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..

Theoretical study of the radiation resistance and the local structure of oxide solid solutions based on mineral lakargiite

.

, ..., .. ...,

.., . .-. ., ... . . .-. .,

..

2015

1. . 1.1 . 1.1.1 . 1.1.2 . 1.1.3 . 1.1.4 . . 1.2.1 1.2.2 1.2.4 1.2.5 1.2.6 1.2.7 3 5 5 5 7 11 15 23 24 27 33 34 35 39 42

1.2 ,

1.2.3

1.3 . 1.3.1 . .46 1.3.2 . 1.3.3 GULP. 1.3.4 DL_POLY. 50 53 55

2. CaXO3 ( X= Zr, Ti, Sn). 2.1 . 2.2 . 57 5 65
3

2.3 CaXO ( X= Zr, Ti, Sn ). 3. CaXO 1

69
3

( X= Zr, Ti, Sn). 4. CaXO3 ( X= Zr, Ti, Sn). . .

70

77 82 83

2

.
, CaXO3 ( X = Zr, Ti, Sn) GULP [J. Gale, 1997]. . , .. .., . , - [http://parallel.ru/cluster]. . CaXO3 ( X = Zr, Ti, Sn ). CaXO3 ( X = Zr, Ti, Sn ). CaXO3 ( X = Zr, Ti, Sn ). . , . CaZrO3-CaTiO3-CaSnO
3.

IV- ": , , " « ABO3 (A=Ca; B=Zr, Ti, Sn) », 29- «Molecular dynamics modeling of radiation stability of Ca(Zr,Ti,Sn)O3 perovskites» 12-05-809 15-05-04575

3

1. . 1.1 . 1.1.1 .
ABX3. , A , B, X. . 1-1 , A 12- , B 6- . X B A. Pm-3m. SrTiO3. P B, , . : BO6-, , (. 1-2).

. 1-1. . 1-2. , . (, 2009). A ( 2009). . X , 4

X, ј . B ј , (. 1-3.). , X F ( ), 4 12 (. 1-4).

. 1-3. . 1-4. ( ). (, 2009) (, 2009). . , . (H, F, Cl, Br, I) (Na, K, Rb). - OH-, , 50% 50% (, MgSn(OH)6). , 6-. (0+6), (1+5), (2+4), (3+3), , (V0+Re6+), (K++Nb5+), (Sr2++Ti4+) (La3++Fe3+). Li+ Eu
2+

BAX3, SrLiF3 EuLiH3. , , XBA3. , 5

Na3OCl Cl- 12- Na+, O2- Na+ (Mitchell, 2002).

1.1.2 .
, Pm-3m. (RX+RB).

(. 1-4). , , : (RX+RA)=

, RA , . :

.

(1.1)

=1, . 0.8 1.11. 0.8 ,

1.11 . , p-T . , Pm-3m,

, : 0.9 .
2+

1.05.

, CaTiO
3

(Pnma) Ca2+ 12- 8-. ("") Ti6 , . , 6

. (. 1-5). : 0.81 1.11, (Mitchell, 2002). , 6 - . , , (Lufazo, Woodard, 2001). , , (Glazer, 1972). ( . .,1976). , . , . : , a, b c . , . , , "+", , "-". "0" , . . 1-5 , a0a0c+ a0a0c-, z . , . . , ("+"), ("-") .

7

()

()

. 1-5. z. () , () (, 2009).

.

1-6.

(, 2009).

a0b0c0. 26 , 15- . (Howard, Stokes, 1998) - , . 8 26-, , , , , . 15 , (. 1-7).

8

. 1-7. , . (Howard, Stokes, 1998).

. 1-8. Pm-3m, I4/mcm

. 1-9. Pnma

Pm-3m,

Cmcm (, 2009). (, 2009).

, , , . , a0a0c- , I4/mcm. . 1-8. a b , a=b= ap, , 9

, c=2ap. , Z=4. . , a0b-c+ ( Cmcm) , (. 1-8). a+b-c- ( Pnma) a b (. 1-9). 15- , 5% . a+b-c-, Pnma (Lufazo, Woodward, 2001). .1-6.

1.1.3 .
ABO3 , (BaTiO3), (S r R u O 3), (LaFeO3), (Y B a 2Cu3O7), (LaCoO3), -, , , (LaAlO3: Nd), ( L a 2C u O 4) (, 2009). B, B-O-B 180. B . B
3+ 3+

.

(A2BB O 6) , . B , B3+ , , , B-O-B-O-B. B-B , (0.4 ). LnFeO3 ( Ln - ) . , - , . , a c 10

.

0.03-0.07µB/

, . LnMnO3 . , Mn
3+

M n 4 +, .
4+

25 35% Mn

Mn .
3+

3+

M n 4 +,

Mn3 +, Mn 4 +, Mn M n 4 +. Co3+ Co4 +, Cr Fe (Pena, Fierro, 2001). , . . , , . , , . , . , , . , L a N i O 3, Ni
III

,

LaTiO3 d-, . LnCrO3 ( L n - ) LaCrO3 . . , 0.27 Dy 0.37 Yb, 0.23 . Cr4 +, p-. Cr-O Ln-O. L a M n O 3 720 . , 11

, . LaCoO
3

. 400 , 823 K; 823 1200 K , , , , 1200 .
III

Co

Co

,
3+

Co 3+. Co Co
2+

Co

III

CoIV. Co

3+

1200 ,

, . , , . . , SrxLa 1 -xM n O 3 x = 0 Mn 3 +. , x Mn
4+

. 0.2

(35 K) (7000 -1). TiO6 . TiO6 , - . () . d-. d3. MTiO3 ( M = Ca , Sr , Ba ) A B O 3 ( A = La , Gd, Y; B = Al, Ga) Cr3 +. Cr3 + , , - , . . , SrTiO3 . , - Cr3 ++Ti 4 + Cr4 ++Ti 3 +, (Pena, Fierro, 2001). .

