O21-High temperature lead-free solder:Phase relations in...
Transcript of O21-High temperature lead-free solder:Phase relations in...
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High temperature leadHigh temperature lead--free solder:free solder:
Phase relations in (Phase relations in (Cu,NiCu,Ni))--SnSn--ZnZn
R. Divakar, C. Schmetterer, H. Flandorfer, H. IpserR. Divakar, C. Schmetterer, H. Flandorfer, H. Ipser
University of Vienna
Department of Inorganic Chemistry / Materials Chemistry
TOFA 2010 Porto, Portuguese September 12-17, 2010
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ContentContent
� Introduction and Bibliography
� The binary systems
• Cu-Sn
• Ni-Zn • Ni-Zn
� Our results on Ni-Sn-Zn
• Isothermal sections at 700, 800 and 900 °C
• Ternary phases
� Summary and Outlook
TOFA 2010 Porto, Portuguese September 12-17, 2010
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°C
1000
800
600
Hard S
oldering
Silver Solders
Copper-Gold-AlloysTraditionalTraditional
SoldersSolders
°C
1000
800
600
Hard S
oldering
Silver Solders
Copper-Gold-AlloysTraditionalTraditional
SoldersSoldersH
ard Soldering
Silver Solders
Copper-Gold-AlloysTraditionalTraditional
SoldersSolders
400
200
Soft S
olderingH
ard Soldering
Tin-Lead Alloys
Bismuth Alloys
Cadmium-Zinc Solders
IndiumAlloys
Lead-Silver Alloys400
200
Soft S
olderingH
ard Soldering
Tin-Lead Alloys
Bismuth Alloys
Cadmium-Zinc Solders
IndiumAlloys
Lead-Silver Alloys
Soft S
olderingH
ard Soldering
Tin-Lead Alloys
Bismuth Alloys
Cadmium-Zinc Solders
IndiumAlloys
Lead-Silver Alloys
TOFA 2010 Porto, Portuguese September 12-17, 2010
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Lead-free Solder materialsfor low temperature soft soldering are well establi shed:
� Ag-Sn (e.g., Sn-3.5Ag), Cu-Sn (e.g., Sn-0.7Cu)� Ag-Cu-Sn („SAC“, e.g.: Sn-3.7Ag-0.7Cu)� In-Sn (e.g., Sn-52In), Ag-In-Sn (e.g., Sn-2.8Ag-20In)� Bi-Sn(e.g.: Sn-58Bi)� Sn-Zn-X, where X = Cu, Ni, Ag, etc…
TOFA 2010 Porto, Portuguese September 12-17, 2010
Lead-free Solder materialswith T m ≥≥≥≥ 230°°°°C up to 350 °C are necessary for:
� power circuits with very high levels of conductivity required� automotive industry under bonnet applications - high
current and low voltage, high temperatures within the engine area
� step soldering approach ⇒ soldering of various levels of the package with different solders of different melting points
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COST Action MP0602
Advanced Solder Materials for High Temperature Application (HISOLD)
Their nature, design, process and control in a mult i-scale domain
TOFA 2010 Porto, Portuguese September 12-17, 2010
Project leaders: Ales Kroupa and Andy Watson
~ 50 Scientist of 17 countries, 2007 - 2011
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The constituent binariesThe constituent binaries
Also PD’s of well established binary systems of high technological importance can be improved!
We should not trust blindly in compilations and ass essments!
• Cu-Sn ⇒ very well established, but almost no experimental investigation since 1950ties! Unclear situation at the Cu-rich side concerningsince 1950ties! Unclear situation at the Cu-rich side concerning
ββββ (W-type) ↔↔↔↔ γγγγ (BiF 3-type) transformation
• Ni-Sn ⇒ new investigation by Schmetterer et al., published 2007
• Cu-Zn ⇒ new investigation ⇒ first results
• Ni-Zn ⇒ new investigation ⇒ preliminary results
• Sn-Zn ⇒ simple eutectic systems
TOFA 2010 Porto, Portuguese September 12-17, 2010
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Literature informationLiterature information
Some information to the phase relations in the ternary Cu-Sn-Zn is available, literature data to Ni-Sn-Zn are very scarce:
Cu-Sn-Zn
• Several vertical sections, 2 isotherms, liquidus projection mainly based on early investigations from 1913-1937.
• Thermodynamic assessment: T. Jantzen and P.J. Spencer, 1998• Further information to the Cu/Zn corner: C. Vilarinho et al., 2004• Phase equilibria: C.-Y. Chou et al., 2006• Liquidus projection and modeling: Y.-C. Huang et al., 2009
Ni-Sn-Zn
• Little information to the Sn-Zn rich side: A. Mayer et al., 1968• Phase equilibria (isotherms at 200, 500, 800 °C): J. Chang et al; 2010
TOFA 2010 Porto, Portuguese September 12-17, 2010
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The The binarybinary CuCu--ZnZn phasephase diagramdiagram
Cu-Zn PD from Massalski‘s compilation based on the assessment of experimental data byG.V. Raynor, 1944
• Extended solid solubility of Zn in Cu, small amount of Cu in Zn.• 5 IMC’s: β, δ (W-type), β’ (CsCl-type), γ (γ-brass type) and ε (Mg-type).• Ordering phases in the (Cu) solid solution (S. Müller and A. Zunger, 2001).
