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,

COST 531 Meeting Vienna, Mai 2007

Riccardo Ferroa , Gabriella Borzonea, Gabriele

Cacciamania, Stefano Amorea,d, Nadia Parodia, Gilda Zanicchia,

Jean-Pierre Brosb, Michèle Gambinob, Daniele Gozzic, Vincenzo Piacentec, Enrica Riccid, Rada Novakovicd, Luca Moliternie, Virginia Cinellif, Andy Watsong

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, Francec 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, Italyf 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

IT 2-1 Università di Genova, Genova – I R.Ferro Alloy thermodynamics; phase diagrams:

experimental and optimizationUK 2-2 University of Leeds, Leeds – UK A.Watson

Thermodynamics optimization and modelling; experimental thermodynamicsFR 2-2 Université Aix-Marseille I , Marseille- F J.P.Bros

Thermodynamics of liquid alloys; heat capacityIT 2-4 Università di Roma La Sapienza – Roma- I D.Gozzi

Thermodynamic properties, tensimetry; kinetics of oxidationIT 2-5 Consiglio Nazionale Ricerche , Genova- IE.Ricci

Surface properties; wetting behaviourIT 2-6 Istituto Italiano della Saldatura, Genova- IL.Moliterni

Brazing testsIT 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

Researchers

Cooperation

Funds

• INSTM ((Italian Interuniversity Consortium on Materials Science and Technology) - PRISMA04

Acknowledgment

Final Meeting COST Action 531 Vienna 17-18 May 2007

WG 1 -WG 2 Thermochemistry and Phase Diagrams – Optimized Phase Diagrams

WG 3 – WG 4 Physical properties – Chemical Properties


Contribution

X-In-Sn systemsAu-In-Sn and binary sub-systemsBi-In-SnPd-InPd-SnPd-Znand X-In-Sn-Zn (X=Ag, Cu) quaternary alloys In-Sn-Zn ternaryCu-In-Sn ternary


AIM…

Au-In-Sn system •To produce a thermodynamic

description by:– Experimental studies of phase equilibria– Experimental studies of thermodynamic

properties• Au4In3Sn3 ternary phase

– Direct reaction calorimetry– Sn solution calorimetry

• Enthalpies of mixing of liquid alloy

– Thermodynamic Modeling by CALPHAD Method


AIM…

Au4In3Sn3 solid phase Enthalpy of formation - Experimental results

2

Q -1

Q Tr) AxByCz, ( H

2Q -

1Q )- AxByCz, ( H

f-

2Q

dropreference drop, Second

-AxByCz-B-A- 1

Q

drop reaction drop, First

f

rT

cT

rT

cTcruH

rT

cTH

frT

cTH

rT

cTH

rT

cTcruH

),(

),(),(),(),(

4673.15K) solution, (in298.15K) (solid,334 3Sn)3InAu4(SnInAu H

4321

)K15.298(f334

334

SnInAu3Sn3InAu4

HHHH

H

Au4In3Sn3 ../0.10.210 atmolkJHΔf ../0.37.210 atmolkJHΔf

DIRECT REACTION DROP DIRECT REACTION DROP CALORIMETERCALORIMETERcalorimeter working calorimeter working T = 653 K

IT 2-1 University of Genova – I

TIN SOLUTION CALORIMETRYTIN SOLUTION CALORIMETRYSETARAM HT1500calorimeter working calorimeter working T = 673 KUK 2-2 University of Leeds - UK

3

2

1

H

H

H

673.15K) (liquid, 298.15K)(solid,

673.15K) solution, (in 298.15K)(solid,

673.15K) solution, (in 298.15K)(solid,

SnSn

InIn

AuAu


• Indium calibration

• One tin sample drop to form In0.5Sn0.5 liquid alloy

• Heat changes measured on dropping gold samples

• T=882K

21(T) 0.50.5(T)0.5 0.5(T)

2(T)(298.15)

1(T) 0.50.5(T)0.5 0.5(298.15)

SnInAuSnInAu

AuAu

SnInAuSnInAu

HHyx

Hxx

Hyx

yyx

yyx


UK 2-2 University of Leeds – UK, A.Watson

Enthalpies of mixing of liquid Au-In-Sn alloys

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)=1/3 Section at x(Sn)/(In)=1/1 Section at x(Sn)/(In)=3/1

-10

-8

-6

-4

-2

0

2

4

6

8

10

103

HM

R(L

IQ)

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

MOLE_FRACTION AU

THERMO-CALC (2007.05.01:23.38) : DATABASE:USER P=1E5, N=1, T=882, 75*X(IN)-25*X(SN)=0;

-15

-10

-5

0

5

103H

MR

(LIQ

)

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

MOLE_FRACTION AU

THERMO-CALC (2007.05.01:23.39) : DATABASE:USER P=1E5, N=1, T=882, X(IN)-X(SN)=0;

-15

-10

-5

0

5

103

HM

R(L

IQ)

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

MOLE_FRACTION AU

THERMO-CALC (2007.05.01:23.39) : DATABASE:USER P=1E5, N=1, T=882, 75*X(SN)-25*X(IN)=0;



Prince et al., assessment, 1990at 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, Au4In3Sn3 is stable between 80 and 428°C.