90- . , .

. , . , . , NO . , , NO. 13

, . . , , , , . . . , , , . , , .

, -. , . (Pena, Fierro, 2001).

1.1.4 .
, . , . , , . 2-1. CaTiO3, 1839 (1798--1873). , 14

. .. . . . , , . , 1957 . CaTiO3. Pbnm (Buttner, Maslen, 1992), . , . Pbnm GdFeO3. , , . , 1894 . . , - . . , Na0,5REE0,5TiO3 . , Na0,5Ce0,5TiO3 Pbnm ( GdFeO3). Na+ + Ce3+ Sr2+ + La2+,
2xNax

Sr1

-

LaxTiO3. Ce3+ Sr2+ La2+ (

I4/mcm). , Ce- , (Mitchell, Chakhmouradian, 1999). NaNbO3 ( ) 1959 . . Pbma, 15

, [010]. NbO6 9.50 80 [100] [010]. Na-, 8 9. . , NaNbO3 Pbnm. , (Muhll et. al., 1984), Pbma Pbnm. SrTiO3 , . , 1984 . . , , Na . , (~ 85% SrTiO3). (2.5-5% SiO2). , , SrTiO3 (a=3.905 ). , Pm-3m (Mitchell et al., 2000). . (Na,La,Ce)(Nb,Ti)O3

. , , , . o La>Ce, , La
16

2007 .

, ( Galuskin et al., 2008). , . 30-35 200 . , , -, , , , , . CaZrO3-CaTiO3-CaSnO
3

x(CaZrO3)=0.93,

x(CaTiO3)=0.22, x(CaSnO3)=0.20. , Sc3+, Cr3+, Fe3+, Ce3+, La3+, Hf4+, Nb5+, U4+, Th4+. , . (800-1000), , , , . CaZrO3 ZrO2-CaCl2-Na2CO3 700. CaZrO3 1100. , CaTiO3. , CaO CO2 . , ZrO2 CaO . CaTiO3 Cl, F, S CaZrO3. Zr. . SiO
2

. , U Th 2.52.8 Ma - . 17 ,

, , . Ca2(Al, Fe3+)2O5 , , , , , . Pcmn (Redhammer et al., 2004). [101] . BO4, , BO6 . ( , ) ( ). , . , . Ca2Fe2O5 , . ( , ). . Mg Mn, , . , (. 1-1) Ca2Fe2O5, Pnma. , (Berggren, 1971).

18

. 1-1. , , (, 2012). . CaTiO
3

a 5.388

b 5.447

C 7.654

Z 4

C (Buttner, Maslen, 1992)

Pnma Pbnm,I 4/mcm P m3m

(Na, REE, Ca)Ti2O6,(Na,La,Th)TiO3

5.4652 3.9052 5.4940 3.9090 5.4479 3.9050 5.4027 5.4253 5.556(1) 3.599

5.4652 3.9052 15.4610 3.9090 5.5259 3.9050 14.6779 14.7687 5.715(1) 3.599

7.7476 3.9052 5.5510 3.9090 7.7579 4.1560 5.5923 5.5980 7.960(1) 3.599

4 1 8 1 4 1 4 4 4 1

(Mitchell, Chakhmouradian, 1999) (Mitchell et al, 2000) (Muhll et al., 1984) (Krivovichev, Chakhmoundian, 2000) (Mitchell et al., 1998) (Glazer, Mabud, 1978) (Redhammer et al., 2004) (Berggren, 1971) (Galuskin et al., 2008) (Wang et. al., 1996)

-

SrTiO

3

NaNbO

3

P c2(1)b
3

(Na, REE) (Nb, Ti)O

P m3m
3

(Ca,Na) (Nb, Fe, Ti)O PbTiO

P bnm P 4mm

3

Ca2(Al,Fe3+)2O Ca2Fe2O
5

5

P nma P nma Pbnm PmЇ3m

CaZrO3 CaSiO3

MgSiO

3

Pbnm P bnm P a3 P 2(1)/n P 2(1)/n
4

4.7787 5.3603 8.1100 5.4139 5.2842 5.8700 7.4865 7.7943 7.5440 7.7449 8.1221

4.9313 5.4884 8.1100 5.6012 5.3698 5.8700 7.4379 7.7943 7.5600 7.7449 8.1221

6.9083 7.6660 8.1100 7.7769 7.5063 5.4940 7.4963 7.7943 7.5580 7.7449 8.1221

4 4 4 2 2 1 8 8 8 4 4

(Horiuchi et al., 1987) (Zhao et al., 1994) (Wyckoff , 1963) (Yang et al., 1993); (Ross, Mitchell, 2003) (Rouse, 1971) (Scott, 1971) (Mullica et al., 1979); (Brich, 1993); (Basciano et al., 1998); (Basciano et al., 1998);

NaMgF3 K2NaAlF6 Na2NaAlF
6

Na2LiAlF6 CuPb2Cl2(OH) Ga(OH)3 In(OH)
3

P 4mm P mn2(1) I m3

In(OH)3(H2O) MgSn(OH) CaSn(OH)

0.25

I mmm P n3 P n3
6

6

6

(Cu,Zn,Fe)Sn(OH)

P 4(2)/nnm 7.5860 7.6900 7.8000 7.5860 7.6900 7.8000 8.1030 7.6900 7.8000 4 4 4 (Morgenstern-Badarau I.J, 1976); (Moore, Smith, 1967); (Cohen-Addad, 1967);

FeSn(OH)

6

P n3m P n3m

ZnSn(OH)

6

20

MnSn(OH) FeGe(OH) NaSb(OH)

6

P n3 P 4(2)/n P 4(2)/n
6

7.8744 7.5940 8.0100 7.7570

7.8744 7.5940 8.0100 7.7570

7.8744 7.4880 7.8800 7.7570

4 4 4 4

(Basciano et al., 1998) (Ross et al., 1988); (Schrewelius, 1938) (Morgenstern-Badarau, Michel, 1976);

6

6

(Fe,Mn)Sn(OH)

P n3

21

1.2 , .
, . . 1-10.

