Department of Chemistry and Industrial Chemistry,

Constitutional Properties of Selected Ternary R-Ni-Al alloys (R= Ce, Sm)

S. Delsante, G. Borzone

University of Genoa,

Department of Chemistry and Industrial Chemistry,

INSTM, UdR Genova

Constitutional Properties of Selected Al alloys (R= Ce, Sm)

, G. Borzone

The addition of misch metal to aluminium• Tensile strength• Heat resistance• Vibration resistance• Corrosion resistance• Extrudability

Low-density glassy alloys contain: • ~ 90 at% Al, • ~ 90 at% Al, • 5 to 9 at% transition metals (Fe, Co, Ni, Rh)• ~ 5 at% rare earths (Ce, Nd, Y)

They have:• High tensile strength• Crystallization temperature between• Nanocrystal dispersions of essentially pure Al• Low density (aerospace industry)

The addition of misch metal to aluminium-based alloys improves :

Amorphous phases formed in the La-Ni-Al system (Inoue 1997)

5 to 9 at% transition metals (Fe, Co, Ni, Rh)

between 250°C and 300°CNanocrystal dispersions of essentially pure Al

(ASM Gschenidner vol.2, 1990)

the La-Ni-Al system (Inoue 1997)

Phase relations of the Sm–Ni–Al ternary system at 500 S. Delsante, R. Raggio and G. Borzone - Intermetallics, 16 (11

The Al-rich region in the Y–Ni–Al system: microstructures and phase equilibria R. Raggio, G. Borzone and R. Ferro - Intermetallics, 8 (3), 2000, 247

A Revision of the Al-Rich Region of the Sm-Al Phase Diagram: The SmS. Delsante, R. Raggio, G. Borzone and R. Ferro - Journal of Phase Equilibria and Diffusion, 28 (3), 2007, 240-242

Chemical and thermodynamic properties of several AlG. Borzone, R. Raggio, S. Delsante and R. Ferro - Intermetallics, 11 (11

Thermodynamic analysis and assessment of the Ce–Ni systemM. Palumbo, G. Borzone, S. Delsante, N. Parodi, G. Cacciamani, R. Ferro,L. Battezzati, M. Baricco - Intermetallics, 12 (12), 2004, 1367

Synthesis and Structural Characterization of Ternary Compounds Belonging to the Series RE2+mNi4+mAl15+4m (RE rare earth metal)S. Delsante, K. W. Richter, H. Ipser and G. Borzone -

Influence of rare earth metals on the characteristics of anodic oxide films on aluminium and their dissolution behaviour in NaOH solutionF. Rosalbino, S. Delsante, G. Borzone and E. Angelini

Hydrogen evolution reaction on Ni-RE (RE=rare earth) next term crystalline alloysF. Rosalbino, G. Borzone, E. Angelinia and R. Raggio

G. Borzone, R. Raggio, S. Delsante and R. Ferro - Intermetallics, 11 (11

Thermodynamic investigation of samarium–nickel alloysG. Borzone, N. Parodi, R. Raggio and R. Ferro - Journal of Alloys and Compounds, 317

Al ternary system at 500 °°°°C in the 40–100 at.% Al regionIntermetallics, 16 (11-12), 2008, 1250-1257

Al system: microstructures and phase equilibria Intermetallics, 8 (3), 2000, 247-257

Al Phase Diagram: The Sm3Al11 PhaseJournal of Phase Equilibria and Diffusion, 28 (3), 2007,

Chemical and thermodynamic properties of several Al–Ni–R systemsIntermetallics, 11 (11-12), 2003, 1217-1222

Ni systemM. Palumbo, G. Borzone, S. Delsante, N. Parodi, G. Cacciamani, R. Ferro,

Intermetallics, 12 (12), 2004, 1367-1372

Synthesis and Structural Characterization of Ternary Compounds Belonging to the Series

- Z. Anorg. Allg. Chem., 635, 2009, 365-368

Influence of rare earth metals on the characteristics of anodic oxide films on aluminium and their

F. Rosalbino, S. Delsante, G. Borzone and E. Angelini - Corrosion Science, 52 (2), 2010, 322-326

RE (RE=rare earth) next term crystalline alloysF. Rosalbino, G. Borzone, E. Angelinia and R. Raggio - Electrochimica Acta, 48 (25-26), 2003, 3939-3944

Intermetallics, 11 (11-12), 2003, 1217-1222

nickel alloysJournal of Alloys and Compounds, 317-318, 2001, 532-536

The aim of this work is the investigationof the R-Ni-Al systems (R= Ce and Sm)similarities and differences in the formationestablished phase relationships

