Date post: | 21-Dec-2015 |
Category: |
Documents |
View: | 221 times |
Download: | 2 times |
COST531 Joint WG1/2 meeting
SGTE/ NPL Database Activities
13 June 2003
Alan DinsdaleNPL Materials Centre
NPL, UK
Scope of presentation
SGTE NPL / SGTE database Conclusions from Paris meeting Uses of the database Specific calculations and assessments Prediction of surface tension
COST531: Working groups
Thermodynamics and Phase Diagrams Literature search and selection of key systems
Optimised phase diagrams Creation of critically assessed thermodynamic database Also estimation of surface tension, wettability, electrical properties
Physical properties Measurement of wettability, surface tension, viscosity, mechanical
behaviour … Chemical properties
Oxidation behaviour, toxicity, environmental aspects Reliability
Thermal shock, overload failure, age hardening …. Processing and Packaging
Flip chip technique etc.
SGTE Members Canada
ThermFact, Montreal. France
Institute National Polytechnique, Grenoble. (LTPCM)Association THERMODATA, Grenoble. IRSID, Maizières-les-Metz. Université Paris Sud, Chatenay-Malabry. (LCPMB)
Germany RWTH, Aachen. (Department of Materials Chemistry)Max Planck Institut für Metallforschung, Stuttgart. (PML)GTT Technologies, Hertzogenrath.
Sweden Royal Institute of Technology, Stockholm. (Department of Materials
Science and Engineering)Thermo-Calc Software AB Stockholm.
United Kingdom National Physical Laboratory, Teddington. (Materials Centre)AEA Technology, Harwell.
USAThe Spencer Group, Ithaca
Possible future members
NIST Tohoku University NASA
Landolt-BörnsteinNumerical Data and Functional Relationships in Science and Technology
New Series / Editor in Chief: W. MartienssenGroup IV: Physical Chemistry
Volume 19
Thermodynamic Properties of Inorganic Materials compiled by SGTE
Subvolume BBinary Systems
Phase Diagrams, Phase Transition Data,Integral and Partial Quantities of Alloys
Part 1Elements and Binary Systems from Ag-Al to Au-Tl
Contents of the NPL / SGTE database
Designed for use in the calculation of phase equilibria involving solders and other low melting alloy systems.
Covers the following 12 elements
Ag, Al, Au, Bi, Cu, Ge, In, Pb, Sb, Si, Sn, Zn
Contains data for Binary systems (all 66 except Au-Zn) Ternary systems (15 systems specifically assessed)
Ag-Bi-Sn, Ag-Cu-Pb, Ag-Cu-Sn, Ag-Pb-Sn, Al-Cu-Si, Al-Sn-Zn, Au-In-Pb, Bi-In-Pb, Bi-In-Sn, Bi-In-Zn, Bi-Pb-Sn, Bi-Sn-Zn, Cu-Pb-Sn, In-Pb-Sn, In-Sn-Zn
Predictions can be made of thermodynamic properties of phase equilibria for wide range of compositions in that 12 component system
Agreement between SGTE and COST531
SGTE to provide a preliminary database for use within COST531 internal research
SGTE, in return, will be able to use COST531 data.
Database management
Need to agree on Scope of the database Unary data Key binary (and ternary ?) data Models
Paris meeting: July 2002
Conclusions from Paris meeting
Concentrate on:
Ag-Bi-Cu-Sn with the addition of
Au, In, Ni, P, Pd, Sb, Zn Plus (?)