, (). - , () - . . . . , - . , . , .

( ) . , . , . , , . , , . , , , . 150 . , . , , , -, , , . U-, Th ( 2012). , TiO2, CaTiO3, ZrO2, Zr[SiO4], CaZrTi2O7, Gd2Ti2O7 Gd2Zr2O7 , (La,Ce,Nd)[PO4] . , , , . , , . () (), .

1.2.1
. , , 23

, . (), , . , , , ( ). , ( , ), , , , «» . (, ), : , . «» . : -, , , . , , , , . , . , , , . , ( ) . , , (0,5-1) . ./, 1 / . . (, ) 24 (100-200 )

«» , . , , ( ), . , 100 400 3 0,9 ( ) 150 . , , . GCR, ( ) , . . , - , , 30 GCR 75 . (FBR) . , , FBR. FBR , , , , , . FBR, , FBR . FBR , , . , ( , » ) ( ). , , , , , , , . 25

, . , , , , , , . , , , . , 260 , 245 . | «» (330-340 ), ( 1600 ) . «» , FBR ( , 1980- ) ( - ). ( - ) , , , , , , . , - 90-100 «» , 240 « » , .

1.2.2
2010 . 400 300 . (, 1998). 3000 , 140 500 -
241 237

Np (

), 120

241

(
129

). , : 250 ", 90 26
135

Cs 60

I (Slesarev I. et

al., 1993). , « » (). , , . . . 90 % : 99, Cm. , , . , , . :
1. 2. 3.
l29

I,

l35

Cs,

137

Cs, 90Sr.

- , - Pu, Np, Am,

. . .

- , . , . . , , (IAEA, 1981). 32 , , 6 27

, 11 , (. 1.2). . 1.3. ( ) 10-50 . , . , 30 . 50 , , , UO2 , . ( ., 1988):
1.

,

.
2.

.
3.

. (SCR-91), (E1S), (Kristallin-l), (TILA-90), (NAGRA), (, 1997) , , .

28

/ (, 2012). 1-2.
- - ( ) - () - - - () - ( ) - () - () - ( ) - () - - () - - () - , , , , , ,

29

. 1-3.
,

,

,

, , , , : , ( ), , , , , . , , , (, , 2000). (, , 2000). : (Yui, 2001). , . 30

. . , , , , . , () . . , :

; ; , (, , 1979). . . , , , . 100 160-260 , . . , . 8 , . , , , . . , , , .., . , .

31

1.2.3

(, , 2001). 1000 960 , 10 , 3 (, , ) 25 (, Zr, Mo, Am, Cm, , Sb, Cd, Nb, Se .). , , . , .. , ( ) . . , , . , . ( U, ) () . (1 -3) . , . , , . . 60 °. . , (, , ), . , . 32
.

10

3

/.

,

,

,

.

1.2.4
, , 0,1
3

1. (, , , 1989). 1/3 . , , , , , . ( 800 /) ( 1500 /). (-1 «») 400 /. , , , (, ). , , «» , , , . , . , , . - , () , . , . , 33

. , . , , , , , , , . : , , , .. ( 1000 °) , . .

1.2.5
, - ( 30 - 40 ). , , ( ). . . , (, ). , . , , , , , , , . , , . 34

, , , . , , , , , .
1.

, , (Lutze, 1988). , . 10 - 30 . %.
2.

Synroc - ,

. : (CaZrTi2O7), (Ba1,2(Al,Ti)8O16), (CaTiO3), (TiO2). , , (A1=mB2O6(O,OH,F)1-n. pH2O; = , REE, U, Th, Pu; = Ti, Nb, ) , . , , ! . . , , Cs, Rb, ; - U, Zr, Np, Pu; - Sr, Np Pu. 20 . % .
3.

(tailored ceramics)

(Harker, 1988). , , (McCarthy, 1977; McCarthy et al., 1979). , Synroc, (McCarthy et al., 1979). (, ). (CaF2), , , (TiO3), (Ce[PO4]), (Ca10[PO4]6F2) (Zr[SiO4]); Sr - (Pb(Fe,Mn)12O19), ; Cs , , , . 35

. , , (MgAl2O4), (12O3) (TiO2). Synroc.
4.

iO2

(Adelhelm et al., 1988). 12 . %. iO2.
5.

.

- . (Whiteshell) (Hayward, 1988). ( - «»), CaTiSiO5 . . , Sr, . , , Cs, . , , , . , . 15 .%. . :
1.

, (Ba[Al2Si2O8]), , (Ba2TiSi2O8),
-n .

(iO3), (CaMg[Si2O6]) (LiAl [SiO4]).
2.

((K,Ba)(Ti,Fe)8O16), (A1-mB2O6(O, OH, F)1 pH2O; = , REE, U, Th, Pu; = Ti, Nb, ) (Ca[WO4]).
3.

, (Ca,Mg,Fe)2[Si2CO6] ,

NiFe2O4.
4.

(

Fe3O4),

(Ca[Al2Si2O8]),

((Ca,Mg,Fe)2[Si2O6]), (10[O4]6F2) (Zr[SiO4]).
6.