Why Ce and Sm? Ce represents the light rare earth, Sm is known to have a “boundary behavior” between light and heavy rare earths

Outline

Literature data on R-Ni-Al systems

Experimental details

Results and discussion

investigation of the isothermal sections at 800°CSm) in the Al-rich part to underline

formation of ternary phases and in the

Ce represents the light rare earth, Sm is known to have a “boundary behavior”

systems (R = Ce and Sm)

Three recent publications about the Ce

1. [08Tang]: Experimental investigation of the Al(Intermetallics 16, 2008, 432-439)

2. [09Tang]: The phase equilibria of the Al2. [09Tang]: The phase equilibria of the Al470, 2009, 222-227)

3. [10Tang]: Correlation between thermodynamics and glass forming ability in the Al-Ce-Ni system (Intermetallics 18, 2010, 900

Three recent publications about the Ce-Ni-Al system:

[08Tang]: Experimental investigation of the Al-Ce-Ni system at 800°C

2. [09Tang]: The phase equilibria of the Al-Ce-Ni system at 500°C (JALCOM 2. [09Tang]: The phase equilibria of the Al-Ce-Ni system at 500°C (JALCOM

3. [10Tang]: Correlation between thermodynamics and glass forming ability in Ni system (Intermetallics 18, 2010, 900-906)

- E1: L → Al + Ce3Al11 + NiAl

- U1: L + Ce4Ni6Al23 → Ce3Al

- U2: L + Ni2Al3 → Ce4Ni6Al

- U3: L + CeNiAl4 →Ce4Ni6Al

After a thermodynamic modeling 10Al-rich corner have been computedThey confirmed some of them by DTA

- U3: L + CeNiAl4 →Ce4Ni6Al

- U4: L + CeNi2Al5 → Ce4Ni6

- P1: L+ CeNiAl4 + CeNi2Al5

- U5: L + CeAl4 → L + Ce3Al11

- U6: L + βCeAl3 → CeNiAl4

- U7: L+ CeAl2 → βCeAl3 + CeNiAl

- P2: L + CeAl4 + CeAl2 → βCeAl

+ NiAl3 (628.2°C)

Al11 + NiAl3 (735.7°C)

Al23 + NiAl3 (843.0°C)

Al23 + Ce3Al11 (896.5°C)

10 invariant reactions in thecomputed by [10Tang].

DTA experiments.

Al23 + Ce3Al11 (896.5°C)

6Al23 + Ni2Al3 (901.1°C)

5 → Ce4Ni6Al23 (998.2°C)

11 (1019.4°C)

4 + CeAl4 (1104.7°C)

+ CeNiAl4 (1167.6°C)

CeAl3 (1191.9°C)

Phase Composition / at.%

Ce Ni

Ce3Al11 22.4 - 78.6

α-CeAl3 25.0 - 75.0

CeAl2 33.3 - 66.7

Al3Ni - 25.0 75.0

Al3Ni2 - 40.0 60.0

Binary and ternary phases in the Al-rich part for the relevant phase diagrams

Al3Ni2 - 40.0 60.0

Ce4Ni6Al23 12.1 18.2 69.7

CeNiAl4 16.7 16.7 66.6

CeNi2Al5 12.5 25.0 62.5

“Ce12.1Ni28.1Al59.8” 12.1 28.1 59.8

In [99Belov] the existence of a ternaryNiAl3 + CeAl4 *) with a global composition627°°°°C has been reported

/ at.% Pearson symbol - type structure

Al

78.6 oI28-La3Al11

75.0 hP8-Ni3Sn

66.7 cF24-Cu2Mg

75.0 cP4-Cu3Au

60.0 hP5-Al3Ni2

rich part for the relevant phase diagrams

60.0 hP5-Al3Ni2

69.7 mS66-Y4Ni6Al23

66.6 oC24-YNiAl4

62.5 oI16-PrNi2Al5

59.8 Unknown (reported only at 800°C)

ternary eutectic reaction (L →→→→ Al +composition Ce2.6Ni2.6Al94.8 and a TE =

Two recent publications about the Sm

1. [08Delsante]: Phase relations of the Smthe 40–100 at.% Al region; (Intermetallics, 16 (11

2. [09Delsante]: Synthesis and Structural Characterization of Ternary 2. [09Delsante]: Synthesis and Structural Characterization of Ternary Compounds Belonging to the Series RE

metal); (Z. Anorg. Allg. Chem., 635, 2009, 365

Two recent publications about the Sm-Ni-Al system:

[08Delsante]: Phase relations of the Sm–Ni–Al ternary system at 500 °C in Intermetallics, 16 (11-12), 2008, 1250-1257)

