Вы находитесь на странице: 1из 364

-

( )

02.00.04





,
,
..

2014

1. ,

5
10


1.1.

10


1.2.

13


1.3.

15

1.4.

19


1.5. ()

23

1.6.

34

2. MeRX ( CuNiO)
2.1. CuNiO

35
35

2.1.1. CuO

35

2.1.2. CuNi

45

2.1.3. NiO

47

2.2. CuNiO

48

2.3. CuNiO

67

2.4.

72

2.5. CuNiO

77

2.6.

82

3. ,
3.1. , ,

85
85

3.1.1. CuSnO

85

3.1.2. CuZnO

93

3.1.3. CuCoO

97

3.1.4. CuFeO

102

3.2. , ,

111

3.2.1. CuPbO

111

3.2.2. CuPbSnO

118

3.2.3. CuPbSnZnO

124

3.2.4. CuAsO, CuSbO CuBiO

132

3.3. ,

143

3.3.1. CuSiO

145

3.3.2. CuFeSiO

152

3.3.3. CuMgO CuCaO

155

3.3.4. CuAlO

160

3.4. c

166

3.4.1. CuSO

166

3.4.2. CuNiSO

179

3.5.

184

3.5.1. CuPO

184

3.5.2. CuZnPO CuPbPO

187

3.6.

191

4. ,
4.1. ,

193
193

4.1.1. CoSiO CoAlO

196

4.1.2. CoCO CoSiCO

197

4.2. ,

199

4.2.1. NiCO, NiCaO, NiAlO, NiCaCO NiAlCO

199

4.2.2. NiSiO NiSiCO

205

4.2.3. NiRO

211

4.2.4. NiRBi

217

4.2.5.

222


4.3.

224

5. ,

226

5.1.

228

5.2.

232

5.2.1. AlMgO

232

5.2.2. AlMgNaO

236

5.2.3. AlMgNaKO

236

5.3.

238

5.3.1. AlNaCl

240

5.3.2. AlKCl AlMgCl

245

5.4.

246

5.4.1. AlNaF AlMgF

248

5.4.2. AlNaMgF

249
3

5.5.

252

6. ,

253

6.1. ,

253

6.1.1. PbAgZn PbAuZn

253

6.1.2. PbCuS

262

6.1.3. PbZnO PbSbO

266

6.2. ,

275

6.2.1. BiAgZn

275

6.2.2. BiPbO BiSnO

281

6.2.3. BiPbS BiCuS

285

6.3. SnAlSb

288

6.4.

293

294

298

1.

341

2. uNiO

352

3.

357

( Cu
SnO)
4. (
Cu2OPbOSnO2 11001280 )

364



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04-03-32081-, 07-08-00365-, 07-08-12092-, 10-03-96061-__, 11-08-12046---2011,
13-08-00545- 13-03-00534-).


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11

- [18].

, [26].
,

Cu + O2 = CuO0,5 ,

(1.1)

xCuO0,5 = K p PO0,25
CuO0,5 ,
2
CuO = 2,84 2,858 xFeO 1.517 xSiO + 6, 54 xCaO +
0,5

+2, 27 xAlO1,5 7, 21 10 2 lg PO 2 + 3, 95 10 3 T

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1.1 1.2.
1.1 1.7.
1.1.
(. %)

[Ni]
[Pb]
[As]
[Sb]
[Bi]
[O]

[Ni]
1
0,235949
0,092362
0,10662
0,23486
0,23392

[Pb]

1
0,074381
0,568983
0,268785
0,12065

[As]

1
0,328722
0,263981
0,00686

[Sb]

1
0,602867
0,0486

[Bi]

1
0,021349

[O]

,

. .

20

1.2.


lg[Ni]
lg[Pb]
lg[As]
lg[Sb]
lg[Bi]
lg[O]
lg[Ni]
1

lg[Pb]
0,244866
1

lg[As]
0,129381
0,103946
1

lg[Sb]
0,182457
0,542759
0,462083
1

lg[Bi]
0,24163
0,200574
0,340899
0,550193
1
lg[O]
0,24262
0,00973
0,03566
0,080646
1
0,12588
-
-
2

0,6

-lg[Pb]

[Pb], %

0,8

0,4
0,2

1,5
1
0,5

0
0

0,02

0,04

0,06

0,08

0,1

0,12

0,14

0,16

0,5

[As], %

1,5

2,5

-lg[As]

. 1.1. [As, % .][Pb, % .] lg[As]lg[Pb]


-
-
2

0,6

-lg[Pb]

[Pb], %

0,8

0,4

1,5
1
0,5

0,2

0
0

0,05

0,1

0,15

0,2

0,25

0,3

0,35

0,4

0,5

1,5

-lg[Sb]

[Sb], %

. 1.2. [Sb, % .][Pb, % .] lg[Sb]lg[Pb]


-

0,005
0,004
0,003
0,002
0,001
0

4
-lg[Bi]

[Bi], %

0,1

0,2

0,3

3
2
1
0

0,4

[Sb], %

0,5

1
-lg[Sb]

. 1.3. [Sb, % .][Bi, % .] lg[Sb]lg[Bi]

21

1,5

0,1

-lg[As]

[As], %

0,15

0,05
0
0

0,1

0,2

0,3

0,4

2,5
2
1,5
1
0,5
0
0

[Sb], %

0,5

1,5

-lg[Sb]

. 1.4. [Sb, % .][As, % .] lg[Sb]lg[As]


-

-
1

0,6

-lg[Ni]

[Ni], %

0,8
0,4

0,5

0,2

0
0

0,002

0,004

0,006

-lg[Bi]

[Bi], %

. 1.5. [Bi, % .][Ni, % .] lg[Bi]lg[Ni]

0,2

0,15

-lg[O]

[O], %

0,1
0,05

1
0

0
0

0,05

0,1

0,15

[As], %

0,5

1,5

2,5

-lg[As]

. 1.6. [As, % .][O, % .] lg[As]lg[O]


[Sb][Pb] lg[Sb]lg[Pb], [Sb][Bi]
lg[Sb]lg[Bi]. [Bi] [Pb] , lg[Bi] lg[Pb]
.
[Ni][Pb], [As][Sb]
[As][Bi], , .
[Ni][Bi] [Ni][O].
22

0,2

0,15

-lg[O]

[O], %

0,1
0,05

1
0

0
0

0,2

0,4

0,6

0,8

0,5

-lg[Ni]

[Ni], %

. 1.7. [Ni, % .][O, % .] lg[Ni]lg[O]


[Pb][O], lg[Ni]lg[As], lg[Ni]lg[Sb], lg[Ni]lg[As]
lg[Pb]lg[O] ( ) .
.
1.1 1.2 ,
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1.5. ()

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FeMnO Fe
SiO , ,
. 1.8 1.9 [5].

24

. 1.8.
FeMnO

.. [5]

ab (. 1.8) ,
. I
, , II
, .
.

. 1.9.
FeSiO
.. [5]

25

FeSiO
(. 1.9 [5]). o ,
. ,
1. n ,
1 2. b ,
2 . I ,
1, II , III
2.
. 1600 kb ,
1, bc , . 1700
kb , 1, bc
2 cf' . . , 1600

( 0,01 %). [5, c.26, 27].

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FeOMnO.
1600

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27

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= + .

(1.4)

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(1.5)

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= + 1 .

(1.6)

(1.6) ,
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= 1.
(1.5)
= + 2 ( + 1).
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= + 1

(1.7)

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= .
28

(1.8)


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CaO + CO2 = CaCO3,

, ,
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, (K = 3)
/ ,
:
1)

(C

0)

( = 1 + 3 = 4). (1.6) (1.7)


, : 0 = 3 + 1 4;

29

2) ( = 1)
( = 1 + 2 = 3). (1.6) (1.7) : 1 = 3 + 1 3;
3) ( = 2)
( = 1 + 1 = 2). (1.6) (1.7) :
2 = 3 + 1 2.
,
(K = 4) ,

(
) (
).
(1.8). ,
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= ( 1) + 1 .

(1.9)


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).

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30

, 4 ,
1.3.
, ,
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, n
(n+3) (n1)
.
1.3.




()

=
0 = 4 (1 + 3)
1 = 4 (1 + 2)
2 = 4 (1 + 1)

= ( 1) + 1
0 = (4 1) + 1 (1 + 3)
1 = (4 1) + 1 (1 + 2)
2 = (4 1) + 1 (1 + 1)

,

,

.
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, XX .
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, . 1.11.
PbCuSn ,
( )
(l). ,
, ,
31

, , (
-). ..
, . ,
(PbAgZn PbCuS), 6.
, , ,
, [91], .
( . 1.12 1.13), [92]
. , [93]
( FeAlTiO) inclusion diagram, ..
.

. 1.11.

PbCuSn [80]

. 1.12. AlFeNi [91]

32

,
[94], 4, :
( ).
, ,
, [95],
NiCrTiAlO 1600 ( . 1.14).

. 1.13.
AlSiMg
[91]

. 1.14. NiCrTiAlO 1600 [95]

33

1.6.

,
.
.

. ,
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,
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,
.


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1.
( ,
) .

2.

.

3.
.

4. ,
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5.
.
. ,
.

6.

, .
34

2. MeRX
( CuNiO)
2.1. CuNiO
2.1.1. CuO
CuO
, XX
[96].
,
(Cu2O CuO). CuO

, ,
1400 ( Kohlmeyer E.J. Sprenger K.V., 1948; Osterwald J., 1968).

70- XX (Gerlach J., Osterwald J., Stichel W.,
1968; Santandler N.H., Kubaschewski O., 1975; Kayahara Y. , 1981, , ,
Neumann J.P., Zhong T., Chang Y.A.). 70-80- XX
, , R.A. Schmid [97].

.
, 1200
1,5 % .
[98]
:
lg [% O]max = 10 090/ +7,17.
[99] 8651216
:
lg [% O]max = 9260/ +6,55,
=10831233 [90]
lg [% O]max = 6500/ +4,468.


. , , [10],
35

Hp= 77,7 /. ,
Cu2O , , , (0,23 % .),
(0,64 % .) 1327 , Hp 180,9 97,27
/ [10].
[10]
. .. .. [100] ,

( CuO ).
,
.

, (. 2.1) :
S[O]=K P1/2 O2 ,
:

. 2.1.

, [10]

,
:
36

O2 = 2 [],
.

, :
G= RT lg (O[O]/ P1/2 O2 ).
G,
(1% .) , [10], :
GO = 159,0+0,02 T, /,
.. [16]
,
(1 . %), /:
GO = 158,26+0,0277T(10831233 ) (K. Sano H. Sakao);
GO = 146,6+0,018T(11101420 ) (W. Fischer W. Ackermann);
GO = 166,0+0,0198T(10831233 ) (M.M.A. El-Nagger N.A.D. Parlee);
GO = 182,0+0,0467 (10831233 ) (T.C. Wilder).
.. .. , GO,
..., :
GO = 159,0+0,02T /.
[97, 101]
GO, .

(Cu2O) = 2 (Cu) + []1% Cu,
[10] >1229 :
GO = 6972048,98 ,
[10] ,
:
[]+2 = O2,
.
, GO

.
, [10],
O2.
. . [16],
Cu+ O2,
37

. [16] Cu2O.

,
,
Cu2O. ,
Cu2O .
[10]
.. [102]

.
[101], , ,
1.
CuO, ,

Cu2O,

[101] .
,
0,9% .
[103] .
. ,

(. 2.2).
.

. 2.2.


[103]. 1
, 1200; 2

38


:
eOO = 630/T+ 0,327.
, [16] ,
0,10,2 . %, (
),
.
0,5 . % ,
.
[103]
. , O
OO , T. Du Y. Sun,
0,12 4,98 T=1200, 0,10 5,35
1100 [10] .
10701500 :
lg O = 8913/ + 4,52.
[104], -11
.. 99,999 . %, a O O,
,
[10], . 2.1.
(1,193,49 [] . %, 1150-1250 C),
[105]
, Cu2O:
lg O = 4220/ + 2,753
OO = 1834/ + 1,042.
2.1.
[],
. % 1200 C [10]
[], . %

xO

aO

0,416
0,560
0,607
0,737
0,846
0,919

5,274103
2,186102
2,868102
2,861102
3,277102
3,552102

0,5708103
0,2012102
0,1860102
0,2356102
0,2549102
0,2983102

0,090
0,092
0,079
0,082
0,078
0,084

39


[16, 106] ,
, , ,
. , ,
, , [107],
.
[16] K.E. Oberg .
11001350 ( ...):
DOCu = 6,9103(12900/RT) 2/ (13731623 ).

CuO
( [108120],

.
R.A. Schmid [97] CuO
. : Cu, Cu2O O.
14 .

, CuO.
, Schmid ,
[101], , ( = 1220)
Schmid . , [101],
,
. ,
CuO 33,3 . % ,
1 ,
. , [101],
Cu2OO Cu2O .
[101] (.. )
CuCu2O ,
.
CuCu2O. ,
, .

(Cu, Cu2O CuO) , (.

40

2.3). ,
.

. 2.3.
1369


(. 2.4), [103].
pT CuO
(. 2.5).

. 2.4.

. 2.5. pT CuO

[101]. L1 L2

[101]

CALPHAD [121, 122].


D. Shishin S. Decterov 2012 . [123],

CuO.

G
.

41

CuO
.. .. [124, 125]. , ,
, 4, pT
CuO + O2 (. 2.6) CuO + Ar.
, Cu2O3, Cu3O2, Cu4O3 [124, 126].
-
,
.

. 2.6. pT
CuO + O2 [124, 125]

, , ,
[97, 101],
.

CuCu2O
[127].
,
.
42

Cu, O Cu2O. (Cu2O) =


2(Cu) + (O). :

2Cu (O) x2Cu xO


K
,
Cu O xCu O
2

:
n

j1

j1 p1

j1

j1 p1

ln i 0,5wij wji xj 0,5wjpxj xp wij wji xj xj / 2 xi wjp wpj x2j xp .


i i- , x
, wij , :

wij cij / T d ij .
,

, , 2.2 2.3,
CuCu2O. . 2.7.

, [128, 129].
, . 2.2 ( 2 3),
:
7

Q eO = 4,216 10 816,1 ,

(. 2.8),
. . 2.7.
2.2.
CuCu2O, ,
[90, 130]

(Cu2O) = 2(Cu) + (O)

K,

a 2Cu a O

lg K
7687 / T + 3,135

a Cu 2O
2

|Cu2O| = (Cu2O)

a Cu 2O

3360 / T + 2,218

|Cu| = (Cu)

aCu

680,3 / T + 0,502

43

. 2.7. CuCu2O [127]: 1-9


, [101]; 10
, [97]; 11
, [101]; 12
,
; 13 , [128]

44

. 2.8.

CuCu2O

2.3.

i

Cu

Cu2O

Cu

134400 / T + 0,493

12800 / T 6,255

9234/ T 2,447

23808 / T + 1,452

10750 / T 4,514

105000 / T + 0,016

j, p

Cu2O

, ,
,
- ( ,
),
.
2.1.2. CuNi
,
.
, ,
.
. , ,
. Benz M.G. Elliott J.F., .. , E. Tankins
. ,
45

[16]. , ..
.. , [131],
.
,
1.
. .. ..
, , Benz M.G. Elliott J.F.
[16].
.. .. [132] ...
:
() Ni| Na2OSiO2 + 5 . % NiO | CuNi (+)
11201250 C 0,26 . %. ...
.
,
,
. [132] 1120 C

0,8 . %. .
,
, 1250 C .
,
.
( 0,006 . %).
.
.
CuNi [133136].
,
CuNi ,
,
(D.J. Chakrabarti , E. Schurmann E. Schulz, B. Predel R.
Mohs, E.A. Feest R.D. Doherty, B.D. Bastow D.H. Kirkwood, B.N. Dey, M. Okamoto, O. Bauer
H. Arndt), .
CuNi ,
Kellogg.
,
46

( Q/Cu//Ni/ = 1200
/). ,

w(Cu)(Ni) =

= w(Ni)(Cu)=0,13. . 2.9.

. 2.9. CuNi
2.1.3. NiO
, NiO
[137], ,
( , , [138]),
.
Neumann J.P., Zhong T., Chang Y.A.,
[139],
1440 [O] = 0,9 . %. NiO,
J.R. Taylor A.T. Dinsdale, ,
,
1939 [140].

. Kellogg.
, NiO. NiO = Ni + O,
:
47

lgK = 13260/T + 4,976.



2.4:
2.4.

i

Ni

NiO

Ni

52320/T 27,007

3160/T 0,294

NiO

194300/T 87,136

29970/T 0,179

. 2.10.
,
, Neumann J.P. .

. 2.10. NiNiO.
1919
2.2. CuNiO

CuNiO,
48

[98,
141154]. , -, , -,
, ,
, , .
[155] ...
Pt|Ni,NiO|O|[O]( Cu)|Mo
CuNi (1,53,0 . %) 11001200.
, .
El-Naggar Parlee [156], ..., (
20 %) .
, .
eNiO NiO 1200C 0,0375 9 .
[145] NiCu
... 1460 C
:
Pt,LaCrO3|Ni, NiO| ZrO2+ CaO|[O] NiCu| LaCrO3,Pt.
,
.

[143]

CuNiO.
, 1500 1027C.
,
CuNiO 1027C. ,
:
2 1+ Cu2O + NiO 1203C,
2 Cu2O + CuO + NiO 1 Cu2O + NiO + (Cu, Ni) ~ 1062
1058C, (Cu, Ni) .

14001527C. (Cu, Ni)O,

CuNi.
,
[90, 157, 158].

. [158, 159].
49

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

.
[98] Claus Leitgebel ,
.
, .
, 40 . %
( . 2.11, [98],
CuNiO).
. [11] ,
Cu2O NiO.
(H. Nestler) Cu2ONiO (
CuNiO), [99]. Cu2O
NiO , 1218 .
: Ni 2,3 . %, O 34,3 . %, Cu 63,4 . %.
CuNiO, Nestler, (.
. 2.12).
P. Taskinen [160]. ...

ZrO2 ,
,
, 5,4 . % 7,5 . % .

10651225,

CuO
10661450. 10651300.

50

. 2.11. CuNiO [98]

. 2.12.
CuNiO [99]

51

, CuO, .
, ,
0,47 . % 0,32 . %
1066,50,5.
,
, .
, CuNiO,
,
NiO, Cu2O (. 2.13). ,
CuNiO 10651225.

. 2.13. CuNiO P. Taskinen [160]


Cu2ONiO
H. Nestler . ,
Cu2ONiO (. . 2.14).

52

.
, :

wCu 2O NiO

28320
T

13,826 ,

wNiOCu 2O

29160
T

18,589 .
. 2.14.
Cu2ONiO:
a
,
[99];


;


;


;
= 1250


[5],

:

lg a1 v1 lg x1

v1 3x12 x22Q1112 x1x22 2 3x1 Q1122 x23 1 3x1 Q1222

lg a2 v2 lg x2

2,3RT

v2 x13

1 3x2 Q1112

x12 x2

2 3x2 Q1122 3x12 x22Q1222

2,3RT

(2.1)

vi ,
, ( Cu2O v =
2, NiO v = 1), x1 x2 Cu+ Ni2+, a Q
.
Q , , . 1
1.

53

,
. ,

. , [161166]
[167170].

:

RT ln ai

H m
Tl Tm ,
Tm

(2.2)

ai ,
(), H m , Tm
i, Tl .
. 2.15
Cu2ONiO = 1250 .
, (2.1) (2.2)
,
100 %, , (
) , ..
.

. 2.15.
Cu2ONiO = 1250 : 1

; 2

; 3 ai = xi


. 2. 1.
. 2.16 CuNiO
. .

54

CuO.
Cu2ONiO.
. 2.16 (T = 1250 ) I ab
(Cu2O, NiO), 12. II
b ( 2) NiO ( 3).
III , bc ,
( 3).

. 2.16. CuNiO:
) = 1250 ; ) = 1230 ; ) = 1150 ; ) = 1150 , [11]

. 2.16 (T = 1230 ) . :
IV, Cu2O, V,
d ( 4)
Cu2O ( 1). 12181242 .
2 4, b d , (I) ,

55

, . 2.16 T = 1150 . III


NiO, IV , VI
, b ,
.
. 2.16 , [11] (. 2.16 ).
1150 ,
. I
, .
II .

, (
) . III
Cu2O.
( IV) ,
Cu2O. , IV, VI, III ,
abc CuNi , IV, III, II I
, [11].
, ,
:

Cu 2O 2Cu O ,

(2.3)

Cu 2O 2Cu O ,

(2.4)

NiO Ni O ,

(2.5)

NiO Ni O .

(2.6)

, ,
. 3 1.
(2.5)
(2.6),
NiO. (2.3)

.
(2.3)(2.6)
:

56

K (2.3) aO a Cu O ,
2

(2.7)

K (2.4) aO ,

(2.8)

K (2.5) aOa Ni a(NiO) ,

(2.9)

K (2.6) aOa Ni .

(2.10)

Cu O Ni 100%,
x


Cu +

Ni 2+

1,

(2.11)

CCu CO CNi 1 1,5CCu 2CNi 1 .

(2.12)

lg a

lg O e OO O e ONi Ni ;

Ni
lg a Ni lg Ni e Ni
Ni e NiO O.

(2.13)

(2.7)(2.13),
(
) , (Cu2O),
.
:
1.
. (. . 2.16 a) I
(2.3) (2.5); II (2.3), (2.5), (2.6); III (2.6); IV (2.4);
V (2.3)(2.5); VI (2.4), (2.6).
2.
(. . 2.14).
3. , (2.7)(210),
( ),

( (2.1)).

57

4. (2.13) (. 4 1)
.
, , ,
T = 1250 .
I . 2.16 ,
12 . 2.14. ,
, ,
( (2.1)).
(2.3) (2.5) ,
( (2.7)),
( (2.9)).
, (
II . 2.16 , ), (2.3),
(2.5) (2.6). ,
, 2 . 2.14,
.
III (. 2.16) .
(2.6). (2.10)
(2.13)
.

() CuNiO [171173].
, , Cu
NiO [174, 175].

,
.

Mathcad.

( , ,
) Mathcad.
Mathcad .
, ,
( [176, 177]).
58


, ( )
( )
.
2 CuNiO
Mathcad.
. 2.17 CuNiO
.
,
[5]. ,
[99]
(. 2 1), . 1 1.