TOFA 2010 Porto, Portuguese September 12-17, 2010
• 5 samples have been prepared!• Annealed at various temperatures
650, 580, 490, and 400 °C• XRD, EPMA, DTA
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The binary NiThe binary Ni--Zn phase diagramZn phase diagram
Ni-Zn PD from Massalski‘scompilation based on the assessmentof experimental data byP. Nash and Y.Y. Pan, 1987
• Extended solid solubility of Zn in Ni, no significant amount of Ni in Zn.• 4 IMC’s: β (CsCl-type), β1 (AuCu-type), γ (γ-brass type) and δ (CoZn13-type).• Metastable phase formation at Ni-rich side (e.g. Murakami et al., 1984).
TOFA 2010 Porto, Portuguese September 12-17, 2010
• First 4, finally 17 samples at all!• Annealed at various temperatures
900, 800, 700, 600, and 400 °C• XRD, EPMA, DTA
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The The binarybinary NiNi--ZnZn phasephase diagramdiagram
• Ni-rich samples quenched from 900 and 800 °C ⇒ β1, (Ni) and up to 3 further phases: bcc Ph. (a=5.0431), “Ni3Zn” (AuCu3-type), trig. Ph. at. ~ 37 at.% Zn (LaF3-type?).
• long period shear structures Q at the Ni-rich part of the homogeneous range of γ-phase (γ-brass type) described by A.J. Morton (1974) and Nover and Schuster (1980) have been confirmed!
TOFA 2010 Porto, Portuguese September 12-17, 2010
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IsothermalIsothermal sectionsection
ofof NiNi--SnSn--ZnZn
700 700 °° CC700 700 °° CC
• Extended ternary solid solubility of β and β1 towards Ni-Sn.• Pronounced ternary solid solubilities of Ni3Zn14, Ni3Sn2-HT and Ni3Sn-LT.• Two ternary compounds, T2 and T3.
TOFA 2010 Porto, Portuguese September 12-17, 2010
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IsothermalIsothermal sectionsection
ofof NiNi--SnSn--ZnZn
800 800 °° CC
• Extended ternary solid solubility of β and β1 towards Ni-Sn.• Pronounced ternary solid solubilities of Ni3Zn14, Ni3Sn2-HT and Ni3Sn-LT.• Stabilization of Ni3Sn-HT (BiF3-type) by additions of Zn.• At least one ternary compound, T2.
TOFA 2010 Porto, Portuguese September 12-17, 2010
800 800 °° CC
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IsothermalIsothermal sectionsection
ofof NiNi--SnSn--ZnZn
900 900 °° CC
• Extended ternary solid solubility of β towards Ni-Sn.• Pronounced ternary solid solubilities in Ni3Sn2-HT and Ni3Sn-LT.• Stabilization of Ni3Sn-HT (BiF3-type) by additions of Zn.
TOFA 2010 Porto, Portuguese September 12-17, 2010
900 900 °° CC
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ττττ2 Ni5Sn4Zn
• Single Crystal XRD
• oC40, a = 4.147 Å, b = 12.582 Å,c = 11.642 Å, SG = Cmcm
• Results sent to ICSD,• Results sent to ICSD,CSD No. 421611
• Analogies to NiAs-type (Ni3Sn2), but not a direct superstructure!
• Isotypic structure Ni5Ga3Ge2 described by Bhargava and Schubert, 1974
TOFA 2010 Porto, Portuguese September 12-17, 2010
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ττττ3 Ni2Sn2Zn
• Single Crystal XRD• cP40, a = 8.843 Å, SG = Pm-3m
• full occupation in the same cell not possible! Either Sn (40 %) or Zn (60 %), randomly distributed.
• Results sent to ICSD,CSD No. 422044
• Analogies to γ-brass type and Ru3Sn7-type structure
• Very similar structure described as Sn8.7(Ni0.5,Zn0.4,Cu0.1)10.4 by Larsson et al., 1994
TOFA 2010 Porto, Portuguese September 12-17, 2010
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Summary and OutlookSummary and Outlook
• A new investigation of Ni-Zn applying various experimental techniques indicates ordering phases in α-(Ni) solid solution and the occurrence of an additional compound at ~ 37 at.% Zn with LaF3 –structure.
• Three isothermal sections of Ni-Sn-Zn at 700, 800, and 900 °C have been established based on available literature data and comprehensive experimental work.
• Two new ternary compounds could be found and their crystal structure • Two new ternary compounds could be found and their crystal structure solved.
• Isothermal sections at 1000 and 1100 °C are under construction.• A liquidus surface projection and various vertical sections will follow.• The binary systems Ni-Zn and Cu-Zn are under investigation. The new
experimental results promise a improved description of the phase relations.
• Cu-Sn-Zn is as well under investigation.
TOFA 2010 Porto, Portuguese September 12-17, 2010
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AcknowledgementsAcknowledgements
Many thanks to:Many thanks to:
• All my colleagues of our department for the excellent collaboration
• The FWF for financing the projects No. P-21507-N19• The FWF for financing the projects No. P-21507-N19
• All the co-operation partner within our COST-Action MP0602
• The organizers of this meeting
TOFA 2010 Porto, Portuguese September 12-17, 2010
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Thank You for Your attention!Thank You for Your attention!Thank You for Your attention!Thank You for Your attention!
TOFA 2010 Porto, Portuguese September 12-17, 2010