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Синтез твердых растворов и исследования низкотемпературных фазовых превращений

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IINEIANEEE I?AeAIA EAIEIA, I?AeAIA IEOssA?UeNEIE ?AAIETHOeEE E I?AeAIA
O?OAeIAIAI E?ANIIAI CIAIAIE AINOAeA?NOAAIIUE OIEAA?NEOAO eiaie
I.A.EIIIIINIAA

OEIE*ANEEE OAEOEUeOAO

Eaoaae?a iai?aaie/aneie oeiee

Eaai?aoi?ey iai?aaie/aneiai iaoa?eaeiaaaeaiey

EO?NIAAss ?AAIOA

ii iai?aaie/aneie oeiee

nooaeaioa 104 a?oiiu

I?eiaie Iaoaeuee Aeeoi?iaiu

NEIOAC E ENNEAAeIAAIEss IECEIOAIIA?AOO?IUO OACIAUO I?AA?AUAIEE OAA?AeUO
?ANOAI?IA A NENOAIA Bi2O3-CaO

Iao/iue ?oeiaiaeeoaeue : ieaaeoee iao/iue nio?oaeiee Eiioueei
A.A.

I?aiiaeaaaoaeue: e.o.i., noa?oee i?aiiaeaaaoaeue Eoi?eyiiaa
A.I.

Iineaa – 1997

Niaea?aeaiea.

1. Aaaaeaiea……………………………………………………………………………

2. Eeoa?aoo?iue iaci?……………………………………………………………….

2.1. Oaciaua niioiioaiey a nenoaia Bi2O3-CaO…………………………..

2.2. Iaoiaeu neioaca ea?aie/aneeo iaoa?eaeia…………………………….

2.2.1. Ea?aie/aneee iaoiae……………………………………………

2.2.2. Iaoiaeu oeie/aneiai inaaeaeaiey………………………………

2.2.3. Cieue-aaeue iaoiae…………………………………………………

2.2.4. ?aniueeoaeueiay nooea………………………………………….

2.2.5. E?eioeie/aneee iaoiae………………………………………

2.3. Oaciaua i?aa?auaiey a oaa?aeii ninoiyiee…………………………

3. Yenia?eiaioaeueiay /anoue…………………………………………………………

3.1. Neioac oaa?aeuo ?anoai?ia Bi2O3-CaO…………………………………..

3.2. Yenia?eiaiou ii ieceioaiia?aoo?iiio ?aniaaeo oaa?aeuo ?anoai?ia..

3.3. Iaoiaeu enneaaeiaaiey…………………………………………………….

4. Ianoaeaeaiea ?acoeueoaoia……………………………………………………………

5. Auaiaeu………………………………………………………………………………

6. Eeoa?aoo?a…………………………………………………………………………..

1.Aaaaeaiea.

A iineaaeiaa a?aiy iaaethaeaaony oneeaiiue eioa?an e enneaaeiaaieyi n
i?eiaiaieai eiiiuo yeaeo?ieeoia. A nayce n yoei aaaeiia cia/aiea eiaao
nicaeaiea oaa?aeuo yeaeo?ieeoia, ?aaioathueo a oe?ieii oaiia?aoo?iii
eioa?aaea. Ecaanoiu oaa?aeua yeaeo?ieeou, ?aaioathuea i?e aunieeo
oaiia?aoo?ao (aieaa 1000 E) (iaoa?eaeu ia iniiaa ieneaeia oee?eiiey
ZrO2, oi?ey ThO2 e o.ae.). A n?aaieoaeueii ieceie oaiia?aoo?iie iaeanoe
(ieiei 700E) oi?ioi ecaanoiu oaa?aeua yeaeo?ieeou ia iniiaa ieneaea
aeniooa (Bi2O3), eaae?iaaiiiai ieneaeaie ?aaeeicaiaeueiuo yeaiaioia
(?CY) e ieneaeaie uaei/ii-caiaeueiuo yeaiaioia (UCY). I?e yoii
ia?acothueany oaa?aeua ?anoai?u eiatho ieceioaiia?aoo?ioth a?aieoeo
noaaeeueiinoe, ieaea eioi?ie oa?iiaeeiaie/anee onoie/eau niaaeeiaiey, ia
iaeaaeathuea caiaoiie eiiiie i?iaiaeeiinoueth. A nayce n /ai aaaeiie
caaea/ae yaeyaony enneaaeiaaiea iecei oaiia?aoo?iuo i?aa?auaiee oaa?aeuo
?anoai?ia ia iniiaa ieneaeia aeniooa. Aeaiiay ?aaioa auiieiaia a
eaai?aoi?ee iai?aaie/aneiai iaoa?eaeiaaaeaiey eaoaae?u iai?aaie/aneie
oeiee Oeie/aneiai oaeoeueoaoa IAO a ?aieao i?iaeoa ?OOE ? 96-03-33097a.

2.Eeoa?aoo?iue iaci?.

