cost 531 meeting vienna, mai 2007 riccardo ferro a, gabriella borzone a, gabriele cacciamani a,...
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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
Final Meeting COST Action 531 Vienna 17-18 May 2007
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
Final Meeting COST Action 531 Vienna 17-18 May 2007
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
Final Meeting COST Action 531 Vienna 17-18 May 2007
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
Final Meeting COST Action 531 Vienna 17-18 May 2007
• 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
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
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;
Final Meeting COST Action 531 Vienna 17-18 May 2007
Final Meeting COST Action 531 Vienna 17-18 May 2007
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
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
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
Final Meeting COST Action 531 Vienna 17-18 May 2007
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
Final Meeting COST Action 531 Vienna 17-18 May 2007
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)
Final Meeting COST Action 531 Vienna 17-18 May 2007
Au-In-Sn systemAu-In-Sn system Surface properties Wetting behaviour
Final Meeting COST Action 531 Vienna 17-18 May 2007
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)
Final Meeting COST Action 531 Vienna 17-18 May 2007
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
Final Meeting COST Action 531 Vienna 17-18 May 2007
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)
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 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.
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
./0.10.700 atmolkJHf
PdIn
./0.10.500 atmolkJHf
PdSn2
Final Meeting COST Action 531 Vienna 17-18 May 2007
Thank you for your attention
Final Meeting COST Action 531 Vienna 17-18 May 2007
./0.10.340 atmolkJHf
Final Meeting COST Action 531 Vienna 17-18 May 2007
H. Flandorfer (2002)H. Flandorfer (2002)
./0.10.700 atmolkJHf
PdIn
Final Meeting COST Action 531 Vienna 17-18 May 2007
./0.10.500 atmolkJHf
PdSn2