Final Meeting of the COST Action 531 Lead-Free Solder Materials May 17th – 18th, 2007 Vienna,...
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Transcript of Final Meeting of the COST Action 531 Lead-Free Solder Materials May 17th – 18th, 2007 Vienna,...
Final Meeting of the COST Action 531Lead-Free Solder Materials
May 17th ndash 18th 2007 Vienna Austria
Report presented by Z Moser
Within COST 531 Program realized from 2003 ndash 2006 at the Institute of Metallurgy and Materials Polish
Academy of Sciences in Krakoacutew Poland the following general research has been undertaken
ldquoExperimental determination and modeling of physicochemical properties of
multi-component alloys on the tin base ldquo
Within this research two studies has been realized
1 2003-2004 ldquoInfluence of Sb additions on surface tension and density of Sn-Ag-Cu-Sb alloys
Experiment vs modelingrdquo
1 Z Moser W Gasior J Pstruś ldquoSurface tension and density of Sn based Sn-Ag-Cu alloys with Sb
additionsrdquo Proceedings of COST Action 531 Lead-free Solder Materials Mid-term Meeting Lausanne
2005 February 24-25 Switzerland 1-16
b ZMoser WGąsior JPstruś IOhnuma KIshida ldquoInfluence of Sb additions on surface tension and
density of Sn-Sb Sn-Ag-Sb and Sn-Ag-Cu-Sb alloysrdquo Experiment vs modeling International Jounal of
Materials Research Zeitschrift fuer Metallkunde 97 2006 p365-370 Dedicated to Professor
Dr Ferdinand Sommer on the occasion of his 65th birthday
2 2005-2006 ldquoInfluence of In additions on surface tension and density of the Sn-Ag-Cu-In alloys
Experiment vs modelingrdquo
This research has been realized jointly with Slovak Academy of Sciences (Pavol Sebo)
bull Z Moser W Gąsior J Pstruś ldquoInfluence of In additions on surface tension and density of In-Sn
Sn-Ag-In and Sn-Ag-Cu-In liquid solders Experiment vs Modelingrdquo COST 531 MC Meeting
(25022006) amp WG1-2-3-4-5-6 Meeting (23-24022006) Genoa Italy
b Zbigniew Moser Pavol Sebo Władysław Gąsior Peter Svec and Janusz Pstruś ldquoWettability Studies of
Sn-Ag-Cu-In Liquid Solders and Interaction with Cu Substraterdquo Program and Abstracts Calphad XXXVI
The Pennsylvania State University State College Pennsylvania USA May 6 -11 2007 p35
This joint research will be presented to day
Wettability Studies of Sn-Ag-Cu-In Liquid Solders and Interaction with Cu Substrate
Zbigniew Moser Pavol Sebo Władysław Gąsior Peter Svec and Janusz Pstruś
Institute of Metallurgy and Materials Science Polish Academy of Sciences
30-059 Krakoacutew Reymonta Street 25 POLANDInstitute of Materials and Machine Mechanics Slovak Academy of Sciences
Racianska 75 831-02 Bratislava 3 SLOVAKIAInstitute of Physics Slovak Academy of Sciences Dubravska cesta 9
845-11 Bratislava 45 SLOVAKIA
Plan of presentation
1 Introduction2 Surface tension and density measurements of the (Sn313Ag074Cu) + In liquid alloys3 Modeling of the surface tension4 Contact angles measurements of the (Sn313Ag074Cu) + In liquid alloys5 Interaction studies of the quaternary alloys with Cu substrate6 Conclusions7 Final remarks
MetalsBinary Alloys
Multicomponent Alloys
PbSnInAgBiSbCuZnAlAu
Pb ndash SnAg ndash SnAg ndash InBi ndash SnIn ndash SnAg ndash BiSb ndash SnSn ndash ZnAg ndash SbCu ndash SnCu ndash Sb
(Sn-Ag)eut +In
(Sn-Ag)eut +Bi
(Sn-Ag)eut +Cu
(Sn-Ag)eut +Sb
(Sn-Ag)eut +Cu+Sb
(Sn-Ag)eut +Cu+Bi
(Sn 313Ag 074Cu)+InThis study
Table 1 The investigated liquid metals and alloysFig 1 The first window of the SURDAT database
[1] Z Moser W Gąsior A Dębski and J Pstruś Database of lead ndash free soldering materials edited by IMIM PAS and printed by Orekop Krakoacutew 2007 ISBN 83-60768-01-3
[2] JAV Butler The Thermodynamics of the Surfaces of Solutions Proceedings of the Royal Society of London series A CXXXV (1932) 348-375
[3] Liu XJ Inohana Y Ohnuma I Kainuma R Ishida K Moser Z Gąsior W Pstruś J Experimental Determination and Thermodynamic Calculation of the Phase Equilibria and Surface tension of the Ag-Sn-In System J Electron Mater 31 (2002) 1139-1151
[4] P Sebo P Stefanik Kovove Mater Effect of In Addition on Sn-Ag Solder Its Wetting and Shear Strength of Copper Joints 43 (2005) 202-209 (Decreasing of contact angles adding 66 and 9 mass In to (Sn-Ag)eut)
[5] M E Loomans SVaynmann G Ghosh M E Fine J Electronic Mater 23 (1994) 741-746 (Similar decreasing of contact angles by In additions)
[6] S Hwang Lead-free Implementation and Production A Manufacturing Guide McGraw-Hill (2005) ISBN 0-07-144374-6 Chapter Three Selecting Lead-free Alloys for Solder Interconnections (From meniscographic studies with flux wetting force and wetting time of Sn 41 Ag05Cu 4In ( mass) nearly equivalent to Sn-Pb eutectic)
1 Introduction
The main aim is to confirm the previous observation of In additions to (Sn-Ag) eut on wettability and to extend
it in the presented studies of quaternary alloys (Sn 313Ag 074Cu) + In combining surface tension density
and modeling of surface tension from Krakow Poland with contact angles and interaction of liquid alloys
with Cu substrate using flux undertaken in Bratislava Slovakia within COST 531 Program
The starting material was nearly eutectic alloy (Sn 313Ag 074Cu) with 2 3 4 15 30 50 and 75 at In
2 Surface tension and density measurements of the (Sn313Ag074Cu) + In liquid alloys
The density and surface tension measurements of the (Sn313Ag074Cu) + In liquid alloys at In
concentrations ( 2 3 4 15 30 50 and 75 at) by the maximum bubble pressure method and dilatometric
technique were conducted in the temperature range from 158 degC to 936 degC Results are presented in Tables 2
and 3 and in Figures 2 and 3 In Figures 4 and 5 are shown isotherms of surface tension and density As
indicated in the introduction no change of both temperature dependence of the surface tension and density is
observed The preliminary results were presented in Genoa [1]
[1] COST Action 531 MC Meeting (25022006) amp WG 1-2-3-4-5-6 Meeting (23-24022006) in Genoa Italy
XIn σ=A+B∙TmN∙m-1
σ 523K
mN∙m-1
σ 1023K
mN∙m-1
Err(a)mN∙m-1
Err(b)mN∙m∙K-1
000200300401503005007510
5851 -008815785 -007665728 -007305743 -007056034 -011555883 -010495879 -010045877 -008575938 -00942
5391 plusmn825385 plusmn715346 plusmn915374 plusmn6
5430 plusmn1015334 plusmn91
5354 plusmn1045429 plusmn1155445 plusmn116
4950plusmn765002plusmn76 4982plusmn86 5022plusmn624853plusmn984810plusmn88
4852plusmn99 5000plusmn176
4974plusmn113
plusmn78plusmn90plusmn99plusmn80
plusmn104plusmn96
plusmn111plusmn185plusmn119
plusmn00085plusmn00120plusmn00113plusmn00096plusmn00124plusmn00115plusmn00127plusmn00308plusmn00144
- Sn 313Ag 074Cu
XIn
at
ρ=A+B∙Tg∙cm-3
ρ 523K
g∙cm-3
ρ 1023K
g∙cm-3
Err(a)g∙cm-3
Err(b)g∙cm-3∙K-1
000200300401503005007510
74615-000070374814-000076975050-000083874130-000074873416-000064173379-000066473159-000063273887-000074073206-0000684
7094plusmn00277079plusmn00297067plusmn00277022plusmn00557006plusmn00706990plusmn00606986plusmn00667002plusmn00156963plusmn0027
6742plusmn003 6695plusmn0036648plusmn004
6648plusmn006 6686plusmn007 6658plusmn0066670plusmn0066632plusmn002
6621plusmn003
plusmn0028plusmn0036plusmn0050plusmn0088plusmn0076plusmn0063plusmn0067plusmn0022plusmn0032
plusmn0000035plusmn0000052plusmn0000078plusmn0000113plusmn0000090plusmn0000073plusmn0000073plusmn0000033plusmn0000039
Table 2 Temperature dependencies of the density of the liquid quaternary (Sn 313Ag 074Cu)+In and ternary alloys with the calculated errors of the A and B parameters and the densities calculated at 523 K and 1032 K
Table 3 Temperature dependencies of the surface tension of the liquid quaternary (Sn 313Ag 074Cu)+In and ternary alloys with the calculated errors of the A and B parameters and the surface tension calculated at 523 K and 1032 K
Fig 2 The temperature dependencies of the density of (Sn 313Ag 074Cu) + In liquid alloys
Fig 3 The temperature dependencies of the surface tension of (Sn 313Ag 074Cu) + In
liquid alloys
Fig 4 The isotherms of the density of (Sn 313Ag 074Cu)+In liquid alloys at 523 K and 1023 K
Fig 5 The isotherms of the surface tension of (Sn 313Ag 074Cu)+In liquid alloys at 523 K and 1023 K
3 Modeling of the surface tension
Two kinds of modeling of surface tension were used for quaternary alloys Sn-Ag-Cu-In similarly as in previous studies on Sn-Ag-Cu-Sb system [1]
[1] ZMoser WGąsior JPstruś IOhnuma KIshida ldquoInfluence of Sb additions on surface tension and density of Sn-Sb Sn-Ag-Sb and Sn-Ag-Cu-Sb alloys Experiment vsmodelingrdquo International Jounal of Materials Research Zeitschrift fuer Metallkunde 97 (2006) 365-370 Dedicated to Professor DrFerdinand Sommer on the occasion of his 65th birthday
1 Butler model with thermodynamic properties of liquid constituent components and surface tension of pure
components This modeling was successfully tested in studies of systems presented in SURDAT database
with observation that the experimental temperature dependence of the surface tension is linear while from
modeling slightly curvilinear dependence was calculated
For such procedure in the case of quaternary Sn-Ag-Cu-In system we should know data of six binaries
Cu-In Cu-Ag Sn-Ag Ag-In Sn-Cu In-Sn four ternaries Sn-Ag-Cu Sn-Ag-In Sn-Cu-In In-Ag-Cu and for
quaternary alloy (one quaternary alloy with equal concentration of components 025 molar fraction was
investigated)
In the case of modeling 2 we are basing on experimental data of surface tension of constituent binary systems
with ternary and quaternary correction factors to elaborate the temperature and concentration dependence of
the surface tension of the Sn-Ag-Cu-In system For the remaining not previously investigated surface tension
and density in this study were determined Cu-In and Cu-Ag ternaries Sn-Ag-Cu Sn-Ag-In In-Ag-Cu and
one quaternary alloy with equal concentration of components 025 molar fraction
As an example in Table 4 are presented surface tension data of ternaries and quaternary alloy
Table 4 Temperature dependencies of the surface tension of the liquid quaternary Sn 25Ag 25Cu 25In and ternary alloys Sn 25Ag 25In Sn 25Ag 25Cu and In 25Ag 25Cu with the calculated errors of the A and B parameters and the
surface tension calculated at 973 K and 1273 K
X at σ = A +BTmNm-1
σ 973K
mNm-1
σ 1273K
mNm-1
Err(A)mNm-1
Err(B)mNm-1middotK-1
Sn25Ag25InSn25Ag25CuIn25Ag25Cu
Sn25Ag25Cu25In
= 6190-00599T = 6142-00235T = 6510-00293T = 7685-00737T
5607plusmn64 5914plusmn42 6225plusmn55
6967plusmn125
5427plusmn765843plusmn456138plusmn64
6746plusmn123
plusmn131 plusmn82
plusmn124 plusmn260
plusmn00133 plusmn00088
plusmn00122 plusmn00227
Fig6 Comparison of calculations of the surface tension of the quaternary system Sn-Ag-Cu-In by Butlerrsquos model and with temperature-concentration dependence and with one experimental alloy (Table 4) with equal 025 molar fractions Thin lines show the Butler model while thick correspond to temperature concentration dependence of the surface tension
Results of calculations by the Butler model show lower values of the surface tension due to the fact that
interaction parameters for Ag-Cu-In and Cu-In-Sn were not taken into calculations In addition only the
limited amount of alloys for binary and ternary alloys of surface tension was investigated with one quaternary
sample
The obtained results from both methods are compared in Fig6
4 Contact angles measurements of the (Sn313Ag074Cu) + In liquid alloys
Wetting of copper substrates was studied by sessile drop method Solder in a cube form was covered by flux
and put on the substrate and after melting at given temperature (250 280 and 320 oC) pictures of drop were
taken by digital camera up to 30 minutes Contact angles were measured by computer After the drop
solidifies specimen were cut perpendicularly for metallographic studies discussed in the next section
Typical course of time dependencies of contact angle for pure (not containing In) Sn 313Ag 074Cu
Sn 252Ag 057Cu 30In and Sn 12Ag 027Cu 75In are presented on Figs7-10 Except the beginning of
wetting the contact angle practically does not depend on the wetting temperature and with the increase of In
concentration is lowered the time to reach the constant values of contact angles which gradually are
decreasing Due to the observed in Figs7-9 the negligible differences in contact angles in the temperature
interval in Fig10 is plotted the change of contact angle after 30 minutes for all investigated alloys The
lowering tendency of the contact angle is observed with some scattering at low In content
Fig7 Change of the contact angle for the starting alloy Sn 313Ag 074Cu
Fig 8 Change of the contact angle for Sn 313Ag 074Cu + 30 at In
Fig 9 Change of the contact angle for Sn 313Ag 074Cu + 75 at In
Fig 10 Change of contact angles for Sn-Ag-Cu-In alloys after 30 minutes
5 Interaction studies of the quaternary alloys with Cu substrate
Metallographic studies of the structure of the boundary between the solder and substrate as well as the
structure of the solder itself was studied by electron scanning microscopy (SEM) Energy dispersive X-ray
analyzer (EDX) was used to measure the chemical composition of the interface as well as the bulk solder The
same specimen which were used for SEM and EDX investigation were also used for X-ray diffraction phase
analysis of the solder and substrate
For low In concentration (up to 15 at) Cu interface is formed by Cu6Sn5 phase For higher concentration of
In (30-50 at) Cu interface if formed by Cu41Sn11 phase For highest In concentration (75 at) Cu
interface is formed by Cu3(SnIn) phase
6 Conclusions
In this presentation investigating the influence of In on wettability of the alloy Sn 313Ag 074Cu close to
ternary eutectic Sn-Ag-Cu it was confirmed starting from previous data on In-Sn and
Sn-Ag-In [1] that due to the nearly the same surface tension and density values of pure In and Sn the
beneficial influence of In is reflected by the lowering of the contact angles with practically no change of
temperature dependence of both surface tension and density Isothermal behaviour of surface tension with ldquoSrdquo
shape starting from In-Sn and Sn-Ag-In proceeding into the investigated in this study Sn-Ag-Cu-In is
probably in addition connected with the peculiar properties of liquid In-Sn alloys showing extrema on
isothermal behaviour of electrical resistivity and viscosity [2] corresponding well to the existence of
intermetallic phases in the phase diagram of In-Sn phase diagram It is the another proof of the mutual
correlations between thermodynamic properties physical properties and the character of the phase diagram
[1] X J Liu Y Inohana I Ohnuma R Kainuma K Ishida Z Moser W Gąsior J Pstruś J Electronic Mater 31 (2002) 1139-51 [2] BPredel MHoch MPool Phase Diagrams and Heterogeneous Equilibria Springer-Verlag Berlin Heidelberg (2004) 289-291
7 Final remarks
1 Presented today joint results with P Sebo will be elaborated for Calphad journal
2 SURDAT database realized in parallel to COST 531 Program has been introduced on website of COST
531 Program
3 In addition from financing of COST 531 Program under research entitled ldquoExperimental determination
and modeling of physicochemical properties of multi-component alloys on the tin base ldquo within
2003-2006 the additional study has been realized by dr Piotr Ozga
ldquo The study of a possibility of the electrodeposition of Sn-Ag alloys from aqueous solutionsrdquo
a POzga ldquoEquilibria in Aqueous Solutions of Ag(I)-Sn(IIIV) in Presence of Strong Complexing
Ligandsrdquo CALPHAD XXXIII Krakow (Poland) May 30 ndash June 4 2004 Abstracts p 153
b POzga ldquoElectrodeposition of Sn-Ag and Sn-Ag-Cu alloys from the thiourea solutionsrdquo Archives of
Metallurgy and Materials 3 (2006) 413-421
The results of this study were used in habilitation thesis of P Ozga edited by the Institute of Metallurgy
and Materials ISBN-83-921845-8-0 Krakow (2006) 1-148
bull Special issue of the Archives of Metallurgy and Materials 32006 has been devoted to results realized
within COST 531 Program
Thank you
for your attention
- Slide 1
- Slide 2
- Slide 3
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- Slide 10
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Slide 18
- Slide 19
- Slide 20
-
Within COST 531 Program realized from 2003 ndash 2006 at the Institute of Metallurgy and Materials Polish
Academy of Sciences in Krakoacutew Poland the following general research has been undertaken
ldquoExperimental determination and modeling of physicochemical properties of
multi-component alloys on the tin base ldquo
Within this research two studies has been realized
1 2003-2004 ldquoInfluence of Sb additions on surface tension and density of Sn-Ag-Cu-Sb alloys
Experiment vs modelingrdquo
1 Z Moser W Gasior J Pstruś ldquoSurface tension and density of Sn based Sn-Ag-Cu alloys with Sb
additionsrdquo Proceedings of COST Action 531 Lead-free Solder Materials Mid-term Meeting Lausanne
2005 February 24-25 Switzerland 1-16
b ZMoser WGąsior JPstruś IOhnuma KIshida ldquoInfluence of Sb additions on surface tension and
density of Sn-Sb Sn-Ag-Sb and Sn-Ag-Cu-Sb alloysrdquo Experiment vs modeling International Jounal of
Materials Research Zeitschrift fuer Metallkunde 97 2006 p365-370 Dedicated to Professor
Dr Ferdinand Sommer on the occasion of his 65th birthday
2 2005-2006 ldquoInfluence of In additions on surface tension and density of the Sn-Ag-Cu-In alloys
Experiment vs modelingrdquo
This research has been realized jointly with Slovak Academy of Sciences (Pavol Sebo)
bull Z Moser W Gąsior J Pstruś ldquoInfluence of In additions on surface tension and density of In-Sn
Sn-Ag-In and Sn-Ag-Cu-In liquid solders Experiment vs Modelingrdquo COST 531 MC Meeting
(25022006) amp WG1-2-3-4-5-6 Meeting (23-24022006) Genoa Italy
b Zbigniew Moser Pavol Sebo Władysław Gąsior Peter Svec and Janusz Pstruś ldquoWettability Studies of
Sn-Ag-Cu-In Liquid Solders and Interaction with Cu Substraterdquo Program and Abstracts Calphad XXXVI
The Pennsylvania State University State College Pennsylvania USA May 6 -11 2007 p35
This joint research will be presented to day
Wettability Studies of Sn-Ag-Cu-In Liquid Solders and Interaction with Cu Substrate
Zbigniew Moser Pavol Sebo Władysław Gąsior Peter Svec and Janusz Pstruś
Institute of Metallurgy and Materials Science Polish Academy of Sciences
30-059 Krakoacutew Reymonta Street 25 POLANDInstitute of Materials and Machine Mechanics Slovak Academy of Sciences
Racianska 75 831-02 Bratislava 3 SLOVAKIAInstitute of Physics Slovak Academy of Sciences Dubravska cesta 9
845-11 Bratislava 45 SLOVAKIA
Plan of presentation
1 Introduction2 Surface tension and density measurements of the (Sn313Ag074Cu) + In liquid alloys3 Modeling of the surface tension4 Contact angles measurements of the (Sn313Ag074Cu) + In liquid alloys5 Interaction studies of the quaternary alloys with Cu substrate6 Conclusions7 Final remarks
MetalsBinary Alloys
Multicomponent Alloys
PbSnInAgBiSbCuZnAlAu
Pb ndash SnAg ndash SnAg ndash InBi ndash SnIn ndash SnAg ndash BiSb ndash SnSn ndash ZnAg ndash SbCu ndash SnCu ndash Sb
(Sn-Ag)eut +In
(Sn-Ag)eut +Bi
(Sn-Ag)eut +Cu
(Sn-Ag)eut +Sb
(Sn-Ag)eut +Cu+Sb
(Sn-Ag)eut +Cu+Bi
(Sn 313Ag 074Cu)+InThis study
Table 1 The investigated liquid metals and alloysFig 1 The first window of the SURDAT database
[1] Z Moser W Gąsior A Dębski and J Pstruś Database of lead ndash free soldering materials edited by IMIM PAS and printed by Orekop Krakoacutew 2007 ISBN 83-60768-01-3
[2] JAV Butler The Thermodynamics of the Surfaces of Solutions Proceedings of the Royal Society of London series A CXXXV (1932) 348-375
[3] Liu XJ Inohana Y Ohnuma I Kainuma R Ishida K Moser Z Gąsior W Pstruś J Experimental Determination and Thermodynamic Calculation of the Phase Equilibria and Surface tension of the Ag-Sn-In System J Electron Mater 31 (2002) 1139-1151
[4] P Sebo P Stefanik Kovove Mater Effect of In Addition on Sn-Ag Solder Its Wetting and Shear Strength of Copper Joints 43 (2005) 202-209 (Decreasing of contact angles adding 66 and 9 mass In to (Sn-Ag)eut)
[5] M E Loomans SVaynmann G Ghosh M E Fine J Electronic Mater 23 (1994) 741-746 (Similar decreasing of contact angles by In additions)
[6] S Hwang Lead-free Implementation and Production A Manufacturing Guide McGraw-Hill (2005) ISBN 0-07-144374-6 Chapter Three Selecting Lead-free Alloys for Solder Interconnections (From meniscographic studies with flux wetting force and wetting time of Sn 41 Ag05Cu 4In ( mass) nearly equivalent to Sn-Pb eutectic)