Al, Pb
Possible initial scope of database:
Ag-Bi-Cu-Pb-Sn with (Ni-P) and Pd
Other datasets available(not in SGTE solders database)
Ag-Ni, Ag-Pd Cu-Ni, Cu-P Ni-P, Ni-Pd, Ni-Sn Pb-Pd Pd-Sn
Missing systems
Binary systems:
Ag-P, Bi-Ni, Bi-P, Bi-Pd, Cu-Pd, P-Sn, Ni-Pb, P-Pb Ternary systems:
Ag-Bi-Cu, Bi-Cu-Sn, Ag-Cu-Ni, Ag-Ni-Sn, Ag-Cu-P,
Ag-P-Sn, Cu-P-Sn, Ag-Cu-Pd, Ag-Pd-Sn, Cu-Pd-Sn
Unary data
Based on CALPHAD 1991, 15(4), 317-425 Updated version for CALPHAD 2003 (?) Major changes for solders relate to:
Sn hcp_a3fcc_a1tetragonal_a6
In fcc_a1tet_alpha1bct_a5rhombohedral_a5biin_epsilonhcp_zn
Key papers from CALPHAD conference
Ursula Kattner: “Thermodynamic assessment of the Sn-Cu-Ni and Sn-Ag-Cu-Ni system”
Zbigniew Moser: “Physical, electrical and mechanical studies of (Sn-Ag_eut+Cu=Pb-free soldering materials”
Ales Kroupa: “Database for calculation of lead free solders”
Nele Moelans: “Thermodynamic optimization of the lead-free solder system Bi-In-Sn-Zn”
Types of properties covered
Enthalpies Vapour pressures Specific heat Phase diagrams Liquidus and solidus temperatures Molar volumes and densities
Uses of the database
To calculate the liquidus and solidus temperatures of a solder
To calculate the effect of contamination of a new lead free solder with a conventional Pb-Sn solder
To calculate the enthalpy release on solidification of a solder
To calculate the volume changes in a solder on solidification and during thermal cycling
Calculation of surface tension
Specific calculations
Binary phase diagrams Ternary phase diagrams Isopleths Effect of pressure Constant composition vs temperature
Mass phase Heat capacity Volume Enthalpy
Prediction of surface tension
0.0 0.2 0.4 0.6 0.8 1.0
400
600
800
1000
1200
1400Cu-Sn
x Sn
Tem
pera
ture
/ K
Cu Sn
Pressure/Pa 1.01325E5
TransformationTemperatures / K
Calculated 14:39:25 30-SEP-2002Data file D:\atd\Data\solders\v2_3\testing\def.mpi
Results file D:\atd\Data\solders\v2_3\testing\def44.nbrLog file D:\atd\Data\solders\v2_3\testing\mt1.log
2002-06-13
911.55688.20499.97460.70505.08460.70
1029.671068.511357.78860.88792.73624.30855.62913.24950.14863.12
0.0 0.2 0.4 0.6 0.8 1.0
400
600
800
1000
1200
1400Au-In
x In
Tem
pera
ture
/ K
Au In
Pressure/Pa 1.01325E5
TransformationTemperatures / K
Calculated 14:37:38 30-SEP-2002Data file D:\atd\Data\solders\v2_3\testing\def.mpi
Results file D:\atd\Data\solders\v2_3\testing\def26.nbrLog file D:\atd\Data\solders\v2_3\testing\mt1.log
2002-06-13
449.63914.80
1337.33907.09765.66759.36591.88486.61723.86783.32730.65722.80759.37770.33811.83429.37429.75
0.0 0.2 0.4 0.6 0.8 1.0
400
600
