Transcript Diapositiva 1 - univie.ac.at

COST 531 Meeting
Vienna, Mai 2007
GP2
Contribution to the Constitutional
Characterisation of Selected Groups of
Lead-free Alloys as Soldering Material
Riccardo Ferroa , 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, 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
Structure of GP2
Coordinator R.Ferro, IT 2-1
IT
2-1 Università di Genova, Genova – I
R.Ferro
Alloy thermodynamics; phase diagrams: experimental and
optimization
UK 2-2 University of Leeds, Leeds – UK
A.Watson
FR 2-2 Université Aix-Marseille I , Marseille- F
J.P.Bros
IT 2-4 Università di Roma La Sapienza – Roma- I
D.Gozzi
IT 2-5 Consiglio Nazionale Ricerche , Genova- I
E.Ricci
Thermodynamics optimization and modelling;
experimental thermodynamics
Thermodynamics of liquid alloys; heat capacity
Thermodynamic properties, tensimetry; kinetics of
oxidation
Surface properties; wetting behaviour
IT 2-6 Istituto Italiano della Saldatura, Genova- I L.Moliterni
Brazing tests
IT 2-7 OMODEO A&S Metalleghe SpA, Milano- I
Preparation of alloys and wave soldering
V.Cinelli
Acknowledgment
Researchers
Cooperation
Funds
• INSTM ((Italian Interuniversity
Consortium on Materials Science and
Technology) - PRISMA04
Final Meeting COST Action 531 Vienna 17-18 May 2007
Contribution
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
AIM…
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…
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
Au4In3Sn3 solid phase Enthalpy of formation - Experimental results
DIRECT REACTION DROP
CALORIMETER
calorimeter working T = 653 K
TIN SOLUTION CALORIMETRY
SETARAM HT1500
calorimeter working T = 673 K
UK 2-2 University of Leeds - UK
IT 2-1 University of Genova – I
First drop, reaction drop
Au(solid,298.15K)  Au(in solution,673.15K)  H1
In(solid,298.15K)  In(in solution,673.15K)  H 2
Sn(solid,298.15K)  Sn(liquid,673.15K)  H 3
Q  H (cru , T - T )  H ( A, T - T )  H ( B, T - T )   H ( AxByCz, T - T )
1
c r
c r
c r
f
c r
Second drop, reference drop
Q  H (cru , T - T )   H ( AxByCz, T - T )  Q - Q
2
c r
f
c r
1 2
 H  ( AxByCz, Tr)  Q - Q
f
1
2
Au4 In 3Sn3(solid, 298.15K)  ( 4 Au  3In  3Sn)(in solution, 673.15K)H4
4 Au  3In  3Sn  Au 4 In 3Sn 3  f H( 298.15K )
 4 H1  3H 2  3H 3  H 4
Δf H 0  21.7  3.0kJ / mol.at.
Au4In3Sn3
Δf H 0  21.0  1.0kJ / mol.at.
Final Meeting COST Action 531 Vienna 17-18 May 2007
Enthalpies of mixing of liquid Au-In-Sn alloys
UK 2-2 University of Leeds – UK, A.Watson
• Indium calibration
• One tin sample drop to form In0.5Sn0.5 liquid alloy
• Heat changes measured on dropping gold samples
• T=882K
xAu(298.15)  yIn0.5 Sn0.5 (T)  Aux In0.5 y Sn0.5 y (T)
xAu(298.15)  xAu(T)
xAu(T)  yIn0.5 Sn0.5 (T)  Aux In0.5 y Sn0.5 y (T)
H 1
H 2
H 1  H 2
Final Meeting COST Action 531 Vienna 17-18 May 2007
Au-In-Sn. Enthalpy of mixing : experimental and calculation results
THERMO-CALC (2007.05.01:23.38) :
DATABASE:USER
P=1E5, N=1, T=882, 75*X(IN)-25*X(SN)=0;
Section at x(Sn)/(In)=1/3
THERMO-CALC (2007.05.01:23.39) :
DATABASE:USER
P=1E5, N=1, T=882, X(IN)-X(SN)=0;
Section at x(Sn)/(In)=1/1
10
THERMO-CALC (2007.05.01:23.39) :
DATABASE:USER
P=1E5, N=1, T=882, 75*X(SN)-25*X(IN)=0;
Section at x(Sn)/(In)=3/1
5
5
0
0
8
6
HMR(LIQ)
HMR(LIQ)
2
0
-2
HMR(LIQ)
4
-5
-5
-4
-10
-10
-6
3
3
3
10
-8
10
10
-10
-15
0
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
MOLE_FRACTION AU
-15
0
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
MOLE_FRACTION AU
0
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
MOLE_FRACTION AU
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).
Final Meeting COST Action 531 Vienna 17-18 May 2007
Au-In-Sn. Isothermal section from literature
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, Au4In3Sn3 is stable between 80 and
428°C.
Final Meeting COST Action 531 Vienna 17-18 May 2007
Au-In-Sn isothermal section at 130°C. Phase equilibria established by
metallographic analysis and DSC
IT 2-1 University of Genova – I, N.Parodi and G.Borzone
 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
Final Meeting COST Action 531 Vienna 17-18 May 2007
Au-In-Sn. Isothermal
section at 130°C
THERMO-CALC (2006.02.22:22.23) :Au-In-Sn at 130 C
DATABASE:USER
P=1E5, N=1, T=403;
IT 2-1 University of Genova – I
1.0
0.9
0.8
MO
LE
_F
RA
CT
IO
NS
N
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0
Prince et al., assessment, 1990
at about 250°C for x(Au) > 0.3,
at about 100°C for x(Au) < 0.3.