1 Introduction
The main aim is to confirm the previous observation of In additions to (Sn-Ag) eut on wettability and to extend
it in the presented studies of quaternary alloys (Sn 313Ag 074Cu) + In combining surface tension density
and modeling of surface tension from Krakow Poland with contact angles and interaction of liquid alloys
with Cu substrate using flux undertaken in Bratislava Slovakia within COST 531 Program
The starting material was nearly eutectic alloy (Sn 313Ag 074Cu) with 2 3 4 15 30 50 and 75 at In
2 Surface tension and density measurements of the (Sn313Ag074Cu) + In liquid alloys
The density and surface tension measurements of the (Sn313Ag074Cu) + In liquid alloys at In
concentrations ( 2 3 4 15 30 50 and 75 at) by the maximum bubble pressure method and dilatometric
technique were conducted in the temperature range from 158 degC to 936 degC Results are presented in Tables 2
and 3 and in Figures 2 and 3 In Figures 4 and 5 are shown isotherms of surface tension and density As
indicated in the introduction no change of both temperature dependence of the surface tension and density is
observed The preliminary results were presented in Genoa [1]
[1] COST Action 531 MC Meeting (25022006) amp WG 1-2-3-4-5-6 Meeting (23-24022006) in Genoa Italy
XIn σ=A+B∙TmN∙m-1
σ 523K
mN∙m-1
σ 1023K
mN∙m-1
Err(a)mN∙m-1
Err(b)mN∙m∙K-1
000200300401503005007510
5851 -008815785 -007665728 -007305743 -007056034 -011555883 -010495879 -010045877 -008575938 -00942
5391 plusmn825385 plusmn715346 plusmn915374 plusmn6
5430 plusmn1015334 plusmn91
5354 plusmn1045429 plusmn1155445 plusmn116
4950plusmn765002plusmn76 4982plusmn86 5022plusmn624853plusmn984810plusmn88
4852plusmn99 5000plusmn176
4974plusmn113
plusmn78plusmn90plusmn99plusmn80
plusmn104plusmn96
plusmn111plusmn185plusmn119
plusmn00085plusmn00120plusmn00113plusmn00096plusmn00124plusmn00115plusmn00127plusmn00308plusmn00144
- Sn 313Ag 074Cu
XIn
at
ρ=A+B∙Tg∙cm-3
ρ 523K
g∙cm-3
ρ 1023K
g∙cm-3
Err(a)g∙cm-3
Err(b)g∙cm-3∙K-1
000200300401503005007510
74615-000070374814-000076975050-000083874130-000074873416-000064173379-000066473159-000063273887-000074073206-0000684
7094plusmn00277079plusmn00297067plusmn00277022plusmn00557006plusmn00706990plusmn00606986plusmn00667002plusmn00156963plusmn0027
6742plusmn003 6695plusmn0036648plusmn004
6648plusmn006 6686plusmn007 6658plusmn0066670plusmn0066632plusmn002
6621plusmn003
plusmn0028plusmn0036plusmn0050plusmn0088plusmn0076plusmn0063plusmn0067plusmn0022plusmn0032
plusmn0000035plusmn0000052plusmn0000078plusmn0000113plusmn0000090plusmn0000073plusmn0000073plusmn0000033plusmn0000039
Table 2 Temperature dependencies of the density of the liquid quaternary (Sn 313Ag 074Cu)+In and ternary alloys with the calculated errors of the A and B parameters and the densities calculated at 523 K and 1032 K
Table 3 Temperature dependencies of the surface tension of the liquid quaternary (Sn 313Ag 074Cu)+In and ternary alloys with the calculated errors of the A and B parameters and the surface tension calculated at 523 K and 1032 K
Fig 2 The temperature dependencies of the density of (Sn 313Ag 074Cu) + In liquid alloys
Fig 3 The temperature dependencies of the surface tension of (Sn 313Ag 074Cu) + In
liquid alloys
Fig 4 The isotherms of the density of (Sn 313Ag 074Cu)+In liquid alloys at 523 K and 1023 K
Fig 5 The isotherms of the surface tension of (Sn 313Ag 074Cu)+In liquid alloys at 523 K and 1023 K
3 Modeling of the surface tension
Two kinds of modeling of surface tension were used for quaternary alloys Sn-Ag-Cu-In similarly as in previous studies on Sn-Ag-Cu-Sb system [1]
[1] ZMoser WGąsior JPstruś IOhnuma KIshida ldquoInfluence of Sb additions on surface tension and density of Sn-Sb Sn-Ag-Sb and Sn-Ag-Cu-Sb alloys Experiment vsmodelingrdquo International Jounal of Materials Research Zeitschrift fuer Metallkunde 97 (2006) 365-370 Dedicated to Professor DrFerdinand Sommer on the occasion of his 65th birthday
1 Butler model with thermodynamic properties of liquid constituent components and surface tension of pure
components This modeling was successfully tested in studies of systems presented in SURDAT database
with observation that the experimental temperature dependence of the surface tension is linear while from
modeling slightly curvilinear dependence was calculated
For such procedure in the case of quaternary Sn-Ag-Cu-In system we should know data of six binaries
Cu-In Cu-Ag Sn-Ag Ag-In Sn-Cu In-Sn four ternaries Sn-Ag-Cu Sn-Ag-In Sn-Cu-In In-Ag-Cu and for
quaternary alloy (one quaternary alloy with equal concentration of components 025 molar fraction was
investigated)
In the case of modeling 2 we are basing on experimental data of surface tension of constituent binary systems
with ternary and quaternary correction factors to elaborate the temperature and concentration dependence of
the surface tension of the Sn-Ag-Cu-In system For the remaining not previously investigated surface tension
and density in this study were determined Cu-In and Cu-Ag ternaries Sn-Ag-Cu Sn-Ag-In In-Ag-Cu and
one quaternary alloy with equal concentration of components 025 molar fraction
As an example in Table 4 are presented surface tension data of ternaries and quaternary alloy
Table 4 Temperature dependencies of the surface tension of the liquid quaternary Sn 25Ag 25Cu 25In and ternary alloys Sn 25Ag 25In Sn 25Ag 25Cu and In 25Ag 25Cu with the calculated errors of the A and B parameters and the
surface tension calculated at 973 K and 1273 K
X at σ = A +BTmNm-1
σ 973K
mNm-1
σ 1273K
mNm-1
Err(A)mNm-1
Err(B)mNm-1middotK-1
Sn25Ag25InSn25Ag25CuIn25Ag25Cu
Sn25Ag25Cu25In
= 6190-00599T = 6142-00235T = 6510-00293T = 7685-00737T
5607plusmn64 5914plusmn42 6225plusmn55
6967plusmn125
5427plusmn765843plusmn456138plusmn64
6746plusmn123
plusmn131 plusmn82
plusmn124 plusmn260
plusmn00133 plusmn00088
plusmn00122 plusmn00227
Fig6 Comparison of calculations of the surface tension of the quaternary system Sn-Ag-Cu-In by Butlerrsquos model and with temperature-concentration dependence and with one experimental alloy (Table 4) with equal 025 molar fractions Thin lines show the Butler model while thick correspond to temperature concentration dependence of the surface tension
Results of calculations by the Butler model show lower values of the surface tension due to the fact that
interaction parameters for Ag-Cu-In and Cu-In-Sn were not taken into calculations In addition only the
limited amount of alloys for binary and ternary alloys of surface tension was investigated with one quaternary
sample
The obtained results from both methods are compared in Fig6
4 Contact angles measurements of the (Sn313Ag074Cu) + In liquid alloys
Wetting of copper substrates was studied by sessile drop method Solder in a cube form was covered by flux
and put on the substrate and after melting at given temperature (250 280 and 320 oC) pictures of drop were
taken by digital camera up to 30 minutes Contact angles were measured by computer After the drop
solidifies specimen were cut perpendicularly for metallographic studies discussed in the next section
Typical course of time dependencies of contact angle for pure (not containing In) Sn 313Ag 074Cu
Sn 252Ag 057Cu 30In and Sn 12Ag 027Cu 75In are presented on Figs7-10 Except the beginning of
wetting the contact angle practically does not depend on the wetting temperature and with the increase of In
concentration is lowered the time to reach the constant values of contact angles which gradually are
decreasing Due to the observed in Figs7-9 the negligible differences in contact angles in the temperature
interval in Fig10 is plotted the change of contact angle after 30 minutes for all investigated alloys The
lowering tendency of the contact angle is observed with some scattering at low In content
Fig7 Change of the contact angle for the starting alloy Sn 313Ag 074Cu
Fig 8 Change of the contact angle for Sn 313Ag 074Cu + 30 at In
Fig 9 Change of the contact angle for Sn 313Ag 074Cu + 75 at In
Fig 10 Change of contact angles for Sn-Ag-Cu-In alloys after 30 minutes
5 Interaction studies of the quaternary alloys with Cu substrate
Metallographic studies of the structure of the boundary between the solder and substrate as well as the
structure of the solder itself was studied by electron scanning microscopy (SEM) Energy dispersive X-ray
analyzer (EDX) was used to measure the chemical composition of the interface as well as the bulk solder The
same specimen which were used for SEM and EDX investigation were also used for X-ray diffraction phase
analysis of the solder and substrate
For low In concentration (up to 15 at) Cu interface is formed by Cu6Sn5 phase For higher concentration of
In (30-50 at) Cu interface if formed by Cu41Sn11 phase For highest In concentration (75 at) Cu
interface is formed by Cu3(SnIn) phase
6 Conclusions
In this presentation investigating the influence of In on wettability of the alloy Sn 313Ag 074Cu close to
ternary eutectic Sn-Ag-Cu it was confirmed starting from previous data on In-Sn and
Sn-Ag-In [1] that due to the nearly the same surface tension and density values of pure In and Sn the
beneficial influence of In is reflected by the lowering of the contact angles with practically no change of
temperature dependence of both surface tension and density Isothermal behaviour of surface tension with ldquoSrdquo
shape starting from In-Sn and Sn-Ag-In proceeding into the investigated in this study Sn-Ag-Cu-In is
probably in addition connected with the peculiar properties of liquid In-Sn alloys showing extrema on
isothermal behaviour of electrical resistivity and viscosity [2] corresponding well to the existence of
intermetallic phases in the phase diagram of In-Sn phase diagram It is the another proof of the mutual
correlations between thermodynamic properties physical properties and the character of the phase diagram
[1] X J Liu Y Inohana I Ohnuma R Kainuma K Ishida Z Moser W Gąsior J Pstruś J Electronic Mater 31 (2002) 1139-51 [2] BPredel MHoch MPool Phase Diagrams and Heterogeneous Equilibria Springer-Verlag Berlin Heidelberg (2004) 289-291
7 Final remarks
1 Presented today joint results with P Sebo will be elaborated for Calphad journal
2 SURDAT database realized in parallel to COST 531 Program has been introduced on website of COST
531 Program
3 In addition from financing of COST 531 Program under research entitled ldquoExperimental determination
and modeling of physicochemical properties of multi-component alloys on the tin base ldquo within
2003-2006 the additional study has been realized by dr Piotr Ozga
ldquo The study of a possibility of the electrodeposition of Sn-Ag alloys from aqueous solutionsrdquo
a POzga ldquoEquilibria in Aqueous Solutions of Ag(I)-Sn(IIIV) in Presence of Strong Complexing
Ligandsrdquo CALPHAD XXXIII Krakow (Poland) May 30 ndash June 4 2004 Abstracts p 153
b POzga ldquoElectrodeposition of Sn-Ag and Sn-Ag-Cu alloys from the thiourea solutionsrdquo Archives of
Metallurgy and Materials 3 (2006) 413-421
The results of this study were used in habilitation thesis of P Ozga edited by the Institute of Metallurgy
and Materials ISBN-83-921845-8-0 Krakow (2006) 1-148
bull Special issue of the Archives of Metallurgy and Materials 32006 has been devoted to results realized
within COST 531 Program
Thank you
for your attention
- Slide 1
- Slide 2
- Slide 3
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- Slide 10
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Slide 18
- Slide 19
- Slide 20
-
2 2005-2006 ldquoInfluence of In additions on surface tension and density of the Sn-Ag-Cu-In alloys
Experiment vs modelingrdquo
This research has been realized jointly with Slovak Academy of Sciences (Pavol Sebo)
bull Z Moser W Gąsior J Pstruś ldquoInfluence of In additions on surface tension and density of In-Sn
Sn-Ag-In and Sn-Ag-Cu-In liquid solders Experiment vs Modelingrdquo COST 531 MC Meeting
(25022006) amp WG1-2-3-4-5-6 Meeting (23-24022006) Genoa Italy
b Zbigniew Moser Pavol Sebo Władysław Gąsior Peter Svec and Janusz Pstruś ldquoWettability Studies of
Sn-Ag-Cu-In Liquid Solders and Interaction with Cu Substraterdquo Program and Abstracts Calphad XXXVI
The Pennsylvania State University State College Pennsylvania USA May 6 -11 2007 p35
This joint research will be presented to day
Wettability Studies of Sn-Ag-Cu-In Liquid Solders and Interaction with Cu Substrate
Zbigniew Moser Pavol Sebo Władysław Gąsior Peter Svec and Janusz Pstruś
Institute of Metallurgy and Materials Science Polish Academy of Sciences
30-059 Krakoacutew Reymonta Street 25 POLANDInstitute of Materials and Machine Mechanics Slovak Academy of Sciences
Racianska 75 831-02 Bratislava 3 SLOVAKIAInstitute of Physics Slovak Academy of Sciences Dubravska cesta 9
845-11 Bratislava 45 SLOVAKIA
Plan of presentation
1 Introduction2 Surface tension and density measurements of the (Sn313Ag074Cu) + In liquid alloys3 Modeling of the surface tension4 Contact angles measurements of the (Sn313Ag074Cu) + In liquid alloys5 Interaction studies of the quaternary alloys with Cu substrate6 Conclusions7 Final remarks
MetalsBinary Alloys
Multicomponent Alloys
PbSnInAgBiSbCuZnAlAu
Pb ndash SnAg ndash SnAg ndash InBi ndash SnIn ndash SnAg ndash BiSb ndash SnSn ndash ZnAg ndash SbCu ndash SnCu ndash Sb
(Sn-Ag)eut +In
(Sn-Ag)eut +Bi
(Sn-Ag)eut +Cu
(Sn-Ag)eut +Sb
(Sn-Ag)eut +Cu+Sb
(Sn-Ag)eut +Cu+Bi
(Sn 313Ag 074Cu)+InThis study
Table 1 The investigated liquid metals and alloysFig 1 The first window of the SURDAT database
[1] Z Moser W Gąsior A Dębski and J Pstruś Database of lead ndash free soldering materials edited by IMIM PAS and printed by Orekop Krakoacutew 2007 ISBN 83-60768-01-3
[2] JAV Butler The Thermodynamics of the Surfaces of Solutions Proceedings of the Royal Society of London series A CXXXV (1932) 348-375
[3] Liu XJ Inohana Y Ohnuma I Kainuma R Ishida K Moser Z Gąsior W Pstruś J Experimental Determination and Thermodynamic Calculation of the Phase Equilibria and Surface tension of the Ag-Sn-In System J Electron Mater 31 (2002) 1139-1151
[4] P Sebo P Stefanik Kovove Mater Effect of In Addition on Sn-Ag Solder Its Wetting and Shear Strength of Copper Joints 43 (2005) 202-209 (Decreasing of contact angles adding 66 and 9 mass In to (Sn-Ag)eut)
[5] M E Loomans SVaynmann G Ghosh M E Fine J Electronic Mater 23 (1994) 741-746 (Similar decreasing of contact angles by In additions)
[6] S Hwang Lead-free Implementation and Production A Manufacturing Guide McGraw-Hill (2005) ISBN 0-07-144374-6 Chapter Three Selecting Lead-free Alloys for Solder Interconnections (From meniscographic studies with flux wetting force and wetting time of Sn 41 Ag05Cu 4In ( mass) nearly equivalent to Sn-Pb eutectic)
1 Introduction
The main aim is to confirm the previous observation of In additions to (Sn-Ag) eut on wettability and to extend
it in the presented studies of quaternary alloys (Sn 313Ag 074Cu) + In combining surface tension density
and modeling of surface tension from Krakow Poland with contact angles and interaction of liquid alloys
with Cu substrate using flux undertaken in Bratislava Slovakia within COST 531 Program
The starting material was nearly eutectic alloy (Sn 313Ag 074Cu) with 2 3 4 15 30 50 and 75 at In
2 Surface tension and density measurements of the (Sn313Ag074Cu) + In liquid alloys
The density and surface tension measurements of the (Sn313Ag074Cu) + In liquid alloys at In
concentrations ( 2 3 4 15 30 50 and 75 at) by the maximum bubble pressure method and dilatometric
technique were conducted in the temperature range from 158 degC to 936 degC Results are presented in Tables 2
and 3 and in Figures 2 and 3 In Figures 4 and 5 are shown isotherms of surface tension and density As
indicated in the introduction no change of both temperature dependence of the surface tension and density is
observed The preliminary results were presented in Genoa [1]
[1] COST Action 531 MC Meeting (25022006) amp WG 1-2-3-4-5-6 Meeting (23-24022006) in Genoa Italy
XIn σ=A+B∙TmN∙m-1
σ 523K
mN∙m-1
σ 1023K
mN∙m-1
Err(a)mN∙m-1
Err(b)mN∙m∙K-1
000200300401503005007510
5851 -008815785 -007665728 -007305743 -007056034 -011555883 -010495879 -010045877 -008575938 -00942
5391 plusmn825385 plusmn715346 plusmn915374 plusmn6
5430 plusmn1015334 plusmn91
5354 plusmn1045429 plusmn1155445 plusmn116
4950plusmn765002plusmn76 4982plusmn86 5022plusmn624853plusmn984810plusmn88
4852plusmn99 5000plusmn176
4974plusmn113
plusmn78plusmn90plusmn99plusmn80
plusmn104plusmn96
plusmn111plusmn185plusmn119
plusmn00085plusmn00120plusmn00113plusmn00096plusmn00124plusmn00115plusmn00127plusmn00308plusmn00144
- Sn 313Ag 074Cu
XIn
at
ρ=A+B∙Tg∙cm-3
ρ 523K
g∙cm-3
ρ 1023K
g∙cm-3
Err(a)g∙cm-3
Err(b)g∙cm-3∙K-1
000200300401503005007510
74615-000070374814-000076975050-000083874130-000074873416-000064173379-000066473159-000063273887-000074073206-0000684
7094plusmn00277079plusmn00297067plusmn00277022plusmn00557006plusmn00706990plusmn00606986plusmn00667002plusmn00156963plusmn0027
6742plusmn003 6695plusmn0036648plusmn004
6648plusmn006 6686plusmn007 6658plusmn0066670plusmn0066632plusmn002
6621plusmn003
plusmn0028plusmn0036plusmn0050plusmn0088plusmn0076plusmn0063plusmn0067plusmn0022plusmn0032
plusmn0000035plusmn0000052plusmn0000078plusmn0000113plusmn0000090plusmn0000073plusmn0000073plusmn0000033plusmn0000039
Table 2 Temperature dependencies of the density of the liquid quaternary (Sn 313Ag 074Cu)+In and ternary alloys with the calculated errors of the A and B parameters and the densities calculated at 523 K and 1032 K
Table 3 Temperature dependencies of the surface tension of the liquid quaternary (Sn 313Ag 074Cu)+In and ternary alloys with the calculated errors of the A and B parameters and the surface tension calculated at 523 K and 1032 K
Fig 2 The temperature dependencies of the density of (Sn 313Ag 074Cu) + In liquid alloys
Fig 3 The temperature dependencies of the surface tension of (Sn 313Ag 074Cu) + In
liquid alloys
Fig 4 The isotherms of the density of (Sn 313Ag 074Cu)+In liquid alloys at 523 K and 1023 K
Fig 5 The isotherms of the surface tension of (Sn 313Ag 074Cu)+In liquid alloys at 523 K and 1023 K
3 Modeling of the surface tension
Two kinds of modeling of surface tension were used for quaternary alloys Sn-Ag-Cu-In similarly as in previous studies on Sn-Ag-Cu-Sb system [1]
[1] ZMoser WGąsior JPstruś IOhnuma KIshida ldquoInfluence of Sb additions on surface tension and density of Sn-Sb Sn-Ag-Sb and Sn-Ag-Cu-Sb alloys Experiment vsmodelingrdquo International Jounal of Materials Research Zeitschrift fuer Metallkunde 97 (2006) 365-370 Dedicated to Professor DrFerdinand Sommer on the occasion of his 65th birthday
1 Butler model with thermodynamic properties of liquid constituent components and surface tension of pure
components This modeling was successfully tested in studies of systems presented in SURDAT database
with observation that the experimental temperature dependence of the surface tension is linear while from
modeling slightly curvilinear dependence was calculated
For such procedure in the case of quaternary Sn-Ag-Cu-In system we should know data of six binaries
Cu-In Cu-Ag Sn-Ag Ag-In Sn-Cu In-Sn four ternaries Sn-Ag-Cu Sn-Ag-In Sn-Cu-In In-Ag-Cu and for
quaternary alloy (one quaternary alloy with equal concentration of components 025 molar fraction was
investigated)
In the case of modeling 2 we are basing on experimental data of surface tension of constituent binary systems
with ternary and quaternary correction factors to elaborate the temperature and concentration dependence of
the surface tension of the Sn-Ag-Cu-In system For the remaining not previously investigated surface tension
and density in this study were determined Cu-In and Cu-Ag ternaries Sn-Ag-Cu Sn-Ag-In In-Ag-Cu and
one quaternary alloy with equal concentration of components 025 molar fraction
As an example in Table 4 are presented surface tension data of ternaries and quaternary alloy
Table 4 Temperature dependencies of the surface tension of the liquid quaternary Sn 25Ag 25Cu 25In and ternary alloys Sn 25Ag 25In Sn 25Ag 25Cu and In 25Ag 25Cu with the calculated errors of the A and B parameters and the
surface tension calculated at 973 K and 1273 K
X at σ = A +BTmNm-1
σ 973K
mNm-1
σ 1273K
mNm-1
Err(A)mNm-1
Err(B)mNm-1middotK-1
Sn25Ag25InSn25Ag25CuIn25Ag25Cu
Sn25Ag25Cu25In
= 6190-00599T = 6142-00235T = 6510-00293T = 7685-00737T
5607plusmn64 5914plusmn42 6225plusmn55
6967plusmn125