. 2.17. CuNiO:
: 1 .. ., 1194 , [151]; 2 .. .,
1124 , [151]; 3 ,
.. . [142], 1200 ; 4 Leitgebel W., 1250 , [98]; 5 ,
1250 ; 6 , 1200 . 7

[151]
, CuO
.
59

ab (. 2.17) ,
Cu2O (Cu2O, NiO). I ,
. II ,
. bc
, ,
III , NiO.
bd ,
. bc bd ,
[11].
,

LMe, .
, ,
, ,
, ,
, , , ,

,
.
, [11], (LNi)
, ,
(. . 2.18,
).
. 2.18.

LMe (Sn,
Pb, Sb, As, Ni, Bi)
1250

[11]

60

NiO

. ,
, 0,40,5 % 1150 ,
0,60,7 % 1200 , 0,91,0 % 1250 , -
bc bd . 2.17.
, CuNiO
, . 2.19
2.20.
- (
1 . % )
1100 . ( 100
), .
.
. 2.19 .

. 2.19.
CuNiO
-
T=1100 [173]


.
, .
CuNiO, . 2.21,
12.
2 . 2.21.
.
. (. 2.21) ,
, 2
3.
61

- .
,
. , ,
. , ..
3. . 2.20
1200 .

. 2.20.
CuNiO
-
T=1200 [173]

. 2.21. CuNiO

, . 2.19 2.20
III I (. 2.17 2.21)
. ,
NiO Cu2O.
, I III
. . 2.22 2.23
62


(
) ( ). . 2.22
1100 , . 2.23 1200 .

. 2.22. CuNiO
T=1100 [173]

. 2.23. CuNiO
T=1200 [173]
63

. 2.23 .
. 2.21 1 2. ,
, .
2. ,
,
, 2.
, , ,
u Cu2O .
, (. 2.21) 23,
,
,
.

. ,
.
. 3.
( 3 )
.
.
(
= 1200
20 . %).
CuNiO (2.17)

,
FactSage 6.01, CALPHAD.
,
.
2.242.27 ,
FactSage .

, -
.
64

. 2.24. CuNiO
FactSage. 11001300 .
50 . FScopp
( ), FToxid

. 2.25. CuNiO
FactSage. 11001300 .
50 . FScopp
( )

65

. 2.26. CuNiO
FactSage. 11001300 .
50 . FScopp
( ), FToxid

. 2.27. CuNiO
FactSage. 11001300 .
50 . FTmisc,
FToxid

66

,

CuNiO, ,
FactSage.
, (. 2.24) 1300

. (. 2.25)

Cu2O
NiO. ,
,
. ,
(
FToxid) (. 2.26) ,
.
,
SiO2, , [99] CuNiO
.
,
FTmisc, FToxid (. 2.27),
, ,
12501300 ,
.
2.3. CuNiO
,
, ,
,
. , ,
, ,
. ,
.
:

67

1) ,
, , ..;
2)
.
3) ,
.

"
" . . ,
[178].
,
( )
.

NIST FactSage [179]. ,
, ,

2
1.


1) (
, , [11, 16, 90]);
2) ( G)
,
( ,
, [90, 131, 180, 181]);
3)
,
, (

(
, , [99, 131, 182184] .)
, ,

68

[54, 80, 92, 98, 139, 185187],


, ).
CuNiO , 3
1.

Cu 2O 2Cu O NiO Ni O
[90].

Cu 2O 2Cu O NiO Ni O

lg( e

H m 1
(T
R

T1 )
m

Al
T

Bl

As
T

Bs ,

H m , Tm , Al Bl
, AS BS
.

,
, :
1)
;
2)
;
3)
.

. , , ,

.
(
) Cu2ONiO .
,
, .
,

,

69

(
, , , [7, 159, 188, 189] .).

.
eOO,
. 4 1, [103].
,
, [90],
CuO, , ,
[190].
eNiNi ..
.. , [131],
CuNi 1703 .
0 10 .%.

eNiO eONi ,
,
CuNiO.
,
eNiO. , [16]
, 1200 0,046,
0,034.

Ni
eONi T e O(1473)
1473 / T ,

eONi

eONi

A(Ni) Ni
eO ,
A(O)

(Ni) A(O) , ,
( bc),
. 2.28.

70

. 2.28. eNiO:
NiO;
Cu2O (1100 0C)
(1300 0C);
bc NiO
( eNiO) bc,
T=1300 0C
, , , . , eNiO
= 0,034 .
NiO T=1300 0C ,
,

( ,
).
,
. eNiO,
,
71

eNiO = 0,026 (. 2.28).


, . 4 1.
2.4.

,
.
,
, . ,
, ,
.

:
1. .
, ,
,

.
2. ,
.

,

,

.
,
, . ,
, ,
, .
3. ,
.

( ),
, ,
72

.
.
4. .
,
,
,
, ,
,
.
,
,
(
). ,
, .
5. , ,
, .
1.5.
6. , , .
( , ,
) ,
, ,
.
7. ( ,
).

.
8. .
,

.
9. .
,
,
, .

73

,

:

n1 lg a[ R '] m1 lg a[ X ] lg K1

n2 lg a[ R ''] m2 lg a[ X ] lg K 2
n lg a m lg a lg K
[ R ''']
3
[X ]
3
3
a[ R '] f (C[ R '] )

a[ R ''] f (C[ R ''] )


a f (C )
[ R ''']
[ R ''']
a[ X ] f (C[ X ] )

C[ R '] C[ R ''] C[ R '''] C[ X ] 100%


:

RnXm = n[R] + m[X],


,
.
,
, 100%.


. ,
, ,
(
).

,

:
(RnXm) = n[R] + m[X],
11 ,
,
,
, .
:

74

n1 lg a[ R '] m1 lg a[ X ] lg a( R ' X ) lg K (1)


n1 m1

n2 lg a[ R ''] m2 lg a[ X ] lg a( R ''n X m ) lg K (2)


2
2

a( R 'n1 X m1 ) f (C( R 'n1 X m1 ) )

a( R ''n2 X m2 ) f (C( R ''n2 X m2 ) )

C( R 'n1 X m1 ) C( R ''n2 X m 2 ) 100%


n1 lg a[ R '] m1 lg a[ X ] lg K1

n2 lg a[ R ''] m2 lg a[ X ] lg K 2
a f (C )
[ R ']
[ R ']

a[ R ''] f (C[ R ''] )


a f (C )
[X ]
[X ]
C[ R '] C[ R ''] C[ X ] 100%
, ,
b CuNiO.
10. .


.
11. .
,
, ,
(. ),
( - ,
).
12. .

n1 lg a[ R '] m1 lg a[ X ] lg K1

n2 lg a[ R ''] m2 lg a[ X ] lg K 2
a f (C )
[ R ']
[ R ']

a[ R ''] f (C[ R ''] )


a f (C )
[X ]
[X ]
C[ R '] C[ R ''] C[ X ] 100%

75

n1 lg a[ R '] m1 lg a[ X ] lg a( R ' X ) lg K (1)


n1 m1

n2 lg a[ R ''] m2 lg a[ X ] lg a( R ''n X m ) lg K (2)


2
2

a( R 'n1 X m1 ) f (C( R 'n1 X m1 ) )

a( R ''n2 X m2 ) f (C( R ''n2 X m2 ) )

C
C( R ''n X m 2 ) 100%
2
( R 'n1 X m1 )
n1 lg a[ R '] m1 lg a[ X ] lg K1

a[ R '] f (C[ R '] )

a[ R ''] f (C[ R ''] )

a[ X ] f (C[ X ] )
C[ R '] C[ R ''] C[ X ] 100%

, , ,

. , ,
, B, C, A, B, D
A B.
13. (
, , ).

, -
(, ,
). ,
, ,
.
14. .
.
,
, :

n1 lg a[ R '] m1 lg a[ X ] lg K1

a[ R '] f (C[ R '] )

a[ X ] f (C[ X ] )
C C C 100%
[ R '']
[X ]
[ R ']
15.
.
76

,

, .
16. .
,
,
, ,
,
.
,
,
.
. , ,
.
:
1.

.
2.
3.
.
2.5. CuNiO
[166]

. :
1) 10 (..), (..) (10 %). . 2.5.
2) 2 , :
2 Cu2O (..), Cu2O NiO (..),
. 2.5, , NiO.
,
1250 CO2.
, .


77

. ( ), ,
[98, 142, 151], . 2.17.
2.5.
CuNiO [166]

1.
, . %
2.
, . %
3.
, . %
4.
, . %

[Ni]
[Cu]
[O]
[Ni]
[Cu]
[O]
[Ni]
[O]
[Ni]
[O]

1
0
66,7
33,3
0
67,7
32,3
0,00
2,32
0,00
2,30

2
2,39
63,48
34,13
2,36
63,49
34,16
0,99
2,41
0,87
2,38

3
50
0
50
49,8
0,3
49,9
1,50
1,21
1,48
1,19

4
50
0
50
50,04
0,05
49,91
2,00
0,84
2,22
0,64

5
50
0
50
50,12
0,01
49,87
4,00
0,49
4,07
0,42


(. 2.5, ).
,
( 3 %) , ,
Cu2O.
Cu2O, , ,

.
(Cu2O).
, ( 3
, [166] CuSnO, CuZnO,
CuCoO, CuFeO, CuPbO CuSbO), .
,
.
,

.
2 ,
.
,
.
2

.. [171].
78

: ( 99,99%), ( 99,99%), Cu2O (


...).
.

13201350 . ( )
, Cu2O.
- .
1200 .
, .
.
5/20.
. 2.6 , CuNiO
( T = 1200 ).
.
. 2.6 ([Ni]).

JEOL JSM6460LV,

Oxford Instruments.
, I, . 2.29.
Cu2O
CuNiO.

().
2.6.
T = 1200 C, . % [171]
I
II
III
IV
V

[Ni], .%
0,250
0,500
0,620
1,000
1,500

[Ni], .%
0,220
0,460
0,610
1,020
1,550

[O], .%
1,700
1,750
1,780
0,660
0,375

Cu2O, .%
15,190
15,640
15,910
5,900
3,350

II . 2.30. ,
, .

79

III . 2.31.
Cu2O
NiO CuNiO.
Cu2O, () NiO.
.
IV (
NiO) . 2.32.
NiO.
V . 2.33. , V,
, .
,
1 . %.
. 2.342.36.
CuOCu2O. ,
, ,

(,

). , NiO.
, NiO,

.

. 2.29.

Cu Ni O,
T=1200 C.
I (. 2.17, [Ni]=0,25 . %),

[Cu]=67,84 . %, [O]=32,16 . %

. 2.30.

Cu Ni O,
T=1200 C.
I (. 2.17, [Ni]=0,5 . %),

[Cu]=68,79 . %, [O]=31,21 . %

80

. 2.31.

Cu Ni O,
T=1200 C.
I III (.
2.17, [Ni]=0,62 . %), -
[Cu]=66,65 . %,
[O]=33,35 . %.,
[Ni]=49,97 . %, [O]=48,32 . %,
[Cu]=1,72 . %

. 2.32.

Cu Ni O,
T=1200 C.
III (. 2.17, [Ni]=1,0 . %),
[Ni]=50,54 .
%, [O]=47,54 . %, [Cu]=1,92 . %

. 2.33.

Cu Ni O,
T=1200 C.
III (. 2.17, [Ni]=1,5 . %),
[Ni]=49,71 .
%, [O]=48,49 . %, [Cu]=1,80 . %

, NiO
(Ni0,67O [191],
, Ni3,75O4 [192]).

81


. %
[Ni]
68,19
[O]
27,46
[Cu]
4,35

. %
39,42
58,26
2,32


. %
. %
[Ni]
0.67
0.48
[O]
17.23
45.24
[Cu]
82.10
54.28
. 2.34.
Cu Ni O

. %
[Ni]
71,83
[O]
21,03
[Cu]
7,14

. %
46,17
49,60
4,24


. %
. %
[Ni]
65,56
42,17
[O]
21,03
49,63
[Cu]
13,41
8,20
. 2.35.
Cu Ni O

. %
[Ni]
57,85
[O]
30,01
[Cu]
12,13

. %
32,29
61,46
6,26


. %
. %
[Ni]
1,13
0,83
[O]
16,08
43,19
[Cu]
82,79
55,99
. 2.36.
Cu Ni O
2.6.
1)

82

,
.

,
.
2)
. ,
,
, ,
,
,
. ,
,
.
.
.
3) ,
, .
Mathcad .

, ) Mathcad.
Mathcad ()
.
, ,
.
,
.
( )
( )
.

Mathcad.
4)

83

,
,
.
5) ,

CuNiO.

, .

,
.

.
6)
Cu2ONiO.

Cu2ONiO

CuNi,
CuCu2O, NiNiO, Cu2ONiO.

CuCu2O,
.
7)
CuNiO.
8) ,
.

,
.

,
, .
9)

CuNiO.

. ,
.
84

3. ,

,
.
( CuSnO, CuZnO, Cu
CoO, CuFeO, CuNiO)
, (
, ),
,

.
( CuPbO, CuAsO, CuSbO, CuBiO)
, (
) .
,
(SiO2) .
CuSiO, CuCaO, CuMgO CuAlO.

,
.
CuSO CuP
O, ,

.
3.1. , ,
3.1.1. CuSnO


( 11 %).
Sn O ,
,
. CuSnO
.

85

,
,
CuSnO
.

, Nanda C. R. Geiger G. H. [193].
CuSn ( 60 .
% ). 1135 ...

Pt|NiNiO||ZrO2+CaO|| CuSnO |W.
,
, 60 . % Sn, 0,143.
SnO 10,5.
. CuSnO Sn
(Z) 1 4,
Sn Z 8. CuSnO
Sn, ~10 . %,
.

. Oishi T. [194, 195] ...
Pt|NiNiO|O2| CuSnO |Mo.
11001200
CuSn (0,753,0 . %). ,
, , .
...
CuSn. ,
SnO2 9001100
GSnO2= 134,7+46,9103 T(/).
Otsuka S. . [196], ,
CuSn 1100 .
o S- ,
, Jacob Alcock.
, CuSn
.
SnO= 2,8 1100 .
86


(. 4 1) eSnO 1400
, .. [103, 197]. eSnSn
CuSn,
Azakami T. (1130 ) Oishi . (1100 )
[131].
. [11]
. 0,010,03 . %
3040, 160200
. SnO2
,

.

SnO2 SnO, ,
600 ,
, .
Cu2OSnO2 [198].
Cu2OSnO2
(Hofmann W. Klein M) [98, 99].
Cu2OSnO2 , 12233 .
: Sn 0,71 . %, O 34,00 . %, Cu 65,29 . %.
Cu2OSnO2 (2.1) (2.2),
. . 3.1.1.

Cu2OSnO2
CuSnO (. 3.1.2).
(e2) CuSnO2
1080, Sn 0,15 . %, O 0,30 . %, Cu 99,55 . %.
[11] Cu2O
, , , SnO2
SnO 44 .
[11, 98, 157],
,
:
87

Cu 2O 2Cu O ,
Cu 2O 2Cu O ,

SnO2 Sn 2 O ,

(3.1)

SnO 2 Sn 2 O .

(3.2)

. 3.1.1.

Cu2OSnO2


1 (. 3). (3.2)
[11], (3.1)
SnO2, Cu2OSnO2
(3.2) .
. 3.1.3
CuSnO
. ab ,
Cu2O ( Sn Cu). I ,
. II ,
. bc
, ,
III ,
SnO2. bd ,
.

88

. 3.1.2.

CuSnO. Hofmann W. Klein M,
[98]

. 3.1.3 ( ) [166]
. (
) . 3.1.

. 3.1.3. CuSnO [199]:


1 [10], 1250 ; 2 , [142],
1200 ; 3 [166], 1250


,
.

89

(
) , .
3.1.
CuSnO [166]


, . %

, . %

[Sn]

0,167

1,8

33,3

33,3

33,3

[Cu]

66,33

65,8

[O]

33,50

32,2

66,7

66,7

66,7

[Sn]

0,172

1,679

33,254

33,320

33,351

[Cu]

66,325

65,914

0,094

0,009

0,074

[O]

33,50

32,407

66,652

66,671

66,575

[157], 95 % Sn
,
. .
,
,
SnO2 . (CuSnPbO).
, [10],
. , .
. 2.5 (. 36) , ,
, Cu2O SnO2.
, bc
, . 3.1.3.
(2.4) (3.2).
, bc . 3.1.3
, , [10].
,
[142]. ,
.

90

1 o (SnO2)
. %

. %

[Cu]

3,74 0,15

2,77

[O]

23,16 1,2

68,20

[Sn]

73,11 1,12

29,03

2
. %

. %

[O]

0,21 0,39

0,85

[Sn]

0,91 0,25

0,49

[Cu] 98,88 0,49

98,66

. 3.1.4.
Cu Sn O
91

. 3.1.5.
( Cu Sn O)
SnO2

III
[16, 200],
SnO2.
,
(. . 3.1.4 3.1.5, ,
3, , .. [201]),
, , .
. 3.1.4 ,
Cu Sn O, ,
,
. SnO2,
, . 3.1.5.

92

3.1.2. CuZnO
CuZnO,

, ,
, , , ,
,
[16, 202]. ,
.
, ,
.
CuZn. , T. Azakami . Yazava [203]
CuZn.

CuZn. 1200 Zn -
0,11. , CuZn
xZn = 00,6:
RTlnZn= 6400xu2 90 850-1200.
Zn
(Baker E. H. [204]) Ar
11001200. 1150
. Zn,
.
, ZnCu
.
Gerling

U.

Predel

B.

[205]

...


CuZn.
,
. , ,

.
eZnZn
( ) ,
Baker E. H., . . ,
93

[131].
, (. 4, 1).
,
eZnO 1200 , [197].
. . [90, 197]
( .. . [16]) (0,087
0,091).

CuZnO [99, 103, 142, 197, 206, 207] ,

.
, .
Cu2OZnO.
, ,
. 3.1.6.

. 3.1.6.
Cu2OZnO

, ,
:

Cu 2O 2Cu O ,
Cu 2O 2Cu O ,

ZnO Zn O ,

(3.3)

ZnO Zn O .

(3.4)

94

, ,
, :

Zn Zn .

(3.5)

,
, . 3 1.
. 3.1.7 CuZn
O . ,
, .

.
.
, ,
.
, ,
. 3.1.7.
. 3.1.7 CuZn
O
. ab ,
Cu2O (Cu2O, ZnO). I

, II ,

. bc
, ,
III , ZnO.
bd ,
. . 3.1.7
( 0,3 . %).

[166]. ( )
. 3.1.7. , . 3.1.7 [142].
, , (
) . 3.2.
() ZnO
[16, 202], ,
( ZnO, [16]), ,
( 0,005 %) ZnO .
95

, , ,
, ZnO
.
3.2.
CuZnO [166]
1

[Zn]

50

50

50

50

50

[Cu]

[O]

50

50

50

50

50

[Zn]

50,07

49,83

50,04

49,80

50,09

[Cu]

0,11

0,24

0,05

0,30

0,07

. %

[O]

49,82

49,93

49,91

49,90

49,83


, . %

. 3.1.7 a.

CuZnO [208]:
1 ,

[142], 1200 ;
2
[166], 1250

. 3.1.7 .

CuZnO [208]:
1 ,

[142], 1200 ;
2
[166], 1250

96

,
ZnO (. 3.1.8, 3.1.9, 3.1.10), Cu2O,
(. 3.1.11).
(> 1 %) .

. 3.1.8. ( CuZnO, [Zn] = 8 . %),


() ,

. 3.1.9.
( CuZnO,
[Zn] = 0,75 . %),

3.1.3. CuCoO
, ,
.
( [11] 500),
. ,
[157, 209] , ,
,
CuCoO, ,
[210].

97

1 o (ZnO)
. %

. %

[Cu]

5.680,27

3,90

[O]

16.090,52

52,22

[Zn]

78.230,54

43,88

2
. %

. %

[O]

[Cu]

99.160,36

99.18

[Zn]

0.840,24

0.82

. 3.1.10.
CuZnO

98

1
(Cu2O + ZnO)
. %

. %

[Zn]

0,170,25

0,12

[O]

11,690,46

34,61

[Cu]

88,150,50

65,27

2
. %

. %

[Zn]

< 0,05

[O]

0,980,33

3,44

[Cu]

99,020,41

96,56

. 3.1.11.
Cu Zn O

99

CuCo ,
[211214]. (Timberg L. .) CuCo (
CuFe)

-.


CuCo. ,
.
. [212]
.
1520.
.

CuCoO , ,
. , ,
.. . [103, 142], Taskinen P [215], .. [216],
.. .. [217]. [16]
eCoO. .. [90] ,
[103, 142]. [11, 90] ,

, .

, , [218, 219].

,
CoO, .. [90] (. . 3
1).

Cu2OCoO. Cu2ONiO ,
, .
,
, . 3.1.12.
, ,
,
,
.

100

CuCoO
. 3.1.13. ab ,
Cu2O ( Co Cu). I
, , II
, . bc
,
. III ,
CoO. bd ,
.

. 3.1.12.
Cu2OCoO

. 3.1.13. CuCoO:
1 , [218],
CoO, 1100; 2 1200 ; 3 ,
[219] , ,
CoO, 1100 ; 4 1200 ; 5 1300
[219]; [166], 1250
101

. 3.1.13
[218, 219]. ,
. [166]:
( A) 43 . %. ( B)
( 26 . %).
( C D) (Cu 0,2 . % 0,25 . %
, . 3.1.14).

. 3.1.14. ( CuoO)
c CoO,

3.1.4. CuFeO

CuFeO
.
, .
CuFeO
,
, [220232].
, (
, ), .
Snches M. [230, 233],

.
102

,
, .
11001300, , .
, , , ,
8 ,
.

, , ,
.
CuFeO.
.
.
, 1100 1300 ,
0,8 2,8 %.
,
CuFeO [234], P. Perrot c .
1200 .
CuFe
[136, 211, 235237].
FeFe ..
.. [131].

.
.. [103] 1400 FeO
0,9. .. , ,
0,87 0,55 (1200 ) [90].
Abracham K.P. 1200 2,73, Kulkarni A.D.
: 2,79, Biswas A.K. Seow H.P. 1250
: 2,32 [16].
Janke D. Fischer W.A. [16]
( 1150 , 2,3 . % Fe):
FeO = 4,9 + 13,73[Fe] 16,23[Fe]2 + 8,02[Fe]3 13,9[Fe]4.
,
, , [16, c. 37] [99, c. 639].