800
1000
1200
1400Au-Sn
x Sn
Tem
pera
ture
/ K
Au Sn
Pressure/Pa 1.01325E5
TransformationTemperatures / K
Calculated 14:37:55 30-SEP-2002Data file D:\atd\Data\solders\v2_3\testing\def.mpi
Results file D:\atd\Data\solders\v2_3\testing\def30.nbrLog file D:\atd\Data\solders\v2_3\testing\mt1.log
2002-06-13
801.261337.34391.46796.91552.42463.92685.80586.06529.10489.69505.08
0.0 0.2 0.4 0.6 0.8 1.0200
300
400
500
600
700Pb-Sn
x Sn
Tem
pera
ture
/ K
Pb Sn
Pressure/Pa 1.01325E5
TransformationTemperatures / K
Calculated 14:41:32 30-SEP-2002Data file D:\atd\Data\solders\v2_3\testing\def.mpi
Results file D:\atd\Data\solders\v2_3\testing\def59.nbrLog file D:\atd\Data\solders\v2_3\testing\mt1.log
2002-06-13
456.14285.83286.14600.62505.08
Ag-Sn-Pb
470 K
1.01325E5 Pa
Ag
Sn
Pb0.8 0.6 0.4 0.2
0.8
0.6
0.4
0.2
0.2
0.4
0.6
0.8
xSn
xPb
xAg
2002-06-13
Plotted 14:42:32 30-SEP-2002
Data D:\atd\Data\solders\v 2_3\testing\def .mpi
Results D:\atd\Data\solders\v 2_3\testing\def 2.tnr
Log D:\atd\Data\solders\v 2_3\testing\mt1.log
0 2 4 6 8440
460
480
500
520
540
560
580
600
620
Weight % Ag
Tem
pera
ture
/ K
Sn-Ag-Cu system: Temperature-composition section0 wt% Ag, 3.27 wt% Cu - 8.9 wt% Ag, 0 wt% Cu
2002-08-30
CONSTRAINTS
P/Pa or V/m3 1.01325E5
Start
Sn 96.7300Ag 0.0000Cu 3.2700
End
Sn 91.1000Ag 8.9000Cu 0.0000
Calculated 12:32:24 2-SEP-2002Replotted 12:35:37 2-SEP-2002Data d:\jag\solders\def.mpi
Results d:\jag\solders\def.isoLog d:\jag\solders\mt65.log
Start End
LIQUID
LIQUID + CU6SN5
LIQUID + AGSB_ORTHO
LIQUID +AGSB_ORTHO +
CU6SN5
BCT_A5 + LIQUID + CU6SN5BCT_A5 + LIQUID
+ AGSB_ORTHO
BCT_A5 + AGSB_ORTHO + CU6SN5
BCT_A5 + AGSB_ORTHO + CU6SN5_P
LIQUIDUS (00MOO/BOE)SECONDARY SOLIDIFICATION (00MOO/BOE)EUTECTIC TEMPERATURE (00MOO/BOE)
Sn-Ag-Cu
Liquidus Contours
491 - 653 K
101325 Pa
Sn 0.8 1.6 2.4 3.2 4.0 4.8
2
4
6
8
10
12
14
wt%Ag
wt%Cu
2002-08-30
Replotted 15:51:46 30-AUG-2002
Data d:\jag\solders\def .mpi
Results d:\jag\solders\def .con
Log d:\jag\solders\mt62.log
Calculated primary phase boundaries (00MOO/BOE)Experimental eutectic (00MOO/BOE)
491493
495497
499
501503
513
523
533
543
553
563
573
583
593
603
613
623
513523
533543
553 563 573 583 593 603 613 623633
643
653
BCT_A5
AGSB_ORTHO
CU6SN5
Cu-Sn-Pb
1108 K
101325 Pa
Cu
Sn
Pb0.8 0.6 0.4 0.2
0.8
0.6
0.4
0.2
0.2
0.4
0.6
0.8
wSn
wPb
wCu
2002-10-23
Plotted 12:15:32 31-OCT-2002
Data d:\jag\solders\def .mpi
Results d:\jag\solders\ternary 389.tnr
Log d:\jag\solders\mt150.log
LIQUID
LIQUID +LIQUID
LIQUID + LIQUID + FCC_A1
LIQUID + FCC_A1
LIQUID +FCC_A1
SEPARATION INTO TWO LIQUIDS AT 1108 K (31BRI)
486 488 490 492 494
7020
7040
7060