5427plusmn765843plusmn456138plusmn64
6746plusmn123
plusmn131 plusmn82
plusmn124 plusmn260
plusmn00133 plusmn00088
plusmn00122 plusmn00227
Fig6 Comparison of calculations of the surface tension of the quaternary system Sn-Ag-Cu-In by Butlerrsquos model and with temperature-concentration dependence and with one experimental alloy (Table 4) with equal 025 molar fractions Thin lines show the Butler model while thick correspond to temperature concentration dependence of the surface tension
Results of calculations by the Butler model show lower values of the surface tension due to the fact that
interaction parameters for Ag-Cu-In and Cu-In-Sn were not taken into calculations In addition only the
limited amount of alloys for binary and ternary alloys of surface tension was investigated with one quaternary
sample
The obtained results from both methods are compared in Fig6
4 Contact angles measurements of the (Sn313Ag074Cu) + In liquid alloys
Wetting of copper substrates was studied by sessile drop method Solder in a cube form was covered by flux
and put on the substrate and after melting at given temperature (250 280 and 320 oC) pictures of drop were
taken by digital camera up to 30 minutes Contact angles were measured by computer After the drop
solidifies specimen were cut perpendicularly for metallographic studies discussed in the next section
Typical course of time dependencies of contact angle for pure (not containing In) Sn 313Ag 074Cu
Sn 252Ag 057Cu 30In and Sn 12Ag 027Cu 75In are presented on Figs7-10 Except the beginning of
wetting the contact angle practically does not depend on the wetting temperature and with the increase of In
concentration is lowered the time to reach the constant values of contact angles which gradually are
decreasing Due to the observed in Figs7-9 the negligible differences in contact angles in the temperature
interval in Fig10 is plotted the change of contact angle after 30 minutes for all investigated alloys The
lowering tendency of the contact angle is observed with some scattering at low In content
Fig7 Change of the contact angle for the starting alloy Sn 313Ag 074Cu
Fig 8 Change of the contact angle for Sn 313Ag 074Cu + 30 at In
Fig 9 Change of the contact angle for Sn 313Ag 074Cu + 75 at In
Fig 10 Change of contact angles for Sn-Ag-Cu-In alloys after 30 minutes
5 Interaction studies of the quaternary alloys with Cu substrate
Metallographic studies of the structure of the boundary between the solder and substrate as well as the
structure of the solder itself was studied by electron scanning microscopy (SEM) Energy dispersive X-ray
analyzer (EDX) was used to measure the chemical composition of the interface as well as the bulk solder The
same specimen which were used for SEM and EDX investigation were also used for X-ray diffraction phase
analysis of the solder and substrate
For low In concentration (up to 15 at) Cu interface is formed by Cu6Sn5 phase For higher concentration of
In (30-50 at) Cu interface if formed by Cu41Sn11 phase For highest In concentration (75 at) Cu
interface is formed by Cu3(SnIn) phase
6 Conclusions
In this presentation investigating the influence of In on wettability of the alloy Sn 313Ag 074Cu close to
ternary eutectic Sn-Ag-Cu it was confirmed starting from previous data on In-Sn and
Sn-Ag-In [1] that due to the nearly the same surface tension and density values of pure In and Sn the
beneficial influence of In is reflected by the lowering of the contact angles with practically no change of
temperature dependence of both surface tension and density Isothermal behaviour of surface tension with ldquoSrdquo
shape starting from In-Sn and Sn-Ag-In proceeding into the investigated in this study Sn-Ag-Cu-In is
probably in addition connected with the peculiar properties of liquid In-Sn alloys showing extrema on
isothermal behaviour of electrical resistivity and viscosity [2] corresponding well to the existence of
intermetallic phases in the phase diagram of In-Sn phase diagram It is the another proof of the mutual
correlations between thermodynamic properties physical properties and the character of the phase diagram
[1] X J Liu Y Inohana I Ohnuma R Kainuma K Ishida Z Moser W Gąsior J Pstruś J Electronic Mater 31 (2002) 1139-51 [2] BPredel MHoch MPool Phase Diagrams and Heterogeneous Equilibria Springer-Verlag Berlin Heidelberg (2004) 289-291
7 Final remarks
1 Presented today joint results with P Sebo will be elaborated for Calphad journal
2 SURDAT database realized in parallel to COST 531 Program has been introduced on website of COST
531 Program
3 In addition from financing of COST 531 Program under research entitled ldquoExperimental determination
and modeling of physicochemical properties of multi-component alloys on the tin base ldquo within
2003-2006 the additional study has been realized by dr Piotr Ozga
ldquo The study of a possibility of the electrodeposition of Sn-Ag alloys from aqueous solutionsrdquo
a POzga ldquoEquilibria in Aqueous Solutions of Ag(I)-Sn(IIIV) in Presence of Strong Complexing
Ligandsrdquo CALPHAD XXXIII Krakow (Poland) May 30 ndash June 4 2004 Abstracts p 153
b POzga ldquoElectrodeposition of Sn-Ag and Sn-Ag-Cu alloys from the thiourea solutionsrdquo Archives of
Metallurgy and Materials 3 (2006) 413-421
The results of this study were used in habilitation thesis of P Ozga edited by the Institute of Metallurgy
and Materials ISBN-83-921845-8-0 Krakow (2006) 1-148
bull Special issue of the Archives of Metallurgy and Materials 32006 has been devoted to results realized
within COST 531 Program
Thank you
for your attention
- Slide 1
- Slide 2
- Slide 3
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- Slide 10
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Slide 18
- Slide 19
- Slide 20
-
Wettability Studies of Sn-Ag-Cu-In Liquid Solders and Interaction with Cu Substrate
Zbigniew Moser Pavol Sebo Władysław Gąsior Peter Svec and Janusz Pstruś
Institute of Metallurgy and Materials Science Polish Academy of Sciences
30-059 Krakoacutew Reymonta Street 25 POLANDInstitute of Materials and Machine Mechanics Slovak Academy of Sciences
Racianska 75 831-02 Bratislava 3 SLOVAKIAInstitute of Physics Slovak Academy of Sciences Dubravska cesta 9
845-11 Bratislava 45 SLOVAKIA
Plan of presentation
1 Introduction2 Surface tension and density measurements of the (Sn313Ag074Cu) + In liquid alloys3 Modeling of the surface tension4 Contact angles measurements of the (Sn313Ag074Cu) + In liquid alloys5 Interaction studies of the quaternary alloys with Cu substrate6 Conclusions7 Final remarks
MetalsBinary Alloys
Multicomponent Alloys
PbSnInAgBiSbCuZnAlAu
Pb ndash SnAg ndash SnAg ndash InBi ndash SnIn ndash SnAg ndash BiSb ndash SnSn ndash ZnAg ndash SbCu ndash SnCu ndash Sb
(Sn-Ag)eut +In
(Sn-Ag)eut +Bi
(Sn-Ag)eut +Cu
(Sn-Ag)eut +Sb
(Sn-Ag)eut +Cu+Sb
(Sn-Ag)eut +Cu+Bi
(Sn 313Ag 074Cu)+InThis study
Table 1 The investigated liquid metals and alloysFig 1 The first window of the SURDAT database
[1] Z Moser W Gąsior A Dębski and J Pstruś Database of lead ndash free soldering materials edited by IMIM PAS and printed by Orekop Krakoacutew 2007 ISBN 83-60768-01-3
[2] JAV Butler The Thermodynamics of the Surfaces of Solutions Proceedings of the Royal Society of London series A CXXXV (1932) 348-375
[3] Liu XJ Inohana Y Ohnuma I Kainuma R Ishida K Moser Z Gąsior W Pstruś J Experimental Determination and Thermodynamic Calculation of the Phase Equilibria and Surface tension of the Ag-Sn-In System J Electron Mater 31 (2002) 1139-1151
[4] P Sebo P Stefanik Kovove Mater Effect of In Addition on Sn-Ag Solder Its Wetting and Shear Strength of Copper Joints 43 (2005) 202-209 (Decreasing of contact angles adding 66 and 9 mass In to (Sn-Ag)eut)
[5] M E Loomans SVaynmann G Ghosh M E Fine J Electronic Mater 23 (1994) 741-746 (Similar decreasing of contact angles by In additions)
[6] S Hwang Lead-free Implementation and Production A Manufacturing Guide McGraw-Hill (2005) ISBN 0-07-144374-6 Chapter Three Selecting Lead-free Alloys for Solder Interconnections (From meniscographic studies with flux wetting force and wetting time of Sn 41 Ag05Cu 4In ( mass) nearly equivalent to Sn-Pb eutectic)
1 Introduction
The main aim is to confirm the previous observation of In additions to (Sn-Ag) eut on wettability and to extend
it in the presented studies of quaternary alloys (Sn 313Ag 074Cu) + In combining surface tension density
and modeling of surface tension from Krakow Poland with contact angles and interaction of liquid alloys
with Cu substrate using flux undertaken in Bratislava Slovakia within COST 531 Program
The starting material was nearly eutectic alloy (Sn 313Ag 074Cu) with 2 3 4 15 30 50 and 75 at In
2 Surface tension and density measurements of the (Sn313Ag074Cu) + In liquid alloys
The density and surface tension measurements of the (Sn313Ag074Cu) + In liquid alloys at In
concentrations ( 2 3 4 15 30 50 and 75 at) by the maximum bubble pressure method and dilatometric
technique were conducted in the temperature range from 158 degC to 936 degC Results are presented in Tables 2
and 3 and in Figures 2 and 3 In Figures 4 and 5 are shown isotherms of surface tension and density As
indicated in the introduction no change of both temperature dependence of the surface tension and density is
observed The preliminary results were presented in Genoa [1]
[1] COST Action 531 MC Meeting (25022006) amp WG 1-2-3-4-5-6 Meeting (23-24022006) in Genoa Italy
XIn σ=A+B∙TmN∙m-1
σ 523K
mN∙m-1
σ 1023K
mN∙m-1
Err(a)mN∙m-1
Err(b)mN∙m∙K-1
000200300401503005007510
5851 -008815785 -007665728 -007305743 -007056034 -011555883 -010495879 -010045877 -008575938 -00942
5391 plusmn825385 plusmn715346 plusmn915374 plusmn6
5430 plusmn1015334 plusmn91
5354 plusmn1045429 plusmn1155445 plusmn116
4950plusmn765002plusmn76 4982plusmn86 5022plusmn624853plusmn984810plusmn88
4852plusmn99 5000plusmn176
4974plusmn113
plusmn78plusmn90plusmn99plusmn80
plusmn104plusmn96
plusmn111plusmn185plusmn119
plusmn00085plusmn00120plusmn00113plusmn00096plusmn00124plusmn00115plusmn00127plusmn00308plusmn00144
- Sn 313Ag 074Cu
XIn
at
ρ=A+B∙Tg∙cm-3
ρ 523K
g∙cm-3
ρ 1023K
g∙cm-3
Err(a)g∙cm-3
Err(b)g∙cm-3∙K-1
000200300401503005007510
74615-000070374814-000076975050-000083874130-000074873416-000064173379-000066473159-000063273887-000074073206-0000684
7094plusmn00277079plusmn00297067plusmn00277022plusmn00557006plusmn00706990plusmn00606986plusmn00667002plusmn00156963plusmn0027
6742plusmn003 6695plusmn0036648plusmn004
6648plusmn006 6686plusmn007 6658plusmn0066670plusmn0066632plusmn002
6621plusmn003
plusmn0028plusmn0036plusmn0050plusmn0088plusmn0076plusmn0063plusmn0067plusmn0022plusmn0032
plusmn0000035plusmn0000052plusmn0000078plusmn0000113plusmn0000090plusmn0000073plusmn0000073plusmn0000033plusmn0000039
Table 2 Temperature dependencies of the density of the liquid quaternary (Sn 313Ag 074Cu)+In and ternary alloys with the calculated errors of the A and B parameters and the densities calculated at 523 K and 1032 K
Table 3 Temperature dependencies of the surface tension of the liquid quaternary (Sn 313Ag 074Cu)+In and ternary alloys with the calculated errors of the A and B parameters and the surface tension calculated at 523 K and 1032 K
Fig 2 The temperature dependencies of the density of (Sn 313Ag 074Cu) + In liquid alloys
Fig 3 The temperature dependencies of the surface tension of (Sn 313Ag 074Cu) + In
liquid alloys
Fig 4 The isotherms of the density of (Sn 313Ag 074Cu)+In liquid alloys at 523 K and 1023 K
Fig 5 The isotherms of the surface tension of (Sn 313Ag 074Cu)+In liquid alloys at 523 K and 1023 K
3 Modeling of the surface tension
Two kinds of modeling of surface tension were used for quaternary alloys Sn-Ag-Cu-In similarly as in previous studies on Sn-Ag-Cu-Sb system [1]
[1] ZMoser WGąsior JPstruś IOhnuma KIshida ldquoInfluence of Sb additions on surface tension and density of Sn-Sb Sn-Ag-Sb and Sn-Ag-Cu-Sb alloys Experiment vsmodelingrdquo International Jounal of Materials Research Zeitschrift fuer Metallkunde 97 (2006) 365-370 Dedicated to Professor DrFerdinand Sommer on the occasion of his 65th birthday
1 Butler model with thermodynamic properties of liquid constituent components and surface tension of pure
components This modeling was successfully tested in studies of systems presented in SURDAT database
with observation that the experimental temperature dependence of the surface tension is linear while from
modeling slightly curvilinear dependence was calculated
For such procedure in the case of quaternary Sn-Ag-Cu-In system we should know data of six binaries
Cu-In Cu-Ag Sn-Ag Ag-In Sn-Cu In-Sn four ternaries Sn-Ag-Cu Sn-Ag-In Sn-Cu-In In-Ag-Cu and for
quaternary alloy (one quaternary alloy with equal concentration of components 025 molar fraction was
investigated)
In the case of modeling 2 we are basing on experimental data of surface tension of constituent binary systems
with ternary and quaternary correction factors to elaborate the temperature and concentration dependence of
the surface tension of the Sn-Ag-Cu-In system For the remaining not previously investigated surface tension
and density in this study were determined Cu-In and Cu-Ag ternaries Sn-Ag-Cu Sn-Ag-In In-Ag-Cu and
one quaternary alloy with equal concentration of components 025 molar fraction
As an example in Table 4 are presented surface tension data of ternaries and quaternary alloy
Table 4 Temperature dependencies of the surface tension of the liquid quaternary Sn 25Ag 25Cu 25In and ternary alloys Sn 25Ag 25In Sn 25Ag 25Cu and In 25Ag 25Cu with the calculated errors of the A and B parameters and the
surface tension calculated at 973 K and 1273 K
X at σ = A +BTmNm-1
σ 973K
mNm-1
σ 1273K
mNm-1
Err(A)mNm-1
Err(B)mNm-1middotK-1
Sn25Ag25InSn25Ag25CuIn25Ag25Cu
Sn25Ag25Cu25In
= 6190-00599T = 6142-00235T = 6510-00293T = 7685-00737T
5607plusmn64 5914plusmn42 6225plusmn55
6967plusmn125
5427plusmn765843plusmn456138plusmn64
6746plusmn123
plusmn131 plusmn82
plusmn124 plusmn260
plusmn00133 plusmn00088
plusmn00122 plusmn00227
Fig6 Comparison of calculations of the surface tension of the quaternary system Sn-Ag-Cu-In by Butlerrsquos model and with temperature-concentration dependence and with one experimental alloy (Table 4) with equal 025 molar fractions Thin lines show the Butler model while thick correspond to temperature concentration dependence of the surface tension
Results of calculations by the Butler model show lower values of the surface tension due to the fact that
interaction parameters for Ag-Cu-In and Cu-In-Sn were not taken into calculations In addition only the
limited amount of alloys for binary and ternary alloys of surface tension was investigated with one quaternary
sample
The obtained results from both methods are compared in Fig6
4 Contact angles measurements of the (Sn313Ag074Cu) + In liquid alloys
Wetting of copper substrates was studied by sessile drop method Solder in a cube form was covered by flux
and put on the substrate and after melting at given temperature (250 280 and 320 oC) pictures of drop were
taken by digital camera up to 30 minutes Contact angles were measured by computer After the drop
solidifies specimen were cut perpendicularly for metallographic studies discussed in the next section
Typical course of time dependencies of contact angle for pure (not containing In) Sn 313Ag 074Cu
Sn 252Ag 057Cu 30In and Sn 12Ag 027Cu 75In are presented on Figs7-10 Except the beginning of
wetting the contact angle practically does not depend on the wetting temperature and with the increase of In
concentration is lowered the time to reach the constant values of contact angles which gradually are
decreasing Due to the observed in Figs7-9 the negligible differences in contact angles in the temperature
interval in Fig10 is plotted the change of contact angle after 30 minutes for all investigated alloys The
lowering tendency of the contact angle is observed with some scattering at low In content
Fig7 Change of the contact angle for the starting alloy Sn 313Ag 074Cu
Fig 8 Change of the contact angle for Sn 313Ag 074Cu + 30 at In
Fig 9 Change of the contact angle for Sn 313Ag 074Cu + 75 at In
Fig 10 Change of contact angles for Sn-Ag-Cu-In alloys after 30 minutes
5 Interaction studies of the quaternary alloys with Cu substrate
Metallographic studies of the structure of the boundary between the solder and substrate as well as the
structure of the solder itself was studied by electron scanning microscopy (SEM) Energy dispersive X-ray
analyzer (EDX) was used to measure the chemical composition of the interface as well as the bulk solder The
same specimen which were used for SEM and EDX investigation were also used for X-ray diffraction phase
analysis of the solder and substrate
For low In concentration (up to 15 at) Cu interface is formed by Cu6Sn5 phase For higher concentration of
In (30-50 at) Cu interface if formed by Cu41Sn11 phase For highest In concentration (75 at) Cu
interface is formed by Cu3(SnIn) phase
6 Conclusions
In this presentation investigating the influence of In on wettability of the alloy Sn 313Ag 074Cu close to
ternary eutectic Sn-Ag-Cu it was confirmed starting from previous data on In-Sn and
Sn-Ag-In [1] that due to the nearly the same surface tension and density values of pure In and Sn the
beneficial influence of In is reflected by the lowering of the contact angles with practically no change of
temperature dependence of both surface tension and density Isothermal behaviour of surface tension with ldquoSrdquo
shape starting from In-Sn and Sn-Ag-In proceeding into the investigated in this study Sn-Ag-Cu-In is
probably in addition connected with the peculiar properties of liquid In-Sn alloys showing extrema on
isothermal behaviour of electrical resistivity and viscosity [2] corresponding well to the existence of
intermetallic phases in the phase diagram of In-Sn phase diagram It is the another proof of the mutual
correlations between thermodynamic properties physical properties and the character of the phase diagram
[1] X J Liu Y Inohana I Ohnuma R Kainuma K Ishida Z Moser W Gąsior J Pstruś J Electronic Mater 31 (2002) 1139-51 [2] BPredel MHoch MPool Phase Diagrams and Heterogeneous Equilibria Springer-Verlag Berlin Heidelberg (2004) 289-291
7 Final remarks
1 Presented today joint results with P Sebo will be elaborated for Calphad journal
2 SURDAT database realized in parallel to COST 531 Program has been introduced on website of COST
531 Program
3 In addition from financing of COST 531 Program under research entitled ldquoExperimental determination
and modeling of physicochemical properties of multi-component alloys on the tin base ldquo within
2003-2006 the additional study has been realized by dr Piotr Ozga
ldquo The study of a possibility of the electrodeposition of Sn-Ag alloys from aqueous solutionsrdquo
a POzga ldquoEquilibria in Aqueous Solutions of Ag(I)-Sn(IIIV) in Presence of Strong Complexing
Ligandsrdquo CALPHAD XXXIII Krakow (Poland) May 30 ndash June 4 2004 Abstracts p 153
b POzga ldquoElectrodeposition of Sn-Ag and Sn-Ag-Cu alloys from the thiourea solutionsrdquo Archives of
Metallurgy and Materials 3 (2006) 413-421
The results of this study were used in habilitation thesis of P Ozga edited by the Institute of Metallurgy
and Materials ISBN-83-921845-8-0 Krakow (2006) 1-148
bull Special issue of the Archives of Metallurgy and Materials 32006 has been devoted to results realized
within COST 531 Program
Thank you
for your attention
- Slide 1
- Slide 2
- Slide 3
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- Slide 10
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Slide 18
- Slide 19
- Slide 20
-
MetalsBinary Alloys
Multicomponent Alloys
PbSnInAgBiSbCuZnAlAu
Pb ndash SnAg ndash SnAg ndash InBi ndash SnIn ndash SnAg ndash BiSb ndash SnSn ndash ZnAg ndash SbCu ndash SnCu ndash Sb
(Sn-Ag)eut +In
(Sn-Ag)eut +Bi
(Sn-Ag)eut +Cu
(Sn-Ag)eut +Sb
(Sn-Ag)eut +Cu+Sb
(Sn-Ag)eut +Cu+Bi
(Sn 313Ag 074Cu)+InThis study
Table 1 The investigated liquid metals and alloysFig 1 The first window of the SURDAT database
[1] Z Moser W Gąsior A Dębski and J Pstruś Database of lead ndash free soldering materials edited by IMIM PAS and printed by Orekop Krakoacutew 2007 ISBN 83-60768-01-3
[2] JAV Butler The Thermodynamics of the Surfaces of Solutions Proceedings of the Royal Society of London series A CXXXV (1932) 348-375
