Ti-Based Bulk Amorphous Alloy Thesis

SYNTHESIS AND CHARACTERIZATION OF
TI-BASED BULK AMORPHOUS/NANOCRYSTALLINE ALLOYS FOR

ENGINEERING APPLICATIONS
A THESIS SUBMITTED TO
THE GRADUATE SCHOOL OF NATURAL AND APPLIED SCIENCES
OF
MIDDLE EAST TECHNICAL UNIVERSITY
BY
ALİ ABDELAL
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE

OF
MASTER OF SCIENCE
IN
THE DEPARTMENT OF METALLURGICAL AND MATERIALS ENGINEERING
JANUARY 2004
ABSTRACT
SYNTHESIS AND CHARACTERIZATION OF TI-BASED BULK

AMORPHOUS/NANO-CRYSTALLINE ALLOYS FOR ENGINEERING
APPLICATIONS
ABDELAL, Ali
M.Sc. Department of Metallurgical and Materials Engineering
Supervisor: Prof. Dr. Vedat AKDENİZ
Co-supervisor: Prof. Dr. Amdulla O. MEKHRABOV
January 2004, 145 pages
Amorphous and bulk amorphous metallic alloys are an intriguing class of structural
materials and possess a range of interesting properties, including near theoretical
strength, high hardness, extremely low damping characteristics, excellent wear
properties, high corrosion resistance, low shrinkage during cooling and almost perfect
as-cast surfaces with good potential for forming and shaping.
In this study, new Ti-based bulk amorphous alloys are tried to be modeled and
synthesized.
iii
For that purpose, electronic theory of alloys in the pseudo potential approximation
was used as a tool for understanding the theory lying beneath the bulk glass forming
ability (BGFA). The results from this approach were evaluated both separately and
together with the other theories supposed by our colleagues. Glass forming parameters
of ordering energy, ∆HM, viscosity, mismatch entropy, Rc was calculated for various
Ti-based binary and ternary and the change in these parameters in both cases was
evaluated.
The results of the theoretical calculations of glass forming parameters has shown good
relation with the literature data that the predicted alloying elements, i.e. Mo, Hf, Zr, B,
Fe, Sn, and Be, to increase GFA for Ti2Ni binary system were generally used in the
production of Ti-based bulk amorphous alloys.
In the second part of this thesis, new Ti-based compositions with high GFA were tried
to be synthesized with light of these results and encouraging conclusions were drawn.
The production of these alloys were made with centrifugal casting method which is
relatively a new technique for producing such alloys and the characterization of these
alloys were made with metallographic, X-ray and thermal means.
Keywords: Bulk amorphous alloys, Ti-based alloys, glass forming ability, atomistic
modeling of alloys systems
iv
ÖZ
MÜHENDİSLİK UYGULAMALARI İÇİN Tİ-ESASLI İRİ VE

HACİMLİ/NANOKRİSTAL MALZEMELERİN ÜRETİMİ VE
KARAKTERİZASYONU
ABDELAL, Ali
Yüksek Lisans, Metalurji ve Malzeme Mühendisliği Bölümü
Tez Yöneticisi: Prof. Dr. Vedat AKDENİZ
Ortak Tez Yöneticisi: Prof. Dr. Amdullah O. MEKHRABOV
Ocak 2004, 145 sayfa
Amorf ve iri ve hacimli amorf metal alaşımlar teorik mukavemetleri, yüksek

sertlikleri, düşük sönümleme karakteristikleri, mükemmel aşınma özellikleri, yüksek
korozyon dirençleri, soğurken düşük çekme özellikleri ve nerdeyese mükemmel
dökülmüş halde yüzeyleri ve şekil verme potansiyelleri de dahil olmak üzere, çok
geniş bir özellik aralığına sahip ilgi çekici yapısal malzemelerdir.
Bu tez çalışmasında, Ti-esaslı iri ve hacimli amorf alaşımların modellenmesi ve

üretilmesi amaçlanmıştır.
v
Bu amaç için, iri ve hacimli cam oluşturma kabiliyetinin altında yatan teorinin
anlaşılmasında, pseudopotansiyel yaklaşımında alaşımların elektronik teorisi bir araç
olarak kullanılmıştır. Bu yaklaşımdan çıkan sonuçlar, hem münferit olarak hem de bu
konuda çalışan meslektaşlarımız tarafından öne sürülen diğer yaklaşımlarla birlikte
değerlendirilmiştir. Çeşitli Ti-esaslı ikili ve üçlü sistmeler için düzenlenme enerjisi,
∆HM, viskozite, yanlış eşleştirme entropisi ve Rc gibi cam oluşturma parametreleri
hesaplanmış, ve her durumdaki değerler karşılaştırılıp değerlendirilmiştir.
Teorik hesaplamalardan çıkan sonuçların literatürdeki verilerle uyum içinde olduğu

görülmüştür. Mo, Hf, Zr, B, Fe, Sn ve Be gibi Ti2Ni ikili sisteminin cam oluşturma
kabiliyetini artıracağı tahmin edilen alaşım elementlerinin birçoğu, daha önce
literatürdeki çalışmalarda Ti-esaslı iri ve hacimli amorf alaşımların üretilmesi için
kullanılmıştır.
Tezin ikinci kısmında, teorik sonuçlardan yararlanarak yüksek cam oluşturma

kapasitesine sahip yeni Ti-esaslı alaşımlar üretilmeye çalışılmış ve cesaretlendirici
sonuçlara varılmıştır. Bu alaşımların üretimi bu konuda nispeten yeni bir teknik olarak
görülen savurma döküm tekniği ile yapılmış ve elde edilen örnekler metalografik, X-
ray ve termal analiz vasıtasıyla karakterize edilmiştir.
Anahtar kelimeler: İri ve hacimli amorf alaşımlar, Ti-esaslı alaşımlar, cam oluşturma
kapasitesi, alaşım sistemlerinin atomistik açıdan modellenmesi
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To my family
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ACKNOWLEDEMENTS
I would like to express my sincere gratitude and respect to my supervisor, Prof. Dr.
Vedat Akdeniz and Co-Supervisor Prof. Dr. Amdulla Mekhrabov for their
supervisions, advice, continual supports and constant encouragement throughout the
course of this study. Thanks to Dr. Kaan Pehlivanoğlu for his vital advices and
support.
I also offer my special thanks to my friends Emrah Erdiller, Hülya Arslan, Selen
Gürbüz, İlkay Saltoğlu and Can Ayas for their mental support and keeping my moral
motivation high in most desperate times.
I am truly grateful to my family for their never-ending support and encouragement,

giving me vital strength through this study.
viii
TABLE OF CONTENTS
ABSTRACT .................................................................................................................. iii
ÖZ ...................................................................................................................................v
DEDICATION ..............................................................................................................vii
ACKNOWLEDGEMENT .......................................................................................... viii
TABLE OF CONTENTS ...............................................................................................ix
LIST OF SYMBOLS ................................................................................................. xiii
CHAPTER
1. INTRODUCTION..................................................................................................1
1.1 General Remarks ........................................................................................1
1.2 Scope of this thesis.....................................................................................3
1.3 Historical Background................................................................................4
1.3 Parameters for defining glass forming alloys.............................................7
1.3.1 Glass transition temperature (Tg) ....................................................8
1.3.2 Reduced glass transition temperature (Trg) ...................................10
1.3.3 Supercooled liquid region (∆Tx) ...................................................10
1.3.4 Maximum attainable thickness in amorphous form (tmax).............10
1.3.5 Critical cooling rate (Rc) ...............................................................11
1.4 Properties of Ti-based amorphous alloys .................................................11
ix
2. THEORETICAL APPROACHES AND MODELLING OF BULK GLASS
FORMING ALLOYS...........................................................................................14
2.1 Theory of glass forming alloys ................................................................14
2.1.1 Semi-empirical Approach .............................................................16
2.1.2 Thermodynamic and Kinetic Approach ........................................19
2.1.2.1 Ordered liquid alloys.........................................................20
2.1.2.2 Viscosity............................................................................26
2.1.2.3 Short range order...............................................................31
2.2 Electronic Theory of Alloys.....................................................................33
2.2.1 Principles of One-electron Theory ................................................33
2.2.2 Nearly-free Electron Model (NFE) ...............................................34
2.2.3 The Pseudopotential Theory of Interatomic Interactions..............38
2.2.4 Application of Pseudopotential Theory to Ti-based Binary

Amorphous Systems.....................................................................39
2.3 Theoretical modeling of Ti-based bulk glass forming systems................39
2.3.1 Selection of candidate Ti-based bulk glass forming system .........39
2.3.2 Evaluation of glass forming parameters........................................41
2.3.3 Fundamental equation of critical cooling rate..............................42
2.3.4 Gibbs free energy for the multicomponent system ......................43
2.3.4.1 Regular solution model ..................................................43
2.3.4.2 Mismatch term in entropy of mixing.............................44
2.3.5 Viscosity at melting temperature for glass-forming alloys ..........45
2.3.6 Modified equation of critical cooling rate....................................46
2.3.7 Ordering energy calculations .......................................................47

x
3. EXPERIMENTAL PROCEDURE ........................................................................50
3.1 Ti-Ni binary system..................................................................................50
3.1.1 Development of candidate bulk amorphous forming alloys ........59
3.1.2 Alloy preparation .........................................................................52
3.2 Crucible Production...............................................................................55
3.3 Structural characterization.....................................................................56
4. RESULTS AND DISCUSSIONS ..........................................................................59
4.1 Discussion of ordering energy and other GFA parameters ...................59
4.1.1 Data Tables................................................................................60
4.1.2 Interpretation of results .............................................................73
4.1.2.1 Binaries........................................................................73
4.1.2.1 Alloying additions .......................................................75
4.2 Discussion of experimental study .........................................................81
4.2.1 Alloy A1, Ti67Ni33 .......................................................................81
4.2.2 Alloy A2, Ti60Ni30Mo10 ................................................................83
4.2.3 Alloy A3, Ti55Ni30Zr8Mo5W2 .........................................................86
4.2.3.1 Copper mould cast.......................................................86
4.2.3.2 Near equilibrium cooled sample .................................92
xi
5. CONCLUSION ..................................................................................................103
6. FUTURE WORKS...............................................................................................105
REFERENCES............................................................................................................107
APPENDIX A .............................................................................................................114
xii
LIST OF SYMBOLS
SYMBOL MEANING
Rc Critical cooling rate
tmax Maximum tickness castable in amorphous form
Tg/Tm or Trg Reduced glass transition temperature
Tg Glass transition temperature
Tl Liquidus temperature
∆Tx Supercooled liquid region
Tm Melting temperature
X Crystallized fraction of alloy
Iv Nucleation frequency
Uc Crystal growth rate
t100(T) Time for whole crystallization transformation to occur
Scc(0) Concentration fluctuation in the long wavelength limit
Vij (r) Interaction energy between i and j atoms
xiii
Vord (r) Interaction energy of ordered structure
PA,B Probability that an A atom exists at site 2 as nearest neighbor of

a given B atom at site 1
ci Concentration of i atom
Q Configurational partition function
gr Degeneracy of the state
Er Configuration energy
kB Boltzmann constant
NA Number of atoms
R Gas constant
GF Formation Gibbs Energy
∆HM Change in mixing enthalpy
∆SM Change in mixing entropy
ξ (c) Viscosity isotherms
ξid Ideal viscosity
F1 Force applied for viscous flow
σi Parameter depends on size and shape of the diffusing particle
η Coefficient of viscosity
xiv
Dm Diffusion coefficient for liquid alloys
φ Parameter obtained from Scc
Ω Atomic volume
ai Activity of component i
ψi Individual electron wave function

Ω0 Volume per ion
EF0 Fermi energy
Ulattice Coloumb repulsion between the ion cores
U0 Volume-dependent electronic contributions to total energy of

crystal
Ubs Structure-dependent electronic contributions to total energy of

crystal
K Structure form factor
χ(q) Linhard’s function
→
α( q ) Ratio of the original potential of the ions to the crystal potential
W(q) Coloumb potential form factor

