Thermodynamic-Kinetic Modeling and Simulation of

Microstructure Development in Cooper Based Alloys

Final Report: Masters Degree of

Science Engineering | Materials Engineering

Student: Ebert Daniel Macedo Alvares

Advisor: Dr. Johannes Preußner

Freiburg im Breisgau, Germany, July 2017

Inhalt
1. INTRODUCTION ........................................................................................................................................................6
1.1 Fraunhofer ................................................................................................................................................................7
1.2 Fraunhofer Institute for Mechanics of Materials (IWM) .......................................................................8
1.3 Introduction to the Work....................................................................................................................................8
1.4 Aims and Goals..................................................................................................................................................... 10
2. BACKGROUND THEORY...................................................................................................................................... 11
2.1 The CuSnZn Alloy System ................................................................................................................................ 11
2.2 The CuNiSi Alloy System .................................................................................................................................. 14
2.3 The CALPHAD Method ...................................................................................................................................... 16
2.3.1 Thermodynamic Model ............................................................................................................................ 17
2.3.2 Kinetic Model ............................................................................................................................................... 19
2.4 Kinetic and Hardening Simulations in MatCalc ...................................................................................... 20
2.4.1 Precipitation Model ................................................................................................................................... 21
2.4.2 Hardening Model ........................................................................................................................................ 23
2.5 Ab Initio Calculations ........................................................................................................................................ 24
3. EXPERIMENTAL AND MODELING METHODS ........................................................................................... 25
3.1 Thermodynamic and Kinetic Model ............................................................................................................ 25
3.1.1 Thermodynamic Modelling of the Cu-Sn-Zn system.................................................................... 25
3.1.2 Kinetic Modelling of the Cu-Sn-Zn system ....................................................................................... 29
3.1.3 Thermodynamic Modelling of the Cu-Ni-Si system...................................................................... 33
3.1.4 Kinetic Modelling of the Cu-Ni-Si system ......................................................................................... 33
3.2 Microstructure and Composition Measurements.................................................................................. 34
4. RESULTS AND DISCUSSION .............................................................................................................................. 34
4.1 Cu-Sn-Zn Alloys.................................................................................................................................................... 34
4.1.1 Thermodynamic Simulations (Cu-Sn-Zn)......................................................................................... 35
4.1.2 Diffusion Simulations (Cu-Sn-Zn) ........................................................................................................ 42
4.1.3 Experiences and Practical Applied Simulations (Cu-Sn-Zn)..................................................... 49
4.2 Cu-Ni-Si Alloys...................................................................................................................................................... 56
4.2.1 Thermodynamic Simulations (Cu-Ni-Si)........................................................................................... 56
4.2.2 Precipitation Simulations (Cu-Ni-Si) .................................................................................................. 59
4.2.3 Mechanical Modeling (Cu-Ni-Si)........................................................................................................... 63
5. CONCLUSION ........................................................................................................................................................... 67
5.1 Cu-Sn-Zn – System .............................................................................................................................................. 67
5.2 Cu-Ni-Si – System ................................................................................................................................................ 69
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 5.3 Next Steps .............................................................................................................................................................. 71
6. BIBLIOGRAPHY ...................................................................................................................................................... 71
7. ABSTRACT ................................................................................................................................................................ 76
8. APPENDIX ................................................................................................................................................................. 77

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Figure Index:

Figure 1. The Fraunhofer Society locations in Germany.......................................................................................... 7

Figure 2. Macrography of some Cu-Sn-Zn coating samples studied in this work .................................................. 11
Figure 3. Most stable IMC structures at 0K of the Cu-Sn-Zn system according to DFT calculations. a) β-ZnCu (B2)
b) CuSn (B8) c) h-Zn3Cu d) ε-Cu3Sn e) γ-Zn8Cu5 f) η2-Cu5Sn4 g) η‘-Cu6Sn5 h) η1-Cu5Sn4. ......................................... 13
Figure 4. Scheme of precipitation hardening in precipitation-hardening superimposed in a copper rich side of a
quasibinary phase diagram of Cu-Ni-Si alloy. ....................................................................................................... 14
Figure 5. Scheme of the typical manufacturing process of Cu strip material. The states S0 to S4 denote key states
between the production steps, which have a particularly great effect on the final state of the copper strip. ..... 15
Figure 6. Crystal structure of the δ-Ni2Si phase. Grey spheres represents the Si while blue ones the Ni atoms. .. 16
Figure 7. a) The influence of the entropy term for T = 1273K on the Gibbs Energy in the alloy system A-B. The
free enthalpies of the pure element are 0𝐺𝐴𝛷 = 0 and 0𝐺𝐵𝛷 = 2000 J / mol. b) The influence of the 𝑘𝐿-
parameters on the excess energy, in each case as a function of the mole fraction 𝑥 of the component B with
0𝐿 = 1𝐿 = 2𝐿 = −10000. The sum of the three curves is also shown. ............................................................ 18
Figure 8. Energy of substitution of an atom by a vacancy in different IMC compounds of the Cu-Sn-Zn system. 31
Figure 9. Position of Cu in η1-Cu5Sn4 phase calculated at 0K. Bigger spheres represent Cu element and smaller
ones, Sn element. Different colors distinguish the different symmetric position of Cu in the structure. .............. 32
Figure 10. Most likely diffusion path in the Cu sublattice of the η1-Cu5Sn4 phase. ............................................... 32
Figure 11. Comparisons of Zn activity in liquid phase at 1023K for conditions of x(Cu)/x(Sn)=1 (blue) and
x(Cu)/x(Sn)=2 (red) composition intersection and with experimental data superimposed. Solid lines represents
calculations results with our database and the dots data from Jantzen and Spencer (1998) [39] and Peng and
Mikula (1997) [40]. ................................................................................................................................................ 35
Figure 12. Example of many comparisons. The Solid lines are calculations of the activity of Zn in different Alloys
of the Cu-Sn-Zn system. The points shown are experimental data S. Sugino, S. Nakamura and H.Hagiwara
(1986)[41].............................................................................................................................................................. 36
Figure 13. Enthalpy of mixing of liquid at 1023K for condition of x(Sn)-x(Cu)=0 with experimental values from
M.Peng and A. Mikula (1997) [40] superimposed. ................................................................................................ 36
Figure 14. Simulated Gibbs of mixing for fcc phase in Cu-Sn-Zn system at 500K. a) Ternary surface plot and b) its
projection. The reference states for all elements are the fcc phase. ..................................................................... 37
Figure 15. Simulated Gibbs of mixing for bcc phase in Cu-Sn-Zn system at 500K. a) Ternary surface plot and b) its
projection. The reference states for all elements are the bcc phase. .................................................................... 37
Figure 16. Simulated Gibbs of mixing for fcc phase in the Cu-Sn-Zn system at 1K through CALPHAD method b) its
projection. The reference states for all elements are the fcc phase. c) Relative energy of formation of the
disordered fcc phase calculated through Ab Initio method d) its projection. ....................................................... 38
Figure 17. Shows the simulated Gibbs of mixing for bcc phase in Cu-Sn-Zn system at 1K through CALPHAD
method b) its projection. The reference states for all elements are the bcc phase. c) Relative energy of formation
of the disordered bcc phase calculated through Ab Initio method d) its projection. ............................................ 39
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Figure 18. a) Calculated binary Sn-Zn phase diagram. b) Experimental phase diagram provided by ASM
International association ...................................................................................................................................... 40
Figure 19. a) Calculated binary Cu-Sn phase diagram. b) Experimental Cu-Sn phase diagram provided by ASM
International association ...................................................................................................................................... 40
Figure 20. a) Calculated binary Cu-Zn phase diagram. b) Experimental Cu-Zn phase diagram provided by ASM
International association ...................................................................................................................................... 41
Figure 21. Calculated isothermal section of the ternary diagram of the Cu-Sn-Zn system at a) 523K and b) 873K,
with experimental data from K. Yagamuchi, I. Nakamura and R. Kenkyusho-Iho (1932) [45] and Chou and Chen
[46] superimposed. ................................................................................................................................................ 41
Figure 22. Simulated concentration profile of a) Cu/Cu-29.5% at Zn at 1057K for 2487600s (691h) and b) Cu/Cu-
0.07%atSn at 1023K for 540000s (150h) superimposed by experimental points obtained by a) Z.P. Jin et al. [50]
and b) L. Zhou et al. [49]. ...................................................................................................................................... 42
Figure 23. Simulated penetration curves at 821°C for 40h of a) Cu-4at% Sn/Cu-4at%Sn- 5.5at%Zn couple and b)
Cu-5at%Zn/Cu-4at%Sn-5.5at%Zn couple. Superimposed with experimental results from J. S. Kirkaldy, R. J.
Bringham and D. H. Weichert. .............................................................................................................................. 43
Figure 24. Simulated penetration curves at 498°C for 2 weeks (1.2*10 4s) of a) Cu-6at% Sn/Cu-6at%Sn- 5at%Zn
couple and b) Cu- 5at%Zn/Cu-5.5at%Sn-5at%Zn couple. Superimposed with experimental results from J. S.
Kirkaldy, R. J. Bringham and D. H. Weichert. ........................................................................................................ 43
Figure 25. Comparison between the calculated and experimentally measured interdiffusion coefficients in the β
Cu-Zn system at 773–1073K. The solid lines are the calculated values from the parameters obtained in the
present work, while the dots are experimental results obtained by Landergren et al. [55]. a) Range of interest
and b) full range .................................................................................................................................................... 45
Figure 26. Comparison between the calculated and experimentally measured interdiffusion coefficients in the β
Cu-Sn system at 874–993K. The solid lines are calculated values from the parameters obtained in the present
work, while the dots are experimental results obtained by M. Yokota, N. Masateru and M. Hiroyasu[54]. a)
Range of interest and b) full range........................................................................................................................ 46
Figure 27. Gibbs energy referenced to the β phase on the Cu-Sn system in function of Sn content, where the
tangent law is applied. .......................................................................................................................................... 46
Figure 28. Diffusion-penetration curves for β brass vapor solid couples at 600°C for 2h and 700°C for 16.5h. Dots
are experimental results obtained by R. Resnick and R. W. Balluffi [56] and solid lines are the simulation results
calculated using the database assessed in this work. ........................................................................................... 48
Figure 29. Isothermal section diagram at 523K of the Cu-Sn-Zn system superimposed with experimental values
.............................................................................................................................................................................. 51
Figure 30. Amount of phase in equilibrium over temperature for hypothetical alloy Cu-44w%Sn-9w%Zn......... 52
Figure 31. Amount of element in a) β b) η-Cu6Sn5 and c) ε-Cu3Sn phases over temperature in the Cu-44w%Sn-
9w%Zn alloy ......................................................................................................................................................... 52
Figure 32. Zinc mass fraction of equilibrium in the phases of Cu-44w%Sn-9w%Zn alloy over temperature. ...... 53

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Figure 33. Amount of phase over mass fraction of Zn for the 50Cu–(50-x)Sn–xZn [w%] system at 250°C. .......... 53
Figure 34. a) Micrography of the deposited layer; b) Concentration profile of the elements of the coated
substrate. .............................................................................................................................................................. 54
Figure 35. Simulated concentration profile during aging of the coating-substrate system for different times. ... 55
Figure 36. Simulated inter-diffusion between coating and substrate superimposed with experimental results for
a) 6h b) 24h and c) 168h. ...................................................................................................................................... 55
Figure 37. Simulated interface position between the deposited layer (η-phase) and substrate (β-phase) over
time ....................................................................................................................................................................... 56
Figure 38. a) Gibbs of mixing for fcc phase in Cu-Ni-Si system at 450°C, and b) its relief projection. ................... 57
Figure 39. Comparison between isopleth diagram found in literature and the calculated with the assessed
database. .............................................................................................................................................................. 57
Figure 40. Simulated Gibbs Energy of phases in the Ni-Si binary system. ............................................................. 58
Figure 41. a) Calculated ternary diagram at 450°C of the copper rich corner of the Cu-Ni-Si system. Arrows
identify the phase field stability and also where the investigated composition is located in the diagram. b)
Calculated phase fraction in equilibrium over temperature of the Cu-1.5wt%Ni-0.34wt%Si alloy. ...................... 59
Figure 42. Simulated Interface between Fcc-Cu and Ni2Si. Brown spheres correspond to Cu, the green ones to Ni
and clear ones to Si. .............................................................................................................................................. 60
Figure 43. Simulated TTT diagram of Ni2Si precipitation in Cu-1.5wt%Ni-0.34wt%Si α matrix. ........................... 61
Figure 44. Calculated phase fraction of precipitated Ni2Si over time a) for different dislocation density and b) for
different interfacial energy ................................................................................................................................... 61
Figure 45. Calculated quantity of precipitated Ni2Si phase over time a) for different dislocation density and b) for
different interfacial energy ................................................................................................................................... 62
Figure 46. Calculated mean radius over time of the Ni2Si phase precipitation in α matrix a) for different
dislocation density and b) for different interfacial energy .................................................................................... 62
Figure 47. Strengthening contribution in the yield strength of the alloy a) due to the precipitates and b) due to
variation of the solid solution, related with the dislocation density rate. ............................................................. 63
Figure 48. Simulated particle distribution histogram at maximum precipitate strength contribution during
process. ................................................................................................................................................................. 64
Figure 49. Strengthening contribution in the yield strength of the alloy a) due to the precipitates and b) due to
variation of the solid solution, related with the Interfacial Energy. ...................................................................... 65
Figure 50. Simulated particle distribution histogram at maximum precipitate strength contribution during
process for different interfacial energy. ................................................................................................................ 65
Figure 51. a) Hardness evolution and b) simulated Yield Stress evolution, over isothermal heat treatment time at
different temperature. .......................................................................................................................................... 66
Figure 52. a) Evolution of the alloy´s conductivity over time and b) Mole fraction of Cu in the fcc matrix. ......... 66

5
 Greetings

I would like to especially thank my family for their patience and support during the years I’ve
been studying abroad, especially to my parents Marinalva C. Macedo and Valter D. Alvares.

Great and special thanks to my adviser Dr. Johannes Preußner for being accompanying and
helping me on the development of the project during the last six months, adding great technical
and scientific contribution and support. Thanks to Dr. Daniel Urban for his technical contribution
on ab initio calculations and his scientific knowledge. To all the coworkers involved in this project,
especially Ms. Hélène Pfändler for her kindness and support with all the other non-technical
difficulties and to Lina M. Pulido for her kindness and help in the writing of the report.

To all the great people that somehow contributed to the base of my scientific career and
technical knowledge, my first scientific advisor Prof Dr. Claudemiro Bolfarini, to the exchange
coordinators Prof. Dr. Walter J. Botta and Brice Duhamel and to the university advisers Prof. Dr.
Guilherme Zepon and Prof. Dr. Annie Antoni.

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 1. INTRODUCTION

1.1 The Fraunhofer-Gesellschaft

The Fraunhofer-Gesellschaft is made up of 67 institutes dedicated to applied research

around Germany, with nearly 24000 staff. It has an estimated budget of 2.1 billion Euros per year
where approximately 1.8 billion comes through contract research. Roughly two thirds of this
amount is provided by contract on behalf of industry and publicly funded research projects and
the complementary one third is generated by the German federal and state governments in the
form of base funding.

Figure 1. The Fraunhofer Society locations in Germany.

The expertise of Fraunhofer is based on subjects as Materials and Components,

Microelectronics, Light & Surfaces, Microelectronics, Life Sciences, Production Defense and
Security VVS and so on. Institutes working in related subject areas cooperate in Fraunhofer
Groups and foster a joint presence on the Research and Development market helping to define the
Fraunhofer society business policy and act to implement the organizational and funding principles
of the Fraunhofer model.

Fraunhofer presents high levels of scientific competence, as evidenced by their recognition

within the scientific community. They are known for a well- balanced financial mix of different
independent sources of funding along with market success and entrepreneurial competence. This
is evidenced by contracts with industry and government as well as professional networking not
only with other Fraunhofer Institutes, but also with partners worldwide, especially German
universities.

These demands enable the Fraunhofer society the capacity to reach its goals which are:
Promoting and conducting applied research in an international context to benefit private and
public enterprises and become an asset to the society as a whole, help to reinforce the competitive

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strength of the economy in their region throughout Germany and in Europe and enable its staff to
develop both professional and personal skills.

1.2 Fraunhofer Institute for Mechanics of Materials IWM

The Fraunhofer Institute for Mechanics of Materials (Fraunhofer IWM) is an institute of

the Fraunhofer-Gesellschaft located in Freiburg and Karlsruhe and counts on average with 300
employees of which approximately 30% have PhD title. Its budget rounded to 19.3 million euros
in 2016 out of which 44% is from industry. Its current directors are Prof. Dr. Peter Gumbsch, Dr.
Rainer Kübler (Deputy Director) and Prof. Dr. Chris Eberl (Deputy Director).

The central technical aims of Fraunhofer IWM are to develop sustainable solutions for the
optimized use of material properties and new material functions. In this context, the research and
development concerning the topics of component and systems reliability, safety, durability and
functionality cover the majority of industry partner’s requirements. Hence, researching to identify
weaknesses and defects in materials and components, determine their causes and finally develop
solutions that lead to the safer use of components as well as the development of functional
materials. An efficient manufacturing process generally requires and points towards the following
range of services at Fraunhofer IWM:

• Solutions to avoid and control defects, crack formation, deformation, fracture, failure,
wear and fatigue in materials and components when subjected to mechanical, thermal,
chemical or electrical loads
• Material characterization, component testing, damage analyses, failure diagnosis and
microstructural analysis
• Materials modeling, process and component simulation on the atomic, microscopic and/or
macroscopic scale
• Surface layer assessment, coatings, tribology, functionalization, bio-surface and interfacial
analysis
• Process and material development

1.3 Introduction to the Work

This work is focused in the thermodynamic-kinetic model of two copper based alloy
systems that are in industrial use, the Cu-Sn-Zn and Cu-Ni-Si systems.

I - The Cu-Sn-Zn Project

Presenting good corrosion, wear and abrasion resistance along with a sleek visual look,
nickel based coatings are already the most widely used electrodeposited alloys. However, when
one needs to utilize these alloys in applications where humans will get in contact with them, these
alloys are not advisable. A large fraction of society, up to 15% (around 65 million people in

8
Europe), develop allergic responses when in body contact with nickel, which ends up limiting its
use. In order to minimize this problem, aiming reducing the nickel concentration, these alloys are
alloyed with copper and tin when its application is directed to contact with people. Additionally,
due to its good corrosion behavior, glossy appearance and wear protection, nickel alloys are also
frequently used as an intermediate layer between chromium coatings and it´s substrate. However,
due to its rapid diffusion, Nickel can diffuse through the upper layers and end up appearing on the
surface of the component and be exposed to the human contact within few years. Therefore,
European regulations limit the usage of nickel in jewelry, buttons, zippers etc. which incentivizes
alternatives to this kind of application.

One potential alternative to nickel coatings are Cu-Sn-Zn coatings. To fabricate these
depositions, a cyanide-based process is used. This process present at least two health problems:
the use of cyanide during the process, which can be harmful for the workers, and the necessity of
the deposition of a pre-layer of nickel based alloy between the substrate and the coating.
Therefore, an alternative process is desired candidate to be used in the next years.

Because of its appearance and chemical properties, being highly resistant to corrosion and
wear, non-magnetic, smooth and non-porous, the ternary Cu-Sn-Zn plating can be used as a
topcoat with those properties. It can create a non-toxic and sleek deposit that is highly resistant
to corrosion. This metal finishing application and deposit has low porosity and a low coefficient
of friction.

On this basis, Fraunhofer IWM and IPA are working to develop a cyanide-free process to
deposit the Cu-Sn-Zn alloy and keeping or improving its mechanical visual and biocompatibility
properties.

At the Fraunhofer IWM, the basic knowledge about the microstructure and the mechanical
properties of the new CuSnZn layers is being created in order to be able to optimally adjust the
production process for the respective layer requirements.

To this end, atomistic and thermodynamic simulation models are being developed in this
project in order to specifically investigate diffusion processes, to calculate diffusion parameters
and to predict physical properties of the layer. This makes it possible, for example, to make
statements about the use at elevated temperatures and to evaluate the long-term stability of the
layers on the particular substrate material during its usage.

II - The Cu-Ni-Si Project

In 2002 the German Copper Institute (DKI) found a serious shortcoming in the
understanding of precipitation hardening in copper based alloys. At the time, the research
institute for precious metals and metal chemistry in Schwäbisch Gmünd (Germany)
commissioned a literature review and evaluation of the Cu-Ni-Si and Cu-Fe-P alloy systems. This
literature research has now been revised and extended and has been supplemented by the latest
publications. The project was continued along the project path to allow the latest findings to be

9
incorporated directly into the project and to transport a comprehensive picture of the scientific
foundations into the economy.

Cu-Ni-Si alloys combine good electrical conductivity with a high strength, which is achieved
by cold rolling and heat treatment. These alloys are used in automotive, connectors, leadframe
and further electrotechnology parts.

The lack of knowledge of the copper materials used a few years ago is evidenced that a more
accurate version of phase diagrams of the Cu-Ni-Si-based alloys was published only in 2006, which
already contains some results from predecessor works.

