o69-constitutional properties of selected ternary r-ni-al...
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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”