O24-Thermodynamic study of the Nb-Ru-Al systemtofa2010/Apresentacoes... · Thermodynamic study of...

Thermodynamic study of the Nb-Ru-Al system

a Fiorani J. M., a David N., b,c Coelho G., b Nunes C., a Vilasi M.

a Institut Jean Lamour, Université Nancy 1, FRANCE

b Departamento de Engenharia de Materiais − EEL- Universidade de São Paulo – Lorena-SP, BRASIL

c Centro Universitário de Volta Redonda (UniFoa), Volta Redonda-RJ, BRASIL

Thermodynamic study of the Nb-Ru-Al system Introduction

Context of this study

Nb alloys are potential candidates for ultra-high temperature structural applications.

Alloying additions and protective coatings are necessary in order to increase their oxydation and corroson resistance

→ HTSMAs→ SME + MT(above 800°C)NbRu

Nb-Ru-Al-……

CALPHAD

1

Thermodynamic study of the Nb-Ru-Al system Introduction

Context of this study

Nb alloys are potential candidates for ultra-high temperature structural applications.

Alloying additions and protective coatings are necessary in order to increase their oxydation and corroson resistance

→ HTSMAs→ SME + MT(above 800°C)NbRu

Nb-Ru-Al-……

CALPHAD

Outline

Nb-Ru

Ru-Al

Nb-Al

Nb-Ru-Al

Conclusion

1


Nb-Ru system

Nb-Ru

Nb-Ru system

T. B. MASSALSKI, “Binary Alloy Phase Diagrams” second edition, ASM International (1990)

Thermodynamic study of the Nb-Ru-Al system Nb-Ru

2



Ideal Stoechiometry → x(Ru) = 0.625

2



Ideal Stoechiometry → x(Ru) = 0.625

Observed at x(Ru) ∼ 0.66

Ru2Nb

2


Phase diagram data from powder metallurgy synthesis and XRD + EPMA

3



52.5 58.4 65.3 67.5 77.3 86.0

B2B2+

Ru2NbRu2Nb

Ru2Nb+

A3A3

x(Ru) %

1200 °C500 h

1 2 3 4annealed

3

67.6 77.4 80.0

Ru2NbRu2Nb

+A3

A3

x(Ru) %

1350 °C360 h

1 2



52.5 58.4 65.3 67.5 77.3 86.0

B2B2+

Ru2NbRu2Nb

Ru2Nb+

A3A3

x(Ru) %

1200 °C500 h

1 2 3 4

67.6 77.4 80.0 x(Ru) %

annealed

3

T = 1350 °Ct = 48 h


Diffusion couple → 20 µm of Ru deposited by PVD on a Nb substrate

annealed

4

80

100

120

Mol

ar F

ract

ion

Nb

A3Ru2Nb

B2

T = 1350 °Ct = 48 h



annealed

0

20

40

60

0 10 20 30 40 50 60

Mol

ar F

ract

ion

Ru

Distance (micrometer)

4

80

100

120

Mol

ar F

ract

ion

Nb

A3Ru2Nb

B2 A2

T = 1350 °Ct = 48 h



annealed

0

20

40

60

0 10 20 30 40 50 60

Mol

ar F

ract

ion

Ru

Distance (micrometer)

← x(Ru) ∼ 20%

4

L

A2

A1B2

NbRu


NbRu2

5

L

A2

A1B2

NbRu


NbRu2

[Mas90] → T. B. MASSALSKI, “Binary Alloy Phase Diagrams”, second edition, ASM International (1990)5

Enthalpies of formation (not considered in the present optimization)


[Cur2005] → S. Curtarolo, D. Morgan, G. Ceder, CALPHAD, 29, (2005)

[Gho2007] → G. Ghosh, G.B. Olson, Acta Mater. 55 (2007)

6

Enthalpies of formation (not considered in the present optimization)




[Ben2009] → My.Y. Benarchid, N. David, J-M. Fiorani, M. Vilasi, T. Benlaharche, Thermochimica Acta 482 (2009)6

Enthalpies of formation (not considered in the present optimisation)




[Ben2009] → My.Y. Benarchid, N. David, J-M. Fiorani, M. Vilasi, T. Benlaharche, Thermochimica Acta 482 (2009)6

Liquid

(Nb,Ru)

A3

(Nb,Ru)

A2(Nb,Ru)


Thermodynamic models

ϕϕϕϕ GGGG ex

id

re

f++=

( )..