7080
7100
7120
7140
7160
7180
7200
D:\atd\Data\solders\v2_3\testing\def4 16:48:20 30-SEP-2002
T/K
10
.3x
(1/(
V/m
3 of s
yste
m))
CONSTRAINTSP/atm=1n(Sn)/mol=84.2531n(Ag)/mol=2.781172n(Cu)/mol=1.573663Worst error=1.690784E-5No. of calculations=100No. shown on plot=100
Data D:\atd\Data\solders\v 2_3\testing\def .mpi Results D:\atd\Data\solders\v 2_3\testing\def 4.GPH
Log D:\atd\Data\solders\v 2_3\testing\MT2.LOG Calculated 16:48:20 30-SEP-2002
Plotted 16:53:37 30-SEP-2002
4.72
486 488 490 492 494
0
1
2
3
4
5
6
7
8
9
10
D:\atd\Data\solders\v2_3\testing\def4 16:48:20 30-SEP-2002
T/K
ma
ss(p
ha
se)/
kgBCT_A5 BCT_A5
BCT_A5
LIQUID
LIQUID
CONSTRAINTSP/atm=1n(Sn)/mol=84.2531n(Ag)/mol=2.781172n(Cu)/mol=1.573663Worst error=1.690784E-5No. of calculations=100No. shown on plot=100
Data D:\atd\Data\solders\v 2_3\testing\def .mpi Results D:\atd\Data\solders\v 2_3\testing\def 4.GPH
Log D:\atd\Data\solders\v 2_3\testing\MT2.LOG Calculated 16:48:20 30-SEP-2002
Plotted 16:50:54 30-SEP-2002
4.72
250 300 350 400 450 500 550
1.45
1.50
1.55
1.60
1.65
1.70
1.75
D:\atd\Data\solders\v2_3\testing\def1 16:37:37 30-SEP-2002
T/K
103 x
V/m
3 of s
yste
mCONSTRAINTS
P/atm=1n(Sn)/mol=84.2531n(Ag)/mol=2.781172n(Cu)/mol=1.573663Worst error=5E-6No. of calculations=151No. shown on plot=151
Data D:\atd\Data\solders\v 2_3\testing\def .mpi Results D:\atd\Data\solders\v 2_3\testing\def 1.GPH
Log D:\atd\Data\solders\v 2_3\testing\MT2.LOG Calculated 16:37:37 30-SEP-2002
Plotted 16:40:24 30-SEP-2002
4.72
486 488 490 492 494
0
500
1000
1500
2000
2500
3000
3500
4000
4500
D:\atd\Data\solders\v2_3\testing\def4 16:48:20 30-SEP-2002
T/K
10-3
x C
p o
f sys
tem
/J K
-1
31
32
KEY
1-AGZN3 2 BCT_A53-BCT_A5 4 LIQUID5 AGSB_ORTHO 6-GAMMA_AGZN7-BCC_A2 8-HCP_A39-HCP_ZN 10-FCC_A111-FCC_A1 12-CUB_A1313-ALCU_EPSILON14-ALCU_ETA 15-GAMMA_DO316-GAMMA_DO3 17-LAVES_C1418-LAVES_C15 19-LAVES_C3620-CU10SN3 21-CU3SN22-CU41SN11 23 CU6SN524-CU6SN5_P 25-DIAMOND_A426-INSN_GAMMA27-RHOMBOHEDRAL_A728-TETRAGONAL_A629-TET_ALPHA1 30-SB1SN131=2,5,23 32=2,4,23
CONSTRAINTSCONSTRAINTS
P/atm=1n(Sn)/mol=84.2531n(Ag)/mol=2.781172n(Cu)/mol=1.573663Worst error=1.690784E-5Ref(Sn)=as dataRef(Ag)=as dataRef(Cu)=as dataNo. of calculations=100No. shown on plot=100
Data D:\atd\Data\solders\v 2_3\testing\def .mpi Results D:\atd\Data\solders\v 2_3\testing\def 4.GPH
Log D:\atd\Data\solders\v 2_3\testing\MT2.LOG Calculated 16:48:20 30-SEP-2002
Plotted 16:56:07 30-SEP-2002
4.72
486 488 490 492 494
500
600
700
800
900
1000
1100
D:\atd\Data\solders\v2_3\testing\def4 16:48:20 30-SEP-2002
T/K
10-3
x E
nth
alp
y o
f sys
tem
/J
31
32
KEY