Z1 Constant of (2x10−6)
f Rate constant in jumps/s unit associated to diffusion
η Viscosity (for Inoue approach)
xv
Gl Gibbs Free Energy of liquid
Gs Gibbs Free Energy of solid
Ωij Regular solution interaction parameter between i and j elements
di Atomic diameter
η0 Pre-exponential term for viscosity
B Constant corresponding to the activation energy
f1 Temperature dependent parameter for calculating critical

cooling rate
f2 Temperature dependent parameter for calculating critical

cooling rate
xvi
CHAPTER 1
INTRODUCTION
1.1 General Remarks
Amorphous metallic alloys (metallic glasses) are one of the best examples of new
generation novel alloys. They are unique from various aspects arising from the lack of
long range order as found in conventional crystalline metallic alloys. The atoms in the
amorphous structure are randomly arranged, like in a liquid, rather than sitting on a
repeatable, orderly lattice which leads to a non-crystalline structure with no
microstructural features such as grain boundaries and dislocations.
As these novel alloys differ from conventional ones from the structural point of view,
they should also have different production methods and their formation (solidification
generally) is completely a different task. They possess nearly the same configuration
with the liquid state metal and that’s why these alloys are also frequently called liquid
metals. To do so, the solidification of these alloys should be so quick, to maintain the
liquid configuration in the solidified alloy, as the formation of the crystalline structure
could be prevented. The process is the freezing of the liquid into a solid state without
any change in the atomic configuration of the system. To achieve such a process
requiring very high solidification rate, a variety of rapid solidification techniques from
atomizing to melt spinning are utilized.
1
These techniques are successful to produce amorphous metals and alloys however
with a drawback which limits the usage of these unique alloys, the small size and
dimensions of the product. Conventional amorphous metals produced by rapid
solidification techniques are generally in the form of ribbons, sheets and other shapes
that are very small in one dimension. The reason for that is the high cooling rate
necessary to have a glassy structure at the end which is achieved by rapid heat transfer
from thin sections of the material.
Although these materials have some application area even in these small dimensions,
the possibility of producing these novel materials in larger dimensions, in bulk form,
is a very important point to be investigated.
Bulk amorphous metals are developing class of bulk metallic alloys which can be
produced in bulk form even with low cooing rates, exceeding a few ten millimeters in
diameter for some cylindrically produced samples [1-10]. The ability of this high glass
forming ability arises from a variety of different effects contributing in amorphous
phase formation. These alloy systems are generally multi-component ones with more
than three elements.
These novel alloys do not posses any weak spots in their structures (grain boundaries,
dislocations etc) as found in conventional crystalline metallic alloys. For this reason,
they are an intriguing class of structural materials and possess a range of interesting
properties, including near theoretical strength, high hardness, extremely low damping
characteristics, excellent wear properties, high corrosion resistance, low shrinkage
during cooling and almost perfect as-cast surfaces with good potential for forming and
shaping. In addition, amorphous alloys have a low coefficient of friction (about half
that of crystalline alloys of the same composition) [1-4]. Also included in this
classification are metallic materials whose crystalline microstructures (nanocrystals)
are formed from an amorphous state or are synthesized/derived from an amorphous
condition and exhibit combinations of crystalline and amorphous features. Research is
2
needed to develop new amorphous alloys and production methods for cost-effectively
producing them in bulk quantities.
The unique properties of these novel alloys maintain a continuing interest for the
development of these kinds of materials. It is clear that such a process requires a great
amount of effort as the theory of glass forming has inconsistencies for different
metallic systems. Hence, the efforts for developing new bulk amorphous systems with
enhanced glass forming ability focused mainly on an experimental basis. However,
the wide range of different elements and possible metallic systems makes it a very
difficult and time consuming process to develop such novel alloys. For that reason it
would be beneficial to somehow limit the possible metallic systems and possible
elements that favor the glass forming ability of these systems.
1.2 Scope of this thesis
The aim of this study is to try to establish such a basis for the theory of glass forming
in Ti-based systems. In order to achieve this, the general idea of glass forming theory
is combined with the electronic theory of alloys. The alloying additions to metallic
systems would affect the glass forming ability of that system for some reasons that
would be explained in latter chapters. So the main aim of this thesis study is to predict
alloying elements that would give a rise to the glass forming ability of the system.
Binary systems were taken to be starting points where a lot of information and data is
available for them. The study was carried out in two main bases; theoretical and
experimental. The stages of these studies are as follows:
1- Selection of Ti-based binary systems to be studied as candidate bulk

glass forming alloys by making use of the semi-empirical rules [5].
2- Calculation of the effects of alloying elements on the ordering energies
of pre-selected Ti-based binary systems by using the electronic theory
of alloys in pseudopotential approximation.
3
3- By combining the ordering energy calculations with the general theory
of glass forming, prediction of the alloying elements that will favor the
glass forming ability of Ti-based systems.
4- By the aid of the theoretical work, synthesis of new Ti-based bulk
glassy alloys.
1.3 Historical Background
It is well known that the first success of producing an Au70Si30 amorphous phase using
rapid solidification was by Duwez and co-workers in 1960 [6], which brought a new
era to amorphous alloys.
In 1990, inspiring news was claimed by Masumoto and Inoue [14]. They
systematically investigated the glass forming ability of some multi-component alloy
systems and succeeded in synthesizing new ternary amorphous alloys in the Mg-TM-
Ln, Ln-Al-TM, Zr-Al-TM, and Ti-Zr-TM (Ln=lanthanide elements, TM=transition
elements) systems where the critical cooling rates were about 10 to 100 K/s. In
addition, beginning in 1991, Johnson and colleagues produced bulk amorphous alloys
in Zr-T-Ni-Cu-Be, Zr-Ti-Ni-Cu, and related systems with lower critical cooling rates
that are even down to 1 K/s [7].
According to the classic nucleation theories, suppressing the nucleation and growth
reaction enable improvement of the formation of an amorphous phase by rapid
solidification. Some techniques have been adopted to suppress heterogeneous
reaction, for example, magnetic levitation, containerless cooling drop tube, and B2O3
melt fluxing method. At present, the high glass forming ability of multi-component
bulk amorphous alloys is interpreted from thermodynamics, kinetics and structures,
respectively. Good bulk metallic glasses are always located in a eutectic point nearby.
Based on new theoretical research, the achievement of large glass-forming ability and
low critical cooling rate comes from the following rules:
4
(1) multi-component alloy systems consisting of more than three elements and the
compositions close to deep eutectic point, (2) possessing high melt viscosity and
negative heats of mixing among the component elements, (3) reasonable different
atomic size ratios [8,9,11].
Since the first synthesis of an amorphous phase in the Au-Si system by a rapid
solidification technique in 1960 [6], a great number of amorphous alloys has been
produced for the last three decades. It is well known that Fe-, Co- and Ni-based
amorphous alloys found before 1990 require high cooling rates above 105 K/s for
glass formation and the resulting sample thickness is limited to less than about 50 µm.
As exceptional examples, one can observe that Pd-Ni-P and Pt-Ni-P amorphous alloys
have lower critical cooling rates of the order of 103 K/s and a large amorphous alloy
sphere with a diameter of about 10 mm is produced by repeated melting of the Pd-Ni-
P alloy covered with a B2O3 flux medium in a quartz crucible [10]. More recently,
since 1988, Inoue has succeeded in finding new multi-component alloy systems with
much lower critical cooling rates in the Mg- [12], Ln- [13], Zr- [14], Fe- [15], Ni- [16]
and Ti-based [17] alloy systems. Figure 1.1 shows the relationship between the
critical cooling rate (Rc), maximum sample thickness (tmax) and reduced glass
transition temperature (Tg/Tm) for amorphous alloys reported to date.
5
Figure 1.1 – Relation among the critical cooling rate for glass formation (Rc),
maximum sample thickness (tmax) and reduced glass transition temperature (Tg/Tm)
for typical amorphous alloys [11]
Some of the mechanical properties of glassy alloys in comparison with conventional

crystalline alloys are given in the below figure.
Figure 1.2 – Mechanical properties of bulk amorphous alloys in comparison with

conventional crystalline alloys [11]
6
Table 1.1 – Typical bulk amorphous alloy systems reported up to date together with
the calendar years when the first paper or patent of each alloy system was published
[11]
1. Nonferrous alloy systems

Mg-Ln-M 1988
(Ln = lanthanide metal, M=Ni, Cu, Zn)
Ln-Al-TM 1989
(TM = VI-VIII group transition metal)
Ln-Ga-TM 1989
Zr-Al-TM 1990
Ti-Zr-TM 1993
Zr-Ti-TM-Be 1993
Zr-(Ti,Nb,Pd)-Al-TM 1995
Pd-Cu-Ni-P 1996
Pd-Ni-Fe-P 1996
Pd-Cu-B-Si 1997
Ti-Ni-Cu-Sn 1998
Cu-(Zr,Hf)-Ti 2001
Cu-(Zr,Hf)-Ti-(Y,Be) 2001
2. Ferrous alloy systems
Fe-(Al,Ga)-(P,C,B,Si,Ge) 1995
Fe-(Nb,Mo)-(Al,Ga)-(P,B,Si) 1995
Co-(Al,Ga)-(P,B,Si) 1996
Fe-(Zr,Hf,Nb)-B 1996
Co-(Zr,Hf,Nb)-B 1996
Ni-(Zr,Hf,Nb)-B 1996
Fe-Co-Ln-B 1998
Fe-(Nb,Cr,Mo)-(C,B) 1999
Ni-(Nb,Cr,Mo)-(P,B) 1999
Co-Ta-B 1999
Fe-Ga-(P,B) 2000
Ni-Zr-Ti-Sn-Si 2001
1.3 Parameters for defining glass forming alloys
As the production methods and formation of bulk glassy alloys are somewhat different
from that of conventional crystalline alloys and also conventional amorphous alloys,
there should be some criteria to explain bulk glass forming systems. For that purpose
there are some empirical and semi-empirical parameters widely used in literature.
7
These parameters are all indications of the glass forming ability of the system, which
is the ability to form an amorphous structure instead of a crystalline phase or to vitrify
to solid from the melt. Also, there are specific characteristics and properties of glassy
systems different than crystalline counterparts.
1.3.1 Glass transition temperature (Tg)
Glass transition temperature (Tg), which is well-known parameter for a glass, is also
utilized for metallic glassy systems as the structure of the amorphous alloy is
considered to be the same with a glass. Glass transition is known to be a phenomenon
that the variation of viscosity with temperature is a continuous curve as shown in
Figure 1.3 (b). It is the point where there is a second order phase transformation in
which the viscosity of the system is a value to let easy plastic flow. The value is
usually defined as 1013 poise. In ordinary crystalline metallic alloys, there is a sharp
and discontinuous behavior at the melting temperature of the alloy. Figure 1.3 (a)
shows such behavior where the viscosity of the system suddenly increases enormously
and at that temperature the system goes to a structure change, usually, from a high
energy liquid state to a solid crystalline phase. Although ordinary metallic systems
behave as shown in Figure 1.3 (a), bulk amorphous alloys, more generally amorphous
alloys, has a behavior as shown in Figure 1.3 (b). That is one of the main aspects to
distinguish amorphous alloys from conventional crystalline ones.
8
a) b)
Figure 1.3 – Viscosity versus temperature (a) typical for metallic alloys, (b) typical for
glasses
For bulk amorphous alloys and conventional amorphous alloys, glass transition
temperature can be examined and defined by a series of thermal analysis techniques,
namely, DSC and DTA. It is defined as the point at which there is slight change in the
heat flow. An example DSC trace is shown in Figure 1.4.
Figure 1.4 – A typical DSC curve for a glassy metal.
9
1.3.2 Reduced glass transition temperature (Trg)
Many readily glass forming systems manifests either one or more deep eutectics, or a
steep and substantial decrease in Tl (liquidus temperature) with increasing percentage
of solute, to a ‘plateau’ over which Tl is low in comparison with the melting point of
the host metal. Thus there is a tendency for the glass forming ability (GFA) to vary
inversely with the ratio Tg/Tl, which is referred to as the reduced glass transition
temperature Trg [18,19]. The lower the Tl and the higher the Tg, then higher tend to be
the GFA. The highest known values of Trg for metallic alloys are in the range 0.66-
0.69, eg. 0.69 for Ca65Al35 [20].
1.3.3 Supercooled liquid region (∆Tx)
∆Tx (Tx – Tg) is another semi-empirically found criterion. Here Tx is the

crystallization temperature of the glassy system. This parameter can be explained as
the thermal stability of the alloy to resist crystallization for increasing the temperature
above the glass transition temperature (Tg). The greater the value ∆Tx, the higher the
stability of the alloy against crystallization. The supercooled liquid region, ∆Tx is also
shown to be linearly related to the largest diameter of a rod with a fully amorphous
phase [21, 22].
1.3.4 Maximum attainable thickness in amorphous form (tmax)
tmax is the maximum thickness that an alloy can be produced in amorphous form. It is
obvious that this is a directly proportional parameter to describe the glass forming
behavior of the system. In fact, all of the efforts in bulk amorphous alloy
investigations directed towards to produce systems with larger sections and to find
new systems with the capability of produced in bulk forms.
10
1.3.5 Critical cooling rate (Rc)
Rc (Critical cooling rate) is perhaps the mostly used parameter for defining the glass
forming behavior of a metallic system. As to be produced in glassy form by
conventional casting methods, where the cooling rate is not as much as high as rapid
solidification methods, an alloy system should have a low critical cooling rate. Rc is
the minimum cooling rate of the alloy at which it can be produced in amorphous form.
The theoretical calculations made in this study are generally intended to calculate the
Rc for the Ti-based alloy systems.
1.4 Properties of Ti-based amorphous alloys
At present, Ti-based bulk amorphous alloys are of significant scientific and