103

[103] ,

- FeO
, [103, c.89]. , ,
,
.

-,

.
-
.
.. ,
Janke D. Fischer W.A. ,

, CuFeO.
,
, , Fe3+ Fe2+
[223225, 229].
(Fe2O3).
(CuFeO2). .. [90],
, CuFeO2. ,
( 104 %) .
. 3.1.15 3.1.16
Cu2OFe2O3 Cu2OFeO .
. ,
Cu+, Fe3+, O2, Cu+, Fe2+, O2.
,
,
. 3 1:

Cu 2O 2Cu O ,
Cu 2O 2Cu O ,

CuFeO 2 Cu Fe O ,
Fe3O 4 3 Fe 4 O ,

Fe2O3 2 Fe 3O ,
104

FeO Fe O ,

FeO Fe O .
[90].
[90]
.
CuFeO [238]
. 3.1.17. I , , II
, Cu2O, III CuFeO2,
IV Fe3O4, V FeO.

. 3.1.15.

Cu2OFe2O3

. 3.1.16.

Cu2OFeO

. 3.1.17 , [166].
1100 , T = 1225 .
. ( 1)
0,98; 0,3 %. ,
, , 1, .
105

( 2) ( 1 %),
(Cu 26,6 . %, Fe 25 . %, O 48,4 . %).
: Cu 9,1 . %, Fe 44,3 . %, O 46,6 . %.

. 3.1.17.

CuFeO [238]


CuFeO ( =
1200 )
(. 3.1.183.1.20). , ,
. 3.3.

. 3.1.18.
( CuFeO)
c CuFeO2

. 3.1.19.
( CuFeO)
c Fe3O4

106

. 3.1.20. ( CuFeO) c
FeOFe3O4: ) ; ) ,

CuFeO2 (. 3.1.18). ,
, CuCu2O,
.
CuFeO2
.
(Fe3O4)
0,1 . % , (
. 3.1.19).
(> 1 . %)
(. 3.1.20),
(FeO).

. , FeO
(. 3.1.20 , . 3.3), ,
.
,
FeO.
( II . 3.1.17)
- .
. 3.1.21 , ,
, ,
( , = 1300 ).
. 3.1.22 ,
. abdfh
107

abdfh, . 3.1.17. , ab
, Cu2O ,
ab (. 3.1.17). bd ,
bd. , df,
df. fh ,
, fh.
3.3.


CuFeO2 ( . 3.1.18)
Fe3O4 ( , . 3.1.19)
. 3.1.20
Fe3O4 (
. 3.1.20 )
FeO ( . 3.1.20 )

[Cu], .
%
27,32
2,23
0,2
0

[Fe], .
%
23,71
41,59
47,16
43,74

[O], .
%
48,97
56,18
52,65
56,26

48,47

51,53

. 3.1.22 , ,
.
Cu2OCuFeO2, CuFeO2Fe3O4 Fe3O4FeO,
abdfh Cu2OCuFeO2Fe3O4FeO
. abdfh
,
.
, abdfh, .
3.1.23.

. 3.1.21. , ,
= 1300 [238]
108

. 3.1.22.
Cu2OFe2O3FeO,
[238]

3.1.24,

[234],

CuFeO
= 1200 .
, . 3.1.24.

. 3.1.23. ,
abdfh (. 3.1.22) [238]
,
; ;
; , , Fe3O4,

; ; Fe3O4 FeO; FeO , FeO .
, ,
Fe3O4CuFe2O4,
109

CuFeO (. 3.1.17,
). , 3.1.25
CALPHAD , 2011 . [239].

. 3.1.24.

CuFeO
= 1200
1 .
[234]

, ,
3.1.24.

. 3.1.25.
CuFeO
= 1200
[239]

2013 . [240],
( CALPHAD,
FactSage) CuFeO. , [240]

110

= 1200 (. 3.1.26),
[234].

. 3.1.26.

CuFeO = 1200
1 .
[240].

,

[233]

3.2. , ,
3.2.1. CuPbO
.
[11] 0,5 . %.

[10].
[241].

. (.
, [242, 243]) CuPbO
.
, CuPbO,

.
, Z. Smeiszek [244]

. ,

111

. .
410 1200 0
5,0107 .
PbO .
, .
RPb= (Pb)/[Pb].

,
:
RPb2,82=1,09+3,23 ([. % Pb]);
RPb1,51=0,73+18,82 ([. %O2]);
RPb0,32=1,26exp {0.18( . % Cu)}.
[244] RPb

318.

, , Pb < 0,3 . %,
RPb > 12, 0,5 %
12 %. [245] (M.
Kucharski) ,
Outokumpu .
, ,
SiO2 .
, ,
.
Cu2OPbOSiO2
1225

C [246].

,
.
, :
lg(xPb2+/x2Cu+) = lgxPb+2,400,5 xPb 0 0,003.
,
( )
.

CuPbO.

112

(. [247249]),
.
[250, 251], (Anik S.,
Frohberg M. G.) ...

ZrO2

MgO, CuPbO 1200C.


,
.

.
PbCuO= 2,7 CuPbO= 7,7.
, CuPbO,
A. P. Taskinen [252]. ...
:
Pt, Cr2O3|[O] [Cu+Pb]|ZrO2(CaO)||Pt
CuPb.
, 1100C
() ( 4 . % )
.
PbO, 8,8; 7,8; 7,1 1100,
1150 1200 C .

PbO = 16,95 35,36103 / .
[253] (Jacob K.T., Jeffes J.H.E.) ... c
:
Pt, NiNiO| |O, , Pt
1100 1300,
1100.
- 1100,
900 750.

.

CuPb, , , [254, 255],

113

, , CuPb
.

CuPb, ,
. ,
, 1907 [256]. ,

. , 80- . XX ,
, , [257].
,
, . , [258]
CuPb
10001200C. ,


CuPb.
:
lnPbo = 3461/T + 0,181
lnCuo = 3852/T 0,945.
:
PbPb= 7828/T3,506
CuCu= 8804/T+3,140.
, 1200C ,

RTPbPb=PbPbTPbPb

Pbo=12,58;

PbPb=8,85; PbPb= 52 197 /; PbPb=38,15 /K; Cuo=5,31; CuCu= 2,92; CuCu=


63 970 / CuCu=19,19 /K.
, Hofmann W. Kohlmeyer J., Gebhardt
E. Obrowski W., CuPbO [98].
, ,
Gebhardt E. Obrowski W., . 3.2.1.
e1M1M2KM3b CuPb,
.

CuPbO

.
1200C,
114

Cu2OPbO,
680C PbO 82 . %. Cu2OPbO,
580C.

. 3.2.1. CuPbO
Gebhardt E. Obrowski W. [98]
[259] Cu2O
PbO ( Hofmann W. Kohlmeyer J., Gebhardt E. Obrowski W.).
.
.
,
CuPbO, (2.3), (2.4) (
2), :

PbO Pb O .

(3.6)

,
, , :

Pb Pb ,
PbO PbO .
. 3.2.2 CuPbO. I (.
3.2.2 ) ab Cu2O, II
b ( 2)
( 1). III , bc,
115

Cu2O PbO ( 23), IV c


( 3) ( 4), PbO Pb
( , PbO). V , cd,
( 4Pb).
( . 3.2.3).
1240 ,
(.
. 3.2.2 ).
. 3.2.3 ()
CuPbO,
, PbO Pb . PbO
,
, , , .

. ab ,
Cu2O . I ,
, II ,
.

CuPbO (.. ). ,
,
,
.

. 3.2.2. CuPbO:
) = 1100; ) = 1250
116

. 3.2.3. CuPbO [199]:


1 [10], 1250 ; 2 , [142],
1200 ; 3 [166]: c, d 1250 , e, f 1100
[166] CuPbO
. 3.2.3 . 3.4.
,
.
(. . 3.2.3) . ,
(
, )
.
3.4.
CuPbO [166]
1250

d 1250

e 1100

f 1100

[Pb]

1,8

1,7

, . %

[Cu]

66,7

65,8

66,7

64,4

[O]

33,3

32,2

33,3

33,9

[Pb]

1,6

0,334

, . %

[Cu]

67,3

65,9

67,1

66,2

[O]

32,7

32,5

32,9

33,4

117


CuPbO
(. 3.2.4, 3.2.5, 3.2.6, 3.2.7).
. 3.2.4 3.2.5.
,
Cu2OPbO.
, .
[10]. , ,
. 3.2.3 ( ). ,
, 1,45 . %.
3.2.2. CuPbSnO
, .
, , [260].
CuPbSn
. , ,
.
. , [261], N2
CuPbSn 1100C.

. 3.2.4. , CuPbO

118

1
(Cu2O +PbO)
. %

. %

[O]

10,35 0,75

50,93

[Cu]

20,02 0,43

23,74

[Pb]

69,23 0,77

25,33

2
(Cu2O)
. %

. %

[Pb]

0,41 0,37

0,09

[O]

12,84 0,49

36,99

[Cu]

86,75 0,62

62,92

3
. %

. %

[Pb]

0,63 0,14

0,18

[O]

1,14 0,14

6,01

[Cu]

98,23 0,21

93,81

. 3.2.5.
CuPbO
119

. 3.2.6.
,
CuPbO

. 3.2.7.
PbO,
CuPbO


.
. CuPbSn
xCu/xSn=7, xPb=0,20,6
, , Cu
Sn, .
: PbPb =
3,6, SnPb = +3,3. , 1100C
:
lg Pb=1,93,6xPb+3,3xSn.
[262, 263] CuPbSn 1100
1200 0
120

, CuPb. ,

.
: SnPb = 8720/T 1,42. , [263]
XPb CuPbX (X Ge, Ga, Sn, Fe, In, Bi,
Ag Au). ,
Pb X.

[264]

CuPbSn
. ,
.
[11] CuPbSn
.

Cu2OPbO . CuSnPbO.
[11].
SnO2 Cu2OPbO.
800 . ,
, ,
, (2.3), (2.4), (3.1), (3.2), (3.6),
. 3 1.

Cu2OSnO2PbO CuSnPbO
, Mathcad.
,
, (,
- , ).
, Cu2OSnO2PbO 11001280
4.
. 3.2.8
Cu2OSnO2PbO. . 3.2.9

.
I , ,
Cu2O, SnO2 PbO. II . III
121

. . 3.2.9
.

. 3.2.8 Cu2OSnO2PbO [199]


) = 1100 ; ) = 1200 ; ) = 1250
122

. 3.2.9. CuSnPbO [199]


) = 1100 ; ) = 1200 ; ) T = 1250

123

3.2.3. CuPbSnZnO
, , ,
, ,
CuRO.
,
, ,
, CuPbSnZnO
-
,
, .
,
0555, 04417, 4-2,5,
LG1, LG2, LG4 ( ), 836, 838, 844, 848,
852, 854, 858

922, 923, 932 (

(CDA)).

CuPbSnZn , 3.
(~ 10 ) 0555 ( 836, LG2), ..
5 . % , .
,
63. 1200 0 Cu2O
1200 0 2- .
, (, .
3.2.10) .
, ,
.
-

, ,
.
. ,
. ,
Cu2O (. 3.2.11).

, Cu2OPbO (. 3.2.12).
124

, , ,

.

. 3.2.10. CuPbSnZnO.

. 3.2.11. CuPbSnZnO.
Cu2O


2ZnOSnO2 ZnO ( -c
, . 3.2.133.2.15). , .
3.2.14, ZnO, 2ZnOSnO2. SnO2
(.3.2.16), , . PbO
(. 3.2.17 3.2.18). ,
,
, .

125

. 3.2.12. CuPbSnZnO.
Cu2O
PbO

. 3.2.13. CuPbSnZnO.

.
2ZnOSnO2.
, ZnO

. 3.2.14. CuPbSnZnO.

.
,
ZnO

126

. 3.2.15. CuPbSnZnO.

.
ZnO

. 3.2.16. CuPbSnZnO.
SnO2

( )

. 3.2.17. CuPbSnZnO.
Cu2O
PbO

127

, - ,
.
(. 3.2.19).
(. 3.2.20),
( ), ( 60 . %)
, .
, ,
(. 3.2.21) (-
), 1317 . % 46 . % .
, (, )
, PbPbO.

. 3.2.18. CuPbSnZnO.
Cu2O
PbO .

, Cu2O

( )

. 3.2.19. CuPbSnZnO.
ZnO
(
)

128

. 3.2.20. CuPbSnZnO.
,
(
)
(
)

. 3.2.21. CuPbSnZnO.
.
-
,
1317 . %
46 . % .
Pb
PbO

, ,
, CuPb(5%)Sn(5%)Zn(5%)
: ZnSnPbCu.
: ZnO, 2ZnOSnO2, SnO2, PbO
Cu2O. ,
2ZnOSnO2, CuSnPbZnO.
CuPbSnZnO,
, . 3.2.223.2.26.
.
1300 0 [Pb] = 5 . % (. 3.2.22)
ZnO, 2ZnOSnO2 SnO2 ( I, II III
), ( IV).
V,

129

, (. 3.2.23
3.2.24). 1242 0 (.. ,
V)
. ,
,
IV.

. 3.2.22. CuPbSnZnO = 1300 0 [Pb] = 5 . %

. 3.2.23. CuPbSnZnO = 1200 0 [Pb] = 5 . %


130

. 3.2.24. CuPbSnZnO = 1100 0 [Pb] = 5 . %



1200 1100 0 [Pb] = 5 .
% (. 3.2.23 3.2.24) [Pb] = 1 . % (. 3.2.25 3.2.26). IV
, .. 1100 0
.

. 3.2.25. CuPbSnZnO = 1200 0 [Pb] = 1 . %


131

. 3.2.26. CuPbSnZnO = 1100 0 [Pb] = 1 . %


3.2.4. CuAsO, CuSbO CuBiO
, , . As Sb
0,35 %, Bi 0,05 % [11].
(
, As = 4,1, Sb = 7,5) [10].
(Bi = 1,4).
, ,

, ,

[265268].
,
,
[269272].
132


[273] (I. Jimbo, S. Goto, O. Ogawa) ,
, ,
.
1200 1250 0 1011107 . ,
Cu2O. As, Sb
Bi , ,
.
.
[274] (K. Itagaki, A. Yazawa)
As, Sb Bi ,
. , ,
, .
,
, , SO2 O2
. [274] SO2,
0,11 , As Bi
.
,
.
K. Itagaki A. Yazawa .
1011
.
.
,
- ,
,
.

,

.
[275]
S, Se, Te, As, Sb Bi.

133

Cu2O.
.
, [276] CuAs
22 .% 9501175 0.
:
(Cu) (. ) || KCl+NaCl, Cu+|| CuAs() (+)
,
, 1840 . % As, 11001200 0.
.
Cu3As 827 0.
CuAs
[277279].
CuSb CuBi.
[280] xBi = 0,1
xSb = 0,3 .
Bi, Bi2, Sb, Sb2 Sb4 . ( )
S. Itoh T. Azakami :
lgPBi0=10,12740,9472104T1 0,0056 (833981 0);
lgPSb0=8,05130,6168104T1 0,0049 (808914 0).
Bi, Bi2, Sb, Sb2 Sb4,
. ,
.
1100 0
2,6.
, [280]
,
, 2,0 102 1100 0, 102 1000 0 4,9103 900 0. Itoh
Azakami ,
Bi Sb ,
.
,
[254, 281, 282]. , ,

SbSb= 7,874+28 402/T
134

:
2{Sb} = {Sb2},

ln K = 5,913+25 426/T.

[241, 283].
, 35
3 3 150 .
Bi, As Sb 11771337 0 330 .
(R. Harris) ,
.
,
. [284] ( . . .)

.
, 525 . % Sb 1100, 1150
1200 0. , Sb CuSb
. ,
, .
, ,
, ,
, . , ,
, .
, , Jiang X.H., Lunch D.C., Davenport W.G. [285].

:
AsBi= 24 + 44 000/T
11251200 0.

CuBiAs. [286] (S. Yao .).

, ,
, . , ,
.

135

(Wypartowicz J., Fitzner K.) [287] CuAsO


1100 0 ZrO2.
AsO= +3,3.
11001150

. :
AsO = 46 632 + 67 288/.
[288] CuAsO
11001200 0

Pt, W|CuOAs|ZrO2CaO|NiNiO|Pt.

2,0105104 . % 15,064104 . %.
0,127 0,223. , 0,0015 . %
.
VB .
[289] (G. Liu, J.M. Toguri, N.M. Stubina)
. . . .
(Pt) LaCrO3, O (CuAsO)|ZrO2MgO|NiO, Ni (Pt).
AsO
CuAsO 9,8(1), 9,1(1) 7,4(2) 1100, 1150 1200 0
.
, CuSb
O. [290] ...
ZrO2 ( CaO)
1100

CuSb.


.
Jacob Alcock:

1
n
O ( A B )

xA

A ( A B )

1
n
O ( A)

xB

B ( A B )

1
n
O(B)

z=8, n=4, =1/2; c h:

V
2
a
h = 2 +0,09
z
Vb

o
o
+0,04|G (A) G (B)|.

[291], :
136

Ni, NiO|ZrO2+CaO|CuSbO,
.
11001200 0 ~0,1
. %, 0 7 . %.
:
SbO = 4,85 11,12103/T.

([290] Otsuka .). ,
BeltonTankins
( .. Bi Sb) .
S. Anik M. G. Frohberg [292].

Pt|CuSbO|| ZrO2(+MgO)|O2()|Pt
1200 0.

CuO Sb2O3.
lnoO(Cu) = 1,55 lnoO(Sb)= 4,68 ,

Cu Sb

O=

1,0;

Sb Cu

O=

6,0.

.

.
CuBiO [293] (S. Otsuka .).
[290].
1100 0.
(ln) xBi,
: Jacob
Alcock,
Alcock Richardson. , ,
,
. (2 . %)
1100 0: BiO = 12.
[251, 294] CuBiO 1200 0

Pt|[O] CuBi||ZrO2(+MgO)||O2( )|Pt.

137


: 0(Cu)=0,212; 0(Bi)=0,170;

Cu Bi

O=

7,05; BiCuO= 6,78.


.
, CuBiO, [295].

. , ,
(1300C),
.
.
1300 C Al2O3
5 ; 1100C
. CO,
CO2 Ar, 400600 3/.
. :
0,0021<xBi<0,0053 3104 <xO<0,044.
:
lgBi= 0,91xO + 0,49,
lgO= 0,91 xBi 0,51,
OBi = 2,1.
, CuRO ( R As, Sb Bi)
,
. ,
[11]. As, Sb Bi
, , +3 +5. , ,
, .
+5
,
(Ni, Pb, Na, Ca .) [10, 11, 15].
, ,
,
:

Cu 2O 2Cu O ,
Cu 2O 2Cu O ,

138

0,5 R2O3 R 1,5O ( R As, Sb Bi).


,
, ,
:

R R .
,
:

R2O3 R2O3 .
. 3.2.27
Cu2OR2O3.
.
.

. 3.2.27.
Cu2OAs2O3, Cu2OSb2O3 Cu2OBi2O3, Cu2OSb2O3
[296]
CuAsO, CuSbO CuBiO . 3.2.28, 3.2.29 3.2.30
. , ,
, ( As Sb)
.
, .

.

139

, , ,
,
. CuAsO CuSbO
,
, .

. 3.2.28. CuAsO [296]


, CuAsO, . 3.2.28.
ab (. 3.2.283.2.30) ,
Cu2O . I ,
, II ,
.
[166]
.
. 3.2.29 . 3.5.
,
. -, .
, ,
Sb2O3 .

140

. 3.2.29. CuSbO [296]:


1 , [142], 1200 ;
2 [166], 1100
3.5.
CuSbO [166]
1

[Sb]

19,35

25,00

30,56

32,43

33,92

, . %

[Cu]

34,41

25,00

15,74

12,61

10,13

[O]

46,24

50,00

53,70

54,95

55,95

[Sb]

19,58

21,04

24,34

27,74

26,38

, . %

[Cu]

33,96

25,13

19,91

14,58

14,85

[O]

46,46

53,83

55,75

57,68

58,77

CuBiO Cu
SbO (

. 3.2.313.2.36).


. (
CuPbO) .
CuSbO (. 3.2.35). ,
Cu2OSb2O3.
[297]
141

,
Cu2OSb2O3.


. ,
. . 3.2.35
Cu2O. (84 . % Sb2O3)
Cu2OSb2O3 ( . 3.2.27).

. 3.2.30.
CuBiO [296]

CuBiO (10 % .)
(. 3.2.31 3.2.32).
(. 3.2.34).
, , 1 % . Bi,
1,5 ( ).
, 10 % . Bi, 5154 % .
, ~ 40 % . 68 % . .
( , Bi2O3)
,
.

( ),
.
(. 3.2.31 3.2.33),
[10].
, ( .
3.2.36 ,
Sb2O3, ).
142

. 3.2.31.
,
CuBiO
([Bi] = 10 % .)

. 3.2.32.

. 3.2.33.

CuBiO

CuBiO

([Bi] = 10 % .)

([Bi] = 1 % .)

143

. 3.2.34.
,
CuBiO
([Bi] = 1 % .)

. 3.2.35.
,
CuSbO
([Sb] = 1 % .)

144

. 3.2.36.
,

CuSbO ([Sb] = 1 % .)

3.3. ,

(I)

(1030 %),
( 3 % Al2O3), ( 4 %) [298].
,
, , .
3.3.1. CuSiO
( )
, .
30-40 . XX ,
CuSi ( N.
Takamoto, A.G.H. Andersen, T. Isawa, C. S. Smith M.G. Corson).
, ,
( CuSi)
, ,

[299303].
. . .
. [304], F. Sommer c [305], V. Witusiewicz .
[306]. [307] CuSiTi
1550 0 SiSi = 6,69.

145

, CuSiO
[308]. , ,
[259],
, ,
.