,

, , (Ce[PO4]) (Boatner, Sales, 1988). 36

. . ( La Dy). , (Beall et al, 1981). ( Er Lu) Y , Zr[SiO4] (Mullica, Sappenfield, Boatner, 1990). . , Sr Ba , . , , ( 20 , ). , , . , 2000 °. 20 . %. 7. «» , . (Ewing, 1988). - , NaZr2[PO4]3 (NZP). , . ( 20 . %) - . NZP , Cs, CsZP. . , . . .

37

1.2.6
, , - (235U, (,
90 239

Pu,

24l

Am,

237

Np,

242

Cm) -

Sr

l37

Cs). - (

- 500 -
137

Cs

90

Sr 30,2 28,1 ). ,

- . - - :
1.

(. -,

- - ) , .
2. 3.

, - -. .

, , , , . - , , - 0,1-0,15 . , (Weber, Wald, Gray, 1981; Weber, Turcotte, Roberts, 1982; Weber et al., 1984; Weber, Roberts, 1983). , (DeNatale, Howitt, 1985; DeNatale, Howitt, 1987; Weber, 1991a) , , 2. 2.1 - - . , - - (. 2.1), - -.

38

1.

-. ,

- . - 4,5-5,5 , , 70-100 . , - 98 % -. , , ( ), (). - . , , . , , , . , , , , -.

. 1-11. - (Weber, Turcotte, Roberts, 1982)

39

. 1-4. , (Weber, 1991)

() 1 10 10 10 10 10 10
2 3 4 5 6

-/ 21014 21015 2x1016 11017 31017 51017 11018

-/ 5x1016 51017 2x1018 5x1018 5x1018 5x1018 5x1018

- , , | . (Reeve, Woolfrey, 1980) , - 6 % ( ). - ( 1020 ) . . . . , , . , SiO2 , (Hobbs, Pascucci, 1980). , , ; 2 (DeNatale, Howitt, 1987). , (Reeve, Woolfrey, 1980) 94 % . 10 . , . 40

2.

-. (0-).

, . . , , - . , - 500 , .
3.

-.

-

, . , - , . , .

1.2.7
, , ! .
1.

,

Pu , . -

- . - , , : ) - 4,5-5,5 1000020000 . - . 100 -200 (Robinson, 1994). ) 70-100 1-2 , . 41

. - , ,
238

Pu ( 87,7 )

244

Cm ( 18,1 ).

10 18-3.1019 / 0,2 % 3 % (Weber et al., 1998). 10 .
2.
-10

10

-8

/.

- .

(Hobbs, Pascucci, 1980), , - (Weber, 1981; Weber, 1982; Weber, 1985) . (10-5-10 . , , . , , , , . - , (. , b) .
3.
-2

/).

-. -

60

l37

Cs

- - (Ewing, Weber, Clinard, 1995; Weber, Roberts, 1983; Weber, 1991a). - . , , -. 42

, - , , , . , - , - .
4.

. ,

, . , 10-16-10 10-10-10
2 -8 -11

/,

/, 10-5 - 10-

/. , (),
238

U,

235

U,

232

Th .

30 . % UO2 , , , 1019 -/. , , , ( 5000 ppm), 109 10
19

-/.

- , «» . , U-, Th- , , , . (Pabst, 1952; 1975; Ewing et al., 1987). , , (Ewing, Haalcer, 1980; Ewing et al., 1988). - 10-17/, . 5. . ( ) . , 43

. , , . , , , .

44

1.3. .
, , . , . , . , . . . , , . , . , . .

1.3.1. . .
. 90% , (, , 2004). [Gale 45

J.D. Rohl A.L., 2003]. , 2.1. -, , - .

A exp( r ) C

r

6

- (-C/r6) . -
A r
m

C

r

6

( m 9 12)

- . , , , - . «» (. 1.2.) (, , 2012).

46

1.5. .

(Buckingham) - (Lennard-Jones) (Morse)

A exp( r ) C

r

6

A

r

m

C

r

6

D (1 exp(

(r

r0 )))

2

1

(Harmonic)

1 k 2 (r r0 ) 2

2

1 k 3 (r r0 ) 6

3

1 k 4 (r r0 ) 24

4

«» (General)

A exp( r ) r
m

C

r

n

«» (Spring)

1 k2 r 2

2

1 k4r 24

4

harmonic) (Three

3

1 k2 ( 2

0

)

2

1 k3 ( 6

0

)

3

1 k4 ( 24

0

)

4

. , . , ,

47

(. 1.5.). , . ,

. , " - " . ( -- ). , R-6. : R-12, . , . , . , , . , : «» (core), , , «» (shell) (.1.12). . «» (Spring) .1.12. . k «-» (. 1.5). , ,

48

. , , . ( ). (. 1.5). (three harmonic) c k «» ( . ., 2009).

1.3.2.
() , (Allen, Tildesley, 1989). , ( ). , - . . , . , . , , t = 0(N2), N - . , « » (Wilson et al., 1997). , , t = 0(N), , ( ). 49

, , . , , - , , . U-, Th- , - . . , , . 3040 . () . , ZrO2, Zr[SiO4], (La,Ce,Nd)[PO4], CaZrTi2O7, Gd2Ti2O7 Gd2Zr2O7 , (Hobbs et al., 1994). , , . , , , . , . . ,

« » (, , .) (Trachenko et al., 2004; Trachenko, Dove, Salje, 2001; Devanathan et al., 2004; Devanathan et al., 2005; Yu, Devanathan, Weber, 2009; Crocombette, Ghaleb, 2001; ., 2009; Uberuaga et al., 2005; Tosi, Fumi, 1964; 50

Matsui, Akaogi, 1991; Tsuneyuki et al., 1988; Murashov, 1995; Veiller, Crocombette, Ghaleb, 2002). . , . «» . ( ) ( ). , - . , . . 10 T

(, , 300 )

NPT ( N , ). ( 1 ) ZBL, (Trachenko et al., 2005; , 2011). , , 0,5-1,0 , . NVE ( N , V ). , . - 25-50 , , , . , , 1 . , 51

20

.