2.1. Oaciaua niioiioaiey a nenoaia Bi2O3-CaO.

Oaciaua ?aaiiaaney a inaaaeiaeia?iuo nenoaiao Bi2O3-MO (M=Ca, Sr, Ba )
eco/aeenue iiiaeie enneaaeiaaoaeyie [1, 2, 3, 4]. Oaciaay aeeaa?aiia
i?eaaaeaia ia ?en.1. Oaeaoaoe e ae?.[2] oaeaea enneaaeiaaee
yeaeo?e/aneea oa?aeoa?enoeee a oaa?aeuo ?anoai?ao nenoaiu Bi2O3-CaO.
Eiioeaio e ae?.[3] i?aaenoaaeee yoo nenoaio a aeaea /aou?ao
eieiia?oyioii ieaayueony niaaeeiaiee (Bi14Ca5O26, Bi2CaO4, Bi10Ca7O22 e
Bi6Ca7O16) e oaa?aeuo ?anoai?ia (aeaa eoae/aneeo e aeaa
?iiaiyae?e/aneeo). Oaeaea iie iaia?oaeeee, /oi ?iiaiyae?e/aneee oaa?aeue
?anoai? noaaeeece?iaaiiiai eaeueoeeai ieneaea aeniooa (Bi2O3) aue
ecino?oeoo?ai nenoaia ieneaeia Bi2O3-CdO (?aiaa yoi auei enneaaeiaaii
Neeeaiii [5]). Oaeaoaoe e ae?. [2] iaoee, /oi ?iiaiyae?e/aneay oaca
iieacuaaao aunieoth eenei?iaeioth e eiiioth i?iaiaeeiinoue. I?e yoii i?e
iiieaeaiee oaiia?aoo?u ieaea 690N eoae/aneee oaa?aeue ?anoai?
i?aoa?iaaaao yaoaeoieaeiue ?aniaae ia iiiieeeiiue ieneae aeniooa
(?anoai?eiinoue eaeueoeey a eioi?ii i?aiaa?aaeeii iaea) e
?iiaiyae?e/aneee oaa?aeue ?anoai?, eioi?ue a naith i/a?aaeue i?e
oaiia?aoo?a 725N ia?aoiaeeo a ?iiaiyae?e/aneee ?anoai? ae?oaie
no?oeoo?u. Auoa 840N e aei oaiia?aoo?u ieaaeaiey nouanoaoao oieueei
eoae/aneee oaa?aeue ?anoai?.

2.2. Iaoiaeu neioaca ea?aie/aneeo iaoa?eaeia.

2.2.1 Ea?aie/aneee iaoiae.

A aieueoeinoaa neo/aaa aeey iieo/aiey ieneaeiuo iaoa?eaeia aeoeaii
eniieuecoaony oae iacuaaaiue “ea?aie/aneee iaoiae”, caeeth/athueeny a
ouaoaeueiii iaoaie/aneii niaoaiee ieneaeia e iiaoi?ythueony oeeeeia
“iaaeea-iiiie” aeey iieiiai iaania/aiey oaa?aeioaciiai acaeiiaeaenoaey.
A ?yaea neo/aaa aianoi ieneaeia eniieuecoaony aieaa eaaeiaeinooiiua
ea?aiiaou, ieo?aou eee ae?oaea niee.

?en. 1. Oaciaay aeeaa?aiia nenoaiu CaO – 1/2 Bi2O3 [4].

Yoio iaoiae aeinoaoi/ii o?aaeeoeeiiai i?e iieo/aiee ethauo aeaeia
eiino?oeoeeiiiie e ooieoeeiiaeueiie ea?aieee, iaeiaei ii iaeaaeaao
?yaeii nouanoaaiiuo iaaeinoaoeia. Aeaaiue aai iaaeinoaoie –
aeeeoaeueiinoue oa?ie/aneie ia?aaioee ec-ca aeinoaoi/ii e?oiiie
e?enoaeee/iinoe e iaiaeii?iaeiinoe niaoaiey ?aaaaioia. I?e yoii /aua
anaai eiaao ianoi iaeiio?iee?oaiue ?ino e?enoaeeia e, eae neaaenoaea,
iiieii oeie/aneie aua e a?aioeiiao?e/aneay iaiaeii?iaeiinoue aac oiai
aiecio?iiiuo ca?ai ea?aie/aneeo iaoa?eaeia, i?eaiaeyuay e
iaaini?iecaiaeeiinoe yeaeo?e/aneeo e iaaieoiuo naienoa.

Iiyoiio aieueoia /enei enneaaeiaaiee a iaeanoe oaoiieiaee ea?aie/aneeo
iaoa?eaeia naycaii n ?ac?aaioeie e i?eiaiaieai oae iacuaaaiuo
“oeie/aneeo iaoiaeia” iieo/aiey ii?ioeia. Oeie/aneea iaoiaeu iicaieytho
iiauneoue aiiiaaiiinoue i?iaeoeoa ca n/ao niaoaiey eiiiiiaioia a
?anoai?a ia iieaeoey?iii o?iaia e nio?aiaiey yoiai o?iaiy (n aieueoeie
eee iaiueoeie oniaoaie) ia iineaaeieo noaaeeyo. Iieo/aaiua ii?ioee
eiatho aeinoaoi/ii aunieoth oaeaeueioth iiaa?oiinoue e, eae neaaenoaea,
aeoeaiu a i?ioeannao oaa?aeioaciiai acaeiiaeaenoaey. Ieaea aoaeoo
?anniio?aiu iaeaieaa ?ani?ino?aiaiiua “oeie/aneea iaoiaeu” iieo/aiey
ea?aie/aneeo ia?acoeia [6,7].

2.2.2. Iaoiaeu oeie/aneiai inaaeaeaiey.

Iaoiaeu oeie/aneiai inaaeaeaiey caeeth/athony a niaianoiii inaaeaeaiee
eiiiiiaioia ea?aieee ec ?anoai?a a aeaea ia?anoai?eiuo nieae. Yoe
iaoiaeu iieo/eee oe?ieia ?ani?ino?aiaiea aeey neioaca ?aciiia?aciuo
aeaeia ea?aieee. I?e i?aaeeueiie iinoaiiaea yenia?eiaioa a ?yaea neo/aaa
oaeaaony aini?iecaiaeeii iieo/eoue aiiiaaiioth aeenia?nioth nianue nieae
n caaeaiiui niioiioaieai eaoeiiia. A eaeaaea iioeiaeueiui iiaeii
n/eoaoue oaeea oneiaey (ia?aaeecoaiua, a iieiie ia?a, ia i?aeoeea ec-ca
?acee/ey oeie/aneeo naienoa eiiiiiaioia), eiaaea eaoeiiu ec ?anoai?a
inaaeaeathony iaeiia?aiaiii e n iaeeiaeiaie nei?inoueth. Iaeaieaa
?ani?ino?aiaiu aeaa oeia oeie/aneiai inaaeaeaiey – oi ienaeaoiue e
ea?aiiaoiue iaoiaeu.