[3] Liu XJ Inohana Y Ohnuma I Kainuma R Ishida K Moser Z Gąsior W Pstruś J Experimental Determination and Thermodynamic Calculation of the Phase Equilibria and Surface tension of the Ag-Sn-In System J Electron Mater 31 (2002) 1139-1151
[4] P Sebo P Stefanik Kovove Mater Effect of In Addition on Sn-Ag Solder Its Wetting and Shear Strength of Copper Joints 43 (2005) 202-209 (Decreasing of contact angles adding 66 and 9 mass In to (Sn-Ag)eut)
[5] M E Loomans SVaynmann G Ghosh M E Fine J Electronic Mater 23 (1994) 741-746 (Similar decreasing of contact angles by In additions)
[6] S Hwang Lead-free Implementation and Production A Manufacturing Guide McGraw-Hill (2005) ISBN 0-07-144374-6 Chapter Three Selecting Lead-free Alloys for Solder Interconnections (From meniscographic studies with flux wetting force and wetting time of Sn 41 Ag05Cu 4In ( mass) nearly equivalent to Sn-Pb eutectic)
1 Introduction
The main aim is to confirm the previous observation of In additions to (Sn-Ag) eut on wettability and to extend
it in the presented studies of quaternary alloys (Sn 313Ag 074Cu) + In combining surface tension density
and modeling of surface tension from Krakow Poland with contact angles and interaction of liquid alloys
with Cu substrate using flux undertaken in Bratislava Slovakia within COST 531 Program
The starting material was nearly eutectic alloy (Sn 313Ag 074Cu) with 2 3 4 15 30 50 and 75 at In
2 Surface tension and density measurements of the (Sn313Ag074Cu) + In liquid alloys
The density and surface tension measurements of the (Sn313Ag074Cu) + In liquid alloys at In
concentrations ( 2 3 4 15 30 50 and 75 at) by the maximum bubble pressure method and dilatometric
technique were conducted in the temperature range from 158 degC to 936 degC Results are presented in Tables 2
and 3 and in Figures 2 and 3 In Figures 4 and 5 are shown isotherms of surface tension and density As
indicated in the introduction no change of both temperature dependence of the surface tension and density is
observed The preliminary results were presented in Genoa [1]
[1] COST Action 531 MC Meeting (25022006) amp WG 1-2-3-4-5-6 Meeting (23-24022006) in Genoa Italy
XIn σ=A+B∙TmN∙m-1
σ 523K
mN∙m-1
σ 1023K
mN∙m-1
Err(a)mN∙m-1
Err(b)mN∙m∙K-1
000200300401503005007510
5851 -008815785 -007665728 -007305743 -007056034 -011555883 -010495879 -010045877 -008575938 -00942
5391 plusmn825385 plusmn715346 plusmn915374 plusmn6
5430 plusmn1015334 plusmn91
5354 plusmn1045429 plusmn1155445 plusmn116
4950plusmn765002plusmn76 4982plusmn86 5022plusmn624853plusmn984810plusmn88
4852plusmn99 5000plusmn176
4974plusmn113
plusmn78plusmn90plusmn99plusmn80
plusmn104plusmn96
plusmn111plusmn185plusmn119
plusmn00085plusmn00120plusmn00113plusmn00096plusmn00124plusmn00115plusmn00127plusmn00308plusmn00144
- Sn 313Ag 074Cu
XIn
at
ρ=A+B∙Tg∙cm-3
ρ 523K
g∙cm-3
ρ 1023K
g∙cm-3
Err(a)g∙cm-3
Err(b)g∙cm-3∙K-1
000200300401503005007510
74615-000070374814-000076975050-000083874130-000074873416-000064173379-000066473159-000063273887-000074073206-0000684
7094plusmn00277079plusmn00297067plusmn00277022plusmn00557006plusmn00706990plusmn00606986plusmn00667002plusmn00156963plusmn0027
6742plusmn003 6695plusmn0036648plusmn004
6648plusmn006 6686plusmn007 6658plusmn0066670plusmn0066632plusmn002
6621plusmn003
plusmn0028plusmn0036plusmn0050plusmn0088plusmn0076plusmn0063plusmn0067plusmn0022plusmn0032
plusmn0000035plusmn0000052plusmn0000078plusmn0000113plusmn0000090plusmn0000073plusmn0000073plusmn0000033plusmn0000039
Table 2 Temperature dependencies of the density of the liquid quaternary (Sn 313Ag 074Cu)+In and ternary alloys with the calculated errors of the A and B parameters and the densities calculated at 523 K and 1032 K
Table 3 Temperature dependencies of the surface tension of the liquid quaternary (Sn 313Ag 074Cu)+In and ternary alloys with the calculated errors of the A and B parameters and the surface tension calculated at 523 K and 1032 K
Fig 2 The temperature dependencies of the density of (Sn 313Ag 074Cu) + In liquid alloys
Fig 3 The temperature dependencies of the surface tension of (Sn 313Ag 074Cu) + In
liquid alloys
Fig 4 The isotherms of the density of (Sn 313Ag 074Cu)+In liquid alloys at 523 K and 1023 K
Fig 5 The isotherms of the surface tension of (Sn 313Ag 074Cu)+In liquid alloys at 523 K and 1023 K
3 Modeling of the surface tension
Two kinds of modeling of surface tension were used for quaternary alloys Sn-Ag-Cu-In similarly as in previous studies on Sn-Ag-Cu-Sb system [1]
[1] ZMoser WGąsior JPstruś IOhnuma KIshida ldquoInfluence of Sb additions on surface tension and density of Sn-Sb Sn-Ag-Sb and Sn-Ag-Cu-Sb alloys Experiment vsmodelingrdquo International Jounal of Materials Research Zeitschrift fuer Metallkunde 97 (2006) 365-370 Dedicated to Professor DrFerdinand Sommer on the occasion of his 65th birthday
1 Butler model with thermodynamic properties of liquid constituent components and surface tension of pure
components This modeling was successfully tested in studies of systems presented in SURDAT database
with observation that the experimental temperature dependence of the surface tension is linear while from
modeling slightly curvilinear dependence was calculated
For such procedure in the case of quaternary Sn-Ag-Cu-In system we should know data of six binaries
Cu-In Cu-Ag Sn-Ag Ag-In Sn-Cu In-Sn four ternaries Sn-Ag-Cu Sn-Ag-In Sn-Cu-In In-Ag-Cu and for
quaternary alloy (one quaternary alloy with equal concentration of components 025 molar fraction was
investigated)
In the case of modeling 2 we are basing on experimental data of surface tension of constituent binary systems
with ternary and quaternary correction factors to elaborate the temperature and concentration dependence of
the surface tension of the Sn-Ag-Cu-In system For the remaining not previously investigated surface tension
and density in this study were determined Cu-In and Cu-Ag ternaries Sn-Ag-Cu Sn-Ag-In In-Ag-Cu and
one quaternary alloy with equal concentration of components 025 molar fraction
As an example in Table 4 are presented surface tension data of ternaries and quaternary alloy
Table 4 Temperature dependencies of the surface tension of the liquid quaternary Sn 25Ag 25Cu 25In and ternary alloys Sn 25Ag 25In Sn 25Ag 25Cu and In 25Ag 25Cu with the calculated errors of the A and B parameters and the
surface tension calculated at 973 K and 1273 K
X at σ = A +BTmNm-1
σ 973K
mNm-1
σ 1273K
mNm-1
Err(A)mNm-1
Err(B)mNm-1middotK-1
Sn25Ag25InSn25Ag25CuIn25Ag25Cu
Sn25Ag25Cu25In
= 6190-00599T = 6142-00235T = 6510-00293T = 7685-00737T
5607plusmn64 5914plusmn42 6225plusmn55
6967plusmn125
5427plusmn765843plusmn456138plusmn64
6746plusmn123
plusmn131 plusmn82
plusmn124 plusmn260
plusmn00133 plusmn00088
plusmn00122 plusmn00227
Fig6 Comparison of calculations of the surface tension of the quaternary system Sn-Ag-Cu-In by Butlerrsquos model and with temperature-concentration dependence and with one experimental alloy (Table 4) with equal 025 molar fractions Thin lines show the Butler model while thick correspond to temperature concentration dependence of the surface tension
Results of calculations by the Butler model show lower values of the surface tension due to the fact that
interaction parameters for Ag-Cu-In and Cu-In-Sn were not taken into calculations In addition only the
limited amount of alloys for binary and ternary alloys of surface tension was investigated with one quaternary
sample
The obtained results from both methods are compared in Fig6
4 Contact angles measurements of the (Sn313Ag074Cu) + In liquid alloys
Wetting of copper substrates was studied by sessile drop method Solder in a cube form was covered by flux
and put on the substrate and after melting at given temperature (250 280 and 320 oC) pictures of drop were
taken by digital camera up to 30 minutes Contact angles were measured by computer After the drop
solidifies specimen were cut perpendicularly for metallographic studies discussed in the next section
Typical course of time dependencies of contact angle for pure (not containing In) Sn 313Ag 074Cu
Sn 252Ag 057Cu 30In and Sn 12Ag 027Cu 75In are presented on Figs7-10 Except the beginning of
wetting the contact angle practically does not depend on the wetting temperature and with the increase of In
concentration is lowered the time to reach the constant values of contact angles which gradually are
decreasing Due to the observed in Figs7-9 the negligible differences in contact angles in the temperature
interval in Fig10 is plotted the change of contact angle after 30 minutes for all investigated alloys The
lowering tendency of the contact angle is observed with some scattering at low In content
Fig7 Change of the contact angle for the starting alloy Sn 313Ag 074Cu
Fig 8 Change of the contact angle for Sn 313Ag 074Cu + 30 at In
Fig 9 Change of the contact angle for Sn 313Ag 074Cu + 75 at In
Fig 10 Change of contact angles for Sn-Ag-Cu-In alloys after 30 minutes
5 Interaction studies of the quaternary alloys with Cu substrate
Metallographic studies of the structure of the boundary between the solder and substrate as well as the
structure of the solder itself was studied by electron scanning microscopy (SEM) Energy dispersive X-ray
analyzer (EDX) was used to measure the chemical composition of the interface as well as the bulk solder The
same specimen which were used for SEM and EDX investigation were also used for X-ray diffraction phase
analysis of the solder and substrate
For low In concentration (up to 15 at) Cu interface is formed by Cu6Sn5 phase For higher concentration of
In (30-50 at) Cu interface if formed by Cu41Sn11 phase For highest In concentration (75 at) Cu
interface is formed by Cu3(SnIn) phase
6 Conclusions
In this presentation investigating the influence of In on wettability of the alloy Sn 313Ag 074Cu close to
ternary eutectic Sn-Ag-Cu it was confirmed starting from previous data on In-Sn and
Sn-Ag-In [1] that due to the nearly the same surface tension and density values of pure In and Sn the
beneficial influence of In is reflected by the lowering of the contact angles with practically no change of
temperature dependence of both surface tension and density Isothermal behaviour of surface tension with ldquoSrdquo
shape starting from In-Sn and Sn-Ag-In proceeding into the investigated in this study Sn-Ag-Cu-In is
probably in addition connected with the peculiar properties of liquid In-Sn alloys showing extrema on
isothermal behaviour of electrical resistivity and viscosity [2] corresponding well to the existence of
intermetallic phases in the phase diagram of In-Sn phase diagram It is the another proof of the mutual
correlations between thermodynamic properties physical properties and the character of the phase diagram
[1] X J Liu Y Inohana I Ohnuma R Kainuma K Ishida Z Moser W Gąsior J Pstruś J Electronic Mater 31 (2002) 1139-51 [2] BPredel MHoch MPool Phase Diagrams and Heterogeneous Equilibria Springer-Verlag Berlin Heidelberg (2004) 289-291
7 Final remarks
1 Presented today joint results with P Sebo will be elaborated for Calphad journal
2 SURDAT database realized in parallel to COST 531 Program has been introduced on website of COST
531 Program
3 In addition from financing of COST 531 Program under research entitled ldquoExperimental determination
and modeling of physicochemical properties of multi-component alloys on the tin base ldquo within
2003-2006 the additional study has been realized by dr Piotr Ozga
ldquo The study of a possibility of the electrodeposition of Sn-Ag alloys from aqueous solutionsrdquo
a POzga ldquoEquilibria in Aqueous Solutions of Ag(I)-Sn(IIIV) in Presence of Strong Complexing
Ligandsrdquo CALPHAD XXXIII Krakow (Poland) May 30 ndash June 4 2004 Abstracts p 153
b POzga ldquoElectrodeposition of Sn-Ag and Sn-Ag-Cu alloys from the thiourea solutionsrdquo Archives of
Metallurgy and Materials 3 (2006) 413-421
The results of this study were used in habilitation thesis of P Ozga edited by the Institute of Metallurgy
and Materials ISBN-83-921845-8-0 Krakow (2006) 1-148
bull Special issue of the Archives of Metallurgy and Materials 32006 has been devoted to results realized
within COST 531 Program
Thank you
for your attention
- Slide 1
- Slide 2
- Slide 3
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- Slide 10
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Slide 18
- Slide 19
- Slide 20
-
The main aim is to confirm the previous observation of In additions to (Sn-Ag) eut on wettability and to extend
it in the presented studies of quaternary alloys (Sn 313Ag 074Cu) + In combining surface tension density
and modeling of surface tension from Krakow Poland with contact angles and interaction of liquid alloys
with Cu substrate using flux undertaken in Bratislava Slovakia within COST 531 Program
The starting material was nearly eutectic alloy (Sn 313Ag 074Cu) with 2 3 4 15 30 50 and 75 at In
2 Surface tension and density measurements of the (Sn313Ag074Cu) + In liquid alloys
The density and surface tension measurements of the (Sn313Ag074Cu) + In liquid alloys at In
concentrations ( 2 3 4 15 30 50 and 75 at) by the maximum bubble pressure method and dilatometric
technique were conducted in the temperature range from 158 degC to 936 degC Results are presented in Tables 2
and 3 and in Figures 2 and 3 In Figures 4 and 5 are shown isotherms of surface tension and density As
indicated in the introduction no change of both temperature dependence of the surface tension and density is
observed The preliminary results were presented in Genoa [1]
[1] COST Action 531 MC Meeting (25022006) amp WG 1-2-3-4-5-6 Meeting (23-24022006) in Genoa Italy
XIn σ=A+B∙TmN∙m-1
σ 523K
mN∙m-1
σ 1023K
mN∙m-1
Err(a)mN∙m-1
Err(b)mN∙m∙K-1
000200300401503005007510
5851 -008815785 -007665728 -007305743 -007056034 -011555883 -010495879 -010045877 -008575938 -00942
5391 plusmn825385 plusmn715346 plusmn915374 plusmn6
5430 plusmn1015334 plusmn91
5354 plusmn1045429 plusmn1155445 plusmn116
4950plusmn765002plusmn76 4982plusmn86 5022plusmn624853plusmn984810plusmn88
4852plusmn99 5000plusmn176
4974plusmn113
plusmn78plusmn90plusmn99plusmn80
plusmn104plusmn96
plusmn111plusmn185plusmn119
plusmn00085plusmn00120plusmn00113plusmn00096plusmn00124plusmn00115plusmn00127plusmn00308plusmn00144
- Sn 313Ag 074Cu
XIn
at
ρ=A+B∙Tg∙cm-3
ρ 523K
g∙cm-3
ρ 1023K
g∙cm-3
Err(a)g∙cm-3
Err(b)g∙cm-3∙K-1
000200300401503005007510
74615-000070374814-000076975050-000083874130-000074873416-000064173379-000066473159-000063273887-000074073206-0000684
7094plusmn00277079plusmn00297067plusmn00277022plusmn00557006plusmn00706990plusmn00606986plusmn00667002plusmn00156963plusmn0027
6742plusmn003 6695plusmn0036648plusmn004
6648plusmn006 6686plusmn007 6658plusmn0066670plusmn0066632plusmn002
6621plusmn003
plusmn0028plusmn0036plusmn0050plusmn0088plusmn0076plusmn0063plusmn0067plusmn0022plusmn0032
plusmn0000035plusmn0000052plusmn0000078plusmn0000113plusmn0000090plusmn0000073plusmn0000073plusmn0000033plusmn0000039
Table 2 Temperature dependencies of the density of the liquid quaternary (Sn 313Ag 074Cu)+In and ternary alloys with the calculated errors of the A and B parameters and the densities calculated at 523 K and 1032 K
Table 3 Temperature dependencies of the surface tension of the liquid quaternary (Sn 313Ag 074Cu)+In and ternary alloys with the calculated errors of the A and B parameters and the surface tension calculated at 523 K and 1032 K
Fig 2 The temperature dependencies of the density of (Sn 313Ag 074Cu) + In liquid alloys
Fig 3 The temperature dependencies of the surface tension of (Sn 313Ag 074Cu) + In
liquid alloys
Fig 4 The isotherms of the density of (Sn 313Ag 074Cu)+In liquid alloys at 523 K and 1023 K
Fig 5 The isotherms of the surface tension of (Sn 313Ag 074Cu)+In liquid alloys at 523 K and 1023 K
3 Modeling of the surface tension
Two kinds of modeling of surface tension were used for quaternary alloys Sn-Ag-Cu-In similarly as in previous studies on Sn-Ag-Cu-Sb system [1]
[1] ZMoser WGąsior JPstruś IOhnuma KIshida ldquoInfluence of Sb additions on surface tension and density of Sn-Sb Sn-Ag-Sb and Sn-Ag-Cu-Sb alloys Experiment vsmodelingrdquo International Jounal of Materials Research Zeitschrift fuer Metallkunde 97 (2006) 365-370 Dedicated to Professor DrFerdinand Sommer on the occasion of his 65th birthday
1 Butler model with thermodynamic properties of liquid constituent components and surface tension of pure
components This modeling was successfully tested in studies of systems presented in SURDAT database
with observation that the experimental temperature dependence of the surface tension is linear while from
modeling slightly curvilinear dependence was calculated
For such procedure in the case of quaternary Sn-Ag-Cu-In system we should know data of six binaries
Cu-In Cu-Ag Sn-Ag Ag-In Sn-Cu In-Sn four ternaries Sn-Ag-Cu Sn-Ag-In Sn-Cu-In In-Ag-Cu and for
quaternary alloy (one quaternary alloy with equal concentration of components 025 molar fraction was
investigated)
In the case of modeling 2 we are basing on experimental data of surface tension of constituent binary systems
with ternary and quaternary correction factors to elaborate the temperature and concentration dependence of
the surface tension of the Sn-Ag-Cu-In system For the remaining not previously investigated surface tension
and density in this study were determined Cu-In and Cu-Ag ternaries Sn-Ag-Cu Sn-Ag-In In-Ag-Cu and
one quaternary alloy with equal concentration of components 025 molar fraction
As an example in Table 4 are presented surface tension data of ternaries and quaternary alloy
Table 4 Temperature dependencies of the surface tension of the liquid quaternary Sn 25Ag 25Cu 25In and ternary alloys Sn 25Ag 25In Sn 25Ag 25Cu and In 25Ag 25Cu with the calculated errors of the A and B parameters and the
surface tension calculated at 973 K and 1273 K
X at σ = A +BTmNm-1
σ 973K
mNm-1
σ 1273K
mNm-1
Err(A)mNm-1
Err(B)mNm-1middotK-1
Sn25Ag25InSn25Ag25CuIn25Ag25Cu
Sn25Ag25Cu25In
= 6190-00599T = 6142-00235T = 6510-00293T = 7685-00737T
5607plusmn64 5914plusmn42 6225plusmn55
6967plusmn125
5427plusmn765843plusmn456138plusmn64
6746plusmn123
plusmn131 plusmn82
plusmn124 plusmn260
plusmn00133 plusmn00088
plusmn00122 plusmn00227
Fig6 Comparison of calculations of the surface tension of the quaternary system Sn-Ag-Cu-In by Butlerrsquos model and with temperature-concentration dependence and with one experimental alloy (Table 4) with equal 025 molar fractions Thin lines show the Butler model while thick correspond to temperature concentration dependence of the surface tension
Results of calculations by the Butler model show lower values of the surface tension due to the fact that
interaction parameters for Ag-Cu-In and Cu-In-Sn were not taken into calculations In addition only the
limited amount of alloys for binary and ternary alloys of surface tension was investigated with one quaternary
sample
The obtained results from both methods are compared in Fig6
4 Contact angles measurements of the (Sn313Ag074Cu) + In liquid alloys
Wetting of copper substrates was studied by sessile drop method Solder in a cube form was covered by flux
and put on the substrate and after melting at given temperature (250 280 and 320 oC) pictures of drop were
taken by digital camera up to 30 minutes Contact angles were measured by computer After the drop
solidifies specimen were cut perpendicularly for metallographic studies discussed in the next section
Typical course of time dependencies of contact angle for pure (not containing In) Sn 313Ag 074Cu
Sn 252Ag 057Cu 30In and Sn 12Ag 027Cu 75In are presented on Figs7-10 Except the beginning of
wetting the contact angle practically does not depend on the wetting temperature and with the increase of In
concentration is lowered the time to reach the constant values of contact angles which gradually are
decreasing Due to the observed in Figs7-9 the negligible differences in contact angles in the temperature
interval in Fig10 is plotted the change of contact angle after 30 minutes for all investigated alloys The
lowering tendency of the contact angle is observed with some scattering at low In content
Fig7 Change of the contact angle for the starting alloy Sn 313Ag 074Cu
Fig 8 Change of the contact angle for Sn 313Ag 074Cu + 30 at In
Fig 9 Change of the contact angle for Sn 313Ag 074Cu + 75 at In
Fig 10 Change of contact angles for Sn-Ag-Cu-In alloys after 30 minutes
5 Interaction studies of the quaternary alloys with Cu substrate