commercial interest due to their high tensile strength and their ability to be produced
in a bulk form by mold casting. As traditional structural and engineering materials,
crystalline Ti alloys are extensively used in many areas due to their excellent
corrosion behavior, low density, and attractive fracture related properties.
It should also be mentioned that their relatively high corrosion resistance at room
temperature and a relatively low density of the main alloying element Ti (4500 kg/m3)
that implies higher strength/density ratio compared to Fe- or Zr- based bulk
amorphous alloys [23–27].
The above mentioned result means that Ti-based amorphous alloys are not more the
subject of scientific curiosity but can be widely industrially applicable, for example as
structural materials.
On the other hand, there are problems in producing Ti-based amorphous alloys. One
of those drawbacks is the highly reactive nature of the Ti element at elevated
temperatures. This may result mainly in the differences between the intended
composition and final composition. Another problematic issue that was concluded
11
from the literature survey in the production of bulk glassy Ti-based alloys is that the
alloy composition rarely exceeds 50 atomic % Ti, in bulk amorphous form. This
probably arises from the nature of Ti element. This limits the advantages of the unique
properties of Ti element in such alloys. If new alloy composition are found where
higher than 50 atomic % Ti is used, the advantages of the Ti element could be used
more effectively.
Ti-based amorphous systems that were studied previously in the literature are given in
the table below.
Table 1.2 - Ti-based amorphous systems studied previously
Reference System
[28] Ti60Ni15Cu10Zr15
[29] Ti60Ni25xCuxZr15
[30] Ti50Ni24Cu20Sn3Si2B1
[2] Ti50Ni20Cu23Sn7
[3] Ti50(100-x)Ni20(100-x)Cu23(100-x)Sn(100-x)Mox
[1] Ti50Ni25Cu25
[31] Ti50Ni30Cu20
[7] Ti(50-x)Ni15Cu25ZrxSn3Be7
Ti34Ni8Cu47Zr11
[32] Ti33Ni8Cu47Zr11Fe1
Ti33Ni8Cu47Zr11Si1
[33] Ti33Ni(8-x)Cu47Zr11SnxSi1
[34] Ti65Ni25Zr(10-x)Yx
[35] Ti38.5Cu32Zr5.5Co14Al10
[36] Ti30Ni15Cu40Zr10Sn5
[37] Ti30(100-x)Ni15(100-x)Cu40(100-x)Zr10(100-x)Snx
[38] (Ti-Zr-Hf-Nb)-(Ni,Cu,Ag)-Al
[39] Ti50Ni15Cu32-xSn3Bex
Ti50Cu25Ni15Sn3Be7
[40]
Ti45Cu25Ni15Sn3Be7Zr5
Ti40Zr25Ni8Cu9Be18
Ti20Zr20Hf20Cu20M(Fe,Co,Ni)20
[41] Ti20Zr20Hf20Cu20M(Fe,Co,Ni)20
Ti20Zr20Hf20Cu20M(Fe,Co,Ni)20
12
In the following chapter, different theoretical approaches for glass forming and the
theories used for the modeling of bulk glass forming alloys in this study will be briefly
explained. Different approaches for the theory of glass forming and the electronic
theory of alloys in pseudopotential approximation will finally be discussed. In Chapter
3, synthesizing and characterizing of Ti-based bulk amorphous alloys will be
presented in detail. The results of the experimental investigation, ordering energy
calculations, predicted alloying elements to increase the glass forming ability,
synthesis of candidate bulk glassy Ti-based alloys and their characterization will be
discussed in Chapter 4. Chapter 5 will be a summary of results obtained in this thesis
study and the future works suggestions will be pointed out in Chapter 6.
13
CHAPTER 2
THEORETICAL APPROACHES AND MODELLING OF BULK GLASS

FORMING ALLOYS
2.1 Theory of glass forming alloys
On cooling, a liquid must undercool below the equilibrium crystallization temperature

before crystallization can begin because of the existence of an energy barrier to the
formation of nucleation. The degree of undercooling depends on several factors,
including the initial viscosity of the liquid, the rate at which viscosity increases with
decreasing temperature, the temperature dependence of the free energy difference
between the undercooled liquid and crystal phase, the interfacial energy between melt
and crystal, the volume density and the efficacy of heterogeneous nucleating particles
and imposed cooling rate. Liquid transition metals such as iron, nickel and cobalt, in
which the heterogeneous nucleants have been largely removed by a flux, can be
undercooled in bulk by more than 200 K under slow cooling conditions [42].
Similarly, when metallic melts are subdivided into very fine discrete droplets,
suspended in a liquid medium, at least some droplets will be devoid of any
heterogeneous nucleating particles and nucleation occurs homogenously at relative
undercoolings typically 0.2Tm-0.3Tm, where Tm is the equilibrium freezing
temperature [43]. However, the growth rates for crystals in metallic melts are very
rapid once nucleated and, where the rate of heat removal to the surroundings is small
rapid recalescence occur.
14
If, however, the liquid is cooled rapidly by heat removal to a sink, the influence of
heterogeneous nucleants is increasingly delayed for kinetic reasons and, as the cooling
rate is increased, the undercooling is enhanced and the recalescence decreased. Thus,
the temperature range over which crystallization proceeds become increasingly
depressed, leading to structural modifications; this leads initially to the refinement of
the microstructural features then, for alloys, depending on the composition, the
extension of solute solubility and the formation of metastable phases. Eventually,
when the cooling rate is sufficiently high, crystallization is suppressed because of
insufficient time for significant growth or, in the extreme, for nucleation.
Although the driving force for the nucleation is continuously increasing, this is
opposed by the rapidly decreasing atomic mobility which, at very high undercoolings,
dominates. Eventually, the atomic configuration of the liquid departs from equilibrium
and then shortly thereafter becomes homogenously frozen, at the so-called glass
transition temperature Tg.
Analysis of diffraction data [44] suggests that the atomic configuration of a metallic
alloy glass bears a rather close resemblance to the static structure of the equilibrium
liquid near its freezing temperature, but with the atoms in the glass vibrating about
positions that are more condensed and now frozen. The glass structure has been
proposed as approximating to an assemblage of dense-random packed hard spheres
[45] of two or more different sphere diameters. For alloys where the solute atoms are
sufficiently concentrated and are sufficiently different in size from those of the
solvent, these configurations are stable against crystallization. As would be expected
for the dense packing of atoms approximating to hard spheres, there is a significant
degree of topological short-range order. There is also clear evidence of chemical
short-range order, i.e. non-random packing of atoms of different species, that is
carried through from the liquid, and, indeed, enhanced [46]. It has been further
suggested [47] that the local structure in a metallic glass resembles that in the
15
derivative ‘inter-metallic’ crystalline phase with an essentially disordered
arrangement of these structural units, similar to network glasses.
The process of vitrifying a liquid is therefore, strictly, one avoiding the nucleation of
crystals during cooling, although a more practical definition would be avoidance of a
just detectable fraction of crystal. The glass forming ability (GFA) of a material is
then determined by the kinetics of nucleation process and, for practical purposes, of
the early stages of crystal growth.
The conventional strategy for developing metallurgical alloys is to select the main
component based on a primary property requirement, and then to use alloying
additions to confer secondary properties. Such alloys have slowly developed into
complex multi-component systems in order to achieve the required balance of in-
service properties needed for advanced engineering applications. Many successful
attempts were reported previously however this approach is very time consuming. The
main reason for that is that the theory lying beneath the bulk glass formation in
metallic systems is still a problematic and unresolved issue although there were some
attempts to settle a theory for glass formation of metallic systems.
The idea in this study is to model the possible glass forming systems by a method
which incorporates the electronic theory of alloys in pseudo potential approximation
into the classical glass forming criteria and theories supposed previously. By doing
such, we can eliminate the systems which seem to have less chance of forming bulk
glasses and this saves a great time and effort in the way of modeling and finding new
glass forming systems.
2.1.1 Semi-empirical Approach
For the formation of an amorphous phase, the essential process is the solidification
from liquid phase to suppress the nucleation and growth reaction of a crystalline phase
16
in the super cooled region between melting temperature (Tm) and glass transition
temperature (Tg). However, it has been succeeded in developing new multi-
component amorphous alloys with much lower critical cooling rate (Rc) ranging from
0,100 K/s to several hundreds K/s, as shown in figure 1. Consequently, the maximum
sample thickness for glass formation (tmax) increases sharply from several millimeters
to about one hundred millimeters. Moreover, figure 1 shows that the new amorphous
alloys have higher reduced glass transition temperature (Tg/Tm) above 0,60 and the
highest Tg/Tm value reaches 0,73. Furthermore, the new multi-component amorphous
alloys have a much wider supercooled liquid region before crystallization which is
defined by the difference between crystallization temperature (Tx) and Tg, ∆Tx = (Tx-
Tg), as shown in Figure 2.5. From the empirical strong relations between Rc, tmax and
Tg/Tm or ∆Tx shown in Figures 2.1 and 2.5, it is known that the high glass-forming
ability is obtained in the satisfaction of the following two factors: (1) high Tg/Tm, and
(2) large ∆Tx.
Figure 2.1 -Relation among Rc, tmax and ∆Tx(=Tx-Tg) for typical bulk amorphous
alloys
17
The reason for the achievement of the large glass-forming ability in these alloy
systems has consistently been proposed from different frameworks; (i) Multi-
component alloy systems consisting of more than three elements, (ii) significantly
different atomic size ratios above about 13%, and (iii) optimum negative heats of
mixing among the constituent elements. The supercooled liquid in the alloy systems
which satisfy the three empirical rules has a higher degree of dense randomly packed
structure which is suitable for the suppression of nucleation of a crystalline phase
through the increase in the liquid/solid interface energy as well as for the difficulty of
the redistribution of constituent atoms on a long range scale leading to the progress of
crystallization [11].
Constituent elements having large negative heats of mixing and large

atomic size ratios above 10%
Formation of amorphous phase with a higher degree of dense random

packed structure
Increase of solid/liquid Difficulty of atomic rearrangement

interfacial energy of the constituent elements on a long
range scale
Suppression of nucleation of cystal phases Suppression of crytsal growth
Figure 2.2 – Summary of the reasons for the achievement of the high glass forming
ability from the semi-empirical point of view
18
2.1.2 Thermodynamic and Kinetic Approach
When a liquid of suitable composition is strongly undercooled, its viscosity becomes

so high that elementary atomic motion can take place only on a time scale for hours or
days and a transition to a solid having a disordered structure takes place. In the case of
metallic alloys, this can happen only if crystal nucleation and growth within the melt
are avoided by means of rapid quenching. Therefore, glass formation is often
discussed in terms of prevention of crystallization in the liquid alloy [18] and the most
widely used framework is the classical Johnson-Mehl-Avrami theory as adapted to the
present problem by the Uhlmann-Davies treatment [48, 49]. In this approach, the
crystallized fraction of the alloy, x, is expressed in isothermal conditions as;
x ≈ IvUc3t4 (2.1)
where t is the time, Iv the nucleation frequency and Uc the crystal growth rate. It is
conventionally accepted that a glass is formed when no detectable crystalline fraction
is found in the material, i.e. x ≤ 10-6 [18]. Both the homogeneous nucleation frequency
and the crystal growth rate are zero at the equilibrium solidification temperature, Tm.
The nucleation rate is very slow in the proximity of Tm; it reaches a maximum at
substantial undercooling and then decreases steadily as the glass transition
temperature, Tg, is approached. The growth rate reaches its maximum soon below Tm
and then decreases steadily.
Nucleation is generally considered a steady-state process, i.e. its rate is constant at any
given temperature. In fact, in most cases the time necessary to reach the steady-state
population of embryos at the very beginning of the transformation is negligible with
respect to the overall time taken to obtain a substantial volume fraction of the new
phase. But, as no transformation is wanted here, the quenching time can become
comparable with the nucleation time lag and transient effects can possibly play an
important role in glass formation.
19
On the other hand, a kinetic perspective of glass formation is considered, from a TTT
curve, a CCT curve can be computed directly, by assuming the additivity of the
amount of transformation, i.e. the instantaneous transformation rate is a function of
temperature and of the amount of transformation, but not of the thermal history of the
material. The transformed fraction is thus given by [50];
4
1 T 
X (T ) =  * ∫ dT / t100 (T ) (2.2)
 q Tm 
where q is the constant cooling rate and t100(T) is the time for the whole
transformation to occur. The integral is computed numerically using a suitable
temperature interval and a CCT curve is obtained by computing the temperature at
which X(T) = 10-6 for each cooling rate. The critical cooling rate for glass formation is
obtained as the highest cooling rate able to transform the predetermined amount of
alloy [50].
On the other hand, the microscopic reasons for glass formation tendency in metallic
alloys have not been understood well by any above approaches to metallic glasses.
More atomistic approach to the amorphous structure formation is required to resolve
and to understand the formation of glassy state by investigating the interatomic
interactions and related properties by means of electronic theory of alloys.
2.1.2.1 Ordered liquid alloys
In a binary alloy, the substructure of the system is either in an ordered condition

(ordered alloy) where unlike atoms prefer each other as nearest neighbors, or in a
disordered condition (disordered alloy) where like atoms are preferred to pairs as
nearest neighbors over unlike atoms from the point of view of interatomic
interactions. Unfortunately, distinguishing the constituent atoms is somehow difficult
20
and that leads to a problem of identification of nearest-neighbor pairs. For that reason
to gather information about interatomic interactions, observed thermodynamic
functions such as, activity, heat of mixing, excess Gibbs free energy of mixing etc or
other thermophysical properties (viscosity, diffusivity, density, surface tension,
electrical resistivity, etc ) as well as structural data of the system under consideration
can be used. The following parameters containing some empirical criteria as well as
microscopic parameters summarized below are used to clarify the ordered alloys:
(a) Alloys exhibiting negative deviations from Raoult’s law.