-aeey inaaeaeaiey ienaeaoia a ea/anoaa enoiaeiuo ?aaaaioia
eniieuecothony ieo?aou eee aoeaoaou , a a ea/anoaa inaaeeoaeae – niane
uaaaeaaay eeneioa – aiieae, uaaaeaaay eeneioa – o?eyoeeaiei , eeai
ecauoie ianuoaiiiai ?anoai?a ienaeaoa aiiiiey i?e oeene?iaaiiie
eeneioiinoe ?anoai?a, eeai aiaeiue ?anoai? aeeiaoeeienaeaoa . I?ioeann
inaaeaeaiey ineiaeiyaony neeueiie e iaiaeeiaeiaie caaeneiinoueth
?anoai?eiinoe ienaeaoia eaeueoeey e aeniooa io aaee/eiu ?I e io
eiioeaio?aoeee enoiaeiuo ?aaaaioia.

-i?eioeeieaeueii inaaeaeaiea ea?aiiaoia aiaeiae/ii ienaeaoai. A ea/anoaa
inaaeeoaey i?e inaaeaeaiee ea?aiiaoiuo nieae eniieuecoaony ecauoie
aeae?iea?aiiaoa aiiiiey, ecauoie ea?aiiaoa iao?ey, ea?aiiao
oao?aiaoeeaiiiiey. Inaaeaeaiea i?iaiaeyo i?e ?I>8, nicaeaaaaiui
aeiaaaeaieai ?anoai?a aiieaea eee aeae?ieneaea iao?ey. A iineaaeiai
neo/aa, ?aaii eae e a neo/aa inaaeaeaiey ea?aiiaoii iao?ey, i?eoiaeeony
oaeaeyoue iniaia aieiaiea noaaeee i?iiuaee inaaeea, iineieueeo i?eiane
uaei/iuo iaoaeeia iiaoo eciaiyoue naienoaa iieo/aaiuo iaoa?eaeia ( yoio
i?ioeann iiaeao nii?iaiaeaeaoueny naeaeoeaiui ?anoai?aieai e ia?ooaieai
noaoeiiao?ee).

2.2.3. Cieue-aaeue iaoiae.

Yoio iaoiae iniiaai ia niiniaiinoe oaeaoiuo eiiieaenia n eiiaie iaoaeeia
(iai?eia? oeeo?aoiuo) ia?aciauaaoue i?e iaa?aaaiee (100-140N) n
iiiaiooieoeeiiaeueiuie nie?oaie (iai?eia?, yoeeaiaeeeieai)
ieceiiieaeoey?iuo ieeaiia?ia (yoa?eoeeaoeey) (?en.2). I?e iaa?aaaiee
iineaaeieo i?ienoiaeeo aeaeueiaeoay iieeia?ecaoeey e ia?acoaony ayceay
niiea (aaeue), i?e ?aceiaeaiee eioi?ie iieo/aaony ieneaeiue ii?ioie.

Anee i?aaeiieiaeeoue, /oi eiiieaenu ea?aieeiia?acothueo iaoaeeia
aiiiaaiii ?ani?aaeaeaiu a ?anoai?a e yoi ?ani?aaeaeaiea nio?aiyaony e
iinea iieeia?ecaoeee, oi ia nouanoaoao i?e/ei, ec-ca eioi?uo ia?ooaaony
aiiiaaiiinoue i?e ?aceiaeaiee. Yoi ianoiyoaeuenoai iicaieyao
?aeiiaiaeiaaoue cieue-aaeue iaoiae aeey ?aaio, iai?aaeaiiuo ia auyaeaiea
i?eianae eee caiauaiee ia naienoaa ea?aie/aneeo iaoa?eaeia.

?en.2. Noaia i?ioeannia, i?ienoiaeyueo i?e oeeo?aoiii cieue-aaeue
neioaca.

Iaoiae nai ii naaa ia aei?ia, o.e. i?aeoe/anee ia o?aaoao aiia?aoo?u
(ionoonoaea iia?aoeee oeaio?eooae?iaaiey, oeeueo?aoeee, i?iiuaee e
nooee), a a ea/anoaa enoiaeiuo iaoa?eaeia /aua anaai eniieuecothony
aeinooiiua ieo?aou.

I?aia?aoeaii oeeo?aoiue aa?eaio cieue-aaeue i?ioeanna inouanoaeyaony
neaaeothuei ia?acii [8]. A niane aiaeiiai ?anoai?a ieo?aoia e
yoeeaiaeeeiey (eiiaaea aeiaaaeytho aiieae aeey iiauoaiey ?I aei 3-5)
aeiaaaeytho ?anoai? eeiiiiie eeneiou a niioiioaiee 1 a-yeaeaaeaio
eeneiou ia 1 a-yeaeaaeaio iaoaeea. Yoeeaiaeeeieue iau/ii aa?oo a
ecauoea, iineieueeo aeae?ieneeueiua a?oiiu noaaeeece?otho a ?anoai?a
iaoaee-oeeo?aoiua eiiieaenu e niinianoaotho ia?aciaaieth
ieceiiieaeoey?iuo ieeaiia?ia.

Ae?oaie iaoiae, /anoi ioiineiue e /eneo “cieue-aaeue” i?ioeannia – oae
iacuaaaiay aeeienioaoiieiaey. Iia iniiaaia ia iieo/aiee ii?ioeia (eee
oiieeo ieaiie) i?e iaaeeaiiii aeae?ieeca niane ?anoai?ia aeeiaieyoia
iaoaeeia. Iaoiae ia?niaeoeaai aeey iieo/aiey iaaieueoeo eiee/anoa i/aiue
/enouo e aiiiaaiiuo ii?ioeia, a oaeaea aieieii, ieaiie, ea?aieee.