XX

CuSiO .

u2 [309].
[259] . .
[310]. ,
CuO. [310] u u2 5 %.
.
A.M.M. Gadalla c [311] (
[259]) uu2SiO2
0,21, 0,5 1 .
, uSiO2
[310].
[312].
: T = 1186 0C, [SiO2]=22,8 . %. ,
,
[310, 311]. , , ,
[189], .
[313] (Peddada S. R. Gaskell D. R.)
u2SiO2 ( )
1300

. ,

, , ,
. [314]
Cu2O
SiO2 15% SiO2.
,
, .
Cu2OSiO2.
Cu2OSiO2. ,
17 . % SiO2 1060 ( [259]).
146

1690
.
Cu2OSiO2.
Bo Bjrkman [315]
, .

.
[316].
.
Cu2OSiO2,
[317].

(. 2

1).
[259].
3.3.1 3.3.2.
. 3.3.1.

Cu2OSiO2 [317]:
1
;
2

;
3
;
4
,
[189];
5
,
;
6
,
[259]

,
: Cu+ O2 SiO44. ,
, Cu+, Si4+ O2,
: T = 793 , 65,9 . % SiO2.

147


(.. )
:
2
aCu 2O aCu
aO , aSiO2 aSi aO2 ,

aCu , aSi , aO

.. :

ai Ci i ,
ij
k

i C j e RT
j 1

ij 0,5( i 2 j 2 ) 2 ,

i, Cj , R
(R = 0,00831 /), (), i, j
, . . 3.6 ,
[168] .
. 3.3.2.
Cu2OSiO2 [317]:
1

;
2
,

;
3
,
[259]

, ,
,
.

148

3.6.

i

Cu

Si

i [168], /

418

1255

172


[318]:
n

ln i 0,5 wij w ji x j 0,5 w jp x j x p


j 1

j 1 p 1

wij w ji x j x j / 2 xi w jp wpj x x p
j 1

j 1 p 1

2
j

i i- , x
, wij , :

wij cij / T d ij .
, [189]
Cu2OSiO2. , ,

3.7, , ,
[259].
3.7.

ij

Cu2O SiO2

55672

27,06

SiO2 Cu2O

25445

23,52

CuSiO
. , [319] 1250
1425 .
-.
40 - ( 0,0173 %)
. (
) ,
. .

. A. Hendry H.B. Bell
149

eSiO= 29 1425 eSiO= 62 1250.


[320] ( .. .)
.
[321]
CuSiO. ,
.
, ,
Cu2O.

(0,2 6,0 . %) 1700 0 ,


,
CuSiO.
()
CuSiO .
Cu2OSiO2
1100 1300
,
.
, [10].
. 3.3.3 CuSiO
. ab ,
Cu2O (Cu2O, SiO2). I
, . II
, . cd
,
, III ,
SiO2. c
.
.
,
. . 3.3.4 SiO2
( ),
~ 0,1 %.
cd
SiO2, [10, 189].
150

, SiO2 , 1180 ,
. ,
1132 1200
ab ( ,
Cu2O) cd.

. 3.3.3. CuSiO
,
, ,
,
. SiO2
1200 105 % ( . 3.3.3).
SiO2
0,0035 % [189], 1260 , , [10],
0,011 % . , , ,
,
Cu2O SiO2 .
-
SiO2. ,
, cd , .
SiO2 ,
.
151

. 3.3.4. SiO2,
[189] ,
,
. (. cd . 3.3.3)

, [10].
cd ,

, 35 % . , ,
, ,
,
cd.
3.3.2. CuFeSiO
,

CuFeSiO,

,
.
( ,
) [221229, 322326].
, [324] 1200
1300C ( O2 )
, Fe3O4 SiO2
CO2/CO.
. ,
: 104,9
~1267C.

152

[326] ...
Pt, NiNiO|O2| Cu, Cr2O3, Pt

Pt, FeFeO| O2| Cu (Fe), Fe


12171307 0,

, .
Cu .
Cu 1% ( ) ~4%
7,2103 . Fe3+/Fe
.

(
CuFeO). CuFeSiO
,
, .
, , [26, 27].
, 1217 ,
CuFeO CuSiO,
(Fe2SiO4),
:

Fe 2SiO 4 2 Fe Si 4 O ,
, 1,
, [180]
,
. (
1217 ) , .
. 3.3.5

1250 [327].
,
. I , ,
Cu+, Fe2+, Fe3+, O2, SiO44; II SiO2;
III , IV .
. 3.3.5 [223] (.. , ..
, .. .. ), ,

153

1250 . ,
.

. 3.3.5.
CuFeSiO
= 1250 [327]:

[223]

, , ,
[222225]. ,

( .. , [90]).

[328, 329]. , Fe2+.

,
.
. 3.3.5
, SiO2,
CuFeSiO = 1250 . (
0,01 . %) [223].
Cu
FeSiO , ,
( ) (. 3.3.6).
, ( 1 . %)
(Fe3Si), , ,
(. 3.3.7).

154

. 3.3.6. ,

CuFeSiO

. 3.3.7. Fe3Si,

CuFeSiO

3.3.3. CuMgO CuCaO


,
, , ,
,
, , CuMgO CuCaO,
. CuCaO.
CuMg,
, [330333]. S.P. Garg, Y.J. Bhatt C.V. Sundaram
Mg CuMg, 1190 . %
Mg

5721072

CuMg.

( ),

Mg 00,33 0,61,0.
.. , ,
CuMg
... :
Mg|KClNaCl, MgCl2 (1%)|MgCu,
MgCu Mg ( 0 100 %).
600900 . , CuMg
,
.

155


E.T. [180].
eMgMg,
.
CuCa .. [334].
Cu2OMgO [335]. , ..
[336] MgOCuOCu2O.
, .
.
Cu2OCaO
. [337], [312] (J. Kuxmann, K. Kurre) [338]
(P. Coursol .).
0 15 . %.
,
Cu2OCaO, .
, ,
,
. 3.3.8.
. 3.3.8.

Cu2OCaO:
1
[338], 2
aO
1235 0 [338],
3
aO
[312], 4

[337],
5

[338], 6

( )
, . . [339
341]. ... [341]:
Mo, NiNiO|ZrO2CaO|[O]CuMg, LaCrO3, Mo
156

CuMgO 11001200
. , .


.

, [341],
. ..
1100 eMgO = 620. , ,
,
.
CuMgO [340] CuCaO.
, ,
.
CuCaO [342].


. , , ,
, ,
,
: CuCaO

CaO Ca O ,
CaO Ca O
CuMgO

MgO Mg O ,
MgO Mg O .
, ,
:

Ca Ca ,

Mg Mg .
CuMgO CuCaO (. 3.3.9, 3.3.10)
CuSiO. ,
,

157

, , .
,
.
ab ,
Cu2O ( Ca Mg Cu). I
, . II ,
. bd
, , III
,
. bc I III,
.
. 3.3.9 3.3.10 , ,
.
.
,
, ,
.

. 3.3.9.
CuMgO:
1
. ,

[335]

E, . 3.3.10,
CaO
1235 0 [338].
, (11
. % CaO) , 1,2 . %.
1,195 . % 4,269*1012 . % .
158

. 3.3.10.
CuCaO


, 1 . % Mg, 3.3.113.3.14.

. 3.3.11. MgO

. 3.3.12.
MgO

. 3.3.13. MgO,

. 3.3.14. Cu2Mg,

159

3.3.4. CuAlO
, ,
,

- [343349].
[350] (Yi S., Trumble K. P., Gaskell D. R.)
Al2O3. Cu
AlO
, ,
CuAlO2, Al2O3 = 1075 0
5,610 7 (0,055 ).

.
[344349],
- , ,

.
, CuAlO (. 3.3.15) ,
, ,
Cu2OAl2O3 ( S.K. Misra A. C.D. Chaklader, [259]),
CuAlO2.
,
(2.3) (2.4)
,
:

Al2O3 2 Al 3O ,
Al2O3 2 Al 3O ,

CuAlO 2 Cu Al 2 O .

[90].
.
CuAlO [351] . 3.3.15.
, ,
160

, .
, ,
, Al2O3.

, [16]. ,
, Al2O3 . .. .. ,
, , . 7080 %
CuO. , ,


Cu2O, CuAlO2 [16].

. 3.3.15. CuAlO [351]:


1 [259]; 2 Cu2OAl2O3
,
, (. 3.3.16,
3.3.17).
, , () ,
(. 3.3.16),

161

, (.
3.3.17).
, Al2O3 ,
, CuAl(O).
D=3
( 65) (110 ).
,
( ) . 3.8.

3.8.
CuAl(O)

Al

,
/.
0,870

Cu

2,591

Cu+
2%Al

,
/.
0,870

Cu+
10%Al

0,126

(
Al2O3)

Cu+2%Al

Cu+10%Al

,
/.
0,117

0,054

. 3.3.16.

. 3.3.17.

Al2O3, CuAlO

Al2O3,
CuAlO

162

, (
, ),
, Al2O3.
Al2O3. ,
:
1) CuAl(1%) 800
C 10 ;
2) CuAl(2%) CuO(1,8%);
3) CuAl(1%) Cu2O,
;
4)

CuAl(2%)

(1,8%) ;
5) CuAl(1%) (2 )
1200 C
;
6) CuAl(1%), Cu2O.
(. 3.9),
, 4 5.
, 1 3.
, 2 6,
.
3.9.
CuAl(O)

,


1
2
4
5
6

,
/
2,60
1,08
2,22
0,5
0,69
2,24


, HBR , HB
34,3
93,5
67,75
71
73,3
43,5

74,7
204
122
130,3
136,3
84,75

, (. 3.9).
( HBR,
D=1,588 100
).
163


,
Al2O3.
, ,
.
, ,
(. 3.3.183.3.20).
-
-
Al2O3 (.
3.3.213.3.24).
, Al2O3 -
, ,

CuAlO.
D=3 , 65,
(110 ).

Al2O3, 1 %,
235 HB. 2
7 ,
, 50 .

. 3.3.18. Al2O3

. 3.3.19.

0,5 1

Al2O3

164

. 3.3.20.

.3.3.21. (100

Al2O3

200 ) Al2O3

. 3.3.22.

.3.3.23.

(250500 ) Al2O3

Al2O3

( 70800 ) ()

. 3.3.24.
( 0,5-1 )
Al2O3

165


- . ,
-
Al2O3 .

,
- .
- . ,
, Al2O3.

AlMgO. ,
,

.
3.4. c
3.4.1. CuSO

. ,
, ,
CuSO. ,

.
,
.
CuSO
, .
CuSO CuS,
CuO. ,
CuS, .. .. [352].
N. Asano T. Ichio (1962 ) [353], M. Kitano (1964 .) [354], B. J.
Skinner (1966 .) [355], . . , .. . . (1974 .) [356],
( [357359]). ,

166

1100

CuCu2S

[360].

[361363]. H.H. Kellogg,
CuS 5271327 C,
S2, S,
Cu, Cu Cu2S.
Cu2S.
CuSO
, ,

. ,
, [364]
COSO2Ar
1200C.
109 107 ., SO2 104 102 . ,
, .
[365]
CuSO.
, , ,
. ,
Cu2S 1200 P(O2)<104 . .

.
(
)
[366, 367].
[368, 369], :
CuSO |ZrO2(+CaO)| , Pt,
,
1150 1250. , xS>0,3333
xS. , ,
1150 SO= 16,4.
.
167

[370]


12001400C (1230 . %
O2).
.
CuSO, . 3.4.1. e
(CuCu2O, CuCu2S Cu2OCu2S),
.

, [371, 372].
[373, 374] ...

Pt, NiNiO|ZrO2 + MgO| CuSO |Cr2O3, Pt
,
. 1200 1300. ,
. ,
CuSO

. CuO
S

O .

. 3.4.1. CuSO
T = 1200 ( [370]):
1 [375]; 2 [370]

168


.
, ... ,
10 4 %
( ) , 5106 %
. SO2.
CuSO
.
[376] Cu, Cu2S Cu2O
. 14 837 1300
( lg p(SO2)lg p(O2)
CuCu2OCu2S ).
CuCu2SCu2O ( CuSO) ,
.
A. Yazawa T. Azakami [377] [81]

(
, [81],
. 3.4.2). ,
( Cu2S) .
Yazawa Azakami [377] CuSO
T = 1200. . 3.4.3.
lg p(S2) lg p(O2) lg p(SO2),
( ). [81]
(
). ,

.
( , ,
[81, 375, 378]), , 1100 1300
CuSO :
, (Cu2O Cu2S) ,
SO2 O2 S2 ,
.

169

. 3.4.2.
CuSO.

[81]

. 3.4.3.
CuSO T =
1200 [377]

, :

Cu 2O 2Cu O ,
Cu 2O 2Cu O ,

Cu 2S 2Cu S ,
Cu 2S 2Cu S ,

SO 2 S 2 O ,
0,5O 2 O ,
0,5S2 S .

1 (. 3).

170

,
( , SO2, S2 O2),
, .

.
. 3.4.4 CuSO
.
.
. 3.4.4 I Cu2O ab.
II b
( SO2, O2 S2, ) ,
2. bc ( III) ,
23, , ,
, SO2. IV
( 34) cd. d
(Cu2S) ( SO2, S2 O2, ,
) 4. VI Cu2S de.
.
. 3.4.4 CuSO T = 1200 .
(T = 1129 C),
, ,
d, ( 4) ,
( 5). de
- , 5Cu2S ( VI).
,
, (. 3.4.4 ). I
ab
.
, :

2 Cu 2O Cu 2S 6Cu SO 2 .
,
.

171

, [81], 730 C
SO2 , ,
0,102 , 1052 0,653 .

. 3.4.4 . CuSO = 1100


, 0,101
, Cu2S
Cu2O. (. 3.4.4). ,
172

, -
, .
Cu2SCu2O . 3.4.4 3.4.4
( Cu2O Cu2S Cu2S Cu2O), ,
,
, .

. 3.4.4 . CuSO = 1200


173

. 3.4.4 . CuSO = 1300

, 1200 . (. 3.4.4 ) [81, 375].


GH
, MH Cu2SCu2OCu ( NO). ,
MHGCu2OON,
174

( . . . [81]) - . , ,
,
(, , )
.
, ,
(. 3.4.4 ). ,
, . 3.4.4.

. 3.4.4 .
CuSO
= 1200 .
[81, 375]

. 3.4.4 .
CuSO
= 1300
[81]

175

. 3.4.5 CuSO,
SO2 .
0,101 1,01 .
ab ,
. bc ,
Cu2O . abc mop
, ,
SO2, .
ef , ,
1:2. mo ,
. op ,
Cu2S .

. 3.4.5.
CuSO

[379]:
1 0,101 ,
2 1,01

, abd, ,
Cu2O, , nmo Cu2S.
dbc ,
Cu2O, nop ,
Cu2S.
,
,
, ,
. 3.4.6. ,

176

abc mop (. 3.4.5), ,


.

, , ( )

/,
, .
, 4 , 1 Cu2O ,
. 3.10, 1200 ,
( ) 10 ,
.
. ,
, . 3.10.
. 3.4.73.4.11. , . 3.4.12
CuCu2S.

. 3.4.6.
()

Cu
SO
0,101 :
) (1) (2);
)

177

3.10.
CuSO

1
2

,
0,003
0,010

[S]/[O],
. %
0,0135
0,045

0,033

0,1495

0,100

0,45

0,333

1,499


29-31 . % ,
25,430,3 . % , 0,03,57 . % (
0,60)
27,029,8 . % , 0,01,92 . % (
0,47)
:
1) , 25 ,
17,331,3 . % ( 24,36 . %), 0,013,8 . %
( 7,16 . %);
2)
25,228,2 . % , 0,01,39 . % .
29,933,0 . % ,

. 3.4.7.
Cu2O,
(. 3.10)

. 3.4.8. ,
(. 3.10)

. 3.4.9. ,
(. 3.10)

. 3.4.10. ,
(. 3.10)
178

. 3.4.11.

. 3.4.12.

CuCu2S

(. 3.10)
3.4.2. CuNiSO
,
[380], ,
, SO2
1100 1300 . , ,
.

, , [380].
CuNiSO
1100, 1200 1300 .
- .
,
[381]. , 11001300
NiO,
Cu2O, Cu2S, - Cu2O -
.
. 3.4.13
CuNiSO 1100 . ,
, .
. 3.4.14 CuNiSO 1100
[175].

. .
179

I , , II
, V Cu2S, IV
. , III,
, ,
, , ,
SO2 (
O2 S2). III
. . 3.4.14 ( . 3.4.14 , )
, , 0,101 .

. 3.4.13.
CuNiSO = 1100

. =
1129 Cu2S V IV. . 3.4.14
= 1200 .
,
Cu2S.
( = 1242 )
Cu2O. = 1300 . 3.4.14 .
: VII
( ) , II NiO, IV
( ) III .
, I II . 3.4.14
, = 1200 Cu2ONiO
.
180

Cu2ONiO, ,
,
(. 2.14).

. 3.4.14. CuNiSO [175]


) = 1100 ;

) = 1200 ; ) = 1300

181

. 3.4.14 Cu
NiSO = 1200 , . 2.14
Cu2ONiO, .
,
, . 3.4.14 .

. 3.4.14 .
CuNiSO
= 1200 ,


CuNiSO, = 1200,
, . 3.4.14.
( )
. ,
, (
3 . %), ,
Cu2S 66-67 . %
33-34 . % . . 3.4.15 3.4.16.

, .
( , , . 3.4.16)
.

. . 3.4.17 ,

Cu2S CuNiSO.
, (
), . , , .

182

, [S] = 37,34 . %, [Ni] = 37,40 . %,


[Cu] = 25,27 . %.
,

.

. 3.4.15.

. 3.4.16.

Cu2S,

Cu2S,


CuNiSO


CuNiSO

. 3.4.17.
,




Cu2S
Cu
NiSO.
,


(
),
.
,
,


( . 3.4.18).

183


Cu2S.
. 3.4.19. ,
Cu2S, .

. 3.4.18. ,

. 3.4.19. ,

Cu2S

CuNiSO.

CuNiSO.

[S] = 31,03

[S] = 39,12 . %, [Ni] = 57,14 . %,

. %, [Ni] = 47,50 . %, [Cu] = 21,47 . %

[Cu] = 3,73 . %

3.5.
3.5.1. CuPO
(
, 711 % P). ,
, . [90]
P2O5 ( P4O10).
[107] Cu2OP2O5 ( CuPO3). ,
, [16],
2Cu2OP2O5 ( Cu4P2O7).
.

184

CuPO,
Janke Fischer [382]. ...
Pt, ||ZrO2(+CaO)|| (CuPO)
( ).
,
. 2 %
:
ePO= 5,91[%P]+10,34[%P]26,80[%P]3+1,48[%P]4 1150
ePO= 2,48[%P]+3,71[%P]22,01[%P]3+0,36[%P]4 1600.
0,1 %
ePO= 5,91 (1150) ePO= 2,48 (1600).
[383, 384]

Mo|Mo, MoO2|ZrO2(MgO)|(Cu+P)+MgO+3MgOP2O5|Mo,
,
(MgO+3MgOP2O5) :
3MgO()+2P( Cu)+5/2O2( Cu)=3MgOP2O5()
12001300 , P2O5 .
O2
.
1 . % .

1/2P2() = P( % Cu)
G0= 130 000 + 4,1T /.
[383] P2O5 MgOP2O5,
MgO, 1400 1014,4.
[385] - Cu2OP2O5,
(SiO2) 1200 .
O2 ...
ZrO2.
. P2O5
39% P2O5 310 3 %. Oishi . Cu2O

Cu2OP2O5

185

,
,
[386]. P2O5
1450C.
MgO Mo MgOP2O5.
ZrO2, MgO.
Mo + MoO2. ,
2P( Cu)+5/2O2()=P2O5( ).
P2O5 1400C [386] :
lg aP2O5 = 14,36. lg aP2O5 xP2O5 lg pO2 lg [% P].
, ,
- . . . . [387] ,
P2O5 40%.

-
.
. , P2O5
.
, ,
CuPO,
, ,
, , ,
,
.
,
, . 3.5.1
.
Cu2OP2O5. [388],
3Cu2OP2O5, 2Cu2OP2O5
Cu2OP2O5. ,
; ,
.
.
I , Cu2O,
II Cu2OP2O5 .
186

III , , CuPO3.
, 10 % ,
, ,
[142]. 0,0150,1 % (
)
CuPO3.
(. . 3.5.2).
. 3.5.1.
CuPO
Cu2O
P2O5 [389].


, 1200 :
1
[142];
2 . ,

[16];
3 .
.,
[99];
4 .
.,

[99];
5 . ,

[99].
6

Cu2OP2O5

3.5.2. CuZnPO CuPbPO



. . 3.5.3
CuZnPO 1100 (. 3.5.3 ), 1200 (. 3.5.3 ) 1300 (.
3.5.3 ), . 3.5.4 CuPbPO
1100 1200 .

187

1 CuPO3
. %

. %

[P]

22,59 0,35 20,40

[O]

34,80 0,57 60,84

[Cu] 42,61 0,50 18,76

2 (Cu3P)
. %

. %

11,21 0,29

20,57

[Cu] 88,79 0,29

79,43

[P]

3
. %
[O]

<0,05

[P]

0,31 0,16

[Cu]

. %
0,64

99,69 0,16 99,36

. 3.5.2.
CuPO

188

. 3.5.3. CuZnPO [390]:


) = 1100 ; ) = 1200 ) = 1300

. ,
CuZnPO Cu+, Zn2+, O2, PO3,
CuPbPO Cu+, Pb2+, O2, PO3.
ZnO
189

P2O5, PbOP2O5 [259], Cu2OP2O5


[388].
CuZnPO I ,
, II c , III c
CuPO3, IV c - .
, = 1300
II IV.
.

( 37 %) . [16],
( ) ( 555,
3751 84) ,
.
ZnO, .
, ,
[16, . 48]. ,
,
.
.
.
, ,
IV II, .
,
ZnO, .
ZnO
ZnO
(, [16]).
0,01 0,1 % ,

, 0,3 % (
II IV . 3.5.3 ),
[16].
, CuPbPO (. 3.5.4),
I , ,

190

II c CuPO3 III c - .
.

. 3.5.4. CuPbPO [390]:


) = 1100 ; ) = 1200

3.6.
1) ,


( ) .
,
.

,
. ,
( ),
(

191

) .

.
2)
Cu2O-RnOm ( RnOm ZnO, CoO, FeO,
Fe2O3, As2O3, Sb2O3, P2O5, SiO2), Cu2O-FeO-Fe2O3.