.

)x(xL)x(xLLxx

) )(xx)(x(xRT

GxGxG

BAA,

B

BAA,

B

A,

B

BA

BBAA

BBAA

+−+−++

++

+=

2210

ln

ln ϕϕϕ

ϕϕϕ

TbaL i,

j

νi

,j

νi

,j

ν ϕϕϕ +=Binary Parameters

7

Li

qN

b,

Ru

L0 - 133800

Li

qN

b,

Ru

L1 - 12970

Liquid

(Nb,Ru)

30 AN

b,

Ru

L - 80655 – 20.181 T

31 AN

b,

Ru

L - 25779

A3

(Nb,Ru)

20 AN

b,

Ru

L - 85598 – 19.681 TA2

(Nb,Ru)

2

3

2


Thermodynamic models

ϕϕϕϕ GGGG ex

id

re

f++=

( )..

.

)x(xL)x(xLLxx

) )(xx)(x(xRT

GxGxG

BAA,

B

BAA,

B

A,

B

BA

BBAA

BBAA

+−+−++

++

+=

2210

ln

ln ϕϕϕ

ϕϕϕ

TbaL i,

j

νi

,j

νi

,j

ν ϕϕϕ +=Binary Parameters

7

B2

(Nb,Ru) (Nb,Ru)


(A,B) (A,B)

'Ay '

By ''Ay

(A, B)

''By A

''A

'A xyy ==

B'

'B'B xyy ==

''A

'A yy ≠

''B

'B yy ≠

B2 A2


''B

'B yy ≠

8

22/B

AGGor

d∆

Gdi

sGib

bs E

nerg

y

Mole fractionA B

(A,B) (A,B)

'Ay '

By ''Ay

(A, B)

''By A

''A

'A xyy ==

B'

'B'B xyy ==

''A

'A yy ≠

''B

'B yy ≠

B2 A2

Thermodynamic study of the Nb-Ru-Al system Nb-RuS

ite fr

actio

n

Mole fractionA B

'Ay

'By

''Ay

''By

''B

'B yy ≠

)x

)

(yG(y

)

G((x)

GG BBA/B

A =−+= 22222

Gor

d∆Gd

is

ΔG

GG or

d

di

s

/B

A +=22

Compound Energy Formalism

orddis dis8

( ) ( )[ ]

..

..

.

L)y(yyyyL)y(yyyyLy)y(yyyLy)y(yyy

LyyyLyyyLyyyLyyy

GyyGyyGyyGyy

)(yy)(yyb)(yy)(yyaRT

G

A:

A,

B

''B

''A

''B

''A

'AB

:A

,B

''B

''A

''B

''A

'B

A,

B:

A

''A

'B

'A

'B

'AA

,B

:B

''B

'B

'A

'B

'A

A:

A,

B

''B

''A

'AB

:A

,B

''B

''A

'B

A,

B:

A

''A

'B

'AA

,B

:B

''B

'B

'A

B:

A

''A

'BA

:B

''B

'AB

:B

''B

'BA

:A

''A

'A

''B

''B

''A

''A

'B

'B

'A

'A

+−+−+

−+−+

++

++

++++

+++=

ϕϕ

ϕϕ

ϕϕ

ϕϕ

ϕϕϕϕ

ϕ

11

11

00

00

ln

ln

ln

ln

ϕGid←←←←

ϕGre

f←←←←

ϕGex←←←←


..

..

.

+

9

( ) ( )[ ]

..

..

.

L)y(yyyyL)y(yyyyLy)y(yyyLy)y(yyy

LyyyLyyyLyyyLyyy

GyyGyyGyyGyy

)(yy)(yyb)(yy)(yyaRT

G

A:

A,

B

''B

''A

''B

''A

'AB

:A

,B

''B

''A

''B

''A

'B

A,

B:

A

''A

'B

'A

'B

'AA

,B

:B

''B

'B

'A

'B

'A

A:

A,

B

''B

''A

'AB

:A

,B

''B

''A

'B

A,

B:

A

''A

'B

'AA

,B

:B

''B

'B

'A

B:

A

''A

'BA

:B

''B

'AB

:B

''B

'BA

:A

''A

'A

''B

''B

''A

''A

'B

'B

'A

'A

+−+−+

−+−+

++

++

++++

+++=

ϕϕ

ϕϕ

ϕϕ

ϕϕ

ϕϕϕϕ

ϕ

11

11

00

00

ln

ln

ln

ln

ϕGid←←←←

ϕGre

f←←←←

ϕGex←←←←


..

