COST531 Joint WG1/2 meeting SGTE/ NPL Database Activities 13 June 2003 Alan Dinsdale NPL Materials Centre NPL, UK.

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





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





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





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


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



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


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



Plotted 16:40:24 30-SEP-2002

4.72

486 488 490 492 494

0

500

1000

1500

2000

2500

3000

3500

4000

4500


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



Plotted 16:56:07 30-SEP-2002

4.72

486 488 490 492 494

500

600

700

800

900

1000

1100


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



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


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()(


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


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



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


Data: C:\MTDATA\Work\surface tension\DEF.MPIExperiment: C:\MTDATA\Work\surface tension\stcalc.mac




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


Data: C:\MTDATA\Work\surface tension\DEF.MPIExperiment: C:\MTDATA\Work\surface tension\stcalc1.mac




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



2002-10-04

Surface tension of pure Sn

Surface tension of pure Pb

COST531 Joint WG1/2 meeting SGTE/ NPL Database Activities 13 June 2003 Alan Dinsdale NPL Materials Centre NPL, UK.

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