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( )
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
132
3.3. ,
143
3.3.1. CuSiO
145
3.3.2. CuFeSiO
152
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
187
3.6.
191
4. ,
4.1. ,
193
193
196
197
4.2. ,
199
199
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
245
5.4.
246
248
5.4.2. AlNaMgF
249
3
5.5.
252
6. ,
253
6.1. ,
253
253
6.1.2. PbCuS
262
266
6.2. ,
275
6.2.1. BiAgZn
275
281
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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(Thermo-Calc, MTDATA, FactSage .)
(SGTE, NIST .). : M.
Hillert, A. Dinsdale, A. Pelton, Zh. Du, H. Ohtani, Bo Sundman, G. Cacciamani,
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( 2.1.2/375, 1540 2448), (
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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1. ,
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1.1.
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60- XX " ":
[18].
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XIX
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. . [20]
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.. , .. .) ,
[18].
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uFS,
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FSiO2, FF23
FF23SiO2 [18]. , , ,
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.
1950- ,
- .
[18]
.
. , .. , . , . , .. , .. ,
(.. , .. , .. ),
[2224].
. (. . , . .
[25]) (.. , .. , .. .) .
H.H. Kellogg, J.M. Toguri,
A. Yazawa.
, - ,
,
, .
, - ,
.
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
Kp- ,
(1.2)
(1.3)
PO2 , C u O 0 ,5
, xi .
111 11 .
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0,95 .
-
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, [27].
(1.2) , (1.3)
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[18].
196080- .
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1960- . [18]
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(1.3)
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(Pengfu Zhang)
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36]
As, Sb, Bi ,
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CALPHAD (CALculation of PHAse Diagrams) [39].
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Thermo-Calc [40], MTDATA [41], HSC Chemistry, ChemSage, FACT
FactSage [42, 43]. ,
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( [44, 45], EQS4WIN,
CompuTherm LLC, .).
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, MALT2 [46], SGTE [47] NIST, IVTANTERMO .
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Internet [48].
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1.3.
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[5154].
[4954]
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[5456].
[5761].
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Thermo-Calc, FactSage, Pandat [62] WinPhaD (
CompuTherm LLC), PhDi TernAPI,
[63].
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[67], , [68, 69].
16
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( ,
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[54, 57, 7279 . .].
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17
(, , ,
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(pTx),
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, [80] , :
: , -, , ..
,
[80, c. 6].
[80]
: , , , ,
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XX ,
[81].
-, -
. ,
.
.
H.H. Kellogg [82, 83].
[8486]. ,
, .. ..
[87],
, .. [81].
. ,
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.
18
. [81, c. 6].
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[81] ,
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1.4.
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308 .
19
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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]
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], %
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]
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
0,6
-lg[Ni]
[Ni], %
0,8
0,4
0,5
0,2
0
0
0,002
0,004
0,006
-lg[Bi]
[Bi], %
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]
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], %
.
1.5. ()
, , ,
.
,
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23
.
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.
.
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,
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.. [5, 6]
,
.
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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].
(- ,
..) .
, , (,
.. [90], . 1.10).
..
. , ,
,
,
(
),
.
, ,
. ?
?
,
pTx
,
.
26
pTx
.
, (
, ) .
)
. 1.10. .. [90].
FeOMnO.
1600
, .
(
),
.
,
( ,
27
)
.
.
(), (,
,
), ()
() , ,
:
= + .
(1.4)
( ),
, :
= + 2 .
(1.5)
, , :
= + 1 .
(1.6)
(1.6) ,
, .
, (1.6) ,
, . ,
.
, ,
() . ,
, , ,
:
= 1.
(1.5)
= + 2 ( + 1).
(1.6) :
= + 1
(1.7)
.
( ,
),
:
= .
28
(1.8)
,
. ,
,
- .
, ,
, , ,
.
, ,
. , , ,
, .
,
,
(
).
,
, ,
. , CaO, CO2 CaCO3,
CaO + CO2 = CaCO3,
, ,
, (
, , ).
, ,
.
, (K = 3)
/ ,
:
1)
(C
0)
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). ,
, ()
, .. ,
. , ,
:
= ( 1) + 1 .
(1.9)
.
,
.
, , ,
. ..,
( ) .
, ,
, .
,
( , ,
).
.
.
30
, 4 ,
1.3.
, ,
, , , ,
, 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)
,
,
.
,
.
,
, .
,
, XX .
, ,
, , .
, , [80],
.
, . 1.11.
PbCuSn ,
( )
(l). ,
, ,
31
, , (
-). ..
, . ,
(PbAgZn PbCuS), 6.
, , ,
, [91], .
( . 1.12 1.13), [92]
. , [93]
( FeAlTiO) inclusion diagram, ..
.
. 1.11.
PbCuSn [80]
32
,
[94], 4, :
( ).
, ,
, [95],
NiCrTiAlO 1600 ( . 1.14).
. 1.13.
AlSiMg
[91]
33
1.6.
,
.
.
. ,
, ,
,
, ,
,
,
.
, ,
, ,
. .