Metallographic studies of the structure of the boundary between the solder and substrate as well as the
structure of the solder itself was studied by electron scanning microscopy (SEM) Energy dispersive X-ray
analyzer (EDX) was used to measure the chemical composition of the interface as well as the bulk solder The
same specimen which were used for SEM and EDX investigation were also used for X-ray diffraction phase
analysis of the solder and substrate
For low In concentration (up to 15 at) Cu interface is formed by Cu6Sn5 phase For higher concentration of
In (30-50 at) Cu interface if formed by Cu41Sn11 phase For highest In concentration (75 at) Cu
interface is formed by Cu3(SnIn) phase
6 Conclusions
In this presentation investigating the influence of In on wettability of the alloy Sn 313Ag 074Cu close to
ternary eutectic Sn-Ag-Cu it was confirmed starting from previous data on In-Sn and
Sn-Ag-In [1] that due to the nearly the same surface tension and density values of pure In and Sn the
beneficial influence of In is reflected by the lowering of the contact angles with practically no change of
temperature dependence of both surface tension and density Isothermal behaviour of surface tension with ldquoSrdquo
shape starting from In-Sn and Sn-Ag-In proceeding into the investigated in this study Sn-Ag-Cu-In is
probably in addition connected with the peculiar properties of liquid In-Sn alloys showing extrema on
isothermal behaviour of electrical resistivity and viscosity [2] corresponding well to the existence of
intermetallic phases in the phase diagram of In-Sn phase diagram It is the another proof of the mutual
correlations between thermodynamic properties physical properties and the character of the phase diagram
[1] X J Liu Y Inohana I Ohnuma R Kainuma K Ishida Z Moser W Gąsior J Pstruś J Electronic Mater 31 (2002) 1139-51 [2] BPredel MHoch MPool Phase Diagrams and Heterogeneous Equilibria Springer-Verlag Berlin Heidelberg (2004) 289-291
7 Final remarks
1 Presented today joint results with P Sebo will be elaborated for Calphad journal
2 SURDAT database realized in parallel to COST 531 Program has been introduced on website of COST
531 Program
3 In addition from financing of COST 531 Program under research entitled ldquoExperimental determination
and modeling of physicochemical properties of multi-component alloys on the tin base ldquo within
2003-2006 the additional study has been realized by dr Piotr Ozga
ldquo The study of a possibility of the electrodeposition of Sn-Ag alloys from aqueous solutionsrdquo
a POzga ldquoEquilibria in Aqueous Solutions of Ag(I)-Sn(IIIV) in Presence of Strong Complexing
Ligandsrdquo CALPHAD XXXIII Krakow (Poland) May 30 ndash June 4 2004 Abstracts p 153
b POzga ldquoElectrodeposition of Sn-Ag and Sn-Ag-Cu alloys from the thiourea solutionsrdquo Archives of
Metallurgy and Materials 3 (2006) 413-421
The results of this study were used in habilitation thesis of P Ozga edited by the Institute of Metallurgy
and Materials ISBN-83-921845-8-0 Krakow (2006) 1-148
bull Special issue of the Archives of Metallurgy and Materials 32006 has been devoted to results realized
within COST 531 Program
Thank you
for your attention
- Slide 1
- Slide 2
- Slide 3
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- Slide 10
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Slide 18
- Slide 19
- Slide 20
-
2 Surface tension and density measurements of the (Sn313Ag074Cu) + In liquid alloys
The density and surface tension measurements of the (Sn313Ag074Cu) + In liquid alloys at In
concentrations ( 2 3 4 15 30 50 and 75 at) by the maximum bubble pressure method and dilatometric
technique were conducted in the temperature range from 158 degC to 936 degC Results are presented in Tables 2
and 3 and in Figures 2 and 3 In Figures 4 and 5 are shown isotherms of surface tension and density As
indicated in the introduction no change of both temperature dependence of the surface tension and density is
observed The preliminary results were presented in Genoa [1]
[1] COST Action 531 MC Meeting (25022006) amp WG 1-2-3-4-5-6 Meeting (23-24022006) in Genoa Italy
XIn σ=A+B∙TmN∙m-1
σ 523K
mN∙m-1
σ 1023K
mN∙m-1
Err(a)mN∙m-1
Err(b)mN∙m∙K-1
000200300401503005007510
5851 -008815785 -007665728 -007305743 -007056034 -011555883 -010495879 -010045877 -008575938 -00942
5391 plusmn825385 plusmn715346 plusmn915374 plusmn6
5430 plusmn1015334 plusmn91
5354 plusmn1045429 plusmn1155445 plusmn116
4950plusmn765002plusmn76 4982plusmn86 5022plusmn624853plusmn984810plusmn88
4852plusmn99 5000plusmn176
4974plusmn113
plusmn78plusmn90plusmn99plusmn80
plusmn104plusmn96
plusmn111plusmn185plusmn119
plusmn00085plusmn00120plusmn00113plusmn00096plusmn00124plusmn00115plusmn00127plusmn00308plusmn00144
- Sn 313Ag 074Cu
XIn
at
ρ=A+B∙Tg∙cm-3
ρ 523K
g∙cm-3
ρ 1023K
g∙cm-3
Err(a)g∙cm-3
Err(b)g∙cm-3∙K-1
000200300401503005007510
74615-000070374814-000076975050-000083874130-000074873416-000064173379-000066473159-000063273887-000074073206-0000684
7094plusmn00277079plusmn00297067plusmn00277022plusmn00557006plusmn00706990plusmn00606986plusmn00667002plusmn00156963plusmn0027
6742plusmn003 6695plusmn0036648plusmn004
6648plusmn006 6686plusmn007 6658plusmn0066670plusmn0066632plusmn002
6621plusmn003
plusmn0028plusmn0036plusmn0050plusmn0088plusmn0076plusmn0063plusmn0067plusmn0022plusmn0032
plusmn0000035plusmn0000052plusmn0000078plusmn0000113plusmn0000090plusmn0000073plusmn0000073plusmn0000033plusmn0000039
Table 2 Temperature dependencies of the density of the liquid quaternary (Sn 313Ag 074Cu)+In and ternary alloys with the calculated errors of the A and B parameters and the densities calculated at 523 K and 1032 K
Table 3 Temperature dependencies of the surface tension of the liquid quaternary (Sn 313Ag 074Cu)+In and ternary alloys with the calculated errors of the A and B parameters and the surface tension calculated at 523 K and 1032 K
Fig 2 The temperature dependencies of the density of (Sn 313Ag 074Cu) + In liquid alloys
Fig 3 The temperature dependencies of the surface tension of (Sn 313Ag 074Cu) + In
liquid alloys
Fig 4 The isotherms of the density of (Sn 313Ag 074Cu)+In liquid alloys at 523 K and 1023 K
Fig 5 The isotherms of the surface tension of (Sn 313Ag 074Cu)+In liquid alloys at 523 K and 1023 K
3 Modeling of the surface tension
Two kinds of modeling of surface tension were used for quaternary alloys Sn-Ag-Cu-In similarly as in previous studies on Sn-Ag-Cu-Sb system [1]
[1] ZMoser WGąsior JPstruś IOhnuma KIshida ldquoInfluence of Sb additions on surface tension and density of Sn-Sb Sn-Ag-Sb and Sn-Ag-Cu-Sb alloys Experiment vsmodelingrdquo International Jounal of Materials Research Zeitschrift fuer Metallkunde 97 (2006) 365-370 Dedicated to Professor DrFerdinand Sommer on the occasion of his 65th birthday
1 Butler model with thermodynamic properties of liquid constituent components and surface tension of pure
components This modeling was successfully tested in studies of systems presented in SURDAT database
with observation that the experimental temperature dependence of the surface tension is linear while from
modeling slightly curvilinear dependence was calculated
For such procedure in the case of quaternary Sn-Ag-Cu-In system we should know data of six binaries
Cu-In Cu-Ag Sn-Ag Ag-In Sn-Cu In-Sn four ternaries Sn-Ag-Cu Sn-Ag-In Sn-Cu-In In-Ag-Cu and for
quaternary alloy (one quaternary alloy with equal concentration of components 025 molar fraction was
investigated)
In the case of modeling 2 we are basing on experimental data of surface tension of constituent binary systems
with ternary and quaternary correction factors to elaborate the temperature and concentration dependence of
the surface tension of the Sn-Ag-Cu-In system For the remaining not previously investigated surface tension
and density in this study were determined Cu-In and Cu-Ag ternaries Sn-Ag-Cu Sn-Ag-In In-Ag-Cu and
one quaternary alloy with equal concentration of components 025 molar fraction
As an example in Table 4 are presented surface tension data of ternaries and quaternary alloy
Table 4 Temperature dependencies of the surface tension of the liquid quaternary Sn 25Ag 25Cu 25In and ternary alloys Sn 25Ag 25In Sn 25Ag 25Cu and In 25Ag 25Cu with the calculated errors of the A and B parameters and the
surface tension calculated at 973 K and 1273 K
X at σ = A +BTmNm-1
σ 973K
mNm-1
σ 1273K
mNm-1
Err(A)mNm-1
Err(B)mNm-1middotK-1
Sn25Ag25InSn25Ag25CuIn25Ag25Cu
Sn25Ag25Cu25In
= 6190-00599T = 6142-00235T = 6510-00293T = 7685-00737T
5607plusmn64 5914plusmn42 6225plusmn55
6967plusmn125
5427plusmn765843plusmn456138plusmn64
6746plusmn123
plusmn131 plusmn82
plusmn124 plusmn260
plusmn00133 plusmn00088
plusmn00122 plusmn00227
Fig6 Comparison of calculations of the surface tension of the quaternary system Sn-Ag-Cu-In by Butlerrsquos model and with temperature-concentration dependence and with one experimental alloy (Table 4) with equal 025 molar fractions Thin lines show the Butler model while thick correspond to temperature concentration dependence of the surface tension
Results of calculations by the Butler model show lower values of the surface tension due to the fact that
interaction parameters for Ag-Cu-In and Cu-In-Sn were not taken into calculations In addition only the
limited amount of alloys for binary and ternary alloys of surface tension was investigated with one quaternary
sample
The obtained results from both methods are compared in Fig6
4 Contact angles measurements of the (Sn313Ag074Cu) + In liquid alloys
Wetting of copper substrates was studied by sessile drop method Solder in a cube form was covered by flux
and put on the substrate and after melting at given temperature (250 280 and 320 oC) pictures of drop were
taken by digital camera up to 30 minutes Contact angles were measured by computer After the drop
solidifies specimen were cut perpendicularly for metallographic studies discussed in the next section
Typical course of time dependencies of contact angle for pure (not containing In) Sn 313Ag 074Cu
Sn 252Ag 057Cu 30In and Sn 12Ag 027Cu 75In are presented on Figs7-10 Except the beginning of
wetting the contact angle practically does not depend on the wetting temperature and with the increase of In
concentration is lowered the time to reach the constant values of contact angles which gradually are
decreasing Due to the observed in Figs7-9 the negligible differences in contact angles in the temperature
interval in Fig10 is plotted the change of contact angle after 30 minutes for all investigated alloys The
lowering tendency of the contact angle is observed with some scattering at low In content
Fig7 Change of the contact angle for the starting alloy Sn 313Ag 074Cu
Fig 8 Change of the contact angle for Sn 313Ag 074Cu + 30 at In
Fig 9 Change of the contact angle for Sn 313Ag 074Cu + 75 at In
Fig 10 Change of contact angles for Sn-Ag-Cu-In alloys after 30 minutes
5 Interaction studies of the quaternary alloys with Cu substrate
Metallographic studies of the structure of the boundary between the solder and substrate as well as the
structure of the solder itself was studied by electron scanning microscopy (SEM) Energy dispersive X-ray
analyzer (EDX) was used to measure the chemical composition of the interface as well as the bulk solder The
same specimen which were used for SEM and EDX investigation were also used for X-ray diffraction phase
analysis of the solder and substrate
For low In concentration (up to 15 at) Cu interface is formed by Cu6Sn5 phase For higher concentration of
In (30-50 at) Cu interface if formed by Cu41Sn11 phase For highest In concentration (75 at) Cu
interface is formed by Cu3(SnIn) phase
6 Conclusions
In this presentation investigating the influence of In on wettability of the alloy Sn 313Ag 074Cu close to
ternary eutectic Sn-Ag-Cu it was confirmed starting from previous data on In-Sn and
Sn-Ag-In [1] that due to the nearly the same surface tension and density values of pure In and Sn the
beneficial influence of In is reflected by the lowering of the contact angles with practically no change of
temperature dependence of both surface tension and density Isothermal behaviour of surface tension with ldquoSrdquo
shape starting from In-Sn and Sn-Ag-In proceeding into the investigated in this study Sn-Ag-Cu-In is
probably in addition connected with the peculiar properties of liquid In-Sn alloys showing extrema on
isothermal behaviour of electrical resistivity and viscosity [2] corresponding well to the existence of
intermetallic phases in the phase diagram of In-Sn phase diagram It is the another proof of the mutual
correlations between thermodynamic properties physical properties and the character of the phase diagram
[1] X J Liu Y Inohana I Ohnuma R Kainuma K Ishida Z Moser W Gąsior J Pstruś J Electronic Mater 31 (2002) 1139-51 [2] BPredel MHoch MPool Phase Diagrams and Heterogeneous Equilibria Springer-Verlag Berlin Heidelberg (2004) 289-291
7 Final remarks
1 Presented today joint results with P Sebo will be elaborated for Calphad journal
2 SURDAT database realized in parallel to COST 531 Program has been introduced on website of COST
531 Program
3 In addition from financing of COST 531 Program under research entitled ldquoExperimental determination
and modeling of physicochemical properties of multi-component alloys on the tin base ldquo within
2003-2006 the additional study has been realized by dr Piotr Ozga
ldquo The study of a possibility of the electrodeposition of Sn-Ag alloys from aqueous solutionsrdquo
a POzga ldquoEquilibria in Aqueous Solutions of Ag(I)-Sn(IIIV) in Presence of Strong Complexing
Ligandsrdquo CALPHAD XXXIII Krakow (Poland) May 30 ndash June 4 2004 Abstracts p 153
b POzga ldquoElectrodeposition of Sn-Ag and Sn-Ag-Cu alloys from the thiourea solutionsrdquo Archives of
Metallurgy and Materials 3 (2006) 413-421
The results of this study were used in habilitation thesis of P Ozga edited by the Institute of Metallurgy
and Materials ISBN-83-921845-8-0 Krakow (2006) 1-148
bull Special issue of the Archives of Metallurgy and Materials 32006 has been devoted to results realized
within COST 531 Program
Thank you
for your attention
- Slide 1
- Slide 2
- Slide 3
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- Slide 10
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Slide 18
- Slide 19
- Slide 20
-
XIn σ=A+B∙TmN∙m-1
σ 523K
mN∙m-1
σ 1023K
mN∙m-1
Err(a)mN∙m-1
Err(b)mN∙m∙K-1
000200300401503005007510
5851 -008815785 -007665728 -007305743 -007056034 -011555883 -010495879 -010045877 -008575938 -00942
5391 plusmn825385 plusmn715346 plusmn915374 plusmn6
5430 plusmn1015334 plusmn91
5354 plusmn1045429 plusmn1155445 plusmn116
4950plusmn765002plusmn76 4982plusmn86 5022plusmn624853plusmn984810plusmn88
4852plusmn99 5000plusmn176
4974plusmn113
plusmn78plusmn90plusmn99plusmn80
plusmn104plusmn96
plusmn111plusmn185plusmn119
plusmn00085plusmn00120plusmn00113plusmn00096plusmn00124plusmn00115plusmn00127plusmn00308plusmn00144
- Sn 313Ag 074Cu
XIn
at
ρ=A+B∙Tg∙cm-3
ρ 523K
g∙cm-3
ρ 1023K
g∙cm-3
Err(a)g∙cm-3
Err(b)g∙cm-3∙K-1
000200300401503005007510
74615-000070374814-000076975050-000083874130-000074873416-000064173379-000066473159-000063273887-000074073206-0000684
7094plusmn00277079plusmn00297067plusmn00277022plusmn00557006plusmn00706990plusmn00606986plusmn00667002plusmn00156963plusmn0027
6742plusmn003 6695plusmn0036648plusmn004
6648plusmn006 6686plusmn007 6658plusmn0066670plusmn0066632plusmn002
6621plusmn003
plusmn0028plusmn0036plusmn0050plusmn0088plusmn0076plusmn0063plusmn0067plusmn0022plusmn0032
plusmn0000035plusmn0000052plusmn0000078plusmn0000113plusmn0000090plusmn0000073plusmn0000073plusmn0000033plusmn0000039
Table 2 Temperature dependencies of the density of the liquid quaternary (Sn 313Ag 074Cu)+In and ternary alloys with the calculated errors of the A and B parameters and the densities calculated at 523 K and 1032 K
Table 3 Temperature dependencies of the surface tension of the liquid quaternary (Sn 313Ag 074Cu)+In and ternary alloys with the calculated errors of the A and B parameters and the surface tension calculated at 523 K and 1032 K
Fig 2 The temperature dependencies of the density of (Sn 313Ag 074Cu) + In liquid alloys
Fig 3 The temperature dependencies of the surface tension of (Sn 313Ag 074Cu) + In
liquid alloys
Fig 4 The isotherms of the density of (Sn 313Ag 074Cu)+In liquid alloys at 523 K and 1023 K
Fig 5 The isotherms of the surface tension of (Sn 313Ag 074Cu)+In liquid alloys at 523 K and 1023 K
3 Modeling of the surface tension
Two kinds of modeling of surface tension were used for quaternary alloys Sn-Ag-Cu-In similarly as in previous studies on Sn-Ag-Cu-Sb system [1]
[1] ZMoser WGąsior JPstruś IOhnuma KIshida ldquoInfluence of Sb additions on surface tension and density of Sn-Sb Sn-Ag-Sb and Sn-Ag-Cu-Sb alloys Experiment vsmodelingrdquo International Jounal of Materials Research Zeitschrift fuer Metallkunde 97 (2006) 365-370 Dedicated to Professor DrFerdinand Sommer on the occasion of his 65th birthday
1 Butler model with thermodynamic properties of liquid constituent components and surface tension of pure
components This modeling was successfully tested in studies of systems presented in SURDAT database
with observation that the experimental temperature dependence of the surface tension is linear while from
modeling slightly curvilinear dependence was calculated
For such procedure in the case of quaternary Sn-Ag-Cu-In system we should know data of six binaries
Cu-In Cu-Ag Sn-Ag Ag-In Sn-Cu In-Sn four ternaries Sn-Ag-Cu Sn-Ag-In Sn-Cu-In In-Ag-Cu and for
quaternary alloy (one quaternary alloy with equal concentration of components 025 molar fraction was
investigated)
In the case of modeling 2 we are basing on experimental data of surface tension of constituent binary systems
with ternary and quaternary correction factors to elaborate the temperature and concentration dependence of
the surface tension of the Sn-Ag-Cu-In system For the remaining not previously investigated surface tension
and density in this study were determined Cu-In and Cu-Ag ternaries Sn-Ag-Cu Sn-Ag-In In-Ag-Cu and
one quaternary alloy with equal concentration of components 025 molar fraction
As an example in Table 4 are presented surface tension data of ternaries and quaternary alloy
Table 4 Temperature dependencies of the surface tension of the liquid quaternary Sn 25Ag 25Cu 25In and ternary alloys Sn 25Ag 25In Sn 25Ag 25Cu and In 25Ag 25Cu with the calculated errors of the A and B parameters and the
surface tension calculated at 973 K and 1273 K
X at σ = A +BTmNm-1
σ 973K
mNm-1
σ 1273K
mNm-1
Err(A)mNm-1
Err(B)mNm-1middotK-1
Sn25Ag25InSn25Ag25CuIn25Ag25Cu
Sn25Ag25Cu25In
= 6190-00599T = 6142-00235T = 6510-00293T = 7685-00737T
5607plusmn64 5914plusmn42 6225plusmn55
6967plusmn125
5427plusmn765843plusmn456138plusmn64
6746plusmn123
plusmn131 plusmn82
plusmn124 plusmn260
plusmn00133 plusmn00088
plusmn00122 plusmn00227
Fig6 Comparison of calculations of the surface tension of the quaternary system Sn-Ag-Cu-In by Butlerrsquos model and with temperature-concentration dependence and with one experimental alloy (Table 4) with equal 025 molar fractions Thin lines show the Butler model while thick correspond to temperature concentration dependence of the surface tension
Results of calculations by the Butler model show lower values of the surface tension due to the fact that
interaction parameters for Ag-Cu-In and Cu-In-Sn were not taken into calculations In addition only the
limited amount of alloys for binary and ternary alloys of surface tension was investigated with one quaternary
sample
The obtained results from both methods are compared in Fig6
4 Contact angles measurements of the (Sn313Ag074Cu) + In liquid alloys
Wetting of copper substrates was studied by sessile drop method Solder in a cube form was covered by flux
and put on the substrate and after melting at given temperature (250 280 and 320 oC) pictures of drop were
taken by digital camera up to 30 minutes Contact angles were measured by computer After the drop
solidifies specimen were cut perpendicularly for metallographic studies discussed in the next section
Typical course of time dependencies of contact angle for pure (not containing In) Sn 313Ag 074Cu
Sn 252Ag 057Cu 30In and Sn 12Ag 027Cu 75In are presented on Figs7-10 Except the beginning of
wetting the contact angle practically does not depend on the wetting temperature and with the increase of In