(b) The heat of formation and the excess Gibbs energy of mixing are negative.
(c) The concentration fluctuation in the long wavelength limit (Scc(0)) is less than the
ideal value.
(d) If Vij (r) (i, j=A, B) are the effective interatomic potential, then one can define the
radial form of the order potential, i.e.
V AA (r ) + V BB (r )
Vordered (r ) = V AB (r ) − (2.3)
2
For ordered alloys, one requires that Vord(r) > 0 around the nearest-neighbor distances.
(e) In the framework of regular solution theory, the interchange energy (or order
energy) ω > 0.
(f) Warren–Cowley short-range order parameter α1 should be less than 0 (-1≤α≤0).
Consider that two liquid metals, say A and B, at standard state are mixed together to
form an alloy. On mixing, if A and B atoms prefer to remain self-coordinated (i.e. A–
A pair or B–B pair) over the heterocoordinated (i.e. A–B pair), then we call it a
segregating alloy. Phase separation is an extreme condition of segregation.
21
In order to quantify it, let us consider the Warren–Cowley (Warren 1969, Cowley
1950) [78] short-range order parameter, α1, for the first-coordination shell, which is
defined in terms of the conditional probability as,
PA,B=cA (1-α1) (2.4)
where PA,B defines the probability that an A atom exists at site 2 as a nearest neighbor
of a given B atom at site 1. Equation (2.4) provides an immediate insight into the local
arrangement of atoms in the mixture. For a random distribution of atoms, PA,B =cA,
then α1=0. If α1 < 0, then A–B pairs of atoms are preferred over A–A or B–B pairs as
nearest neighbors. By taking a probabilistic approach one can easily show that the
limiting values of α1 lie in the range,
cA
− ≤ α1 ≤ 1 for cA ≤ 1/2
cB
(2.5)
cB
− ≤ α1 ≤ 1 for cA ≤ 1/2
cA
For CA=CB= ½ and -1≤α1≤1 (2.6)
The minimum possible value α1, min=-1, means complete ordering of A–B pairs in the
melt, whereas the maximum value, α1, max =1, suggests that the A–A and B–B pairs in
the melt are totally segregated. For ordering alloys, α1 varies from -1 to 0.
Let start with the configurational partition function, Q, which can be expressed as
[51],
Q = ∑ g r e − E r / k BT (2.7)
r
22
where gr stands for degeneracy of the state r > Er is the configuration energy.
The basic task is to obtain gr and Er for a binary alloy consisting of NA(= NCA) atoms
of element A and NB (=NCB) atoms of element B.
To begin with, the work under the crudest approximation that: (1) the constituent
atoms A and B are sufficiently similar in size and shape so that they are
interchangeable on the lattice and (2) all configurations of atoms, whether in pure
state A or pure state B, or in the alloy A–B, have equal energy. It is equivalent to
saying that the mixing of atoms leaves this energy unchanged, i.e. there is no energetic
effect. Therefore, we have
QA≡QB (2.8)
V AA + V BB
V AB = (2.9)
2
where Vij is the mutual energy of a pair of nearest neighbors. Within these
approximations, one readily writes
N!
gr = (2.10)
N A! N B !
Er= -cA (NAA VAA)-cB ( NBB VBB) (2.11)
The bracketed terms in equation (2.11) represent the energy of pure substances A and
B, respectively. For solid and liquid phases
F ≈ GF = -kB T lnQ (2.12)
23
one obtains
G F = −c A ( N AAV AA ) − c B ( N BBV BB ) + RT ∑ c i ln ci (2.13)

i
or
GM = RT ∑ ci ln ci (2.14)
i
 ∂G 
S M = − M  = − R ∑ c i ln c i HM=0 (2.15)
 ∂T  i
and finally,
−1
 ∂ 2GM 
S cc (0) = RT   = c AcB (2.16)
 ∂c
2

Thus, under these approximations Scc(0) turns out to be a well behaved function which
is always symmetrical at cA = cB = 1/2 and is independent of any physical constraints.
We also conclude that if the size and the enthalpic effects are absent, systems behave
as an ideal mixture.
Lets now incorporate the ‘energetic effect’ and consider that there will be
contributions to the potential energy from A–B pairs of neighbors as well as from A–
A and B–B pairs. In contrast to approximation (2.9), now assume that
V AA + V BB
V AB = −ω (2.17)
2
24
where ω is usually known as the interchange energy or order energy. In effect A–A,
B–B and A–B pairs of atoms are now energetically distinguishable. Therefore the
configurational energy, E, becomes,
Er = -cA(NAAVAA)-cB(NBBVBB)- N AB ω (2.18)
where N AB represents the equilibrium or average value of A–B pairs of atoms. In the
simplest approximation where the atoms NA and NB are distributed completely
randomly, NAB can be given by,
NANB
N AB = (2.19)
NA + NB
By substituting these values into equations (2.7) and (2.12),
GM = RT ∑ ci ln ci − Nc Ac Bω (2.20)
i
Hence
 dω 
S M = − R ∑ ci ln ci − Nc A c B   (2.21)
i  dT 
 dω 
H M = Nc A c Bω − Tc A c B N   (2.22)
 dT 
In particular, equation (2.20) is often referred to as the conformal expression.

Equation (2.20) can readily be used to obtain an expression for Scc(0) [53]:
25
c AcB
S cc (0) = (2.23)
1 + c A c B (2ω / k BT )
It may be noted that at a given T and P, GM and Scc(0), which in turn are responsible
for yielding the conditions of critical mixing, depend on the absolute value of ω ,
whereas SM and HM depend on both ω as well as d ω /dT.
Equation (2.23) suggests that Scc(0) diverges for:
−ω
= 2.0 at cA=cB=1/2 (2.24)
k BT
The divergence in Scc(0) is linked to enthalpic effect. Positive ω (VAB>(VAA+VBB)/2)

favors heterocoordination over homocoordination or segregation. A system which is
dominated by positive ω infuses divergence in Scc(0). It is equivalent to saying that
phase separation in a binary mixture seems to be induced by energetic effects.
2.1.2.2 Viscosity
Viscosity (ξ) of liquid alloys is equally important in the understanding of the atomic
level structure and interactions. As in the case of thermodynamic functions, the
composition dependence of ξ of liquid alloys is also found to exhibit either a linear
variation, or positive or negative deviations from the linear law ( ξ = c Aξ A0 + c Bξ B0 ). ξ i0
is the viscosity of pure component i. The viscosity isotherms ξ (c), for simple liquid
alloys such as Na–K, Ag–Au, Sn–Pb, Pb–Bi and others, are usually either linear or
slightly concave. Large positive deviations from a linear law in viscosity isotherms ξ
(c) have been observed for compound-forming liquid alloys. However, the data ξ (c),
for segregating and immiscible liquid alloys present a mixed picture.
26
Moelwyn-Hughes [79] presented a simple formula for the viscosity of a binary
solution:
  2ω 
ξ = ξ id 1 + c A c B   (2.25)
 k T
 B 
where ξ is, as usual, the interchange energy (see equation (15)). One sees that ξ < ξid
for ω > 0 and vice versa, if ω < 0. We shall see later that ω is negative for ordering
liquid alloys. In view of relation (2.25) (take d ω /dT ≡ 0), ξ becomes:
(ξ − ξ id ) = −2c c
HM
(2.26)
ξ id
A B
RT
From another point of view, taking the starting point the quasilattice theory (QLT)
[52], in which one considers a binary mixture consisting of Nc1 atoms of component 1
and Nc2 of component 2. One assumes that a small gradient of concentration c1 is
maintained is an equilibrium condition along the x-direction by the application of a
force F1, such that for a dilute alloy we can write:
d ln c1
F1 = − K BT (2.27)
dx
here, K B is the Boltzman constant and T is the temperature. Using equation (2.27),
Singh and Sommer [52] showed that it is possible to derive an expression relating the
viscosity and the diffusion coefficient Dm for liquid alloys as:
K BT  c1 c2 
η=  + φ (2.28)
Dm  σ 2 σ 1 
27
where σi depends on size and shape of the diffusing particle. η is the coefficient of
viscosity. The thermodynamic property of viscosity is:
c1c2
φ= (2.29)
S cc (0 )
It may be pointed out that Dm in equation (2.28) is not the measured (Dmexp)
interdiffusion coefficient, but stands for Dmexp = Dm φ . A more convenient expression
for η is:
η = η 0φ (2.30)
with
K BT  c1 c2 
η0 =  +  (2.31)
Dm  σ 2 σ 1 
Ideally, one expects that η0 should be linear in c1, the implication of this is that the
deviation of η − c1 isotherm from the additive rule of mixing, i.e. η = ∑i c iη i can be
ascribed to the factor φ . This factor has been extensively studied in literature [53] for
a large number of binary liquid alloys. The important inference that can be drawn is
that
{ ~ 1 for simple liquid alloys

φ = {« 1 for compound forming alloys
{» 1 for segregating and immiscible alloys
Osman and Singh [54] have carried out thermodynamic investigation of φ for the
more general case, in which one incorporates the entropic effects (through the size
ratio γ=Ω2/ Ω1, Ω2> Ω1, Ω being the atomic volume). They derived an expression for
φ given by:
28
φ = 1 − c1c2 g (γ , ω ) (2.32)
where
2γ 2W − (γ − 1) {c1 + γc2 }
2
g (γ , ω ) = (2.33)
(c1 + γc2 )3
with
 ω 
W = Ω1   (2.34)
 K BT 
ω = (Z [V AB (V AA + V BB ) / 2]) being the interchange energy. ω AB , ω AA and ω BB are the

energies for 1-2, 1-1 and 2-2 pairs of atoms, respectively, and Z is the coordination
number of the liquid alloy. Using Equation (2.30) and Equations (2.33-2.35), we can
∆η
express :
η0
∆η
= −c1c2 g (γ , ω ) (2.35)
η0
The factor g (γ , ω ) which incorporates both energetic and size effects is responsible
for the characteristic behavior of ∆η for a given liquid binary alloy. In the light of
conformal solution results Singh [55], one can show that:
∆η − HM
= (2.36)
η0 RT
where R is the ideal gas constant and HM is the enthalpy of formation.
29
Using the equations as illustrated above, one does not have enough thermodynamic
quantities in order to relate it toη . To do this, we note that the general expression for
the Gibbs free energy of mixing GM is;
GM = −TS M + H M (2.37)
where SM is the entropy of mixing and HM the enthalpy. From Guggenheim’s theory
of mixtures of polymers [56], QLT makes it possible to write an expression for GM as
GM
= c2 lnψ + c1 ln(1 −ψ ) + c1ψW (2.38)
RT
where,
γc 2
ψ = (2.39)
c1 + γc 2
and Scc(0) can easily be calculated form the standard relationship
−1 −1 −1
 ∂ 2 GM   ∂a   ∂a 
S cc (0 ) = RT   = c2 a1  1  = c1a2  2  (2.40)
 ∂c1  ∂c1 T , P  ∂c2 T , P
2
T ,P , N
ai is the activity component of i. the first of these identities together with Equation
(2.39) yield an expression for φ which is same as in Equation (2.33). Alternatively
Scc(0) can be evaluated directly from the measured activity data by using the last two
equalities of Equation (2.41). Scc(0) obtained from the activity data can now be used in
Equation (2.33) to ascertain the unknown parameters i.e. γ and ω.
η − η 0 ∆η
= = −c A c B g (γ , ω ) (2.41)
η0 η0
30
2.1.2.3 Short range order
By virtue of the basic thermodynamic relations, Scc(0) and αl (chemical short-range

order (SRO) parameter) are directly related. For a mixture where size effects are
negligible there exists an exact relation between Scc(0) and αl for different shells,
S cc (0)
= 1 + ∑ Z lα l (2.42)
c AcB l
where Zl and αl are the coordination number and SRO parameters for the lth shell (l
varies from first-neighbor shells to higher shells). Later, Bhatia and Singh (1982) used
the lattice model theory to obtain expressions for αl and Scc(0), [53].
s −1
αl = (2.43)
s +1
and
c AcB
S cc (0) = (2.44)
1
1 + Z (1 / s − 1)
2
with
[ (
s = 1 + 4c AcB e −2ω / ZkbT − 1) 1/ 2
] (2.45)
It is obvious that for ω /kBT→0, equation (2.45) implies αl = 0, i.e. a random

