, 2009, 51, .

10

,
(Fe, Cr)3 C (Fe, Cr)7 C3
.. , ..
,
,
E-mail: medvedeva@ihim.uran.ru

( 10 2008 .
11 2009 .)
,
(Fe, Cr)3 C, (Fe, Cr)7 C3 .

.
,
.
, ( 52-08-01)
PACS: 71.15.Nc, 71.20.Be, 74.62.Dh, 74.70.Ad

1.


. ,
, , [13].
,
(FeCr)3 C, (CrFe)3 C2 , (CrFe)7 C3 (CrFe)4 C.
Fe3 C,
18 at% .
(Fe, Cr)3 C (Cr, Fe)7 C3 Cr7 C3 .
(632 at%)
, Cr7 C3
. Cr7 C3 ,
Cr3 C (Fe3 C-) [4].
,
: , , [57].

[814],
, FeCrC,
.

,
Cr7 C3 ,
.

, Fe3 C
Fe7 C3 .
Fe3 C (Fe, Cr)3 C Cr3 C Fe7 C3 (Cr, Fe)7 C3 Cr7 C3
Fe3(1x )Cr3x C Fe7(1x )Cr7x C3
x 0 1 .

2.

(PAW) [1516] Vienna ab initio Simulation Package (VASP),

, LAPW
. - [17], 66 6 k-,
(cutoff) 400 eV.

3.
3.1. .
,

(. ),

,

.
(Fe, Cr)3 C. Fe3 C
( Pnma),
Fe (Feg )

1965

.. , ..

1966

(Fe, Cr)3 C,
(Fe, Cr)7 C3

Fe3 C a, b, c, A
Feg
Fes
C

5.058, 6.703, 4.506

0.177, 0.059, 0.343
0.031, 0.25, 0.843
0.873, 0.25, 0.432

5.089, 6.743, 4.523 [14]

0.186, 0.063, 0.328
0.036, 0.25, 0.850
0.890, 0.25, 0.450

Cr3 C a, b, c, A
Crg
Crs
C

5.186, 6.648, 4.507

0.177, 0.060, 0.343
0.031, 0.25, 0.843
0.873, 0.25, 0.433

5.12, 6.80, 4.58 [7]

4.488, 6.968, 11.986

Cr7 C3 a, b, c, A
0.253, 0.067, 0.019
Cr1
0.053, 0.064, 0.811
Cr2
0.249, 0.25, 0.203
Cr3
0.268, 0.25, 0.416
Cr4
0.055, 0.25, 0.627
Cr5
0.036, 0.033, 0.346
C1
0.467, 0.25, 0.564
C2

4.53, 7.01, 12.14 [18]

0.251, 0.066, 0.022
0.057, 0.064, 0.812
0.250, 0.25, 0.206
0.262, 0.25, 0.417
0.058, 0.25, 0.626
0.029, 0.29, 0.343
0.459, 0.25, 0.563

4.507, 6.850, 11.777 4.537, 6.892, 11.913 [19]

Fe7 C3 a, b, c, A
0.251, 0.067, 0.015
0.25, 0.07, 0.02
Fe1
0.064, 0.063, 0.808
0.00, 0.07, 0.81
Fe2
0.294, 0.25, 0.198
0.24, 0.25, 0.20
Fe3
0.270, 0.25, 0.412
0.25, 0.25, 0.42
Fe4
0.083, 0.25, 0.628
0.00, 0.25, 0.63
Fe5
0.037, 0.26, 0.353
0.11, 0.03, 0.35
C1
0.471, 0.25, 0.562
0.38, 0.25, 0.57
C2

(Fes ) , - . a = 5.089, b = 6.743,

[14].
c = 4.523 A
Fes (1.99 A),

Feg (2.02 A),

,
Feg - (2.45 A)
Fes - (2.64 A).

Fe3 C
(. ). Cr3 C

. Cr3 C
2.5%
Fe3 C a.

Feg C Fes C 2.02 1.99 A

2.04 2.02 A .
Feg ,
Fes - (Fe, Cr)3 C.