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
MOLE_FRACTION IN
Experimental tie-lines and
tie-triangles determined in
this work are drawn in blue.
Final Meeting COST Action 531 Vienna 17-18 May 2007
1.0
Thermodynamic modeling of the Au-In-Sn system
UK 2-2 University of Leeds – UK, A.Watson
THERMO-CALC
:Au-In-Sn - Liquidus surface
IT 2-1 University of
Genova (2006.02.22:23.07)
– I, G.Cacciamani
DATABASE:USER
P=1E5, N=1,FIXED PHASES: LIQUID=1;
section 1
1.0
Au-In-Sn > Liquidus surface
0.9
0.8
228
218
265
section 2
X(L
IQ
,SN
)
0.7
0.6
392
411
0.5
427
0.4
455
0.3
0.2
472
495
410
0.1
0
0
0.1 0.2
0.3 0.4
Experimental points by G. Borzone et al.
0.5 0.6
0.7 0.8
0.9 1.0
X(LIQ,IN)
Final Meeting COST Action 531 Vienna 17-18 May 2007
Au-In-Sn: Experimental and Calculation Results
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;
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.
400
300
200
100
500
400
300
200
100
Vertical section at
x(Au)=0.4
THERMO-CALC (2007.05.01:23.25) :Au-In-Sn x(Au)=0.40
DATABASE:USER
P=1E5, N=1, X(AU)=0.40001;
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0
0
0.9 600
MOLE_FRACTION SN
Vertical section at
x(Au)-x(In)=0.1
0.1
0.2
0.3
0.4
0.5
MOLE_FRACTION IN
Vertical section at
x(Sn)2/3x(In)=0.1
500
TEMPERATURE_CELSIUS
TEMPERATURE_CELSIUS
500
600
TEMPERATURE_CELSIUS
600
THERMO-CALC (2007.05.01:23.19) :Au-In-Sn x(Sn)-2/3*x(In)=0.1
DATABASE:USER
P=1E5, N=1, X(SN)-0.66667*X(IN)=0.1;
400
300
200
100
0
0
0.1
0.2
0.3
0.4
0.5
0.6
MOLE_FRACTION
SN
Final Meeting COST Action
531 Vienna
17-18 May 2007
8
Au-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
Surface Tension + modelling:
Binary systems
Wetting behaviour:
Ternary systems:
Au-Sn
Au-In
In-Sn
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
Bi-In-Sn system. Thermodynamic Properties
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
Aim……
Thermodynamic description
 DSC MEASUREMENTS
(liquidus surface)
 BISMUTH ACTIVITY
MEASUREMENTS
Final Meeting COST Action 531 Vienna 17-18 May 2007
IT 2-4 Università di Roma La Sapienza – Roma- I
D.Gozzi
EXPERIMENTAL
effusion holes
 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
1250 1000
log ( p/Pa)
5
500 K
At 1000 K
Bi/In = 200
Bi/Sn = 3x105
0
-5
xBi variable
-10
-20
xSn/xIn = 0.85
Bi
In
Sn
-15
6
8
10
12
14
16
18
20
4
10 /T /K
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
Surface Tension + modelling:
Binary systems
Wetting behaviour:
Ternary systems:
Bi-In
In-Sn
Bi-In-Sn/Cu
Binary sub-systems:
Bi-In/Cu
In-Sn /(Cu,Ni)
Final Meeting COST Action 531 Vienna 17-18 May 2007
Ag-In-Sn-Zn system
FR 2-3 Marseille-F, J.P.Bros, M.Gambino, A.Sabbar,AZrineh,J.M.Miane
Ag
Section xAg= 0.045
In
Section xIn/xSn = 1.1
Section xIn/xSn = 0.25
Liquidus temperatures
Points 3 and 5: 289°C
Point 4 :
315°C
Eutectic surface: 114°C
Zn
Sn xZn = 0.10
Ag-In-Sn-Zn system
FR 2-3 Marseille-F, J.P.Bros and M.Gambino
T/°C
Ag-In-Sn-Zn Liquidus
xIn/xSn = 0.25 section
xAg= 0.09
xAg= 0
xZn
T/°C
xAg= 0.05
xAg= 0
Ag-In-Sn-Zn Liquidus
xIn/xSn = 1.1 section
Final Meeting COST Action 531 Vienna 17-18 May 2007
xZn
Electrochemical measurements
Potentiodynamic polarization curves recorded in 0.1 M NaCl solution
using a saturated calomel electrode (SCE) as a reference
100
10
1
2
J (mA/cm )
0,1
0,01
Sn88.7Ag2.3In9.0
Sn86.6Ag3.0Bi10.4
Sn96.1Ag3.1Cu0.8
Sn90.4Ag2.9Cu6.7
Sn73.9Pb26.1
1E-3
1E-4
1E-5
1E-6
-850
-575
-300
-25
250
E (mV/SCE)
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
Pd-X (X= In, Sn, Zn) HT drop calorimetry
IT 2-1 Università di Genova– I, S.Amore, N.Parodi and G.Borzone
PdIn
PdSn2
 f H 0  70.0  1.0 kJ / m ol at.
 f H 0  50.0  1.0 kJ / m ol at.
Our data ,dir. reaction cal, 298K
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
 f H 0  34.0  1.0 kJ / mol at.
Final Meeting COST Action 531 Vienna 17-18 May 2007
H. Flandorfer (2002)
PdIn
 f H 0  70.0  1.0 kJ / m ol at.
Final Meeting COST Action 531 Vienna 17-18 May 2007
PdSn2
 f H 0  50.0  1.0 kJ / m ol at.
Final Meeting COST Action 531 Vienna 17-18 May 2007