1-AGZN3 2 BCT_A53-BCT_A5 4 LIQUID5 AGSB_ORTHO 6-GAMMA_AGZN7-BCC_A2 8-HCP_A39-HCP_ZN 10-FCC_A111-FCC_A1 12-CUB_A1313-ALCU_EPSILON14-ALCU_ETA 15-GAMMA_DO316-GAMMA_DO3 17-LAVES_C1418-LAVES_C15 19-LAVES_C3620-CU10SN3 21-CU3SN22-CU41SN11 23 CU6SN524-CU6SN5_P 25-DIAMOND_A426-INSN_GAMMA27-RHOMBOHEDRAL_A728-TETRAGONAL_A629-TET_ALPHA1 30-SB1SN131=2,5,23 32=2,4,23
CONSTRAINTSCONSTRAINTS
P/atm=1n(Sn)/mol=84.2531n(Ag)/mol=2.781172n(Cu)/mol=1.573663Worst error=1.690784E-5Ref(Sn)=as dataRef(Ag)=as dataRef(Cu)=as dataNo. of calculations=100No. shown on plot=100
Data D:\atd\Data\solders\v 2_3\testing\def .mpi Results D:\atd\Data\solders\v 2_3\testing\def 4.GPH
Log D:\atd\Data\solders\v 2_3\testing\MT2.LOG Calculated 16:48:20 30-SEP-2002
Plotted 16:56:24 30-SEP-2002
4.72
Prediction of surface tension
Based on the approach of Tanaka
Using the Butler equation to estimate the surface tension from bulk thermodynamic properties
Tested with success for metallic and ionic melts
Assumes an equilibrium between the bulk liquid and the surface liquid
Generalised and extended in this project to cover multicomponent systems
Tested in detail for solder systems
Uses the new database for solders
Makes use of Brian Keene’s review of experimental surface tension data for tin and lead free solders (1993)
Provides good basis for virtual measurement system for solders
Model for surface tension (1)
As originally presented:
This relates the surface tension of the binary alloy to the surface tension of the pure components and the thermodynamic properties of the bulk and the surface monolayer
BESE
B
S
BESE
B
S
GA
GAx
x
A
RT
GA
GAx
x
A
RT
,2
2
,2
22
2
22
,1
1
,1
12
2
11
11ln
11
)1(
)1(ln
Model for surface tension (2)
These equations can be transformed into:
and expresses that the chemical potential of the components is equal in the bulk and surface layer
The thermodynamic properties of the bulk are well represented by standard thermodynamic models
BEBSES GxRTGxTRA,
11
,1111 )ln()ln()(
BEBSES GxTRGxTRA,
22
,2222 )ln()ln()(
Model for surface tension (3)
The thermodynamic properties of the surface layer is given by:
Where A1 is the surface area of component 1, 1 is the surface tension of component 1
N0 is the Avogadro number and V1 the molar volume of component 1
mixSSSS GAxAxG ,222111 )()(
3/21
3/101 091.1 VNA
Model for surface tension (4)
There is an empirical relationship between Gmix , the excess Gibbs energy of mixing, for the surface and Gmix for the bulk
Gibbs energy of surface layer given by:
The surface tension, , is calculated to be the value which just brings the surface into equilibrium with the bulk.