Up to now no optimal heat treatment for these alloys is known.. Since the experimental plans
were initially based on old and not accurate thermodynamic experiments, the temperatures
necessary for the solution annealing could not be precisely investigated. Based on this situation,
this project tries to eliminate this deficit. Up to now, higher hardnesses were already achieved by
targeted improvements in the heat treatment of these alloys in the laboratory than in industrial
semi-finished products. To support these achievements, thermodynamic-kinetic modeling was
done based in the most recent publications. With the help of thermodynamic and kinetic databases
and further simulations, it is possible to calculate phase transformations, diffusion processes and
precipitation of this alloy´s series and afterwards optimize a possible industrial heat treatment.

1.4 Aims and Goals

This project aimed to work with the thermodynamic/kinetic modelling and simulations on the
development of two different copper based alloys of the Cu-Sn-Zn and the Cu-Ni-Si systems to:

• Deepen the studies of cooper based alloys systems

• Deepen the study and comprehension of materials modeling and simulation methods and
cooper based alloys systems

• Comprehend the influences of physical properties and external variables on the behavior
of the alloys during process and on the finished ones.

• Compare and correlate the Ab Initio calculations (DFT) method and CALPHAD method in
the prevision of phase stability.

• Optimize possible treatments within the laboratory and in industrial process.

• Predict and simulate the behavior of the microstructure, their evolution and influences in
the alloy properties during their process and application.

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 2. BACKGROUND THEORY

2.1 The CuSnZn Alloy System

The CuSnZn system in this work is reduced to the composition range of interest which is
correlated to compositions of white bronze. Nevertheless, all the occurring phases of this alloy
system were described thermodynamically.

White bronze is a tri-metal white color alloy, similar to the bright color of nickel, silver or
rhodium (Figure 2) and is resistant to tarnish and corrosion. Its composition range is reported in
the literature to be centered around 55% copper, 30% tin and 15% zinc [1]. Despite this range,
satisfactory results with deposits based on alloys composition of 30% to 60% copper, 36% to 63%
tin and 5% to 24% of zinc have been found in previous work of this study.

Figure 2. Macrography of some Cu-Sn-Zn coating samples studied in this work

In this range of composition the present phases found are α-Cu, bct-Sn, β, ε-Cu3Sn, η-
Cu6Sn5, η‘-Cu6Sn5, γ-Cu5Zn8 and Liquid. Their crystallography and temperature stability
information reported in the literature are summed up in Table 1 [17].

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 Table 1. Most reported phases of white bronze alloys and their crystallographic
parameters.

Phase/ Pearson Symbol/ Lattice Parameters

Temperature Range Space Group [pm]
[°C]
α-Cu < 1084.62 𝑐𝐹4 a = 369.612 ±
𝐹𝑚3𝑚 0.014

bct-Sn < 231.96 𝑡𝐼4 a = 583.18

𝐼41 c = 318.18

ε-Cu3Sn < 676 𝑜𝐶80 a = 552.9

𝐶𝑚𝑐𝑚 b = 477.5
c = 432.3

η-Cu6Sn5 415 – 186 ℎ𝑃4 a = 419.0

𝑃63/𝑚𝑚𝑐 c = 508.6
𝐴𝑠𝑁𝑖

η‘-Cu6Sn5 < 189 h** a = 2087.0

c = 2508.1

γ-Cu5Zn8 < 835 𝑐𝐼52 a = 886.9

𝐼43𝑚

β 903 - 454 𝑐𝐼2 a = 297.81 to

𝐼𝑚3𝑚 295.39

The α-Cu is the stable phase of pure copper which has an FCC (face centred cubic) structure
and is reported to dissolve up to 9.1 at% Sn at 586°C [18] and up to 38.27 at% Zn at 454°C [19].
The bct-Sn phase has a BCT (body centered tetragon) symmetry. The ε-Cu3Sn, η-Cu6Sn5, η‘-Cu6Sn5
and γ-Cu5Zn8 phases are intermetallic compounds (IMC) which have an ordered structure. When
these phases are present, the alloy shows hardening by presence of ordered structure and their
pure mechanical and abrasion resistance are improved. The Figure 3 shows previous results of
IMC structures calculated by Dr. Daniel Urban (IWM) using DFT methods.

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 Cu -Sn -Zn

a) β-ZnCu (B2) b) CuSn (B8)

c) h-Zn3Cu d) ε-Cu3Sn

e) γ-Zn8Cu5 f) η2-Cu5Sn4

g) η‘-Cu6Sn5 h) η1-Cu5Sn4

Figure 3. Most stable IMC structures at 0K of the Cu-Sn-Zn system according to DFT calculations.
a) β-ZnCu (B2) b) CuSn (B8) c) h-Zn3Cu d) ε-Cu3Sn e) γ-Zn8Cu5 f) η2-Cu5Sn4 g) η‘-Cu6Sn5 h) η1-Cu5Sn4.

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 The ordered phases η-Cu6Sn5/η‘-Cu6Sn5 and ε-Cu3Sn are regarded as most relevant in this
project because these phases have been measured in XRD analyses on samples that have been
produced in the project. Their contribution to the mechanical proprieties and layer formation
between subtract and coating is of importance. The η-Cu6Sn5 and η‘-Cu6Sn5 phases have at least
five unique crystal structures, hexagonal, monoclinic and variants, see e.g. G .Zeng et al [65]. The
crystal structure depends on composition, process conditions and temperature. Some of its
variants are shown in Figure 3 f) g) and h). These phases are often seen in white bronzes
depositions. Within this system, Cu is the dominant diffusing species and the addition of Zn may
stabilize the hexagonal η-Cu6Sn5 phase.

2.2 The CuNiSi Alloy System

Materials used for electronic components, such as connectors, are required to present high
conductivity and good strength. Cu-based alloys are broadly applied in these cases because pure
copper is the second best alloy in terms of conductivity right after silver. Despite its higher price
compared with aluminum, circa of 4 times more expensive, it is very often in use. Due to its higher
conductivity, components out of copper alloys can be designed with smaller cable-diameters,
which results in a cheaper product. Additionally, there are copper based alloy systems that also
allow precipitation-hardening. Among the copper based alloys, alloys from the copper rich side of
the Cu-Ni-Si system are widely used due to their relatively low cost, good processability, the
possibility of precipitation hardening in short periods of time under reasonable temperatures and
good electric and strength properties [2].

New applications often require better strength properties, especially as electric

components need to be smaller in size to realize a higher level of integration. To meet this demand,
effort has being done to preserve or improve conductivity and strength. By using alloys of the
copper rich side of the Cu-Ni-Si system, ordered phases can be precipitated homogeneously in the
matrix, which increase the energy of motion of dislocations and hence the mechanical properties.
Figure 4 shows a scheme of a possible heat treatment superimposed on the quasi-binary diagram
of copper based alloys [68].
1
2
a) 3 b)

4
5

Figure 4. Scheme of precipitation hardening in precipitation-hardening superimposed in a copper

rich side of a quasibinary phase diagram of Cu-Ni-Si alloy.
14
 The Figure 4 shows the possible steps taken by the industry to strengthen the Cu-Ni-Si
alloy. These steps consist of rapid cooling (quenching) from region 3 to region 4 to room
temperature (blue arrows on Figure 4). After this process, the alloy consists practically only out
of pure metastable α-phase (fcc) at room temperature. In the following, a targeted heating of the
previously quenched metastable solid solution crystal from room temperature to region 5 (red
arrows) is done. This process allows getting a technically desired homogeneous and fine
precipitation of the precipitating phases and hence, allowing optimum properties of the
precipitation-hardening alloy to take place. Figure 5 shows a path of manufacturing of the alloy in
the industry.

Figure 5. Scheme of the typical manufacturing process of Cu strip material. The states S0 to S4
denote key states between the production steps, which have a particularly great effect on the final state of
the copper strip [69].

This process not only increases the mechanical properties of the alloy. The reduction of
alloying content in the α-phase matrix increases the electron mobility in the matrix and hence
raises the electrical conductivity.

The strengthening mechanism is reported by Z.H. Jin et al. [20] in more detail where the
supersaturated solid solution decomposes by the spinodal mechanism into periodic Si-rich and
Si-poor regions, when during the proceeding aging treatments, results then in a ordering
metastable phase of DO22 [(Cu,Ni)3Si] structure and further in the coherent δ-Ni2Si with
orthorhombic lattice nucleating within the (Cu,Ni)3Si. They also reported that the δ-Ni2Si phase
can be cut by dislocation, but the significant difference of the matrix and precipitates structure
causes a higher interfacial energy whose interaction with the dislocations make them
energetically easier to be rounded instead of being cut. Figure 6 shows the crystal structure of the
δ-Ni2Si phase.

15
 Figure 6. Crystal structure of the δ-Ni2Si phase. Grey spheres represents the Si while blue ones the
Ni atoms.

2.3 The CALPHAD Method

For the development of new alloys, phase diagrams play a special role. They indicate the
equilibrium state of a material as a function of temperature, pressure or concentration of the
components. As the pressure does not have a big influence on the phase transformations in
metallic alloys, the state of a material consisting of two components can be represented
completely by a binary phase diagram in a 2D diagram with the temperature as ordinate. The
dependence on the ambient pressure is neglected in the following calculation and it was taken as
constant. In the case of ternary systems, an additional dimension is necessary for the
representation, so isothermal cuts or projections are used. With multicomponent systems, this
display mode is no longer simply possible. Likewise, with the number of components, the
experimental effort also determines the basic state of the respective alloy. For multicomponent
systems, one needs to calculate two different concentrations for each element and so we have an
exponential-like formula to describe the possible individual alloys in the system:

2𝑛 = 𝐶 (1)

Where n is the number of elements and C the number of individual alloys.

When the value of n is relatively high, the experimental examination on the system
becomes not feasible and computational simulation methods are then required.

The CALPHAD (CALculation of PHAse Diagrams) method is based on the minimization of

Gibbs free energy, also called free enthalpy for each phase of the alloy system. The advantage of
this thermodynamic view is that it can be expanded for several alloying components and is based
on physical principles. The thermodynamic ground state of an alloy (from the elements ABC), and
thus the phases that form, can be predicted in the first approximation by the extrapolation of the
Gibbs free energy of the subsystems (A-B, A-C, B-C). Although the visual representation of
multicomponent systems is still difficult, 3D diagrams and quasi-binary sections can be generated,
or the basic state can be calculated at a certain concentration. The program package Thermo-Calc

16
is often used for this work. When the thermodynamic models of individual phases are present, the
equilibrium state of an alloy can be calculated and the most important properties determined.
Another important tool within this program package is the PARROT module, with which it is
possible to relate the parameters of thermodynamic and kinetic models to the experimental data
using the method of regression analysis of least error squares.

2.3.1 Thermodynamic Model

The general thermodynamic model is summed up in this chapter [3]. The total Gibbs
energy 𝐺𝑡𝑜𝑡𝑎𝑙 of a system is calculated from the sum of the molar free enthalpies of the individual
phases Φ, 𝐺𝑚Φ
, multiplied by the mole fraction of phase 𝑥 Φ in the system. In thermodynamic
equilibrium, the total Gibbs energy is minimized:

(𝑠,Φ)
min(𝐺𝑡𝑜𝑡𝑎𝑙 ) = min (∑ 𝑥 Φ . 𝐺𝑚
Φ
(𝑇, 𝑥𝑖Φ 𝑎𝑛𝑑/𝑜𝑟. 𝑦𝑘 )) (2)
Φ

The free enthalpies of the individual phases depend on the temperature 𝑇 and the molar
(𝑠,Φ)
fraction 𝑥𝑖Φ of a component 𝑖 in the phase 𝜙 or the proportion 𝑦𝑘 of an element 𝑘 on the
sublattice 𝑠 of a phase 𝜙. Usually the temperature 𝑇 is known, the variables 𝑥 Φ and 𝑥𝑖Φ and / or
(𝑠,Φ)
𝑦𝑘 are calculated, a mathematical description of the Gibbs energy is required for each phase of
the alloy systems.

A common model for the representation of a solid solution binary crystal is the model of
the substitutional solution, where the Gibbs energy is represented as:

Φ
𝐺𝑚 = 0𝐺𝐴Φ 𝑥𝐴 + 0𝐺𝐵Φ 𝑥𝐵 + 𝑅𝑇(𝑥𝐴 𝐿𝑛(𝑥𝐴 ) + 𝑥𝐵 𝐿𝑛(𝑥𝐵 ) ) + 𝐸𝐺𝑚
Φ (3)

Where 𝑅 is the universal gas constant.

In the binary system we have 𝑥𝐴 = 1 − 𝑥𝐵 . The first two terms describe the mechanical
mixing of two elements and can be viewed as the remoteness of the properties of a solution. In a
graph of Gibbs energy versus concentration, this reference is a straight line, as can be seen in
Figure 7.

The molar free enthalpies of the pure element 0𝐺 Φ are temperature-dependent and are
approximated by:

0 Φ 𝑆𝐸𝑅
𝐺 − 𝐻𝑚 = 𝑎 + 𝑏𝑇 + 𝑐𝑇𝑙𝑛𝑇 + ∑ 𝑑𝑖 𝑇 𝑖 (4)
𝑖
17
 In this work the parameters 𝑎, 𝑏, 𝑐, 𝑑𝑖 were taken from Dinsdale, where the constants 𝑑𝑖
are typically defined for i = -1, 2, 3 and the entropy at 0K (S = 0) as well as the enthalpy 𝐻 𝑆𝐸𝑅 in
the standard state of the element, it means, the stable state of the element at room temperature
298.15K, serves as a reference to the Gibbs energy of the pure elements.

Taking into account until the third term of Eq. 3, one indicates an ideal mixture. This term
describes the entropy of the system when mixing the atoms. In principle, it is responsible for the
fact that the shape of the Gibbs energy takes the form of a “hanging rope” [4] instead of a straight
line as can be seen on Figure 7 a).

If one additionally takes the fourth term from equation (8) into consideration, one speaks
of a real mixture. The excess energy G describes any deviation from the ideal behavior and takes
into account the interaction of the atoms with each other. This term is described by the Redlich-
Kister-Polynomial equation:
𝑛
𝐸 Φ
𝐺𝑚 = 𝑥𝐴 𝑥𝐵 ∑ 𝑘𝐿Φ (𝑥𝐴 − 𝑥𝐵 )𝑘 (5)
𝑘=0

The 𝑘𝐿-parameters can be adapted to experimental data using the CALPHAD method and
are of the form 𝐿 = 𝑎 + 𝑏 , which means that they can again be temperature-dependent. Figure 7
b) illustrates the individual effect of the 𝑘𝐿-parameters on the excess energy.

a) b)
2000
2000 1500 Excess
k=1
1000 L0
0 Mechanical Mixing L1
500
Gibbs Energy [J/mol]

Gibbs Energy [J/mol]

L2
0
-2000
-500 k=2
-4000 -1000
-1500
-6000
-2000
k=0
-2500
-8000 Ideal Mixing
-3000
Sum
-10000 -3500
-4000
0,0 0,2 0,4 0,6 0,8 1,0 0,0 0,2 0,4 0,6 0,8 1,0
Element B [Mole Fraction] Element B [Mole Fraction]

Figure 7. a) The influence of the entropy term for T = 1273K on the Gibbs Energy in the alloy
system A-B. The free enthalpies of the pure element are 𝟎𝑮𝚽 𝑨 = 𝟎 and 𝑮𝑩 = 2000 J / mol. b) The influence
𝟎 𝚽

of the 𝑳-parameters on the excess energy, in each case as a function of the mole fraction 𝒙 of the component
𝒌

B with 𝟎𝑳 = 𝟏𝑳 = 𝟐𝑳 = −𝟏𝟎𝟎𝟎𝟎. The sum of the three curves is also shown.

If Gibbs's energy is known, Eq. 2 can be used to calculate not only the stable phases, but
also a number of other thermodynamic parameters, such as [21]:
𝜕𝐺𝑚
Entropie 𝑆 = −( )
𝜕𝑇 𝑁𝑖
(6)

18
 𝜕𝐺
Enthalpie 𝐻 = 𝐺 + 𝑇𝑆 = 𝐺 − 𝑇 ( ) (7)
𝜕𝑇 𝑁𝑖

𝜕2 𝐺
Heat capacity 𝐶𝑝 = −𝑇 ( 𝜕𝑇 2 ) (8)
𝑁𝑖

With 𝑁𝑖 the mole of component 𝑖

The model of the substitution solution from Eq. 3 can be extended to phases which have
several non-identical lattice sites.

Thus, for instance, an A Wyckoff position can be modeled as a sublattice. Furthermore, the
compound-energy formalism (CEF) has been described by Hillert [4]. This formalism is similar in
its kind of equation, but has been expanded for several lattice sites. Each sublattice 𝑠 has a certain
(𝑠)
concentration of elements 𝑦𝑘 , whereby for each sublattice 𝑠:

(𝑠)
∑ 𝑦𝑘 = 1 (9)
𝑘

More specifically, the ordinal reaction of the lattice grating is to be considered here.
Comparing the fcc lattice structure with the 𝐿12 -structure, one can note that the atoms are located
on the same lattice sites. This also applies to the 𝐿10 -structure, which is tetragonal distorted. The
difference compared to the fcc structure lies only in the fact that in the 𝐿12 or and in the 𝐿10 phase
the atoms are ordered.

2.3.2 Kinetic Model

The views on the mathematical description of the alloy seen in chapter 2.3.1 all refer to
the thermodynamic equilibrium of the system. In order to represent diffusion-controlled
processes, the thermodynamic as well as the kinetic parameters of the system must be mapped.
In order to describe diffusion processes, knowledge of the diffusion coefficients, which depend on
the temperature and the element concentrations, is generally necessary [3].

In the DICTRA software, kinetic processes are not calculated on the basis of diffusion
constants, but on the basis of the mobilities of the atoms. This has the advantage that the required
coefficients, which can be determined, can be greatly reduced. Thus, in an alloy system with n
components, there are n mobilities, but (n-1)2 interdiffusion coefficients[6].

The diffusion coefficients can be calculated from the mobilities if the thermodynamic
𝜕𝜇𝑖
factor 𝜕𝑐𝑗
and chemical potential of the element 𝑖 , 𝜇𝑖 , and the concentration of the element 𝑗, 𝑐𝑗 ,

19
are known. This factors are able to be calculated by using the thermodynamic database for this
alloy system [7].

The tracer-diffusion coefficients 𝐷𝑖∗ are directly connected with the mobility by the
Einstein-Relation [8]:

𝐷𝑖∗ = 𝑀𝑖 𝑅𝑇 (10)

Where the mobility 𝑀𝑖 has the following form:

𝑀𝑖0 −𝑄𝑖
𝑀𝑖 = 𝑒𝑥𝑝 ( ) (11)
𝑅𝑇 𝑅𝑇

With the frequency factor 𝑀𝑖0 and the activation energy 𝑄𝑖 .

Representing the composition dependency as a linear combination of the values at each

endpoint of the composition space and a Redlich-Kister expansion we arrive to the relation [9]:

𝑚
𝑖𝑗 𝑟
𝛷𝐵 = ∑ 𝑥𝑖 𝛷𝐵𝑖 + ∑ ∑ 𝑥𝑖 𝑥𝑗 [∑ 𝑟𝛷𝐵 (𝑥𝑖 − 𝑥𝑗 ) ] (12)
𝑖 𝑖 𝑗>𝑖 𝑟=0

Where 𝛷𝐵 represents 𝑙𝑛𝑀𝐵0 or 𝑄𝐵 . The term 𝛷𝐵𝑖 is the value of 𝛷𝐵𝑖 for pure 𝑖 and thus
𝑖𝑗
represents one of the endpoint values in the composition space. The term 𝑟𝛷𝐵 represents binary
interaction parameters, and 𝑖 and 𝑗 are mole factions of the elements 𝑖 and, respectively.

2.4 Kinetic and Hardening Simulations in MatCalc

In MatCalc [10] the calculation of precipitation kinetics is based on the thermodynamic

and kinetic data of the individual phases. The same database used for ThermoCalc/ DICTRA can
be read and used by MatCalc. In addition, further microstructural parameters can be taken into
account in the program, such as, surface homogeneity, homogeneous or heterogeneous
nucleation, preferred sites of heterogeneous nucleation (e.g., dislocations, grain boundaries or
other precipitates), composition of the nuclei, nucleating model, etc.

20
 While in Dictra the precipitation formation over the concentration profiles of all involved
elements is calculated by numerical solution of the diffusion equations, MatCalc uses the extremal
principle according to Onsager [11] and the concentration gradients in the matrix phase can be
averaged in the calculation (mean-field approach). This only leads to negligibly small errors [12].
The advantage of this method is that the computations can be carried out much more quickly. A
direct implementation of the models in finite element codes is theoretically feasible and the
influence of different microstructural parameters on the precipitation kinetics can also be
examined much more efficiently. The model makes it possible to compute a large number of
precipitates of different sizes and different phases in a mixed crystal matrix, the size distribution,
number and composition of the precipitating particles, as well as the average composition of the
matrix phase at each time step of the nucleation and growth phase.