Au-In-Sn. Isothermal section from literature


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

Au4In3Sn3 phase

other invariant reactions were identified

E1 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


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

MO

LE_F

RA

CTI

ON

SN

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

MOLE_FRACTION IN

THERMO-CALC (2006.02.22:22.23) :Au-In-Sn at 130 C DATABASE:USER

P=1E5, N=1, T=403;

2006-02-22 22:23:12.49 output by user gabriele from

Experimental tie-lines and tie-triangles determined in this work are drawn in blue.

Prince et al., assessment, 1990at 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


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

X(L

IQ,S

N)

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

X(LIQ,IN)

THERMO-CALC (2006.02.22:23.07) :Au-In-Sn - Liquidus surface DATABASE:USER

P=1E5, N=1,FIXED PHASES: LIQUID=1;

218 228

455

265

495

427

472

410

411 392

2006-02-22 23:07:01.33 output by user gabriele from

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.WatsonIT 2-1 University of Genova – I, G.Cacciamani

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 Au4In3Sn3.

Vertical section at x(Au)-x(In)=0.1

Vertical section at

x(Sn)-2/3x(In)=0.1

Vertical section at

x(Au)=0.40

100

200

300

400

500

600

TE

MP

ER

AT

UR

E_C

EL

SIU

S

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

MOLE_FRACTION SN

THERMO-CALC (2007.05.01:23.08) :Au-In-Sn x(Au)-x(In)=0.1 [ais5] DATABASE:USER P=1E5, N=1, X(AU)-X(IN)=0.1;

0

100

200

300

400

500

600

TE

MP

ER

AT

UR

E_C

EL

SIU

S

0 0.1 0.2 0.3 0.4 0.5

MOLE_FRACTION IN

THERMO-CALC (2007.05.01:23.19) :Au-In-Sn x(Sn)-2/3*x(In)=0.1 [ais5] DATABASE:USER P=1E5, N=1, X(SN)-0.66667*X(IN)=0.1;

0

100

200

300

400

500

600

TE

MP

ER

AT

UR

E_C

EL

SIU

S

0 0.1 0.2 0.3 0.4 0.5 0.6

MOLE_FRACTION SN

THERMO-CALC (2007.05.01:23.25) :Au-In-Sn x(Au)=0.40 DATABASE:USER P=1E5, N=1, X(AU)=0.40001;

IT 2-5 Consiglio Nazionale Ricerche , Genova- IE. Ricci, D. Giuranno, F. Gnecco, S. Amore, T. Lanata, R. Novakovic

Surface Tension + modelling:

Binary systems Au-SnAu-InIn-Sn

Wetting behaviour:

Ternary systems: Au-In-Sn/CuBinary sub-systems:Au-In/CuAu-Sn/(Cu,Ni)In-Sn /(Cu,Ni)


Au-In-Sn systemAu-In-Sn system Surface properties Wetting behaviour


Aim……

Thermodynamic Thermodynamic descriptiondescription

DSC DSC MEASUREMENTSMEASUREMENTS (liquidus surface)

BISMUTH ACTIVITY BISMUTH ACTIVITY MEASUREMENTSMEASUREMENTS

IT 2-4 Università di Roma La Sapienza – Roma- I D.Gozzi , V.Piacente, B.BrunettiIT 2-1 University of Genova – I, G.Zanicchi, N.Parodi and G.Borzone

Bi-In-Sn system. Thermodynamic Properties

EXPERIMENTAEXPERIMENTAL L

-20

-15

-10

-5

0

5

6 8 10 12 14 16 18 20

BiInSn

log

( p/

Pa)

104/T /K

1000 5001250 K

effusion flow–rate, Je, generates the torsion of W–wire.

torsion is measured through deviation of the beam light.

the torsion angle Je Je = pe(2 mKT)–1/2

effusion holes

At 1000 KBi/In = 200Bi/Sn = 3x105

IT 2-4 Università di Roma La Sapienza – Roma- I D.Gozzi

xBi variable

xSn/xIn = 0.85

Surface Tension + modelling:

Binary systems Bi-InIn-Sn

Wetting behaviour:

Ternary systems: Bi-In-Sn/CuBinary sub-systems:Bi-In/CuIn-Sn /(Cu,Ni)


Bi-In-Sn systemBi-In-Sn system Surface properties Wetting behaviour

IT 2-5 Consiglio Nazionale Ricerche , Genova- IE. Ricci, D. Giuranno, F. Gnecco, S. Amore, T. Lanata, R. Novakovic

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

AgLiquidus temperatures Points 3 and 5: 289°CPoint 4 : 315°CEutectic surface: 114°C

Ag-In-Sn-Zn system


FR 2-3 Marseille-F, J.P.Bros and M.Gambino

Ag-In-Sn-Zn Liquidus xIn/xSn = 0.25 section

Ag-In-Sn-Zn Liquidus xIn/xSn = 1.1 section

T/°CxZn

xZn

T/°C

xAg= 0

xAg= 0.05

xAg= 0

xAg= 0.09

Ag-In-Sn-Zn system

-850 -575 -300 -25 2501E-6

1E-5

1E-4

1E-3

0,01

0,1

1

10

100

Sn88.7

Ag2.3

In9.0

Sn86.6

Ag3.0

Bi10.4

Sn96.1

Ag3.1

Cu0.8

Sn90.4

Ag2.9

Cu6.7

Sn73.9

Pb26.1

J (m

A/c

m2 )

E (mV/SCE)


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 Sn73.9Pb26.1 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.


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

./0.10.700 atmolkJHf

PdIn


PdSn2


Thank you for your attention




H. Flandorfer (2002)H. Flandorfer (2002)


PdIn



PdSn2

Documents

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,