concentration is lowered the time to reach the constant values of contact angles which gradually are
decreasing Due to the observed in Figs7-9 the negligible differences in contact angles in the temperature
interval in Fig10 is plotted the change of contact angle after 30 minutes for all investigated alloys The
lowering tendency of the contact angle is observed with some scattering at low In content
Fig7 Change of the contact angle for the starting alloy Sn 313Ag 074Cu
Fig 8 Change of the contact angle for Sn 313Ag 074Cu + 30 at In
Fig 9 Change of the contact angle for Sn 313Ag 074Cu + 75 at In
Fig 10 Change of contact angles for Sn-Ag-Cu-In alloys after 30 minutes
5 Interaction studies of the quaternary alloys with Cu substrate
Metallographic studies of the structure of the boundary between the solder and substrate as well as the
structure of the solder itself was studied by electron scanning microscopy (SEM) Energy dispersive X-ray
analyzer (EDX) was used to measure the chemical composition of the interface as well as the bulk solder The
same specimen which were used for SEM and EDX investigation were also used for X-ray diffraction phase
analysis of the solder and substrate
For low In concentration (up to 15 at) Cu interface is formed by Cu6Sn5 phase For higher concentration of
In (30-50 at) Cu interface if formed by Cu41Sn11 phase For highest In concentration (75 at) Cu
interface is formed by Cu3(SnIn) phase
6 Conclusions
In this presentation investigating the influence of In on wettability of the alloy Sn 313Ag 074Cu close to
ternary eutectic Sn-Ag-Cu it was confirmed starting from previous data on In-Sn and
Sn-Ag-In [1] that due to the nearly the same surface tension and density values of pure In and Sn the
beneficial influence of In is reflected by the lowering of the contact angles with practically no change of
temperature dependence of both surface tension and density Isothermal behaviour of surface tension with ldquoSrdquo
shape starting from In-Sn and Sn-Ag-In proceeding into the investigated in this study Sn-Ag-Cu-In is
probably in addition connected with the peculiar properties of liquid In-Sn alloys showing extrema on
isothermal behaviour of electrical resistivity and viscosity [2] corresponding well to the existence of
intermetallic phases in the phase diagram of In-Sn phase diagram It is the another proof of the mutual
correlations between thermodynamic properties physical properties and the character of the phase diagram
[1] X J Liu Y Inohana I Ohnuma R Kainuma K Ishida Z Moser W Gąsior J Pstruś J Electronic Mater 31 (2002) 1139-51 [2] BPredel MHoch MPool Phase Diagrams and Heterogeneous Equilibria Springer-Verlag Berlin Heidelberg (2004) 289-291
7 Final remarks
1 Presented today joint results with P Sebo will be elaborated for Calphad journal
2 SURDAT database realized in parallel to COST 531 Program has been introduced on website of COST
531 Program
3 In addition from financing of COST 531 Program under research entitled ldquoExperimental determination
and modeling of physicochemical properties of multi-component alloys on the tin base ldquo within
2003-2006 the additional study has been realized by dr Piotr Ozga
ldquo The study of a possibility of the electrodeposition of Sn-Ag alloys from aqueous solutionsrdquo
a POzga ldquoEquilibria in Aqueous Solutions of Ag(I)-Sn(IIIV) in Presence of Strong Complexing
Ligandsrdquo CALPHAD XXXIII Krakow (Poland) May 30 ndash June 4 2004 Abstracts p 153
b POzga ldquoElectrodeposition of Sn-Ag and Sn-Ag-Cu alloys from the thiourea solutionsrdquo Archives of
Metallurgy and Materials 3 (2006) 413-421
The results of this study were used in habilitation thesis of P Ozga edited by the Institute of Metallurgy
and Materials ISBN-83-921845-8-0 Krakow (2006) 1-148
bull Special issue of the Archives of Metallurgy and Materials 32006 has been devoted to results realized
within COST 531 Program
Thank you
for your attention
- Slide 1
- Slide 2
- Slide 3
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- Slide 10
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Slide 18
- Slide 19
- Slide 20
-
Fig 2 The temperature dependencies of the density of (Sn 313Ag 074Cu) + In liquid alloys
Fig 3 The temperature dependencies of the surface tension of (Sn 313Ag 074Cu) + In
liquid alloys
Fig 4 The isotherms of the density of (Sn 313Ag 074Cu)+In liquid alloys at 523 K and 1023 K
Fig 5 The isotherms of the surface tension of (Sn 313Ag 074Cu)+In liquid alloys at 523 K and 1023 K
3 Modeling of the surface tension
Two kinds of modeling of surface tension were used for quaternary alloys Sn-Ag-Cu-In similarly as in previous studies on Sn-Ag-Cu-Sb system [1]
[1] ZMoser WGąsior JPstruś IOhnuma KIshida ldquoInfluence of Sb additions on surface tension and density of Sn-Sb Sn-Ag-Sb and Sn-Ag-Cu-Sb alloys Experiment vsmodelingrdquo International Jounal of Materials Research Zeitschrift fuer Metallkunde 97 (2006) 365-370 Dedicated to Professor DrFerdinand Sommer on the occasion of his 65th birthday
1 Butler model with thermodynamic properties of liquid constituent components and surface tension of pure
components This modeling was successfully tested in studies of systems presented in SURDAT database
with observation that the experimental temperature dependence of the surface tension is linear while from
modeling slightly curvilinear dependence was calculated
For such procedure in the case of quaternary Sn-Ag-Cu-In system we should know data of six binaries
Cu-In Cu-Ag Sn-Ag Ag-In Sn-Cu In-Sn four ternaries Sn-Ag-Cu Sn-Ag-In Sn-Cu-In In-Ag-Cu and for
quaternary alloy (one quaternary alloy with equal concentration of components 025 molar fraction was
investigated)
In the case of modeling 2 we are basing on experimental data of surface tension of constituent binary systems
with ternary and quaternary correction factors to elaborate the temperature and concentration dependence of
the surface tension of the Sn-Ag-Cu-In system For the remaining not previously investigated surface tension
and density in this study were determined Cu-In and Cu-Ag ternaries Sn-Ag-Cu Sn-Ag-In In-Ag-Cu and
one quaternary alloy with equal concentration of components 025 molar fraction
As an example in Table 4 are presented surface tension data of ternaries and quaternary alloy
Table 4 Temperature dependencies of the surface tension of the liquid quaternary Sn 25Ag 25Cu 25In and ternary alloys Sn 25Ag 25In Sn 25Ag 25Cu and In 25Ag 25Cu with the calculated errors of the A and B parameters and the
surface tension calculated at 973 K and 1273 K
X at σ = A +BTmNm-1
σ 973K
mNm-1
σ 1273K
mNm-1
Err(A)mNm-1
Err(B)mNm-1middotK-1
Sn25Ag25InSn25Ag25CuIn25Ag25Cu
Sn25Ag25Cu25In
= 6190-00599T = 6142-00235T = 6510-00293T = 7685-00737T
5607plusmn64 5914plusmn42 6225plusmn55
6967plusmn125
5427plusmn765843plusmn456138plusmn64
6746plusmn123
plusmn131 plusmn82
plusmn124 plusmn260
plusmn00133 plusmn00088
plusmn00122 plusmn00227
Fig6 Comparison of calculations of the surface tension of the quaternary system Sn-Ag-Cu-In by Butlerrsquos model and with temperature-concentration dependence and with one experimental alloy (Table 4) with equal 025 molar fractions Thin lines show the Butler model while thick correspond to temperature concentration dependence of the surface tension
Results of calculations by the Butler model show lower values of the surface tension due to the fact that
interaction parameters for Ag-Cu-In and Cu-In-Sn were not taken into calculations In addition only the
limited amount of alloys for binary and ternary alloys of surface tension was investigated with one quaternary
sample
The obtained results from both methods are compared in Fig6
4 Contact angles measurements of the (Sn313Ag074Cu) + In liquid alloys
Wetting of copper substrates was studied by sessile drop method Solder in a cube form was covered by flux
and put on the substrate and after melting at given temperature (250 280 and 320 oC) pictures of drop were
taken by digital camera up to 30 minutes Contact angles were measured by computer After the drop
solidifies specimen were cut perpendicularly for metallographic studies discussed in the next section
Typical course of time dependencies of contact angle for pure (not containing In) Sn 313Ag 074Cu
Sn 252Ag 057Cu 30In and Sn 12Ag 027Cu 75In are presented on Figs7-10 Except the beginning of
wetting the contact angle practically does not depend on the wetting temperature and with the increase of In
concentration is lowered the time to reach the constant values of contact angles which gradually are
decreasing Due to the observed in Figs7-9 the negligible differences in contact angles in the temperature
interval in Fig10 is plotted the change of contact angle after 30 minutes for all investigated alloys The
lowering tendency of the contact angle is observed with some scattering at low In content
Fig7 Change of the contact angle for the starting alloy Sn 313Ag 074Cu
Fig 8 Change of the contact angle for Sn 313Ag 074Cu + 30 at In
Fig 9 Change of the contact angle for Sn 313Ag 074Cu + 75 at In
Fig 10 Change of contact angles for Sn-Ag-Cu-In alloys after 30 minutes
5 Interaction studies of the quaternary alloys with Cu substrate
Metallographic studies of the structure of the boundary between the solder and substrate as well as the
structure of the solder itself was studied by electron scanning microscopy (SEM) Energy dispersive X-ray
analyzer (EDX) was used to measure the chemical composition of the interface as well as the bulk solder The
same specimen which were used for SEM and EDX investigation were also used for X-ray diffraction phase
analysis of the solder and substrate
For low In concentration (up to 15 at) Cu interface is formed by Cu6Sn5 phase For higher concentration of
In (30-50 at) Cu interface if formed by Cu41Sn11 phase For highest In concentration (75 at) Cu
interface is formed by Cu3(SnIn) phase
6 Conclusions
In this presentation investigating the influence of In on wettability of the alloy Sn 313Ag 074Cu close to
ternary eutectic Sn-Ag-Cu it was confirmed starting from previous data on In-Sn and
Sn-Ag-In [1] that due to the nearly the same surface tension and density values of pure In and Sn the
beneficial influence of In is reflected by the lowering of the contact angles with practically no change of
temperature dependence of both surface tension and density Isothermal behaviour of surface tension with ldquoSrdquo
shape starting from In-Sn and Sn-Ag-In proceeding into the investigated in this study Sn-Ag-Cu-In is
probably in addition connected with the peculiar properties of liquid In-Sn alloys showing extrema on
isothermal behaviour of electrical resistivity and viscosity [2] corresponding well to the existence of
intermetallic phases in the phase diagram of In-Sn phase diagram It is the another proof of the mutual
correlations between thermodynamic properties physical properties and the character of the phase diagram
[1] X J Liu Y Inohana I Ohnuma R Kainuma K Ishida Z Moser W Gąsior J Pstruś J Electronic Mater 31 (2002) 1139-51 [2] BPredel MHoch MPool Phase Diagrams and Heterogeneous Equilibria Springer-Verlag Berlin Heidelberg (2004) 289-291
7 Final remarks
1 Presented today joint results with P Sebo will be elaborated for Calphad journal
2 SURDAT database realized in parallel to COST 531 Program has been introduced on website of COST
531 Program
3 In addition from financing of COST 531 Program under research entitled ldquoExperimental determination
and modeling of physicochemical properties of multi-component alloys on the tin base ldquo within
2003-2006 the additional study has been realized by dr Piotr Ozga
ldquo The study of a possibility of the electrodeposition of Sn-Ag alloys from aqueous solutionsrdquo
a POzga ldquoEquilibria in Aqueous Solutions of Ag(I)-Sn(IIIV) in Presence of Strong Complexing
Ligandsrdquo CALPHAD XXXIII Krakow (Poland) May 30 ndash June 4 2004 Abstracts p 153
b POzga ldquoElectrodeposition of Sn-Ag and Sn-Ag-Cu alloys from the thiourea solutionsrdquo Archives of
Metallurgy and Materials 3 (2006) 413-421
The results of this study were used in habilitation thesis of P Ozga edited by the Institute of Metallurgy
and Materials ISBN-83-921845-8-0 Krakow (2006) 1-148
bull Special issue of the Archives of Metallurgy and Materials 32006 has been devoted to results realized
within COST 531 Program
Thank you
for your attention
- Slide 1
- Slide 2
- Slide 3
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- Slide 10
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Slide 18
- Slide 19
- Slide 20
-
Fig 4 The isotherms of the density of (Sn 313Ag 074Cu)+In liquid alloys at 523 K and 1023 K
Fig 5 The isotherms of the surface tension of (Sn 313Ag 074Cu)+In liquid alloys at 523 K and 1023 K
3 Modeling of the surface tension
Two kinds of modeling of surface tension were used for quaternary alloys Sn-Ag-Cu-In similarly as in previous studies on Sn-Ag-Cu-Sb system [1]
[1] ZMoser WGąsior JPstruś IOhnuma KIshida ldquoInfluence of Sb additions on surface tension and density of Sn-Sb Sn-Ag-Sb and Sn-Ag-Cu-Sb alloys Experiment vsmodelingrdquo International Jounal of Materials Research Zeitschrift fuer Metallkunde 97 (2006) 365-370 Dedicated to Professor DrFerdinand Sommer on the occasion of his 65th birthday
1 Butler model with thermodynamic properties of liquid constituent components and surface tension of pure
components This modeling was successfully tested in studies of systems presented in SURDAT database
with observation that the experimental temperature dependence of the surface tension is linear while from
modeling slightly curvilinear dependence was calculated
For such procedure in the case of quaternary Sn-Ag-Cu-In system we should know data of six binaries
Cu-In Cu-Ag Sn-Ag Ag-In Sn-Cu In-Sn four ternaries Sn-Ag-Cu Sn-Ag-In Sn-Cu-In In-Ag-Cu and for
quaternary alloy (one quaternary alloy with equal concentration of components 025 molar fraction was
investigated)
In the case of modeling 2 we are basing on experimental data of surface tension of constituent binary systems
with ternary and quaternary correction factors to elaborate the temperature and concentration dependence of
the surface tension of the Sn-Ag-Cu-In system For the remaining not previously investigated surface tension
and density in this study were determined Cu-In and Cu-Ag ternaries Sn-Ag-Cu Sn-Ag-In In-Ag-Cu and
one quaternary alloy with equal concentration of components 025 molar fraction
As an example in Table 4 are presented surface tension data of ternaries and quaternary alloy
Table 4 Temperature dependencies of the surface tension of the liquid quaternary Sn 25Ag 25Cu 25In and ternary alloys Sn 25Ag 25In Sn 25Ag 25Cu and In 25Ag 25Cu with the calculated errors of the A and B parameters and the
surface tension calculated at 973 K and 1273 K
X at σ = A +BTmNm-1
σ 973K
mNm-1
σ 1273K
mNm-1
Err(A)mNm-1
Err(B)mNm-1middotK-1
Sn25Ag25InSn25Ag25CuIn25Ag25Cu
Sn25Ag25Cu25In
= 6190-00599T = 6142-00235T = 6510-00293T = 7685-00737T
5607plusmn64 5914plusmn42 6225plusmn55
6967plusmn125
5427plusmn765843plusmn456138plusmn64
6746plusmn123
plusmn131 plusmn82
plusmn124 plusmn260
plusmn00133 plusmn00088
plusmn00122 plusmn00227
Fig6 Comparison of calculations of the surface tension of the quaternary system Sn-Ag-Cu-In by Butlerrsquos model and with temperature-concentration dependence and with one experimental alloy (Table 4) with equal 025 molar fractions Thin lines show the Butler model while thick correspond to temperature concentration dependence of the surface tension
Results of calculations by the Butler model show lower values of the surface tension due to the fact that
interaction parameters for Ag-Cu-In and Cu-In-Sn were not taken into calculations In addition only the
limited amount of alloys for binary and ternary alloys of surface tension was investigated with one quaternary
sample
The obtained results from both methods are compared in Fig6
4 Contact angles measurements of the (Sn313Ag074Cu) + In liquid alloys
Wetting of copper substrates was studied by sessile drop method Solder in a cube form was covered by flux
and put on the substrate and after melting at given temperature (250 280 and 320 oC) pictures of drop were
taken by digital camera up to 30 minutes Contact angles were measured by computer After the drop
solidifies specimen were cut perpendicularly for metallographic studies discussed in the next section
Typical course of time dependencies of contact angle for pure (not containing In) Sn 313Ag 074Cu
Sn 252Ag 057Cu 30In and Sn 12Ag 027Cu 75In are presented on Figs7-10 Except the beginning of
wetting the contact angle practically does not depend on the wetting temperature and with the increase of In
concentration is lowered the time to reach the constant values of contact angles which gradually are
decreasing Due to the observed in Figs7-9 the negligible differences in contact angles in the temperature
interval in Fig10 is plotted the change of contact angle after 30 minutes for all investigated alloys The
lowering tendency of the contact angle is observed with some scattering at low In content
Fig7 Change of the contact angle for the starting alloy Sn 313Ag 074Cu
Fig 8 Change of the contact angle for Sn 313Ag 074Cu + 30 at In
Fig 9 Change of the contact angle for Sn 313Ag 074Cu + 75 at In
Fig 10 Change of contact angles for Sn-Ag-Cu-In alloys after 30 minutes
5 Interaction studies of the quaternary alloys with Cu substrate
Metallographic studies of the structure of the boundary between the solder and substrate as well as the
structure of the solder itself was studied by electron scanning microscopy (SEM) Energy dispersive X-ray
analyzer (EDX) was used to measure the chemical composition of the interface as well as the bulk solder The
same specimen which were used for SEM and EDX investigation were also used for X-ray diffraction phase
analysis of the solder and substrate
For low In concentration (up to 15 at) Cu interface is formed by Cu6Sn5 phase For higher concentration of
In (30-50 at) Cu interface if formed by Cu41Sn11 phase For highest In concentration (75 at) Cu
interface is formed by Cu3(SnIn) phase
6 Conclusions
In this presentation investigating the influence of In on wettability of the alloy Sn 313Ag 074Cu close to
ternary eutectic Sn-Ag-Cu it was confirmed starting from previous data on In-Sn and
Sn-Ag-In [1] that due to the nearly the same surface tension and density values of pure In and Sn the
beneficial influence of In is reflected by the lowering of the contact angles with practically no change of
temperature dependence of both surface tension and density Isothermal behaviour of surface tension with ldquoSrdquo
shape starting from In-Sn and Sn-Ag-In proceeding into the investigated in this study Sn-Ag-Cu-In is
probably in addition connected with the peculiar properties of liquid In-Sn alloys showing extrema on
isothermal behaviour of electrical resistivity and viscosity [2] corresponding well to the existence of
intermetallic phases in the phase diagram of In-Sn phase diagram It is the another proof of the mutual
correlations between thermodynamic properties physical properties and the character of the phase diagram
[1] X J Liu Y Inohana I Ohnuma R Kainuma K Ishida Z Moser W Gąsior J Pstruś J Electronic Mater 31 (2002) 1139-51 [2] BPredel MHoch MPool Phase Diagrams and Heterogeneous Equilibria Springer-Verlag Berlin Heidelberg (2004) 289-291
7 Final remarks
1 Presented today joint results with P Sebo will be elaborated for Calphad journal
2 SURDAT database realized in parallel to COST 531 Program has been introduced on website of COST
531 Program
3 In addition from financing of COST 531 Program under research entitled ldquoExperimental determination
and modeling of physicochemical properties of multi-component alloys on the tin base ldquo within
2003-2006 the additional study has been realized by dr Piotr Ozga
ldquo The study of a possibility of the electrodeposition of Sn-Ag alloys from aqueous solutionsrdquo
a POzga ldquoEquilibria in Aqueous Solutions of Ag(I)-Sn(IIIV) in Presence of Strong Complexing
Ligandsrdquo CALPHAD XXXIII Krakow (Poland) May 30 ndash June 4 2004 Abstracts p 153
b POzga ldquoElectrodeposition of Sn-Ag and Sn-Ag-Cu alloys from the thiourea solutionsrdquo Archives of
Metallurgy and Materials 3 (2006) 413-421