.
-

,
Feg , [20].
(
)
. , Fe2.75 Cr0.25 C, Fe2.5 Cr0.5 C,
Fe2.25 Cr0.75 C Fe2.0 CrC
0.08, 0.05, 0.03 0.01 eV. Cr3 C
.
(Fe, Cr)7 C3 . Cr7 C3 ( Pnma),
.

.
Cr7 C3 [18].
Cr7 C3 Cr28 C12 ,

(a, b, c) (. ).
(Fe, Cr)7 C3 40-
( Fe7y Cry C3 ,
y = 0, 0.25, 1.25, 5.75, 6.75, 7).
CrC CrCr Cr7 C3
. (Cr, Fe)7 C3
1.91 2.45 A

Fe, Cr7 C3
Fe7 C3 [21]. (Cr, Fe)7 C3
3%.
Fe Cr

Cr7 C3 .
Cr2 0.05, 0.08, 0.14
0.03 eV Cr1, Cr3, Cr4
Cr5 . ,
.
Cr2
(0.26 B ),
0.28 B (Cr3) 1.02 B (Cr4).
Cr Fe
Fe7 C3 . Cr3 ,
0.07, 0.08, 0.05 0.08 eV
Cr1, Cr2, Cr4 Cr5 .
,
. Cr3 0.84 B ,
+0.19 B (Cr4)
0.57 B (Cr1). ,
, 2009, 51, . 10

 , ...

1967

: Fe Cr Cr7 C3
,
, Cr Fe
Fe7 C3
.
3.2. .
(Fe, Cr)3 C (Fe, Cr)7 C3
. 1 2 .
(Fe, Cr)3 C. Fe3 C (. 1) [13, 2227]. 4 eV EF
3d- , 2p-

8 4 eV Fe3dC2p- . EF -

. 2. (Fe, Cr)7 C3 . ,
. .

. 1. (Fe, Cr)3 C. ,
. .
, 2009, 51, . 10

Fe3d- (Fe3d ) Fe3d-
(Fe3d ), N(EF )
1.5 .

Fe3d , Fe3d
(. 1).

,
Fe3d- ( 5 3 eV).

C2p- (A) C2p 3d- (A B) . N(EF )
1.19 (d ) 1.79 (d ) Fe3 C 1.32
Cr3 C, . .
3d -.

1968

(Fe, Cr)7 C3 . Fe7 C3 (. 2),

Fe3 C, , , ( 8
4 eV) C2p-, Fe3d- .
( 4 eV ) 3d-
2p- . ,
Fe3 C, Fe3d- (Fe3d )
Fe3d-
(Fe3d ).
d- ,
Fe3 C- N(EF )
(Fe , Fe )
2 .
Fe7 C3 (Fe, Cr)7 C3 Cr7 C3 .
Fe3 C,
Fe3d -,
Fe3d .
N(EF ) () 2.4 Fe7 C3 (2.41
5.75 states/(eV f. u.) ), 1.9
Fe6.75 Cr0.25 C3 (2.94 5.70 states/(eV f. u.))
Cr7 C3 4.48 states/(eV f. u.).
3.3.
. ,
, .

( )

.
(B /atom Fe)
Fe3 C (Fe, Cr)3 C Cr3 C, Cr7 C3 (Cr, Fe)7 C3 Fe7 C3
. 3. ,
x > 0.8.

. 3. x Fe3(1x) Cr3x C
Fe7(1x) Cr7x C3 .

.. , ..

. 4. x Fe3(1x) Cr3x C
Fe7(1x) Cr7x C3 .

Fe3 C , Fe7 C3 ,

, Fe/C.
3.4. .

,
,
Eform (Fe3y Cry C) = Etot (Fe3y Cry C)


(3 y)Etot (Fe) + yEtot (Cr) + Etot (C) ,
Eform (Fe7y Cry C3 ) = Etot (Fe7y Cry C3 )


(7 y)Etot (Fe) + yEtot (Cr) + 3Etot (C) ,
(Etot (C)) , Etot (Fe) Etot (Cr) -
.
. 4.
(Fe, Cr)3 C. Fe3 C , .
Eform (Fe3 C) = +0.07 eV/atom

(+0.05, +0.08 eV/atom) [28,29], (+0.07, +0.08 eV/atom) [13,27]. Fe3 C , ,
Fe3 CCr
.
Fe3y Cry C y > 0.16. Cr3 C
0.07 eV/atom, 0.13 eV/atom [21].
(Fe, Cr)7 C3 . Cr7 C3
0.098 eV/atom, , 2009, 51, . 10

 , ...