distribution of atoms in the alloy. If ω =kBT > 0, αl is positive, i.e. like atoms (A–A
or B–B) tend to pair as nearest neighbors and for ω =kBT < 0, αl is negative which
shows a preference for unlike atoms (A–B) to pair in the alloy.
31
By taking (2.43) and (2.44) together, one obtains an explicit relation between Scc(0)
and αl for the first-neighbor shell,
S cc (0) 1+αl
= (2.46)
c A c B 1 − ( Z − 1)α l
This can also be expressed in expanded form, i.e.
S cc (0)
= 1 + Zα l + Zα l ([( Z − 1)α l ] + Zα l [( Z − 1)α l ] + ...
2
(2.47)
c AcB
The two results, equation (2.42) and (2.47), are only in agreement if Zlαl rapidly tends
to zero for higher shells. Therefore, in the nearest-neighbor shell l=1 equation (2.46)
can be used to determine αl from Scc(0) i.e.
( S * − 1) S cc (0)
αl = S* = (2.48)
S * ( Z − 1) + 1 c AcB
As T→Tc, Scc(0)→ ∞, therefore equation (2.48) implies that
1
αl = (2.49)
( Z − 1)
Equation (2.49) is of considerable physical significance in the light of results that have
been obtained from the pioneering experiments of Hensel and coworkers. The neutron
diffraction experiments on expanded fluid Cs by these authors exhibit a significant
decrease in the coordination number as one approaches the critical point of the liquid–
vapor interface. Liquid Rb also shows similar features.
32
These results suggest that Z= 2 at the critical point of the phase boundary.
Interestingly, if one substitutes Z = 2 in equation (2.49), one gets αl =+1 which is the
maximum possible value of αl that is needed for total segregation. This result is in
contrast to the general belief that the lattice model theory which is the basis of
equation (2.49) does not yield the required value of αl ~ (1.0) for phase separation.
Ordinarily for Z = 10, equation (2.49) gives αl = 0.11 which is far lower than the
required value for phase separation.
As it was mentioned previously, researchers have been working not only for
producing bulk amorphous metallic alloys but also for glass formation theory.
Consequently, many different approaches have been established with doubtful validity
and generality. Here, the most familiar and accepted criteria were briefly summarized.
2.2 Electronic Theory of Alloys
2.2.1 Principles of One-electron Theory
In principle, it is possible to find out everything about a structure by solving

Schrödinger’s equation for a system of interacting nuclei and electrons that form the
structure. This problem, however, is too hard to solve and some simplifications are
therefore unavoidable.
First, it is generally assumed that the nuclei are too massive to follow the rapidly
changing spatial distribution of the electrons (the adiabatic approximation). For this
reason, two Schrödinger’s equations will be considered one for the electrons and the
other for the nuclei. In the following, the one with the behavior of electrons will be
concerned.
It is further assumed that instead of treating the electronic subsystem as a whole, it is

possible to consider separately the motions of individual electrons. Each of them is
then thought of as moving in the effective field of the (stationary) nuclei and all other
33
electrons (hence the name – the effective field approximation). Accordingly, the total
electron wave function is expressed in terms of individual electron wave functions, ψi.
Further approximations are made in the actual evaluation of the total function and in
the consequent determination of the effective potential as seen by a single electron
(Pauli-exclusion principle). This leads to a system of one-electron Schrödinger
equation in the Hartree-Fock approximation including both Coulomb and exchange
interactions between the electrons.
The one electron theory is the primitive or basis. It has been worked in detail by
several times, however it will be surveyed in some detail through, first of all, nearly-
free electron model.
2.2.2 Nearly-free Electron Model (NFE)
In this model, a structure is viewed as a spatial lattice of ions embedded in an electron

gas. While in linear combination of atomic orbitals the perturbation in the eigenvalue
problem is the departure of the true potential from the atomic potential, in an NFE
model it is the departure from zero. For a zero potential (in i.e. vacuum) an electron
wave function is a plane wave normalized to all space. In a structure, the
normalization integral may be conveniently presented as the sum of contributions
from all the structural sites. In the following, more complicated effective potentials
→
(pseudopotentials) will be introduced with formfactors dependent both on q , any
→
vector and on K wave vector. These formfactors and potentials are called nonlocal.
Moreover, a perturbation theory must be introduced here. It is assumed that the flat-
bottomed potential well of free electron theory is a good approximation to the real
potential in a metal.
34
Additionally, in the Fermi free-electron gas model, the structure formation process is
as follows: N neutral isolated atoms are each stripped of Z outer (valance) electrons.
The resulting ions are then brought together to form a structural lattice, with a volume
of Ω0 per ion. An electron gas is then allowed into the lattice, its spatial distribution
being assumed uniform, so that its density is Z / Ω0. If the fact that the lattice potential
is not constant is ignored, the electron dispersion law is simply E = K2. The energy
levels occupied by the electrons range from zero to a maximum, which is known as
the Fermi level of a free electron gas:
2
 3π 2 Z  3
E F = 
0
 = K F2 (2.50)
 Ω0 
To calculate the total structure energy in the NFE model, the dispersion laws are
summed over all the occupied states. This is performed by integrating the perturbation
theory expansion in the Rayleigh-Schrödinger form over all the wave vectors within
the Fermi sphere. As a result, the total structure energy, Σstr, takes the form;
Σ str = U 0 + U bs + U lattice (2.51)
where Ulattice takes account the Coulomb repulsion between the ion cores; U0 and Ubs
are respectively the volume and structure-dependent electronic contributions to the
total energy:
Ω  2 → →
 3
U0 = 2* * ∫ 
(2π )3 inside
 K + K V K d K
 (2.52)
the
Fermi
sphere
35
2
→ → →
2 K+ qV K
Ω →
(2π )3 ∑ ∫
U bs = −2 * * S q d 3 K − U elint (2.53)
  → 2
q  →

K+ q − K
inside 2
the
Fermi
sphere
 
→
where the gn are replaced, for generality, by the ordinary position vectors q . The U0
term describes a “free” electron gas with the inclusion of electron-electron interaction;
Ubs is associated with band characteristics and is therefore called the band-structure
→
energy. If a potential V is local, its formfactor is K -independent and can be taken out
→
of the K integral that appears then in Ubs is known as Lindhard’s function:
→ Ω 1 d 3K
χ  q  = −2 * * * ∫ (2.54)
  (2π )3 N inside  → →
2 →
K+ q − K
2
the
Fermi  
sphere
The structure potential is composed of the ionic potentials (that is, about the screening
→
mechanism). χ(q) is a function arising from perturbation theory whereas α( q ) is the
ratio of the original potential of the ions to the crystal potential. A frequently used
characteristic function Vbs(q) is defined as;
Vbs(q) = |V(q)|2X(q)α(q) (2.55)
The interatomic interaction potential has the form of
∫ [W ]
Z 2e2 2Ω 2
→→
V (r ) = + str
(q) χ (q)ε (q)e * iq r
d 3q (2.56)
r (2π )3
36
It is considered the simplest pseudopotential, namely the Coulomb potential (-Ze2 / r)
with a formfactor;
4πZe 2 1
W (q) = − (2.57)
Ω0 q 2
This is in fact a Heine-Abarenkov type potential with R = 0. The ordering potential

itself is
V ( g i ) = VAA ( g i ) + VBB ( g i ) − 2VAB ( g i ) (2.58)
will take the form
ı
2 →→
V ( gi ) =
N
∑ F ( q )e
q
p
i q gi
(2.59)
or
Ω sin qg i
V ( gi ) = ∫ dq * q Fp (q)
2
(2.60)
π2 qg i
here
−
Ω 1 − ε (q ) 2π 2 1  − q2 
( )
2
Fp (q ) = ∆W b (q ) q 2 + ∆Z exp  = Fbs (q ) + Fes (q ) (2.61)
8π ε0 −
Ω q 2
 4η 
It is easy matter to show that V(gi) may be written as
37
Ω  Ω 2 1 − ε (q) b 2π * 2  − q 2 
V ( gi ) =
π2 ∫ dq * q
2

sin qg i
q W ( q )
2
+ Z ( )
exp  4η 
 8π ε * (q) B B
qg i q2 
2Ω sin qg i  Ω 2 1 − ε (q) b 2π * *  − q 2 
− 2 ∫ dq * q 2  q W ( q )W b
( q ) + Z Z exp
π qg i  8π ε * (q)
A B
q2
A B
 4η 
Ω sin qg i  Ω 2 1 − ε (q ) b 2π  2 
+− ∫ dq * q
2
 q
qg i  8π
2 2
( )
W A (q ) + 2 Z * exp − q
4η 
(2.62)
π 2
ε (q )
*
q  
Here short range order parameter for the first coordination sphere is given:
α1   V ( gi )  
= c (1 − c ) exp −  − 1 (2.63)
(1 − α1 )2   K B Τ  
However, it is more consistent to obtain:
→→ →
−i q g i
e dq
α ( gi ) = ∫ (2.64)
c(1 − c) → →→
1+ ∑ i
K B Τ g ≠0
V ( g ) e i q gi
2.2.3 The Pseudopotential Theory of Interatomic Interactions
In the calculation of potential seen by an atomic electron, Hartree-Fock approximation

is used. The motion of an atomic electron is usually described in the Hartree-Fock
approximation and it consists of attraction by the nucleus, Coulomb repulsion from
the rest of the electrons and the exchange potential which is again attractive and
contains exchange self-action term, ψi. Here, a valance electron of a neutral atom may
thus be said to move in the field of a singly-ionized atom, the potential it feels being
produced by all the electrons except itself. In the Hartree-Fock approximation, a
potential depends on the state it acts upon.
38
2.2.4 Application of Pseudopotential Theory to Ti-based Binary Amorphous
Systems
By using above equations, interatomic potentials of Ti-based binary metallic systems,

namely Ti-Ni, Ti-Cu, Ti-Al, Ti-Fe, Ti-Co, have been calculated by FORTRAN
programs which are available in METU Metallurgical and Materials engineering
Department. These calculations show ordering conditions for having short range order
(SRO) or disorder structures. However, as the above theory does not apply well for
the noble metals such as Cu, the results from Ti-Cu binary system can not be
evaluated. As a result this binary system will be out of consideration.
2.3 Theoretical modeling of Ti-based bulk glass forming systems
2.3.1 Selection of candidate Ti-based bulk glass forming system
It was tried to determine the glass forming ability in the view of previously introduced
models and theoretical formulas by combining them with a new approach for
determining the glass forming ability, the electronic theory of alloys in the pseudo
potential approximation. This theory relates the viscosity, ∆HM etc. terms that are used
to determine the glass forming ability theoretically with the ordering energy of alloys.
The theory lying beneath the pseudopotential approximation was described in the
previous chapters.
It was first decided which systems should be studied in detail. The determination of
the systems was done by choosing the two base elements in the previously studied
systems and also by choosing the possible new glass forming binary systems.
The decision of these possible glass forming systems was based on some criteria. The
empirical and semi-empirical rules were used in decision making of possible glass
forming alloys.
39
The approach here was to look at the phase diagrams of titanium and to search for the
intermetallic containing deep eutectics. The reason for being good candidates of glass
forming alloys in these portions of the phase diagrams were described in the above
sections. Intermetallics show non-faceted type growth behavior where the growth of
the intermetallic phase is relatively small. This is a key factor for obtaining high GFA
as the growth of phases should be inhibited in order to end with a glassy structure
instead of a crystalline one. It is clear that system compositions in the range of phases
having growth problems such as intermetallics are good candidates for finding high
GFA alloys. Also systems that have a sequential peritectic and eutectic
transformations seem to be particularly important in Bulk Glass Formation of alloys.
It has been reported that [71, 72] the alloy systems, which readily forms intermetallic
phases through peritectic reactions and subsequently undergo eutectic reactions,
appear to be a potential candidate for the production of bulk amorphous alloys. The
alloy composition under consideration has such a characteristic behavior that confirms
the possibility of producing bulk amorphous alloys in the vicinity of this alloy
composition.
The systems that were used in the following parts of this thesis were concluded as in
the below table:
Table 2.1 – Systems studied
System Subsystem
Ti-Ni Ti67Ni33 Ti50Ni50 Ti33Ni67
Ti-Al Ti75Al25 Ti50Al50 Ti33Al67
Ti-Fe Ti67Fe33 Ti50Fe50 Ti33Fe67
Ti-Co Ti67Co33
40
As it was seen, the first system was Ti-Ni system, a part of Ti-Ni-Cu system that was
the most commonly used titanium based system in the literature to achieve high glass
forming ability and to produce practically bulk amorphous specimens [1-3, 28-33, 36,
37, 40]. As a result this system is a must to study on. Also Ti-Cu system was thought
to be studied however the attempts to calculate the ordering energy of Ti-Cu based
systems were unsuccessful because of the noble nature of Cu element.
The second system was Ti-Al system. The reason for selecting this system is the
practical and potential application areas of Ti-Al intermetallics.
Other systems are Ti-Fe and Ti-Co where they have both intermetallics and deep-like
eutectics in their phase diagrams.
Being selected the systems to study, the approach for predicting the systems that are
more likely to form bulk glasses is based on the effect of the third element in terms of
∆HM, viscosity, entropy as well as the ordering energy of the system. It was well
known that the decrease in the ∆HM or the increase in viscosity and entropy of the
system will lead to an increase in the tendency for the glass forming ability of the
system. By the virtue of these, we can conclude the systems having better glass
forming ability by considering the optimum effects of the alloying elements on these
criteria.
2.3.2 Evaluation of glass forming parameters
The Rc and the empirical rules, thus, correlate with the GFA of metallic glasses. This
implies that Rc can be derived from the empirical rules if the rules are described as
thermodynamical functions, which are in general difficult for multi-component
systems. The description of the rules as a function of composition is essential for the
analyses in which the Rc is compared among the alloys with different compositions.
41
The purpose of the following approaches is to evaluate critical cooling rates
quantitatively for candidate metallic glasses in Ti-based systems using the
thermodynamically described three empirical rules for the achievement of high GFA.
2.3.3 Fundamental equation of critical cooling rate
Since a dimensional unit of Rc is K/s, it is reasonable to assume that Rc is in

