E, ye? aoee ?ai?oa aeine?aeaeai?
/anoeiai.

Ia iniia? aiae?co e?oa?aoo?ieo oa iaea?aeaieo aenia?eiaioaeueieo aeaieo
aeyaeaii, ui iaea?eueoo caeaoi?noue aei ooai?aiiy oa?ia?ieo niieoe
i?iyaeythoue ia?ao?aei? iaoaee, ye? ciaoiaeyoueny ia ii/aoeo ? a e?ioe?
ia??iaeo. Oea iia’ycaii c iniaeeainoyie aeaeo?iiii? iaieiiee aeaiaio?a,
?o ?ici??aie oa oa?iiaeeiai?/ieie oa?aeoa?enoeeaie. Aeey ia?ao?aeieo
aeaiaio?a 4 ia??iaeo ooai?aiiy iaea?eueoi? e?eueeino? oa?ia?ieo niieoe
niinoa??aa?oueny o iio??eieo nenoaiao I?ae?, aeey ia?ao?aeieo aeaiaio?a
5 ia??iaeo – o iio??eieo nenoaiao Iaeaae?th.

Aeyaeaii, ui a?eueo?noue oaa?aeeo ?ic/ei?a ia iniia? a?ia?ieo niieoe o
nenoaiao Li-Si(Ge) oa Ti(V)-Si(Ge) ooai?ththoueny oeyoii /anoeiaiai
aca?iiiai cai?uaiiy aoii?a Li ? Ti(V). Aecia/aii, ui oaa?ae? ?ic/eie ia
iniia? a?ia?ieo niieoe Ti5Si3, Ti5Ge3, V5Si3 oa V5Ge3 ooai?ththoueny ye
oeyoii /anoeiaiai aca?iiiai cai?uaiiy aoii?a Ti(V) ia Li, oae ?
aeeth/aiiyi aoii?a Li o ionoioe a iieiaeaii? 2(b):000.

Anoaiiaeaii, ui o aeine?aeaeaieo nenoaiao ooai?th?oueny 38 oa?ia?ieo
niieoe. ?nioaaiiy 29 niieoe aoei aeyaeaii aia?oa. Aeey 21 niieoee
iiai?noth aecia/aia e?enoae?/ia no?oeoo?a, aeey 3 niieoe – /anoeiai.
?icoeo?iaaii ? iienaii 5 iiaeo no?oeoo?ieo oei?a.

Ia iniia? aiae?co neeaae?a niieoe o aeine?aeaeaieo nenoaiao anoaiiaeaii,
ui ia?aaaaeia a?eueo?noue (~50%) oa?ia?ieo ?ioa?iaoae?ae?a ooai?th?oueny
i?e eiioeaio?aoe?eiiio ni?aa?aeiioaii? Li:Si(Ge)=1:1. I?e/eiith oeueiai
iiaea aooe ooai?aiiy noaa?eueieo aeaeo?iiieo eiio?ao?aoe?e, ye?
aeieeathoue caaaeyee /anoeiai caiiaiaiei 3d- oa 4d-??aiyi ia?ao?aeieo
iaoae?a.

I?e aiae?c? e?enoae?/ieo no?oeoo? oa?ia?ieo niieoe o aeine?aeaeaieo
nenoaiao aoei aeyaeaii, ui aiie a?aeiinyoueny aei 4 a?oi:

aaenaaiiaeuei? niieoee c ?iiaiaeiaeaeaaae?e/iith eii?aeeiaoe??th aoii?a;

iiiiee?ii? niieoee c aeaoi?iiaaii-?iiaiaeiaeaeaaae?e/iith
eii?aeeiaoe??th aoii?a;

eoa?/i? niieoee c ?iiaiaeiaeaeaaae?e/iith oa eoaieoaaae?e/iith
eii?aeeiaoe??th aoii?a;

neeaaei? e?enoae?/i? no?oeoo?e c ??cieie niiniaaie oeeaaeee oa??a
aoii?a.

