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The analytic expressions of the free energy, the mean nearest neighbor distance between two atoms, the elastic moduli such as the Young modulus, the bulk modulus, the rigid[r]
(1)
Review article
Study on Elastic Deformation of Interstitial Alloy FeC with BCC Structure under Pressure
Nguyen Quang Hoc1, Tran Dinh Cuong1, Nguyen Duc Hien2,*
1
Hanoi National University of Education, 136 Xuan Thuy, Cau Giay, Hanoi, Vietnam
2Mac Dinh Chi High School, Chu Pah District, Gia Lai, Vietnam
Received 03 December 2018
Revised 16 January 2019; Accepted 04 March 2019
Abstract: The analytic expressions of the free energy, the mean nearest neighbor distance between
two atoms, the elastic moduli such as the Young modulus E, the bulk modulus K, the rigidity modulus G and the elastic constants C11, C12, C44 for interstitial alloy AB with BCC structure under pressure are derived from the statistical moment method The elastic deformations of main metal A is special case of elastic deformation for interstitial alloy AB The theoretical results are applied to alloy FeC under pressure The numerical results for this alloy are compared with the numerical results for main metal Fe and experiments
Keywords: interstitial alloy, elastic deformation, Young modulus, bulk modulus, rigidity modulus,
elastic constant, Poisson ratio
1 Introduction
Elastic properties of interstitial alloys are specially interested by many theoretical and experimental researchers [1-4, 7-12] For example, in [3] the strengthening effects interstitial carbon solute atoms in (i.e., ferritic or bcc) Fe-C alloys are understood, owning chiefly to the interaction of C with crystalline defects (e.g., dislocations and grain boundaries) to resist plastic deformation via dislocation glide High-strength steels developed in current energy and infrastructure applications include alloys where in the bcc Fe matrix is thermodynamically supersaturated in carbon In [4], structural, elastic and thermal properties of cementite (Fe3C) were studied using a Modified Embedded
Atom Method (MEAM) potential for iron-carbon (Fe-C) alloys The predictions of this potential are in good agreement with first-principles calculations and experiments In [7], the thermodynamic
Corresponding author
E-mail address: n.duchien@gmail.com
(2)properties of binary interstitial alloy with bcc structure are considered by the statistical moment method (SMM) The analytic expressions of the elastic moduli for anharmonic fcc and bcc crystals are also obtained by the SMM and the numerical calculation results are carried out for metals Al, Ag, Fe, W and Nb in [12]
In this paper, we build the theory of elastic deformation for interstitial AB with body-centered cubic (BCC) structure under pressure by the SMM [5-7] The theoretical results are applied to alloy FeCunder pressure
2 Content of research
2.1 Analytic results
In interstitial alloy AB with BCC structure, the cohesive energy of the atom B (in face centers of cubic unit cell) with the atoms A (in body center and peaks of cubic unit cell) in the approximation of three coordination spheres with the center B and the radii r r1, 1 2,r1 5 is determined by [5-7]
0 1
1
( ) ( ) ( 2) ( 5),
i
n
B AB i AB AB AB
i
u r r r r
(2.1)
where AB is the interaction potential between the atom A and the atom B, ni is the number of
atoms on the ith coordination sphere with the radius r ii( 1, 2,3),
1
1 1B 01B 0A( )
r r r y T is the nearest
neighbor distance between the interstitial atom B and the metallic atom A at temperature T, r01Bis the nearest neighbor distance between the interstitial atom C and the metallic atom A at 0K and is determined from the minimum condition of the cohesive energyu0 B,
