1. COST 531 Meeting Vienna, Mai 2007 Riccardo Ferro  a, Gabriella Borzone a, Gabriele Cacciamani a, Stefano Amore a,d, Nadia Parodi a, Gilda Zanicchi a, Jean-Pierre Bros b, Michèle Gambino b, Daniele Gozzi c, Vincenzo Piacente c, Enrica Ricci d, Rada Novakovic d, Luca Moliterni e, Virginia Cinelli f, Andy Watson g a Dipartimento di Chimica e Chimica Industriale Università di Genova, Italy, b Université Aix-Marseille I Ecole Polytechnique Universitaire de Marseille Mécanique et Energétique, Marseille, France c Dipartimento di Chimica, Università di Roma "La Sapienza", Italy, d National Research Council of Italy Institute of the Energetics and Interphases, Department of Genoa, Italy, e Dept: Area Corsi Microsaldatura, Istituto Italiano della Saldatura, Genova, Italy f OMODEO A&S Metalleghe SpA, Milano, Italy g IMR/SPEME, University of Leeds, UK GP2 Contribution to the Constitutional Characterisation of Selected Groups of Lead-free Alloys as Soldering Material

2. IT 2-1 Università di Genova, Genova – IR.Ferro Alloy thermodynamics; phase diagrams: experimental and optimization UK 2-2 University of Leeds, Leeds – UK A.Watson Thermodynamics optimization and modelling; experimental thermodynamics FR 2-2 Université Aix-Marseille I, Marseille- F J.P.Bros Thermodynamics of liquid alloys; heat capacity IT 2-4 Università di Roma La Sapienza – Roma- I D.Gozzi Thermodynamic properties, tensimetry; kinetics of oxidation IT 2-5 Consiglio Nazionale Ricerche, Genova- IE.Ricci Surface properties; wetting behaviour IT 2-6 Istituto Italiano della Saldatura, Genova- IL.Moliterni Brazing tests IT 2-7 OMODEO A&S Metalleghe SpA, Milano- IV.Cinelli Preparation of alloys and wave soldering Structure of GP2 Coordinator R.Ferro, IT 2-1

3. Researchers Cooperation Funds INSTM ((Italian Interuniversity Consortium on Materials Science and Technology) - PRISMA04 Acknowledgment Final Meeting COST Action 531 Vienna 17-18 May 2007

4. WG 1 -WG 2 Thermochemistry and Phase Diagrams – Optimized Phase Diagrams WG 3 – WG 4 Physical properties – Chemical Properties Final Meeting COST Action 531 Vienna 17-18 May 2007 Contribution

5. X-In-Sn systems Au-In-Sn and binary sub-systems Bi-In-Sn Pd-In Pd-Sn Pd-Zn and X-In-Sn-Zn (X=Ag, Cu) quaternary alloys In-Sn-Zn ternary Cu-In-Sn ternary Final Meeting COST Action 531 Vienna 17-18 May 2007 AIM …

6. Au-In-Sn system To produce a thermodynamic description by: –Experimental studies of phase equilibria –Experimental studies of thermodynamic properties Au 4 In 3 Sn 3 ternary phase –Direct reaction calorimetry –Sn solution calorimetry Enthalpies of mixing of liquid alloy –Thermodynamic Modeling by CALPHAD Method Final Meeting COST Action 531 Vienna 17-18 May 2007 AIM …

7. Au4In3Sn3 solid phase Enthalpy of formation - Experimental results Au 4 In 3 Sn 3 DIRECT REACTION DROP CALORIMETER calorimeter working calorimeter working T = 653 K IT 2-1 University of Genova – I TIN SOLUTION CALORIMETRY SETARAM HT1500 calorimeter working calorimeter working T = 673 K UK 2-2 University of Leeds - UK Final Meeting COST Action 531 Vienna 17-18 May 2007

8. Indium calibration One tin sample drop to form In 0.5 Sn 0.5 liquid alloy Heat changes measured on dropping gold samples T=882K Final Meeting COST Action 531 Vienna 17-18 May 2007 UK 2-2 University of Leeds – UK, A.Watson Enthalpies of mixing of liquid Au-In-Sn alloys

9. Au-In-Sn. Enthalpy of mixing : experimental and calculation results Experimental points by A. Watson et al. Enthalpy of mixing in the liquid at 609°C (reference states for calculation are fcc Au and liquid In and Sn; reference states for experiment are fcc Au and liquid In-Sn alloy at the reported composition). Section at x(Sn)/(In)=1/3Section at x(Sn)/(In)=1/1Section at x(Sn)/(In)=3/1 Final Meeting COST Action 531 Vienna 17-18 May 2007

10. Prince et al., assessment, 1990 at about 250°C for x(Au) > 0.3, at about 100°C for x(Au) < 0.3. The ternary phase Au4In3Sn3 was reported to melt congruently at about 430°C. No thermodynamic data are available in literature. Isothermal section calculated at about 25°C by Liu et al., 2003. According to this work, Au 4 In 3 Sn 3 is stable between 80 and 428°C. Au-In-Sn. Isothermal section from literature

11. Final Meeting COST Action 531 Vienna 17-18 May 2007  the melting behaviour of the different alloys have been investigated  the results agree with the general feature of the isothermal section of the literature and the corresponding two and three phase equilibria  incongruent formation at 380°C of the Au 4 In 3 Sn 3 phase  other invariant reactions were identified  E 1 ternary Sn-rich eutectic at Au3.5In0.5Sn95.0, T = 204°C IT 2-1 University of Genova – I, N.Parodi and G.Borzone Au-In-Sn isothermal section at 130°C. Phase equilibria established by metallographic analysis and DSC