. , - (70-100 ) , 5-10 , , - (Devanathan et al., 2005). - ( Th-231, - U-235) U-235, - Pu-239. U-235 Th-231 , , , , , (Devanathan et al., 2005). , , - U-235, , Th 20 3,5, - -239 - 4,5.

1.3.3. GULP.
, . , WMIN, EMIN, METAPOCS, PLUTO, CASCADE, GULP . . . : , , ( 15 -20 е). , . -. GULP (Gale, Rohl, 2003). . :

52

1)

, (conjugate gradients) (rfo). 2) . 3) . 4) P-T . 5) -. 6) : , , , , . , - . 7) : ,

,

. 8) -. 9)

(electronegativity equilization model); 10) . , , , , . GULP ( .., .., 2004).

53

1.3.4 DL_POLY.
, (. NaCl, l), (. MgO, 2), (. , ), , (Todorov, Smith, 2008). 4- (CONFIG, CONTROL, FIELD, TABLE). CONFIG (, ), , , ( ). CONTROL , : , , (NVE, NPT .), , , , . FIELD , 2011). . , « ». , [3]. , . . - . . . . TABLE , (,

54

2. CaXO3 ( X= Sn, Ti, Zr ).
(Galuskin et al., 2008). CaZrO3-CaTiO3-CaSnO3 x(CaZrO3) = 0.93, x(CaTiO3) = 0.22 x(CaTiO3) = 0.20. , Sc, Cr, Fe, Ce, La, Hf, Nb, U, and Th. CaZrO3 , , . CaSnO
3

. . CaZr1-xTixO3 (Krayzman et al., 2006; Levin et al., 2006), CaZr1-xSnxO3 CaSn1-xTixO3 . , CaZrO3, CaTiO3, CaSnO3 - . - CaTiO3, CaSnO3 CaZrO3 Pnma. CaTiO3 ( = 0.97), CaSnO3 ( =0.93) CaZrO3

( =0.92) (Woodward, 1997). Ti4+, Sn4+ Zr4+ (0.61, 0.69 0.72 е, ).

2.1 .
, CaTiO3, CaZrO3 (Bassoli et. al., 2008; Mather, Islam, Figuriendo, 2007; Davies, Islam, Gale, 1999; Davies et. al., 2000) . . , CaTiO3 (Bassoli et. al., 2008) .

55

(Corgne, Allan, Wood, 2003; Alfreddson et. al, 2005) MgSiO
3

CaSiO

3

O-Si-O. (Corgne, Allan, Wood, 2003) , (Alfreddson et. al, 2005), MgSiO3 . (Hu, Xie, Ma, 2010) BaTiO3 PbTiO3, , . , . . , BaTiO3 (. 2-1). (Khan, Islam, Bates, 1998; De Souza et. al, 1999; Islam, 2000; Islam, Davies, 2004; Jones, Islam, 2008) La- LaCoO3, LaFeO3, LaGaO3, LaMnO3, LaScO3, LaYO3. (. 2-1).

56

. 2-1. a, b, , K < s> < > , , .
BaCeO BaCeO BaPrO
3

a, е 4.427 6.2422 6.213 6.213 4.012 4.001 4.188 5.564 3.599 3.662 3.991 4.199 5.588 3.572 3.566 5.564 4.44467 6.2347 6.181 6.181

b, е

c, е U, 136.68

K

< s>

< >

(Wu et.al., 2004) (Kruth et al., 2007) (Stokes, Islam, 2010) (Stokes, 2010) (Hu, Xie, Ma, 2010) (Hu, Xie, Ma, 2010) (Stokes, Islam, 2010) (Stokes, 2010) (Corgne, Allan, Wood, 2003) (Watson, Wall, Parker, 2000)

3

6.2304 6.221 6.221 4.005

6.2153 6.214 6.214

8.8179 8.789 8.789

8.7763 8.722 8.722 215 134 191 144

3

BaThO3 BaTiO BaTiO
3

3

4.035

4.035

BaZrO BiFeO

3

3

5.588

13.904

13.867

CaSiO3 CaSiO3

289.5

281

CaTiO

3

(Bassoli et. al., 2008) (Mather, Islam, Figuriendo,

5.411

5.3812

5.439

5.4405

7.689

7.6436

149.4

197.89

171

77.7

5.12

CaTiO

3

2007) (Davies, Islam, Gale, 1999) (Davies et. al., 2000) (Islam, 2000) (Jones, Islam, 2008) (Islam, 2000) (Khan, Islam, Bates, 1998) (Souza et. al, 1999) (Souza et. al, 1999) (Souza et. al, 1999) (Islam, 2000) (Islam, 2000) (Corgne, Allan, Wood, 2003)