The results of this study were used in habilitation thesis of P Ozga edited by the Institute of Metallurgy
and Materials ISBN-83-921845-8-0 Krakow (2006) 1-148
bull Special issue of the Archives of Metallurgy and Materials 32006 has been devoted to results realized
within COST 531 Program
Thank you
for your attention
- Slide 1
- Slide 2
- Slide 3
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- Slide 10
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Slide 18
- Slide 19
- Slide 20
-
3 Modeling of the surface tension
Two kinds of modeling of surface tension were used for quaternary alloys Sn-Ag-Cu-In similarly as in previous studies on Sn-Ag-Cu-Sb system [1]
[1] ZMoser WGąsior JPstruś IOhnuma KIshida ldquoInfluence of Sb additions on surface tension and density of Sn-Sb Sn-Ag-Sb and Sn-Ag-Cu-Sb alloys Experiment vsmodelingrdquo International Jounal of Materials Research Zeitschrift fuer Metallkunde 97 (2006) 365-370 Dedicated to Professor DrFerdinand Sommer on the occasion of his 65th birthday
1 Butler model with thermodynamic properties of liquid constituent components and surface tension of pure
components This modeling was successfully tested in studies of systems presented in SURDAT database
with observation that the experimental temperature dependence of the surface tension is linear while from
modeling slightly curvilinear dependence was calculated
For such procedure in the case of quaternary Sn-Ag-Cu-In system we should know data of six binaries
Cu-In Cu-Ag Sn-Ag Ag-In Sn-Cu In-Sn four ternaries Sn-Ag-Cu Sn-Ag-In Sn-Cu-In In-Ag-Cu and for
quaternary alloy (one quaternary alloy with equal concentration of components 025 molar fraction was
investigated)
In the case of modeling 2 we are basing on experimental data of surface tension of constituent binary systems
with ternary and quaternary correction factors to elaborate the temperature and concentration dependence of
the surface tension of the Sn-Ag-Cu-In system For the remaining not previously investigated surface tension
and density in this study were determined Cu-In and Cu-Ag ternaries Sn-Ag-Cu Sn-Ag-In In-Ag-Cu and
one quaternary alloy with equal concentration of components 025 molar fraction
As an example in Table 4 are presented surface tension data of ternaries and quaternary alloy
Table 4 Temperature dependencies of the surface tension of the liquid quaternary Sn 25Ag 25Cu 25In and ternary alloys Sn 25Ag 25In Sn 25Ag 25Cu and In 25Ag 25Cu with the calculated errors of the A and B parameters and the
surface tension calculated at 973 K and 1273 K
X at σ = A +BTmNm-1
σ 973K
mNm-1
σ 1273K
mNm-1
Err(A)mNm-1
Err(B)mNm-1middotK-1
Sn25Ag25InSn25Ag25CuIn25Ag25Cu
Sn25Ag25Cu25In
= 6190-00599T = 6142-00235T = 6510-00293T = 7685-00737T
5607plusmn64 5914plusmn42 6225plusmn55
6967plusmn125
5427plusmn765843plusmn456138plusmn64
6746plusmn123
plusmn131 plusmn82
plusmn124 plusmn260
plusmn00133 plusmn00088
plusmn00122 plusmn00227
Fig6 Comparison of calculations of the surface tension of the quaternary system Sn-Ag-Cu-In by Butlerrsquos model and with temperature-concentration dependence and with one experimental alloy (Table 4) with equal 025 molar fractions Thin lines show the Butler model while thick correspond to temperature concentration dependence of the surface tension
Results of calculations by the Butler model show lower values of the surface tension due to the fact that
interaction parameters for Ag-Cu-In and Cu-In-Sn were not taken into calculations In addition only the
limited amount of alloys for binary and ternary alloys of surface tension was investigated with one quaternary
sample
The obtained results from both methods are compared in Fig6
4 Contact angles measurements of the (Sn313Ag074Cu) + In liquid alloys
Wetting of copper substrates was studied by sessile drop method Solder in a cube form was covered by flux
and put on the substrate and after melting at given temperature (250 280 and 320 oC) pictures of drop were
taken by digital camera up to 30 minutes Contact angles were measured by computer After the drop
solidifies specimen were cut perpendicularly for metallographic studies discussed in the next section
Typical course of time dependencies of contact angle for pure (not containing In) Sn 313Ag 074Cu
Sn 252Ag 057Cu 30In and Sn 12Ag 027Cu 75In are presented on Figs7-10 Except the beginning of
wetting the contact angle practically does not depend on the wetting temperature and with the increase of In
concentration is lowered the time to reach the constant values of contact angles which gradually are
decreasing Due to the observed in Figs7-9 the negligible differences in contact angles in the temperature
interval in Fig10 is plotted the change of contact angle after 30 minutes for all investigated alloys The
lowering tendency of the contact angle is observed with some scattering at low In content
Fig7 Change of the contact angle for the starting alloy Sn 313Ag 074Cu
Fig 8 Change of the contact angle for Sn 313Ag 074Cu + 30 at In
Fig 9 Change of the contact angle for Sn 313Ag 074Cu + 75 at In
Fig 10 Change of contact angles for Sn-Ag-Cu-In alloys after 30 minutes
5 Interaction studies of the quaternary alloys with Cu substrate
Metallographic studies of the structure of the boundary between the solder and substrate as well as the
structure of the solder itself was studied by electron scanning microscopy (SEM) Energy dispersive X-ray
analyzer (EDX) was used to measure the chemical composition of the interface as well as the bulk solder The
same specimen which were used for SEM and EDX investigation were also used for X-ray diffraction phase
analysis of the solder and substrate
For low In concentration (up to 15 at) Cu interface is formed by Cu6Sn5 phase For higher concentration of
In (30-50 at) Cu interface if formed by Cu41Sn11 phase For highest In concentration (75 at) Cu
interface is formed by Cu3(SnIn) phase
6 Conclusions
In this presentation investigating the influence of In on wettability of the alloy Sn 313Ag 074Cu close to
ternary eutectic Sn-Ag-Cu it was confirmed starting from previous data on In-Sn and
Sn-Ag-In [1] that due to the nearly the same surface tension and density values of pure In and Sn the
beneficial influence of In is reflected by the lowering of the contact angles with practically no change of
temperature dependence of both surface tension and density Isothermal behaviour of surface tension with ldquoSrdquo
shape starting from In-Sn and Sn-Ag-In proceeding into the investigated in this study Sn-Ag-Cu-In is
probably in addition connected with the peculiar properties of liquid In-Sn alloys showing extrema on
isothermal behaviour of electrical resistivity and viscosity [2] corresponding well to the existence of
intermetallic phases in the phase diagram of In-Sn phase diagram It is the another proof of the mutual
correlations between thermodynamic properties physical properties and the character of the phase diagram
[1] X J Liu Y Inohana I Ohnuma R Kainuma K Ishida Z Moser W Gąsior J Pstruś J Electronic Mater 31 (2002) 1139-51 [2] BPredel MHoch MPool Phase Diagrams and Heterogeneous Equilibria Springer-Verlag Berlin Heidelberg (2004) 289-291
7 Final remarks
1 Presented today joint results with P Sebo will be elaborated for Calphad journal
2 SURDAT database realized in parallel to COST 531 Program has been introduced on website of COST
531 Program
3 In addition from financing of COST 531 Program under research entitled ldquoExperimental determination
and modeling of physicochemical properties of multi-component alloys on the tin base ldquo within
2003-2006 the additional study has been realized by dr Piotr Ozga
ldquo The study of a possibility of the electrodeposition of Sn-Ag alloys from aqueous solutionsrdquo
a POzga ldquoEquilibria in Aqueous Solutions of Ag(I)-Sn(IIIV) in Presence of Strong Complexing
Ligandsrdquo CALPHAD XXXIII Krakow (Poland) May 30 ndash June 4 2004 Abstracts p 153
b POzga ldquoElectrodeposition of Sn-Ag and Sn-Ag-Cu alloys from the thiourea solutionsrdquo Archives of
Metallurgy and Materials 3 (2006) 413-421
The results of this study were used in habilitation thesis of P Ozga edited by the Institute of Metallurgy
and Materials ISBN-83-921845-8-0 Krakow (2006) 1-148
bull Special issue of the Archives of Metallurgy and Materials 32006 has been devoted to results realized
within COST 531 Program
Thank you
for your attention
- Slide 1
- Slide 2
- Slide 3
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- Slide 10
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Slide 18
- Slide 19
- Slide 20
-
In the case of modeling 2 we are basing on experimental data of surface tension of constituent binary systems
with ternary and quaternary correction factors to elaborate the temperature and concentration dependence of
the surface tension of the Sn-Ag-Cu-In system For the remaining not previously investigated surface tension
and density in this study were determined Cu-In and Cu-Ag ternaries Sn-Ag-Cu Sn-Ag-In In-Ag-Cu and
one quaternary alloy with equal concentration of components 025 molar fraction
As an example in Table 4 are presented surface tension data of ternaries and quaternary alloy
Table 4 Temperature dependencies of the surface tension of the liquid quaternary Sn 25Ag 25Cu 25In and ternary alloys Sn 25Ag 25In Sn 25Ag 25Cu and In 25Ag 25Cu with the calculated errors of the A and B parameters and the
surface tension calculated at 973 K and 1273 K
X at σ = A +BTmNm-1
σ 973K
mNm-1
σ 1273K
mNm-1
Err(A)mNm-1
Err(B)mNm-1middotK-1
Sn25Ag25InSn25Ag25CuIn25Ag25Cu
Sn25Ag25Cu25In
= 6190-00599T = 6142-00235T = 6510-00293T = 7685-00737T
5607plusmn64 5914plusmn42 6225plusmn55
6967plusmn125
5427plusmn765843plusmn456138plusmn64
6746plusmn123
plusmn131 plusmn82
plusmn124 plusmn260
plusmn00133 plusmn00088
plusmn00122 plusmn00227
Fig6 Comparison of calculations of the surface tension of the quaternary system Sn-Ag-Cu-In by Butlerrsquos model and with temperature-concentration dependence and with one experimental alloy (Table 4) with equal 025 molar fractions Thin lines show the Butler model while thick correspond to temperature concentration dependence of the surface tension
Results of calculations by the Butler model show lower values of the surface tension due to the fact that
interaction parameters for Ag-Cu-In and Cu-In-Sn were not taken into calculations In addition only the
limited amount of alloys for binary and ternary alloys of surface tension was investigated with one quaternary
sample
The obtained results from both methods are compared in Fig6
4 Contact angles measurements of the (Sn313Ag074Cu) + In liquid alloys
Wetting of copper substrates was studied by sessile drop method Solder in a cube form was covered by flux
and put on the substrate and after melting at given temperature (250 280 and 320 oC) pictures of drop were
taken by digital camera up to 30 minutes Contact angles were measured by computer After the drop
solidifies specimen were cut perpendicularly for metallographic studies discussed in the next section
Typical course of time dependencies of contact angle for pure (not containing In) Sn 313Ag 074Cu
Sn 252Ag 057Cu 30In and Sn 12Ag 027Cu 75In are presented on Figs7-10 Except the beginning of
wetting the contact angle practically does not depend on the wetting temperature and with the increase of In
concentration is lowered the time to reach the constant values of contact angles which gradually are
decreasing Due to the observed in Figs7-9 the negligible differences in contact angles in the temperature
interval in Fig10 is plotted the change of contact angle after 30 minutes for all investigated alloys The
lowering tendency of the contact angle is observed with some scattering at low In content
Fig7 Change of the contact angle for the starting alloy Sn 313Ag 074Cu
Fig 8 Change of the contact angle for Sn 313Ag 074Cu + 30 at In
Fig 9 Change of the contact angle for Sn 313Ag 074Cu + 75 at In
Fig 10 Change of contact angles for Sn-Ag-Cu-In alloys after 30 minutes
5 Interaction studies of the quaternary alloys with Cu substrate
Metallographic studies of the structure of the boundary between the solder and substrate as well as the
structure of the solder itself was studied by electron scanning microscopy (SEM) Energy dispersive X-ray
analyzer (EDX) was used to measure the chemical composition of the interface as well as the bulk solder The
same specimen which were used for SEM and EDX investigation were also used for X-ray diffraction phase
analysis of the solder and substrate
For low In concentration (up to 15 at) Cu interface is formed by Cu6Sn5 phase For higher concentration of
In (30-50 at) Cu interface if formed by Cu41Sn11 phase For highest In concentration (75 at) Cu
interface is formed by Cu3(SnIn) phase
6 Conclusions
In this presentation investigating the influence of In on wettability of the alloy Sn 313Ag 074Cu close to
ternary eutectic Sn-Ag-Cu it was confirmed starting from previous data on In-Sn and
Sn-Ag-In [1] that due to the nearly the same surface tension and density values of pure In and Sn the
beneficial influence of In is reflected by the lowering of the contact angles with practically no change of
temperature dependence of both surface tension and density Isothermal behaviour of surface tension with ldquoSrdquo
shape starting from In-Sn and Sn-Ag-In proceeding into the investigated in this study Sn-Ag-Cu-In is
probably in addition connected with the peculiar properties of liquid In-Sn alloys showing extrema on
isothermal behaviour of electrical resistivity and viscosity [2] corresponding well to the existence of
intermetallic phases in the phase diagram of In-Sn phase diagram It is the another proof of the mutual
correlations between thermodynamic properties physical properties and the character of the phase diagram
[1] X J Liu Y Inohana I Ohnuma R Kainuma K Ishida Z Moser W Gąsior J Pstruś J Electronic Mater 31 (2002) 1139-51 [2] BPredel MHoch MPool Phase Diagrams and Heterogeneous Equilibria Springer-Verlag Berlin Heidelberg (2004) 289-291
7 Final remarks
1 Presented today joint results with P Sebo will be elaborated for Calphad journal
2 SURDAT database realized in parallel to COST 531 Program has been introduced on website of COST
531 Program
3 In addition from financing of COST 531 Program under research entitled ldquoExperimental determination
and modeling of physicochemical properties of multi-component alloys on the tin base ldquo within
2003-2006 the additional study has been realized by dr Piotr Ozga
ldquo The study of a possibility of the electrodeposition of Sn-Ag alloys from aqueous solutionsrdquo
a POzga ldquoEquilibria in Aqueous Solutions of Ag(I)-Sn(IIIV) in Presence of Strong Complexing
Ligandsrdquo CALPHAD XXXIII Krakow (Poland) May 30 ndash June 4 2004 Abstracts p 153
b POzga ldquoElectrodeposition of Sn-Ag and Sn-Ag-Cu alloys from the thiourea solutionsrdquo Archives of
Metallurgy and Materials 3 (2006) 413-421
The results of this study were used in habilitation thesis of P Ozga edited by the Institute of Metallurgy
and Materials ISBN-83-921845-8-0 Krakow (2006) 1-148
bull Special issue of the Archives of Metallurgy and Materials 32006 has been devoted to results realized
within COST 531 Program
Thank you
for your attention
- Slide 1
- Slide 2
- Slide 3
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- Slide 10
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Slide 18
- Slide 19
- Slide 20
-
Fig6 Comparison of calculations of the surface tension of the quaternary system Sn-Ag-Cu-In by Butlerrsquos model and with temperature-concentration dependence and with one experimental alloy (Table 4) with equal 025 molar fractions Thin lines show the Butler model while thick correspond to temperature concentration dependence of the surface tension
Results of calculations by the Butler model show lower values of the surface tension due to the fact that
interaction parameters for Ag-Cu-In and Cu-In-Sn were not taken into calculations In addition only the
limited amount of alloys for binary and ternary alloys of surface tension was investigated with one quaternary
sample
The obtained results from both methods are compared in Fig6
4 Contact angles measurements of the (Sn313Ag074Cu) + In liquid alloys
Wetting of copper substrates was studied by sessile drop method Solder in a cube form was covered by flux
and put on the substrate and after melting at given temperature (250 280 and 320 oC) pictures of drop were
taken by digital camera up to 30 minutes Contact angles were measured by computer After the drop
solidifies specimen were cut perpendicularly for metallographic studies discussed in the next section
Typical course of time dependencies of contact angle for pure (not containing In) Sn 313Ag 074Cu
Sn 252Ag 057Cu 30In and Sn 12Ag 027Cu 75In are presented on Figs7-10 Except the beginning of
wetting the contact angle practically does not depend on the wetting temperature and with the increase of In
concentration is lowered the time to reach the constant values of contact angles which gradually are
decreasing Due to the observed in Figs7-9 the negligible differences in contact angles in the temperature
interval in Fig10 is plotted the change of contact angle after 30 minutes for all investigated alloys The
lowering tendency of the contact angle is observed with some scattering at low In content
Fig7 Change of the contact angle for the starting alloy Sn 313Ag 074Cu
Fig 8 Change of the contact angle for Sn 313Ag 074Cu + 30 at In
Fig 9 Change of the contact angle for Sn 313Ag 074Cu + 75 at In
Fig 10 Change of contact angles for Sn-Ag-Cu-In alloys after 30 minutes
5 Interaction studies of the quaternary alloys with Cu substrate
Metallographic studies of the structure of the boundary between the solder and substrate as well as the
structure of the solder itself was studied by electron scanning microscopy (SEM) Energy dispersive X-ray
analyzer (EDX) was used to measure the chemical composition of the interface as well as the bulk solder The
same specimen which were used for SEM and EDX investigation were also used for X-ray diffraction phase
analysis of the solder and substrate
For low In concentration (up to 15 at) Cu interface is formed by Cu6Sn5 phase For higher concentration of
In (30-50 at) Cu interface if formed by Cu41Sn11 phase For highest In concentration (75 at) Cu
interface is formed by Cu3(SnIn) phase
6 Conclusions
In this presentation investigating the influence of In on wettability of the alloy Sn 313Ag 074Cu close to
ternary eutectic Sn-Ag-Cu it was confirmed starting from previous data on In-Sn and
Sn-Ag-In [1] that due to the nearly the same surface tension and density values of pure In and Sn the
beneficial influence of In is reflected by the lowering of the contact angles with practically no change of
temperature dependence of both surface tension and density Isothermal behaviour of surface tension with ldquoSrdquo
shape starting from In-Sn and Sn-Ag-In proceeding into the investigated in this study Sn-Ag-Cu-In is
probably in addition connected with the peculiar properties of liquid In-Sn alloys showing extrema on
isothermal behaviour of electrical resistivity and viscosity [2] corresponding well to the existence of
intermetallic phases in the phase diagram of In-Sn phase diagram It is the another proof of the mutual
correlations between thermodynamic properties physical properties and the character of the phase diagram
[1] X J Liu Y Inohana I Ohnuma R Kainuma K Ishida Z Moser W Gąsior J Pstruś J Electronic Mater 31 (2002) 1139-51 [2] BPredel MHoch MPool Phase Diagrams and Heterogeneous Equilibria Springer-Verlag Berlin Heidelberg (2004) 289-291
7 Final remarks
1 Presented today joint results with P Sebo will be elaborated for Calphad journal
2 SURDAT database realized in parallel to COST 531 Program has been introduced on website of COST
531 Program
3 In addition from financing of COST 531 Program under research entitled ldquoExperimental determination
and modeling of physicochemical properties of multi-component alloys on the tin base ldquo within
2003-2006 the additional study has been realized by dr Piotr Ozga
ldquo The study of a possibility of the electrodeposition of Sn-Ag alloys from aqueous solutionsrdquo
a POzga ldquoEquilibria in Aqueous Solutions of Ag(I)-Sn(IIIV) in Presence of Strong Complexing
Ligandsrdquo CALPHAD XXXIII Krakow (Poland) May 30 ndash June 4 2004 Abstracts p 153