Cu2ORnOm ( RnOm SnO2, PbO, Bi2O3, SiO2,
MgO, CaO, Al2O3), Cu2OSnO2PbO.

Cu2O
SiO2.
3)
CuRO ( R Ni, Sn, Zn, Co, Fe, Pb, As, Sb, Bi, Si,
Al, Ca, Mg, S, P), CuPbSnO, CuPbSnZnO, CuFeSiO, CuZnPO, CuPbPO Cu
NiSO.
4)
CuRO ( R Ni,
Sn, Zn, Co, Fe, Pb, Sb, Bi, Si, Al, S, P), CuPbSnO, CuPbSnZnO, CuFeSiO, CuNiSO.

. ,
.
5)
,
. ,
, () ,
, ,

CuAlO (
).

192

4. ,

4.1. ,

, .
,
, , ,
[391].
, ,
,
[392].
( ,
) , ,
, .
, ,
, .
.
, [393],
- ,
.
[394]
, ,
.
.
, ,
.
[395],
( ) ,
, 1500, 1600
1700.
CoC.
[396].

193


, 70- . XX [397].
[180].
,
, , ,
[398]. ,
10 . %
1600.
, 1
.% 3 .%
. ,
CoVO : CoOCoV2O4
V2O3V1+x. [398] 1 .% 3
.% , V2O3,
.
,
, . . . . [94].

15101700,

CoAlO CoSiO. ,
,

( 14931700) ( ) (.
4.1). .. , , CoAlO CoSiO.
, CoAlO,
, (CoO),
, Al2O3.
CoAl2O4. ,
CoSiO, I ,
CoO, II . III
, SiO2.
, [94] CoSiO
. , .. ., [197]. ,
, 16000 1 . %
194

0,0005 . %. (. 4.1)
0,01 . %. , -, .
, , ( )
, . , ,
, .

1600 0,0045
. %. ,
(, , .).

. 4.1. CoAlO CoSiO .. .. [94]


, [94]
CoSiO.
,
CoAlO.
CoAlO
[399]. 14971702

195

, CoO(1+x)Al2O3 ( )
Al2O3.
.
~50 Co , , ~2,5 .
. 1,5 64 .
[399]
:
lg [O]Co, . %= 10 400/T+4,64(0,08).
.
x 0,22 1497 0,28 1702.
, ,
Al2O3, -
.
Co O . .
[197]. ( .. .)
1600 (0,001 %)
0,6 . % .
,
Co O, Co Si O, Co Al O, Co Si O
15001600 , 90 %,

, , . 5 6
1. [90],
, .
4.1.1 CoSiO CoAlO
. 4.2 ()
Co Si O,
. ab ,
. cd
, , . I
, , II
. III ,
.

196

. 4.2.
Co Si O [400]

. 4.3 ()
Co Al O
.

. 4.3.
Co Al O [400]

ab ,
CoO (CoAl2O4). I ,
, II CoAl2O4. cd
,
, III ,
Al2O3.
4.1.2. CoO CoSiO
. 4.4 CoCO.
.
,
0,1 . 1 .
. 4.4. I , ,
197

II (, O2). O2 .
ab , . ,
ab
( ab).
. 4.4.
CoCO [400]:
1
0,0101 M;
2
0,1013 M

.
, ,
.
Co Si C O ,
.
, ,
. . 4.5 1550
1 .

. 4.5.
Co Si C O 1550

0,1013 M [400]

1550 ab ,
, bc
, be CoO, ce ,
, , cf
, , .
198

4.2. ,
, , ,
.
, .
, , , [90, 202].
NiMeCO
(. . [401403]).

NiCO, NiCaO, NiAlO, NiSiO, NiCaCO, NiSiCO NiAlCO
15001800 90%
,
.
, ,
. 7 8 1. [90].
, NiO,
Neumann, Zhong Chang [139].
NiCaO [404].
4.2.1. NiCO, NiCaO, NiAlO, NiCaCO NiAlCO
NiCO [405].

1 . 0,1 .
. 4.6. I , Ni, II
(, O2). 12 ,
. ,
12 .
. 4.7 NiCaO [405],
.
[259],
NiOCaO ( . 4.7).
M. Tikkanen,
[259].
NiO CaO CaO NiO.
.
NiOCaO .
199

. 4.6.
NiCO:

0,1013 M

0,01013
M [405]

12 ,
NiO CaO CaO NiO. 23 ,
CaO NiO .
24 , ,
NiO CaO.

. 4.7.
NiCaO [405]

. 4.8 NiAlO [405].


I ,
. II ,
. III ,
.
12 ,
NiO (NiAl2O4). I ,

200

. II ,
NiAl2O4. 34 ,
, III
, Al2O3.

,
.

. 4.8.
NiAlO [405]

, , ,
, ,

. ,
, ,
NiAlO NiCaO.

,
[406].
. 4.9 NiAlCO 1550
1 .
.
ab , (, O2)
, bc NiAl2O4, be NiO
, cd ,
, , cf , ,
NiAl2O4. .

201

,
, .
, . 4.10 4.11.

. 4.9. NiAlCO
0,1013 M = 1550 [406]

. 4.10. NiAlCO
0,1013 M = 1650 [406]

202

NiAlCO 1650
1 . , , ,
, be cf
.
. 4.11 1550,
, 0,1 .
,
abcd .

. 4.11. NiAlCO
0,01013 M = 1550 [406]
. 4.12 NiaCO 1550
1
.
I
CaO NiO.
, II,
NiO CaO. ,
( III)
.
, NiaCO
,

203

, . 4.13 4.14. (,
. 4.13) NiCaO , 1720
NiaCO
.

. 4.12. NiCaCO
0,1013 M = 1550 [406]

. 4.13. NiCaCO
0,1013 M = 1650 [406]

204

. 4.14. NiCaCO
0,01013 M = 1550 [406]

,
.
4.2.2. NiSiO NiSiCO
NiSiO NiSiO
, .
, , , ,
,
, ,
.

NiSiO NiSiO. , ,
. 1. ,
(
Ni2SiO4, )

.

205

NiOSiO2
.
,
[259], A. Muan F. Osborn,
[407]. [408]
. 4.15.

. 4.15.

NiOSiO2 [408]

. 4.16 NiSiO [408],


. I
, . II ,
. III ,
(). IV V
, : IV ,
(,
1 NiO
SiO2), V , ( 2
. 4.15).
. 4.17 NiSiO,
.
, ,

.
NiSiO .
206

. 4.16. NiSiO [408]

. 4.17.


NiSiO

[408]


, , . . 4.18
1460 1 .
.
I
NiO. ,
II, .

( III). , ,
( IV)
.
207


: . ,
, .
4.19 1600 .
,
, . 4.20.
, 0,1 ., 1600 .
4.19 4.20 ,
, , ,
,
.
,
, ,
NiOSiO2.
1649 ,
(. 4.21), (
1684 )
NiOSiO2 (. 4.22). ,
, 1720
(. 4.23).

. 4.18. NiSiCO
0,1013 M = 1460 [408]

208

. 4.19. NiSiCO
0,1013 M = 1600 [408]

. 4.20. NiSiCO
0,01013 M = 1600 [408]

. 4.21. NiSiCO
0,1013 M = 1670 [408]
209

. 4.22. NiSiCO
0,1013 M = 1700 [408]

. 4.23. NiSiCO
0,1013 M = 1750 [408]

, ,
.

210

4.2.3. NiRO
,
,
,
, .
,
, ,
, , ,

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

.

, NiRO ( R Cr, Fe, Mn, Nb,
Pb, Bi, S, Sb, Sn, Ti, W) [409].

,
, ,
.
10 , 1 5 . %
( ),
(D=8 ) (
). 15001530 0,
NiO (0,4 ).
. NiO
.

,

211

NiO (. 4.24),
, .

. 4.24. NiO
,

, .

JEOL

JSM-6460LV

, .

NiAlRO,
,
() ,
.
( - MgO) ,
.
,

.
1 . %
.
,
, . ,
.
, , , () .
, - ,
, , SO2,
.

212

, ,
( Cr, Fe, Mn, Nb, Ti, W).
NiPbO ~ 1
. % (. 4.25).
NiO , (~ 40
80 . %), .
, . ,
(Ni+PbOx NiO+Pb), ,
, .
c
, , ,
NiBi, NiBi
( ~ 50 55 . %) [410]. ,
, NiO.
(. 4.26),
, , .

, .

. 4.25. NiPbO.

. 4.26.

NiBi(1 . %),

NiO,

(~ 40 80 . %)

NiBi, NiO

NiSbO NiSnO.
, NiSbO, NiO, ,
, ( 15 . %) ,

213

, ,
(. 4.27).

. 4.27. NiSbO. NiO .



, NiSnO, Ni3Sn,
( 10 . %) ,
, ,
(. 4.28). 0,5 . %.

. 4.28. NiSnO.
. Ni3Sn
,
.
, NiSO,
: NiO
,
NiNi3S2 ([S] = 33 . %). , ,
214

( , , . 4.29),
.
, .

. 4.29. NiSO.
(,
NiO)

, , .
NiNbO
(. 4.30),
. , , NiO,
, ( ),
: 4666 . % O, 2229 . % Nb, 532 .
% Ni. ~ 1 %,
( 61 . % O, 34 . % Nb, 5 . % Ni).
NiFeO
(~ 4 %), (. 4.31) : 4753 . % O, 34
40 . % Fe, 413 . % Ni.

. 4.30. NiNbO.

. 4.31. NiFeO.

215

, NiMnO
2 4 . % ,
(. 4.32), MnO.
NirO, 15 17 . %
, (.4.33),
, , Cr2O3.

. 4.32. NiMnO.

. 4.33. NiCrO.

MnO

Cr2O3

, 1,5 2,7 . %
, WO3 (. 4.34).
.
,
Al2O3, Ni
TiO NiTiAlNO.

~ 12 . % .
(. 4.35).
, .
, Al2O3.
+3 +4, ,
,
.

216

. 4.35. NiTiAlNO.

. 4.34. NiWO.

WO3

4.2.4. NiRBi

(Pr, Er, Dy, Nd).
, ,
[411].
NiPrBi, NiNdBi,
NiDyBi NiErBi, -60-2
, .
-0, 00,
(, , ).
35 ; (, ,
) . 10
0,1 ,
. .
.
, .

, .

217


JEOL JSM-6460LV
500..10000 .
. 4.36.
,
, ,
. PrBi,
Pr5Bi3, Pr4Bi3.
1225..1800C [139].
. 4.36.


)

) ; ) ;

) ;

. 4.37
.

.4.37.

NiBiPr

.
, ,
.

, . 4.38 4.39.
,
,
.

218

. 4.38.

. 4.39.

, 10000

, 4000

,
. 4.40, PrBi, Pr4Bi3 Pr5Bi3.

. 4.40.
,

NiBiPr

,
( ,
. 4.41, ).
, .
, ,
,
, Bi Nd (
NiBi).

. 4.41 4.42 .

219

. 4.41.

. 4.42.

, 5000

,
, . 4.43. ,
NdBi NdBi2.

. 4.43.
,
NiBiNd

, , ,
[139], , , NdBi,
NdBi2.
:

. , .
, .
,
, . 4.44.
4.45.

220

. 4.44.

. 4.45.
, 5000


. 4.46.

. 4.46.
,
NiBiDy

DyBi, Dy5Bi3,
Dy2Ni12. ,
1321 [139], ,
, DyBi Dy5Bi3.
,
. . 4.47.
, .

,
.
NiBi.
.
. 4.48.
221

. 4.47.
.

( )

. 4.48.
, 6000

4.2.5.

, . 4.2.24.2.4,
,
,
[412417], .. ,
( , , . [418
422]),
,
3.

.
,
[423, 424].
,
, , ,
, . ,
, :
1. , 78 75
:

..
222

, ,
[425].
2. ,
,
.
, ,
.
, .
,
. [425, 426]. ,
75 ,
[427].
3.

[424],
,

.
78 75
.
4. , 2080
40% 40
( , -

2,7 ).
5. , 2080
, 100
, 0,10 0,03%.

,
[428430].
6. ,

NiMoNb . (
, 5:2:1)
223


[431].
,

.
,
2080, .
3 ,
1,8 . 2 ,
2,5 [428].
NiMoNb
.
, NiMoNb
602
[431, 432].
.
, .%: 25-35, 2-10, .

[433].


4,
( , , , )
[434].
4.3.
1) ,


.

, .
,
,
4

..
.. .
224

. ,
,
.
2)

CoOSiO2,
NiOCaO NiOSiO2.
NiOCaO NiOSiO2.
3) , CoO, CoSi
O, CoAlO, CoSiO, 15001600 , ,
NiO, NiCaO, NiSiO, NiAlO, NiAlO, NiCaO
NiSiCO, 15001800 .
,
.
4)
NiRO ( R Cr, Fe, Mn, Nb, Pb, Bi, S, Sb, Sn, Ti, W)
. , ,
.
5)
NiRBi ( R Pr, Er, Dy, Nd).
,
.
6)
, ,

225

5. ,

,

[181].

,
,
, .

2- .

.
,
,
, .
, , [91, 92, 186].
, ,
, .. ,
, 1 , .

,
(Fe, Si, Cu, Mn .), .
,
, ..
, .
,

( , ,
, , [435438]).

,

226


, , .
,
, , ,
.

,
1000C [120]. ,
.
, ,
( ),
.
.

.
.
,

,
( 1040 ). .


(,

Al2O

AlF3),

.
, ,

. , AlMg , ,
, . AlNa
AlK .
, AlMg,
, ,
, AlMg
.

(
227

, . 9 10 1).
[187],
[181],
[180] .
5.1.
AlO AlMg (
AlMgO)
. ,
.

. [184] :
[184, . 114]. [186]
. 1976
. :
50 . 1 . . ,
, 1 . . [186, c. 121].
, AlO
( Wriedt H.A. [139] 2046
0,3 . %). 700900
, .
,
,
Al2O3.
Al2O Al2O2.
. Al2O .
1000
Al2O3 Al. ,
,
.
AlO ,

(, Al8O9 [186]), , , -,

Al2O3.
228


.
.
.. [180] :
2 Al + 3/2 {O2} = /Al2O3/
:
G = 403260 + 78,11 T ().
.. [90] .. . :
G = 403150 + 77,66 T ().
E. . [99] , O. Kubaschewski .,
:
G = 403692 + 78,902 T ().
(. 9 1)
.
AlMg .
... , [439]
10 77 . % 680850

W, Mg()|(LiCl+KCl) + MgCl2|AlMg(), W
...,
Mg Al. ,
.
[440] . . .

() Mg()|(KCl+NaCl) + MgCl2| AlMg() (+)
700830.
0,3 90 . % . 10 . %
, .

[441]

770800

MgCl2 MgCl2+CaCl2.
800:
lgMg= 0,68 (1xMg)3;
lgAl= 1,02 (1xAl)2+0,68 (1xAl)3;

MgCl2 :
229

G0= 144600 (2000)+29,98 (1,85) T ().


, AlMg
. , , [442].
687807
. Mg Al ( 7
89 . %). , MgAl
,
, Al3Mg4.
[443]
627972 594 . % .
. ,
AlMg .
[444]
AlMg ( AlCuMg) 719865 .
,
.
AlMg

, [445] -

MgAl- 49,2 . % Mg.


.
[446] AlMg
. :
Al-10% Mg lgp=9,12786894,6/T;
Al-35% Mg lgp=10,25077650,8/T;
Al-50% Mg lgp=9,81696802,6/T; p (); T ().
,
, [181].
, . . . .
[447] AlMg
4 :
1
637797 0,10,7 654 0,02160,1430;
2 ...
CaF2 648820 0,050,9;
230

3 649915
0,04240,8885;
4 750 ,
0,0660,499
0,5220,906.

AlMg, .. . [181].
, ,
( ) [448, 449].
AlNa AlK
.

XX
( AlNa .H. Mathewson 1905/6 . AlK
D.P. Smith 1907/8 .). M.
Ono (1944 .).
,
,
, .
.

. , Ransley C.E. Neufeld H.
700 0,178 . %, 800 0,274 . % [450].
(Fink W.L. . [451]) ,
660800
, ,
. , .. ,
[186] Ransley C.E. Neufeld H.

...
Sun M. Yang S. [452] (
, , ).
Na-Al2O3 .
.

231


.
(.
10 1) , Ransley C.E.
Neufeld H. [186].
,
[442],
,
.

. AlCl AlF
, ,
( )
[186]. ,
,
, AlCl3, Al2Cl6, AlCl, AlF3 AlF.
,
.. [180].
5.2. c

,
.
,
.
.
.

, , [453459]. AlMg.
5.2.1. AlMgO

MgOAl2O3, [259]
[460], [461, 462] (. 5.1).

232

AlMgO . 5.2.
. 9 10
1. , AlMgO,
:
|Al2O3| = 2Al+1,5{O2},
{Al2O} = 2Al+0,5{O2},
{Al2O2} = 2Al+{O2},
|MgO| = [Mg]+0,5{O2},
|MgAl2O4| = [Mg]+2Al+2{O2},
Al = {Al},
[Mg] = {Mg},
{O2} = 2{O}.

. 5.1.
MgOAl2O3
[460]

, . 5.2, ,

. .
I
(Al2O3), II (MgAl2O4),
III (MgO).
.

, Al2O, Al2O2, .
. 5.1.

233

[442]. AlMgO ,
.

. 5.2. AlMgO
[463]

5.1.
( AlMgO)

I II

II III

lg pAl2O

14,20

14,86

[Mg], . %
5
30
15,57
15,95

lg pAl2O2

26,98

28,31

29,72

30,49

lg pMg

6,88

5,05

4,34

3,95

lg pAl2O

12,54

13,14

13,66

14,17

lg pAl2O2

24,21

25,42

26,46

27,47

lg pMg

6,17

4,35

3,83

3,33

lg pAl2O

11,11

11,68

12,03

12,64

lg pAl2O2

21,83

22,96

23,67

24,88

lg pMg

5,56

3,76

3,40

2,80

T, C / ,
680 C
lg pAl = 20,28
760 C
lg pAl = 18,99
840 C
lg pAl = 17,88

, [464]
19 . % 725.
, MgO,
. ,
, ,
,

, ,
[458], . I
II, , 0,0050,02 %,
. ,
.
234

,
, . ,
.
, ,
[458].
[465467].
, ,
, II/III . 5.2
.
. 5.3
5.6 , ,
-
.

. 5.3. ,
MgO ,
6,0 . % [468]

. 5.4. ,
MgO ,
1,5 . % [468]

. 5.5. MgAl2O4,
,
0,25 . % [468]

. 5.6. Al2O3,
,

[468]

235

5.2.1. AlMgNaO
, Al2O3Na2O Al2O3K2O
[469, 470],
, ,
, ,
680840 , . , ,
,
,

( , , [471]).
AlMgNaO . 5.7.

.
.
. I
,
II , III .

( ). ,
, ,
.

. 5.7.

AlMgNaO
[463]

5.2.1. AlMgNaKO

.
236


, :
K
ln aNa ln xNa Na
Na xNa Na xK ,

K
ln aK ln xK K
xK KNa xNa ,

, x ,
.
, ,
. 10 1 ( , KN a KN a ),

,
.
680 840 , ,
. 5.8.

. 5.8.

[463]

,
- , .
,

AlMgNaKO

. . 5.9 ( = 840 )
0,1, 0,01, 0,001 . %.
,
.
,
,

237

, . ,
, ,
, , ,
.

. 5.9.

Al Mg Na K O
= 840 C

[463]

5.3.
, , ,
,
.
,
,
.
, ,
[472, 473].

NaClKClMgCl2AlCl3.
6000

238

. .
, AlCl3 ( 5 15%)
2730%. 500 635
.
[473] . KCl,
NaCl AlCl3 Al-.

(Al+4,7% Mg) (Al+6,4% Zn)
(KCl+NaCl) (KCl+NaCl+AlCl3)
.
,
. 760
. [473]
,
,
.

[474, 475] .
, ,
, , ,
. ,
, , ,
.
,
, [475479].
L.G. Boxall c NaClAlCl3,
5070 . % AlCl3, 175355. ,
, :
2 AlCl3() = Al2Cl6() ,
AlCl4 + AlCl3 = Al2Cl7 ,
2 AlCl4 = Al2Cl7 + Cl .
...
Al|AlCl3 (C), NaCl| |AlCl3, NaCl|Al
Al2Cl6, NaAlCl4
NaAl2Cl7. 175
239

2,86107; 2,4104 1,06107 ( ).


, AlCl3 50 . %
AlCl4.
.
NaClAlCl3 W. Fisher, A.-L. Simon
. . [480]. [477] (Sato Y., Ejima T.)
LiClAlCl3 NaClAlCl3
, . ~50 . % AlCl3
LiAlCl4 NaAlCl4 143 154
. NaClAlCl3 >79 . % AlCl3
. AlCl3 < 50 .%
0 40
. %, ~50 .%
AlCl3. LiClLiAlCl4 NaClNaAlCl4
050 . % AlCl3 .
Sato Y. Ejima T.
.

NaClLiClAlCl3 [478].

. , ,

Sorrel

C.A.

[479].


[481].

. ,
, -, :
AlCl4, Al2Cl7 Al3Cl10.
AlCl3NaCl, AlCl3KCl AlCl3MgCl2 . 5.10.
5.3.1. AlNaCl
AlNaCl 680
840 :
(AlCl3) = Al+1,5{Cl2},
(Al2Cl6) = 2Al+3{Cl2},
240

{AlCl3} = Al+1,5{Cl2},
{AlCl} = Al+0,5{Cl2},
|NaCl| = [Na] +0,5{Cl2},
(NaCl) = [Na] +0,5{Cl2},
(NaAlCl4) = [Na] +Al+2{Cl2},
(NaAl2Cl7) = [Na] +2Al+3,5{Cl2},
(NaAl3Cl10) = [Na] +3Al+5{Cl2},
(NaAlCl4) = [Na] +Al+2{Cl2},
Al = {Al},
[Na] = {Na}.

. 5.10.


AlCl3 NaCl, AlCl3 KCl AlCl3 MgCl2
( )

. 5.11 AlNaCl [482, 483]. I


,
, , , AlCl3, NaAlCl4 AlCl,
II , III
NaCl.
.
,
.
,
, , .
I II
. . 5.11 ,
0,101 ( ) 0,304 (
). , I II,
: . ,
241

I II (
0,101 ), ,
, . 5.2. ,
II III, .
. 5.3.
,
AlCl3NaCl ( AlCl3 ).
.