5.3796 4.011 5.608 3.82 5.6 3.875 5.485 3.904 5.541 5.528 3.82 6.052 4.8244

5.3907 4.02 5.591 3.823 5.565 3.875 5.527 3.904 5.522 5.582 3.823 6.086 4.7787

5.4446

5.4423

7.6401

7.6802 146.41 55.18 16.39 2.55 2.54

CaZrO3 CaZrO3 LaCoO LaFeO
3

7.985

8.017

5.665

5.762

146.64

3

7.862

7.855

5.557

5.556

LaGaO3 LaGaO3 LaMnO LaMnO LaMnO LaScO LaYO
3

5.481

5.496

7.752

7.781

143.25 139.69

16.79 52.71 33.54 18.69

25

2.02 2.16 2.18 2.19

3

13.511 5.553 5.583 7.818

13.332 7.89

139.84 139.87

3

3

3

5.936 4.8454

5.89 4.9313

8.512 6.8416

8.511 6.9083

MgSiO

3

58

MgSiO

3

(Alfreddson et. al, 2005) (Tealdi et.al, 2006) (Tealdi et.al, 2006) (Hu, Xie, Ma, 2010) (Hu, Xie, Ma, 2010) (Mather, Islam, 2005) (Beale et al., 2009) (Islam, 2000) (, 2012) (, 2012) (, 2012)

4.784 3.770 5.3501 3.985 3.861 6.0744 5.533 4.095 5.385 5.539 5.6011

4.775 3.770 5.3312 3.97 3.904 6.1312 5.453 4.101

4.903

4.932

6.901

6.899

301

281.97

NdCoO NdCoO PbTiO PbTiO

3

3

7.5473

7.5482

5.3347

5.3461

3

3

4.156 8.5421 8.6504 5.9834 13.496

4.152 5.9944 13.137 144.31 15.71 215 198 184 2.65 139.82

SrCeO SrTiO

3

3

SrZrO3 CaTiO
3

5.440 5.640 5.7085

7.672 7.957 8.0775

CaSnO

3

CaZrO3

59

(Mather et al., 2007) , (. 2-2). CaTiO3, TiO2, CaO. , VO O1 O2 . , , , CaTiO3 . Va VO , , . , , (>3.6 ), . Fe4+. VO, , , . O1 O2, , O2. , (Pnma) (0k0) O2. (Calleja et al., 2003) VO [001]90o. T=10 K 2.3 , , Ti (001). ( ) 1.2 . (Davies et al., 2000) CaZrO3 SrZrO3. CaTiO3 (Mather, Islam, Figuriendo, 2007), o . CaZrO3, SrZrO3 - . AO . , SrZrO3 ZrO2

SrO2, , SrTiO3. , , A . ( .., 2012) K (Ross et al., 2002), 19%. . ST GULP 300 1500 K. 0.3% 300 K (. 2-4, ,,). , , 5.9% T=1500 K. CaZrO3, CaTiO3 CaSnO3, ( .., 2012).

61

. 2-2. , .
A-O 2.13 2.8 4.51 2.92 1.26 2.68 3.03 3.2 3.5 B-O 5.3 3.75 6.25 3.03 3.09 4.45 3.7 3.72 3.94 -

BaPrO3 BaZrO3 BiFeO3 CaTiO3 CaZrO SrZrO
3

(Stokes, Islam, 2010) (Stokes, Islam, 2010) (Stokes, 2010)

V

'' A

V

'''' X

VO1
-

VO2
-

A
-

i

X
-

i

O
-

'' i

A 5.96 6.97 12.55 4.21 6.00 9.79 10.08 9.25 11.19

X 12.78 10.22 9.10 11.38 8.57 8.79 9.19 11.17

O 4.89 5.58 4.26 2.63 4.76 4.25 4.02 4 3.5

4.49 3.2 4.98 2.49 2.22 3.51 3.6 3.48 3.73 2.94

-

-

(Mather et al., 2007) 22.15 82.27 19.64 19.63 (Davies et. al., 2000) (Davies et. al., 2000) (Jones, Islam, 2008) (Souza et. al, 1999) (Souza et. al, 1999) (Tealdi et.al, 2006) -

3

LaFeO

3

LaMnO LaMnO NdCoO

3

3

3

NdCoO

3

(Tealdi et.al, 2006) (Mather, Islam,

-

-

-

-

-

-

-

11.29

9.54

4.53

3.74

-

-

SrCeO

3

2005) (Thomas et al.,

21.23 81.58 19.99 19.98

-10.52

-57.95

-11.02

5.36

11.81

4.48

4.57

3.9

5.45

SrTiO SrTiO YAlO

3

2005) (Beale et. al., 2009) (Kuklja, 2000)

18.3

41.7

11.4 -

-1.8 -33.48 -13.64 -12.63 -14.86

-23.5 -37.40 -61.52 -59.51 -57.12

-1.3 -12.31 -12.31 -11.58 -11.78

16.5 7.35 4.84 4.98 4.04

18.2 7.61 11.31 13.02 12.35

10.1 4.30 4.31 .4.34 4.15

4.26 4.53 3.55 4.02

3.70 4.11 3.42 3.50

3.21 5.17 3.98 4.52

3

20.92 81.16 18.89 48.70 52.09 20.90

3

CaSnO CaTiO

3

(, 2012) (, 2012) (, 2012)

23.31 84.14 20.94 20.98 22.60 85.56 20.26 20.39 22.94 81.82 20.07 20.47

3

CaZrO

3

63

2.2 .
- , , . .. . , , , . ( a, b, c V) CaTiO3, CaSnO3 CaZrO3 . (Buttner, Maslen, 1992; Koopmans et al., 1983; Vegas et al., 1986) 0.2% (. 2-7, ,,). . 2-6 , , CaTiO3, CaSnO3 CaZrO3
.

K (Ross et al., 2002), 5%. S
T

GULP 300 1500 K. 0.2% 300 K (. 2-7, ,,). , (Yashima, Ali, 2009) , 1512±13 K Pnma CaTiO3 I4/mcm, 1635±2 K - Pm3m.