This allow the model to be generalised to any number of components
mixBmixS GG ,, 83.0
mixSSSS GAxAxG ,222111 )()(
Sample calculations: Bi-Sn 608 K
0.0 0.2 0.4 0.6 0.8 1.00.30
0.35
0.40
0.45
0.50
0.55
0.60Calculated Surface Tension of Bi-Sn liquid at 608 K
x(Sn)
Su
rfa
ce T
en
sio
n /
Nm
-1
PARAMETER VALUES
Optimisation: 10:17:54 30-MAY-2002Plotted: 10:19:24 30-MAY-2002
Data: D:\atd\Data\surface tension\def.mpiExperiment: D:\atd\Data\surface tension\stcalc.mac
Results: D:\atd\Data\surface tension\def.mprLog: D:\atd\Data\surface tension\mt15.log
Parameters as in datafile
Mean squ error = 0.017305
DEV
Surface composition: Bi-Sn 608 K
0.0 0.2 0.4 0.6 0.8 1.00.0
0.2
0.4
0.6
0.8
1.0Calculated x(Sn) of Surface of Bi-Sn liquid at 608 K
x(Sn)
x(S
n<
SU
RF
AC
E>
)PARAMETER VALUES
Optimisation: 14:35:19 26-SEP-2002Plotted: 14:35:26 26-SEP-2002
Data: C:\MTDATA\Work\surface tension\DEF.MPIExperiment: C:\MTDATA\Work\surface tension\stcalc2.mac
Results: C:\MTDATA\Work\surface tension\DEF.MPRLog: C:\MTDATA\Work\surface tension\MT60.LOG
Parameters as in datafile
Mean squ error = 0.058
2002-06-13
Ag-Sn 1273 K
0.0 0.2 0.4 0.6 0.8 1.00.4
0.5
0.6
0.7
0.8
0.9
1.0Calculated Surface Tension of Ag-Sn liquid at 1273 K
x(Sn)
Su
rfa
ce T
en
sio
n /
Nm
-1PARAMETER VALUES
Optimisation: 13:32:47 26-SEP-2002Plotted: 13:32:56 26-SEP-2002
Data: C:\MTDATA\Work\surface tension\DEF.MPIExperiment: C:\MTDATA\Work\surface tension\stcalc.mac
Results: C:\MTDATA\Work\surface tension\DEF.MPRLog: C:\MTDATA\Work\surface tension\MT58.LOG
Parameters as in datafile
Mean squ error = 0.132513
2002-06-13
Ag-Sn 40%Sn : effect of temperature
400 600 800 1000 12000.50
0.55
0.60
0.65
0.70Calculated Surface Tension of 60:40 Ag-Sn liquid
T/K
Su
rfa
ce T
en
sio
n /
Nm
-1
PARAMETER VALUES
Optimisation: 14:15:43 26-SEP-2002Plotted: 14:15:50 26-SEP-2002
Data: C:\MTDATA\Work\surface tension\DEF.MPIExperiment: C:\MTDATA\Work\surface tension\stcalc1.mac
Results: C:\MTDATA\Work\surface tension\DEF.MPRLog: C:\MTDATA\Work\surface tension\MT59.LOG
Parameters as in datafile
Mean squ error = 0.103516
2002-06-13
Sn-Ag-Cu: variation with temperature
500 550 600 650 700 750 8000.50
0.52
0.54
0.56
0.58
0.60Calculated Surface Tension of Sn-Ag-Cu liquid
T/K
Su
rfa
ce
Te
nsio
n / N
m-1
PARAMETER VALUES
Optimisation: 12:17:13 11-OCT-2002Plotted: 12:17:26 11-OCT-2002
Data: D:\atd\Data\surface tension\DEF.MPIExperiment: D:\atd\Data\surface tension\stcalc3.mac
Results: D:\atd\Data\surface tension\DEF.MPRLog: D:\atd\Data\surface tension\MT64.LOG
Parameters as in datafile
Mean squ error = 0.063161
2002-10-04
Surface tension of pure Sn
Surface tension of pure Pb