1
0A( )
y T is the displacement of the atom A1 (the atom A stays in the body center of cubic unit cell) from equilibrium position at
temperature T The alloy’s parameters for the atom B in the approximation of three coordination spheres have the form [5-7]
2
(2) (1) (1)
1 1
2
1
1 16
( ) ( 2) ( 5),
2 5
AB
B AB AB AB
i i eq
k r r r
u r r
42
(3) (2) (1)
2
1 1
1
(3)
(2) (1) (4) (3)
1 1
2
1
6 48
1
( ) ( ) ( )
4
2 5
5
( )
8
1
( ) ( ) ( ) ( )
8 25 25
AB i i i eq
B AB AB AB AB
AB AB AB AB
u u r r r r r r r r
r r r r
r r r
(2) (1)
1
2
1
5
5
2
( ) ( ),
25r AB r 25r AB r (2.2)
4 ,
B B B
4
(4) (2)
1
1
(1) (4) (3)
1 1
3
1
1 48
1
( )
24
2
2 ( 2) ( 5),
16 150 125
AB i i eq
B AB AB
AB AB AB
u r r r
r r r
r r
(3)where AB( )m mAB( ) /ri rim(m1, 2,3, 4, , x y z, , and ui is the displacement of the
ith atom in the direction
The cohesive energy of the atom A1 (which contains the interstitial atom B on the first
coordination sphere) with the atoms in crystalline lattice and the corresponding alloy’s parameters in the approximation of three coordination spheres with the center A1 is determined by [5-7]
1
0A 0A AB 1A ,
u u r
1 1 1 2 (2) (1) 1 , i A AB
A A A
i eq A
AB A AB A
r r
k k
u k r r r
1 11 ,
A A A
1
1
1 1
1
4
1
1
(4) (2) (1)
1 1
1 48 1 8 1 ( ) ( ) ( ), 24 i A AB
A A A
i eq A A
AB A AB A AB A
r r
u r r r r r
1
1
1 1
4
2 2
1
(3) (2) (1)
2 2
1 1
6 48
1 3
( ) ( ) ( )
2 4
i
AB
A i i eq
A
A A AB A AB A AB A
A A A
r r
u u r r r r r r (2.3)
where is the nearest neighbor distance between the atom A1 and atoms in crystalline lattice
The cohesive energy of the atom A2 (which contains the interstitial atom B on the first
coordination sphere) with the atoms in crystalline lattice and the corresponding alloy’s parameters in the approximation of three coordination spheres with the center A2 is determined by [5-7]
2
0A 0A AB 1A ,
u u r
2 2
2 2 (2) (1) 1 1 , 4 2 i A AB A A i eq
A AB A AB A
A r r
k k
u k r r r
2 2 ,
A A A
2 2
2
2
2
4
1
(4) (3) 1 (2) (1) 1 1 48 1 ( ) ( ) 24 1 ( ) ( ), 8 i A AB
A A A
i eq
AB A AB A
A r r
AB A AB A
A A
u r r r
r r r r 2 (4)
2 2 2
6 48 ( ) i A AB
A A AB A
i i eq
A r r
r u u
2 2
2 2
2
1
(3) (2) (1)
1
1 3 ( ) ( ) ( ), 8 A A
AB A AB A AB A
A
(4)where is the nearest neighbor distance between the atom A2 and atoms in crystalline lattice at 0K
and is determined from the minimum condition of the cohesive energy
2
0A , 0B( )
u y T is the displacement of the atom C at temperature T
In Eqs (2.3) and (2.4),u0A,kA, 1A, 2A are the coressponding quantities in clean metal A in the approximation of two coordination sphere [5-7]
The equation of state for interstitial alloy AB with BCC structure at temperature T and pressure P is written in the form
0
1
1
cth
6
u k
Pv r x x
r k r
(2.5)
where
3 3
r
v is the unit cell volume per atom, r1 is the nearest neighbor distance, θ k T Bo ,
Bo
k is the Boltzmann constant,
2
k ω
x
θ m θ
, m is the atomic mass and ω is the vibrational frequencies of atoms At temperature T 0 K, Eq (2.5) will be simply reduced to
0
1
1
6
u k
Pv r
r k r
(2.6)
Note that Eq.(2.5) permits us to find r1 at temperature T under the condition that the quantities k, x,
u0 at temperature T0 (for example T0 = 0K) are known If the temperature T0 is not far from T, then one
can see that the vibration of an atom around a new equilibrium position (corresponding to T0) is
harmonic Eq.(2.5) only is a good equation of state in that condition Eq (2.6) also is the equation of state in the case of T0 = 0K In Eq (2.6), the first term is the change of energy potential of atoms in