. 2-6. CaZrO3, CaTiO3 CaSnO3, . Ca2+-O
1.73(3)-

, 1340.18 770.02 790.2 766.2 22764.0

,е 0.321 0.3698 0.3809 0.3640 0.1490

C, ·е 0.0 0.0 0.0 0.0 43.0

6

Zr3.2+-O Ti
3.2+

1.73(3)-

-O1

.73(3)-

Sn O

3.2+

-O1 -O

.73(3)-

1.73(3)-

1.73(3)-

. 2-7 (). V a, b, c, K, E S
300

CaTiO3,

. CaTiO3 (Buttner, Maslen, 1992; Ross et al., 2002) V, е3 a, е b, е c, е K, E, / S
300

( .., 2012) 224.754 5.385 5.440 7.672 215 -14586.22

(Mather et al., 2007) 226.3 5.411 5.439 7.689 -

222.037 5.384 5.403 7.631 170.1 -10672.40

223.682 5.388 5.447 7.654 171(1) -

,

/·K

93.64

94.34

-

93.49

65

. 2-7 (). V a, b, c, K, E S
300

CaSnO3,

. (Vegas et al., 1986; Ross et al., 2002) 248.4642 5.5320 5.6810 7.9060 163(1) ( .., 2012) 248.6584 5.5398 5.6406 7.9575 198 -14240.69 248.383 5.544 5.636 7.948 157.7 -10384.40

CaSnO3

V, е3 a, е b, е c, е K, E, / S
300

,

/·K

-

95.02

98.89

66

. 2-7 (). V a, b, c, K, E S
300

CaZrO3,

. CaZrO
3

( .., 2012) 258.269 5.6011 5.7085 8.0775 184 -13981.11

(Davies et al., 2000) 253.678 5.608 5.665 7.985 -

(Koopmans et al., 1983; Ross et al., 2002)

258.242 5.411 5.441 7.677 149.2 -10217.65

V, е3 a, е b, е c, е K, E, / S
300

258.265 5.5912 5.7616 8.0171 154(1) -

,

/·K

96.4

96.3

-

97.81

, , ( a, b V ) CaTiO3, CaSnO3 CaZrO3. K . . . , CaTiO3 (Mather et al., 2007; Bassoli et al., 2008; .., 2012) CaZrO3 (Davies et al., 2000; .., 2012). V CaTiO3 and CaZrO
3

, ( Davies et al., 2000; Bassoli et al., 2008; .., 2012). 67

, , .

2.3 CaXO3 ( X=Zr, Ti, Sn).
( ) - , . 2-6. (. 2-8, ). , , TiO2, SnO2 (, 2008) ZrO2 (Khan et al., 1998) - , CaO (Lide, 1994). . 2-8 , , , . , , Ca-O . CaZrO3 (Davies et al., 1999). , , . . CaZr1-xTixO3, CaZr1-xSnxO3 and CaSn1-xTixO3 .

68

2-8 (). (, ), . Ca B O O
1
' VA'

CaSnO3 21.94 56.51 15.02 15.10 -12.18 -40.01
'' i

CaTiO3 21.42 58.27 14.25 14.32 -9.88 -43.05 -6.87

CaZrO 21.58 58.30 14.53 14.61 -11.30 -42.51 -6.97

3

' VB'

''

VO1 VO2
Ca B
i i

2

Ca B O

O

-7.71

. 2-8 (). (, ), . (Davies et al., 1999) 4.21 9.10 2.63

CaSnO3 CaTiO3 CaZrO

3

A B O

Ca B

A

' VA' ' VB'' '

Ca B
i

i

4.88 8.25

5.77 7.61 3.69

5.14 7.895 3.78

B

O Ca 2V
'' A

O

VO B
B

O 3O
O

'' i

3.65

A

3.19

2.38

2.65

2.22

V

'''' B

3VO

CaBO

3

69

3. CaXO3 ( X= Sn, Ti, Zr ).
, CaZrO3CaTiO3-CaSnO3 x(CaZrO3)=0.93, x(CaZrO3)=0.22, x(CaSnO3)=0.20. CaZrO3 , . CaSnO
3

, . CaZr1-xTixO3 (Krayzman et al., 2006; Levin et al., 2006), CaZr1
xSnxO3 -

CaSn1-xTixO3 .

2012 .. ( .., 2012), , K . , . . , -, , -, , , (. . 1 ) . , , , . . , , . GULP. 70 5в5в5

(. 3.1).

. 3.1 555. (Urusov V.S., 1992). , a, b, c (A1-Bx)C : a(x) = (1-x)a1 + xa2, (3.1)

, 1, 2 (A1-Bx)C AC BC ; (1-x) x AC BC. , : R(x )= (1-x)R1 + xR2=R2 - (1-x)R = R1 xR , (3.2)

R1 R2 AC BC ; R = R2 - R1 > 0. 71

(Urusov V.S., 1992, 2001), , (R=1) (R=0) . R :
R R
BC 0 BC

R R
BC

AC 0 AC

,

(3.3)

R0

AC

R0

AC BC, RBC

(A1-Bx)C.

, (R=0).

, (3.1). (R=1) .3.2. (), () 0R1 ( ) [Urusov V.S., 1992]. , R0 (A1-Bx)C
AC BC

RBC RC R0

. , , 0 R 1 ( .., .., 2012). . , ,

(Newton, R.C., Wood, B.J., 1980). 72

R, CsR, (Dollase W.A., 1980). «» . , R : sR=1 R. (3.4)

, : V(x)= (1-x)V1 + xV2. (3.5)
R s

R (3.3) C
V V s

(3.4)

C .

. 3.3 . 73

. 2.6 ( . 2 ) , , CaTiO3, CaSnO3 CaZrO3. 300 1500 K . 300 0.7%. K 5% ( . 2.7 () . 2 ).