,
AlCl3NaCl.

. 5.11.
AlNaCl [482, 483]

[481] ,
( )
, , ,
. [481]
. (
) . 5.12 ,
AlCl3NaCl .
.

, ,
.
,

.
242

243

680
700
720
740
760
780
790
800

680
700
720
740
760
780
800
820
840

0,097
0,095
0,092
0,090
0,086
0,083
0,079
0,074
0,070

0,003
0,005
0,007
0,010
0,013
0,016
0,020
0,024
0,028

0,0003
0,0004
0,0005
0,0007
0,0009
0,0012
0,0015
0,0019
0,0024

0,006
0,011
0,017
0,026
0,038
0,055
0,077
0,106
0,144

0,037
0,031
0,027
0,023
0,020
0,017
0,014
0,012
0,010

0,337
0,202
0,123
0,075
0,046
0,028
0,017
0,011
0,007

0,578
0,713
0,794
0,841
0,866
0,875
0,870
0,854
0,825

0,039
0,040
0,038
0,033
0,029
0,025
0,020
0,017
0,014

10

0,0026
0,0023
0,0018
0,0013
0,0010
0,0007
0,0005
0,0003
0,0002

5.3.
, II III ( AlNaCl)
AlCl3



AlCl3
x
AlCl3NaCl [484]
x (Al2Cl6)
x (NaAl2Cl7) x (NaAl3Cl10)
(AlCl
x (NaCl)
x (NaAlCl4)
3)
6

106
1010
10
104
0,37
0,378
0,394
5,76
82,6
0,605
634
6651
0,33
0,348
0,467
5,33
58,2
0,532
507
4837
0,29
0,310
0,551
4,72
38,0
0,449
373
3104
0,24
0,263
0,644
3,91
21,9
0,355
241
1638
0,17
0,200
0,750
2,88
10,0
0,250
123
608
0,09
0,117
0,867
1,60
2,61
0,133
35,8
96,7
0,03
0,065
0,930
0,85
0,69
0,069
9,93
14,2
<0,01
0,006
0,995
0,07
0,004
0,006
0,06
0,008

0,687
0,617
0,574
0,546
0,526
0,511
0,498
0,485
0,471

5.2.
, I II AlNaCl,
0,101



, AlCl3 ,

pAlCl
pNaAlCl4
pAlCl
x AlCl
x Al Cl
x NaAl Cl
x NaAl Cl
x NaCl
x NaAlCl

. 5.12.
NaClAlCl3

( xAlCl3 ):
1, 2 827 ,

[481];
3, 4, 5 775 ,

[481];
6
840 ;
7
780
AlNaCl, . 5.11,
.
, ,
. ,
.


. 660760
0,010,001 . % ( ) ,
.

. NaCl
- ,
, ,
.
800 ,
, .
,
( II)
I II.
(, , [485, 486])
( Al2O3
,

NaCl)

.
244

( [202],
2-3104 %)
I II AlNaCl, ,
. , ,
,
( AlCl3).
5.3.2. AlKCl AlMgCl
AlKCl AlMgCl . 5.13 5.14 [482, 483].
AlNaCl, :
(KCl MgCl2 ),
,
.

. AlNaCl,
I II , 0,101 0,304 .

. 5.13.
AlKCl
[482, 483]

AlMgCl
.
30 . %.
Mg
Mg
.
245

AlNaCl,

, 1,
, ,
.

. 5.14.
AlMgCl
[482, 483]

,
AlNaCl, , AlKCl (0,52104
AlCl3 0,05 0,45 [481])
(, , KCl MgCl2),
[485, 486],
.
AlCl
AlMgNaCl [472]
AlCl AlMgNaKCl.
NaClKClMgCl2AlCl3,
650 , [472], ~ 1020 .
680
.
5.4.


,
.
- [487493].
246

,
, , Dewing van der Kouwe [494].
1200 .
Mg Na Al NaFMgF2AlF3 .
NaF/AlF3 2,5 4,0. MgF2
0,13. , 970,
Mg, .
, CaF2 Al2O3, ,
MgF2 AlF3.

. NaF , AlF3 MgF2
. MgF2
, Na2MgF4 Na2MgF6.
MgF2 NaF , AlF3 .
MgF2 .
[495] Na Mg ,
.
MgF2 Mg/Na
, MgF2 < 4 %,
, MgF2 > 4 %.
, [496]
... Al2O3,
, NaFAlF3.
NaF AlF3 NaFAlF3
.
NaF , AlF3 .
P. Fellner I. Kotensk ,

NaFAlF3LiF

NaFAlF3MgF2

[497],

AlNaFLiF AlNaFMgF2.
:
Al + 4 Na+F = 3 Na + Na+AlF4
2 Al + 3 Na+MgF3 = Mg + 2 Na+AlF4 + Na+F
2 Al + 3 (2 Na+MgF42 ) = 3 Mg + 2 Na+AlF4 + 4 Na+F

. ,
247

, , ,
, . ,
,
.
5.4.1. AlNaF AlMgF
AlF3 NaF (. 5.15).
, , , , [480].
. 5.15.
AlF3
NaF:
1 . .,

[480];
2 ..
..,
[480];
3 .,

[480];
4 ..
..,

[259];
5

. ,
, , ,
, .
248

, , , 680840
(AlF3, Na5Al3F14, Na3AlF6 NaF),
[498].
, Al Na F,
. 5.16. I ,
AlF3, II , ,
III (Na5Al3F14), IV
, .
(Na3AlF6).
AlF3MgF3 ,
. . . , [480],
. 1000 ,
42,5 . %. , . 5.17,
: I,
, , II, ,
( ) ,
. ,
.

. 5.16. Al Na F

. 5.17. Al Mg F

5.4.2. AlNaMgF
,
,
(Na3AlF6).
. Al Mg Na F.
, 680 , . 5.18.
249

I
.
. II
MgF2, III . IV
, , V
(Na2MgAlF7). , ,
, .
AlF3MgF2NaF, [499],
NaMgF3. ,

, ,
,
. ,
.

Al Mg Na F .
.
= 725 ( Na5Al3F14) .
= 750 C (. 5.18 ) I
, ; II
; IV (Na3AlF6); V ; VI
, .
, [500] NaFMgF2
AlF3

NaMgAlF6.

, ,
. I, II, V VI,
. 5.18 .
NaMgAlF6,
,
, , .

.
. ,
840 C, [499], Na2MgAlF7.
. 5.18 Al Mg Na F 850 .
250

(750 ), : IV (
) V ( 840 ), VI.
, , ,
,
( ) (III) ,
.

. 5.18. Al Mg Na F:
) = 680 ; ) = 750 ; ) = 850

251

,
( 950 ),
, , ,
[501].
5.5.
1)
.
2) ,

,
, .
,
( ),
(
) .
3)
AlCl3NaCl, AlCl3KCl, AlCl3MgCl2,
AlF3NaF.
4)
, AlMgO, AlMgNaO,
AlMgNaKO, AlMeCl ( Me Na, Mg, K), AlNaF, AlMgF, AlMgNaF.
5) ,

.
AlMgO. , ,
.
, .
6)
,
.

252

6. ,

6.1. ,
,
.
[502].
, ,
,
, .
6.1.1. PbAgZn PbAuZn

, .
,
, ,
.

Pb Ag Zn

(,
, [80]).
( 1 ) ,
Pb Ag Zn [503].
Pb Ag Zn [80].
,
- AgZn.
.
. 6.1 Ag Zn.
, ,
, () ()
(, ).
, [80],
.
Pb Zn,
Ag . , ,
- [80].
253

. 6.1.
Ag Zn [80]

[80] -
,
PbAgZn (. 6.2).
,
,
AgZn.

. 6.2.
Pb Ag Zn [80]

, . 6.2,
, [80], 315 .
PbAg PbZn. (.

254

. 6.2)
N, .
, [80], ,
, NZ.
-, ( )
, .
.
- ( N) -
( PbZn).
N,

( 5 / Ag) [80]. ,
PbZn.

-.
,

.
[80] ,
- AgZn.
, AgZn3 [504].
PbAgZn
[80, 504]. ,
[503] (. . 6.3). [80]
.
:
[Ag] + [Zn] = AgZnm,
[Ag] [Zn] ; AgZnm -
( [80], AgZn3).
,
, ..
.
,
[80]:

255

,
.
, ,
, ( PbZn
0,55 . % ), ,
.
[80] :
Q = 0,55 + Ag/r,
Q, Ag , . % ; r
Ag/Zn .
,
,
, r,
Ag/Zn .
,
( ) - -
PbAgZn, . 6.3 [503]. [80]
.
AgZnm ( -).
. ,
, , N
N PbZn.
(. 6.3), [80]
.
Pb Ag Zn, Pehlke
R. D. Okajima K. [505]. ... Zn
: ZnPb (450800, 0,05 . Zn), PbAgZn [550670. 0,015; 0,022; 0,030
0,037 . Zn 0,01; 0,02 0,03 (0,033) . Ag], PbAuZn (680800, 0,012;
0,016; 0,020 0,024 . Zn 0,012; 0,024 0,036 . Au) ZnPb
Zn, PbAuZn.
ZnPb 0,0375 . Zn
.
lg =1215/T0,418.
:
AgZn= 4610/+3,74
256

AuZn= 27100/+21,6.
...
.

. 6.3.

[80]:
1 ,
2

ZnPb Z. Moser
[506]. ... ( 1, 3, 5 7 . %
Zn) ZnZn 441604
4,87 2,68.

PbAg ( PbAu PbPt) Jena A. K. Bever M. B. [507].
350 .
0,51 621 Pb.
Ag, Au Pt 22,88,
3,73 37,12 /.
Sugimoto E. [508]
PbAg 400800 .
:
Pb, PbO/ZrO2+Y2O3/PbAg, PbO
H, S, G, T
PbAg.
. ,
257

PbAg 540 740


.
PbAg [139] eAgAg,
. 12 1.
,
. 6.1, Pb Ag Zn 325
419 . 6.4 [509]. I ( )
(). II
, ,
- (AgZn ). III
-. IV
(Ag2Zn3 ).
(V),

-. , VI - -.
VII - (AgZn2,57). VIII
- .
IX .

. 6.4.

Pb Ag Zn T < 419 C
[509]

, ,
.
,
, . 11
12 1.

258

, . ,
[503].
Pb Ag Zn [510]
. 6.5.
,
.

. 6.5.
PbAgZn [510].

[503]:
1 330 C; 2 350 C;
3 375 C; 4 400 C;
5 425 C

I ,
, II AgZn . III
, Ag2Zn3.
IV , -
(AgZn2,57).
, IV .

1 . % , .

. , V ,
.

,
(
3).

259

, . 6.6 6.7.

1
(AgZn)
. %

. %

[Pb]

10,57 0,50

4,72

[Zn]

33,17 0,63

47,15

[Ag]

56,26 0,86

48,13

2
. %

. %

[Zn]

0,15 0,29

0,48

[Ag]

0,17 0,44

0,32

[Pb]

99,68 1,03

99,20

. 6.6.
Pb Ag Zn

260

1
(Ag2Zn3)
. %

. %

[Pb]

0,90 0,48

0,36

[Ag]

53,17 0,64

40,91

[Zn]

45,93 0,63

58,73

2
. %

. %

[Ag]

0,120,24

0,23

[Zn]

0,710,28

2,22

[Pb]

99,170,73

97,55

. 6.7.
Pb Ag Zn
, ,

AgZn3,

, , ,
- AgZn5 (. . 11 1).
261


.
PbAuZn
325 525 , . 6.8.
I ,
II Au2Pb, IIIVIII c
Au3Zn, AuZn, AuZn2, AuZn3, AuZn4 AuZn7
. , (IX) ,
.

. 6.8. PbAuZn
6.1.2. PbCuS
( PbS, CuS,
PbSCu2S) .

262

PbS XX .
, ,
1923 . (W. Guertler H. Schack) [511]. H. Nishimura
(1928) [512], .. .. (1951) [352], Miller E. Komarek K.L. (1966) [513],
Kullerud G. (1969) [514], .. . ([515], 1983),
, Lin J.C., Sharma R.C., Chang Y.A. [516].
[517].
PbS
Rytknen T., Pelto M., Taskinen A. [518].
...
. .
[518] 3,82 14,22 . %
:
lnSo= 2,71+9,16 102/.
. . . [519] (..., ,
-) Pb, S PbS
500 1100.
pT- PbS.

.
PbS [520
523].
CuS ( 3),
PbSCu2S , , [524526].
, PbCuS
, .
,
. , ,
1200 [527530]. ,
, (
) ,
.
,
. , ,
, , (
263

) ,
Cu2S.

Grant R. M. Russel B. [531].
60900.
, ,
:
0

lg S = 0, 1228

2371

[531]
:
Cu

eS

79790

63, 25.

F. Belis [532]
. , 360
Cu1,7S Cu1,4S. ,
, .
Cu1,9S , Cu1,8S
, . [532],

, CuS. ,
,
Cu2-xS , , .
, .
As, Sb, Te, Sn Ag.


( 1105 . %) [533] ( .., ..
..). ,
Cu2SPbS
,
.
, ( . %): Ag 0,14
0,2, As 0,10,5, Sb 0,30,8, Bi 0,20,3, Sn 0,010,005.
, ,
264

PbSCu2S.
.

PbSCu2S,

. , , Davey (
[80]) (. 6.9)
( ) PbCuS
.
, PbS Cu2S. [80, . 236]
, Cu2S
0,02 . %.
,
( 0,04 . %).
. 6.9.
()
PbCuS,
Davey T.R.A.,
[80]. l
(
).


PbCuS Davey
,
(. 11 12 1).
PbCu PbS [139],
,
[180].
PbCuS [534] . 6.10.

.
(. %)
.
,
265

. I ( )
, , , II
(Cu2S), III c (PbS).

. 6.10.
PbCuS [534]


[8, 209],
[80, 98, 535].
, [534],
, . 6.116.13.
, ,
.
2013 . [536]
PbCuS 763 1573 K,
.
, , 763788 K
Cu16Pb2S10.

, ,
,
.
6.1.3. PbZnO PbSbO

.

266

1
. %

. %

[Pb]

10,66 0,45

3,53

[Cu]

89,34 0,43

96,47

[S]

. %

. %

[Pb]

99,46 0,23

98,25

[Cu]

0,54 0,42

1,75

[S]

. 6.11.
Pb Cu S

267

1 Cu2S
. %

. %

[Pb]

10,82 0,82

2,92

[Cu]

67,76 0,43

59,66

[S]

21,42 0,74

37,42

2
. %

. %

[Pb]

99,57 0,43

98,62

[Cu]

0,43 0,32

1,38

[S]

. 6.12.
Pb Cu S Cu2S

268

1 PbS
. %

. %

[Pb]

91,42 0,63

62,26

[Cu]

[S]

8,58 0,71

37,74

2
. %

. %

[Pb]

99,71 0,39

99,06

[Cu]

0,29 0,34

0,94

[S]

. 6.13.
Pb Cu S PbS
269

, [537
539]. , ,
Pb2+. , ,
, -
. ,

.

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

- .
PbO . ,
.
PbO 1972 . (Szwarc R. . [540]).

[541543].
[544],
450610 ...
.
:
O2 = 2 [O]
(/)
G0 = 121386 43,76 .
A. Taskinen [545]

G= 166717,3+50,989 T, /.
OO
OO = 52,070900/T.
270


Paulin A. [546, 547].
,
,
,
. Paulin
,
, , ,
. ,
, .
( PbO, Paulin)
.
PbRO
.

. , PbZnO
.
PbSbO
, ,
, , .
,
, . ,

[548],

.
A. Paulin [546, 547] Pb
SbO ( PbSnO PbAsO) , PbO

, .

.
Taskinen A. [545, 549], ...
ZrO2,
7 . % CaO, ,
(Ag, Au, Bi, Cu, In, Ni, Sn Te)
762 1000.
271

,
,
:
SbO= 15,322160/T
Taskinen
RO, .
, McLellan PbRO.
(Jacob Alcock)
.
Otsuka S. [550]
[545, 549].
,
OO,

(. 11 1) PbO [549].

.
Taskinen.
PbZnO PbSbO
. 6.14 6.15 .
I,
(PbO), II ,
III c , IV .
PbSbO .
(. 6.15) :
I , ;
I, III IV ,
5PbOSb2O3, 3PbOSb2O3 PbOSb2O3 ;
V ,
(Sb2O3);
VI .
PbZnO
PbSbO . 6.16 6.17.
, ,
. 6.1 6.2.

272

. 6.14. PbZnO

. 6.15. PbSbO
273

6.1.
PbZnO (. 6.16)
a) Zn
) ZnO
) PbO
[Pb], . %
0,53
2,48
48,84
[Zn], . %
99,47
61,01
0,50
[O], . %
0
36,51
50,66
6.2.
PbSbO (. 6.17)
a) PbO
) PbOSb2O3
) 3PbOSb2O3
) Sb
[Pb], . %
42,65
12,68
21,93
12,70
[Sb], . %
2,32
20,17
15,80
87,30
[O], . %
55,03
67,15
62,27
0
,
,
.

. 6.16. ,

PbZnO.
, ZnO, PbO

274

. 6.17. ,
PbSbO. PbO, PbOSb2O3, 3 PbOSb2O3, Sb
6.2. ,
6.2.1. BiAgZn

,
. ,
, ,
.

,
, ,

275

.
()
, .

, ,


.

, BiAgZn [551].

,
, ,
.
(~ 10 %) (~
23 %) .
() ( 6-09-3616-82) = 500 .
ZnCl2. ,
, ( 999) .
,
9 . , ,
.

.
3-5 .
3, 6 9 .

: ,
, .
1 ,
. .

, .

, ,
276

350 0 .

.
.
, .
JEOL JSM-6460LV

, .
-
.
,
,
BiAgZn , ,
AgZn.

.
.
, AgZn,
, , . 6.18.

. 6.18. , ,
AgZn,
,
, (. 6.19).
277

. 6.19.
AgZn
AgZn,
[139] K.W. Andrews, H.E. Davies, W. Hume-Rothery, C.R. Oswin
(1940-1941 ).

.
, , ,
, . 6.19
.
278

. , , ,
AgZn .
, ,
1927 1941 ( ..
Owen I.G. Edmunds, .. ).

. . 6.20
.
)

. 6.20. .
,
: , ,
; ,
: (Bi), Ag0,45Zn0,55 (-) Ag0,34Zn0,66 (-)

279


.
.
.
BiAgZn .
6.21.

. 6.21.

BiAgZn


,
.
I ,
, II , AgZn
. III ,
Ag2Zn3. IV
, -
(AgZn2,57). , IV .

,
.
. , V ,
.

280

6.2.2. BiPbO BiSnO





, ,
.
, [552].
,
Bi O PbO Bi O SnO2,
2


[553].

,
,
, (
JEOL JSM-6460LV).
, BiPbO,

500 0,
0,5 Bi2O3,
,

350

, ).
20 ,
. , .

JEOL

JSM-6460LV

, .
2,5; 5;
7,5; 10; 15; 20; 25 30 . %.
BiSnO.
10 . %. ,
.
-
, .

281

BiPbO,

. 6.3,
, . 6.22 6.29

. 6.22.
BiPbO.
[Pb] = 2,5 . %

. 6.23.
BiPbO.
[Pb] = 5 . %

. 6.24.
BiPbO.
[Pb] = 7,5 . %

. 6.25.
BiPbO.
[Pb] = 10 . %

. 6.26.
BiPbO.
[Pb] = 15 . %

. 6.27.
BiPbO.
[Pb] = 20 . %

[552]
Bi2O3PbO, ,
PbBi12O19 Pb5Bi8O17, : Pb3Bi2O6, Pb2Bi6O11,
Pb7Bi6O16, PbBi8O13 Pb2Bi2O5.
.
Bi2O3 PbO,
PbBi12O19 Pb3Bi2O6.

282

6.3.
BiPbO
[Pb], . %
[O], . %
(

)
2,5 . %
59,15
(. 6.22)
56,76
56,42
57,37
5,0 . %
55,33
(. 6.23)
54,83
51,66
55,75
55,44
49,97
56,67
7,5 . %
47,70
(. 6.24)
43,03
10,0 . %
55,95
(. 6.25)
54,60
54,41
53,24
53,07
15,0 . %
50,79
(. 6.26)
50,93
51,75
49,82
48,66
50,67
53,08
52,08
49,26
50,09
20,0 . %
51,09
(. 6.27)
50,24
49,17
43,77
33,38
25,0 . %
51,57
(. 6.28)
51,64
18,33
36,56
46,62
30,0 . %
49,06
(. 6.29)
44,61

[Pb], . %

1,88
1,50
1,59
1,58
0
0
0
0
0
3,86
2,70
32,31
37,14
27,47
26,56
26,49
27,23
26,69
49,21
49,07
48,25
50,18
51,34
44,36
46,92
47,92
50,74
45,33
48,91
49,76
50,83
33,49
46,31
48,43
48,36
55,77
43,41
30,45
50,94
50,64

[Bi], . %

38,97
41,73
41,99
41,05
44,67
45,17
48,34
44,25
44,56
46,17
40,63
19,99
19,82
16,58
18,83
19,10
19,53
20,24
0
0
0
0
0
4,97
0
0
0
4,58
0
0
0
22,74
20,31
0
0
25,90
20,03
22,93
0
4,76

283

,

Bi2O3PbBi12O19
Bi2O3PbBi12O19
Bi2O3PbBi12O19
Bi2O3PbBi12O19
Bi2O3
Bi2O3
Bi2O3
Bi2O3
Bi2O3
PbBi12O19
PbBi12O19
Pb3Bi2O6
Pb3Bi2O6
Pb3Bi2O6
Pb3Bi2O6
Pb3Bi2O6
Pb3Bi2O6
Pb3Bi2O6
PbO
PbO
PbO
PbO
PbO
PbO
PbO
PbO
PbO
PbO
PbO
PbO
PbO
Pb3Bi2O6
PbO
PbO
PbO
PbO
PbO
Pb3Bi2O6
PbO
PbO

. 6.28.

. 6.29.