proportion to melting temperature and in inverse proportion to incubation time to
crystallize τ . Under this assumption, Eq. (2.65) was proposed to evaluate Rc for oxide
glasses by Sarjeant and Roy [2]:
Tm
RC = Z 1 = ZfT m (2.65)
τ
where Rc is the critical cooling rate, Z1 the constant of 2x10−6 which is determined by
the analysis of Rc for NaCl, f the rate constant in jumps/s unit associated to diffusion
or viscosity, and Tm the melting temperature. The rate constant f is expressed by
Eyring’s relation with kB the Boltzmann constant, a is the interatomic distance, and η
the viscosity:
k B Tm
f = (2.66)
a 3η
Substitution of Eq. (2.66) at Tm in Eq. (2.65) leads to Eq. (2.67):

k BTm2
Rc = Z 3 (2.67)
a ηT =Tm
Although the formula of Eq. (2.67) is simple, the analysis of Rc was confirmed to be
valid for oxide glasses represented by silica glass as well as pure elements, e.g. Pb.
42
The details of exploration of Eq. (2.67) for metallic glasses will be discussed in the
next section.
2.3.4 Gibbs free energy for the multi-component system
For the analysis of solidification, the difference in energy between solid- and liquid-
state, Gl − Gs, is generally required [4]. For multi-component systems, however, it is
impossible to estimate the energies accurately as a function of composition and
temperature. For this reason, an assumption is proposed in the present study: Gl − Gs
at a composition is proportional to the free energy of mixing ∆GM of the liquid phase.
In the following, ∆GM consisting of multi-component systems will be introduced.
∆GM is defined in terms of its enthalpy of mixing ∆HM and entropy of mixing ∆SM as
expressed in Eq. (2.68) when consisting pure elements are standard states:
∆G M = ∆H M − T∆S M (2.68)
In the present study, ideal configurational entropy ∆Sideal and mismatch term of
entropy ∆Sσ resulting from atomic size were considered:
∆S M = ∆S ideal + ∆S σ (2.69)
2.3.4.1 Regular solution model
According to the regular solution model, ∆HM and ∆Sideal are defined as Eqs. (2.70)
and (2.71) for the multi-component systems with N elements:
N
∆H M = ∑Ω
i =1, i ≠ j
ij ci c j (2.70)
43
N
∆S ideal = − R ∑ (ci ln ci ) (2.71)
i =1
where Ωij is the regular solution interaction parameter between i and j elements, and R
the gas constant. Ωij is assumed to be independent of both the composition and
temperature in the present study, which enable the model to extend for
multicomponent systems. In the calculation, the values of enthalpy of mixing
∆H AB
mix
on the basis of Miedema macroscopic model for binary liquid alloys [5] were
substituted for Ωij in Eq. (2.70) with the following relation: ∆H AB

mix
= 1 / 4Ω ij . The
relation is due to definition in Eq. (2.70) at the equiatomic composition in a binary A–

B system. The number of relevant values of ∆H AB
mix
were calculated for 2628 (=73 x
72/2) atomic pairs [6].
2.3.4.2 Mismatch term in entropy of mixing
Mansoori et al. [7] proposed an equation of state for the mixture of hard spheres based
on an averaging process over the two results of the solution of the Percus–Yevik
integral equation for the mixture of hard spheres. As a result, the mixing entropies
consisting of four terms were derived: ideal gas-, concentration-, packing- and misfit-
term. In the present study, only misfit term Sσ was taken into account to describe the
entropy of mixing concerning the differences in atomic radii. Sσ is expressed as in Eq.
(2.72) [8]:
 3 3 1  
S σ = k B ( (ζ 2 − 1) y1 + (ζ − 1) 2 y 2 −  (ζ − 1)(ζ − 3) + ln ζ  (1 − y 3 ) (2.72)
 2 2 2  
where ζ is defined as ζ=1/(1−ξ), using packing fraction ξ. y1, y2 and y3 are parameters
having a relation of y1+y2+y3=1, and are defined as Eqs. (2.73)–(2.76).
44
These equations were derived by transforming original formulae of Mansoori et al.
[7]:
n
1
y1 =
σ3
∑ (d
j > i =1
i + d j )(di − d j ) 2 ci c j (2.73)
σ2 n
y2 =
(σ 3 ) 2
∑ d d (d
j > i =1
i j i − d j ) 2 ci c j (2.74)
(σ 2 )3
y3 = 3 2 (2.75)
(σ )
n
σk = ∑cd
j > i =1
i i
k
, k = 2,3 (2.76)
where di is the atomic diameter of ith element. By Equations. (3.72)–(3.76), mismatch

term of entropy of mixing of the multi-component system consisting of N elements is
calculated as a function of atomic diameter, composition and packing fraction.
2.3.5 Viscosity at melting temperature for glass-forming alloys
Vogel–Fulcher–Tanmann (VFT) equation was proposed for estimation of viscosity of

glass-forming alloys:
 B 
η = η0 exp  (2.77)
 T − T0 
where η0 is the pre-exponential term, B the constant corresponding to the activation

energy, T0 the temperature at which excess configurational entropy or the free volume
is zero, being usually lower than Tg. The values of η0, B and T0 were examined for the
glass-forming alloys [3]. For the systems of which the viscosity was not expressed as
VFT equation, η(Tm) was estimated by modified Andrade’s equation [9]:
45
ATm
η (Tm ) = c A (2.78)
V 2/3
where cA is the constant, A the atomic weight, and V the molar volume. The constant
cA =1.85x10−7 (J/K.mol1/3)1/2 is adopted for glass-forming systems [9].
2.3.6 Modified equation of critical cooling rate
The evaluation of Rc on the basis of Eq. (2.67) was carried out by A. Inoue [30] for
typical metallic glasses. He concluded that the decrease in Rc by over 105, which is
required for fabrication of metallic glasses, does not cause even if all the physical and
thermodynamical parameters change on alloying as far as Eq. (2.67) is used for the
evaluation of Rc. This indicates that the decrease in Rc is only achieved by
modification of constant Z in Eq. (2.). Consequently, a modified probability Z1 in
addition to Z was assumed as shown in Eq. (2.79):
 ∆G 
Z1 = exp  (2.79)
 RT 
Note the sign in the exponential term is defined to be plus, so that the system with a
large negative value of ∆G has a large tendency to decrease Rc. In addition, ∆G of
pure elements is zero, indicating the modification is only adopted for the systems with
two or more elements. Combining Equations (2.67) and (2.79), eventually, Equations
(2.80) was obtained for the evaluation of Rc. Equations (2.80) is, thus, taken into
account the effect of decrease in Rc on alloying:
k B Tm2  ∆G 
Rc = Z exp  (2.80)
a η T =Tm
3
 RT 
46
Furthermore, the calculated values of Rc by Equation (2.80) were subjected to fit with
that of Davies or that experimentally determined. Because ∆G consists of two terms,
regular solution model term and misfit excess entropy term as shown in Equation
(2.68)–(2.71), fitting parameters related above two terms at 300K were put as f1 and f2
as is seen in Equation (2.81):
k BTm2   ∆H − Tm ∆S ideal   T S 
Rc = Z exp  f1   − f 2  m σ  (2.81)
a ηT =Tm
3
  300 R   300 R 
2.3.7 Ordering energy calculations
The next thing to do is to connect these with the knowledge of electronic theory of
alloys in pseudo potential approximation which was done by calculating the ordering
energies of pre-selected systems by FORTRAN programs.
FORTRAN programs were written by Prof. Dr. Amdulla Mekhrabov for the purpose
of ordering energy calculations which were used in calculating ∆HM and critical
cooling rate of the possible bulk glass forming systems. These programs are available
for use in METU Metallurgical and Materials Department. The results taken from
these programs are the change in ordering energy of the binary system by the addition
of alloying elements. The data obtained from the programs are the ordering energy
change in 3 pairs of atoms in the system (if A and B forms the binary system and X is
the alloying element added, AB, AX, BX). As the change of ordering energy in the
components of the system known, the change of that property of the system can be
simply found by rule of mixing:
ω system = c A c Bω AB + c A c X ω AX + c B c X ω BX (2.82)
where cA, cB and cX are the fractions of A, B and X atoms respectively.
47
For our purpose the alloying element additions were made with only 1 %, as the
higher percentages of the alloying elements may result in less accurate results which
arise from the features of the FORTRAN programs.
The data obtained were evaluated for the nearest neighbor distance of the base system
which was determined by adding the radii of the elements forming the base system.
The nearest neighbor distances were generally found in the area of highest ordering
potential which is a desired situation.
After then obtaining the ordering energy data, these were processed to evaluate the
corresponding mixing enthalpy (∆HM) data by the following formula [30];
N
∆H mix = ∑W
i =1,i ≠ j
ij .c i c j (2.83)
W ij is the ordering energy between i and j atoms and ci and cj are the fractions of the i
and j atoms respectively.
Also for calculating the ∆HM of binary systems, Sommer et.al. [57] suppose the
following formulas:
 c 
 cC + A 
∆S  cA   γcB  1  c + γcB  1 γ 
= −cA ln  − cB ln  − z AcA ln A  − zqBcB ln (2.84)
 cA 
NkB  cA + γcB   cA + γcB  2  cA + qcB  2  cB + 
 q
For binary systems, ∆H of the system can be calculated as follows;
48
2c A c B q A q B
∆H = N ω (2.85)
(h + 1)(c A q A + c B q B )
where h is represented by the formula;
1
 2  
( )  where k is, k = exp ω 
4c A c B q A q B
h = 1 + k 2
− 1    (2.86)
 (c A q A + c B q B )
2
  Zk B T 
ω here is the ordering energy of the binary system given by the formula;
2ω
= (2V AB − (V AA + V BB )) with V AB , VAA and VBB are the mutual energies of AB, AA
Z
and BB pairs respectively.
γB qB
γ= , q= (2.87)
γA qA
γ B ΩB
γ= = ( Ω B > Ω A , Ω is the atomic volume) (2.88)
γ A ΩA
1
Z (γ i − qi ) = γ i − 1 , i = A, B (2.89)
2
The data generated by these calculations will be given in Chapter 4.
49
CHAPTER 3
EXPERIMENTAL PROCEDURE
By the virtue of the data obtained from ordering energy and critical cooling rate
calculations, a candidate system was chosen in order to see the practical applications
of this theoretical study. As it is known that producing bulk amorphous metallic alloys
require very low cooling rates so the system chosen shall have to be a tendency to
lower the critical cooing rate by alloying element additions. It was succeeded to find
possible alloying elements in candidate bulk amorphous forming systems that can
favor the glass forming of the system.
3.1 Ti-Ni binary system
The selection of the system to be practically studied was based on some criteria. As
the most common Ti-based system forming bulk glasses are found in the vicinity of
Ti-Ni-Cu ternary system, this shall be a good starting point for practical study Also,
the studies based on the ordering energy and other glass forming parameters
calculations show that this system has a better glass forming tendency among other
Ti-Ni compositions and most of other selected systems for this study. The results of
the calculations will be shown and interpreted in 4th Chapter.
As taking the binary Ti-Ni system the starting point, it has to be seeked for the best
possible compositions which has the greatest chance to form bulk glasses.
50
At Ti67Ni33 there exists a peritectic followed by a eutectic reaction which favors the
glass forming ability of the alloy. The eutectic under consideration is a very deep one;
there is a big decrease in the liquidus temperature with changing composition (1672oC
at 100% titanium to 943oC at 71.6% titanium). At this composition, the Ti2Ni
intermetallic is also makes the system for a good candidate composition for bulk glass
forming as intermetallics are known as growth problematic phases because of their
non-faceted growth mechanism.
As it can be seen from the binary Ti-Ni phase diagram Figure 3.1, near this
composition range, the binary alloy also obey the semi-empirical rules supposed by
[5]; being a deep eutectic and having a relatively low melting point. Also, the atomic
size difference of Ti and Ni elements is around %14 percent which is in the range for
good glass forming systems.
Figure 3.1 – Ti-Ni Binary Phase Diagram
51
This information is adequate to choose Ti67Ni33 binary composition as a candidate
starting point for the investigation of practical applicability of theoretical studies made
in this thesis and also for the investigation of finding possible Ti-based bulk
amorphous forming alloy compositions.
3.1.1 Alloy preparation
The equipment for producing samples are centrifugal casting machine, copper moulds
of wedge and cylindrical shapes, argon gas tube, Al2O3 based crucibles and a vacuum
pump. Multihertz neutromag digital induction casting machine is used for alloy
preparation by means of melting and precision casting of Ti-based alloys. This
machine can heat the alloy as high as 2000oC so melting of any kind of Ti-based alloy
is not a problematic issue. This machine offers the opportunity of melting/casting
either in natural atmosphere, vacuum or neutral atmosphere (argon gas) by choosing a
cycle by means of the special selector. It can work continuously at a 1 casting-every-6
minutes pace using ceramic, graphite lined crucibles in several sizes according to type
and quantity of melting alloy. The casting machine is also equipped with a digital
display self-regulating optical pyrometer which allows to constantly reading of metal
temperature, both during its rising to melting temperature and stabilization of the
latter. This pyrometer is only accurate for temperatures above 800oC however this did
not cause any problems because the melting point of all alloys studied was above
800oC.
The alloys were prepared by the mixture of the elements in appropriate compositions
for each system and induction melted in an argon atmosphere. The purity and form of
the elements are given in Table 3.1.
52
Table 3.1 – Purities and form of elements used in alloy preparation
Element Purity (mass %) Form Supplier
Ti 99.9 % Granules Alfa Aesar