Iniiaiee ci?no aeena?oaoe?? aeeeaaeaii o ianooiieo ioae?eaoe?yo:

Iaaethe A.A., Eaai?eia Ae.A., Aiaeae I.E. E?enoaeee/aneay no?oeoo?a
niaaeeiaiey LiAg2Ge.// Iai?aaie/aneea iaoa?eaeu.- 1993.- O.29, ?5.-
C.723-724.

Iaaethe A.A., Eaai?eia Ae.A., Aiaeae I.E., Ia/a?neee A.E.
E?enoaeee/aneay no?oeoo?a LiCu3Si2.// E?enoaeeia?aoey.- 1995.- O.40,
?1.- N.178-179.

Iaaethe A.A., Eaai?eia Ae.A., Aiaeae I.E., Ia/a?neee A.E.
E?enoaeee/aneay no?oeoo?a Li7Cu7Si5.// E?enoaeeia?aoey.- 1995.- O.40,
?1.- N.180-182.

Iaaethe A.A., Eaai?eia Ae.A., Aiaeae I.E., Ia/a?neee A.E.
E?enoaeee/aneay no?oeoo?a Li113Cu54Si57.// E?enoaeeia?aoey.- 1995.-
O.40, ?1.- N.185-187.

Iaaethe A.A., Eaai?eia Ae.A., Aiaeae I.E., Ia/a?neee A.E.
E?enoaeee/aneay no?oeoo?a Li119Cu145Si177.// E?enoaeeia?aoey.- 1995.-
O.40, ?1.- N.188-189.

Eaai?eia Ae.A., Iaaethe A.A., Aiaeae I.E., Noaiaiue-Aeaii TH.
E?enoaeee/aneay no?oeoo?a LiPdSi3.// E?enoaeeia?aoey.- 1995.- O.40, ?1.-
N.177.

Iaaethe A.A., Eaai?eia Ae.A., Aiaeae I.E., Ia/a?neee A.E.
E?enoaeee/aneay no?oeoo?a Li13Pd12Si12.// E?enoaeeia?aoey.- 1995.- O.40,
?1.- N.183-184.

Kevorkov D.G., Pavlyuk V.V., Bodak O.I. X-ray investigation of the
Li-Ag-{Si,Ge} systems at 470K. // Polish J. Chem.- 1997.- V.71.-
P.712-715.

Kevorkov D.G., Pavlyuk V.V., Stempien-Damm J. Isothermal sections of the
Li-Ti-{Si,Ge} phase diagrams at 470K.// The fifth international school
“Phase diagram in material science”.- Katsyvely. 23-29 September 1996.-
P.63-64.

AIIOAOe?ss

Eaai?eia Ae.A. Oacia? ??aiiaaae oa e?enoae?/ia no?oeoo?a niieoe o
nenoaiao {Ti,V,Ag,Pd}-Li-{Si,Ge} oa Cu-Li-Si. ?oeiien.

Aeena?oaoe?y ia caeiaoooy iaoeiaiai nooiaiy eaiaeeaeaoa o?i?/ieo iaoe
ca niaoe?aeuei?noth 02.00.01 – Iai?aai?/ia o?i?y. -Euea?anueeee
aea?aeaaiee oi?aa?neoao ?i. ?.O?aiea, Euea?a, 1998.

Aeena?oaoe?y i?noeoue ?acoeueoaoe aeine?aeaeaiiy aca?iiae?? eiiiiiaio?a
o iio??eieo nenoaiao {Ti,V,Ag,Pd}-Li-{Si,Ge} oa Cu-Li-Si. Aeey nenoai
{Ti,V}-Li-{Si,Ge} oa Cu-Li-Si aia?oa aeine?aeaeai? ? iiaoaeiaai?
?cioa?i?/i? ia?a??ce ae?aa?ai noaio i?e 570E, a aeey nenoai
{Ag,Pd}-Li-{Si,Ge} caaa?oaii aeine?aeaeaiiy ? iiaoaeiaai? ?cioa?i?/i?
ia?a??ce ae?aa?ai noaio i?e 470E. Aeyaeaii ?nioaaiiy 38 oa?ia?ieo
niieoe, na?aae ieo – 29 aia?oa. Iiai?noth aecia/ai? e?enoae?/i?
no?oeoo?e aeey 21 niieoee, aeey 3 niieoe – /anoeiai.

m, a=1.3137(7), c=4.164(2) ii), Cu3LiSi2 (i?. a?. P6/mmm, a=1.7083(5),
c=0.7853(3) ii).