BiPbO. [Pb] = 25 . %

BiPbO. [Pb] = 30 . %

Bi2O3PbBi12O19Pb3Bi2O6PbO
2,5 30 . %.
,
BiSnO, . 6.4. ,
,
,
Bi2Sn2O7 [554].
6.4.
BiSnO,
10 . %
[O], . %
47,97
50,49
50,88
55,04
55,47
56,04
56,63
56,93
57,34
57,42
58,31
59,54
64,49

[Sn], . %
13,15
7,69
16,53
12,72
11,78
12,44
23,02
21,54
10,00
9,37
23,02
24,30
19,91

[Bi], . %
38,88
41,82
32,60
32,24
32,76
31,52
20,35
21,53
32,67
33,21
18,67
16,16
15,61

Bi2Sn2O7 + Bi
Bi2Sn2O7 + Bi2O3 + Bi
Bi2Sn2O7 + Bi2O3
Bi2Sn2O7 + Bi2O3 + Bi
Bi2Sn2O7 + Bi2O3 + Bi
Bi2Sn2O7 + Bi2O3 + Bi
Bi2Sn2O7
Bi2Sn2O7
Bi2Sn2O7 + Bi2O3 + Bi
Bi2Sn2O7 + Bi2O3 + Bi
Bi2Sn2O7
Bi2Sn2O7
Bi2Sn2O7

284

, Bi2Sn3O9 [555],
.
, -, Bi2Sn2O7 (. 6.30),
,
, Bi2O3 ,
, Bi2Sn2O7.

. 6.30.
BiSnO. [Sn] = 10 . %

6.2.3. BiPbS BiCuS


,
.
, ,
,
.
, BiPbS BiCuS ,
,
,
, , .
BiPbS
10 % . BiCu
400 0,
.

, 400 0, .
5 ,
.
. 6.5 6.6, (. 6.316.39).

285

6.5.
BiPbS
[S], . %
56,37
44,44
42,87
44,27
51,78
51,81
50,57
50,86
48,78
50,14
48,38
46,77
48,77
48,46

[Pb], . %
2,09

28,44
28,95
34,22
30,51
51,22
49,86
51,62
53,23
51,23
51,54
54,39
59,06
72,45

. 6.31.

Bi
PbS
(. 6.5).
Bi2S3 +
PbBi2S4

,
, ,


Bi2S3 + PbBi2S4, . 6.31

[Bi], . %
41,54
55,56
57,13
55,73
19,78
19,24
15,21
18,63

Bi2S3+Bi, . 6.32
Pb2Bi2S5 + PbS, . 6.32

PbS, . 6.33

45,61
40,94
27,55

Pb + Bi, . 6.34

. 6.32.

Bi
PbS (. 6.5).

,

Bi2S3+Bi.


Pb2Bi2S5 + PbS

. 6.33.

Bi
PbS (. 6.5).
PbS

286

. 6.34.

Bi
PbS
(. 6.5).

Pb + Bi

, , ,
.
,

.
6.6.

BiCuS


[S],
[Bi],
[Cu],
. %
. %
. %
94,93 5,07

,
87,44 12,56
. 6.35
95,79 4,21
51,51 39,58 8,92
Bi2S3 + CuBiS2,
. 6.36
48,30 25,24 26,46
CuBiS2,
50,02 25,87 24,11
. 6.36
41,19
39,76
39,44
40,76
40,88
39,74
39,59
40,99
40,03
39,83
40,41
38,72
40,23
35,80
37,16
35,84
35,34
35,14
35,18
35,97
34,40
2,61
2,93
1,40
6,15

14,35
13,15
11,14
13,61
13,60
13,00
12,54
13,85
12,39
13,10
12,69
10,80
11,77
5,52
4,87
4,07
3,48
4,33
3,29
3,51
2,08

44,47
47,09
49,42
45,64
45,52
47,26
47,87
45,16
47,58
47,07
46,89
50,48
48,00
58,68
57,97
60,09
61,18
60,53
61,54
60,52
63,51
97,39
97,07
98,60
93,85

. 6.35.
BiCuS (. 6.6).
(
Cu Bi)

Cu3BiS3, . 6.37,
6.38

. 6.36.
BiCuS (. 6.6).
, Bi2S3
+ CuBiS2. CuBiS2
Cu2S + Cu3BiS3,
. 6.38

Cu + Cu2S, .
6.39

. 6.37.
BiCuS (. 6.6).
,
Cu3BiS3
287

. 6.38.
BiCuS (. 6.6).
, Cu3BiS3.
,
Cu2S + Cu3BiS3

. 6.39.
BiCuS (. 6.6).
,

6.3. SnAlSb

[556].
SnAlSb
[557].

,
[558],
:

ai xi e

x j 2Q
RT

ai xi e

x j Qij xk Qik xi x j Qij x j xk Q jk xi xk Qik


RT

- . x
(i, j k ), , R
, Q ( ).
,
:
Q x q
x q
1 12
2 21

q.
(. 6.7) Al
Sb, SnAl SnSb (. 6.40, 6.41 6.42 ),

288

[139, 559].
AlSb, SnAl, SnSb, SnAlSb

(. 6.8).
. 6.9
.
6.7.

qAB
qSnAl
qAlSb
qSnSb

,
SnAlSb
/
qBA
/
10850
qAlSn
19500
9800
qSbAl
9800
13535
qSbSn
8356

6.8.


, K;

a , .
, lg K
|Sn3Sb2| = 3[Sn] + 2[Sb]
K = a[Sn]3a[Sb]2
7400/T + 9,653
|SnSb| = [Sn] + [Sb]
K = a[Sn]a[Sb]
2509/T + 2,899
|AlSb| = [Al] + [Sb]
K = a[Al]a[Sb]
1940/T + 1,045
6.9.
,
T,
H, /
Sn
505,06
7196
Al
933,52
10794
Sb
903,65
20083

. 6.40.

AlSb

289

. 6.41.


SnAl

. 6.42.

SnSb

,
SnAlSb
.

290

,

350400 0.
, ,
JEOL
JSM-6460LV.
SnAlSb
() . 6.43.

,
.
I ,
, II , Sn3Sb2
. III ,
SnSb. IV ,
. , V
, AlSb.

. 6.446.46.

. 6.43.

SnAlSb

,
SnAlSb
SnSb (. 6.44). , ()

291

, , ,
.
, .
, ,
, AlSb .

(. 6.45) . , ,

, AlSbOx. , ,
,
AlSb .

. 6.44. ,

. 6.45.

. 6.46.

()

SnSb ( SnSb

AlSbOx

()

24 . %

,
,
550 0
,
AlSb. ,
,
292

, ,
.
6.4.
1) ,
,
( , , ,
, ).
2) ,

, .
3) ,
, ,
(PbAgZn, PbAuZn, PbCuS, PbZnO, PbSbO), (BiAgZn)
(SnAlSb).
4) ,
,
.
5)
PbAgZn, PbCuS,
PbZnO, PbSbO, BiAgZn, BiCuS, BiPbS, BiPbO, BiSnO SnAlSb.
, ,
. ,
.
6)
, , , ; ; .

293


1)

,

. .
2) ,
.

, .
3)

, .
, :
)
,
, ;
) ,
, (
, , , );
)
(
);
)
1000
( ).

.
4)
. ,
,
, ,
,
, .
,

294

,
. .

.
5) ,
, .
Mathcad .

, ) Mathcad.
Mathcad ()
, .
, ,
.
,
.
( ) (
)
.

, Mathcad.
6)

.

. ,
, ,
.
7)

,
,
.
8) ,


. , :
295

- ;
- , , , ;
- ,
;
-
;
-
.

, .

, ,
, , , . ,

( ),
( )
.

.
9)
Cu2ORnOm ( RnOm NiO, ZnO, CoO,
FeO, Fe2O3, As2O3, Sb2O3, P2O5, SiO2), Cu2OFeOFe2O3, AlCl3NaCl, AlCl3KCl, AlCl3MgCl2,
AlF3NaF.
Cu2ORnOm ( RnOm NiO, SnO2, PbO, Bi2O3, SiO2, MgO,
Al2O3, CaO), Cu2OSnO2PbO, NiOCaO.

CuNi, CuCu2O, NiNiO, Cu2ONiO, Cu2OSiO2.

CuCu2O,
.
10)
CuRO ( R Ni, Sn, Zn, Co, Fe, Pb, As, Sb, Bi, Si,
Al, Ca, Mg, S, P), CuPbSnO, CuPbSnZnO, CuFeSiO, CuZnPO, CuPbPO
CuNiSO; AlMgO, AlMgNaO, AlMgNaKO, AlMeCl
( Me Na, Mg, K), AlNaF, AlMgF, AlMgNaF; CoCO,
296

CoSiO, CoAlO, CoSiCO; NiO, NiCaO, NiAlO,


NiSiO, NiCaCO, NiAlCO, NiSiCO; PbAgZn, PbAuZn,
PbCuS, PbZnO PbSbO; SnAlSb;
BiAgZn.
11) ,
,
, , , .
, .

, ,
.
12)
CuRO ( R Ni, Sn,
Zn, Co, Fe, Pb, Sb, Bi, Si, Mg, Al, S, P), CuPbSnO, CuPbSnZnO, CuFeSiO, CuNiSO,
NiRO ( R Cr, Fe, Mn, Nb, Pb, Bi, S, Sb, Sn, Ti, W), NiRBi ( R Pr, Er, Dy, Nd),
AlMgO, PbAgZn, PbCuS, PbZnO, PbSbO, SnAlSb, BiAgZn, BiPbS, BiCuS,
BiPbO BiSnO. , ,
.
, .
13)
,
. , ,
() ,
, , ,

CuAlO ( ),
,
. ,
,
.
14)



, , ,
.
297


1. , .. / .. ,
.. . .: , 1993. 416 .
2.

..

/ .. , .. , .. . .: , 1994.
353 .
3. , .. :
/ .. , .. : - , 1999. 256 .
4. , .. / .. , ..
// -, , 2008. 254 .
5. , .. / .. , ..
.: , 1993. 144 .
6. , ..
: . - . /
.. .: - , 1986. 43 .
7. , .. / .. ,
.. , .. . .: . , 2009. 520 .
8. , .. / .. .: ,
2002. 442 .
9. , .. / .. , .. , .. ,
.. . : , 2010. 317 .
10. , .. / .. , .. , .. ,
.. : - -, 2001. 431 .
11. , .., / .. , .. , ..
.: , 1992. 268 .
12. , .. / .. , .. . .:
, 2005. 114 .
13. , ..
/ .. , .. , ..
// . 2004. 7. . 17-22.
14. , .. / .. ,
.. , .. , .. , .. , .. //
. 2004. 9. . 46-47.

298

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Verwimp, J.R. Roos // Met. Trans. 1976. 7. 1. P. 149150.
533. , .. / ..
, .. , .. // 1989. 7. . 7478.
534. , .. PbCuS // ..
, .. , .. // XII
338

. . 2.
.
: , 2008. . 121123.
535. , 1984 / .:
. .(. .) . .: , 1986.
536. Johto, H. Phase stabilities and thermodynamic assessment of the system CuPbS / H.
Johto, P. Taskinen // Minerals Engineering. V. 42. 2013. March. P. 6875.
537. Taskinen, A.I. Thermodynamics of slags in direct lead smelting / A.I. Taskinen, L.M.
Toivonen, T.T. Talonen // 2nd Int. Symp. Met. Slags and Fluxes, Fall Extract. and Process Met. Meet.,
Lake Tahoe, Nev., Nov. 1114, 1984. Warrendale, Pa, 1984. P. 741756.
538. Schlesinger, M.E. PbO solubility in lead-blast furnace slags / M.E. Schlesinger, D.C. Lynch
// Met. Trans.. 1986. 17. 14. P. 817827.
539. , .. / ..
, .. , .. , .. // 1983. 8.
. 3135.
540. Szwarc, R. The Diffusivity and Solubility of Oxygen in Liquid Lead from Electrochemical
Measurements / R. Szwarc, K.E. Oberg, R.A. Rapp // High Temperature Science. 1972. 4. P.
347356.
541. , .. Pb+PbO Sn+SnO
/ .. , .. , ..
, .. // . . .
. . . 33. ., 1989. . 411.
542. , .. ,
PbO / .. , .. // . 1996. 4. .
2227.
543. , .. 44,5% Pb
55,5% Bi / .. , .. , .. , .. // 10
. . 2.
. , : . 2001. . 188189.
544. Conochie, D.S. Oxygen solubility in molten lead / D.S. Conochie, C. Ebiogwu, D.G.C.
Robertson // Trans. Inst. Mining and Met. 1984. 93. March. P. 4548.
545. Taskinen, A. Oxygenmetal (Ag, Au, Bi, Cu, In, Ni, Sb, Sn, Te) interactions in dilute
molten lead alloys / A. Taskinen // Acta polytech scand. Chem. incl. Met. Ser.1981. 146. 44 pp.

339

546. Paulin, A. Uporaba kisika pri rafinaciji svinca Vpihovanje plina v talino / A. Paulin //
Rud.met. zb. 1989. 36. 3. P. 479491.
547. Paulin, A. Uporaba kisika pri rafinaciji svinca. Termodinamicne osnove / A. Paulin // Rud.
met. zb.. 1989. 36. 1. P. 1727.
548. Kozuka, Z. Pb PbOSiO2
/ Z. Kozuka, Y. Hirato, K. Kuroda // (J. Jap. Inst. Metals). 1973. 37.
9. C. 10381044.
549. Taskinen, A. Activity coefficient of oxygen in PbBi and PbSb melts / A. Taskinen // Z.
Metallk.. 1982. 73. 3. P. 163168.
550. Otsuka, S. Activity of oxygen in liquid PbSb alloys determined by a modified coulometric
titration method / S. Otsuka, Y. Kurose, Z. Kozuka // Z. Metallk.. 1984. 75. 1. P. 4652.
551. , .. , BiAgZn / .
. , . . // - .
. 2011. 14(231). . 811.
552. , .. / ..
, .. // Journal of Siberian Federal University. Chemistry. 2009. V. 3.
2. P. 254258.
553. ..
/ ..
// . 2012. 3. . 3743.
554. Wang, P.L. Phase relation of Bi2O3SnO2 system and crystal growth of Bi2Sn2O7 and its
ceramic preparation / P.L. Wang, J.C. Liu, G.B. Cao, J.D. Wu, D.Y. Li. Journal of The Chinese
Ceramic Society. 1982. V. 10. 2. P. 141145.
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of the American Ceramic Society. 1953. V.36. 7. . 207214.
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. . .: . 1992. . 382384.
557. , .. , SnAl
Sb / .. // . 2012.
2. . 7682.
558. , ..
IIV / . . // .
. 1963. 8. . 3540.
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Schwermann. Journal of the Institute of Metals. 1971. V. 99. P. 169173.
340

1.

1.
(/)
1
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
Cu2O
SnO2
CoO
NiO()
NiO()
NiO()

2
NiO
SnO2
PbO
SiO2
MgO
CaO
Al2O3
Bi2O3
PbO
SiO2
SiO2()
O()
O()

Q1112

Q1122

Q1222

26 123
25 823
16 788
38 100
19 464
25 323
4164
5661
7678
91 327
29 500
3272
45 246

28 429
339 790
18449
318 000
5110
9573
34 179
41 812
18 326
333 607
20 000
30 000
65 000

28 177
22 369
5288
59 300
12 932
11 354
21 444
9626
10 888
125 566
72 000
41 596
42 057
2.

Tm ,

H m , /

Cu2O
FeO
Fe3O4
SiO2,
SiO2,
Al2O3
CaO
SnO2
ZnO
NiO
CoO
MgO
PbO
As2O3
Sb2O3
Bi2O3
CuFeO2
CuAlO2
Cu2S
CuPO3

1242
1360
1540
1680
1720
2050
2580
1630
1975
1957
1810
2800
886
585
929
824
1197
1260
1129
1240

64 300
32 200
138 160
9002
7704
113 000
75 400
47 700
54 392
50 660
50 240
77 500
25 540
22 594
55 020
59 831
73 800
77 000
12 300
69 000

341

342

Cu 2O 2Cu O

16

15

14

13

12

11

10

Al2O3 2 Al 3 O
Al2O3 2 Al 3 O
CuAlO4 Cu Al 4 O
CaO Ca O
CaO Ca O
MgO Mg O
MgO Mg O
NiO Ni O
NiO Ni O
PbO Pb O
SiO2 Si 2 O
SiO 2 Si 2 O
ZnO Zn O
ZnO Zn O

2
Cu 2O 2Cu O

1
1

11 491 / T + 5,838
14 333 / T + 7,102

K a O a Zn

38 183 / T + 10,726

37 713 / T + 10,485

K a2OaSi a SiO 2
K a2OaSi
K aOa Zn a ZnO

5524 / T + 5,492

9803 / T + 6,365

7156 / T + 5,178

25 870 / T + 7,084

21 825 / T + 5,778

27 610/ T + 6,730

23 670/ T + 5,349

36 876/ T + 11,191

67 016/ T + 17,960

61 112/ T + 15,422

6500/ T + 4,468

4
3140/ T + 2,250

lg K

K aOa Ni
K aOa Pb a PbO

K aOa Mg
K aOa Ni a NiO

K aOaCa
K aOa Mg a MgO

K a4Oa Al
K aOaCa a CaO

a3Oa2Al

K a3Oa2Al a Al O
2 3

K aO

, K;
a , . %
3
K aO a Cu 2O

3.

343

1924 / T + 1,201
2514 / T + 1,622
6520 / T 0,996

K a1,5
a
a 0,5
O Bi
Bi 2O 3
K aS a Cu 2S
K aS
K a2OaS pSO 2

0,5 Bi 2O3 Bi 1,5 O

28

K a4OaSia2Fe
K aO p0,5
O 2

Fe2SiO 4 2 Fe Si 4 O

0,5O2 O

32

33

31

30

29

Cu 2S 2Cu S
Cu 2S 2Cu S
SO2 S 2 O

K a1,5
a
a 0,5
O Sb
Sb 2O 3

0,5 Sb 2O3 Sb 1,5 O

K aOa Fe a (FeO)
K aOaCo a CoO
K aOaCo

4451 / T + 0,336

64 854 / T + 21,996

8419 / T + 7,772

10 674 / T + 6,836

9343 / T + 5,678

10 903 / T + 5,663

8277 / T + 4,403

10 706 / T + 4,054

12 389 / T + 5,084

27

26

25

24

23

22

21

33 158 / T + 14,500

49 773 / T + 20,984

22 562 / T + 10,776

K a1,5
a
a 0,5
O As
As 2O 3

K a4Oa3Fe

Fe3O 4 3 Fe 4 O

20
K a2Fea3O a Fe O
2 3
K aOa Fe

K a2Oa Fe

CuFeO 2 Cu Fe 2 O

19

21 780 / T + 11,652

19 288 / T + 10,342

Fe2O3 2 Fe 3 O
FeO Fe O
FeO Fe O
CoO Co O
CoO Co O
0,5 As 2O3 As 1,5 O

K a2OaSn

SnO2 Sn 2 O

a SnO 2

18

17

a2OaSn

2
SnO2 Sn 2 O

. 3.

344

48

47

46

45

44

43

42

41

40

39

38

37

36

35

34

Zn2SnO4 = 2[Zn] + [Sn] + 4[O]

Zn Zn
Pb Pb
As As
Sb Sb
Bi Bi
Ca Ca
Mg Mg
PbO PbO
As2O3 As2O3
Sb2O3 Sb2O3
CuPO3 Cu P 3O
CuPO3 Cu P 3 O
P4O10 4 P 10 O

0,5S2 S

p0,5
S 2

6915 / T + 8,471
9071 / T + 10,023

K pMg a Mg
K pPbO a PbO
K pAs O a As O
2 3
2 3
K pSb O a Sb O

K a[2Zn ] a[ Sn ] a[4O ]

4
K a10Oa[P]
pP O
4 10

K a3Oa P

K a3Oa P a CuPO
3

2 3

7776 / T + 7,601

K pCa aCa

2 3

5583 / T + 5,551

51 418 / T + 26,127

94 804 / T + 47,742

46 952 / T + 23,745

3712 / T + 7,153
46 494 / T + 23,443

3061 / T + 9,176

7587 / T + 6,702

6453 / T + 10,202

9646 / T + 7,276

6243 / T + 8,288

6247 / T + 0,686

K pAs a As
K pSb aSb
K pBi a Bi

K aS
K pZn a Zn
K pPb a Pb

. 3.

4.

e ij

e ij

eOO

630 / T + 0,327

11,8 / T 0,00195

Si
eSi

159 / T

Al
e Al

891 / T + 0,128

Ca
e Ca

880 / T

Pb
eSn
Sn
e Pb
Ni
e Fe
Fe
e Ni

Mg
e Mg

385 / T

Si
e Pb

19 / T

eSS

1154 / T + 0,664

Pb
eSi

144 / T

Ni
e Ni

63 /

Si
e Fe

31 / T

Sn
eSn

306 / T + 0,19

Fe
eSi

63 / T

Pb
e Pb

67,6 / + 0,0012

As
e As

119,5 / T

Co
e Co

227 / T + 0,018

Sb
eSb

123 / T 0,191

Zn
e Zn

926 / T + 0,6

Bi
e Bi

50,2 / T 0,022

Fe
e Fe

209 / T + 0,138

ePP

259 / T 0,0046

e OSi

3166 / T + 1,725

O
eSi

5540 / T + 3,019

371 / T

O
e Al
eSO
O
e Ni
O
eSn
O
e Pb
O
e Co
O
e Zn

626 / T

e OAl
e OS
e ONi
e OSn
e OPb
e OCo
e OZn
As
O

339 / T
38 /
25 / T
22 / T
300 / T
128 / T

20,3 / T 0,00325
50 / T
47 / T

678 / T
139 / T
187 / T
281 / T
550 / T
523 / T

O
As

eOSb

9/T

O
eSb

69 / T

eOBi

14 / T

O
eBi

183 / T

eSNi

135 / T

S
eNi

249 / T

eOP

177 / T

ePO

342 /

e OCa

(905107[Ca]) / T

O
e Ca

(22512,5107[Ca]) / T

e OMg

(2004108[Mg]) / T

O
e Mg

(3046,08108[Mg]) / T

eOFe
O
eFe

(50,1368,3[Fe]+73,7[Fe]24,42[Fe]3) / T
(175,31288,9[Fe]+257,8[Fe]215,47[Fe]3) / T
345

5.