2.4.1 Precipitation Model

A general multi-component system nucleation theory is not yet available in the literature
[66]. MatCalc uses the classical nucleation theory to run the simulations. For a binary system, the
classical nucleation theory describes the state nucleation rate (𝑚𝑠𝑠
̇ ) as

−𝛥𝐺 ∗
̇ = 𝑍𝛽 ∗ 𝑁𝑐 exp (
𝑚𝑠𝑠 ) (13)
𝑘𝐵 𝑇

With 𝑍 being the Zeldovich factor [66], 𝛽 ∗ the atomic attachment rate for the critical
nucleus, 𝑁𝑐 the number of available nucleation sites, 𝑘𝐵 the Boltzmann constant and 𝛥𝐺 ∗ is the
nucleation barrier given by

𝑓𝛾𝑘3
𝛥𝐺 ∗ = (14)
𝐹2

Where 𝑓 is the shape factor of the nucleus (𝑓 = 16𝜋/3 in the case of homogeneous
nucleation of spherical nuclei and 𝑓 < 16𝜋/3 for heterogeneous nucleation). 𝐹 is the driving force.
In a simplified binary system with A-B atoms where A is the dilute component and the precipitates
consisting only of B atoms, 𝛽 ∗ can be calculated as

4𝜋𝜌∗2 𝐷0𝐵 𝜇0𝐵

𝛽∗ = (15)
𝑎2 𝑎2

With
2𝛾𝑘
𝜌∗ = (16)
𝐹

Where 𝑎 is the lattice parameter and 𝜌∗ is the critical radius. In the Eq. 15, the first factor
corresponds to the number of available atomic sites on the surface of the critical nucleus and the
second, represents the mean exchange frequency per atomic site of B atoms between the matrix
and the critical nucleus at the interface. A more complex cases involving multi-component system,

21
one can likely have precipitation of different phases of different chemical composition, which can
nucleate simultaneously. In this case the second factor of the Eq. 15 is not valuable. To solve this
problem, the second factor used in Eq. 15 must be modified to account for differences in chemical
composition of the matrix and precipitates as well as for the different values of diffusion
coefficient of the components.

Using the evolution equations concept [67], in the case of the binary A-B system, the
growth rate of the precipitate become

𝐹 − (2𝛾𝑘 /𝜌𝑘 )
𝜌𝑘̇ = 𝑢0𝐵 𝐷0𝐵 𝛺 (17)
𝑅𝑇𝜌𝑘

Considering a multi-component system without any change in chemical composition in

the precipitates, the growth rate of the precipitate is given by:

𝑛 −1
𝐹 − (2𝛾𝑘 /𝜌𝑘 ) (𝑐𝑘𝑖 − 𝑐0𝑖 )2
𝜌𝑘̇ = [∑ ] (18)
𝑅𝑇𝜌𝑘 𝑐0𝑖 𝐷0𝑖
𝑖=1

In the binary case, the kinetics of nucleation as well as the growth of precipitates are
controlled by diffusion of B atoms in the matrix, evidenced by the product 𝐷0𝐵 𝜇0𝐵 of Eq 15. If one
assumes that the nucleation of precipitates is multi-component and is also controlled by the same
combinations of diffusive processes as the growth of the precipitates, the expression
−1
(𝑐𝑘𝑖 −𝑐0𝑖 )2
[𝛺 ∑𝑛𝑖=1 𝑐0𝑖 𝐷0𝑖
] can replace the 𝐷0𝐵 𝜇0𝐵 term and the equation can then be rewritten as

𝑛 −1
∗
4𝜋𝜌∗2 (𝑐𝑘𝑖 − 𝑐0𝑖 )2
𝛽 = 4 [∑ ] (19)
𝑎 𝛺 𝑐0𝑖 𝐷0𝑖
𝑖=1

Based on the Eq. 13, 14 and 19, the steady state nucleation rate 𝑚𝑠𝑠
̇ can be evaluated. The
transient nucleating rate 𝑚𝑛𝑢𝑐
̇ is given by
𝜏
𝑚𝑛𝑢𝑐
̇ = 𝑚𝑠𝑠
̇ 𝑒𝑥𝑝 (− ) (20)
𝑡

With 𝜏 the incubation time calculated from

1
𝜏= (21)
2𝛽 ∗ 𝑍 2
22
 To finish, the dissolution rate, 𝑚𝑑𝑖𝑠𝑠
̇ , is given by the rate of number of precipitates whose
radius lies below the predefined minimum radius, 𝜌𝑘 . The total rate, 𝑚̇ , follows as

𝑚̇ = 𝑚𝑛𝑢𝑐
̇ − 𝑚𝑑𝑖𝑠𝑠
̇ (22)

2.4.2 Hardening Model

In MatCalc, an alloy yield strength model is also implemented using broadly known
equations. The principal approach takes into account the contribution of different factors to
approximate the final mechanical properties.

𝜎𝑌𝑆 = 𝑓(𝜎𝑖 , 𝜎𝑑𝑖𝑠𝑙 , 𝜎𝑔𝑏 , 𝜎𝑠𝑔𝑏 , 𝜎𝑠𝑠 , 𝜎𝑝𝑟𝑒𝑐 ) (23)

Eq. 23 shows the contributions to yield strength 𝜎𝑌𝑆 in function of the parameters of
influence. Where 𝜎𝑖 is the intrinsic strength of the basic alloy, 𝜎𝑑𝑖𝑠𝑙 is the contribution by work
hardening. 𝜎𝑔𝑏 , 𝜎𝑠𝑔𝑏 are grain and subgrain boundary strengthening, respectively. 𝜎𝑠𝑠 is the solid
solution strengthening and 𝜎𝑝𝑟𝑒𝑐 the precipitation strengthening.

The work hardening parameter, in turn, is described by the Taylor equation:

𝜎𝑑𝑖𝑠𝑙 = 𝐴𝛼𝐺𝑏√𝜌 (24)

Where 𝛼 is the Taylor factor, 𝐺 is the shear stress, 𝑏 as the Burger´s vector and 𝜌 the
dislocation density.

The shear stress is then calculated as:

𝐸
𝐺= (25)
2(1 − 𝜐)

Where 𝐸 is the Young´s Modulus and 𝜐 the Poisson´s ration

23
 The Grain/subgrain boundary strengthening, 𝜎𝑔𝑏 , 𝜎𝑠𝑔𝑏 , are modeled by the Hall-Petch
equation:

𝑘𝑔𝑏
𝜎𝑔𝑏 = (26)
√𝐷

𝑘𝑠𝑔𝑏
𝜎𝑠𝑔𝑏 = (27)
√𝛿

Where 𝐷 is the grain diameter, 𝛿 is the subgrain diameter and 𝑘𝑛 a constant.

The solid solution strengthening parameter, 𝜎𝑠𝑠 is important due its direct inverse
correlation with the conductivity properties. Once atoms are diffusion from the matrix to the
precipitates, we have a decrease of mechanical properties in the matrix and an increase of the
electrical conductivity of the matrix. The solid solution strengthening is an indicative of these
variations and is modeled as:
1
𝑚𝑡𝑜𝑡 𝑚𝑡𝑜𝑡 𝑚𝑡𝑜𝑡
𝑚𝑠𝑢𝑏 𝑚𝑠𝑢𝑏
𝑛 𝑚𝑠𝑢𝑏
𝜎𝑠𝑠 = [(∑(𝑘𝑖 𝑐𝑖 𝑖 ) ) + (∑(𝑘𝑖 𝑐𝑖𝑛 )𝑚𝑖𝑛𝑡 ) ] (28)
𝑖 𝑠𝑢𝑏 𝑖 𝑖𝑛𝑡

Where 𝑘𝑖 is the coefficient for element 𝑖 , 𝑐𝑖 the element 𝑖 content in the precipitation
domain, 𝑛𝑖 is the exponent for element 𝑖 , 𝑚𝑠𝑢𝑏 and 𝑚𝑖𝑛𝑡 exponent for substitutional and
interstitial elements, respectively, and 𝑚𝑡𝑜𝑡 the global exponent.

The precipitation strengthening parameter, 𝜎𝑝𝑟𝑒𝑐 , despite of showing the most important
contribution and being aimed in this work, is described by several parameters [13] which in turn
are differently described for some special cases.

2.5 Ab Initio Calculations

The demand from the industry and from the science to offer simulations and methods that
can make accurate predictions of individual properties is huge. Almost all simulations from
material science are based on models, where the accuracy is dependent on the precision of stored
parameters. One example of this is the CALPHAD method, whose exactness depends on a great
extent on the databases deposited. Ab initio methods are fundamentally different in character.
The term "first principles" has the same meaning as "ab initio" and stands for a theory that
requires no parameters and is based purely on physical principles and quantities. The result of
such simulations thus depends solely on the transformation of the theory into numerical models.

24
A description of the ab initio methods can be found in some broadly referenced publications such
as [14] [15].

Ab initio calculations are based on Density Functional Theory (DFT), where

approximation methods for treating an inhomogeneous system of interacting electrons are
developed. The method is exact when applied to a homogeneous system.

These methods are applied in this project and were used to calculate the most stable
structure of the phases of interest, most probable path of diffusion of foreign atoms in these
structures and also to calculate energy of formation of disordered phases.

3. EXPERIMENTAL AND MODELING METHODS

3.1 Thermodynamic and Kinetic Model

The study of the syntax to write a database as well as the one for the usage of the
ThermoCalc®, DICTRA-module and PARROT-module was carried out using the ThermoCalc® and
DICTRA User-Guide apostilles as well as published lectures from experts on the field of materials
modelling and simulation [9][16].

The assessment of the thermodynamic properties database of the Cu-Sn-Zn and Cu-Ni-Si
systems was then written using parameters of the Gibbs free energy as function of temperature
found in the latest literature publications and optimized using the PARROT-module and
eventually theoretic equations. Moreover, results from ab initio calculations done at the
Fraunhofer IWM and experimental results from other different authors supported the consistence
of the implemented parameters.

After and during the assessment of the database, the software ThermoCalc® was used to
calculate relevant thermodynamic equilibrium properties. Kinetic calculations, such as
composition profiles after heat treatment, penetration curves in coupled alloys and boundary and
layer growth problems were carried out with the DICTRA-module of ThermoCalc®. Some other
kinetic calculations as Time-Temperature-Transformation (TTT) diagrams, particle distribution
evolution over time, mechanical strengthening/ properties over time, particles size over time and
so on were calculated using the MatCalc® software

The results obtained by the simulations were supported and compared with previous
experiments done at the Fraunhofer IWM and Fraunhofer IPA as well from the companies
affiliated to the project.

3.1.1 Thermodynamic Modelling of the Cu-Sn-Zn system

25
 Because commercial thermodynamic databases including the Cu-Sn-Zn systems were not
available, the thermodynamic database written in this work was based on literature publications.
The ternary alloy system Cu-Sn-Zn thermodynamic database was assessed and optimized by
Gierlotka et al [23] and Mittinen [24] and their results show good agreement with experimental
results of the experimental binaries and ternary equilibrium phase diagrams. The thermodynamic
parameters used in this work were then taken mainly from these publications and summed with
ternary pure element parameters from SGTE (Scientific Group Thermodata Europe) to write the
final thermodynamic database used in this work. Even though these parameters were in good
agreement with experimental values, some parameters related to important phases in this work
as α-Cu and β demonstrate no satisfactory results for temperature ranges below 200°C which
could influence in the aim of this work. Therefore, parameters assessed by J. Spenser [25] and G.
Wnuk et al. [26] were taken in account and used on the assessment to improve accuracy also at
lower temperatures.

In the range of temperature of interest one can sum up the following present phases in the
Cu-Sn-Zn system: α-Cu; bct-Sn; hcp-Zn; β; δ-CuZn3; Liquid; ζ-Cu10Sn3; ε-Cu3Sn; δ-Cu41Sn11; η-
Cu6Sn5; η’- Cu6Sn5; γ-Cu5Zn8; ε-CuZn5 and γ-(Cu-Sn). In Table 2 the phase names are listed and the
corresponding database description is given.

TABLE 2. Correlation between the phase names with their corresponding names in the
database descriptions.

Phase Database description

α-Cu FCC_A1
bct-Sn BCT_A5
hcp-Zn HCP_ZN
β BCC_A2
δ-CuZn3 BCC_A2
Liquid LIQUID
ζ-Cu10Sn3 CU10SN3
ε-Cu3Sn CU3SN
δ-Cu41Sn11 CU41SN11
η-Cu6Sn5 CU6SN5
η’- Cu6Sn5 CU6SN5 P
γ-Cu5Zn8 CUZN_GAMMA
ε-CuZn5 EPSILON
γ-(Cu-Sn) GAMMA DO3

The substitutional solution phases as: α-Cu (FCC_A1), δ-CuZn3 (BCC_A2) , β (BCC_A2), bct-
Sn (BCT_A5), hcp-Zn (HCP_ZN), ε-CuZn5 (EPSILON) and Liquid (LIQUID) were described by the
regular solution model [21].

𝐺𝑚 (𝑡) = ∑ 𝑥𝑖0 𝐺𝑖 (𝑇) + 𝑅𝑇 ∑ 𝑥𝑖 ln(𝑥𝑖 ) + ∑ ∑ 𝑥𝑖 𝑥𝑗 (∑ 𝐿𝑖𝑗 (𝑥𝑖 − 𝑥𝑗 )𝑣 ) (29)

𝑖 𝑖 𝑖 𝑗>𝑖 𝑣

26
 Where the left part contribution: ∑𝑖 ∑𝑗>𝑖 𝑥𝑖 𝑥𝑗 (∑𝑣 𝐿𝑖𝑗 (𝑥𝑖 − 𝑥𝑗 )𝑣 ) represents the Redlich-
Kister polynomial for excess Gibbs energy.

The binary stoichiometric compound such as ζ-Cu10Sn3 (CU10SN3) and δ-Cu41Sn11

(CU41SN11) were described as line compounds using the Eq. 30, where the state of reference is
pondered and added as contribution on the Gibbs energy following the stoichiometric fraction of
the element in the phase as represented:

𝐺𝑚 (𝑇) = 𝑎 + 𝑏𝑇 + ∑ 𝑥𝑖 𝐺𝐻𝑆𝐸𝑅𝑖 (30)

𝑖

The ordered phase γ-(Cu-Sn) (GAMMA DO3) is formed by the atomic ordering process of
the β phase and its Gibbs free energy is described in the literature [27] as a two-sublattice model
as (Cu,Sn)0.75(Sn,Cu)0.25 and was represented by Eq. 31:

𝛾 1 2 0 𝛾 1 2 0 𝛾 1 2 0 𝛾 1 2 0 𝛾
𝐺𝑚 (𝑇) = 𝑌𝐶𝑢 𝑌𝐶𝑢 𝐺𝐶𝑢:𝐶𝑢 + 𝑌𝐶𝑢 𝑌𝑆𝑛 𝐺𝐶𝑢:𝑆𝑛 + 𝑌𝑆𝑛 𝑌𝐶𝑢 𝐺𝑆𝑛:𝐶𝑢 + 𝑌𝑆𝑛 𝑌𝑆𝑛 𝐺𝑆𝑛:𝑆𝑛

1 1 1 1 ) 2 2 2 2 ) 𝛾
+0.75𝑅𝑇(𝑌𝐶𝑢 𝑙𝑛𝑌𝐶𝑢 + 𝑌𝑆𝑛 𝑙𝑛𝑌𝑆𝑛 + 0.25𝑅𝑇(𝑌𝑆𝑛 𝑙𝑛𝑌𝑆𝑛 + 𝑌𝐶𝑢 𝑙𝑛𝑌𝐶𝑢 + 𝑋𝑆𝐺𝑚 (31)

𝛾
Where 𝑋𝑆𝐺𝑚 is the excess Gibbs energy:

𝑋𝑆 𝛾 1 1 2 𝛾 1 1 2 𝛾 1 2 2 𝛾
𝐺𝑚 = 𝑌𝐶𝑢 𝑌𝑆𝑛 𝑌𝐶𝑢 𝐿𝐶𝑢,𝑆𝑛:𝐶𝑢 + 𝑌𝐶𝑢 𝑌𝑆𝑛 𝑌𝑆𝑛 𝐿𝐶𝑢,𝑆𝑛:𝑆𝑛 + 𝑌𝐶𝑢 𝑌𝑆𝑛 𝑌𝐶𝑢 𝐿𝐶𝑢:𝑆𝑛,𝐶𝑢
𝛾 𝛾
1 2 2
+ 𝑌𝑆𝑛 1 1 2
𝑌𝑆𝑛 𝑌𝐶𝑢 𝐿𝑆𝑛:𝑆𝑛,𝐶𝑢 +𝑌𝐶𝑢 𝑌𝑆𝑛 𝑌𝐶𝑢 𝐿𝐶𝑢,𝑆𝑛:𝑆𝑛,𝐶𝑢 (32)

In which 𝑌𝑖𝑁 denotes the site fraction of element i on sublattice N, symbol “:” indicates
separation of elements on the different sublattices, and “,” indicates separation of elements on
the same sublattice.

Gierlotka et al. [2] demonstrated that ε-Cu3Sn shows a solubility in the Cu-Sn-Zn ternary
system which is not negligible when compared with the small solubility of the same phase in a
binary Cu-Sn alloy. This phase is usually found in Cu-Sn based systems and is one of the major
phase presents in the alloys that were studied in this work. Its solubility may highly influence on
the stable position and diffusion of the Zn atoms during the application and process of the alloys
and hence this phase was carefully taken into account. The Cu3Sn phase is described by the two-
sublattice model (Cu,Sn)0.75:(Cu,Sn,Zn)0.25, as described in Eq 33:

27
 𝐶𝑢3 𝑆𝑛 1 2 0
𝐶𝑢3 𝑆𝑛 1 2 𝐶𝑢3 𝑆𝑛 0
1 2 0
𝐶𝑢3 𝑆𝑛 1 2 𝐶𝑢3 𝑆𝑛 0
𝐺𝑚 (𝑇) = 𝑌𝐶𝑢 𝑌𝐶𝑢 𝐺𝐶𝑢:𝐶𝑢 + 𝑌𝐶𝑢 𝑌𝑆𝑛 𝐺𝐶𝑢:𝑆𝑛 + 𝑌𝑆𝑛 𝑌𝐶𝑢 𝐺𝑆𝑛:𝐶𝑢 + 𝑌𝑆𝑛 𝑌𝑆𝑛 𝐺𝑆𝑛:𝑆𝑛

1 2 0 3 𝐶𝑢 𝑆𝑛
1 2 3 0 𝐶𝑢 𝑆𝑛
1 1 1 1 )
+ 𝑌𝑆𝑛 𝑌𝑍𝑛 𝐺𝑆𝑛:𝑍𝑛 + 𝑌𝐶𝑢 𝑌𝑍𝑛 𝐺𝐶𝑢:𝑍𝑛 + 0.75𝑅𝑇(𝑌𝐶𝑢 𝑙𝑛𝑌𝐶𝑢 + 𝑌𝑆𝑛 𝑙𝑛𝑌𝑆𝑛

𝑋𝑆 𝐶𝑢3 𝑆𝑛
2
+ 0.25𝑅𝑇(𝑌𝑆𝑛 2
𝑙𝑛𝑌𝑆𝑛 2
+ 𝑌𝐶𝑢 2
𝑙𝑛𝑌𝐶𝑢 1
+ 𝑌𝑍𝑛 1 )
𝑙𝑛𝑌𝑍𝑛 + 𝐺𝑚 (33)

The η’- Cu6Sn5 is hexagonal and present a superstructure developed from a NiAs-type
structure. The η-Cu6Sn5 transforms into the η-Cu6Sn5 phase, which has a NiAs-type structure
between 459 and 502K. These phases are also important in this work due to their presence in the
alloys studied here and due to their formation between layers while applied under temperature
ranges concerning the process of fabrication and possible use. As in the case of the Cu3Sn phase,
the solubility of the phase is small in the binary Cu-Sn system but can be of importance in high
order systems. The η’- Cu6Sn5 and η-Cu6Sn5 phases were modeled using the three-sublattice model
(Cu)0.3333(Cu,Sn,Zn)0.3334(Sn)0.3333. Eq. 34 describes the Gibbs free energies of both phase as
function of temperature:
𝐶𝑢6 𝑆𝑛5 1 2 3 0
𝐶𝑢6 𝑆𝑛5 1 2 3 0
𝐶𝑢6 𝑆𝑛5
𝐺𝑚 (𝑇) = 𝑌𝐶𝑢 𝑌𝐶𝑢 𝑌𝑆𝑛 𝐺𝐶𝑢:𝐶𝑢:𝑆𝑛 + 𝑌𝐶𝑢 𝑌𝑆𝑛 𝑌𝑆𝑛 𝐺𝐶𝑢:𝑆𝑛:𝑆𝑛

𝑋𝑆 𝐶𝑢6 𝑆𝑛5
2
+0.3334𝑅𝑇(𝑌𝐶𝑢 2
𝑙𝑛𝑌𝐶𝑢 2
+ 𝑌𝑆𝑛 2)
𝑙𝑛𝑌𝑆𝑛 + 𝐺𝑚 (34)