euilibrium position and the second term is the change of energy of zeroth vibration If knowing the form of interaction potential i0,eq (2.6) permits us to determine the nearest neighbor distance
1X , 0 , , 1,
r P X B A A A at K and pressure P After knowing , we can determine alloy parametrs kX( , 0),P 1X( , 0),P 2X( , 0),P X( , 0),P X(P, 0) at 0K and pressure P After that, we
can calculate the displacements [5-7]
2
0
2 ( , 0)
( , ) ( , )
3 ( , 0) ,
X
X X
X
P
y P T A P T
k P
1
2
5
2
2
2 3
,
2
3
4
1
, , , ,
2
13 47 23 25 121 50 16
,
3 6 3
43 93 169 83 22
,
3 3
X X
X X
X
X
i
X
X iX X X X
i
Y Y Y Y Y Y Y
X X X X X X X X X
Y Y Y Y Y
X X X X X
Y
A a a k m x a
k
a a
a
2
5
103 749 363 733 148 53
,
3 Y Y Y Y Y 2Y
X X X X X X X
a
(5),
561 1489 927 733 145 31
65 coth
2 Y X X Y Y 3Y 2Y Y
X X Y Y X X X X X X X
a x x (2.7)
From that, we derive the nearest neighbor distance r1X P T, at temperature T and pressure P
1
1B( , ) 1B( , 0) A ( , ), 1A( , ) 1A( , 0) A( , ),
r P T r P y P T r P T r P y P T
1 2
1A( , ) 1B( , ), 1A ( , ) 1A ( , 0) y ( , ).B
r P T r P T r P T r P P T (2.8)
Then, we calculate the mean nearest neighbor distance in interstitial alloy AB by the expressions as follows [5-7]
1A , 1A , , ,
r P T r P y P T
r1A( , 0)P 1 cBr1A( , 0)P c rB 1A( , 0),P r1A( , 0)P 3r1B( , 0),P (2.9) where r1A( , )P T is the mean nearest neighbor distance between atoms A in interstitial alloy AB at pressure P and temperature T, r1A( , 0)P is the mean nearest neighbor distance between atoms A in interstitial alloy AB at pressure P and 0K, r1A( , 0)P is the nearest neighbor distance between atoms A in clean metal A at pressure P and 0K, r1A( , 0)P is the nearest neighbor distance between atoms A in the zone containing the interstitial atom B at pressure P and 0K and cB is the concentration of
interstitial atoms B
The free energy of alloy AB with BCC structure and the condition cB cA has the form
1 ,
AB cB A cB B cB A cB A TSc
2
2
0 2
2
3
2
X X
X X X X X
X
X N
u N X
k
3
2
2 1
4
2
1 2 1 ,
3 2
X X
X X X X X X
X
X X
X X
k
2
0 ln(1 ) , coth ,
X
x
X N xX e XX xX xX
(2.10)
where X is the free energy of atom X, AB is the free energy of interstitial alloy AB, Sc is the
configuration entropy of interstitial alloy AB
The Young modulus of alloy AB with BCC structure at temperature T and pressure P is determined by
1
2
2
2 2
2
2
2
, , ,
A A
B
AB B A B B
A
E c P T E c c
1 1
, A
A A
E
r A
2
1
2
1 1 ,
2
A A
A A
A A
X
A X
(6)2
2
2
01
2 2
1 1
1
4
2
X
X X X X
X
X X X X X
u k k
r
r k r k r
01
1
1
2 ,
2 2
X X
X X X
X X X
u k
cthx r
r k r
(2.11)
where is the relative deformation
The bulk modulus of BCC alloy AB with BCC structure at temperature T and pressure P has the form
, , , ,
3(1 )
AB B AB B
AB
E c P T
K c P T
(2.12)
The rigidity modulus of alloy AB with BCC structure at temperature T and pressure P has the form
, ,
, ,
2
AB B AB B
AB
E c P T
G c P T (2.13)
The elastic constants of alloy AB with BCC structure at temperature T and pressure P has the form
11
, ,
, , ,
1
AB B AB
AB B
AB AB E c P T
C c P T
(2.14)
12
, ,
, , ,
1
AB B AB AB B
AB AB
E c P T
C c P T
(2.15)
(2.16) The Poisson ratio of alloy AB with BCC structure has the form
,
AB cA A cB B A
(2.17)
where A and B respectively are the Poisson ratioes of materials A and B and are determined
from the experimental data
When the concentration of interstitial atom B is equal to zero, the obtained results for alloy AB become the coresponding results for main metal A
2.2 Numerical results for alloy FeC
For pure metal Fe, we use the m – n potential as follows
0
( ) ,
n m
r r
D
r m n
n m r r
where the m – n potential parameters between atoms Fe-Fe are shown in Table For alloy FeC, we use the Finnis-Sinclair potential as follows
44
, ,
, ,
2
AB B AB B