[09Delsante]: Synthesis and Structural Characterization of Ternary [09Delsante]: Synthesis and Structural Characterization of Ternary RE2+mNi4+mAl15+4m (RE rare earth

Z. Anorg. Allg. Chem., 635, 2009, 365-368)

E1: L → Al + Sm3Al11+Sm4NiE2: L → Al + NiAl3+Sm4Ni

1 Sm4Ni6Al23

2 SmNiAl4

3 SmNiAl3

4 SmNi2Al3

5 SmNiAl2

6 SmNiAl

Isothermal section at 500°°°°C

Ni6Al23 (Sm2.5Ni2.5Al95)Ni6Al23 (Sm1Ni2Al97)

Phase / T range (°C) Composition / at.%

Sm Ni Al

SmAl 50.0 - 50.0

SmAl3 25.0 - 75.0

SmAl2 33.3 - 66.7

AlNi - 50.0 50.0

Al3Ni - 25.0 75.0

Binary and ternary phases in the Al-rich part for the relevant phase diagrams

3

Al3Ni2 - 40.0 60.0

Sm3Ni5Al19 11.1 18.5 70.4

Sm4Ni6Al23 12.1 18.2 69.7

SmNiAl4 16.7 16.7 66.6

SmNiAl3 20.0 20.0 60.0

SmNiAl2 25.0 25.0 50.0

SmNi2Al3 16.7 33.3 50.0

/ at.% Pearson symbol - type structure

Al

50.0 oP16-ErAl

75.0 hP8-Ni3Sn

66.7 cF24-Cu2Mg

50.0 cP2-CsCl

75.0 cP4-Cu3Au

rich part for the relevant phase diagrams

3

60.0 hP5-Al3Ni2

70.4 oS108-Gd3Ni5Al19 (stable only at

800°°°°C)

69.7 mS66-Y4Ni6Al23

66.6 oC24-YNiAl4

60.0 oP20-YNiAl3

50.0 oS16-CuMgAl2

50.0 hP18-HoNi2.6Ga2.4

Experimental techniques

Pieces of the elements in pure Ar atmosphereSynthesis in alumina crucibles

by induction melting

Annealing for 10-15 daysQuenching in ice

ISOTHERMALSECTION INVESTIGATIONSSECTION INVESTIGATIONS

CHARACTERIZATION OF THE

Differential Scanning Calorimetry and Thermal Analysis were also performed on some Ce-Ni-Al alloys

Pieces of the elements in pure Ar atmosphereSynthesis in alumina crucibles

days at 800°°°°CQuenching in ice-water

SECTION INVESTIGATIONSSECTION INVESTIGATIONS

CHARACTERIZATION OF THEALLOYS

XRDLOMSEM

EPMA

Differential Scanning Calorimetry and Thermal Analysis were also performed

Ce-Ni-Al system: 11 alloys incomposition range 70 - 100 at.% Albeen synthesized and completelycharacterized

Sm-Ni-Al system: 19 alloys incomposition range 55 – 100 at.% Albeen synthesized and completelycharacterized

in theAl have

completely

in theAl have

completely

ResultsResultsResultsResults

Ce-Ni-Al: isothermal section at 800

Grey phase: NiAl3

White phase: Ce3Al11

liquidus (ternary eutectic morphology)

Composition and crystal structures of the ternary phases CeY4Ni6Al23, CeNiAl4 (oS24-YNiAl4 ) were confirmed

For the Ce3Al11 a Ni solubility of ~2 at.% was observed.

The previously established phase relationships have been confirmed

Al: isothermal section at 800°°°°C1.Ce4Ni6Al23

2.CeNiAl4

Composition and crystal structures of the ternary phases Ce4Ni6Al23 (mS66-) were confirmed

a Ni solubility of ~2 at.% was observed.

The previously established phase relationships have been confirmed

BSE micrograph of a Ce2.5Ni3.0Al94.5 sample:

As cast

Annealed

TE= 622°Cmeasured by DSC

The microstructure of the ternary eutectic is greatly affected by the solidification

sample: ternary eutectic morphology

After DSC analysis, 1°C/minat 500°C

Cmeasured by DSC

The microstructure of the ternary eutectic is greatly affected by the solidification

DTA performed Vienna by Dr. K. Richter

2nd cycle

The experimental resultsexperimental results by DTA analysis confirmed the for the invariant reactions reported by [10Tang], with a good agreement for U3 and P1

U1: L + Ce4Ni6Al23 → Ce3Al11 + NiAl3

U3: L + CeNiAl4 → Ce4Ni6Al23 + Ce3Al11

P1: L + CeNiAl4 + CeNi2Al5 → Ce4Ni6Al23

1st cycle

Vienna by Dr. K. Richter

by DTA analysis confirmed the calculated temperaturesfor the invariant reactions reported by [10Tang], with a good agreement