0.12 eV/atom, [10].

(Cr, Fe)7 C3 . Fe7 C3 +0.058 eV/atom,
.

4.
Ab initio ,
, (Fe, Cr)3 C (Cr, Fe)7 C3 .
(a, b, c), Fe Cr Cr Fe. , Fe3 C
, Cr3 C
.
Fe Cr Cr7 C3 Cr Fe Fe7 C3

. Cr7 C3 Cr2
, Fe7 C3
Fe3
. ,

(Fe, Cr)3 C (Fe, Cr)7 C3 . , Fe3 C Fe7 C3
,

, (Cr, Fe)7 C3
,
(Fe, Cr)3 C (Cr, Fe)7 C3 Cr7 C3 .

[1] .. . . , . (1986).
544 .
[2] .. , .. , .. .
. . . (1977). 238 .
[3] . . . , . (1968).
736 .
[4] S.K. Ko, C.W. Won, I.J. Shon. Scripta Mater. 37, 889 (1997).
[5] D.Y. Wang, K.W. Weng, C.L. Chang, W.Y. Ho. Surf. Coat.
Technol. 622, 120 (1999).
[6] S. Matthews. M. Hyland, B. James. Acta Mater. 51, 4267
(2003).
[7] A. Inoue, T. Tasumoto. Scripta Mater. 13, 711 (1979).
[8] A.V. dos Santos, M.I. da Costa, C.A. Kuhnen. J. Magn. Magn.
Mater. 166, 223 (1997).
[9] H. Faraon, Y. Zhang, C. Esling, H. Aourag. J. Appl. Phys. 99,
093508-1 (2007).
[10] C. Jianga. Appl. Phys. Lett. 92, 041 909 (2008).
[11] A.V. dos Santos. Physica B 387, 136 (2007).
[12] D. Music, U. Kreissig, R. Mertens, J.M. Schneider. Phys. Lett.
A 326, 473 (2004).
7

, 2009, 51, . 10

1969

[13] .. , .. , .. . 48,
17 (2006).
[14] E.J. Fasiska, G.A. Jeffry. Acta Cryst. 19, 463 (1965).
[15] P.E. Blochl. Phys. Rev. B 50, 17 953 (1994).
[16] G. Kresse, D. Joubert. Phys. Rev. B 59, 1758 (1999).
[17] J.P. Perdew, J.A. Chevary. Phys. Rev. B 46, 6671 (1992).
[18] .. . . .
, (1987). 207 .
[19] M.A. Rouault, P. Herpin, M.R. Fruchart. Ann. Chim. 5, 461
(1970).
[20] L.D. Teng, X.G. Lu, R.E. Aune, S. Seetharaman. Met. Mater.
Trans. 35A, 3673 (2004).
[21] J.P. Bouchard. Ann. Chim. 2, 353 (1967).
[22] J. Haglund, G. Grimvall. Phys. Rev. B 44, 2914 (1991).
[23] C.W. Chiou, jr., E.A. Carter. Surf. Sci. 12, 87 (2003).
[24] S. Yamamoto, Y. Kobayashi, A. Kirihata. Proc. Fourth
Int. Symp. on the physical metallurgy oh cast iron /
Ed. E. Niyama. Materials Research Society, Pittsburg, PA.
(1990). P. 103.
[25] .. , .. , .. , .. , .. . 18, 21 (1996).
[26] .. , .. , .. .
96, 16 (2003).
[27] I.R. Shein, N.I. Medvedeva, A.L. Ivanovskii. Physica B 371,
126 (2006).
[28] S.V. Meshel, O.J. Kleppa. J. Alloys Comp. 257, 227 (1997).
[29] A.F. Guillermet, G. Grimvall. Phys. Rev. B 40, 10 582 (1989).