, K;

a , . %
, lg K
K a O a CoO
CoO Co O
1
6463 / T + 3,37
2

CoO Co O

3
4

SiO2 Si 2 O
SiO 2 Si 2 O

Al2O3 2 Al 3 O

CoAl2O4 Co 2 Al 4 O

CO C O

CO 2 C 2 O

K a O

2
a[O]
a[Si]

9090 / T + 4,56

aSiO 2

36 181 / T + 13,046

2
K a[O]
a[Si]

36 584 / T + 13,248

3
2
K a[O]
a[Al]

65 832 / T + 21,942

4
2
K a[O]
a[Al]

76 888 / T + 26,808

K a[O]a[C] pCO

4310 / T 1,576

15 693 / T + 3,659
6.

eij
eij
eij

Al
O
Al
375 / T
243 /

1050
/

1772 / T
e
e

eij

eOO

a [2O ] a [ C ]

eAl

pCO

Si
eSi

369 /

eCC

375 / T

eOC

1853 / T

eCO

1390 / T

eOSi

Al

386 / T

O
eSi

676 /

7.

N

, K; a ,
.%; p , .

, lg K

(NiO) = [Ni] + [O]

K a[ ] / a NiO

10318 / T + 5,813

|NiO| = [Ni] + [O]

K a[ ] / a NiO

12966 / T + 7,000

{CO} = [C] + [O]

K a[ O ] a[ C ] / pCO

5093 / T 1,878

{CO2} = [C] + 2[O]

K a[2O ] a[ C ] / pCO2

15433 / T + 2,852

(CaO) = [Ca] + [O]

K a[ O ] a[ Ca ] / a CaO

15489 / T + 3,969

|CaO| = [Ca] + [O]

K a[ O ] a[ Ca ] / a CaO

19430 / T + 5,350

|Al2O3| = 2[Al] + 3[O]

K a[3O ] a[2Al ]

63924 / T + 21,027

|NiAl2O4|=[Ni]+2[Al]+4[O]

K a[4O ] a[2Al ]

74480 / T + 25,805

(SiO2) = [Si] + 2[O]

K a[2O ] a[ Si ] / a SiO2

33467 / T + 12,338

10

|SiO2| = [Si] + 2[O]

K a[2O ] a[ Si ]

33870 / T + 12,540

11

|Ni2SiO4|=2[Ni]+[Si]+4[O]

K a[4O ] a[ Si ]

60610 / T + 26,984

eJ
O

e O
Al
e O
Ca
e O
O
e Si

8.

i
i
i
eJ
eJ
eJ

Al
a
Si
41,7 / T
e Al
337 /
e Ca
290 /
e Si
274 /
O
C
O
82,6 /
e Al
139,4 / T
e C
395 / T
e C
120 / T
O
Si
C
69 / T
e Ca
172 /
e O
73,1 / T
e O
160 / T
127,8 /

346

347

pAlCl

NaAl2Cl7 Na 2Al 3,5Cl2

NaAl3Cl10 Na 3Al 5Cl2


NaAlCl4 Na Al 2 Cl2
Na Na

10

14

13

12

(KCl) = [K]+{Cl2}

K Na p5Cl2 a NaAl Cl
3 10

KCl K 0,5Cl2

11

K a Na p3,5
a NaAl2Cl4
Cl2

NaAlCl4 Na Al 2 Cl2

K a K p0,5
a KCl
Cl2

K a Na p2Cl2 pNaAlCl4
K pNa a[Na]

K a K p0,5
Cl2

K a Na p2Cl2 a NaAlCl4

K a Na p0,5
a NaCl
Cl2

K a Na p0,5
Cl2

K p0,5
pAlCl
Cl2
K p{Al}

p1,5
Cl2

K p3Cl2 a Al Cl
2 6

, K; a ,
; p ,
3
1,5
K pCl a AlCl

NaCl Na 0,5Cl 2

AlCl Al 0,5Cl2
Al Al
NaCl Na 0,5Cl 2

Al2Cl6 2Al 3Cl2


AlCl3 Al 1,5Cl2

2
AlCl3 Al 1,5Cl2

19 048 / T + 4,708

6594 / T + 3,236

52 231 / T + 9,739

126 612 / T + 29,921

92 029 / T + 21,938

21 473 / T + 7,034

57 446 / T + 13,955

18 739 / T + 4,850

22 176 / T + 8,012

15 918 / T + 5,721

4047 / T 3,039

31 463 / T + 3,551

72 378 / T + 17,461

34 256 / T + 7,735

,
lg K
4

9.

348

|MgCl2| = [Mg] + {Cl2}

(MgCl2) = [Mg] + {Cl2}

20

21

31

30

29

28

27

26

25

24

23

78821 / T + 13,476

24 596 / T + 1,509
1,5
p{F
2}

K p{O 2 } pAl2O 2

8920 / T 2,580

88 258 / T + 17,250

5882 / T + 4,166

132 108 / T + 24,129

0,5
K p{O
} p{Al2O}

1,5
p{O
2}

K a Mg p5,5
pMgAl Cl
Cl2
3 11
K pMg a[Mg]

MgAl3Cl11 Mg 3Al 5,5Cl2


Mg Mg
Al2O3 2Al 1,5 O 2
Al2O 2Al 0,5O2
Al2O2 2Al O2
AlF3 Al 1,5F2

122 705 / T + 28,458

K p5Cl2a0,5
a Mg Al Cl
Mg
0,5 3 10

97 852 / T + 16,394

88 449 / T + 20,723

K p3,5
a 0,5 a Mg Al Cl
Cl2 Mg
0,5 2 7
K a Mg p4Cl2 pMgAl Cl
2 8

54193 / T + 12,988

32 455 / T + 7,085

40 673 / T + 15,411

5722 / T + 2, 181

51 803 / T + 8,447

K p2Cl2a0,5
a Mg AlCl
Mg
0,5 4

K pCl2 a Mg
K pCl2a Mg a MgCl2

K a K p2Cl2 pKAlCl4
K pK a[K]

127 788 / T + 29,860

K K p5Cl2 a KAl Cl
3 10

58 806 / T + 13,944
93 297 / T + 21,902

a KAlCl4

K a K p3,5
a KAl2Cl4
Cl2

a K p2Cl2

MgAl2Cl8 Mg 2Al 4Cl2

Mg0,5AlCl4 0,5 Mg Al 2Cl2


Mg0,5Al2Cl7 0,5 Mg 2Al 3,5Cl2
Mg0,5Al3Cl10 0,5 Mg 3Al 5Cl2

K K

19

22

{KAlCl4} = [K] + Al + 2{Cl2}

KAl2Cl7 K 2Al 3,5Cl2


KAl3Cl10 K 3Al 5Cl2

2
KAlCl4 K Al 2Cl2

18

17

16

15

. 9.

349

(KF) = [K] + 0,5{F2}

(K3AlF6) = 3[K] + Al + 3{F2}

47

Na 3AlF6 3 Na Al 3F2
NaAlF4 Na Al 2 F2
Na 5 Al3F14 5 Na 3Al 7 F2

Na 3AlF6 3 Na Al 3 F2

K 2O 2 K 0,5 O2
KAlO2 K Al O2
NaF Na 0,5F2

46

45

44

43

42

41

40

39

38

37

26 020 / T + 5,246
162 906 / T + 29,508

K a3K p3F2 a K AlF


3
6

385 450 / T + 70,637

102 613 / T + 13,267

K a Na p2F2 a NaAlF4

K a5Na p7F2
K a K p0,5
a KF
F

164 451 / T + 29,245


3AlF6

169 557 / T + 33,607

27 088 / T + 5,498

K a Na p0,5
a NaF
F2
K a3Na p3F2
K a3Na p3F a Na

54 110 / T + 12,935

7704 / T + 3,673

15 137 / T + 11,003

54 110 / T + 11,412

4613 / T + 1,365

16 939 / T + 8,326

15 262 / T 2,833

64 132 / T + 3,995

75 123 / T + 11,656

K a2K p0,5
pK 2O
O2
K a K pO2 a KAlO2

a K 2O

K a2Na p0,5
pNa 2O
O2
K a Na pO2 a NaAlO2

Na 2O 2 Na 0,5 O2
NaAlO2 Na Al O2
K 2O 2 K 0,5 O2
K

K a2Na p0,5
a Na 2O
O2

Na 2O 2 Na 0,5O2

35

a2K p0,5
O2

K p0,5
pAlF
F2

AlF Al 0,5F2

34

36

K p1,5
pAlF
F2
3

AlF3 Al 1,5F2

33

a AlF

p1,5
F2

AlF3 Al 1,5F2

32

. 9.

350

54

53

52

F2 2 F
O2 2 O

197 100 / T + 31,837

K aMga2Na p3,5
F

26 421 / T + 6,797

K p2O pO2


12 700 / T + 10,025
9512 000 / T 6627
67 710 000 / T 46 660

ij

Mg
Mg

Na
Na

K
K

KNa KNa

K
Mg
K Mg

Na
Mg
Na Mg

ij

5846 190 / T + 3863

17 150 / T 8,8

125 800 / T 221,3

10.

6237 / T + 3,949

K p2F pF2

56 931 / T + 8,195

59 998 / T + 10,191

122 803 / T + 23,588

32 687 / T + 6,447

K pF2a Mg a MgF2

MgF2 Mg F2
Na 2 MgAlF7 2 Na Mg Al 3,5F2

MgF2 Mg F2

50

51

K a Mg p2O2
K pF a Mg

MgAl2O 4 Mg 2Al 2 O 2

49
2

a Mg p0,5
O2

MgO Mg 0,5 O 2

48

. 9.

11.

, K;

a , . %
, lg K
K a Ag
1
|Ag| = [Ag]
2422 / T + 4,776
2
3
4

|AgZn| = [Ag] + [Zn]


|AgZn1,5| = [Ag] + 1,5 [Zn]

|AgZn5| = [Ag] + 5 [Zn]


|Zn| = [Zn]

K a Ag a Zn

3676 / T + 4,764

K a Ag a

1,5
Zn

4322 / T + 5,219

K a Ag a

5
Zn

9940 / T + 12,577

K aZn

1838 / T + 2,690

(Zn) = [Zn]

K aZn

1056/ T + 1,558

|Cu| = [Cu]

K aCu

1830 / T + 1,830

|Sb| = [Sb]

K aSb

3340 / T + 8,345

(Sb) = [Sb]

K aSb

2303 / T + 7,197

10

|Au| = [Au]

K a Au

188 / T + 1,700

11

|Au2Pb| = 2 [Au] + Pb

2
Au

788 / T + 3,983

12

|Au3Zn| = 3 [Au] + [Zn]

K a 3Au a Zn

4602 / T + 9,970

13

|AuZn| = [Au] + [Zn]

K a Au a Zn

2826 / T + 4,345

14

|AuZn2| = [Au] + 2 [Zn]

K a Au a 2Zn

5064 / T + 6,786

15

|AuZn3| = [Au] + 3 [Zn]

K a Au a

3
Zn

7202 / T + 9,248

16

|AuZn4| = [Au] + 4 [Zn]

K a Au a

4
Zn

9140 / T + 11,458

17

|AuZn7| = [Au] + 7 [Zn]

K a Au a

7
Zn

15354 / T + 19,728

18

|PbS| = Pb + [S]

19

|Cu2S| = 2 [Cu] + [S]

20

|PbO| = Pb + [O]

K a O

4327 / T + 4,723

21

|ZnO| = [Zn] + [O]

K a Zn a O

12748 / T + 7,211

22

|Sb2O3| = 2 [Sb] + 3 [O]

23

|PbOSb2O3| = Pb + 2 [Sb] + 4 [O]

24

|3 PbOSb2O3| = 3 Pb + 2 [Sb] + 6 [O]

25

|5 PbOSb2O3| = 5 Pb + 2 [Sb] + 8 [O]

K a

K a S

K a

4409 / T + 3,768

2
Cu

a S

6891 / T + 5,086

K a

2
3
Sb O

22267 / T + 27,629

K a

2
4
Sb O

27653 / T + 33,007

K a

2
6
Sb O

37366 / T + 43,108

K a

2
8
Sb O

46550 / T + 52,882

12.

eij
eOO
eSS
eCuCu
eAuAu
eCuS
eSCu

4132000/T 3257
1576/T 1,39
408/T + 0,295
1,876/T 0,00305
1596/T + 1,265
3192/T + 2,530

eij
eZnZn
eAgAg
eSbSb
eOSb
eSbO
eOZn

174 / T + 0,128
38 / T + 0,004
70,12/T 0,0464
566,4/T + 0,213
74,4/T + 0,028
0,04
351

eij
eAuZn
eZnAu
eAgZn
eZnAg
eZnO

3,8/T + 0,0027
11,45/T + 0,00813
76 / T + 0,054
128 / T + 0,084
0,01

2.
u Ni O


ttt 1491
ooo 1
hhh 0.85

nio 0.06765

ncu 0.5

cu2o 1 nio

nni 0.5

Q1112 26123
Q1122 28429

Q1222 28177

Given

630
38
63
139
ttt .327 ooo ttt hhh log( ooo ) ttt hhh ttt 0 ooo log( hhh )

7156

5.178
ttt

2
2
2
3

3 ncu nni Q1222 ncu nni ( 2 3 nni ) Q1122 ncu ( 1 3 nni ) Q1112
log ( nni )

2.303 8.31 ttt

630
38
3140
ttt .327 ooo ttt 0 hhh log( ooo ) ttt 2.250

3 ncu 2 nni2 Q1112 ncu nni2( 2 3 ncu ) Q1122 nni3( 1 3ncu ) Q1222
2 log ( ncu ) 2

2.303 8.31 ttt

630
38
ttt .327 ooo ttt 0 hhh log( ooo )

63
139


hhh
0 ooo log ( hhh )
ttt
ttt

630
38
ttt .327 ooo ttt 0 hhh log( ooo )

cu2o nio
ncu nni

ttt
ooo
hhh
cu2o
nio
ncu
nni

1
1

ncu

9803
ttt

6500
ttt

6.365

4.468

2 cu2o
2 cu2o nio

Find( ttt ooo hhh cu2o nio ncu nni)

352

ttt
ooo
hhh
cu2o
nio
ncu
nni

1.49292 103

2.19056
0.72123

0.91646
0.08354
0.95641

0.04359

(Cu2O NiO)
tt 1348

oo .1

( 0)

hh 10

Given

630 .327 oo 38 hh log( oo ) 63 hh 139 oo log( hh ) 9803 6.365

tt

tt
tt
tt
tt
630 .327 oo 38 hh log( oo )
tt
tt

6500
tt

4.468

Fricfac( tt ) Find( oo hh )
tt 1351 round ( ttt )

oo tt

Fricfac( tt )
hh tt


tt1 1348

oo1 .1

( 4)

hh1 10

ncu1 0.9787

nni1 0.0213

Given

630 .327 oo1 38 0 hh1 log( oo1 ) 63 hh1 139 0 oo1 log( hh1 )
0

tt1
tt1

tt1

tt1

2
2
2
3

3 ncu1 nni1 Q1222 ncu1 nni1 ( 2 3 nni1) Q1122 ncu1 ( 1 3 nni1) Q1112
log ( nni1)

2.303 8.31 tt1

7156

5.178
tt1

630 .327 oo1

tt1

38 0 hh1 log( oo1 )


tt1

6500
tt1

4.468

ncu1 nni1

630 .327 oo1 38 0 hh1 log( oo1 ) 3140 2.250


tt1
tt1
tt1

2
2
2

3 ncu1 nni1 Q1112 ncu1 nni1 ( 2 3 ncu1 ) Q1122 nni13( 1 3ncu1 ) Q1222
2 log ( ncu1 ) 2

2.303 8.31 tt1

Fricfac( tt1) Find( oo1 hh1 ncu1 nni1)


tt1 round ( ttt ) 1515

oo1 tt1
hh1 tt1
ncu1 tt1
nni1 tt1

Fricfac( tt1)

353


tt2 1491

( 0)

oo2 1

hh2 10

ncu2 0.9

nni2 0.1

Given

630 .327 oo2 38 0 hh2 log( oo2 ) 63 hh2 139 0 oo2 log( hh2 )
0
tt2

tt2

tt2


tt2

2
2
2
3

3 ncu2 nni2 Q1222 ncu2 nni2 ( 2 3 nni2) Q1122 ncu2 ( 1 3 nni2) Q1112

log ( nni2)
2.303 8.31 tt2

7156

5.178

tt2

630 .327 oo2 38 0 hh2 log( oo2 )


tt2

tt2

63
139


hh2 tt2 0 oo2 log( hh2 )
tt2

9803
tt2

6.365

ncu2 nni2

630 .327 oo2 38 0 hh2 log( oo2 ) 3140 2.250


tt2

tt2

tt2

3 ncu2 2 nni22 Q1112 ncu2 nni22( 2 3 ncu2 ) Q1122 nni23( 1 3ncu2 ) Q1222

2 log ( ncu2 ) 2
2.303 8.31 tt2

Fricfac( tt2) Find( oo2 hh2 ncu2 nni2)


tt2 round ( ttt ) 1600

oo2 tt2
hh2 tt2
ncu2 tt2
nni2 tt2

Fricfac( tt2)


t 1573

o .001

h 3

Given

630 .327 o

38 h log( o ) 63 h


t
t

Fricfac( t o ) Find( h )
i 1 9
j 0 1000

t i 1348 i 25
ai

oo ti if t i ttt
oo2 ti if t i ttt

o i j ai 0.01 j
h i j Fricfac t i o i j

354

139 o log( h )

9803
t

6.365


t1 1373

( 3)

o1 .01

h1 10

Given

630 .327 o1 38 0 h1 log( o1)


t1
t1

6500
t1

4.468

Fricfac( t1 h1) Find( o1)


i 1 6

t1i 1348 i 25

j1 0 100

b i

hh t1i if t1i ttt


hh1 t1i if t1i ttt

h1i j1 b i 0.01 j1
o1i j1 Fricfac t1i h1i j1


t2 1448

o2 .01

( 3)

h2 10

ncu3 0.9787 nni3 0.0213

Given

630 .327 o2 38 0 h2 log( o2) 63 h2 139 0 o2 log( h2)


t2

t2

t2
t2

7156

5.178

t2

2
2
2
3

3 ncu3 nni3 Q1222 ncu3 nni3 ( 2 3 nni3) Q1122 ncu3 ( 1 3 nni3) Q1112
log ( nni3)

2.303 8.31 t2

630 .327 o2 38 0 h2 log( o2) 3140 2.250


t2

t2

t2

2
2
2

3 ncu3 nni3 Q1112 ncu3 nni3 ( 2 3 ncu3 ) Q1122 nni33( 1 3ncu3 ) Q1222
2 log ( ncu3 ) 2

2.303 8.31 t2

ncu3 nni3

Fricfac( t2 h2) Find( o2 ncu3 nni3)


i 2 5

t2i 1448 i 25
d i

0.001 if t2i 1515


hh1 t2i if t2i 1515

j2 1 40

hh2 t2i d i
j2
40

f i j2

h2i j2 d i f i j2
o2i j2

ncu3 i j2
nni3
i j2

Fricfact2i h2i j2

355

u-Ni-O.
1100, 1150, 1200, 1250, 1300 .
3

oo1tt1

2.5

oott
oo2tt2
o1 j

o3 j
o5 j
o7 j

1.5

o9 j
o11 j1
o13 j1
o15 j1

o21 j2
o23 j2
o25 j2
0.5

10

10

hh1tt1 hhtt hh2tt2 h1 j h3 j h5 j h7 j h9 j h11 j1 h13 j1 h15 j1 h21 j2 h23 j2 h25 j2

u-Ni-O.
1125, 1175, 1225, 1275 .
3

ooo

2.5

oo1tt1
oott
oo2tt2

o2 j
o4 j
o6 j
o8 j

1.5

o10 j
o12 j1
o14 j1

o16 j1
o22 j2
o24 j2
o26 j2

0.5

hhh hh1tt1 hhtt hh2tt2 h2 j h4 j h6 j h8 j h10 j h12 j1 h14 j1 h16 j1 h22 j2 h24 j2 h26 j2

356

3.


( CuSnO)

,
.. , ,
, ,
.

.
:
,
;
, ;
, ;
, ;
;

;
;
;
,
( , .);
.
.
, CuSnO.
.
-1,2-0,5 ( 1200)
.
- .
( 89 )
( 00) ( 1 ..).
357

, 10 .

,
(. ) , , ( ,
) ( ,
, ).
, 1200.
,
1200, 20 .
, ,
,
(Cu2O, ..., 0,9 ).
,
1200 ( 80 ), 2 .

. . -1,2-0,5 :
1 , 2 ,
3 , 4

358

,
Cu2O .
,
, .

.
,

CuO .

, 10 .
Cu2O 1200
. 0, 1, 2, 4, 8 16 .
( 2023 ) ,
( ,
) , ,
( 15 )
.
36 . 8 16
. ,
24 .
.
, (
) , (
, .. ).
.
,
.
,
.
,
. Cu2O
, , ,
,
.
359

, Cu2O,
, .
, .
,
,
(, CaO, Al2O3, MgO). ,
, .

. ,
,
.
Cu2O
, ,
. Cu2O

, ,
,
, .

, () .
( )
. ,

JEOL

JSM6460LV,

Oxford Instruments.
,
. ,

.
,

.
.

,
.
360

,
.
..
, .
, , .
,

(,

) ,

.

,
.

,
.
.
,
, , .

. ,
.

.
, ,
, .
,
, :
1) (, ,
, );
2) (
);
3) ;
4) ;
5) .

361

,
, ,
. ,
Cu2O CuCu2O.

Cu2O, . , ,
.
,
, .

,

. ,

( ,

L C0 ( f L )k 1 S kC0 (1 f S ) k 1 ,
k , fS fL
), ,
, ,
.

362



PbZnAg ( PbCu
S, PbZnO PbSbO) ,
.
.
, , , PbZn
Ag, PbCuS, PbZnO PbSbO . ,
ZnCl2.

350 ,
(
,
,
. ), (
) (
8 , ~ 10 ). 5 ,

, ,
.

.

JEOL JSM-6460LV,

, .

363

. .

4.
(
Cu2O PbO SnO2 11001280 )

364

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