Ni 99.9+ % Turnings Alfa Aesar
Zr 99.2 % Wire Alfa Aesar
Mo 99.7 % Pellets (crushed) Alfa Aesar
W 99.9 % Rods (crushed) Alfa Aesar
Alloy A1 and A2 was prepared by pouring into a cylindrical shaped copper mould as
we do not expect any glassy phase to form. Other alloys are poured into a wedge
shaped copper mould. The schematic view of the moulds and important dimensions
are given in the below figure. Thickest section of wedge shaped mould is 1 cm.
Cylindrical mould has a diameter of 1 cm and both moulds are 7 cm long.
a) b)
Figure 3.2 – Copper moulds of wedge (a) and cylindrical (b) shape.
53
The aim of the wedge casting is obtaining different cooling rates in the same casting.
It can easily be seen from Figure 3.2 (a) that at thicker section of the mould, there is
larger amount of cast metal hence there is larger amount of heat to be taken from the
system, on the other hand the thinner sections smaller amounts of alloy is accumulated
with less heat energy to absorb. As the mould’s volume is relatively large and the
copper thermal properties are in favor for very fast heat transfer and, the thinner
section’s cooling rate is greater then the thicker sections cooling rate. As a result it can
be obtained different cast structures in the alloys as the cooling rate is varying along
the mould from thinner to thicker sections.
The first two alloys are poured into cylindrical shaped moulds as it was only intended
to examine the structure of these alloys to gain information about structure of these
systems to gather valuable information for developing multi-component alloy systems
with high glass forming ability. Other alloys are prepared by pouring into the wedge
shaped copper moulds. 10 grams of alloys A1 and A2 and 15 grams of other alloys are
prepared.
The experiments were conducted in the controlled atmosphere of argon gas. As

titanium, which is used as the base element in this study, has a very reactive nature
which can cause problems such as loss of material as it can be easily oxidized at high
temperatures and this may lead to variations in the composition of the alloy. As a
result, if the atmosphere of the melting chamber could not be kept in a controlled
state, it can not be achieved to obtain the intended composition of the as cast alloy.
The volume of the melting chamber that is a part of the centrifugal casting machine
used in this study is relatively large that efficient vacuuming can hardly be done
without a diffusion vacuum device. As a general use vacuum device with a capacity to
vacuum 0.2 Atm level, it would be better to repeat the vacuuming and purging process
a few times to achieve a higher level of control (less oxygen content) in the melting
chamber. For this reason, every casting was done with 2 flushes of argon into the
melting chamber.
54
3.2 Crucible Production
The crucibles we used to melt the pure elements were made in laboratory conditions
instead of purchasing them. Previous crucibles were made of fused silica but the
reactive nature of some elements (ex: titanium which is used in relatively high
quantities in the alloy mixtures) lead to contamination of the alloy. As a result we
decided to make our crucibles from castable alumina which worked better for our
purposes. The crucibles were made by mixing appropriate amounts of castable
alumina and water and by casting them into previously made iron or copper moulds.
Alumina dries in 24 hours in the moulds and then appropriate heat treatment were
conducted in order to satisfy the adequate thermal shock resistance to the crucibles.
Crucibles have a volume capacity of approximately 21 cm3.
The heat treatment procedure is given in the table below.
Table 3.2 – Heat treatment procedure of Al2O3 based crucibles
Temperature (oC) Minimum Holding time (h)

100 12
200 1
300 1
400 1
500 1
600 12
700 1
800 1
900 1
1000 1
55
Figure 3.3 – Schematic view of a crucible
3.3 Structural characterization
The characterization of the alloys produced was done by means of thermal, optical
and X-ray analysis.
3.3.1 Metallographic examination
Firstly the specimens of cast alloys were prepared metallographically and then
examined by optical and scanning electron microscopes. The equipment used for SEM
is a JSM-6400 Electron Microscope (JEOL) equipped with NORAN Series II Micro-
analyzer System. This microscope is equipped with secondary and backscattered
electron imaging facilities and X-Ray microanalysis system and is capable of
providing both topographical and compositional information about the specimen. Its
magnification is in the range of 10x - 300000x and maximum attainable resolution in
secondary image and back-scatter image modes are 3.5 nm and 10 nm respectively (at
35 kV acceleration voltage). The phases formed in the alloys can be seen by
metallographic examination and gives a better understanding of microstructure.
56
The specimens were prepared metallographically by grinding, polishing and etching.
Etching of the specimens was done with a specially prepared mixture of 10% HF, 5%
HNO3 and balance water.
3.3.2 X-ray analysis
After metallographic examinations, the specimen was examined with X-ray

diffraction analysis. The equipment used is a 100 kV Philips twin tube X-ray
diffractometer (PW/1050) equipped with various tubes, horizontal and vertical
goniometers, high temperature attachment, Laue and Debye-Scherrer cameras,
proportional, scintillation and Geiger-Müller counters. Co Kα radiation was used
during this thesis study with λ= 1.79026Ao. The data were taken at 100 cps and
between 2θ angles 20o and 100o. X-ray analysis is a very valuable one as it is one of
the indicators of glassy phase if there were any in the specimens. It also gives a wide
range of information about the crystalline and amorphous phases found in the
specimen.
3.3.3 Thermal analysis
The final and the most important examinations for determining the glassy phase and
its properties is thermal analysis of the alloys. This is done by using SETARAM DSC
131 and SETARAM SETSYS TGA- (DTA/DSC) thermal analyzer with facilities for
simultaneous TGA and DTA/DSC measurements for quantitative and qualitative
calorimetric studies. DSC/DTA are measurements of the difference of heat
flux/temperature between a sample and a reference material whereas TGA is the
measurement of mass variation of a sample when it is subjected to a thermal cycle.
The TGA measurements can be linked with a DTA or DSC measurements: this is
known as simultaneous TGA-DTA or TGA-DSC measurements. DSC 131 is used for
the need of simple and fast analysis and controls within the temperature range of -170
°C to 700 °C, while SETSYS TG-DTA/DSC is a modular of thermal analyzers with a
57
remarkably wide temperature ranges (ambient to 1650 °C) and high sensitivity for
high precision measurements, even under complex experimental conditions. This is
the most critical analysis for our purpose as thermal analysis can provide very
important information whether an alloy contains an amorphous phase and critical data
such as the glass transition (if it were any), crystallization melting and other
transformations in the alloy under a thermal cycle. The specimens for thermal analysis
were taken from the thinnest section of the wedge shaped alloys as the most expected
location to have amorphous structure is there. Thermal analysis was done at a heating
rate 40 oC/min for all samples. The amount of specimens range from 20-30 mg.
58
CHAPTER 4
RESULTS AND DISCUSSIONS
4.1 Development of candidate bulk amorphous forming alloys
Following casting experiments were done taking into consideration the results of
ordering energy, ∆HM and critical cooling rate calculations and the information
gathered from the literature. As it was expected from the ordering energy calculations
that molybdenum is one of the best candidate metals to improve glass forming ability
in Ti67Ni33 (A1) binary system, 10% molybdenum was added to form the ternary
Ti60Ni30Mo10 (A2). The next system studied was Ti55Ni30Zr8Mo5W2 (A3). The
zirconium addition is because of the high effect of this element in the favor of glass
forming ability and the high glass forming ability of the zirconium based systems
from the previous studies. Tungsten is the other alloying element in the system which
is also expected to favor the glass forming ability of the system based from the
ordering energy and critical cooling rate calculations. Different castings were done
with same five element system but with different compositions namely,
Ti57Ni28Zr8Mo5W2 (A4), Ti59Ni25Zr9Mo5W2 (A5). For comparison of different
structures formed by near equilibrium conditions with copper mould cast ones, slowly
cooled sample of alloy A3 will also be examined.
59
4.2 Discussion of ordering energy and other GFA parameters
4.2.1 Data Tables
These tables represents the glass forming ability in terms of ordering energy, ∆HM,
viscosity, entropy and by critical cooling rate in which all the former terms contribute
in.
According to theory of liquid and/or amorphous glassy alloys, the ordering energy of
the system are directly related to heat of mixing, viscosity, entropy of mixing and
critical cooling rate of the alloy systems. Therefore, an increase in the ordering energy
of the alloy systems in the liquid state will increase heat of mixing, entropy of mixing,
viscosity of melt subsequently decreasing the critical cooling rate for easier metallic
glass formation [57-62]. So, the calculations of ordering energy of the selected Ti-
based systems provide very valuable information and data for enhancing the glass
forming ability of these systems. The calculations represent the change in the ordering
energy of the binary systems by addition of 1 atomic % of alloying elements to these
systems. The ordering energies between both three species of atoms were calculated,
namely, A-B, A-X, B-X. A and B atoms the ones that are forming the binary and the
X atoms are alloying elements. Hence the total ordering energies of systems can be
calculated for each ternary system.
∆HM and Rc then calculated by using ordering energies of systems. Viscosity,