Supported by experimental information, the Zn in the Cu6Sn5 is presumed to reside on the

second sublattice, then:
𝐶𝑢6𝑆𝑛5 1 2 3 0
𝐶𝑢6 𝑆𝑛5 1 2 3 0
𝐶𝑢6 𝑆𝑛5 1 2 3 𝐶𝑢6 𝑆𝑛50
𝐺𝑚 (𝑇) = 𝑌𝐶𝑢 𝑌𝐶𝑢 𝑌𝑆𝑛 𝐺𝐶𝑢:𝐶𝑢:𝑆𝑛 + 𝑌𝐶𝑢 𝑌𝑆𝑛 𝑌𝑆𝑛 𝐺𝐶𝑢:𝑆𝑛:𝑆𝑛 + 𝑌𝐶𝑢 𝑌𝑍𝑛 𝑌𝑆𝑛 𝐺𝐶𝑢:𝑍𝑛:𝑆𝑛

𝑋𝑆 𝐶𝑢6 𝑆𝑛5
2
+0.3334𝑅𝑇(𝑌𝐶𝑢 2
𝑙𝑛𝑌𝐶𝑢 2
+ 𝑌𝑆𝑛 2)
𝑙𝑛𝑌𝑆𝑛 + 𝐺𝑚 (35)

The solubility limit of Zn in the γ-Cu5Zn8 phase depends strongly on temperature and
changes from 61 to 63 at.%-Zn at 300K to 56–69 at.%-Zn at 800K. On the other hand, the solubility
of Sn in this phase is negligible. The four-sublattice model, (Cu,Zn)0.15385:(Cu,Zn)0.15385:
(Cu)0.23076:(Zn)0.46154, was used and its Gibbs free energy model is given by Eq. 36:
γ−Cu5Zn8 1 2 3 4 0
γ−Cu5 Zn8 1 2 3 4 0
γ−Cu5 Zn8
𝐺𝑚 (𝑇) = 𝑌𝐶𝑢 𝑌𝐶𝑢 𝑌𝐶𝑢 𝑌𝑍𝑛 𝐺𝐶𝑢:𝐶𝑢:𝐶𝑢:𝑍𝑛 + 𝑌𝑍𝑛 𝑌𝐶𝑢 𝑌𝐶𝑢 𝑌𝑍𝑛 𝐺𝑍𝑛:𝐶𝑢:𝐶𝑢:𝑍𝑛

1 2 3 4 0 5 γ−Cu Zn
8 1 2 3 4 05 γ−Cu Zn
8
+𝑌𝐶𝑢 𝑌𝑍𝑛 𝑌𝐶𝑢 𝑌𝑍𝑛 𝐺𝐶𝑢:𝑍𝑛:𝐶𝑢:𝑍𝑛 + 𝑌𝐶𝑢 𝑌𝐶𝑢 𝑌𝐶𝑢 𝑌𝑍𝑛 𝐺𝑍𝑛:𝑍𝑛:𝐶𝑢:𝑍𝑛

1 1 1 1 )
+0.15385𝑅𝑇(𝑌𝐶𝑢 𝑙𝑛𝑌𝐶𝑢 + 𝑌𝑍𝑛 𝑙𝑛𝑌𝑍𝑛
2 2 2 2 )
+0.15385𝑅𝑇(𝑌𝐶𝑢 𝑙𝑛𝑌𝐶𝑢 + 𝑌𝑍𝑛 𝑙𝑛𝑌𝑍𝑛
γ−Cu5 Zn8
+ 𝑋𝑆𝐺𝑚 (36)

For the case of the γ-Cu5Zn8 , the Gibbs excess energy is equal to zero.

28
 3.1.2 Kinetic Modelling of the Cu-Sn-Zn system

I. Analytical Model

The ternary alloy system Cu-Sn-Zn kinetic database was assessed and evaluated based on
different parameters and experimental results published in the literature. Some of the parameters
were optimized in this work using the ThermoCalc-PARROT module.

Due to the instability of some phases under standard pressure and temperature
conditions, experimental data of the diffusion of elements in theses phases cannot be found in the
literature. Due to these difficulties, theoretically self-diffusion coefficients were calculated by use
of the Langmuir-Dushman equation:

𝑄
𝑄𝑎2
𝐷= 𝑒 −𝑅𝑇 (37)
𝑁0 ℎ

Where 𝑎 is the lattice constant, 𝑁0 is Avogadro´s number, and ℎ is Planck´s constant. In

general a good agreement is found from the Langmuir-Dushman equation when correlated with
the activation energy. Many systems of diffusion metal pairs obey this formula with some
precision. Its very simple form provides opportunity to predict the diffusivity in some abnormal
structures, e.g. metastable structures if values of 𝑄 and 𝑎 are given.

From the relation proposed by Askill [28], Sherby and Simnad [29] had reasonable success
correlating the activation energy for self-diffusion in pure metals with melting point, structure
and number of valence electrons:

𝑄 = 𝑅𝑇𝑚 (𝐾0 + 𝑉) (38)

Where 𝑅 is the gas constant, 𝑉 is the number of valence electrons, and 𝐾0 =14, 17, 17 and
21 for the bcc, fcc, hcp and diamond structure, respectively.

Le Claire [30] improved the relationship evidencing the importance of the contribution of
the valence value:

𝑄 = 𝑅𝑇𝑚 (𝐾0 + 1.5𝑉) (39)

29
 Where in this case K=13, 15.5 and 20 for bcc, fcc hcp and more open covalently bonded
structures, respectively.

These approaches were used to the assessment of the β phase in this work.

The modeling of stoichiometric intermetallic phases are considered of high complexity by

the database developer community due to its complex diffusion mechanisms. Generally only a
single inter-diffusion coefficient is available.

For the modelling of the ε-Cu3Sn phase one assumes no composition dependence of
mobility parameters; all the parameters were set equal; use of “GENERAL” diffusion model in
DICTRA where the mobilities on the individual sublattices are summed [70]:

Example: (A,B)(A,B)2

𝑝ℎ𝑎𝑠𝑒 𝑦1
𝑀𝐴 = (𝑦𝐴1 𝑦𝐵2 𝐴𝑀𝐴:𝐵
1
+ 𝑦𝐵1 𝑦𝐴2 𝐴𝑀𝐵:𝐴
1 𝐴
) 𝑅𝑇 (40)

And
𝑅𝑇
𝐷𝐴∗ = (𝑦1𝐴 𝑀1𝐴 + 𝑦1𝐴 𝑀2𝐴 ) 𝑢(𝐴) (41)

The diffusion model for the ternary intermetallic followed a similar approach:

Example: (A%, B, Va)(A, B%, Va)C2

𝑅𝑇
𝐷𝐴∗ = (𝑦1𝐴 𝑀1𝐴 + 𝑦2𝐴 𝑀2𝐴 ) 𝑢(𝐴) (42)

𝑅𝑇
𝐷𝐵∗ = (𝑦𝐵1 𝑀𝐵1 + 𝑦𝐵2 𝑀𝐵2 ) 𝑢(𝐵) (43)

𝑅𝑇
𝐷𝐶∗ = ( 𝑀𝐶3 ) 𝑢(𝐶) (44)

These models were then taken into account and applied for the case of ε-Cu3Sn and η-
Cu6Sn5:

ε-Cu3Sn: (Cu,Sn)0.75(Cu,Sn,Zn)0.25

η-Cu6Sn5: (Cu)0.3333(Cu,Sn,Zn)0.3334(Sn)0,3333

30
 II. Ab initio Model

In order to accurately the model the diffusion and gain a better understanding about the
diffusion in the η-Cu6Sn5 phase, DFT calculations were done by Dr. D. Urban to track the less
energetic and hence most likely path of a foreign atom in the phase.

Figure 8 shows the energy to replace a vacancy for atoms of the Cu-Sn-Zn system in
different intermetallic compounds.

Figure 8. Energy of substitution of an atom by a vacancy in different intermetallic compounds of

the Cu-Sn-Zn system.

One can note an interesting behavior for the η-phase family. The energy of substitution of
a Cu atom for a vacancy in these phases is closer to 0, equal to 0 or even smaller. It means that
some of these substitutions are likely to spontaneously occur at slightly higher temperature or
even for 0K. These results give us a clue about on which lattice site diffusion is likely to occur and
therefore should be considered in the model.

Figure 9 shows the most likely structure of η-Cu6Sn5 evidencing the symmetric positions
of Cu in the structure calculated.

31
 1

3
5
4

Figure 9. Position of Cu in η1-Cu5Sn4 phase calculated at 0K. Bigger spheres represent a Cu element
and smaller ones an Sn element. Different colors distinguish the different symmetric position of Cu in the
structure.

From Figure 9 one can note that we have 20 Cu positions and among them, 5 different
symmetric ones.

The energy of vacancy formation of each different symmetric position was calculated and
is shown in Table 3.

Table 3. Energy of vacancy formation for each Cu position in the

Type Neighbor Eform [vacancy]

1 2,3,5,5’ 0.25eV
2 1,4,5,5’ 0.37eV
3 1,4,5 0.33eV
4 2,3,5 0.41eV
5 1,1’,2,2’,3,4 0.02eV

Figure 10 shows one suggested, very likely diffusion path in the Cu sublattice according to
previous DFT calculations.

Figure 10. Possible diffusion path in the Cu sublattice of the η1-Cu6Sn5 phase.

32
 The result shown in Figure 10 was used to model the mobility of Cu and Sn in the η-Cu6Sn5
phase on the correct lattice site.

3.1.3 Thermodynamic Modelling of the Cu-Ni-Si system

The thermodynamic modelling of the Cu-Ni-Si system was done in a previous work and is
quickly reviewed in this report.

A commercial databases of the Cu-Ni-Si alloy system is available for Pandat®. For the
ThermoCalc software the TTNi8 database contains the Cu-Ni-Si system but is focused on the Ni
rich side, which means, that the relevant phases are not modelled. In the published literature we
can find assessments done by Mittienen[31] and Wang et al [32]. However, the description in
these publications takes into account only measurements at relatively high temperatures and
therefore results in problems when temperatures below 700°C are regarded. A description for
lower temperatures is given by Lu et al. [33]. The used parameters in this work were then
evaluated and taken from references. The parameters chosen were choosing the ones that
correspond better the and conditions for the calculations that should be done.

3.1.4 Kinetic Modelling of the Cu-Ni-Si system

The kinetic modelling of the Cu-Ni-Si system was concentrated on the disordered fcc phase
(α-phase). The α-phase is the most important one because it represents the matrix of the alloy in
study and hence, in order to calculate the precipitation of the ordered phases in the alloy of study,
it is only necessary to describe each element’s mobility in this phase.

The mobility parameters of Cu, Ni and Si and their binary and ternary interaction in the α-
phase of the Cu-Ni-Si system were assessed by H. Xu et al [34] and were used to write the kinetic
database in this work. Table 4 shows the assessed parameters.

Table 4. Assessed atomic mobility parameters of α Cu-Ni-Si alloys.

Mobility Parameters (J/mol) Reference

Mobility of Cu
𝐶𝑢
𝑄𝐶𝑢 -205872.0-82.52*T [35]
𝑁𝑖
𝑄𝐶𝑢 -263689.7-77.04*T [36]
𝑆𝑖
𝑄𝐶𝑢 -155634.9-77.04*T [37]
𝐶𝑢,𝑁𝑖
𝑄𝐶𝑢 14204.2-4.98*T [36]
𝐶𝑢,𝑆𝑖
𝑄𝐶𝑢 415375.2 [37]
𝑁𝑖,𝑆𝑖
𝑄𝐶𝑢 -132185.9 [34]
Mobility of Ni

33
 𝐶𝑢
𝑄𝑁𝑖 -229936.8-72.83*T [36]
𝑁𝑖
𝑄𝑁𝑖 -271377.6-81.79*T [38]
𝑆𝑖
𝑄𝑁𝑖 -155634.9-81.03*T [37]
𝐶𝑢,𝑁𝑖
𝑄𝑁𝑖 39620.8-24.19*T [36]
𝑁𝑖,𝑆𝑖
𝑄𝑁𝑖 -104334.0+279.94*T [37]
Mobility of Si
𝐶𝑢
𝑄𝑆𝑖 -178667.5-95.02*T [37]
𝑁𝑖
𝑄𝑆𝑖 -243008.0-89.15*T [37]
𝑆𝑖
𝑄𝑆𝑖 -155634.9-81.03*T [37]
𝐶𝑢,𝑆𝑖
𝑄𝑆𝑖 11889.5 [37]
𝑁𝑖,𝑆𝑖
𝑄𝑆𝑖 -342901.5 [37]
𝐶𝑢,𝑁𝑖
𝑄𝑆𝑖 -99513.4 [34]

3.2 Microstructure and Composition Measurements

The surface microstructure and composition of the Cu-Sn-Zn alloys were measured using
the scanning electron microscopes (SEM) from HITACHI S-3400 equipped with a EDX Oxford INCA
Energy 250 EDX measuring system and a ZEISS supra 40 VP coupled with an EDAX Genesis II EDX
measuring system. The energy dispersive X-ray analysis (EDX) was used to measure the general
composition of the alloys.

The general compositions were measured on the surface of the Cu-Sn-Zn coatings after
cleaning with ethanol in an ultrasonic bath. The SEM was used to analyze the samples with a
voltage of 20keV in a spot on average of 200μm2. Traces of elements which were likely prevenient
from the substrate as iron and nickel, were systematically neglected from the quantitative
measurements but their qualitative relevance where noted and taken into account.

4. RESULTS AND DISCUSSION

4.1 Cu-Sn-Zn Alloys

In this chapter, the obtained experimental and simulation results referring to the Cu-Sn-
Zn are presented. In the following two chapters (4.1.1 and 4.1.2), one finds the validation of the
simulated results by comparing them with experimental results found in the literature.
Additionally, discussions about the simulation results and their comparison with obtained ones
from other emerging simulation methods are reported aiming to deepen the knowledge in
complementary simulation methods.

34
 4.1.1 Thermodynamic Simulations (Cu-Sn-Zn)

Based on the model showed in the section 3.1.1, the parameters were assessed and are
listed in Table 5 in the APPENDIX, section 8. Thermodynamic calculations were then carried out
and compared with experimental data found in the literature. Figure 11 shows the activity of Zn
in liquid for different conditions and literature data.

1,0
Peng and Mikula (1997) - Cu:Sn(w%) = 1 T=1023K
0,9 Jantzen and Spencer (1998) - Cu:Sn(w%) = 2
Cu:Sn (w%) = 1 - Calculated
Cu:Sn (w%) = 2 - Calculated
0,8

0,7
Activity of Zn

0,6
lt
0,5 aou
R
0,4

0,3

0,2

0,1

0,0
0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0
Mole fraction, Zn

Figure 11. Comparisons of Zn activity in liquid phase at 1023K for conditions of x(Cu)/x(Sn)=1
(blue) and x(Cu)/x(Sn)=2 (red) composition intersection and with experimental data superimposed. Solid
lines represents calculations results with our database and the dots data from Jantzen and Spencer (1998)
[39] and Peng and Mikula (1997) [40].

2,0E-2
x(Sn)=0.02 - Calculated
1,8E-2 x(Sn)=0.04 - Calculated
x(Sn)=0.06 - Calculated
Activity of Zn in Liquid phase

1,6E-2 x(Sn)=0.08 - Calculated

x(Sn)=0.02 - Experimental (Ref)
1,4E-2 x(Sn)=0.04 - Experimental (Ref)
x(Sn)=0.06 - Experimental (Ref)
1,2E-2 x(Sn)=0.08 - Experimental (Ref)

1,0E-2 T=1373K

8,0E-3

6,0E-3

4,0E-3

2,0E-3
Ref: S. Sugino, S. Nakamura and H. Hagiwara:
J Japan Inst. Metals, 50 (1986) 462-66.
0,0
0,00 0,02 0,04 0,06 0,08 0,10
Mole fraction, Zn

35
 Figure 12. The solid lines are calculations of the activity of Zn in different alloys of the Cu-Sn-Zn
system. The points shown are experimental data from S. Sugino, S. Nakamura and H.Hagiwara (1986)[41].

Figure 11 shows excellent agreement between the calculated and experimental values for
the whole Zn range analyzed. Figure 12 demonstrates that the calculated results of Zn activity
match the experimental observations on the Cu rich side.

The Figure 13 shows the enthalpy of mixing of the liquid phase at 1023K for the section of
x(Sn)-x(Cu)=0.

0
Calculated
M. Peng, A. Mikula, J. Alloys Compd. 247 (1997) 185.
-500
Enthalpy of mixing [J/mol]

T=1023K
x(Sn)-x(Cu)=0
-1000

-1500

-2000

-2500

-3000
0,0 0,2 0,4 0,6 0,8 1,0
Mole fraction , Zn

Figure 13. Enthalpy of mixing of liquid at 1023K for condition x(Sn)-x(Cu)=0 with experimental
values from M.Peng and A. Mikula (1997) [40] superimposed.

Figure 13 shows good qualitative agreement evidenced by the shape of the calculated
curve in comparison with the experimental points. Quantitatively, one can note that, despite of
little deviations of the calculated curves from the expermental data points in the region with few
Zn, the results are in good numerical agreement at the Zn-rich side.

In order to evaluate and better understand the stability of the principal matrix phases of
the Cu-Sn-Zn system, the Gibbs energy of mixing of the fcc and bcc phases were calculated. See
Figure 14 and 15.

36
 a) b)
0,00 -1,240E+04

1,00 -9338
-6275
-3213
-150,0
0,25
2913
0,75

Sn
]
on
5975

cti

[
Mo
9038

Fra

le
1,210E+04
0,50

ole

Fra
0,50

[M

cti
on
Zn

]
0,75
0,25

1,00
0,00
0,00 0,25 0,50 0,75 1,00
Cu [Mole Fraction]

Figure 14. Simulated Gibbs energy of mixing for fcc phase in Cu-Sn-Zn system at 500K. a) Ternary
surface plot and b) its projection. The reference states for all elements are the fcc phase.

a) b)
0,00 -1,470E+04

1,00 -1,178E+04
-8850
-5925
-3000
0,25
-75,00
0,75

Mo
]
[Zn

2850

le 5775
on

fra 8700
cti

0,50 c
tio
fra

0,50 n
le

[Sn
Mo

0,75
0,25

1,00
0,00
0,00 0,25 0,50 0,75 1,00
Mole fraction [Cu]

Figure 15. Simulated Gibbs Energy of mixing for bcc phase in Cu-Sn-Zn system at 500K. a) Ternary
surface plot and b) its projection. The reference states for all elements are the bcc phase.

One can see from Figure 14 that at 500K the Gibbs energy of mixing is positive on the Cu
depleted side, and it reaches its maximum at 50at%Sn-50at%Zn. This shows that the fcc phase is
less stable the closer we are to this composition. The opposite occurs on the Sn depleted side, as
it reaches its minimum around 50at%Cu-50at%Zn. This is where the Gibbs energy of mixing
reaches its lowest values, which means that the fcc would be more stable the closer to this
composition when in a system with more other phases.

Similar behavior is shown in Figure 15. The bcc phase shows positive values in the region
of the Sn rich side reaching its maximum around compositions of 60Sn-25Zn-15Cu at%. Its
minimum occurs around 55Cu-45Zn-5Sn at% where the phase is also stable according to the
published (or calculated) phase diagrams.

37
 In order to compare both the CALPHAD and Ab Initio calculation methods, the Gibbs
energy of mixing of the fcc and bcc phases at temperatures close to 0K were calculated. The energy
of formation of these phases was calculated by Dr. Daniel Urban using 16 atom SQS cells. The
results of both calculations are shown in Figure 16 and 17.

a) b)
0,00 -1,080E+04

1,00 -7575
-4350
-1125
2100
0,25
5325
0,75

Sn
]
on
8550

cti

[M
1,178E+04

Fra

ole
1,500E+04
0,50

ole

Fra
0,50

[M

cti
on
Zn

]
0,75
0,25

1,00
0,00
0,00 0,25 0,50 0,75 1,00
Cu [Mole Fraction]

0,00 -5600

1,00 -862,5

c) d) 3875
8613
1,335E+04
0,25
1,809E+04
0,75

Sn
]
on

2,283E+04
cti

[M
2,756E+04
Fra

ole
3,230E+04
0,50
ole

Fra
0,50
[M

cti
on
Zn

]
0,75
0,25

1,00
0,00
0,00 0,25 0,50 0,75 1,00
Cu [Mole Fraction]

Figure 16. Simulated Gibbs energy of mixing for fcc phase in the Cu-Sn-Zn system at 1K through
CALPHAD method b) its projection. The reference states for all elements are the fcc phase. c) Relative energy
of formation of the disordered fcc phase calculated through Ab Initio method and d) its projection.

One can see from Figure 16 a) and c) that the shape of the surfaces does not really agree.
For the results from CALPHAD method, Figure 16 a) and b), the binary fcc Cu-Zn is negative in all
the ranges of composition whereas the Cu-Sn is negative for compositions closer to the Cu rich
side. In contrast, the thermodynamic calculations show positive values for the Sn-Zn binary
system.