1.
( ,
) .
2.
.
3.
.
4. ,
. .
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]
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
:
n
j1
j1 p1
j1
j1 p1
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]
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
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
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
. 2.12.
CuNiO [99]
51
, CuO, .
, ,
0,47 . % 0,32 . %
1066,50,5.
,
, .
, CuNiO,
,
NiO, Cu2O (. 2.13). ,
CuNiO 10651225.
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
lg a2 v2 lg x2
2,3RT
v2 x13
1 3x2 Q1112
x12 x2
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
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)
(2.9)
K (2.6) aOa Ni .
(2.10)
Cu O Ni 100%,
x
Cu +
Ni 2+
1,
(2.11)
(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
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
.
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 '] )
74
n2 lg a[ R ''] m2 lg a[ X ] lg K 2
a f (C )
[ R ']
[ R ']
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 ']
75
C
C( R ''n X m 2 ) 100%
2
( R 'n1 X m1 )
n1 lg a[ R '] m1 lg a[ X ] lg K1
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[ 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
().
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.
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
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 %) .
. 3.1.9.
( 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
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;
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
. 3.2.2. CuPbO:
) = 1100; ) = 1250
116
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
.
123
3.2.3. CuPbSnZnO
, , ,
, ,
CuRO.
,
, ,
, CuPbSnZnO
-
,
, .
,
0555, 04417, 4-2,5,
LG1, LG2, LG4 ( ), 836, 838, 844, 848,
852, 854, 858
(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.
[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
. :
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)
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=
.
, 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
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
,
, .
140
[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
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
, 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
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
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].
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 .
, -
, .
Cu2SCu2O . 3.4.4 3.4.4
( Cu2O Cu2S Cu2S Cu2O), ,
,
, .
( . . . [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
/,
, .
, 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).
) = 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
. 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
[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
187
1 CuPO3
. %
. %
[P]
[O]
2 (Cu3P)
. %
. %
11,21 0,29
20,57
79,43
[P]
3
. %
[O]
<0,05
[P]
0,31 0,16
[Cu]
. %
0,64
. 3.5.2.
CuPO
188
190
II c CuPO3 III c - .
.
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
. %. ,
(, , .).
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]
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]
. 4.17.
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).
. 4.28. 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
, [445] -
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
. , ,
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
( )
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
-. , 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
[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 . %
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
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AlF3NaF.
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Al2O3, CaO), Cu2OSnO2PbO, NiOCaO.
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1. , .. / .. ,
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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
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
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
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
K a[ ] / a NiO
10318 / T + 5,813
K a[ ] / a NiO
12966 / T + 7,000
K a[ O ] a[ C ] / pCO
5093 / T 1,878
K a[2O ] a[ C ] / pCO2
15433 / T + 2,852
K a[ O ] a[ Ca ] / a CaO
15489 / T + 3,969
K a[ O ] a[ Ca ] / a CaO
19430 / T + 5,350
K a[3O ] a[2Al ]
63924 / T + 21,027
|NiAl2O4|=[Ni]+2[Al]+4[O]
K a[4O ] a[2Al ]
74480 / T + 25,805
K a[2O ] a[ Si ] / a SiO2
33467 / T + 12,338
10
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
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
2
AlCl3 Al 1,5Cl2
19 048 / T + 4,708
6594 / T + 3,236
52 231 / T + 9,739
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
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
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]
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]
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
K K
19
22
2
KAlCl4 K Al 2Cl2
18
17
16
15
. 9.
349
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 a Na p2F2 a NaAlF4
K a5Na p7F2
K a K p0,5
a KF
F
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
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
17 150 / T 8,8
10.
6237 / T + 3,949
K p2F pF2
56 931 / T + 8,195
59 998 / T + 10,191
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
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
K a 3Au a Zn
4602 / T + 9,970
13
K a Au a Zn
2826 / T + 4,345
14
K a Au a 2Zn
5064 / T + 6,786
15
K a Au a
3
Zn
7202 / T + 9,248
16
K a Au a
4
Zn
9140 / T + 11,458
17
K a Au a
7
Zn
15354 / T + 19,728
18
|PbS| = Pb + [S]
19
20
|PbO| = Pb + [O]
K a O
4327 / T + 4,723
21
K a Zn a O
12748 / T + 7,211
22
23
24
25
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 )
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
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
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
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
tt1
6500
tt1
4.468
ncu1 nni1
2
2
2
3 ncu1 nni1 Q1112 ncu1 nni1 ( 2 3 ncu1 ) Q1122 nni13( 1 3ncu1 ) Q1222
2 log ( ncu1 ) 2
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
tt2
63
139
hh2 tt2 0 oo2 log( hh2 )
tt2
9803
tt2
6.365
ncu2 nni2
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
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
6500
t1
4.468
t1i 1348 i 25
j1 0 100
b i
h1i j1 b i 0.01 j1
o1i j1 Fricfac t1i h1i j1
t2 1448
o2 .01
( 3)
h2 10
Given
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
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
t2i 1448 i 25
d i
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
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