..

.

+

22 BB

:A

BA

:B

GG =

2020 BA

:A

,B

BA

,B

:A

LL =2020 B

B:

A,

B

BA

,B

:B

LL =2121 B

A:

A,

B

BA

,B

:A

LL =

2121 BB

:A

,B

BA

,B

:B

LL =

Constraints

9

B2

(Nb,Ru) (Nb,Ru)

22 BR

u:

Nb

BN

b:

Ru

GG = - 14037 + 0.88 T

2121 BR

u:

Nb

,R

u

BN

b,

Ru

:R

u

LL = - 11291

2020 BN

b:

Nb

,R

u

BN

b,

Ru

:N

b

LL = 14037 - 0.88 T

2020 BR

u:

Nb

,R

u

BN

b,

Ru

:R

u

LL = 14037 - 0.88 T3


10

NbRu2

(Nb,Ru)0.375 (Ru)0.625

(A,B) (A,B)


(A,B)0.375 (A,B)0.625

11

NbRu2

(Nb,Ru)0.375 (Ru)0.625

(A,B) (A,B)


(A,B)0.375 (A,B)0.625

'Ay '

By

0=''Ay

1=''By

( )[ ]

ϕ

ϕϕ

ϕ

A,

B:

B

'B

'A

A:

B

'AB

:B

'B

'B

'B

'A

'A

LyyGyGy

)(yy)(yyaRT

G

0

ln

ln

+

++

+=

11

NbRu2

(Nb,Ru)0.375 (Ru)0.625

2Nb

Ru

Nb

:R

u

G - 17140 – 7.4 T

20 Nb

Ru

Nb

,R

u:

Ru

L - 51044 + 1.08 T

2Nb

Ru

Ru

:R

u

G 40000

(A,B) (A,B)

5


(A,B)0.375 (A,B)0.625

'Ay '

By

0=''Ay

1=''By

( )[ ]

ϕ

ϕϕ

ϕ

A,

B:

B

'B

'A

A:

B

'AB

:B

'B

'B

'B

'A

'A

LyyGyGy

)(yy)(yyaRT

G

0

ln

ln

+

++

+=

11

Li

qN

b,

Ru

L0 - 133800

Li

qN

b,

Ru

L1 - 12970

Liquid

(Nb,Ru)

30 AN

b,

Ru

L - 80655 – 20.181 T

31 AN

b,

Ru

L - 25779

A3

(Nb,Ru)

20 AN

b,

Ru

L - 85598 – 19.681 TA2

(Nb,Ru)

2

3

2


NbRu2

(Nb,Ru)0.375 (Ru)0.625

2Nb

Ru

Nb

:R

u

G - 17140 – 7.4 T

20 Nb

Ru

Nb

,R

u:

Ru

L - 51044 + 1.08 T

2Nb

Ru

Ru

:R

u

G 40000

B2

(Nb,Ru) (Nb,Ru)

22 BR

u:

Nb

BN

b:

Ru

GG = - 14037 + 0.88 T

2121 BR

u:

Nb

,R

u

BN

b,

Ru

:R

u

LL = - 11291

2020 BN

b:

Nb

,R

u

BN

b,

Ru

:N

b

LL = 14037 - 0.88 T

2020 BR

u:

Nb

,R

u

BN

b,

Ru

:R

u

LL = 14037 - 0.88 T3

5

15

12


Ru-Al system

Ru-Al

Ru-Al system

[Pri2003 ] → S.N. Prins, L.A. Cornish, W.E. Stumpf,B. Sundman, Calphad 2003, 27(1) (2003)

Thermodynamic study of the Nb-Ru-Al system Ru-Al

13

[Pri2003 ] → S.N. Prins, L.A. Cornish, W.E. Stumpf,B. Sundman, Calphad 2003, 27(1) (2003)


[Müc2005 ] → F. Mücklich, N. Ilic, Intermetallics 13 (2005)

13

Tem

pera

ture

(K

)