Iaaeinoaoie iaoiaea – iaeay aeinooiiinoue e aei?iaiaecia enoiaeiuo aeey
neioaca ?aaeoeaia. E?iia oiai, niaoeeoe/aneay aeey ea?aie/aneeo
iaoa?eaeia i?iaeaia aeeieneaeiiai iaoiaea caeeth/aaony a o?oaeiinoe
i?eaioiaeaiey aiiiaaiiie niane aeeieneaeia, iineieueeo i?aeoe/anee ia
nouanoaoao aeeiaieyoia eaeueoeey, ?anoai?eiuo a ?ani?ino?aiaiiuo
?anoai?eoaeyo.

2.2.4. ?aniueeoaeueiay nooea.

Ie iaeei ec oeie/aneeo iaoiaeia iieo/aiey ea?aie/aneeo iaoa?eaeia ia
iieo/ee oaeiai ?ani?ino?aiaiey, eae iaoiae ?aniueeoaeueiie nooee. Yoi
iaeaieaa e?oiiiianooaaiue iooue iieo/aiey iaeeiaeenia?niuo, aeoeaiuo
ii?ioeia aeey i?iecaiaenoaa ea?aie/aneeo iaoa?eaeia. Nooue iaoiaea
ninoieo a oii, /oi nianue ?anoai?ia nieae, ia?aaaaeaiiay iin?aaenoaii
oeueo?acaoeiaiai ?aniueeoaey a ninoiyiea ay?iciey n ?acia?ii /anoeoe
0.5-0.8 iei, ia?aiineony aacii-iineoaeai a ai?y/oth eaia?o, aaea
i?ienoiaeeo iaiiaaiiia (iieiia eee /anoe/iia) ?aceiaeaiea /anoeoe;
ia?aciaaaoeeny ieneaeii-nieaaie i?iaeoeo niae?atho ia oeeueo?a.

Niaoaiea eiiiiiaioia a ?anoai?a ia aoiiiii o?iaia, i?aeoe/anee
iaiiaaiiia iaacaiaeeaaiea e ?aceiaeaiea iee?ieaiaeue ay?iciey iicaieyao
iieo/eoue aiiiaaiiue i?iaeoeo, ecaaaeaa oa?aeoa?iua ea?aie/aneiio
iaoiaeo i?ioeannu iiaoi?iiai ia?aiiea e iaaeeaa, caa?yciythuea i?iaeoeo
e i?eaiaeyuea e iaii?ie?iaaiiiio ?inoo ca?ai. Aianoa n oai iieo/aaiua
ii?ioee iiaoo caa?yciyoueny iaoa?eaeaie, ec eioi?uo naeaeaia eaia?a aeey
?aniueaiey (aunieea oaiia?aoo?u, i?enoonoaea naiaiaeiie eeneiou); iiieii
yoiai aeey oiai, /oiau ecaaaeaoue ia?aciaaiea ea?aiiaoia, i?eoiaeeony
ouaoaeueii i/euaoue aieueoea iauaiu aaca-iineoaey (eenei?iaea) io
i?eianae NI2.

Iaeaieaa ?ani?ino?aiaiiui aeey aeaiiiai iaoiaea oeiii nieae yaeythony
ieo?aou.

2.2.5.E?eioeie/aneee iaoiae.

Iaaeinoaoie aieueoeinoaa oeie/aneeo iaoiaeia neioaca ea?aie/aneeo
ii?ioeia oaeaaony a cia/eoaeueiie ia?a ono?aieoue i?e eo neioaca
iaoiaeii e?eioeie/aneie oaoiieiaee [9]. Nooue aa naiaeeony e iieo/aieth
oiieiaeenia?niiai e aunieiaiiiaaiiiai nieaaiai ?anoai?a (a caoai e
ieneaeiiai) i?aeo?ni?a iin?aaenoaii auno?iai caii?aaeeaaiey oiiei
?aniueaiiiai ?anoai?a nieae (iieo/aiea e?eia?aioeyoa) e iineaaeothuaai
noaeeiaoeeiiiiai oaeaeaiey aiaeu. I?e yoii iaiaoiaeeii noa?aoueny
i?iaiaeeoue yenia?eiaio a oneiaeyo, eneeth/athueo i?ioaeaiey
oeceei-oeie/aneeo i?ioeannia, i?eaiaeyueo e ia?ooaieth oeie/aneie e
a?aioeiiao?e/aneie iaeii?iaeiinoe i?iaeoeoa. Oaeiauie iiaoo auoue:

1.?anneiaiea ?aniueyaiuo iee?ieaiaeue ia iaeanoe iaiaauaiiua e
iaaaeiaiiua ?anoai?eoaeai ec-ca iaaeinoaoi/ii aunieeo nei?inoae
ioeaaeaeaiey (yoiai oaeaaony ecaaaeaoue, anee ?aniueyoue ?anoai? ia a
aeeaeeee acio (eee ioeaaeaeaiiue aaenai), a ia ianneaioth ioeaaeaeaiioth
aei oaiia?aoo?u aeeaeeiai acioa iaoaeee/aneoth ieanoeio).

2.Iiaeieaaeaiea e?eia?aioeyoa a i?ioeanna noaeeiaoeeiiiie nooee ca n/ao
ia?aciaaiey ieceiieaaeeo yaoaeoee (a neo/aa ?anoai?ia ieo?aoia –
yaoaeoeee H2O-HNO3 n oaiia?aoo?ie -43N). Aeey yoiai iuoathony
caiaieoue, aaea aiciiaeii, ?anoai?u ieo?aoia ia aoeaoaoiua (ii oiaaea
aicieeaao i?iaeaia ia?aciaaiey e ?aceiaeaiey ea?aiiaoia), eee
ieo?ao-ieo?eoiuo, eeai eniieuecotho ?acaaaeaiiua ?anoai?u ieo?aoia n
iaaunieie eeneioiinoueth (0.1 iieue ii aeniooo n ?I 0.7).