12. Final Meeting COST Action 531 Vienna 17-18 May 2007 Experimental tie-lines and tie-triangles determined in this work are drawn in blue. Prince et al., assessment, 1990 at about 250°C for x(Au) > 0.3, at about 100°C for x(Au) < 0.3. IT 2-1 University of Genova – I Au-In-Sn. Isothermal section at 130°C

13. Final Meeting COST Action 531 Vienna 17-18 May 2007 section 1 section 2 Experimental points by G. Borzone et al. Au-In-Sn > Liquidus surface Thermodynamic modeling of the Au-In-Sn system UK 2-2 University of Leeds – UK, A.Watson IT 2-1 University of Genova – I, G.Cacciamani

14. Final Meeting COST Action 531 Vienna 17-18 May 2007 8 Au-In-Sn: Experimental and Calculation Results Experimental points determined in this work by DSC are reported in blue. Not all of them are exactly in the sections. Notice, here below, the incongruent melting of Au 4 In 3 Sn 3. Vertical section at x(Au)-x(In)=0.1 Vertical section at x(Sn)- 2/3x(In)=0.1 Vertical section at x(Au)=0.4

15. IT 2-5 Consiglio Nazionale Ricerche, Genova- I E. Ricci, D. Giuranno, F. Gnecco, S. Amore, T. Lanata, R. Novakovic Surface Tension + modelling: Binary systems Au-Sn Au-In In-Sn Wetting behaviour: Ternary systems:Au-In-Sn/Cu Binary sub-systems: Au-In/Cu Au-Sn/(Cu,Ni) In-Sn /(Cu,Ni) Final Meeting COST Action 531 Vienna 17-18 May 2007 Au-In-Sn system Au-In-Sn system Surface properties Wetting behaviour

16. Final Meeting COST Action 531 Vienna 17-18 May 2007 Aim…… Thermodynamic description  DSC MEASUREMENTS (liquidus surface)  BISMUTH ACTIVITY MEASUREMENTS MEASUREMENTS IT 2-4 Università di Roma La Sapienza – Roma- I D.Gozzi, V.Piacente, B.Brunetti IT 2-1 University of Genova – I, G.Zanicchi, N.Parodi and G.Borzone Bi-In-Sn system. Thermodynamic Properties

17. EXPERIMENTAL  effusion flow–rate, J e, generates the torsion of W–wire.  torsion is measured through deviation of the beam light.  the torsion angle  J e  J e = p e (2  mKT )–1/2 effusion holes At 1000 K Bi/In = 200 Bi/Sn = 3x10 5 IT 2-4 Università di Roma La Sapienza – Roma- I D.Gozzi x Bi variable x Sn /x In = 0.85

18. Surface Tension + modelling: Binary systems Bi-In In-Sn Wetting behaviour: Ternary systems:Bi-In-Sn/Cu Binary sub-systems: Bi-In/Cu In-Sn /(Cu,Ni) Final Meeting COST Action 531 Vienna 17-18 May 2007 Bi-In-Sn system Bi-In-Sn system Surface properties Wetting behaviour IT 2-5 Consiglio Nazionale Ricerche, Genova- I E. Ricci, D. Giuranno, F. Gnecco, S. Amore, T. Lanata, R. Novakovic

19. Table 1. Au-In-Sn alloys. Experimental data. FR 2-3 Marseille-F, J.P.Bros, M.Gambino, A.Sabbar,AZrineh,J.M.Miane Section xAg= 0.045 Section xIn/xSn = 1.1 Section xIn/xSn = 0.25 xZn = 0.10 Zn In Sn Ag Liquidus temperatures Points 3 and 5: 289°C Point 4 : 315°C Eutectic surface: 114°C Ag-In-Sn-Zn system

20. Final Meeting COST Action 531 Vienna 17-18 May 2007 FR 2-3 Marseille-F, J.P.Bros and M.Gambino Table 1. Au-In-Sn alloys. Experimental data. Ag-In-Sn-Zn Liquidus xIn/xSn = 0.25 section Ag-In-Sn-Zn Liquidus xIn/xSn = 1.1 section T/°C xZn T/°C xAg= 0 xAg= 0.05 xAg= 0 xAg= 0.09 Ag-In-Sn-Zn system

21. Final Meeting COST Action 531 Vienna 17-18 May 2007 Electrochemical measurements Potentiodynamic polarization curves recorded in 0.1 M NaCl solution using a saturated calomel electrode (SCE) as a reference Copper addition enhances the corrosion resistance of Sn-Ag solder alloys which show more passive behaviour than Sn 73.9 Pb 26.1 one. Increasing the copper content from 0.8 to 6.7 wt % results in a significant improvement of the corrosion behaviour of Sn-Ag solders.

22. Final Meeting COST Action 531 Vienna 17-18 May 2007 IT 2-1 Università di Genova– I, S.Amore, N.Parodi and G.Borzone Pd-X (X= In, Sn, Zn) HT drop calorimetry Our data,dir. reaction cal, 298K

23. Final Meeting COST Action 531 Vienna 17-18 May 2007 Thank you for your attention

24. Final Meeting COST Action 531 Vienna 17-18 May 2007

25. H. Flandorfer (2002)

26. Final Meeting COST Action 531 Vienna 17-18 May 2007