[This work][Müc2005 ] → F. Mücklich, N. Ilic, Intermetallics 13 (2005)


Mole fraction Ru

Tem

pera

ture

(K

)

14


[Müc2005 ] → F. Mücklich, N. Ilic, Intermetallics 13 (2005)15

Enthalpies of formation → B2


[Jun92] → W. G. Jung, O. J. Kleppa, Met. Trans. B, 23B, (1992)

[Su2005] → H. N. Su, P. Nash, J. of Alloys and Compounds, 403, (2005)

[Lin92] → W. Lin, J. Xu, A. J. Frreeman, J. Mat. Res., 7, (1992)

[Ngu99] → D. Nguyen-Manh, D. G. Petitfor, Intermetallics, 7, (1999)

[Gar2003] → P. Gargano, H. Mosca, G. Bozzolo, R. D. Noebe, Scripta Materialia, 48, (2003)16

Li

qR

u,

Al

L0 - 106693 – 2.762 T

Li

qR

u,

Al

L1 - 16488 – 19.662 T

Liquid

(Ru,Al)

30 AR

u,

Al

L - 163141 + 28 T

31 AR

u,

Al

L - 46065

A3

(Ru,Al)

10 AR

u,

Al

L - 10000A1

(Ru,Al)

4

3

1


20 AR

u,

Al

L - 169171 + 34 TA2

(Ru,Al)

B2

(Ru,Al) (Ru,Al)

22 BR

u:

Al

BA

l:

Ru

GG = - 37529

2121 BR

u:

Al

,R

u

BA

l,

Ru

:R

u

LL = - 1514

2020 BR

u:

Al

,R

u

BA

l,

Ru

:R

u

LL = 37529 - 1514

2020 BA

l:

Al

,R

u

BA

l,

Ru

:A

l

LL = 37529 - 27136

2121 BA

l:

Al

,R

u

BA

l,

Ru

:A

l

LL = 27136

2

3

13

17

6Ru

Al

Al

:R

u

G - 33082 + 4.492 TRuAl6

(Al)0.833(Ru)0.167

13

4Al

RuAl

:R

u

G - 43032 + 3.086 TRu4Al13

(Al)0.765(Ru)0.235

52Al

RuAl

:R

u

G - 40790 – 0.982 TRu2Al5

(Al)0.714(Ru)0.286

RuAl2

10


2Ru

Al

Al

:R

u

G - 46534 + 0.058 TRuAl2

(Al)0.667(Ru)0.333

32Al

RuAl

:R

u

G - 49810 + 0.981 TRu2Al3

(Al)0.6(Ru)0.4

bBaAA

:B

SE

RB

SE

RA

bBaA GGba

aGba

aG +

+

+

+

=

18


Nb-Al system

Nb-Al

Nb-Al system


Thermodynamic study of the Nb-Ru-Al system Nb-Al

19

Liq (Al,Nb)

A1 (Al,Nb)

A2 (Al,Nb)

AlNb3 (Al,Nb)0.75(Nb)0.25

[Sau98 ] → N. Saunders in COST 507-(1998)

Tem

pera

ture

(K

)Thermodynamic study of the Nb-Ru-Al system Nb-Al

(Al)8(Nb)4(Al,Nb)18σ

Al3Nb (Al)0.75(Nb)0.25

Mole fraction Al

Tem

pera

ture

(K

)

20


Nb-Ru-Al system

Nb-Ru-Al

Nb-Ru-Al system

[Cer93 ] → P. Cerba, M. Vilasi, B. Malaman, J. SteinmetzJ. of Alloys and Compounds, 201(1-2), (1993)

Thermodynamic study of the Nb-Ru-Al system Nb-Ru-Al

T = 1100 °C

21



T = 1100 °C

[Hoh2002] → J. Hohls, P.J. Hill, I.M. WolffMat. Sci. and Eng. A329–331, (2002)T = 1200 °C

21


Phase diagram data from powder metallurgy synthesis T = 1100 °C t = 1000 h



T = 1100 °C

T = 1200 °C

A3

B2 B2

L21

T = 1100 °C

21

[Hoh2002] → J. Hohls, P.J. Hill, I.M. WolffMat. Sci. and Eng. A329–331, (2002)


Isothermal sectionT = 1100 °C

22



Redlich-Kister Muggianu

Liquid (Nb,Ru,Al)