3.Naa?aaaoeey eiiiiiaioia i?iaeoeoa noaeeiaoeeiiiie nooee (niaea?aeauaai
aua aei 3 iann.% aiaeu) i?e aai oa?ie/aneie ia?aaioea ca n/ao ieaaeaiey
aeae?aoia Ca(NO3)2*4H2O (42C) e Ca(NO3)2*3H2O (112C). A yoii neo/aa
nooeo ?aeiiaiaeoaony i?iaiaeeoue a oiieii neia i?e iaaeeaiiii (5N//an)
iaa?aaaiee aei 125N a oiea a?aiia.

4.Iaaeaeaoaeueiia ia?aciaaiea ea?aiiaoia ec-ca i?enoonoaey NI2 a
aoiinoa?a i?e ioaeeaa. Iaaeinoaoi/ii eniieueciaaoue a yoii neo/aa
i/euaiiue io oaeaeeneiai aaca aicaeoo – aieaa yooaeoeaii nicaeaiea
iaiaoiaeeiiai ia?oeeaeueiiai aeaaeaiey eenei?iaea niaoaieai eenei?iaea e
a?aiia a niioaaonoaothueo eiee/anoaao.

Eniieueciaaiea iaeeiaeenia?niuo (nioie aiano?ai) e aunieiaiiiaaiiuo
i?aeo?ni?ia, i?eaioiaeaiiuo n eniieueciaaieai i?eaiia e?eioeie/aneie
oaoiieiaee iicaieeei iieo/eoue o?oaeii neioace?oaiua n eniieueciaaieai
ae?oaeo iaoiaeia ea?aie/aneea oacu.

2.3. Oaciaua i?aa?auaiey a oaa?aeii ninoiyiee.

I?e iineaaeiaaoaeueiii iino?iaiee oai?ee oaciauo i?aa?auaiee [10]
?anniao?eaathony i?e/eiu eciaiaiey oaciaiai ninoiyiey e iaoaieci
i?aa?auaiey. I?e/eiie oaciauo i?aa?auaiee yaeyaony eciaiaiea
noaaeeueiinoe oac a caaeneiinoe io aiaoieo aicaeaenoaee. Iai?eia?,
noaaeeueiay a ii?aaeaeaiiie oaiia?aoo?iie iaeanoe oaca noaiiaeony
ianoaaeeueiie i?e iiieaeaiee eee iiauoaiee oaiia?aoo?u.

I?e ethaii oaciaii i?aa?auaiee a oaa?aeii ninoiyiee i?ienoiaeeo
ia?ano?ieea aoiiiie no?oeoo?u nenoaiu. A oaa?aeii ninoiyiee ia?ano?ieea
no?oeoo?u eiaao ianoi, e?iia oiai, i?e i?ioeannao, ia yaeythueieny
oaciauie i?aa?auaieyie, iai?eia?, i?e ?ae?enoaeeecaoeee, ieanoe/aneie
aeaoi?iaoeee neieueaeaieai e aeaieieeiaaieai. Oaeea i?ioeannu
ioee/athony io oaciauo i?aa?auaiee i?e/eiie ia?ano?ieee e?enoaeee/aneie
?aoaoee: aoiiu caieiatho iiaua iieiaeaiey iiae aeaenoaeai iiaa?oiinoiuo
eee oi?oaeo nee, aiaoiaai iai?yaeaiey, a ia aneaaenoaea oiai, /oi
oa?iiaeeiaie/aneee iioaioeeae iaeiie eiioeao?aoeee aoiiia ieaea, /ai
ae?oaie.

Eeanneoeeaoeey oaciauo i?aa?auaiee iiaeao auoue i?iaaaeaia ia iniiaa
n?aaiaiey oaciaiai ninoaaa nenoaiu a ia/aeueiii e eiia/iii ninoiyieyo.
I?iaeoeo oaciaiai i?aa?auaiey iiaeao ioee/aoueny io enoiaeiie
(iao?e/iie) oacu:

1. ninoaaii i?e nio?aiaiee eii?aeeiaoeee aoiiia a ?aoaoea
(ecino?oeoo?iue ?aniaae oaa?aeiai ?anoai?a);

2. no?oeoo?ie e oaciaui ninoaaii (yaoaeoieaeiue ?aniaae, auaeaeaiea
ecauoi/iie oacu);

3.e?enoaeee/aneie no?oeoo?ie, o.a. eii?aeeiaoeeae aoiiia a ?aoaoea
(ia?oaineoiia e ianneaiia i?aa?auaiey, oii?yaei/aiey
aoiiii-e?enoaeee/aneie no?oeoo?u).

Ae?oaay eeanneoeeaoeey oaciauo i?aa?auaiee a oaa?aeii oaea iiaeao auoue
iniiaaia ia iaoaiecia i?ioaeathueo i?ioeannia.

Aeeoooceiiiua i?ioeannu. E iei ioiinyony eae i?ioeannu, i?ioaeathuea
/a?ac noaaeee ia?aciaaiey e ?inoa ca?iaeuoae iiaie oacu, oae e
i?ioeannu, naycaiiua n ?anneaeaaieai oaa?aeiai ?anoai?a ia o/anoee n
aieueoae e iaiueoae eiioeaio?aoeeae eiiiiiaioa (nieiiaeaeueiue ?aniaae,
ia?aciaaiea cii Aeiuea – I?anoiia).

Aacaeeoooceiiiua i?ioeannu. Yoi i?ioeannu, i?ienoiaeyuea ca n/ao
eieeaeoeaiuo ia?aa?oiie?iaie aoiiia ia ?annoiyiey ii?yaeea iaaeaoiiiuo
(iai?eia? ia?oaineoiia e ianneaiia i?aa?auaiey).

Auaiae i i?ioaeaiee i?ioeanna ii oiio eee eiiio iaoaiecio iiaeii
naeaeaoue enoiaey ec ii?oieiaee iieo/aiiiai i?iaeoeoa ii aeaiiui
yeaeo?iiiie eee iioe/aneie iee?ineiiee.