With the DFT method, calculations shown in Figure 16 c) and d), show negative values for
the Gibbs energy only for Cu-Zn, while the mixing of fcc Sn-Zn and fcc Cu-Sn is positive.

38
 a) b)
0,00 -1,490E+04

1,00 -1,151E+04
-8125
-4738
-1350
0,25
2038
0,75

Sn
]
on
5425

cti

[M
8813

Fra

ole
1,220E+04
0,50

ole

Fra
0,50

[M

cti
on
Zn

]
0,75
0,25

1,00
0,00
0,00 0,25 0,50 0,75 1,00
Cu [Mole Fraction]

c) d) 0,00 -9200

1,00 -3750
1700
7150
1,260E+04
0,25
1,805E+04
0,75

Sn
]
on

2,350E+04
cti

[M
2,895E+04
Fra

ole
3,440E+04
0,50
ole

Fra
0,50
[M

cti
on
Zn

]
0,75
0,25

1,00
0,00
0,00 0,25 0,50 0,75 1,00
Cu [Mole Fraction]

Figure 17. The simulated Gibbs energy of mixing for the bcc phase in the Cu-Sn-Zn system at 1K
through CALPHAD method b) its projection. The reference states for all elements are the bcc phase. c)
Relative energy of formation of the disordered bcc phase calculated through Ab Initio method d) its
projection.

One can see from Figure 17 a) and c) that the shape of the energy surfaces differs between
the phases. For the results from CALPHAD method, Figure 17 a) and b), the binary bcc Cu-Zn and
bcc Cu-Sn are negative in all the composition ranges of the binary alloys. On the other hand we
have a complete positive energy of mixing in the Sn-Zn binary system.

The DFT calculations shown in Figure 17 c) and d) again only show negative values for the
bcc Cu-Zn system, while for the bcc Sn-Zn and bcc Cu-Sn phases the values are positive.

The Figures 18, 19 and 20 show the binary equilibrium phase diagram calculated using
the assessed thermodynamic database in this work in comparison with the experimental ones
provided by the ASM International association [18].

39
 a) b)

Figure 18. a) Calculated binary Sn-Zn phase diagram. b) Experimental phase diagram provided by
ASM International association.

a) b)

Figure 19. a) Calculated binary Cu-Sn phase diagram. b) Experimental Cu-Sn phase diagram
provided by ASM International association.

40
 Figure 20. a) Calculated binary Cu-Zn phase diagram. b) Experimental Cu-Zn phase diagram
provided by ASM International association.

The Figures 18, 19 and 20 show that the calculated binary sections of the ternary system
Cu-Sn-Zn are in good agreement with the experimental data provided by ASM International. In
order to verify the same consistence on the ternary interaction parameters, isothermal sections
of the ternary phase diagram were plotted and experimental data from the literature were
superimposed, see Figure 21.

a) b)

 Cu3Sn 

 + + Liq
 + Liq
 + Liq
 + Epsilon + Liq
Epsilon + Liq
HCP_Zn + Epsilon + Liq
 + + Cu3 Sn
 + Cu3Sn

Figure 21. Calculated isothermal section of the ternary diagram of the Cu-Sn-Zn system at a) 523K
and b) 873K with experimental data from K. Yagamuchi, I. Nakamura and R. Kenkyusho-Iho (1932) [45] and
Chou and Chen [46] superimposed.

The calculated isothermal sections at 523K and 873K of the ternary diagram shown in
Figure 21 are in good agreement with the experimental results obtained by Yamaguchi and
41
Nakamura and Chou and Chen which demonstrate a high general confidence level in the
parameters implemented in the thermodynamic database. However, this confidence can be
questionable as we have discrepancy at low temperature.

4.1.2 Diffusion Simulations (Cu-Sn-Zn)

In this section, the assessment optimization, evaluation and validation of the ternary Cu-
Sn-Zn kinetic database, based on different parameters and experimental results published on the
most recent literature, are shown.

The PARROT module of ThermoCal was used to optimize the variables, and the DICTRA
module was used to calculate the diffusion behavior of the alloy. The phases taken in to account
in this work were the ones previously identified as most relevant for CuSnZn coatings: α-Cu, bct-
Sn, β, ε-Cu3Sn and η-Cu6Sn5.

I. α- Phase

The mobility parameters of the binary Cu-Sn and Cu-Zn α-Cu phases are the most divulged
in the literature and recent reassessments were carried out by Z.P. Jin et al. [47], L. Shuhong et al.,
G. Ghosh [48] and L. Zhou et al. [49]. Some experiments proposed in the literature were simulated
trough the ThermoCalc DICTRA module using these parameters. The results and comparison of
these simulations are shown in Figure 22.

a) b)
0,07
Simulated
Experimental Points Simulated
0,06 0,25 Experimental Points
Mole Fraction (Zn)
Mole Fraction (Sn)

0,05 0,20

0,04 (100%at)Cu
Cu(0,07%at)Sn 0,15
(100%at)Cu Cu(29.5%at)Zn
0,03
0,10
0,02

T: 1023K 0,05
0,01 T: 1073K
time: 691h time: 691h
0,00 0,00
0,000 0,001 0,002 0,003 0,004 0,005 0,006 0,007 0,001 0,002 0,003 0,004 0,005 0,006 0,007
Distance (m) Distance (m)

Figure 22. Simulated concentration profile of a) Cu/Cu-29.5% at Zn at 1057K for 2487600s (691h)
and b) Cu/Cu-0.07%atSn at 1023K for 540000s (150h) superimposed by experimental points obtained by
a) Z.P. Jin et al. [50] and b) L. Zhou et al. [49].

Good agreements were obtained for the two simulated diffusion binary couples shown in
Figure 22. This reveals the accuracy of the binary interaction parameters for these binary systems.
In order to evaluate the ternary interaction parameters, the experiments proposed and carried

42
out by J. S. Kirkaldy, R. J. Bringham and D. H. Weichert where simulated and compared with their
results and are shown in Figures 23 and 24.

a) b)
Cu-4Sn/Cu-4Sn-5.5Zn [at%] - Diffusion in  -phase Cu-5Zn/Cu-4Sn-5.5Zn [at%] - Diffusion in  -phase
0,06 0,06
t = 40h
T= 1094K
0,05 0,05
Mole Fraction [Sn]

0,04 0,04
t = 40h

Mole Fraction
T= 1094K
0,03 0,03

0,02 0,02

Zn Zn Simulated Sn Sn simulated
Sn Sn Simulated Zn Zn simulated
0,01 0,01
[Ref] : Acta Metalllurgica (1965)
[Ref] : Acta Metalllurgica (1965)
J.S Kirkaldy; R.J Brigham; D.H. Weichert
J.S Kirkaldy; R.J Brigham; D.H. Weichert
0,00 0,00
0,0000 0,0002 0,0004 0,0006 0,0008 0,0010 0,0012 0,0014 0,0016 0,0000 0,0002 0,0004 0,0006 0,0008 0,0010 0,0012 0,0014 0,0016

Distance [m] Distance [m]

Figure 23. Simulated penetration curves at 821°C for 40h of a) Cu-4at% Sn/Cu-4at%Sn- 5.5at%Zn
couple and b) Cu-5at%Zn/Cu-4at%Sn-5.5at%Zn couple superimposed with experimental results from J. S.
Kirkaldy, R. J. Bringham and D. H. Weichert.

a) b)
Cu-6Sn/Cu-6Sn-5Zn [a%] - Diffusion in  -phase Cu-5Zn/Cu-5.5Sn-5Zn [a%] - Diffusion in  -phase
0,08 7
T = 498°C T = 498°C
0,07 t = 1.2*106 s t = 1.2*106 s
6 (2 weeks)
(2 weeks)
0,06
5
Atomic Fraction

Atomic percent

0,05
4
0,04
3
0,03

2
0,02
Sn Simulated Sn
Zn Simulated Zn Sn Simulated Sn
0,01 1 Zn Simulated Zn
[Ref] : Acta Metalllurgica (1965) [Ref] : Acta Metalllurgica (1965)
J.S Kirkaldy; R.J Brigham; D.H. Weichert J.S Kirkaldy; R.J Brigham; D.H. Weichert
0,00 0
0,0 5,0E-5 1,0E-4 1,5E-4 2,0E-4 0,0 5,0E-5 1,0E-4 1,5E-4
Distance [m] Distance [m]

Figure 24. Simulated penetration curves at 498°C for 2 weeks (1.2*10 4s) of a) Cu-6at% Sn/Cu-
6at%Sn- 5at%Zn couple and b) Cu- 5at%Zn/Cu-5.5at%Sn-5at%Zn couple superimposed with experimental
results from J. S. Kirkaldy, R. J. Bringham and D. H. Weichert.

Figure 24 shows that for relatively high temperatures, the simulated mobility of Zn is in
good agreement with experimental values both qualitatively and quantitatively. Nevertheless, the
simulated mobility of Sn for the same temperature seems a bit faster than observed
experimentally. Despite this, the simulated curves show a good qualitative behavior.

Figure 24 shows that for lower temperatures the quantitative behavior of the mobility of
both elements is acceptable. The behavior of both elements is in good agreement with
experimental values with exception of the mobility of the Zn element in Figure 24 b). This different
behavior comes from the mobility parameter of interaction of Zn diffusion in the Cu-Zn and Cu-
43
Sn-Zn fcc disordered phase, which needs to be better evaluated and optimized in order to obtain
better kinetic simulation results.

II. β – Phase

The diffusion process in the β phase is of importance due to its primary formation during
the solidification of the majority of the Cu-Sn-Zn alloy system and due to its presence under certain
conditions of processing and usage of these alloys [51].

Mobility parameters of the copper β phase is hardly found in the literature due to its
natural instability at room temperature and its small composition solubility field as can be seen
on the binaries and ternary diagrams showed in Figures 19, 20 and 21.

Due to the rare presence of optimized and assessed parameters in the literature, the
mobility parameters of the β phase of the Cu-Sn-Zn alloys system were assessed and optimized in
this work.

Different from pure cooper, which has an fcc crystal structure at room temperature, pure
tin and pure zinc have BCT and HCP phases, respectively. Hence, there are no experimental
measurements of self-diffusion of the β-Sn and β-Zn phases available.

In this case, using the Langmuir-Dushman equation, X. J. Liu, C. P. Wang and J. J. Han [52]
one can calculate the theoretical self-diffusion through the theoretical β-Sn and β-Zn phases.
Their results are shown in Table 6.

Table 6. Theoretically calculated self-diffusion of β Sn and Zn.

bcc
Element (stable phase) D0 (10-4m2s-1) Q (kJ/mol)
Zn (hcp) 0.17 67.54
Sn (bct) 0.15 40.30

Apart from self-diffusion, another important parameter is the intrinsic diffusion of foreign
elements in these unstable phases. To overcome this problem, the tracer diffusion of Cu in
theoretical β-Sn and Cu in theoretical β-Zn were estimated from the difference between the values
of the Cu diffusion in the stable phases of Zn and Sn [53], hcp and bct, respectively, and the values
of self-diffusion of Sn and Zn in its stable phases. These base values and the estimation are shown
in Table 7.

44
 Table 7. Base for estimation and estimated Cu tracer-diffusion parameter in β-Sn and β-
Zn

Q(J/mol) D0 (m2s-1) Q(J/mol) D0 (m2s-1)

Diffusing Element bct-Sn β-Sn
Sn -22800 1.4e-4 -40300 1.5e-4
Cu -33020 2.4e-7 -50520 3.61e-7
hcp-Zn β-Zn
Cu -125300 2.0e-4 -94940 1.91e-4
Zn -97900 2.6e-5 -67540 1.7e-5

Based on these parameters, the assessment of the interaction parameter of the atomic
mobility in the β-(Cu-Zn) and β-(Cu-Sn) alloys were conducted in the PARROT module of the
DICTRA software supported by the thermodynamic database assessed in this work. The
experimental support data of interdiffusion in β phase of Cu-Sn was taken from previews work of
H. Mitani et al.[54] while the interdiffusion of β phase of Cu-Zn was taken from Landrergren et al.
[55]. The results of the optimization with experimental data superimposed are shown in Figure
25 and Figure 26.

a) b)
1E-9
1073K 973K 873K 773K 1073K 973K 873K 773K
Optimized this work 1E-8 Optimized in this work
Ref: Ulf S. Landergren et. al
Interdiffusion Coeficient [m2s-1]

Interdiffusion Coeficient [m2s-1]

Ref: Ulf S. Landergren et. al

1E-9

1E-10
1E-10

1E-11

1E-12
1E-11
1E-13

1E-14
DC(BCC,Cu,Cu,Zn) DC(BCC,Cu,Cu,Zn)
1E-12 1E-15
0,42 0,44 0,46 0,48 0,50 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8
Mole fraction of Zn mole fraction of Zn [%]

Figure 25. Comparison between the calculated and experimentally measured interdiffusion
coefficients in the β Cu-Zn system at 773–1073K. The solid lines are the calculated values from the
parameters obtained in the present work, while the dots are experimental results obtained by Landergren
et al. [55]. a) Range of interest and b) full range.

45
 a) b)
1E-8
874K 907K 926K 973K 993K 874K 907K 926K 973K 993K
Optmized in this work
Optmized in this work

Interdiffusion Coeficient [m2s-1]

Interdiffusion Coeficient [m2s-1]

1E-10
1E-9

1E-10

1E-11
1E-11
x(Sn)

Ref: Yokota et. al x(Sn)

Ref: Yokota et. al
1E-12
0,13 0,14 0,15 0,16 0,17 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0
mole fraction of Sn mole fraction of Sn

Figure 26. Comparison between the calculated and experimentally measured interdiffusion
coefficients in the β Cu-Sn system at 874–993K. The solid lines are calculated values from the parameters
obtained in the present work, while the dots are experimental results obtained by M. Yokota, N. Masateru
and M. Hiroyasu[54]. a) Range of interest and b) full range.

One can see in Figure 26 b) that the values of the interdiffusion coefficient show a constant
behavior after a certain amount of Sn. This shape comes from the Gibbs energy curve referenced
to the bcc phase. Figure 27 shows the curves of the Gibbs energy at this temperature range.

2000
T=993K
T=874K
0
GMr (BCC) [J/mol]

-2000

-4000

-6000

-8000
x(Sn) 
-10000 x(Sn) 

0,0 0,2 0,4 0,6 0,8 1,0

Sn [Mole Fraction]

Figure 27. Gibbs energy referenced to the β phase on the Cu-Sn system in function of Sn content,
where the tangent law is applied.

The shape of the curve implies that a new β phase with another composition is forming
according to the tangent rule. Therefore, when optimizing the interdiffusion coefficient, the values
of the interdiffusion coefficients become constant at the tangent interception, which corresponds
to compositions between 0.31at%Sn and 0.33at%, depending on the temperature.

46
 The optimized interdiffusion coefficient of the β Cu-Zn system in Figure 26 shows good
agreement between the experimentally measured results from Landergren et al. in the whole
range of temperature studied.

Figure 26 shows good agreement between the optimized values and experimental values
for temperatures above 926K, for lower temperatures, 874K and 907K, one can note that the
numerical values found in this work are close to the experimental ones but the trend of the curve
qualitatively shows that for these temperatures the addition of Sn lowers the inter-diffusion
coefficient of Sn in the alloy which wasn´t predicted by the optimization. Finally, the reduced sum
of squares changed in the optimization is of 8.14*10-21 for the Cu-Zn system and 5.27*10-21 for the
Cu-Sn system.

The finally obtained atomic mobility parameters of β Cu-Zn and β Cu-Sn alloys are listed
in Table 8.

Table 8. Atomic mobility parameters of β Cu-Sn-Zn alloys assessed in the present work

Mobility Parameters (J/mol) Reference

Mobility of Cu
𝐶𝑢
𝑄𝐶𝑢 -151800-79*T Calculated in this work
𝑆𝑛
𝑄𝐶𝑢 -50520+R*T*LN(3.61E-07) Estimated in this work
𝑍𝑛
𝑄𝐶𝑢 -94940+R*T*LN(1.91E-04) Estimated in this work
𝐶𝑢,𝑍𝑛
𝑄𝐶𝑢 -37389.47+11.99*T Optimized in this work
𝐶𝑢,𝑆𝑛
𝑄𝐶𝑢 123250.6+123.45*T Optimized in this work
Mobility of Zn
𝐶𝑢
𝑄𝑍𝑛 -151958+R*T*LN(4.23E-06) J. Mittinen [5]
𝑍𝑛
𝑄𝑍𝑛 -67540+R*T*LN(1.7E-05) Calculated in this work
𝐶𝑢,𝑍𝑛
𝑄𝑍𝑛 123353.37-77.60*T Optimized in this work
Mobility of Sn
𝐶𝑢
𝑄𝑆𝑛 -156195+R*T*LN(4.277E-04) J. Mittinen [5]
𝑆𝑛
𝑄𝑆𝑛 -40300+R*T*LN(1.5E-05) Calculated in this work
𝐶𝑢,𝑆𝑛
𝑄𝑆𝑛 293195.93-257.9*T Optimized in this work

In order to visualize and approve the parameters assessed in this work, the experiment
proposed in the literature by R. Resnick and R. W. Balluffi [56] were simulated using the
thermodynamic and kinetic mobility database of the β Cu-Sn-Zn phase assessed in this work. The
results are shown in Figure 28.

47
 Diffusion-Penetration Curve: ß-Brass
0,475

600°C - 2h
0,470
700°C - 16.5h
0,465 Simulation (2h - 600°C)
Simulation (16.5h - 700°C)
Atomic Fraction [Zn] 0,460

0,455

0,450

0,445

0,440

0,435
Ref : R. Resnick and R. W. Balluffi
0,430
0,000 0,001 0,002 0,003 0,004 0,005 0,006 0,007
Distance [m]

Figure 28. Diffusion-penetration curves for β brass vapor solid couples at 600°C for 2h and 700°C
for 16.5h. Dots are experimental results obtained by R. Resnick and R. W. Balluffi [56] and solid lines are the
simulation results calculated using the database assessed in this work.

Figure 28 shows that the simulations are in good agreement with the experimental
measured values of diffusion-penetration curves in β Cu-Zn brass. Due to the phase’s instability
and therefore, the lack of experimental diffusion data in the copper β-pahse, no more simulated
results could be compared with experimental values.

III. ε-Cu3Sn / η-Cu6Sn5 - Phases

Studies of the reactive diffusion between copper based alloys and Sn based alloys are
largely divulged in the literature. When processed under moderated heat treatment, one can see
that a double layer of intermetallic compounds (IMC) forms at the interface between Cu based and
Sn based alloys, where the η-Cu6Sn5 is reported to form on the Sn rich side and the ε-Cu3Sn
forming on the Copper rich side [57],[58],[59],[60]. Not only in literature but also in previous
works from Fraunhofer IWM group, IMC compounds of these phases were found between the
coating and the substrate. The diffusion through the substrate and coating is then influenced by
the presence and the development of these IMCs.

The aim of the simulation of these phenomena was to predict the kinetics of the layer
growth of the IMCs compounds as well as the behavior of element diffusion between coating and
substrate. The mobility database of the ε-Cu3Sn and η-Cu6Sn5 were studied and are shown in this
section.

The tracer and integrated diffusion coefficients of the Cu and Sn elements in the ε-Cu3Sn
and η-Cu6Sn5 intermetallic compounds were determined by A. Paul, C. Ghosh and W. J. Boettinger
[61] and used as parameters of the kinetics database in this work. The values of the tracer
diffusion of Cu and Sn elements in the IMCs are shown in the Table 9.

48
 Table 9. Tracer-diffusion of Cu and Sn in ε-Cu3Sn and η-Cu6Sn5 IMCs [61].

Q(J/mol) D0 (m2s-1) Q(J/mol) D0 (m2s-1)

Diffusing Element
ε-Cu3Sn η-Cu6Sn5
Cu 78800 1.8*10-8 80500 6.2*10-8
Sn 79700 7.9*10-10 85200 5.88*10-7

The values shown in Table 9 were used as parameters in the diffusion database of these
compounds following the model shown in section 3.1.1 supported by DFT calculations of the most
likely sublattice path shown in section 3.1.2 – II.

4.1.3 Experiences and Practical Applied Simulations (Cu-Sn-Zn)

After validation of the thermodynamic and kinetic database of the Cu-Sn-Zn system shown
in the previous chapter, (4.1.1 and 4.1.2), simulations were carried out. This chapter shows the
experimental and simulation results on the alloy of interest on the process and behavior of the
alloy studied.

First, the compositions of the commercial Cu-Sn-Zn coatings (Miralloy) were measured
and compared with the ternary diagram. These results are shown in Table 10.

Table 10. Commercial Miralloy samples composition.