. 3.4 Ti-O, Sn-O Ti
200

Sn

300

O15

00.

74

. 3.5 Ti-O, Zr-O Ti
200

Zr

300O1500.

. 3.6 Zr-O, Sn-O Zr200 Sn
300

O1

500.

75

. 3.4-3.6 , , . .3.1. . 3.1. . - , е Zr-O=2.088 Sn-O=2.049 Zr-O=2.088 Ti-O=1.923 Ti-O=1.923 Sn-O=2.049 - , е Zr-O=2.085 Sn-O=2.055 Zr-O=2.075 Ti-O=1.962 Ti-O=1.953 Sn-O=2.037 ZrO6 SnO6 ZrO6 TiO6 TiO6 SnO6 = = = = = =

Zr200 Zr200 Ti200 Ti200 Ti200 Ti200 Sn Sn Zr Zr Sn Sn O1500 300O1500 300O1500 300O1500 300O1500 300O1500
300

6

85% 60% 80% 62% 61% 76%

-

, ( ), , , ( ), , -, .

76

4. CaXO3 ( X= Sn, Ti, Zr ).
CaZr 0.8Sn0.1Ti0.1O3 (. 3.3) 310290315 е3, 1.4 . , c «» Zr, Ti Sn ( ) 20 . DL_POLY, 1. , - . , , 30-40 . . , CaZrTi2O7, ZrO2, ZrSiO4, Gd2Ti2O7 Gd2Zr2O7 , (La, Ce, Nd)PO4 (Hobbs L.W., 1994). , , . , 20 . , , . . t = 0.71 ( N
max

11500) «»

. (t = 20 ) ( NFP) N
final

= 340 (. 4.1 4-2).

M- (Urusov V.S. et al.,2012) (Urusov V.S. et al.,2012), ( .. ., 2013), , , 77

, , .
4000
N(Ca) (10/8)N(Zr) 10N(Ti) 10N(Sn) N(O)/3

1000

100

10 t = 0.71 t = 20

4.1. Ca, Zr, Ti, Sn, O, .

4.2. Ca(Zr,Ti,Sn)O3 () . « » - GULP 78

(Buttner R.H. et al., 1992). . (Urusov V.S. et al,2012), ( .., .. 2012). EFP (EFP=EV+EI, EV EI ) Ca, Zr, Ti, Sn O . 3.1. , (Urusov V.S. et al.,2012) :
1 E
PKA i

E FP (i ) N FP (i ) ,

(4.1)
N FP (i )

E FP (i ) i,
PKA

i, E

.

4.1. (EFP), , (NFP) .

Ca Zr Sn Ti O

EFP, 9.24 16.87 19.82 16.83 9.01

NFP 122 88 26 9 99

, 0.21 , (0.68) (Urusov V.S. et al,2012) LaPO4 YbPO4 ( ) = 0.39 1.00, ( .. ., 2013). CaZr0.8Sn0.1Ti0.1O3, . 79

(Galuskin

et

al.,

2008),

. , , Ca/Zr/Sn . . 4-3 , Ti .

4.2. CaZrO3-CaTiO3-CaSnO

3

CaZrO CaTiO
3

0.055 0.112 0.057 0.070 0.069 0.056 0.088 0.098 0.080 0.092

3 3

CaSnO

CaZr0.8Sn0.1Ti0.1O3 CaZr0.33Sn0.33Ti
0.33

O3

CaZr0.5Sn0.5Ti0O3 CaZr0Sn0.5Ti0.5O3 CaZr0.5Sn0Ti0.5O3 CaZr0.1Sn0.8Ti0.1O3 CaZr0.1Sn0.1Ti0.8O3

80

. 4.3. .

4.3. CaZrO3-CaTiO3-CaSnO

3

CaZrO CaTiO
3

() 77 222 82 97 108 77 168 170 142 149 81

3 3

CaSnO

CaZr0.8Sn0.1Ti0.1O3 CaZr0.33Sn0.33Ti
0.33

O3

CaZr0.5Sn0.5Ti0O3 CaZr0Sn0.5Ti0.5O3 CaZr0.5Sn0Ti0.5O3 CaZr0.1Sn0.8Ti0.1O3 CaZr0.1Sn0.1Ti0.8O3

.
- GULP DL_POLY. - - , , . - CaXO3 (X=Zr, Ti, Sn). - .

-
- , , , . - , , , . - , Ti . , , .

82

.
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3

Proton Conductor: A Combined EXAFS and Computer Simulation Study // Sol. St.

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14. 15. 16. 17.

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18. 19.

Howard C. J., Stokes H.T. // Acta Cryst. B54, 1998, P. 782-789. Hu X.Q., Xie G.F., Ma Y. A new optimization method for shell model interatomic potential parameters of perovskite ferroelectrics // Physica B. 2010. V. 405. P. 2577 2580.

20. 21.

Islam M. S. Ionic transport in ABO3 perovskite oxides: a computer modelling tour // J. Mater. Chem. 2000. V. 10. P. 1027-1038. Islam M. S., Davies R. A. Atomistic study of dopant site-selectivity and defect association in the lanthanum gallate perovskite // J. Mater. Chem. 2004. V.14. P. 86 93.

22. 23.

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24.

Koopmans H.J.A., van de Velde G.M.H., Gellings P.J. Powder neutron diffraction study of the perovskites CaTiO3 and CaZrO3 // Acta Crystallogr. C. 1983. V. 39. No 10. P. 13231325.

25.

Krayzman V., Levin I., Woicik J.C., Yoder D., Fischer D.A. Effects of local atomic order on the pre-edge structure in the Ti K x-ray absorption spectra of perovskite CaTi
1-x

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26. 27.

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28.

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