3. Yenia?eiaioaeueiay /anoue.

3.1. Neioac oaa?aeuo ?anoai?ia Bi2O3-CaO.

Aeey ia?aie noaaeee yenia?eiaioa a ea/anoaa enoiaeiuo aauanoa auee acyou
ieneae aeniooa (Bi2O3) e ea?aiiao eaeueoeey (CaCO3) a iieueiuo
niioiioaieyo Bi2O3/CaCO3 – 0.96:0.04, 0.9:0.1, 0.8:0.2, 0.76:0.24,
0.7:0.3, 0.6:0.4, 0.5:0.5. Eaaeeoeeaoeey anao enoiaeiuo i?aia?aoia auea
ia ieaea “/.ae.a.”. ?aaaaiou niaoeaaeenue aeey iieo/aiey eae iiaeii
aieaa iaeii?iaeiie niane, iinea /aai i?ieaeeaaeenue ia aicaeooa i?e
oaiia?aoo?a 750N a oa/aiea 24 /ania a o?oa/aoie ia/e n iineaaeothuei
?aioaaiioaciaui aiaeecii iieo/aiiuo ia?acoeia. A oiaea ?aaeoeee

0.5(1-o) Bi2O3 + o CaCO3 == Bi1-oNaoI1.5-0.5x+ o CO2 (niaeaiea i?e 750N,
24 /ana)

auaeaeyeny oaeaeeneue aac (CO2) e ia?aciauaaeny aeaeoue ii?ioie. Aeey
iaiaeiioaciuo, ii aeaiiui ?OA , ia?acoeia oeeee “iiiie-ioaeea” aue
iiaoi?ai i?e oao aea oneiaeyo.

Iieo/aiiue a ?acoeueoaoa i?aaeuaeouae noaaeee yenia?eiaioa ii?ioie
ninoaaa Bi1-xCaxOy (o = 0.02, 0.05) aue ?anoai?ai a ?acaaaeaiiii
?anoai?a acioiie eeneiou (30%) e oia?ai ia ai?aeea aei ia/aea auaeaeaiey
BiONO3 a aeaea oiieie ieaiee ia iiaa?oiinoe ?anoai?a:

Bi(NO3)3 = BiONO3 + 2 NO2 + 0.5 O2

Iinea yoiai aue i?iecaaaeai oae iacuaaaiue “aoiaaeiue neioac” [11] :
ia?aciaaaoeiny ?anoai?ii i?iieoaee ianeieueei eenoia aoiaaeiiai oeeueo?a
(aeey i?aaeioa?auaiey ?anneiaiey eiiiiiaioia ?anoai?a i?e ?aceiaeaiee) e
i?iecaiaeeee ?aceiaeaiea ia ai?aeea aei ieii/aiey ?aaeoeee
ainnoaiiaeaiey ecauoi/iie acioiie eeneiou aetheicie, ia?aciaaaoaeny i?e
aeae?ieeca oeaeetheicu aoiaae (i?eciaeii ieii/aiey ?aaeoeee auei
i?ae?auaiea auaeaeaiey ao?iai aaca NO2), ieo?ao aeniooa i?e yoii
iieiinoueth ?aceiaeeeny aei ieneieo?aoa. Caoai i?iaeoeo ?aaeoeee a
oa/aiee 30 ieioo ioaeeaaee a iooaeueiie ia/e i?e oaiia?aoo?a 750N, a
iinea i?iecaaee caeaeeo ia aicaeooa. I?e yoii i?ienoiaeeei ?aceiaeaiea
ieo?aoia n iaeiia?aiaiiui ia?aciaaieai oaa?aeiai ?anoai?a:

(1-o) BiONO3 + x Ca(NO3)2 = Bi1-xCaxO1.5-0.5x + (1+2x) NO2 + 0.25(1+2x)
O2

Neaaeothuae noaaeeae yenia?eiaioa aue iiiie iieo/aiiiai aauanoaa n
iineaaeothuae ia?aaioeie a o?oa/aoie ia/e a oa/aiea 24 /ania i?e
oaiia?aoo?a 750N, n iineaaeothuae caeaeeie ia aicaeooa e niyoeai
?aioaaiia?aii iieo/aiiiai aauanoaa.

3.2. Yenia?eiaiou ii ieceioaiia?aoo?iiio ?aniaaeo iieo/aiiiai aauanoaa.

Aeey enneaaeiaaiey ieceioaiia?aoo?iiai ?aniaaea oaa?aeiai ?anoai?a
Bi0.98Ca0.02O1.49 auea i?iaaaeaia na?ey ioaeeaia i?e oaiia?aoo?a 550N ia
aicaeooa n a?aiaiaie 1, 2, 5, 15 ieioo e iineaaeothuei
?aioaaiia?aoe/aneei e yeaeo?iiiiiee?ineiie/aneei aiaeecii iieo/aiiuo
ia?acoeia.

3.3. Iaoiaeu enneaaeiaaiey.

Aeey enneaaeiaaiey iieo/aiiuo ia?acoeia auee eniieueciaaiu iaoiaeu
?aioaaiioaciaiai aiaeeca e i?inaa/eaathuae yeaeo?iiiie iee?ineiiee.

Aeey ?aioaaiioaciaiai aiaeeca ia?acoeu nieiaee ia aeeo?aeoiiao?a
Ae?II-3I (eceo/aiea CuKan?) n oaaii nuaiee 0.1 I, a?aiaiai yeniiceoeee 2
nae., eioa?aaeii nuaiee 20I-60I, a ea/anoaa aioo?aiiaai noaiaea?oa aeey
?an/aoa ia?aiao?ia yeaiaioa?iie y/aeee eniieueciaaee e?aiiee.

Iieo/aiiua ?aioaaiia?aiiu ia?aaaouaaee i?e iiiiue iaeaoa i?ia?aii
“POWDER” (eaai?aoi?ey iai?aaeaiiiai iai?aaie/aneiai neioaca, Oeie/aneee
oaeoeueoao IAO) e i?eaeiaeueiuo i?ia?aii, ?ac?aaioaiiuo a eaai?aoi?ee
iai?aaie/aneiai iaoa?eaeiaaaeaiey Oeie/aneiai oaeoeueoaoa IAO.