Miralloy Cu [w%] Sn [w%] Zn [w%]

M2850 R1 45.64 46.05 8.32
M2850 R2 45.66 45.6 8.74
M2850 R3 48.45 44.48 7.07
M2850 R4 45.58 43.38 11.03
M2850 PK1 47.62 44.39 7.99
M2850 PK2 46.65 45.17 8.18
M2850 PK3 47.52 44.16 8.32
M2850 PK4 46.54 43.92 9.55
M2851 R1 51.83 35.2 12.97
M2851 R2 51.24 35.23 13.53
M2851 R3 48.94 38.42 12.64
M2851 R4 49.88 36.76 13.37
M2851 PK1 49.45 37.04 13.51
M2851 PK2 48.77 38.52 12.72
M2851 PK3 50 37.32 12.68
M2851 PK4 47.7 39.43 13.1

Miralloy is a commercially available cyanide-containing electrolyte to produce Cu-Sn-Zn

coatings. Due to their good properties, this range of composition is set as a goal to be reached
within the processes of cyanide-free Cu-Sn-Zn in development in this work.

49
 Cyanide-free samples processed by Fraunhofer IPA were then processed and had their
composition measured. The results of these measurements are shown in Table 11.

Table 11. Cyanide-Free samples composition

Cyanide-Free Cu [w%] Sn [w%] Zn [w%]

R1 37.55 60.81 1.64
R1.1 45.88 52.94 1.17
R1.2 49.41 43.05 7.54
R1.3* 52.52 6.49 40.98
R1.4 29.8 63.2 7
R1.5 31.83 58.22 9.95
R2 39.23 59.65 1.12
R2.1 43.39 54.5 2.11
R2.2 55.47 36.78 7.75
R2.3 35.22 41.1 23.63
R2.4 22.82 56.99 20.19
R3 37.89 62.05 0.05
R3.1 40.54 59.32 0.14
R3.2 47.5 51.42 1.08
R3.3 54.57 62.05 0.05
R3.4 35.82 60.94 3.24
R3.5 37.59 58.16 4.25
P1.6 33.35 57.21 9.44
P1.7 33.52 55.55 10.93
4.1 – V4N 50.43 36.8 12.78
5.1 – V1N 51.13 38.64 10.23
5.2 – V4N 47.87 48.55 3.58
PEG2 55.48 36.34 9.18
PEG2.1 50.66 32.91 16.43
PEG4 48.06 40.25 11.69
PEG14 46.25 47.41 6.34
* Nickel found (Probably provided from the interlayer). Measures are likely not to correspond the real
composition of the layer

An isothermal section at 250°C of the ternary Cu-Sn-Zn system was calculated. The
measured experimental composition of all samples was then superimposed on this diagram to
visualize and to better understand which stable phases are present during the process of
production of the coating. See Figure 29. One can note that the range composition of the Cyanide-
free samples differs from the Miralloy ones. Few samples present a satisfactory amount of Zinc
and in general they present a bigger amount of Sn, which is more than the amount of Cu.

50
 Cyanidfrei
Miralloy 4.1 - V4N Sn [w%] R1
5.1 - V4N 0 R1.1
M2850 R1
5.2 - V1N 100 R1.2
M2850 R2
M2850 R3 R1.3
PEG2 R1.4
M2850 R4
PEG2.1 R1.5
M2850 PK1
M2850 PK2 PEG4 R2
M2850 PK3 PEG14 R2.1
M2850 PK4 25 R2.2
R2.3
75

Cu6Sn5
M2851 R1 R2.4
M2851 R2 R3
M2851 R3 R3.1
M2851 R4 R3.2
M2851 PK1 R3.3
M2851 PK2 R3.4
M2851 PK3 50 R3.5
M2851 PK4 50 P1.6
Cu3Sn

P1.7

75
25

(Zn)
100
0
Cu [w%] 0 25 50 75 100
Zn [w%]
(Cu) CuZn Cu5Zn8 ε-Cu0,2Zn0,8

Figure 29. Isothermal section diagram at 523K of the Cu-Sn-Zn system superimposed with
experimental values

It can be noted that the results of the deposited alloys are distributed over at least 5
different fields of phase stability in the ternary diagram. The Miralloy results are concentrated in
the same field, and the cyanide-free ones spread in a bigger range and different fields. As can be
seen, the composition of the layer can be controlled over a wide range by changing the deposition
parameters. With the knowledge of the equilibrium phase composition by means of phase analysis
and modeling, further conclusions can be drawn about the properties of the different alloys.
Figure 29 also shows that the parameters applied to process the samples R1.2 and R2.2 are the
ones that result in depositions of compositions leading to the same phase field as the commercial
ones. This field corresponds to the stability of ε-Cu3Sn, η’-Cu6Sn5 and β.

Due to these results, an ideal composition range was set as Cu-44w%Sn-9w%Zn in order
to have a model alloy to calculate and predict behaviors. The result is shown in Figure 30.

51
 Cu-44Sn-9Zn [w%]
1,0
CuZn_GAMMA
Liquid
BCT_A5
0,8 Cu6Sn5
BCC_A2
Cu6Sn5_P
Cu3Sn

Phase Fraction 0,6

0,4

0,2
637°C
205°C 434°C

0,0
0 100 200 300 400 500 600 700 800
Temperature [°C]

Figure 30. Amount of phase in equilibrium over temperature for hypothetical alloy Cu-44w%Sn-
9w%Zn.

Figure 30 shows three important temperatures where transformations occur. Around

640°C we have the beginning of the alloy´s solidification at equilibrium. As previously cited, the
first phase formed is the β phase followed at around 600°C by the formation of the ε-Cu3Sn phase.
At 434°C we have the formation of the IMC η-Cu6Sn5 forming due to the detriment of the other
phases formed. Its stability goes down to 205°C where the phase is no longer stable and
transforms again into ε-Cu3Sn and bct-Sn.

In order to better understand the role of the different elements and their stability in these
phases, simulations of composition of phases over temperature, as well amount of phases over
composition, were done and are shown in Figure 31 and 32.

a) b) c)
Thermodynamic Equilibrium Composition - Cu-44Sn-9Zn [w%] alloy Thermodynamic Equilibrium Composition - Cu-44Sn-9Zn [w%] alloy
Thermodynamic Equilibrium Composition - Cu-44Sn-9Zn [w%] alloy
0,40 0,6
0,22
Amount of Element in Cu6Sn5 Phase [mol]

Cu Cu Cu
Amount of Element in BCC_A2 [mol]

0,20
Amount of Element in Cu3Sn [mol]

Zn 0,35 Zn Zn
0,5
0,18 Sn Sn Sn
0,30
0,16
0,4
0,14 0,25

0,12
0,20 0,3
0,10

0,08 0,15
0,2
0,06
0,10
0,04 0,1
0,05
0,02

0,00 0,00 0,0

0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 200 250 300 350 400 450 0 100 200 300 400 500 600

Temperature [°C] Temperature [°C] Temperature [°C]

Figure 31. Amount of element in a) β b) η-Cu6Sn5 and c) ε-Cu3Sn phases over temperature in the Cu-
44w%Sn-9w%Zn alloy

52
 Figure 31 shows that Zn is more stable in β compared to the other phases. It is important
information to better understand the tendencies of diffusion of each element when knowing the
phases present and their location as in the case of the coatings.

Figure 32. Zinc mass fraction of equilibrium in the phases of Cu-44w%Sn-9w%Zn alloy over
temperature.

Figure 32 shows that Zn is mainly stable in the β phase and is inversely proportional in β
and ε-Cu3Sn over temperature. On the other hand, Zn varies poorly its fraction in η-Cu6Sn5 over
temperature.

In order to see the Zn influence in the stability of these phases, simulations of Zn content
at the expense of Sn content were done and are shown in Figure 33.

0,6
Cu6Sn5 Cu3Sn BCC_A2
Amount Phase [mol]

0,4

0,2

T=250°C
50Cu-(50-x)Sn-xZn [w%]
0,0
0 1 2 3 4 5 6 7 8 9 10
Mass percent Zn

Figure 33. Amount of phase over mass fraction of Zn for the 50Cu–(50-x)Sn–xZn [w%] system at
250°C.

53
 Figure 33 shows the positive influence the Zn content has in the β-phase formation from
2w% on. This stabilization represents an opposite effect on the stabilization of ε-Cu3Sn and η-
Cu6Sn5 phases. One can also see a slightly bigger influence on the stabilization of η-Cu6Sn5
compared with ε-Cu3Sn up to 2w% of Zn. For bigger amounts of Zn their stability decreases at the
same rate.

In order to have a first view of the behavior of the diffusion, phase transformation and
layer growth of our real coating-substrate system, simulations of the inter-diffusion between the
deposited layer and the substrate were calculated. Figure 34 shows the micrography of the initial
state of the system and a scheme of its composition over distance.

a) b)
1,0

0,9 Cu6Sn5  Cu
Sn
0,8
Zn
0,7
Mole Fraction
0,6

0,5

0,4

0,3

0,2

0,1
t: 0h
0,0
0,0 5,0x10-6 1,0x10-5 1,5x10-5 2,0x10-5
Distance [m]

Figure 34. a) Micrography of the deposited layer; b) Concentration profile of the elements of the
coated substrate.

The substrate shown in Figure 34 a) appears in tones of yellow. The substrate is a β-Brass,
consisting mainly of β-phase. Its composition was previously measured as Cu-37at%Zn and
characterized by X-ray diffraction where only the β-phase was found. The composition of the coating
layer was introduced based on the average values of the sample compositions registered in Figure
29 whose presence are related to the same field of the commercial alloys. The predicted stable
phases in this field are in agreement with XRD measurement showing that the η-phase is the main
present phase. To simplify the process and save time, only this phase was taken in to account in
the first layer growth simulation. These microstructural and compositional features are related
and illustrated in Figure 34 b) where one can see the initial composition of the system and the
input phases in each region.

Taking in to account this initial state, simulations of the annealing behavior of the system
at 200°C for 6h 24h and 168h were done. Figure 35 shows the concentration profile for different
simulation times.

54
 0,7
Cu6Sn5  T = 200°C
0,6

0,5 Cu - 0h

Mole Fraction
Sn - 0h
Zn - 0h
0,4
Cu - 6h
Sn - 6h
0,3 Zn - 6h
Cu - 24h
Sn - 24h
0,2 Zn - 24h
Cu - 168h
Sn - 168h
0,1 Zn - 168h

0,0
0,000000 0,000005 0,000010 0,000015 0,000020
Distance [m]
Figure 35. Simulated concentration profile during aging of the coating-substrate system for
different times at 200°C.

Figure 35 shows the tendencies of the diffusion behavior of the atoms in the system. One
can see that, while the layer shows an overall shrinkage, Cu and Sn tend to diffuse to the coating
whereas Zn goes the substrate.

The results of the simulation superimposed with experimental dots previously measured
are shown in Figure 36.

a) b) c)
1,0 1,0 1,0
Cu - Simulated t=24h Cu - Simulated t=168h Cu - Simulated
t=6h
0,9 Sn - Simulated Sn - Simulated 0,9 Sn - Simulated
Zn - Simulated Zn - Simulated Zn - Simulated
0,8 Cu - Experimental 0,8 Cu - Experimental 0,8 Cu - Experimental
Sn - Experimental Sn - Experimental Sn - Experimental
0,7 Zn - Experimental Zn - Experimental 0,7 Zn - Experimental
Mole Fraction
Mole Fraction
Mole Fraction

0,6 0,6 0,6

0,5 0,5

0,4 0,4 0,4

0,3 0,3

0,2 0,2 0,2

0,1 0,1

0,0 0,0 0,0

0,0 5,0x10-6 1,0x10-5 1,5x10-5 2,0x10-5 0,0 5,0x10-6 1,0x10-5 1,5x10-5 2,0x10-5 0,0 5,0x10-6 1,0x10-5 1,5x10-5 2,0x10-5
Distance [m] Distance [m] Distance [m]

Figure 36. Simulated inter-diffusion between coating and substrate superimposed with experimental
results for a) 6h b) 24h and c) 168h.

The simulation of the layer growth shown in Figure 36 qualitatively shows good
agreement compared to the evolution of the experimental concentration profile. The experimental
dots evidence the variation of the positioning of the layer over time. The profiles of element
concentration suggests that the layer first tends to shrink for short periods of aging time and is
then followed by the growth of the layer as can be more clearly seen for long periods of time. See

55
Figure 36 c). The plot of the simulation of the layer’s position is shown in Figure 37 to illustrate
the simulated behavior.

4,0x10-6

Position of the interface [m]

3,5x10-6

3,0x10-6

2,5x10-6

2,0x10-6

1,5x10-6

101 102 103 104 105 106 107 108

time [s]

Figure 37. Simulated interface position between the deposited layer (η-phase) and substrate (β-
phase) over time

As can be seen in Figure 37 the layer position changes in the direction of shrinkage for
short aging periods, tend to grow after an hour and returns to the shrinkage behavior for aging
times longer then 24h, resulting in a general reduction in the layer thickness. This overall behavior
is not in accordance with the experimental measurements where we see a net positive growth of
the η-phase layer into the substrate for long incubation time. Despite these differences, the results
are satisfactory for a first simplified two-phase simulation. More accurate results might be
reached by making the system more complex with inputs of the other real present phases in the
layer whose diffusion coefficients of the elements imply faster mobility in those phases.

4.2 Cu-Ni-Si Alloys

In this chapter, the results of thermodynamic simulations referring to the Cu-Ni-Si system
will be presented. They were then used in the chapter 4.2.2 for the simulations of the evolutions
of precipitate distribution. From these results the mechanical properties of the alloy could be
estimated as shown in chapter 4.2.3.

4.2.1 Thermodynamic Simulations (Cu-Ni-Si)

This section presents thermodynamic calculations based on the database assessed by

Miettinen et al. and implemented in this work. With these results the knowledge of the state of
equilibrium of the phases can be obtained and basic predictions of the precipitation behavior can
be inferred.

56
 In order to obtain good kinetic results, the thermodynamic description of the matrix phase
needs to be sound, likely without abrupt changes or several local minima. Figure 38 shows the
simulated Gibbs energy of mixing for the fcc phase in the Cu-Ni-Si system at 450°C, and the
respective contour plot of the ternary composition diagram.

a) b)
0,00 -6,040E+04

1,00 -5,073E+04
-4,105E+04
-3,138E+04
-2,170E+04
0,25
-1,203E+04
0,75

Ni
]
on
-2350

[M
cti
7325

ole
fra
1,700E+04
0,50

ole

frac
0,50

[M

ti
on
Si

]
0,75
0,25

1,00
0,00
0,00 0,25 0,50 0,75 1,00
Cu [Mole fraction]

Figure 38. a) Gibbs energy of mixing for fcc phase in Cu-Ni-Si system at 450°C, and b) contour plot.

Figure 38 shows that the surface Gibbs energy doesn´t present any discontinuity or special
curved shape which could lead the stabilization of another FCC phase of different equilibrium
composition.

Figure 39 shows a ternary isopleth diagram calculated with the assessed thermodynamic
database and its comparison with experimental results found in the literature [62].

a) b)

Figure 39. Comparison between isopleth diagram found in literature [31] and the calculated with
the assessed database.

One can see that, for most of the phases, the assessed database provides results in good
agreement with further results in the literature. On the other hand, the ternary field of

57
stabilization between Ni2Si, Ni5Si2 and Fcc appears in a different shape and needs to be further
analyzed. For temperatures below 300°C, this field seems to fit the literature results better.
Further calculations were carried out keeping this in mind and assuming slight errors when
related to this field.

Aiming an understanding of the potential formation energy of hardening phases in the

Cu-Ni-Si system, the Gibbs energy of all phases in the Ni-Si binary system were calculated. The
result is shown in Figure 40.

20000
NiSi
T=450°C
Gibbs Energy [J/mol]

-20000

GM(BCC_A2)
-40000 GM(CBCC_A12)
GM(CUB_A13)
GM(FCC_A1)
GM(HCP_A3)
GM(LIQUID)
GM(S_NI2SI)
-60000 GM(D_NI2SI)
GM(NI5SI2_G)

0,0 0,2 0,4 0,6 0,8 1,0

Mole Fraction, Si

Figure 40. Simulated Gibbs energy of phases in the Ni-Si binary system.

Figure 40 evidences the more negative Gibbs energy of ordered phases Ni2Si and Ni5Si2 in
the system, suggesting its spontaneous presence in equilibrium within a large range of
composition.

The copper rich side of the Cu-Ni-Si ternary diagram and the plot of phase fraction in
equilibrium over temperature were calculated based on the thermodynamic database
implemented in this work. With these results one can see the temperatures of phase
transformation and the amount of phases present in equilibrium. These quantities show the
maximum amount expected of each phase when precipitation is completed. The results are shown
in Figure 41.

58
 a) b)
Cu-1.5Ni-0.34Si [w%]
0,030
0,028
0,026 (400,02227)

Amount of Phase [mole fraction]

0,024 (450,02184)
0,022
0,020
0,018
0,016
0,014
0,012
0,010
0,008
LIQUID
0,006
FCC_A1
NI5SI2_G
0,004
D_NI2SI
0,002
0,000
0 200 400 600 800 1000 1200 1400
Temperature [°C]

Figure 41. a) Calculated ternary diagram at 450°C of the copper rich corner of the Cu-Ni-Si system.
Arrows identify the phase fields and also where the investigated composition is located in the diagram. b)
Calculated phase fraction in equilibrium over temperature of the Cu-1.5wt%Ni-0.34wt%Si alloy.

Figure 41 shows that Ni2Si is not stable at 450°C for the Cu-1.5wt%Ni-0.34wt%Si alloy.
Thus, for infinite time, we can expect a complete dissolution of the Ni2Si phase, where the nickel
and Si goes into the matrix. Moreover, it is known from the literature that Ni2Si is usually the first
phase to precipitate, showing faster kinetics of nucleation and growth [63], [64]. The maximum
amount of Ni2Si expected is around 1.8% for temperatures below 300°C. Due to the
thermodynamic stability of Ni5Si2 in this database further calculations of the Ni5Si2 phase were
planned to be done aiming to better understand the general process of the alloy.

Despite the instability of the Ni2Si phase in the range of temperatures from 400 to 500°C
when all the phases are active, the precipitation behavior can be calculated. The simulation is
possible because the Ni5Si2 phase can be ignored in the calculations.

4.2.2 Precipitation Simulations (Cu-Ni-Si)

Based on the assessments of literature database [31],[32],[34], in this section, we

investigate the behavior of the Ni2Si phase precipitation, its dependence on temperature, time,
dislocation density and interfacial energy. The other external variables were fixed based on
literature data, requirement of industrial manufacture and experiments. These investigations
serve as base to understand the hardening behavior discussed in the following section, 4.2.3.

S. Suzuki et al. [64] show the correlation between the amount of cold rolling of alloys in
the Cu rich side of the Cu-Ni-Si system and the expected dislocation density created due the
process. After cold-rolling the alloy Cu-2.47wt%-Ni 0.58wt%Si by 50%, they obtained a
59
dislocation density around 2*1015 m-2. In our case, we know from section 2.2 that the maximum
deformation due to cold work is about 51%. Hence, our investigations were carried varying its
values around the order of 1015.

The interfacial energy between the α matrix and Ni2Si phase is reported to vary around 0.3
to 0.6 J/m2 depending on the composition of the matrix, curvature of the interface, and on the
plane direction between the matrix and the precipitates, R. Monzen & C. Watanabe [63].

Moreover, ab initio calculations were done to calculate the theoretical interfacial energy
between fcc-Cu and Ni2Si. Figure 42 shows a model of the first atomistic calculations done by
Johannes Müller, from Fraunhofer IWM.

Figure 42. Simulated interface between Fcc-Cu and Ni2Si. Brown spheres correspond to Cu, the
green ones to Ni and bright ones to Si.

Figure 42 shows an interface between [110] oriented Ni2Si and [001] oriented α-Cu
([110]_Cu || [001]_Ni2Si). The value of 0.556 J/m2 was found and is close to the experimental
results reported in the literature.

Based on the literature, the dislocation density was set as 2.5*1015 m-2 and the Interfacial
energy set as 0.4J/m2[63]. In order to have a first insight and view of the precipitation behavior of
the Ni2Si phase in the α-matrix, a Time Temperature Transformation (TTT) diagram was calculated.
The result is shown in Figure 43.

60
 TTT Diagram - Ni2Si in Cu-1.5wt%Ni-0.34wt%Si
600

550

Ni2Si - t0.05

Temperature [°C]
500
Ni2Si - t0.5
Ni2Si - t0.95
450

400

350

300
100 101 102 103 104 105 106
time [h]

Figure 43. Simulated TTT diagram of Ni2Si precipitation in Cu-1.5wt%Ni-0.34wt%Si α matrix.

Figure 43 shows three curves corresponding to different fixed precipitation mole fraction.
The green curve represents the time to precipitate 0.05% of Ni2Si in Cu-1.5wt%Ni-0.34wt%Si α
matrix, the blue one 0.5% and the black one 0.95%.

One can note that the precipitation and the transformation itself are faster and starts
sooner in the range between 450 and 500 °C. Between these values, the precipitation starts
around 3 hours and the transformation develops in tens of hours, without exceeding 60 hours to
reach 95% of complete precipitation.