b POzga ldquoElectrodeposition of Sn-Ag and Sn-Ag-Cu alloys from the thiourea solutionsrdquo Archives of
Metallurgy and Materials 3 (2006) 413-421
The results of this study were used in habilitation thesis of P Ozga edited by the Institute of Metallurgy
and Materials ISBN-83-921845-8-0 Krakow (2006) 1-148
bull Special issue of the Archives of Metallurgy and Materials 32006 has been devoted to results realized
within COST 531 Program
Thank you
for your attention
- Slide 1
- Slide 2
- Slide 3
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- Slide 10
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Slide 18
- Slide 19
- Slide 20
-
4 Contact angles measurements of the (Sn313Ag074Cu) + In liquid alloys
Wetting of copper substrates was studied by sessile drop method Solder in a cube form was covered by flux
and put on the substrate and after melting at given temperature (250 280 and 320 oC) pictures of drop were
taken by digital camera up to 30 minutes Contact angles were measured by computer After the drop
solidifies specimen were cut perpendicularly for metallographic studies discussed in the next section
Typical course of time dependencies of contact angle for pure (not containing In) Sn 313Ag 074Cu
Sn 252Ag 057Cu 30In and Sn 12Ag 027Cu 75In are presented on Figs7-10 Except the beginning of
wetting the contact angle practically does not depend on the wetting temperature and with the increase of In
concentration is lowered the time to reach the constant values of contact angles which gradually are
decreasing Due to the observed in Figs7-9 the negligible differences in contact angles in the temperature
interval in Fig10 is plotted the change of contact angle after 30 minutes for all investigated alloys The
lowering tendency of the contact angle is observed with some scattering at low In content
Fig7 Change of the contact angle for the starting alloy Sn 313Ag 074Cu
Fig 8 Change of the contact angle for Sn 313Ag 074Cu + 30 at In
Fig 9 Change of the contact angle for Sn 313Ag 074Cu + 75 at In
Fig 10 Change of contact angles for Sn-Ag-Cu-In alloys after 30 minutes
5 Interaction studies of the quaternary alloys with Cu substrate
Metallographic studies of the structure of the boundary between the solder and substrate as well as the
structure of the solder itself was studied by electron scanning microscopy (SEM) Energy dispersive X-ray
analyzer (EDX) was used to measure the chemical composition of the interface as well as the bulk solder The
same specimen which were used for SEM and EDX investigation were also used for X-ray diffraction phase
analysis of the solder and substrate
For low In concentration (up to 15 at) Cu interface is formed by Cu6Sn5 phase For higher concentration of
In (30-50 at) Cu interface if formed by Cu41Sn11 phase For highest In concentration (75 at) Cu
interface is formed by Cu3(SnIn) phase
6 Conclusions
In this presentation investigating the influence of In on wettability of the alloy Sn 313Ag 074Cu close to
ternary eutectic Sn-Ag-Cu it was confirmed starting from previous data on In-Sn and
Sn-Ag-In [1] that due to the nearly the same surface tension and density values of pure In and Sn the
beneficial influence of In is reflected by the lowering of the contact angles with practically no change of
temperature dependence of both surface tension and density Isothermal behaviour of surface tension with ldquoSrdquo
shape starting from In-Sn and Sn-Ag-In proceeding into the investigated in this study Sn-Ag-Cu-In is
probably in addition connected with the peculiar properties of liquid In-Sn alloys showing extrema on
isothermal behaviour of electrical resistivity and viscosity [2] corresponding well to the existence of
intermetallic phases in the phase diagram of In-Sn phase diagram It is the another proof of the mutual
correlations between thermodynamic properties physical properties and the character of the phase diagram
[1] X J Liu Y Inohana I Ohnuma R Kainuma K Ishida Z Moser W Gąsior J Pstruś J Electronic Mater 31 (2002) 1139-51 [2] BPredel MHoch MPool Phase Diagrams and Heterogeneous Equilibria Springer-Verlag Berlin Heidelberg (2004) 289-291
7 Final remarks
1 Presented today joint results with P Sebo will be elaborated for Calphad journal
2 SURDAT database realized in parallel to COST 531 Program has been introduced on website of COST
531 Program
3 In addition from financing of COST 531 Program under research entitled ldquoExperimental determination
and modeling of physicochemical properties of multi-component alloys on the tin base ldquo within
2003-2006 the additional study has been realized by dr Piotr Ozga
ldquo The study of a possibility of the electrodeposition of Sn-Ag alloys from aqueous solutionsrdquo
a POzga ldquoEquilibria in Aqueous Solutions of Ag(I)-Sn(IIIV) in Presence of Strong Complexing
Ligandsrdquo CALPHAD XXXIII Krakow (Poland) May 30 ndash June 4 2004 Abstracts p 153
b POzga ldquoElectrodeposition of Sn-Ag and Sn-Ag-Cu alloys from the thiourea solutionsrdquo Archives of
Metallurgy and Materials 3 (2006) 413-421
The results of this study were used in habilitation thesis of P Ozga edited by the Institute of Metallurgy
and Materials ISBN-83-921845-8-0 Krakow (2006) 1-148
bull Special issue of the Archives of Metallurgy and Materials 32006 has been devoted to results realized
within COST 531 Program
Thank you
for your attention
- Slide 1
- Slide 2
- Slide 3
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- Slide 10
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Slide 18
- Slide 19
- Slide 20
-
Fig7 Change of the contact angle for the starting alloy Sn 313Ag 074Cu
Fig 8 Change of the contact angle for Sn 313Ag 074Cu + 30 at In
Fig 9 Change of the contact angle for Sn 313Ag 074Cu + 75 at In
Fig 10 Change of contact angles for Sn-Ag-Cu-In alloys after 30 minutes
5 Interaction studies of the quaternary alloys with Cu substrate
Metallographic studies of the structure of the boundary between the solder and substrate as well as the
structure of the solder itself was studied by electron scanning microscopy (SEM) Energy dispersive X-ray
analyzer (EDX) was used to measure the chemical composition of the interface as well as the bulk solder The
same specimen which were used for SEM and EDX investigation were also used for X-ray diffraction phase
analysis of the solder and substrate
For low In concentration (up to 15 at) Cu interface is formed by Cu6Sn5 phase For higher concentration of
In (30-50 at) Cu interface if formed by Cu41Sn11 phase For highest In concentration (75 at) Cu
interface is formed by Cu3(SnIn) phase
6 Conclusions
In this presentation investigating the influence of In on wettability of the alloy Sn 313Ag 074Cu close to
ternary eutectic Sn-Ag-Cu it was confirmed starting from previous data on In-Sn and
Sn-Ag-In [1] that due to the nearly the same surface tension and density values of pure In and Sn the
beneficial influence of In is reflected by the lowering of the contact angles with practically no change of
temperature dependence of both surface tension and density Isothermal behaviour of surface tension with ldquoSrdquo
shape starting from In-Sn and Sn-Ag-In proceeding into the investigated in this study Sn-Ag-Cu-In is
probably in addition connected with the peculiar properties of liquid In-Sn alloys showing extrema on
isothermal behaviour of electrical resistivity and viscosity [2] corresponding well to the existence of
intermetallic phases in the phase diagram of In-Sn phase diagram It is the another proof of the mutual
correlations between thermodynamic properties physical properties and the character of the phase diagram
[1] X J Liu Y Inohana I Ohnuma R Kainuma K Ishida Z Moser W Gąsior J Pstruś J Electronic Mater 31 (2002) 1139-51 [2] BPredel MHoch MPool Phase Diagrams and Heterogeneous Equilibria Springer-Verlag Berlin Heidelberg (2004) 289-291
7 Final remarks
1 Presented today joint results with P Sebo will be elaborated for Calphad journal
2 SURDAT database realized in parallel to COST 531 Program has been introduced on website of COST
531 Program
3 In addition from financing of COST 531 Program under research entitled ldquoExperimental determination
and modeling of physicochemical properties of multi-component alloys on the tin base ldquo within
2003-2006 the additional study has been realized by dr Piotr Ozga
ldquo The study of a possibility of the electrodeposition of Sn-Ag alloys from aqueous solutionsrdquo
a POzga ldquoEquilibria in Aqueous Solutions of Ag(I)-Sn(IIIV) in Presence of Strong Complexing
Ligandsrdquo CALPHAD XXXIII Krakow (Poland) May 30 ndash June 4 2004 Abstracts p 153
b POzga ldquoElectrodeposition of Sn-Ag and Sn-Ag-Cu alloys from the thiourea solutionsrdquo Archives of
Metallurgy and Materials 3 (2006) 413-421
The results of this study were used in habilitation thesis of P Ozga edited by the Institute of Metallurgy
and Materials ISBN-83-921845-8-0 Krakow (2006) 1-148
bull Special issue of the Archives of Metallurgy and Materials 32006 has been devoted to results realized
within COST 531 Program
Thank you
for your attention
- Slide 1
- Slide 2
- Slide 3
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- Slide 10
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Slide 18
- Slide 19
- Slide 20
-
Fig 9 Change of the contact angle for Sn 313Ag 074Cu + 75 at In
Fig 10 Change of contact angles for Sn-Ag-Cu-In alloys after 30 minutes
5 Interaction studies of the quaternary alloys with Cu substrate
Metallographic studies of the structure of the boundary between the solder and substrate as well as the
structure of the solder itself was studied by electron scanning microscopy (SEM) Energy dispersive X-ray
analyzer (EDX) was used to measure the chemical composition of the interface as well as the bulk solder The
same specimen which were used for SEM and EDX investigation were also used for X-ray diffraction phase
analysis of the solder and substrate
For low In concentration (up to 15 at) Cu interface is formed by Cu6Sn5 phase For higher concentration of
In (30-50 at) Cu interface if formed by Cu41Sn11 phase For highest In concentration (75 at) Cu
interface is formed by Cu3(SnIn) phase
6 Conclusions
In this presentation investigating the influence of In on wettability of the alloy Sn 313Ag 074Cu close to
ternary eutectic Sn-Ag-Cu it was confirmed starting from previous data on In-Sn and
Sn-Ag-In [1] that due to the nearly the same surface tension and density values of pure In and Sn the
beneficial influence of In is reflected by the lowering of the contact angles with practically no change of
temperature dependence of both surface tension and density Isothermal behaviour of surface tension with ldquoSrdquo
shape starting from In-Sn and Sn-Ag-In proceeding into the investigated in this study Sn-Ag-Cu-In is
probably in addition connected with the peculiar properties of liquid In-Sn alloys showing extrema on
isothermal behaviour of electrical resistivity and viscosity [2] corresponding well to the existence of
intermetallic phases in the phase diagram of In-Sn phase diagram It is the another proof of the mutual
correlations between thermodynamic properties physical properties and the character of the phase diagram
[1] X J Liu Y Inohana I Ohnuma R Kainuma K Ishida Z Moser W Gąsior J Pstruś J Electronic Mater 31 (2002) 1139-51 [2] BPredel MHoch MPool Phase Diagrams and Heterogeneous Equilibria Springer-Verlag Berlin Heidelberg (2004) 289-291
7 Final remarks
1 Presented today joint results with P Sebo will be elaborated for Calphad journal
2 SURDAT database realized in parallel to COST 531 Program has been introduced on website of COST
531 Program
3 In addition from financing of COST 531 Program under research entitled ldquoExperimental determination
and modeling of physicochemical properties of multi-component alloys on the tin base ldquo within
2003-2006 the additional study has been realized by dr Piotr Ozga
ldquo The study of a possibility of the electrodeposition of Sn-Ag alloys from aqueous solutionsrdquo
a POzga ldquoEquilibria in Aqueous Solutions of Ag(I)-Sn(IIIV) in Presence of Strong Complexing
Ligandsrdquo CALPHAD XXXIII Krakow (Poland) May 30 ndash June 4 2004 Abstracts p 153
b POzga ldquoElectrodeposition of Sn-Ag and Sn-Ag-Cu alloys from the thiourea solutionsrdquo Archives of
Metallurgy and Materials 3 (2006) 413-421
The results of this study were used in habilitation thesis of P Ozga edited by the Institute of Metallurgy
and Materials ISBN-83-921845-8-0 Krakow (2006) 1-148
bull Special issue of the Archives of Metallurgy and Materials 32006 has been devoted to results realized
within COST 531 Program
Thank you
for your attention
- Slide 1
- Slide 2
- Slide 3
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- Slide 10
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Slide 18
- Slide 19
- Slide 20
-
5 Interaction studies of the quaternary alloys with Cu substrate
Metallographic studies of the structure of the boundary between the solder and substrate as well as the
structure of the solder itself was studied by electron scanning microscopy (SEM) Energy dispersive X-ray
analyzer (EDX) was used to measure the chemical composition of the interface as well as the bulk solder The
same specimen which were used for SEM and EDX investigation were also used for X-ray diffraction phase
analysis of the solder and substrate
For low In concentration (up to 15 at) Cu interface is formed by Cu6Sn5 phase For higher concentration of
In (30-50 at) Cu interface if formed by Cu41Sn11 phase For highest In concentration (75 at) Cu
interface is formed by Cu3(SnIn) phase
6 Conclusions
In this presentation investigating the influence of In on wettability of the alloy Sn 313Ag 074Cu close to
ternary eutectic Sn-Ag-Cu it was confirmed starting from previous data on In-Sn and
Sn-Ag-In [1] that due to the nearly the same surface tension and density values of pure In and Sn the
beneficial influence of In is reflected by the lowering of the contact angles with practically no change of
temperature dependence of both surface tension and density Isothermal behaviour of surface tension with ldquoSrdquo
shape starting from In-Sn and Sn-Ag-In proceeding into the investigated in this study Sn-Ag-Cu-In is
probably in addition connected with the peculiar properties of liquid In-Sn alloys showing extrema on
isothermal behaviour of electrical resistivity and viscosity [2] corresponding well to the existence of
intermetallic phases in the phase diagram of In-Sn phase diagram It is the another proof of the mutual
correlations between thermodynamic properties physical properties and the character of the phase diagram
[1] X J Liu Y Inohana I Ohnuma R Kainuma K Ishida Z Moser W Gąsior J Pstruś J Electronic Mater 31 (2002) 1139-51 [2] BPredel MHoch MPool Phase Diagrams and Heterogeneous Equilibria Springer-Verlag Berlin Heidelberg (2004) 289-291
7 Final remarks
1 Presented today joint results with P Sebo will be elaborated for Calphad journal
2 SURDAT database realized in parallel to COST 531 Program has been introduced on website of COST
531 Program
3 In addition from financing of COST 531 Program under research entitled ldquoExperimental determination
and modeling of physicochemical properties of multi-component alloys on the tin base ldquo within
2003-2006 the additional study has been realized by dr Piotr Ozga
ldquo The study of a possibility of the electrodeposition of Sn-Ag alloys from aqueous solutionsrdquo
a POzga ldquoEquilibria in Aqueous Solutions of Ag(I)-Sn(IIIV) in Presence of Strong Complexing
Ligandsrdquo CALPHAD XXXIII Krakow (Poland) May 30 ndash June 4 2004 Abstracts p 153
b POzga ldquoElectrodeposition of Sn-Ag and Sn-Ag-Cu alloys from the thiourea solutionsrdquo Archives of
Metallurgy and Materials 3 (2006) 413-421
The results of this study were used in habilitation thesis of P Ozga edited by the Institute of Metallurgy
and Materials ISBN-83-921845-8-0 Krakow (2006) 1-148
bull Special issue of the Archives of Metallurgy and Materials 32006 has been devoted to results realized
within COST 531 Program
Thank you
for your attention
- Slide 1
- Slide 2
- Slide 3
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- Slide 10
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Slide 18
- Slide 19
- Slide 20
-
6 Conclusions
In this presentation investigating the influence of In on wettability of the alloy Sn 313Ag 074Cu close to
ternary eutectic Sn-Ag-Cu it was confirmed starting from previous data on In-Sn and
Sn-Ag-In [1] that due to the nearly the same surface tension and density values of pure In and Sn the
beneficial influence of In is reflected by the lowering of the contact angles with practically no change of
temperature dependence of both surface tension and density Isothermal behaviour of surface tension with ldquoSrdquo
shape starting from In-Sn and Sn-Ag-In proceeding into the investigated in this study Sn-Ag-Cu-In is
probably in addition connected with the peculiar properties of liquid In-Sn alloys showing extrema on
isothermal behaviour of electrical resistivity and viscosity [2] corresponding well to the existence of
intermetallic phases in the phase diagram of In-Sn phase diagram It is the another proof of the mutual
correlations between thermodynamic properties physical properties and the character of the phase diagram
[1] X J Liu Y Inohana I Ohnuma R Kainuma K Ishida Z Moser W Gąsior J Pstruś J Electronic Mater 31 (2002) 1139-51 [2] BPredel MHoch MPool Phase Diagrams and Heterogeneous Equilibria Springer-Verlag Berlin Heidelberg (2004) 289-291
7 Final remarks
1 Presented today joint results with P Sebo will be elaborated for Calphad journal
2 SURDAT database realized in parallel to COST 531 Program has been introduced on website of COST
531 Program
3 In addition from financing of COST 531 Program under research entitled ldquoExperimental determination
and modeling of physicochemical properties of multi-component alloys on the tin base ldquo within
2003-2006 the additional study has been realized by dr Piotr Ozga
ldquo The study of a possibility of the electrodeposition of Sn-Ag alloys from aqueous solutionsrdquo
a POzga ldquoEquilibria in Aqueous Solutions of Ag(I)-Sn(IIIV) in Presence of Strong Complexing
Ligandsrdquo CALPHAD XXXIII Krakow (Poland) May 30 ndash June 4 2004 Abstracts p 153
b POzga ldquoElectrodeposition of Sn-Ag and Sn-Ag-Cu alloys from the thiourea solutionsrdquo Archives of
Metallurgy and Materials 3 (2006) 413-421
The results of this study were used in habilitation thesis of P Ozga edited by the Institute of Metallurgy
and Materials ISBN-83-921845-8-0 Krakow (2006) 1-148
bull Special issue of the Archives of Metallurgy and Materials 32006 has been devoted to results realized
within COST 531 Program
Thank you
for your attention
- Slide 1
- Slide 2
- Slide 3
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- Slide 10
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Slide 18
- Slide 19
- Slide 20
-
7 Final remarks
1 Presented today joint results with P Sebo will be elaborated for Calphad journal
2 SURDAT database realized in parallel to COST 531 Program has been introduced on website of COST
531 Program
3 In addition from financing of COST 531 Program under research entitled ldquoExperimental determination
and modeling of physicochemical properties of multi-component alloys on the tin base ldquo within
2003-2006 the additional study has been realized by dr Piotr Ozga
ldquo The study of a possibility of the electrodeposition of Sn-Ag alloys from aqueous solutionsrdquo
a POzga ldquoEquilibria in Aqueous Solutions of Ag(I)-Sn(IIIV) in Presence of Strong Complexing
Ligandsrdquo CALPHAD XXXIII Krakow (Poland) May 30 ndash June 4 2004 Abstracts p 153
b POzga ldquoElectrodeposition of Sn-Ag and Sn-Ag-Cu alloys from the thiourea solutionsrdquo Archives of
Metallurgy and Materials 3 (2006) 413-421
The results of this study were used in habilitation thesis of P Ozga edited by the Institute of Metallurgy
and Materials ISBN-83-921845-8-0 Krakow (2006) 1-148
bull Special issue of the Archives of Metallurgy and Materials 32006 has been devoted to results realized
within COST 531 Program
Thank you
for your attention
- Slide 1
- Slide 2
- Slide 3
- Slide 4
- Slide 5
- Slide 6
- Slide 7
- Slide 8
- Slide 9
- Slide 10
- Slide 11
- Slide 12
- Slide 13
- Slide 14
- Slide 15
- Slide 16
- Slide 17
- Slide 18
- Slide 19
- Slide 20
-