Ia?aaioea aeaiiuo, iieo/aiiuo ia aeeo?aeoiiao?a, aeeth/aea a naay
neaaeothuaa:

1. au/eneaiea iaaeieineinoiuo ?annoiyiee;

2. n?aaiaiea iieo/aiiie ?aioaaiia?aiiu n aeaiiuie aeaeeioaee ASTM e
ii?aaeaeaiey oaciaiai ninoaaa ia?acoeia;

3. eiaeeoee?iaaiea eeiee ii iaeeaeaaiui cia/aieyi ia?aiao?ia
yeaiaioa?iie y/aeee;

4. au/eneaiea ia?aiao?ia yeaiaioa?iie y/aeee ii iieo/aiiui eiaeaenai
Ieeea?a.

Ooi/iaiea ia?aiao?ia yeaiaioa?iie y/aeee i?iaiaeeeinue ii noaiaea?oiiio
iaoiaeo iaeiaiueoeo eaaae?aoia.

Yeaeo?iiiiiee?ineiie/aneea enneaaeiaaiey iieo/aiiuo ia?acoeia auee
i?iecaaaeaiu i?e iiiiue i?inaa/eaathuaai yeaeo?iiiiai iee?ineiia
JEM2000FXII (JEOL, ssiiiey) i?e onei?ythuai iai?yaeaiee 200 eA e
oaaee/aieyo aei 300000 e?ao. Ea?oeiu yeaeo?iiiie aeeo?aeoeee nieiaeenue
i?e aeeeia eaia?u 100 ni.

4. Ianoaeaeaiea ?acoeueoaoia.

Ii aeaiiui aiaeecia ia?acoeia, iieo/aiiuo ea?aie/aneei neioacii,
oaa?aeua ?anoai?u Bi1-xCaxOy n o = 0.1, 0.12, 0.15, 0.2 eiaee
?iiaiyae?e/aneoth no?oeoo?o, iiaeiaioth oacai Neeeaia [5] n ia?aiao?aie
aaenaaiiaeueiie yeaiaioa?iie y/aeee, i?eaaaeaiiuie a oaaeeoea 1.

Oaaeeoea 1. Cia/aiey ia?aiao?ia e iauaiia yeaiaioa?iie aaenaaiiaeueiie
y/aeee (() oaa?aeuo ?anoai?ia Bi1-xCaxOy (aaea a – noi?iia ?iiaa,
eaaeauaai a iniiaaiee yeaiaioa?iie y/aeee, n – aunioa, a V – iauai).

x=0.05 x=0.1 x=0.12 x=0.15 x=0.2

a 3.958(3) 3.939(3) 3.948(2) 3.946(2) 3.932(3)

n 28.67(3) 27.92(3) 27.85(2) 27.81(2) 27.84(4)

V 388.9 375.2 375.9 375.0 372.7

Eae aeaeii ec oaaeeoeu, n oaaee/aieai niaea?aeaiey eaeueoeey a oaa?aeii
?anoai?a iaaethaeaaony caeiiiia?iia oiaiueoaiea iauaia yeaiaioa?iie
y/aeee, /oi aucaaii iaiueoei eiiiui ?aaeeonii Ca2+, ii n?aaiaieth n
Bi3+.

Ia?acaoe ninoaaa Bi0.75Ca0.25Oy ninoiye ec ?iiaiyae?e/aneiai oaa?aeiai
?anoai?a e oacu Ca5Bi14O26, /oi niaeanoaony n oaciaie aeeaa?aiiie
CaO-Bi2O3. Ia?acoeu ninoaaia Bi0.98Ca0.02Oy, Bi0.95Ca0.05Oy inoaeenue
iaiaeiioaciuie (ninoiyuea ec iiiieeeiiiai ieneaea aeniooa e
?iiaiyae?e/aneiai oaa?aeiai ?anoai?a) iinea o?ao oeeeeia “iiiie-iaaeea”,
oioy ii oaciaie aeeaa?aiia aeaiiua ninoaau ioiinyony e iaeanoe
nouanoaiaaiey eoae/aneiai oaa?aeiai ?anoai?a. Iaiaeiioaciinoue
ia?acoeia, ii-aeaeeiiio, naycaia n enoiaeiie iaiaeii?iaeiinoueth
i?aeo?ni?a i?e ea?aie/aneii neioaca. A nayce n /ai aue i?iaaaeai
“aoiaaeiue neioac” aeaiiuo ninoaaia.

Iieo/aiiue ii aeaiiie iaoiaeeea oaa?aeue ?anoai? ninoaaa Bi0.95Ca0.05Oy
eiae ?iiaiyae?e/aneoth no?oeoo?o n ia?aiao?aie y/aeee, i?eaaaeaiiie a
oaaeeoea 1. Iaiiiioiiiia eciaiaiea ia?aiao?ia a neo/aa yoiai ia?acoea,
aiciiaeii, naycaii n aai oa?iiaeeiaie/aneie ia?aaiiaaniinoueth.
Ia?aciaaiey eoae/aneiai oaa?aeiai ?anoai?a a aeaiiii neo/aa, aiciiaeii,
ia iaaethaeaeinue ec-ca iaaeinoaoi/iie nei?inoe caeaeee ia?acoeia
(caeaeea ia ioeaaeaeaiiie aei 0N iaoaeee/aneie ieeoa).