To better understand the behavior of precipitation after industrial cold rolling, principal
parameters like the phase fraction, the number density of particles and the mean radius of the
particles were calculated with varying dislocation density, see Figure 44, 45 and 46.

a) b) Precipitation of Ni2Si in Cu-1.5wt%Ni-0.34wt%Si

Precipitation of Ni2Si in Cu-1.5wt%Ni-0.34wt%Si
0,025 0,025
Dislocation Density m -3 Dislocation Density = 2.5x1015 [m-2]
T= 450 °C
1e14
0,020 1e15 0,020
6e15
Phase Fraction

Phase Fraction

1e16
0,015 0,015

Interfacial
0,010 0,010 Energy [J/m2]

0.2
0,005 T= 450 °C 0,005 0.3
 = 0.4 [J/m2] 0.4
0.45
0,000 0,000
0,1 1 10 100 1000 10000 10-2 10-1 100 101 102 103 104
time [h] time [h]
Figure 44. Calculated phase fraction of precipitated Ni2Si over time at 450°C a) for different
dislocation density and b) for different interfacial energy

61
 From Figure 44 one can note that the kinetics of transformation have high influence with
the dislocation density. The incubation time varies from fractions of hours to tens of hours. The
more dislocations we have per unit area, the more rapidly the precipitation occurs and more
rapidly it develops into its maximum value.

a) Precipitation of Ni2Si in Cu-1.5wt%Ni-0.34wt%Si

b) Precipitation of Ni2Si in Cu-1.5wt%Ni-0.34wt%Si
3,0x1022 24 T= 450 °C; Dislocation Density = 2.5x1015 [m-2] Interfacial Energy : 0.2 J/m-2
Dislocation Density : 1e14 1,2x10 Interfacial Energy : 0.3 J/m-2
Dislocation Density : 1e15 Interfacial Energy : 0.4 J/m-2
23
Dislocation Density : 6e15 8,0x10 Interfacial Energy : 0.45 J/m-2
2,5x1022 Dislocation Density : 1e16
4,0x1023

Number Density [m-3]

Number Density [m-3]

T= 450 °C
2,0x10 22
 = 0.4 [J/m2]

1,0x1022
1,5x1022
8,0x1021

6,0x1021
1,0x1022

1,5x1020
5,0x1021 1,0x1020
5,0x1019
0,0 0,0
10-2 10-1 100 101 102 103 104 105 106 10-2 10-1 100 101 102 103 104 105 106
time [h] time [h]

Figure 45. Calculated quantity of precipitated Ni2Si phase over time at 450°C a) for different
dislocation density and b) for different interfacial energy

Figure 45 shows the relationship between the dislocation density and the number of
precipitates present over time. One can see that the higher the number of dislocations, the higher
the number of precipitates in the matrix. The opposite occurs with the interfacial energy, for lower
values of interfacial energy, the maximum numbers of precipitates will be higher. One can also
see an initial development of the number of precipitation within the first 10 hours. After that, the
number reaches a plateau for many hours. After that it starts decreasing until we have one big
precipitate at the end reaching the theoretical phase fraction

a) b)
Precipitation of Ni2Si in Cu-1.5wt%Ni-0.34wt%Si Precipitation of Ni2Si in Cu-1.5wt%Ni-0.34wt%Si
40 40
Dislocation Density = 2.5x1015 [m-2]
Dislocation Density : 1e14
T= 450 °C
35 Dislocation Density : 1e15 35
Dislocation Density : 6e15 Interfacial Energy : 0.2 J/m-2
Dislocation Density : 1e16 Interfacial Energy : 0.3 J/m-2
30 30 Interfacial Energy : 0.4 J/m-2
Interfacial Energy : 0.45 J/m-2
T= 450 °C
Mean Radius [nm]

Mean Radius [nm]

25  = 0.4 [J/m2] 25

20 20

15 15

10 10

5 5

0 0
10-1 100 101 102 103 104 105 106 10-1 100 101 102 103 104 105 106
time [h] time [h]

Figure 46. Calculated mean radius over time of the Ni2Si phase precipitation at 450°C in α matrix a) for
different dislocation density and b) for different interfacial energy

62
 From Figure 46 a) and b), one can qualitatively see that we only have positive values for
the first derivative of the curves. This means that the mean radius is expected to always increase
during precipitation. Correlating these results with the ones from Figure 46, one can note that
there is a decrease of the number density while there is an intense increase of the mean radius,
meaning that we are experiencing a coarsening phenomenon. One can also note that the mean
radius seems not to be bigger than 10 nm for the first tens of hours (corresponding to industrial
parameters).

4.2.3 Mechanical Modeling (Cu-Ni-Si)

Based on the precipitation simulations shown in the chapter 4.2.2, the evolutions of the
mechanical behavior during heat treatment were simulated and are discussed in this section.

The correlation of the precipitation features with the mechanical properties is discussed
with the support of Figure 47.

a) Stregthening Contribution due to Precipitation b) Stregthening Contribution due to Solid Slution

45
Ni2Si in Cu-1.5wt%Ni-0.34wt%Si Dislocation Density : 1e14 Dislocation Density : 1e14
50
Dislocation Density : 1e15 Dislocation Density : 1e15
40 Dislocation Density : 6e15 Dislocation Density : 6e15
Dislocation Density : 1e16 45 Dislocation Density : 1e16
35
T= 450 °C
 = 0.4 [J/m2] 40
30
Stress [MPa]

Stress [MPa]

35
25

30
20

15 25

10 20

5 15

0 10
10-2 10-1 100 101 102 103 104 105 106 10-2 10-1 100 101 102 103 104 105 106
time [h] time [h]

Figure 47. Strengthening contribution of the yield strength of the alloy a) due to the precipitates
and b) due to variation of the solid solution, calculated for different dislocation densities.

Figure 47 a) shows the influence of the precipitations on the mechanical properties of the
alloy during processing. The maximum contribution occurs sooner for the alloys presenting a
higher cold-worked rate. For these alloys, the coarsening phenomena also occur in shorter times.
These results can be correlated with the variation of solid solution contribution. One can see that
the more cold-worked the alloy, the faster the kinetic of precipitation. Therefore, the depletion
rate of element content in the matrix phase becomes faster. Correlating the solid solution
contribution with the conductivity of the matrix, we can see that for all the cases, there is a
minimum plateau which should correspond to the moment when the composition of
thermodynamic equilibrium is reached.

In order to have a better understanding about the optimal particle distribution regarcing
mechanical properties, the simulated particle distribution at the maximum strength contribution
of the curves present on Figure 47 a) was plotted as a histogram. See Figure 48.
63
 Particle Distribution at Maximum Strengthen Contribution
21
1,8x10 Dislocation Density
21
1,6x10
1e14 m-2
Number of Precipitates [m-2]
1,4x1021 1e15 m-2
1,2x1021
1e16 m-2

1,0x1021

8,0x1020

6,0x1020

4,0x1020

2,0x1020

0,0
2 4 6 8 10 12 14 16 18
Precipitate Radius [nm]

Figure 48. Simulated particle distribution histograms at maximum precipitate strength

contribution during process.

One can see in Figure 48 that the higher the cold-rolled rate, the smaller and more
numerous the particles. For a dislocation density of 1e16 m-2, the particles are concentrated in a
range of 1 to 7 nm showing average radius around 6 nm. This cold-rolled rate corresponds to the
maximum strengthening in this case. For a dislocation density of 1e15 m-2 we see an evolution in
the particle radius. The distribution is concentrated in the range of 5 to 11 nm and on average
presents one order of magnitude less particles as for the last case. For a dislocation density of
1e14 m-2 the particles are concentrated from 11 to 18 nm, presenting the least effective
strengthening contribution among them.

The same approach was taken to analyze the influence of the interfacial energy on the
mechanical properties and particle distribution after and during the heat treatment. See Figure
49 and 50.

A higher value of dislocation density means more sites of nucleation which in turn leads
to many particles to nucleate at the same time. Thus, we expect to have more homogeneous,
smaller and more numerous particles for higher cold-worked values.

64
 a) Stregthening Contribution due to Precipitation
b)
Stregthening Contribution due to Solid Slution
70
Ni2Si in Cu-1.5wt%Ni-0.34wt%Si Interfacial Energy [J/m2] 50 Dislocation Density = 2.5x1015 [m-2]
65 Dislocation Density = 2.5x1015 [m-2] T= 450 °C
60 T= 450 °C
0.2 45
55
0.3 Interfacial Energy [J/m2]
50 40
0.4
45 0.2
0.45
Stress [MPa]

Stress [MPa]
35 0.3
40
35
0.4
30
0.45
30
25
25
20 20
15
10 15

5
10 Ni2Si in Cu-1.5wt%Ni-0.34wt%Si
0
10-2 10-1
100 1
10 10 2 3
10 10 4
10 5
10 6
0,01 0,1 1 10 100 1000 10000 100000 1000000
time [h] time [h]

Figure 49. Strengthening contribution of the yield strength of the alloy a) due to the precipitates
and b) due to variation of the solid solution, related with the Interfacial Energy.

Particule Distribution at Maximum Strengthen Contribution

1,2x1023
1,0x1023 Interfacial Energy
22
8,0x10
0,2 J/m2
Number of Precipitates [m-2]

6,0x1022
0,3 J/m2
4,0x1022 0,4 J/ m2
2,0x1022

8,0x1020

6,0x1020

4,0x1020

2,0x1020

0,0
1,0 1,5 2,0 2,5 4 5 6 7 8 9
Precipitate Radius [nm]

Figure 50. Simulated particle distribution histograms at maximum precipitate strengthening

contribution during process for different interfacial energy.

One can see the opposite influence that the interfacial energy has on the hardening and on
the number of precipitates. For energies of 0.2 and 0.3 J/m2 the particles are numerous, up to 1023
particles, and are distributed in a range from 1 to 2.75 nm, whereas for 0.4 J/m-2 the particles
present a three times bigger mean radius and are concentrated in the range of 3.75 to 9 nm. It´s
fraction is also lower, reaching maximum value of 8*1020.

With lower interfacial energy the nucleation can occur sooner. With many particles
nucleating at the same time we expect to have more homogeneous, smaller and more numerous
particles.

Experimental results of the conductivity and precipitation hardening evolution during

heat treatment were provided from the project consortium. The tendency of these results can be
65
compared with simulations of the total yield strength and chemical composition of matrix,
respectively. The yield strength during the precipitation heat treatment was calculated. Figure 51
and 52 show these comparisons.

a) b)
Yield Stress Evolution during precipitation of the Ni2Si phase

T: 410°C
T: 425°C
T: 450°C
T: 475°C

Yield Stress [a.u]

Cold-Rolled rate: 51%
Dislocation Density: 5.1015
Interfacial Energy: 0,4 J/m2

0,1 1 10
time [h]

Figure 51. a) Hardness evolution (results provided by the project consortium) for different
temperatures at 51% cold rolling and b) simulated yield stress evolution, over isothermal heat treatment
time at different temperatures.

Figure 51 a) and b) evidences the hardening/strengthening behavior of the alloy while heat
treated between 410°C and 475°C. The qualitative behavior of the curves of both graphs is in good
agreement. The maximum hardening/strengthening occurs approximately at the same time. One
can also note that the position of the curves for different temperatures corresponds to the result
of the TTT diagram (see Figure 43).

a) b) Matrix´s Copper content evolution during precipitation of the Ni2Si phase

T= 450°C
1,000
Mole Fraction of Cu in the Matrix

0,995

0,990

0,985

0,980

Cold-Rolled rate: 51%

0,975 Dislocation Density: 2.51015
Interfacial Energy: 0,4 J/m2
0,970
0,1 1 10 100
time [h]

Figure 52. a) Evolution of the alloy´s conductivity over time (provided by the project consortium) and
b) mole fraction of Cu in the fcc matrix.

The conductivity of an alloy decreases with the amount of alloying elements. In Figure 52 one
can see the similarity of measured evolution of the conductivity and the simulated Cu content in
the α-matrix. During precipitation, the content of alloying elements of the matrix decreases
66
whereas the fraction of copper increases. This phenomenon leads to fewer dissoluted elements in
the matrix and hence a bigger value of electrical conductivity. The qualitative match of both curves
together with the good agreement of the kinetic results shows the big potential of process
simulations of these alloys.

5. CONCLUSION

In this work, the knowledge concerning two copper alloy systems was deepened through
literature research, study of the precipitation hardening, interpretation of thermodynamic-kinetic
simulations, ab initio calculations and experimental EDX and SEM analysis and through
cooperation with other research groups that act in the development of these alloys. Moreover,
within the development of the thermodynamic-kinetic database of the Cu-Sn-Zn and Cu-Ni-Si
systems, the functionality and working syntax of the ThermoCalc software and its modules as
DICTRA and PARROT and the further software package MatCalc were studied and familiarized.

5.1 Cu-Sn-Zn – System

The complete thermodynamic model and the mobility of the atoms in several phases of
the Cu-Sn-Zn system were described through the construction of databases based on the
literature.

The equilibrium simulations ran with ThermoCalc using the thermodynamic database of
the Cu-Sn-Zn system from the literature show good agreement with experimental and simulated
results also reported in the literature. This good agreement demonstrates that the database can
be used for further simulations.

The Gibbs energy of the FCC phase shows significant differences to the ideal mixing for the
three binaries. The Gibbs energy used for thermodynamic simulations of the FCC phase is more
negative towards the Cu-Zn binary system of 0.5at%Cu-0.5at%Zn composition and more positive
the closer it gets towards the Sn-Zn binary system of 0.5at%Sn-0.5at%Zn composition. For
temperatures varying from 1 to 500K, the Gibbs energy of the α-phase in the Sn-Zn binary is
positive for virtually any composition in this system and is negative in the complete range of the
Cu-Zn binary system. In the same range of temperature, the Gibbs energy of the α-phase in the Cu-
Sn binary system seems to vary its values over temperature. At lower temperatures, the Cu-Sn α-
phase present negative values only in the Cu rich side, whereas at higher temperatures it is
completely positive.

The Gibbs energy behavior of the BCC phase also shows two critical values, one point of
maximum and one of minimum. The maximum point is located around compositions of 60at%Sn-
25at%Zn-15at%Cu, meaning that around these compositions the BCC phase tend to be unstable
in the overall system. The opposite occurs at 55 at%Cu-45 at%Zn-5-at%Sn. At this point we have
the most negative Gibbs energy associated.

67
 The Gibbs free energy of the FCC and BCC phases calculated by the CALPHAD method were
compared with the energy of formation calculated through DFT, which was carried out at
Fraunhofer IWM. The comparison shows different results between the energy of formation
calculated with DFT and the Gibbs energy calculated with the CALPHAD method. Using DFT it is
only possible to calculate at zero Kelvin. The temperature factor present in the CALPHAD
approach coupled with the fact that the assessed parameters were acquired at high temperature,
and can be the cause of the mismatch. Further investigations on why this difference occurs, how
the temperature influences these values and comparisons with other similar ternary systems
should be done. These results will be further evaluated in the next steps and an article is planned
to be published to illustrate these discrepancies.

The kinetic database of the FCC phase of the Cu-Sn-Zn system was assessed and used to
calculate experiments proposed in the literature. The results show excellent agreement for
experiments using binary systems and good agreement for the ones using the ternary system.
Within the ternary system, the simulated diffusion presents good qualitative and quantitative
behavior compared with literature data.

Despite this, the simulated Sn diffusion was faster than the experimentally observed. This
difference is not critical to the simulations proposed in further investigations but can be improved
in further steps if more relevant experimental data are created. Another important point to be
further investigated is the interaction parameter of Zn diffusing in Cu-Sn-Zn. When this parameter
is to be used, the simulated diffusion of Zn into the α-phase, interacting with Sn and Cu in the same
sublattice, shows the right tendency but the values are not exact compared with experimental
results.

The diffusion in the ternary Cu-Sn-Zn BCC phase was assessed in this work using
theoretical calculations, estimations and experimental data. The parameters were optimized
through the PARROT module of the ThermoCalc Software. The results are in good agreement with
the experimental values of the diffusivity of Zn and Sn in the β-phase. A penetration curve of Zn in
a Cu-Zn alloy proposed in the literature was simulated using the database assessed in this work.
The results show excellent agreement for short and long heat treatment times under different
temperatures.

The assessment of the ternary Cu-Sn-Zn system diffusion in β-phase is not yet present in
the literature and therefore, an article of the assessment done in this work is to be published in
the next steps.

The diffusion in IMCs phases of interest of the Cu-Sn-Zn system were assessed based on
ab initio calculations and experimental works found in the literature. This assessment enables the
simulation of IMC layer growth, which is one of the phenomena that limit the usage of the Cu-Sn-
Zn coating.

The chemical composition of the reference CuSnZn Miralloy series were measured with
EDX and analyzed through thermodynamic simulations. It can be seen that in equilibrium at 523K,
the phases present in the Miralloys should be ε-Cu3Sn, η’-Cu6Sn5 and β phases.

Different new CuSnZn coatings deposited with a newly developed electrolyte provided by
Fraunhofer IPA were analyzed with SEM and EDX. The analysis of the thermodynamic stability of
68
the sample composition shows that we have a wide composition range that is spread over 5
different fields of phase stability. This means that we are able to track a chemical and an in-
equilibrium phase composition of interest and correlate it with the variables of the deposition
process, obtaining the desired alloy with approximately the composition of interest.

Setting a reference composition of the alloy as Cu-44wt%Sn-9wt%, an average of the

values measured for the Miralloy´s sample, we could calculate some thermodynamic features to
serve as a base of knowledge. By simulations using this composition, one can note that, from 100
to 500°C, we have two different equilibrium transformations over temperature. Following the
cooling direction, One transformation occurs at 205°C and consists in the transformation of the
η’-Cu6Sn5 into ε-Cu3Sn and BCT-Sn. The second transformation occurs at 434°C with the partial
transformation of the ε-Cu3Sn phase into the η’-Cu6Sn5.

The composition of the ε-Cu3Sn, η’-Cu6Sn5 and β phases were calculated over
temperature. By these calculations, one can note that the solubility of the Zn in the IMC phases is
really low but rises for lower temperature. The composition of the β-phase changes with
temperature but always has Cu as its primary element followed by Zn and Sn. These results are
important to better understand the possible diffusion path of Zn during heat treatments or
processing.

Further analysis shows that Zn will be present mainly in the β-phase. It also shows that a
higher amount of Zn, to the detriment of Sn content, stabilizes the β-phase while destabilizing the
IMCs.

The thermodynamic-kinetic assessment of the Cu-Sn-Zn system, including the disordered

and IMC phases, allows the simulation of the layer growth. The first results do not show accurate
predictions due to the simplification imposed by the simulations. This can be improved in further
calculations with the input of the other present phases in the system.

5.2 Cu-Ni-Si – System

The complete thermodynamic database of the Cu-Ni-Si and the kinetic database of the FCC
phase were taken from the assessments from the literature.

The FCC Gibbs energy was analyzed and reviewed. The shape of the energy surface shows
only one minimum at compositions around Ni-0.33at%Si meaning that no other FCC phase of
different composition (spinoidal decomposition) needs to be taken into account and that the
precipitation simulation can be calculated without any numerical difficulties.

Despite the non-equilibrium at 450°C of the Ni2Si phase (resulting from the
thermodynamic database but present in real alloys), its precipitation could be simulated because
the Ni5Si2 phase was ignored. and the dependence of parameters such as the dislocation density
and interfacial energy on the evolution of the particle radius, number density, mechanical

69
properties and amount of alloying elements in the matrix as well as its contribution in the
conductivity properties and particle distribution could be calculated.

Using preliminary parameters from the literature, the precipitation of the Ni2Si phase in
FCC matrix of the Cu-1.5wt%Ni-0.34wt%Si alloy was calculated. The dislocation density was
estimated to be around 1015 dislocation/m2 and the interfacial energy of the Ni2Si face was
estimated to 0.4 J/m2. The simulations showed that faster precipitation occurs for isothermal
temperatures around 450°C and 500°C, starting the first nucleation within the first 10 hours in
isotherm and finalizing around 50 hours.

The variation of the cold-work rate has important influence on the precipitation behavior
of the Ni2Si phase. The variation of dislocation density around 1e15 J/m2 (50%cold-rolled) shows
that the incubation time can vary from some minutes to tens of hours. The variation from 0.2 to
0.45 J/m2 of the interfacial energy changes the incubation time from 0.03 to 20 hours. Parameter
variation shows a big influence of dislocation density on the number of precipitates. The influence
of interfacial energy was even bigger. The mean radius also varies, in the region of highest reached
mechanical properties, one can expect a distribution of small particles with a size of 6 to 15 nm
due to variations of the dislocation density and from 2 to 30 nm due to variation of interfacial
energy.

The mechanical properties are also heavily dependent on these parameters. The
contribution of the precipitates in the mechanical properties is higher with increased cold-rolling
and is even bigger for an interfacial energy of 0.3 J/m2. The correlation of histograms of particle
distribution with the mechanical properties shows that the optimum strengthening would be
reached when the particle’s distribution is concentrated in the range of 2 to 5 nm.

There is a large range of values for the interfacial energy given in the literature. Due to the
high impact of the interfacial energy on the particle evolution, it is necessary to accurately
estimate this parameter in further calculations.

The correlation between the conductivity and the solid solution contribution on the
mechanical properties shows that the bigger the cold-rolled rate (more dislocations per volume
unit and more sites of nucleation) sooner nucleation occurs. This causes the matrix to be depleted
of soluted elements at an earlier stage, bringing its conductivity closer in proximity to the
conductivity of pure Cu.