B2 (Nb,Ru,Al) (Nb,Ru,Al)

A1 (Nb,Ru,Al)

A2 (Nb,Ru,Al)

A3 (Nb,Ru,Al)

22

∑=

−=0ν

νBAA

,B

νBA

ex )x(xLxxG ϕ

∑=

−+0ν

νCAA

,C

νCA )x(xLxx ϕ

∑=

−+0ν

νCBB

,C

νCB )x(xLxx ϕ

Binary Parameters

RuAl6 (Al)0.833(Ru)0.167

Ru4Al13 (Al)0.765(Ru)0.235

Ru2Al5 (Al)0.714(Ru)0.286

NbRu2 (Nb,Ru)0.375 (Ru)0.625 Nb-Ru

Ru-Al

Phases without a considered ternary extension



RuAl2 (Al)0.667(Ru)0.333

Ru2Al3 (Al)0.6(Ru)0.4

(Al)8(Nb)4(Al,Nb)18σ

Al3Nb (Al)0.75(Nb)0.25

AlNb3 (Al,Nb)0.75(Nb)0.25

Nb-Al

23



L21 (Nb,Al) (Ru)

12LA

l:

Ru

G - 51542

12LN

b:

Ru

G - 34513

120 LA

l,

Nb

:R

u

L - 44910

C14 (Nb)0.333 (Ru,Al)0.667

14

CN

b:

Ru

G - 16852

14

CN

b:

Al

G - 109300

14

0 CN

b:

Ru

,A

l

L - 343000

6

24

Ru

Isothermal section T = 1100 °C

Calculated Experimental


25


Enthalpies of formation (not considered in the present optimisation)


[Wat98] → R.E. Watson, M. Weinert, M. Alatalo, Phys. Rev. B 57 (1998)

[Ben2009] → My.Y. Benarchid, N. David, J-M. Fiorani, M. Vilasi, T. Benlaharche, Thermochimica Acta 482 (2009)

26

A3


Liquidus projection (without L21 and C14)

B2

A2

AlNb3

σ

Al3Nb

RuAl2

Ru2Al5

Ru4Al13

RuAl2

A1

27

A3

→Max

L + AlNb3 ↔ σ + A2 1881 °C

L + σ ↔ Al3Nb + B2 1374 °C

L + Ru4Al13 ↔ Al3Nb + Ru2Al5 1345 °C

L + Ru4Al13 ↔ Al3Nb + RuAl6 734 °C

L + Al3Nb ↔ RuAl6 + A1 660 °C

L ↔ Al3Nb + Ru2Al5 + RuAl2 1345 °C

L ↔ Al3Nb + RuAl2 + B2 1315 °C

Peritectic

Eutectic


Liquidus projection (without L21 and C14)

B2

A2

AlNb3

σ

Al3Nb

RuAl2

Ru2Al5

Ru4Al13

RuAl2

A1

→Max

27


Arc-melted alloys + XRD + SEM

28


L2

L21 → melts congruently


L21

28


L2 Ternary eutectic

L21 → melts congruently

C14 → melts congruently


σσσσ

C14

NbAl3

RuAl2

L21

B2

Ternary eutectic

Maximum

28


L ↔ C14 + NbAl3 + RuAl2

17 Nb17 Ru66 Al

L↓

C14 (light gray)

NbAl3(dark gray)

RuAl2(gray)

29


L ↔ C14 + NbAl3 + RuAl2

17 Nb17 Ru66 Al

L ↔ C14 + NbAl3 + σ

40 Nb5 Ru55 Al

L↓

L↓

C14 (light gray)

NbAl3(dark gray)

RuAl2(gray)

C14(gray)

σ(light gray)

NbAl3(dark gray)

29

Thermodynamic study of the Nb-Ru-Al system Conclusion

New assessment(Nb-Ru)

→ Enthalpies (B2 and A3)

→ Displacive transformations

30


New assessment(Nb-Ru)

→ Enthalpies (B2 and A3)

→ Displacive transformations

New assessmentNew assessment(Ru-Al-Nb)

→ New experiments (DTA) → Temperatures of invariant reactions, liquidus …

→ Enthalpies (L21 and C14)

→ Diagram data (T = 1100 °C, Liquidus projection)

→ New Nb-Ru assessment

30

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