Iieo/aiiue oaa?aeue ?anoai? ninoaaa Bi0.98Ca0.02Oy eiae oao?aaiiaeueioth
(eneaaeaiioth eoae/aneoth) no?oeoo?o n ia?aiao?aie yeaiaioa?iie y/aeee a
= 7.737(6) (, n = 11.30(1) (. Aeey ioeaiee nei?inoe ieceioaiia?aoo?iiai
oaciaiai i?aa?auaiey auea i?iaaaeaia na?ey ioaeeaia ?acee/iie
aeeeoaeueiinoe i?e oaiia?aoo?a 550N ia aicaeooa. ?aioaaiia?aiiu aeaiiuo
ia?acoeia i?eaaaeaiu ia ?enoiea 3. Eae aeaeii ec ?enoiea iieiue ?aniaae
oao?aaiiaeueiiai oaa?aeiai ?anoai?a ia iiiieeeiiue ieneae aeniooa e
?iiaiyae?e/aneee oaa?aeue ?anoai? i?ienoiaeeo oaea /a?ac aeaa ieioou
iinea ia/aea ioaeeaa i?e 550N. Aeey ii?aaeaeaiey oeia i?ienoiaeyuaai
oaa?aeioaciiai i?aa?auaiey ia?acaoe iinea iaeiie ieioou ioaeeaa aue
enneaaeiaai ia i?inaa/eaathuai yeaeo?iiiii iee?ineiia. Iee?ioioia?aoey e
ea?oeia yeaeo?iiiie aeeo?aeoeee aeey ciiu [310] i?eaaaeaiu ia ?enoiea 4.
Ia iee?ioioia?aoee aeaeii ia?aciaaiea aeeth/aiee i?iecaieueiie oi?iu a
iao?eoea enoiaeiiai oaa?aeiai ?anoai?a. I?e yoii ia yeaeo?iiia?aiia
i?enoonoaotho oaioe/anee ?aniieiaeaiiua aeiiieieoaeueiua neaaua
io?aaeaiey. O/eouaay aunieoth nei?inoue i?aa?auaiey i?e n?aaieoaeueii
ieceeo oaiia?aoo?ao e ii?oieiaeth ia?acoea, iiaeii naeaeaoue
i?aaeiieiaeaiea, /oi ia/aeueiay noaaeey oaa?aeioaciiai ?aniaaea
i?ioaeaao ii iaoaiecio “ianneaiiai i?aa?auaiey” /a?ac i?iiaaeooi/ioth
noaaeeth ia?aciaaiey oa?iiaeeiaie/anee iaonoie/eaiai iiiieeeiiiai
oaa?aeiai ?anoai?a n iineaaeothuei auaeaeaieai ec iaai ?iiaiyae?e/aneie
oacu, /oi iiaeoaa?aeaeaaony iaeie eioaineaiinoueth e aieueoie oe?eiie
ieeia ?iiaiyae?e/aneie oacu ia ?aioaaiia?aiiao (?en.3). I?e aieueoeo
niaea?aeaieyo eaeueoeey (5 e 10 aoiiiuo %) ia ia?aie noaaeee ?aniaaea
auaeaeyaony, ii-aeaeeiiio, n?aco ?iiaiyae?e/aneay oaca.

?en.3 ?aioaaiia?aiiu oaa?aeiai ?anoai?a Bi0.98Ca0.02Oy iinea ?acee/iuo
a?aiai ioaeeaa i?e 550N (a – 1 iei, a – 2 iei, a – 5 iei, a – 15 iei).
– eoae/aneee oaa?aeue ?anoai?, – iiiieeeiiue oaa?aeue ?anoai?, –
?iiaiyae?e/aneee oaa?aeue ?anoai?.

?en. 4. Yeaeo?iiiay iee?ioioia?aoey (oaaee/aiea 300000x ) e ea?oeia
yeaeo?iiiie aeeo?aeoeee aeey ciiu [310] (oaaee/aiiay a 1.76 ?ac)
oaa?aeiai ?anoai?a ninoaaa Bi0.98Ca0.02Oy iinea iaeiie ieioou ioaeeaa
i?e 550N.

5. Auaiaeu.

1. Neioace?iaaiu oaa?aeua ?anoai?u Bi1-xCaxOy (o = 0.02, 0.05, 0.1,
0.12, 0.15, 0.2).

2. ?ann/eoaiu ia?aiao?u yeaiaioa?iuo y/aae iieo/aiiuo oaa?aeuo
?anoai?ia.

3. I?iaaaeaiu enneaaeiaaiey ieceioaiia?aoo?iiai oaciaiai ?aniaaea
oaa?aeiai ?anoai?a Bi0.98Ca0.02Oy, iicaieeaoea naeaeaoue i?aaeiieiaeaiey
i i?ioaeaiee ia/aeueiie noaaeee aeaiiiai i?ioeanna ii iaoaiecio
ianneaiiai i?aa?auaiey.

6. Eeoa?aoo?a.

1. Levin E.M. and Roth R.S. // J. Res. Nat. Bur. Stand, 68 A, 1964, 199.

2. Takahashi T., Iwahara H. and Nagai T. // J. Appl. Elektrochem, 2,
1972, 93.

3. Conflant P., Boivin J.C. and Tomas D. // J.Solid State Chem. 18,
1976, 133.

4. Burtor B.P., Rown C.J. and Roth R.S. // J.Res. Natl. Inst.
Stand.Technol. 98, 1993, 469.

5. Sillen L.G. and Sillen B. // Z. Phys. Chem. 49B, 1944, 27.

6. Metlin Yu.G. and Tretyakov Yu.D. // J. Mater. Chem. 4(11), 1994,
1659.

7. Iiaeaaa A.I., Ia?oei A.E., Oaaaoei A.I. // AEAOI ei.
Ae.E.Iaiaeaeaeaa, 34(4),1989, 504

8. Eakihana M., Yoshimura M., Masaki H., Yasuoka H., Borjersson L. //
J.Appl.Phys., 71, 1992, 3904.

9. O?aoueyeia TH.Ae., Ieaeieeia I.I., Iiaeaaa A.I. // “Iniiau
e?eioeie/aneie oaoiieiaee”, I, “Aunoay oeiea”, 1987.

10. AEaeaiia A.N., Ooiaeaeoa A.A. // “Eaeoeee ii oeceea oaa?aeiai oaea”,
I, IAO, 1988.

11. Ei?naeia E.A.// aeenn. eaiae. oei. iaoe, I, IAO, 1993.

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