70
 5.3 Next Steps

The next advised steps on development of the project are summarized:

• Analyze and optimize the mobility parameters of the diffusion of Zn in the Cu-Sn/Cu-
Zn FCC phase.

• Evaluate simulated results from the kinetic assessment of the Cu-Sn-Zn system in the
BCC phase with further experimental results.

• Compare ab initio results of formation energy of phases of interest in the Cu-Sn-Zn

system with other ternary systems and correlate this with thermodynamic predictions
from CALPHAD method.

• Simulate the layer growth phenomena including the other expected present phases
and evaluate the accuracy of the mobility parameters in IMC phases

• Calculate the interfacial energy of the precipitating phases via ab initio methods
changing parameters of influence (chemical composition of the matrix and
crystallographic orientation i.e.)

• Reassess and evaluate the thermodynamic parameters of the Ni5Si2 and Ni2Si phase
and simulate the contribution of its precipitation in the hardening of the Cu-Ni-Si alloy.

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Journal of Alloys and Compounds, 661 (2006) 282-293.

[61] Yuan et al.: Investigation of diffusion behavior in Cu-Sn solid state diffusion couples,
Journal of Alloys and Compounds, 661 (2016) 282-293.

[62] Phase Diagrams of Cu-Ni-Si Base Alloys, Materials Design Technology Co., Ltd. (2006)

[63] R. Monzen & C. Watanabe: Coarsening of δ-Ni2Si precipitates in a Cu–Ni–Si alloy, J. Mater.
Sei (2011), 4327-4335.

[64] S. Suzuki et al.: Characterization of Aging Behavior of Precipitates and Dislocations in

Copper-Based Alloys, International Centre for Diffraction Data (2010) 1097-2002

[65] G. Zeng et al: Kinetics of the polymorphic phase transformation of Cu6Sn5, Acta Materialia,
69 (2014), 135-148.

[66] K. Russell: Adv. Colloid Interface Sci. 13 (1980) 205.

[67] J. Svoboda et al.: Modelling of kinetics in multi-component multi-phase systems with

spherical precipitates, Materials Science and Engineering, A 385 (2004), 166-174.

[68] Informationsschrift des Deutschen Kupferinstituts (1999)

[69] Untersuchung und Modellierung des Relaxationsverhaltens von höherfesten und

hochleitfähigen Cu-Legierungen, Fraunhofer IWM, Germany

[70] C. E. Campbell: Development of a Diffusion Mobility Database for Cu-In-Se, NIST Diffusion
Workshop, 2009.

75
 7. ABSTRACT

Student: Ebert Daniel Macedo Alvares

Study year: 5th year

Company: Fraunhofer IWM

Adresse: Wöhlerstr. 11 , 79108 Freiburg im Breisgau

Phone: +49 076151420

Academic Tutor: Annie Antoni

Phone: +33 04 76 82 67 47

E-mail: aantoni@simap.grenoble-inp.fr

Work Tutor: Johannes Preußner

Phone: +49761-5142-101

E-Mail: johannes.preussner@iwm.fraunhofer.de

Title: Thermodynamic-Kinetic Modeling and Simulation of Microstructure Development in

Cooper Based Alloys

Abstract: Processes are being developed for the deposition of alloying layers, which in the
future can replace the currently established nickel-based coatings. White bronze coatings from
the CuSnZn system can fulfill both decorative and functional tasks. They can be potentially used
within a wide range of applications where tribological or abrasive properties are important and
can further be used for special decorative surfaces (levelling of surfaces) and corrosion protection.

Moreover, the precipitation of intermetallic phase in the CuNiSi system is being investigated.
The precipitation of theses phases can contribute to the hardening of the alloys as well as improve
the conductivity of the matrix.

With the help of thermodynamic and kinetic databases and simulations it is possible to
calculate phase transformations, diffusion processes and precipitation of alloys. Here, these
calculations will be done to assist the production process of the coatings/ alloys and also to
optimize possible heat treatment. Furthermore it is possible to estimate the long time stability of
the coatings. Therefore, this work is aimed at the assessment of thermodynamic and
mobility/diffusion database and simulations on properties of the ternary alloy systems Cu-Sn-Zn
and Cu-Ni-Si.

Keywords: Copper based alloys, Thermodynamic-Kinetics Simulation, CALPHAD, ab initio,

Microstructure, Diffusion, Precipitation.

76
 8. APPENDIX

Table 5. Implemented thermodynamic Interaction parameters of the Cu-Sn-Zn system.

Phase Parameter Temperature Value [J/mol] Reference

Range [K]
LIQUID G(LIQUID,CU;0) 298.15<T<1357.77 +5194.277 SGTE [42]
+120.97331*T
-24.112392*T*LN(T)
-2.65684E
-3*T^2
+0.129223E
-6*T^3
+52478*T^(-1)
-584.89E-23*T^7

1357.77<T<3200 -46.545
+173.881484*T
-31.38*T*LN(T)

G(LIQUID,SN;0) 100<T<250 -855.425 SGTE [42]

+108.677684*T
-25.858*T*LN(T)
+0.51185E-3*T**2
-3.192767E
-6*T**3+18440*T**(-1)
+147.031E-20*T**7

250<T<505.078 +1247.957
+51.35548*T
-15.961*T*LN(T)
-18.8702E
-3*T**2
+3.121167E-6*T**3
-61960*T**(-1)
+147.031E-20*T**7

505.078<T<800 +9496.31-9.809114*T
-8.2590486*T*LN(T)
-16.814429E-3*T**2
+2.623131E-6*T**3
-1081244*T**(-1)

800<T<3000 -1285.372
+125.182498*T
-28.4512*T*LN(T)

G(LIQUID,ZN;0) 298.15<T<692.68 -128.565 SGTE [42]

+108.177019*T
-23.701314*T*LN(T)
-1.712034E-3*T**2
-1.264963E-6*T**3
-358.949E-21*T**7

692.68<T<1700 -3620.385+161.60854*T-
31.38*T*LN(T)
77
 L(LIQUID,CU,SN;0) 298.15<T<3000 -15583.768 Gierlotka
+40.6239*T et al [23]
-5.6172*T*LN(T)

L(LIQUID,CU,SN;1) 298.15<T<3000 -27739.285+41.9270*T Gierlotka

-4.4641*T*LN(T) et al [23]

L(LIQUID,CU,SN;2) 298.15<T<3000 -13228.943+0.9058*T Gierlotka

et al [23]
L(LIQUID,CU,ZN;0) 298.15<T<3000 -84075.696 Gierlotka
+335.9801*T et al [23]
-40.5377*T*LN(T)

L(LIQUID,CU,ZN;1) 298.15<T<3000 -7230.333+3.8906*T Gierlotka

et al [23]
L(LIQUID,CU,ZN;2) 298.15<T<3000 +3104.189-0.1243*T Gierlotka
et al [23]
L(LIQUID,CU,SN,ZN;0) 298.15<T<3000 +75398.727-52.1071*T Gierlotka
et al [23]
L(LIQUID,CU,SN,ZN;1) 298.15<T<3000 -1564.006+27.0787*T Gierlotka
et al [23]
L(LIQUID,CU,SN,ZN;2) 298.15<T<3000 +108586.603-54.1147*T Gierlotka
et al [23]
FCC_A1 G(FCC_A1,CU:VA;0) 298.15<T<1357.77 -7770.458 SGTE [42]
+130.485235*T
-24.112392*T*LN(T)
-2.65684E
-03*T**2
+0.129223E
-6*T**3
+52478*T**(-1)

1357.77<T<3200 -13542.026
+183.803828*T
-31.38*T*LN(T)
+364.167E+27*T**(-9)

G(FCC_A1,SN:VA;0) 100<T<250 -2448.517 SGTE [42]

+114.305451*T
-25.858*T*LN(T)
+0.51185E-3*T**2
-3.192767E-6*T**3
+18440*T**(-1)

250<T<505.078 -345.135
+56.983315*T
-15.961*T*LN(T)
-18.8702E
-3*T**2
+3.121167E
-6*T**3
-61960*T**(-1)

505.078<T<800 +8034.724
-4.454731*T
-8.2590486*T*LN(T)
-16.814429E
78
 -3*T**2
+2.623131E
-6*T**3
-1081244*T**(-1)
-123.07E+23*T**(-9)

800<T<3000 -2746.959+130.53688*T
-28.4512*T*LN(T)
-123.07E+23*T**(-9)

G(FCC_A1,ZN:VA;0) 298.15<T<692.68 -4315.967+116.900389*T SGTE [42]

-23.701314*T*LN(T)
-1.712034E-3*T**2
-1.264963E-6*T**3

692.68<T<1700 -8100.726 SGTE [42]

+170.775964*T
-31.38*T*LN(T)
+470.47E
+24*T**(-9)
L(FCC_A1,CU,SN:VA;0) 298.15<T<6000 -10672.845+1.1484*T Mittinen
[5]
L(FCC_A1,CU,SN:VA;1) 298.15<T<6000 -15331.032+6.954*T Gierlotka
et al [23]
L(FCC_A1,CU,ZN:VA;0) 298.15<T<6000 -42803.750+10.0225*T Gierlotka
et al [23]
L(FCC_A1,CU,ZN:VA;1) 298.15<T<6000 +2936.390-3.0532*T Gierlotka
et al [23]
L(FCC_A1,CU,ZN:VA;2) 298.15<T<6000 +9034.200-5.3931*T Gierlotka
et al [23]
L(FCC_A1,SN,ZN:VA;0) 298.15<T<6000 +33433.94-11.14466*T Vassilev et
al [43]
L(FCC_A1,CU,SN,ZN:VA;0) 298.15<T<6000 -263943.497+229.5618*T Gierlotka
et al [23]
L(FCC_A1,CU,SN,ZN:VA;1) 298.15<T<6000 +5817.747+681.3901*T Gierlotka
et al [23]
L(FCC_A1,CU,SN,ZN:VA;2) 298.15<T<6000 +56058.235+316.3027*T Gierlotka
et al [23]
BCC_A2 G(BCC_A2,CU:VA;0) 298.15<T<1357.77 -3753.458 SGTE [42]
+129.230235*T
-24.112392*T*LN(T)
-2.65684E
-3*T**2
+0.129223E
-6*T**3+52478*T**(-1)

1357.77<T<3200 -9525.026
+182.548828*T
-31.38*T*LN(T)
+364.167E
+27*T**(-9)

G(BCC_A2,SN:VA;0) 100<T<250 -3558.517 SGTE [42]

+116.765451*T
-25.858*T*LN(T)
+0.51185E-3*T**2
-3.192767E
-6*T**3
79
 +18440*T**(-1)

250<T<505.078 -1455.135
+59.443315*T
-15.961*T*LN(T)
-18.8702E
-3*T**2
+3.121167E
-6*T**3
-61960*T**(-1)

505.078<T<800 +6924.724
-1.994731*T
-8.2590486*T*LN(T)
-16.814429E-3*T**2
+2.623131E-6*T**3
-1081244*T**(-1)

800<T<3000 -3856.959
+132.99688*T
-28.4512*T*LN(T)
-123.07E+23*T**(-9)

G(BCC_A2,ZN:VA;0) 298.15<T<692.68 -4398.827 SGTE [42]

+115.959669*T
-23.701314*T*LN(T)
-1.712034E
-3*T**2-1.264963E-6*T**3

692.68<T<1700 -8183.586
+169.835244*T
-31.38*T*LN(T)
+470.47E
+24*T**(-9)

L(BCC_A2,CU,SN:VA;0) 298.15<T<3000 -41774.195+47.8773*T Gierlotka

et al [23]
L(BCC_A2,CU,SN:VA;1) 298.15<T<3000 -12316.502-50.4458*T Gierlotka
et al [23]
L(BCC_A2,CU,ZN:VA;0) 298.15<T<3000 -51595.87+13.06392*T J. Spenser
[43]
L(BCC_A2,CU,ZN:VA;1) 298.15<T<3000 +7562.13-6.45432*T J. Spenser
[43]
L(BCC_A2,CU,ZN:VA;2) 298.15<T<3000 +30743.74-29.91503*T J. Spenser
[43]
L(BCC_A2,SN,ZN:VA;0) 298.15<T<3000 +12000 Gierlotka
et al [23]
L(BCC_A2,CU,SN,ZN:VA;0) 298.15<T<3000 -370216.293+244.5855*T Gierlotka
et al [23]
L(BCC_A2,CU,SN,ZN:VA;1) 298.15<T<3000 +1362407.440-820.0000*T Gierlotka
et al [23]
L(BCC_A2,CU,SN,ZN:VA;2) 298.15<T<3000 -196932.732+581.1043*T Gierlotka
et al [23]
BCT_A5 G(BCT_A5,SN;0) 100<T<3000 +GHSERSN# SGTE [42]

G(BCT_A5,ZN;0) 298.15<T<692.68 -4398.827 SGTE [42]

+115.959669*T
-23.701314*T*LN(T)
80
 -.001712034*T**2
-1.264963E
-06*T**3

692.68<T<1700 -8183.599
+169.83526*T
-31.38*T*LN(T)
+4.70514E+26*T**(-9)

L(BCT_A5,SN,ZN;0) 100<T<3000 6846.010+24.5560*T SGTE [42]

CU10SN3 G(CU10SN3,CU:SN;0) 298.15<T<3000 -7080.1944 Gierlotka

-0.9553*T et al [23]
+.769*GHSERCU#
+.231*GHSERSN#

CU3SN G(CU3SN,CU:CU;0) 298.15<T<3000 +5534.454 Gierlotka

-.2416*T+GHSERCU# et al [23]

G(CU3SN,SN:CU;0) 298.15<T<3000 +15470.377 Gierlotka

+7.7319*T et al [23]
+.75*GHSERSN#
+.25*GHSERCU#

G(CU3SN,CU:SN;0) 298.15<T<3000 -8406.738 Gierlotka

+0.1001*T et al [23]
+.75*GHSERCU#
+.25*GHSERSN#

G(CU3SN,SN:SN;0) 298.15<T<3000 +14564.708 Gierlotka

+0.1001*T et al [23]
+GHSERSN#

G(CU3SN,CU:ZN;0) 298.15<T<3000 +9000 Gierlotka

+0.75*GHSERCU# et al [23]
+0.25*GHSERZN#

L(CU3SN,CU:SN,ZN;0) 298.15<T<3000 -57019+65.612*T Gierlotka

et al [23]
L(CU3SN,CU:SN,*;0) 298.15<T<3000 0.0955+0.1000*T Gierlotka
et al [23]
L(CU3SN,*:CU,SN;0) 298.15<T<3000 217.494-1.8316*T Gierlotka
et al [23]
CU41SN11 G(CU41SN11,CU:SN;0) 298.15<T<3000 -6498.0861 Gierlotka
-1.0645957*T et al [23]
+.788*GHSERCU#
+.212*GHSERSN#

CU6SN5 G(CU6SN5,CU:CU:SN;0) 298.15<T<3000 -5570.949 Gierlotka

-1.1108*T et al [23]
+0.6667*GHSERCU#
+0.3333*GHSERSN#

G(CU6SN5,CU:SN:SN;0) 298.15<T<3000 +930.597 Gierlotka

-0.4804*T et al [23]
+0.3333*GHSERCU#
+0.6667*GHSERSN#

81
 G(CU6SN5,CU:ZN:SN;0) 298.15<T<3000 -8220.4+2.6531*T Gierlotka
+0.3333*GHSERCU# et al [23]
+0.3333*GHSERSN#
+0.3334*GHSERZN#

L(CU6SN5,CU:CU,SN:SN;0) 298.15<T<3000 -7841.425-0.7127*T Gierlotka

et al [23]
CU6SN5_P G(CU6SN5_P,CU:CU:SN;0) 298.15<T<3000 -4297.175-3.9531*T Gierlotka
et al [23]
+0.6667*GHSERCU#
+0.3333*GHSERSN#

G(CU6SN5_P,CU:SN:SN;0) 298.15<T<3000 5334.887-10.2934*T Gierlotka

et al [23]
+0.3333*GHSERCU#
+0.6667*GHSERSN#

G(CU6SN5_P,CU:ZN:SN;0) 298.15<T<3000 -7500+1.0000*T Gierlotka

et al [23]
+0.3333*GHSERCU#
+0.3333*GHSERSN#
+0.3334*GHSERZN#

L(CU6SN5_P,CU:CU,SN:SN;0) 298.15<T<3000 -21100.152+28.6728*T Gierlotka

et al [23]
GAMMA_CU5 G(CUZN_GAMMA,CU:CU:CU:ZN;0) 298.15<T<3000 -9132.295-3.2576*T Gierlotka
ZN8 et al [23]
+0.53846*GHSERCU#
+0.46154*GHSERZN#

G(CUZN_GAMMA,ZN:CU:CU:ZN;0) 298.15<T<3000 -3395.352-5.2657*T Gierlotka

et al [23]
+0.38462*GHSERCU#
+0.61538*GHSERZN#

G(CUZN_GAMMA,CU:ZN:CU:ZN;0) 298.15<T<3000 -11552.71-1.6782*T Gierlotka

et al [23]
+0.38462*GHSERCU#
+0.61538*GHSERZN#
G(CUZN_GAMMA,ZN:ZN:CU:ZN;0) 298.15<T<3000 -5815.766-3.6863*T Gierlotka
et al [23]
+0.23077*GHSERCU#+0.769
24*GHSERZN#

G(CUZN_GAMMA,CU:CU:CU:SN;0) 298.15<T<3000 +100000 Gierlotka

+0.53846*GHSERCU# et al [23]

+0.46154*GHSERSN#
EPSILON- G(EPSILON,CU;0) 298.15<T<3000 GHSERCU# Gierlotka
CUZN5 et al [23]
G(EPSILON,ZN;0) 298.15<T<3000 +2969.82- Gierlotka
1.5696*T+GHSERZN# et al [23]

L(EPSILON,CU,ZN;0) 298.15<T<3000 -35433.3+5.2451*T Gierlotka

et al [2]
L(EPSILON,CU,ZN;1) 298.15<T<3000 +25276.81-9.9698*T Gierlotka
et al [2]

82
GAMMA_DO G(GAMMA_DO3,CU:CU;0) 298.15<T<3000 +4017 Gierlotka
3 -1.255*T et al [23]
+GHSERCU#

(GAMMA_DO3,SN:CU;0) 298.15<T<3000 126652.75 Gierlotka

-2.9875*T et al [23]
+.75*GHSERSN#
+.25*GHSERCU#
G(GAMMA_DO3,CU:SN;0) 298.15<T<3000 -5912.468 Gierlotka
-2.4398*T +0.75*GHSERCU# et al [23]
+.25*GHSERSN#

G(GAMMA_DO3,SN:SN;0) 298.15<T<3000 +4400-6*T+GHSERSN# Gierlotka

et al [23]
G(GAMMA_DO3,CU:ZN;0) 298.15<T<3000 -3000 Gierlotka
+.75*GHSERCU# et al [23]
+.25*GHSERZN

L(GAMMA_DO3,CU:CU,SN;0) 298.15<T<3000 -2672.875-1.7927*T Gierlotka

et al [23]
L(GAMMA_DO3,CU:CU,SN;1) 298.15<T<3000 +57.375-3.7672*T Gierlotka
et al [23]
L(GAMMA_DO3,CU,SN:SN;0) 298.15<T<3000 +46820.857-42.2613*T Gierlotka
et al [23]
L(GAMMA_DO3,CU:SN,ZN;0) 298.15<T<3000 4000 Gierlotka
et al [23]
L(GAMMA_DO3,CU:SN,ZN;2) 298.15<T<3000 -11750 Gierlotka
et al [23]
HCP_ZN G(HCP_ZN,ZN:VA;0) 298.15<T<3000 GHSERZN# SGTE [1]

G(HCP_ZN,CU:VA;0) 298.15<T<1357.77 -7170.458+130.685235*T SGTE [42]

-24.112392*T*LN(T)-
.00265684*T**2+1.29223E-
07*T**3+52478*T**(-1)
1357.77<T<3200 -12942.026+184.003828*T-
31.38*T*LN(T)+3.64167E+2
9*T**(-9)

G(HCP_ZN,SN:VA;0) 298.15<T<505.08 -1950.135 SGTE [42]

+57.797315*T
-15.961*T*LN(T)
-.0188702*T**2
+3.121167E-06*T**3
-61960*T**(-1)

505.08<T<800 +6429.724-3.640731*T
-8.2590486*T*LN(T)
-.016814429*T**2
+2.623131E-06*T**3
-1081244*T**(-1)
-1.2307E+25*T**(-9)

800<T<3000 -4351.959
+131.35088*T
-28.4512*T*LN(T)
-1.2307E+25*T**(-9)

83
L(HCP_ZN,CU,ZN:VA;0) 298.15<T<6000 -14432.17-10.7814*T Gierlotka
et al [23]
L(HCP_ZN,SN,ZN:VA;0) 298.15<T<6000 21310.7476+65.5652*T Gierlotka
et al [23]
L(HCP_ZN,SN,CU:VA;0) 298.15<T<6000 5000 Gierlotka
et al [23]

84