AB
E c P T
C c P T
(7)
1 ,
2
ij ij
i j i j
U A r r
2 3
1 1
( )r t r R t r R r R ,
2 2
2
( )r r R k k r k r r R
(2.19)
where the Finnis-Sinclair potential parameters between atoms Fe-C are shown in Table
Our numerical results are summarized in tables and illustrated in figures Our calculated results for Young modulus E of alloy FeC in Table 3, Table 4, Fig.5 and Fig.6 are in good agreement with experiments [10]
Table The m-n potential parameters between atoms Fe-Fe [8] Interaction m n D eV
o A
r
Fe – Fe 7.0 11.5 0.4 2.4775
Table The Finnis-Sinclair potential parameters between atoms Fe-C [9] A
eV
R1
o
A
t1
2 o
A
t2
3 o
A
R2
o
A
k1
2 o
eV A
k2
o 3
A eV
k3
4 o eV A
2.958787 2.545937 10.024001 1.638980 2.468801 8.972488 -4.086410 1.483233 Table The dependence of Young modulus E(1010Pa) for alloy FeC with c
C = 0.2% from the SMM and alloy FeC with cC0.3% from EXPT[10] at zero pressure
T(K) 73 144 200 294 422 533 589 644 700 811 866
SMM 22.59 22.03 21.58 20.75 19.49 18.28 17.65 16.96 16.26 14.81 14.06 EXPT 21.65 21.24 20,82 20.34 19.51 18.82 18.41 17.58 16.69 14.07 12.41
Table The dependence of Young modulus E(1010Pa) for alloy FeC with c
C = 0.4% from the SMM and alloy FeC with cC0.3% from EXPT[10] at zero pressure
T(K) 73 144 200 294 422 533 589 644 700 811 866 922
SMM 22.46 21.90 21.45 20.62 19.38 18.18 17.53 16.87 16.17 14.72 13.98 13.21 EXPT 21.51 21.10 20.68 20.20 19.37 18.62 18.27 17.44 16.55 13.93 12.34 10.62
(8)Fig C11, C12, C44 (cC) for FeC at P = Fig C11, C12, C44 (T) for FeC at P =
Fig E(T) for alloy FeC with cC = 0.2% from the SMM and alloy FeC with cC0.3% from EXPT
[17]
Fig E(T) for alloy FeC with cC = 0.4% from the SMM and alloy FeC with cC0.3% from
EXPT[17]
Fig Fig.7 E(P), G(P), K(P) for alloy FeC with cC = 1% at T = 300K
(9)Fig C11(P), C12(P), C44(P) for alloy FeC with cC = 3% at T = 300K
Fig 10 C11(cC), C12(cC), C44(cC) for alloy FeC at P = 10 GPa at T = 300K
For alloy FeC at the same temperature and pressure when the concentration of interstitial atoms increases, the elastic moduli E, G, K and the elastic constants C11, C12, C44 decrease For example, for
FeC at T = 1000K , P = when cC increases from to 5%, E decreases from 12.28.1010 to 10.39.1010
Pa, G decreases from 4.87.1010 to 4.12.1010 Pa, K decreases from 8.53.1010 to 7.21.1010Pa, C 11
decreases from 15.02.1010 to 12.71.1010 Pa, C
12 decreases from 5.28.1010 to 4.46.1010 Pa and C44
decreases from 4.87.1010 to 4.12.1010 Pa
For alloy FeC at the same pressrure and concentration of interstitial atoms when temperature increases, the elastic moduli E, G, K and the elastic constants C11, C12, C44 also decrease For example,
for FeC at cC = 5%, P = when T increases from 100 to 1000K, E decreases from 19.39.1010 to
10.39.1010 Pa, G decreases from 7.69.1010 to 4.12.1010 Pa, K decreases from 13.47.1010 to
7.21.1010Pa, C
11 decreases from 23.72.1010 to 12.71.1010 Pa, C12 decreases from 8.33.1010 to 4.46.1010
Pa and C44 decreases from 7.69.1010 to 4.12.1010 Pa
For alloy FeC at the same temperature and concentration of interstitial atoms when pressure increases, the elastic moduli E, G, K and the elastic constants C11, C12, C44 increase For example, for
FeC at cC = 5%, T = 300K when P increases from 10 to 70 GPa, E increases 22.27.1010 to 46.36.1010
Pa, G increases 8.84.1010 to 18.40.1010 Pa, K increases 15.46.1010 to 32.20.1010 Pa, C
11 increases
27.24.1010 to 56.73.1010 Pa, C
12 increases 9.57.1010 to 19.93.1010 Pa and C44 increases 8.84.1010 to
18.40.1010 Pa
For main metal Fe in alloy FeC at T = 300 K, our calculated results of elastic moduli and elastic constantsare in good agreement with experiments in Tables 5-7