700°°°°C [736°°°°C]896°°°°C [896.5°°°°C]

23 990°°°°C [998°°°°C]

Ce4Ni6Al23

Sm-Ni-Al: isothermal section at 800

1.Sm4Ni6Al23

2.Sm3Ni5Al19

3.SmNiAl4

4.SmNiAl3

5.SmNiAl2

6.SmNi2Al3

7.”Sm13Ni30Al57”

Bright phase: SmAl2

Dark Grey phase: SmNi2Al3

Light grey phase: SmNiAl2

Al: isothermal section at 800°°°°C

Bright phase: Sm3Ni5Al19

Grey phase: NiAl3

Light grey phase: Ni2Al3

Grey phase: Sm4Ni6Al23

Bright phase : SmAl3

liquidus

Grey phase: NiAlLight grey phase: SmNiAl4

- The existence of the Sm3Ni5Al19 in samples annealed at 800confirmed.

- The existence of the Sm4Ni6Al23, SmNiAlternary phases previously reported for the isothermal section at 500confirmed.

- A new phase with a composition ~Sm

- The relationships between binary and ternary phases have been proposed.

in samples annealed at 800°C was also

, SmNiAl4, SmNiAl3, SmNiAl2 and SmNi2Al3

previously reported for the isothermal section at 500°C were

A new phase with a composition ~Sm13Ni30Al57 was found.

The relationships between binary and ternary phases have been proposed.

500°C

800°C

Ce-Ni-Al and Sm-Ni-Al systems:

1.Sm2.Sm3.SmNiAl7.”Sm

1.Ce4Ni6Al23

2.CeNiAl4

Different behaviour of R-Ni-Al systems containing Ce or Sm

But, the phase reported by [08Tang]structure and a composition ~Ce12.1Ni28

with a composition ~ Sm13Ni30Al57

Al systems: Isothermal sections at 800°°°°C

1.Sm4Ni6Al23

2.Sm3Ni5Al19

3.SmNiAl4

7.”Sm13Ni30Al57”

Al systems containing Ce or Sm

Tang] to exist at 800°C with an unknown28.1Al59.8 can be the same observed by us

- Composition and crystal structuresCeNiAl4 were confirmed

- For the Ce3Al11 a Ni solubility of ~2 at.

- The previously established phase relationships

- Temperature of several invariant reactions

Conclusions -1

- Temperature of several invariant reactionsand DTA analysis

structures of the ternary phases Ce4Ni6Al23,

.% was observed.

relationships have been confirmed

reactions have been determined by DSCreactions have been determined by DSC

- The existence of the ternary phasesSmNiAl2 and SmNi2Al3 previously reported500°C were confirmed. The existence ofat 800°C was also confirmed.

- A new phase with a composition ~Sminvestigation is still needed.

- The relationships between binary and

Conclusions -2

- The relationships between binary and

- The differences between the relationshipshave been highlighted.

- Similarities and differences in the formationthe established phase relationshipssystems have been underlined.

phases Sm4Ni6Al23, SmNiAl4, SmNiAl3,reported for the isothermal section atof the Sm3Ni5Al19 in samples annealed

~Sm13Ni30Al57 was found. A structural

ternary phases have been proposed.ternary phases have been proposed.

relationships occurring at 500°C and 800°C

formation of ternary phases and inrelationships for the Ce-Ni-Al and Sm-Ni-Al

THANK YOU FOR YOUR ATTENTIONTHANK YOU FOR YOUR ATTENTIONTHANK YOU FOR YOUR ATTENTIONTHANK YOU FOR YOUR ATTENTION

Al

RAl3

R4Ni6Al23RNi

R= heavy rare earths

R4Ni6Al23

R= Y, Sm, Gd, Yb

Al15+4mNi4+mR2+m structure series

R4Ni6Al23RNi

18.1812.12R4Ni6Al23

23.087.69RNi3Al9

18.5211.11R3Ni5Al19

at% Niat% RPhase

R3Ni5Al19

NiAl3

RNi Al

R3Ni5Al19R= Gd

RNi3Al9

R= Y, Gd, Dy, Er

Ni2Al3RNi3Al9

69.23

69.7

70.37

at%Al

mS66- Y4Ni6Al23

hR78- ErNi3Al9

oS108-Gd3Ni5Al19

structure type

Bright phase: Sm3Ni5Al19

Grey phase: NiAl3

liquidus

Bright phase: SmNiAl4

Dark Grey phase: “new phase” Grey phase: SmNiAlGrey phase: SmNiAl3

19

Dark Grey phase: “new phase”