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The Intermetallic SystemThe Intermetallic System
CuCu--NiNi--SnSn
H. Flandorfer, C. Schmetterer and H. Ipser
University of Vienna
Department of Inorganic Chemistry / Materials Chemistry
COST-Action MP0602 WG-Meeting Genova, Italy Feb. 21-22, 2008
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OutlineOutline
� Why working on Cu-Ni-Sn
� Literature information
• Key papers
• Special sections
• Ternary compounds?
� Our preliminary results
• 700 °C isothermal section
• 400 °C isothermal section
• 500 °C isothermal section
• 220 °C isothermal section
COST-Action MP0602 WG-Meeting Genova, Italy Feb. 21-22, 2008
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Why working on CuWhy working on Cu--NiNi--SnSn
Technical applications
• Cu-Ni alloys (Ni-bronzes) with additions of Sn as deformable
alloys and conducting materials in electric devices,
automobiles and household.
• Solder alloys and Ni as contact material or as a component in
lead-free solder applications.
Basic research
• Occurrence of a very special solidification behavior in the
(Cu,Ni)-rich corner of the diagram
COST-Action MP0602 WG-Meeting Genova, Italy Feb. 21-22, 2008
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AgAg--CuCu--NiNi--SnSn is currently the most important systemis currently the most important system
for leadfor lead--free soldering!free soldering!
Cu and Ni show total mutual solubility and the TM’s solve
significant amounts of tin. Beyond that there is practically no
mutual solid solubility: Extended ternary
solubility of the binary IMC’s exists only in Cu-Ni-Sn!
From a huge amount of diffusion couple studies it turned out
that the formation of ternary solid solutions of the types
Cu6-xNixSn5, Cu3-xNixSn, Ni3-xCuxSn4, and Ni3-xCuxSn
have tremendous influence on the operation and performance
of solder joints.
COST-Action MP0602 WG-Meeting Genova, Italy Feb. 21-22, 2008
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Literature informationLiterature information
Earlier work was mainly concerned with the (Cu,Ni)-rich part whereas
more recent publications are focused on the Sn-rich part.
Key papers
• E. Wachtel and E. Bayer, Z. Metallkde., 75, (1984)
Isotherm at 647 °C, Isopleth at 25 at.% Sn, part. liquidus projection
• J.S. Lee Pak and K. Mukherjee, O.T. Tinal and H.-R. Pak, Mat.
Sci. Eng., A117, (1989) and A130, (1990).
part. isopleth at 25 at.% Sn, two ternary phases (2H and d2H)
• G. Ghosh, Landolt-Börnstein, New Series IV, Vol. 11C3; MSIT
Comprehensive compilation and assessment of experimental and
calculated data to structure, phase relations and thermodynamics
129 references from 1928 to 2006, 70 describe experimental work!
COST-Action MP0602 WG-Meeting Genova, Italy Feb. 21-22, 2008
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TheThe verticalvertical sectionsection at 25 at.% Snat 25 at.% Sn
• Low ternary solubility of the ε-Cu3Sn phase• Stabilization of phases to lower T by additions of the second TM
• Complex phase equilibria below ~ 500 °C at the Cu-rich side
• Martensitic phase transformations at the Ni-rich part
• Stable ternary phases 2H (β-Cu3Ti type) and dH2 (distorted β-Cu3Ti type)
647 °C
COST-Action MP0602 WG-Meeting Genova, Italy Feb. 21-22, 2008
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IsothermalIsothermal sectionssections
Many isothermal sections have been published in recent years:
• Most of them are based on experimental data (XRD and EPMA) and
calculations at low temperatures (approx. 240 °C).
• Conventional equilibration and quenching techniques are not
suitable to describe phase relations below ~ 40 at.% Sn at these
temperatures.
• Because of complex phase transformations, possible metastable
phase transformations, coring effects, etc., the experimental
investigation of the (Cu,Ni)-rich part is very difficult.
• Some of the published sections are erroneous simply from a
theoretical point of view and neglect well accepted literature data
published long time before.
COST-Action MP0602 WG-Meeting Genova, Italy Feb. 21-22, 2008
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IsothermalIsothermal sectionssections
240 °C
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IsothermalIsothermal sectionssections
COST-Action MP0602 WG-Meeting Genova, Italy Feb. 21-22, 2008
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IsothermalIsothermal sectionssections
235 °C
COST-Action MP0602 WG-Meeting Genova, Italy Feb. 21-22, 2008
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Ternary compoundsTernary compounds
Are there separate ternary phases in Cu-Ni-Sn?
Three ternary phases along (NixCu1-x)3Sn have been mentioned in literature:
• Cu2NiSn ⇒ “Heusler Phase”, AlCu2Sn-type, L21
• CuNi5Sn2 ⇒ martensitic phase, β-Cu3Ti type, from TEM and ED
• CuNi2Sn ⇒ martensitic phase, distorted β-Cu3Ti type, triclinic
Two ternary phases along (NixCu1-x)6Sn5 have been mentioned in literature:
• Cu27Ni29Sn44 ⇒ EPMA of samples annealed at 235 °C (2 month)?
• Cu4Ni2Sn5 ⇒ First principle calculations of the stabilities along the section (NixCu1-x)6Sn5. Ordered partially filled NiAs-type phase.
No experimental evidence, no proposal of formation mechanism!
According to our experimental findings and assessments the existence of a ternary phase around CuNi5Sn2 is most likely!
COST-Action MP0602 WG-Meeting Genova, Italy Feb. 21-22, 2008
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Experimental challengesExperimental challenges
• The large difference of m.p. of Cu, Ni and in particular Sn
• The very slow dissolution of Ni in the matrix
of Cu and Sn ⇒ difficult homogenization
• The small difference in the atomic number of Cu and Ni ⇒ limited
distinction of different phases and structures in SEM and XRD
• Many phase transformation in a narrow concentrational
region with closely related structures
COST-Action MP0602 WG-Meeting Genova, Italy Feb. 21-22, 2008
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Experimental effortsExperimental efforts
• Cross-check of Cu-Sn with 10 samples
• New investigation of Ni-Sn:
C. Schmetterer, H. Flandorfer*, K. W. Richter, U. Saeed, M. Kauffman,P. Roussel, H. Ipser, Intermetallics, 15, (2007), 869.
• Preparation of approx. 100 ternary samples, annealing at different
temperatures ⇒ XRD, SEM, EPMA
COST-Action MP0602 WG-Meeting Genova, Italy Feb. 21-22, 2008
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Isothermal Section at 700 Isothermal Section at 700 °°CC
COST-Action MP0602 WG-Meeting Genova, Italy Feb. 21-22, 2008
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Isothermal Section at 400 Isothermal Section at 400 °°CC
COST-Action MP0602 WG-Meeting Genova, Italy Feb. 21-22, 2008
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Isothermal Section at 500 Isothermal Section at 500 °°CC
COST-Action MP0602 WG-Meeting Genova, Italy Feb. 21-22, 2008
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Isothermal Section at 220 Isothermal Section at 220 °°CC
COST-Action MP0602 WG-Meeting Genova, Italy Feb. 21-22, 2008
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AcknowledgementsAcknowledgements
Thanks to:Thanks to:
• All my colleagues of the Materials Chemistry Departmentfor the excellent collaboration
• The FWF for financing the project No. P-16495-N11
• All the co-operation partner of the project and COST-531 Action
COST-Action MP0602 WG-Meeting Genova, Italy Feb. 21-22, 2008
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Thank You for Your attention!Thank You for Your attention!
TMS 2008 137th Annual Meeting New Orleans, Louisiana March 9-13 , 2008