Eeth/ia? neiaa: ?cioa?i?/iee ia?a??c, ae?aa?aia noaio, e?enoae?/ia
no?oeoo?a, no?oeoo?iee oei.

AIIIOAOeEss

Eaai?eia Ae.A. Oaciaua ?aaiiaaney e e?enoaeee/aneay no?oeoo?a
niaaeeiaiee a nenoaiao {Ti,V,Ag,Pd}-Li-{Si,Ge} oa Cu-Li-Si. ?oeiienue.

Aeenna?oaoeey ia nieneaiea o/aiie noaiaie eaiaeeaeaoa oeie/aneeo iaoe
ii niaoeeaeueiinoe 02.00.01 – Iai?aaie/aneay oeiey. -Eueaianeee
ainoaea?noaaiiue oieaa?neoao ei. E.O?aiei, Eueaia, 1998.

Aeenna?oaoeey niaea?aeeo ?acoeueoaou enneaaeiaaiey acaeiiaeaenoaey
eiiiiiaioia a o?ieiuo nenoaiao {Ti,V,Ag,Pd}-Li-{Si,Ge} e Cu-Li-Si. Aeey
nenoai {Ti,V}-Li-{Si,Ge} e Cu-Li-Si aia?aua enneaaeiaaiu e iino?iaiu
ecioa?ie/aneea na/aiey aeeaa?aii ninoiyiey i?e 570E, a aeey nenoai
{Ag,Pd}-Li-{Si,Ge} caaa?oaii enneaaeiaaiea e iino?iaiu ecioa?ie/aneea
na/aiey aeeaa?aii ninoiyiey i?e 470E. Iaia?oaeaii 38 oa?ia?iuo
niaaeeiaiee, n?aaee ieo – 29 aia?aua. Iieiinoueth ii?aaeaeaiu
e?enoaeee/aneea no?oeoo?u aeey 21 niaaeeiaiey, aeey 3 niaaeeiaiee –
/anoe/ii.

m, a=1.3137(7), c=4.164(2) ii), Cu3LiSi2 (i?. a?. P6/mmm, a=1.7083(5),
c=0.7853(3) ii).

Eeth/aaua neiaa: ecioa?ie/aneia na/aiea, aeeaa?aiia ninoiyiey,
e?enoaeee/aneay no?oeoo?a, no?oeoo?iue oei.

SUMMARY

Kavorkov D.G. Phase equilibria and crystal structures of the compounds
in the systems {Ti,V,Ag,Pd}-Li-{Si,Ge} and Cu-Li-Si. Manuscript.

Thesis for getting a scientific degree of candidate of chemical
sciences by speciality 02.00.01 – Inorganic chemistry. -I.Franko Lviv
State University, Lviv, 1998.

The dissertation contains the results of the investigation of
components interactions in the {Ti,V,Ag,Pd}-Li-{Si,Ge} and Cu-Li-Si
ternary systems. The isothermal sections of phase diagrams at 570K are
investigated and constructed for the {Ti,V}-Li-{Si,Ge} and Cu-Li-Si
ternary systems. The isothermal sections of phase diagrams at 470K are
investigated and constructed for the {Ag,Pd}-Li-{Si,Ge} ternary systems.
38 ternary compounds are observed, the 29 compounds form them are new.
The crystal structures for 21 compounds are completely determined, for 3
compounds are partly determined.

m, a=1.3137(7), c=4.164(2) nm), Cu3LiSi2 (sp.gr. P6/mmm, a=1.7083(5),
c=0.7853(3) nm) are investigated and described.

Key words: isothermal section, phase diagram, crystal structure,
structure type.

I?aeienaii aei ae?oeo 9.12.98, Oi?iao 60o84/16.

Ae?oe. A?eoo?a 1,0. Oe?aae 100 i?ei. Caiiae. ?485

Euea?a. Ae?iaie/i-eiia?oe?eia i?aei?e?inoai “AIN”.

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