Table The elastic moduli E, G, K (10-10Pa) and elastic constants C
11, C12, C44(1011Pa) according to the SMM and EXPT[11] for Fe at P = and T = 300 K
E G K C11 C12 C44
SMM 20.82 8.26 14.46 2.55 0.90 0.83
(10)Table The shear modulus G (GPa) according to the SMM, EXPT [13] and CAL [14] for Fe at T = 300 K and P = 0, 9.8 GPa
P (GPa) SMM EXPT [13] CAL [14]
0 82.6 84 100
9.8 101.6 101 120
Table Isothermal elastic modulus for Fe at P = and T = 300K according to the SMM, CAL[16] and EXPT [15]
Method SMM EXPT[150] CAL[16]
[GPa]
T
B 170.09 168 281
3 Conclusion
The analytic expressions of the free energy, the mean nearest neighbor distance between two atoms, the elastic moduli such as the Young modulus, the bulk modulus, the rigidity modulus and the elastic constants depending on temperature, concentration of interstitial atoms for interstitial alloy AB with BCC structure under pressure are derived by the SMM The numerical results for alloy FeC are in good agreement with the numerical results for main metal Fe The numerical results for alloy FeC with
cC = 0.2% and cC = 0.4% at zero pressure are in good agreement with experiments The
temperature changes from 73K to 1000K and the concentration of interstitial atoms C changes from to 5%
References
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[4] L S I Liyanage, S-G Kim, J Houze, S Kim, M A Tschopp, M I Baskes, M F Horstemeyer, Structural, elastic, and thermal properties of cementite Fe2C calculated using a modified embedded atom method, Phys Rev B89 (2014) 094102 https://doi.org/10.1103/PhysRevB.89.094102
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APPENDIX
The Hamiltonian of atom X can be written in the form
0
ˆ ˆ ˆ
X X X X
H H α V (A1)
where αX is the parameter and proceeding from the condition of normalization for the statistical operator, it is easy to find the expression
( )
ˆ X
X X
X α
X
ψ α V
α
(A2)
where X
α
expresses the averaging over the equilibrium ensemble with the Hamiltonian HˆX
and ψ αX( X) is the free energy
Expression (A2) gives the general formula
0
0 ˆ
( )
X
X
X X X VX d X (A3)
in which ψ0 X is the free energy of atom X corresponding to the Hamiltonian H0 X For many cases
X
X α
V can be written through the moments and thus we can determine it with the aid of the momentum formula Therefore, using (A3) the free energy ψ αX( X) can be found
In the approximation up to fourth order the average potential energy is equal to
2
2
0 3
2
X
X X X X X X X
k
U U N u γ u γ u
(A4)
where 0 0
2
X X
N
U u , kX,γ1X, γ2X are the crystal parameters, u2X and u4X have been derived by using statistical moment method in [6]
(12)2
2
2
2
0
,
X X
γ γ
X X X X
u dγ u dγ
(A5)
By combining the equations (A3), (A4) and (A5) we have
2
0 2
2
3 ln(1 ) 3 1
2 3 2
X
x X X
X X X X X
X
X N
u N x e N X
k
3
2
2 1
4
2 4
1 2 2 1 1
3 2 2
X X
X X X X X X
X
X X
X X
k
(A6)
Thus free energy of interstitial alloy AB per atom with BCC structure can be simply given by
1
1
( )
1
A A
AB A B
B B B B c
B B B B
A B A A c
ψ ψ
ψ ψ ψ
N N N N N TS
N N N N N
N N N N
ψ ψ ψ ψ TS
N N N N
1 7 2 4 , B,
B A B B B A B A c B
N c ψ c ψ c ψ c ψ TS c
N
(7) where cB is the concentration of interstitial atom B, N is the number of atoms in crystal, NB is is
the number of atoms in crystal and Sc is the configuration entropy In crystal, there are NB atoms B,
https://doi.org/10.1103/PhysRevLett.98.215501. https://doi.org/10.1103/PhysRevB.89.094102 http://www.engineeringtoolbox.com/young-modulus-d_773.htm/ https://doi.org/10.1016/S0927-0256(98)00117-7. https://doi.org/10.1103/PhysRevLett.85.3209 https://doi.org/10.1103/PhysRevB.74.214111/. https://doi.org/10.1103/PhysRevB.59.8526 https://doi.org/10.1103/PhysRevB.54.4519