mismatch entropy, ideal entropy, mixing entropy and Rc parameters for Ti-Ni system
will be all given in the Tables 4.1-4.12 together with ∆η/η0 parameter calculated form
(∆Η/RT) of binary and ternary systems. The details of these data for other studied
systems will be given in Appendix A.
60
Table 4.1 – Ti49Ni50X1
ω(AB) (atu) ω(AC) (atu) ω(BC) (atu) −ω system in J/mol (−ω)∗Ζ/2 in
Alloying
J/mol
element (X)
x10-4 x10-3 x10-4 x102 x103
none 2,03 -1,33 -0,53
Ag 1,71 -9,04 8,09 -0,02 -0,01
Al 2,02 0,38 -32,24 -0,93 -0,37
B 2,28 11,22 175,40 -5,20 -2,06
Ba 0,51 557,60 4643,00 -133,20 -52,69
Be 2,12 2,59 1,55 -1,72 -0,68
Bi 1,75 28,68 437,70 -10,52 -4,16
C 2,47 4,34 42,62 -2,70 -1,07
Ca 1,09 108,00 687,40 -23,71 -9,38
Cd 1,72 -3,38 1,34 -0,68 -0,27
Co 2,03 0,22 0,00 -1,33 -0,53
Cr 2,14 2,14 2,21 -1,69 -0,67
Cs -1,07 151,30 1160,00 -34,09 -13,48
Cu 1,87 -4,30 -5,42 -0,57 -0,22
Fe 2,14 1,10 1,55 -1,54 -0,61
Ga 1,93 -1,74 10,16 -1,15 -0,45
Ge 1,99 0,27 -3,07 -1,27 -0,50
Hf 1,99 14,45 172,20 -5,39 -2,13
K 0,11 85,01 604,80 -19,01 -7,52
La 1,40 7,34 121,00 -3,42 -1,35
Li 1,59 -4,48 -6,08 -0,36 -0,14
Mg 1,68 2,98 -15,18 -1,28 -0,51
Mn 2,00 -0,13 5,01 -1,33 -0,53
Mo 2,44 21,72 228,00 -7,35 -2,91
Nb 2,24 12,49 114,80 -4,56 -1,80
Pb 1,76 13,15 310,10 -6,85 -2,71
Rb -0,36 147,80 1083,00 -33,09 -13,09
Re 2,60 16,30 146,80 -5,70 -2,25
Sb 1,90 11,09 142,20 -4,51 -1,78
Sc 1,77 1,05 2,80 -1,31 -0,52
Se 2,14 2,04 40,47 -2,16 -0,86
Si 2,06 -1,31 -38,57 -0,66 -0,26
Sn 1,85 6,11 65,21 -2,83 -1,12
Ta 2,24 11,36 107,60 -4,32 -1,71
V 2,36 -0,61 -49,93 -0,79 -0,31
W 2,44 23,86 238,00 -7,76 -3,07
Zn 1,91 -1,28 5,67 -1,14 -0,45
Zr 1,96 14,41 154,50 -5,14 -2,03
61
Viscosity ∆HM Rc ∆η/η0
Alloying mismatch
Sideal SM (kg,m3)
Element (X) entropy
x10-3 x103 x108 x10-1
none 0,10 5,76 6,76 3,58 -1,05 2,96 1,01
Ag 1,00 6,17 7,16 3,59 -0,02 3,07 0,02
Al 1,00 6,17 7,16 3,56 -1,11 2,86 1,06
B 1,12 6,17 7,29 3,57 -6,16 1,95 5,90
Ba 1,83 6,17 7,99 3,52 -158,00 0,00 151,00
Be 1,04 6,17 7,20 3,57 -2,04 2,65 1,95
Bi 1,23 6,17 7,40 3,59 -12,50 1,21 11,90
C 1,30 6,17 7,47 3,57 -3,21 2,35 3,07
Ca 1,44 6,17 7,60 3,52 -28,10 0,39 26,90
Cd 1,01 6,17 7,18 3,58 -0,81 2,90 0,78
Co 1,00 6,17 7,17 3,58 -1,58 2,75 1,51
Cr 1,00 6,17 7,17 3,57 -2,00 2,67 1,92
Cs 3,36 6,17 9,53 3,43 -40,50 0,13 38,70
Cu 1,00 6,17 7,16 3,58 -0,67 2,93 0,64
Fe 1,00 6,17 7,17 3,58 -1,83 2,70 1,75
Ga 0,99 6,17 7,16 3,57 -1,36 2,80 1,30
Ge 1,01 6,17 7,18 3,56 -1,51 2,77 1,44
Hf 1,04 6,17 7,21 3,60 -6,39 1,92 6,11
K 2,18 6,17 8,35 3,47 -22,60 0,53 21,60
La 1,29 6,17 7,46 3,56 -4,06 2,21 3,88
Li 1,02 6,17 7,18 3,54 -0,42 3,01 0,40
Mg 1,05 6,17 7,22 3,55 -1,52 2,76 1,45
Mn 1,04 6,17 7,21 3,58 -1,58 2,73 1,51
Mo 0,99 6,17 7,16 3,58 -8,72 1,65 8,34
Nb 1,00 6,17 7,16 3,58 -5,41 2,09 5,17
Pb 1,00 6,17 7,17 3,60 -8,12 1,71 7,77
Rb 0,99 6,17 7,16 3,46 -39,30 0,19 37,60
Re 0,99 6,17 7,16 3,61 -6,76 1,88 6,47
Sb 1,07 6,17 7,24 3,57 -5,35 2,08 5,12
Sc 1,05 6,17 7,22 3,55 -1,56 2,75 1,49
Se 1,03 6,17 7,20 3,56 -2,57 2,56 2,46
Si 1,02 6,17 7,19 3,55 -0,78 2,92 0,75
Sn 1,01 6,17 7,18 3,57 -3,36 2,42 3,21
Ta 1,00 6,17 7,17 3,60 -5,12 2,12 4,90
Ti 1,00 6,17 7,17 3,56 -1,62 2,75 1,55
V 0,99 6,17 7,16 3,57 -0,94 2,88 0,90
W 0,99 6,17 7,16 3,61 -9,21 1,58 8,81
Zn 0,99 6,17 7,16 3,57 -1,35 2,80 1,29
Zr 1,04 6,17 7,21 3,57 -6,10 1,98 5,83
62
Alloying
J/mol
element (X)
x10-4 x10-3 x10-4 x102 x103
none 2,03 -1,33 -0,53
Ag 1,62 -9,07 7,89 0,02 0,01
Al 1,93 0,39 -32,22 -0,87 -0,34
B 2,20 11,23 175,40 -5,16 -2,04
Ba 0,41 557,00 4637,00 -132,70 -52,50
Be 2,04 2,59 1,54 -1,66 -0,66
Bi 1,66 28,63 437,10 -10,49 -4,15
C 2,39 4,34 42,72 -2,65 -1,05
Ca 1,00 108,10 688,50 -23,58 -9,33
Cd 1,64 -3,38 1,27 -0,63 -0,25
Co 1,94 0,21 0,00 -1,27 -0,50
Cr 2,06 2,13 2,15 -1,62 -0,64
Cs -1,18 151,30 1158,00 -33,88 -13,40
Cu 1,78 -4,32 -5,49 -0,52 -0,20
Fe 2,06 1,09 1,54 -1,48 -0,59
Ga 1,84 -1,75 10,00 -1,09 -0,43
Ge 1,90 0,27 -3,19 -1,22 -0,48
Hf 1,90 14,44 171,70 -5,33 -2,11
K 0,02 85,02 604,20 -18,87 -7,46
La 1,31 7,31 120,50 -3,37 -1,33
Li 1,50 -4,49 -6,18 -0,31 -0,12
Mg 1,60 3,01 -15,03 -1,22 -0,48
Mn 1,91 -0,14 5,01 -1,28 -0,50
Mo 2,36 21,69 227,10 -7,29 -2,88
Nb 2,15 12,51 114,40 -4,50 -1,78
Pb 1,67 13,12 309,90 -6,83 -2,70
Rb -0,47 147,70 1081,00 -32,89 -13,01
Re 2,53 16,29 146,00 -5,64 -2,23
Sb 1,82 11,08 141,90 -4,46 -1,76
Sc 1,68 1,05 2,80 -1,25 -0,50
Se 2,06 2,03 40,04 -2,11 -0,83
Si 1,98 -1,30 -38,71 -0,59 -0,24
Sn 1,77 6,11 65,08 -2,78 -1,10
Ta 2,15 11,37 107,10 -4,25 -1,68
V 2,28 -0,62 -50,02 -0,73 -0,29
W 2,36 23,85 237,40 -7,70 -3,05
Zn 1,82 -1,28 5,65 -1,08 -0,43
Zr 1,87 14,42 154,20 -5,08 -2,01
63
Alloying mismatch
Sideal SM (kg,m3)
Element (X) entropy
x10-3 x103 x108 x10-1
none 1,00 5,76 6,69 3,58 -1,05 2,99 1,01
Ag 1,00 6,17 7,17 3,60 0,03 3,06 -0,03
Al 1,00 6,17 7,17 3,57 -1,03 2,86 0,99
B 1,12 6,17 7,29 3,58 -6,12 1,95 5,86
Ba 1,84 6,17 8,01 3,53 -158,00 0,00 151,00
Be 1,04 6,17 7,21 3,58 -1,97 2,65 1,89
Bi 1,24 6,17 7,41 3,60 -12,40 1,21 11,90
C 1,30 6,17 7,47 3,58 -3,15 2,35 3,01
Ca 1,45 6,17 7,61 3,53 -28,00 0,39 26,80
Cd 1,01 6,17 7,18 3,59 -0,75 2,90 0,72
Co 1,01 6,17 7,17 3,59 -1,51 2,75 1,45
Cr 1,01 6,17 7,17 3,59 -1,93 2,67 1,84
Cs 3,38 6,17 9,55 3,45 -40,20 0,13 38,50
Cu 1,00 6,17 7,17 3,59 -0,61 2,93 0,59
Fe 1,01 6,17 7,18 3,59 -1,76 2,70 1,68
Ga 1,00 6,17 7,16 3,58 -1,29 2,80 1,24
Ge 1,01 6,17 7,18 3,58 -1,44 2,77 1,38
Hf 1,05 6,17 7,22 3,61 -6,32 1,92 6,05
K 2,20 6,17 8,36 3,48 -22,40 0,53 21,40
La 1,30 6,17 7,47 3,58 -4,00 2,21 3,82
Li 1,02 6,17 7,19 3,56 -0,37 3,00 0,35
Mg 1,06 6,17 7,22 3,56 -1,45 2,76 1,38
Mn 1,05 6,17 7,21 3,59 -1,51 2,73 1,45
Mo 1,00 6,17 7,16 3,60 -8,65 1,65 8,27
Nb 1,00 6,17 7,17 3,59 -5,33 2,09 5,10
Pb 1,01 6,17 7,17 3,61 -8,10 1,70 7,75
Rb 1,00 6,17 7,16 3,47 -39,00 0,19 37,30
Re 1,00 6,17 7,16 3,63 -6,69 1,88 6,40
Sb 1,07 6,17 7,24 3,58 -5,29 2,08 5,06
Sc 1,06 6,17 7,22 3,57 -1,49 2,75 1,42
Se 1,03 6,17 7,20 3,57 -2,50 2,56 2,39
Si 1,03 6,17 7,19 3,57 -0,71 2,92 0,68
Sn 1,02 6,17 7,19 3,59 -3,30 2,42 3,15
Ta 1,01 6,17 7,17 3,62 -5,05 2,12 4,83
Ti 1,00 6,17 7,16 3,59 -0,86 2,89 0,83
V 1,00 6,17 7,16 3,63 -9,13 1,58 8,74
W 1,23 6,17 7,40 3,57 -2,97 2,41 2,84
Zn 1,05 6,17 7,22 3,58 -6,03 1,98 5,76
Zr 1,00 6,17 7,17 3,60 0,03 3,06 -0,03
64
Alloying
J/mol
element (X)
x10-4 x10-3 x10-4 x102 x103
none 3,27 -1,91 -0,75
Ag 3,00 -8,50 10,85 -0,30 -0,12
Al 3,26 0,13 -32,49 -1,59 -0,63
B 3,48 11,18 175,80 -5,41 -2,14
Be 3,35 2,59 1,60 -2,36 -0,93
Bi 3,03 29,39 445,20 -10,62 -4,20
C 3,64 4,31 41,06 -3,16 -1,25
Ca 2,47 105,70 667,10 -25,52 -10,09
Cd 3,01 -3,36 2,41 -1,13 -0,45
Co 3,27 0,35 0,00 -1,91 -0,75
Cr 3,37 2,28 3,09 -2,33 -0,92
Cs 0,59 151,90 1191,00 -36,98 -14,63
Cu 3,13 -3,98 -4,41 -1,04 -0,41
Fe 3,36 1,19 1,63 -2,12 -0,84
Ge 3,23 0,24 -1,29 -1,85 -0,73
Hf 3,23 14,62 179,60 -5,90 -2,33
K 1,63 84,71 611,30 -20,91 -8,27
Li 2,90 -4,45 -4,51 -0,82 -0,33
Mg 2,98 2,58 -17,51 -1,98 -0,78
Mn 3,25 -0,02 5,10 -1,87 -0,74
Mo 3,61 22,11 241,10 -7,94 -3,14
Nb 3,44 12,24 121,00 -5,11 -2,02
Rb 1,21 148,40 1105,00 -35,98 -14,23
Re 3,75 16,52 159,10 -6,35 -2,51
Se 3,35 2,25 46,80 -2,68 -1,06
Si 3,29 -1,42 -36,48 -1,30 -0,51
Sn 3,11 6,09 67,16 -3,39 -1,34
Ta 3,44 11,21 114,60 -4,87 -1,93
V 3,55 -0,48 -48,57 -1,51 -0,60
W 3,61 23,97 247,80 -8,33 -3,29
Zn 3,17 -1,21 6,09 -1,63 -0,64
Zr 3,20 14,30 160,30 -5,67 -2,24
65
Alloying mismatch
Sideal SM (kg,m3)
Element (X) entropy
x10-3 x103 x108 x10-1
none 0,82 5,29 6,10 3,35 -1,51 2,67 1,44
Ag 0,80 5,67 6,47 3,35 -0,36 3,44 0,34
Al 0,80 5,67 6,47 3,33 -1,88 3,11 1,80
B 0,94 5,67 6,61 3,34 -6,42 2,20 6,14
Be 0,86 5,67 6,52 3,33 -2,80 2,88 2,68
Bi 1,00 5,67 6,66 3,36 -12,60 1,39 12,10
C 1,12 5,67 6,79 3,33 -3,75 2,59 3,58
Ca 1,18 5,67 6,85 3,30 -30,30 0,39 29,00
Cd 0,81 5,67 6,48 3,35 -1,34 3,21 1,29
Co 0,82 5,67 6,49 3,35 -2,26 3,00 2,17
Cr 0,82 5,67 6,49 3,34 -2,76 2,90 2,64
Cs 2,93 5,67 8,60 3,22 -43,90 0,12 42,00
Cu 0,81 5,67 6,48 3,35 -1,23 3,24 1,18
Fe 0,82 5,67 6,49 3,34 -2,51 2,95 2,40
Ge 0,83 5,67 6,49 3,33 -2,20 3,02 2,10
Hf 0,84 5,67 6,50 3,37 -7,00 2,12 6,70
K 1,85 5,67 7,52 3,25 -24,80 0,53 23,70
Li 0,82 5,67 6,48 3,31 -0,98 3,33 0,93
Mg 0,84 5,67 6,51 3,32 -2,35 3,00 2,25
Mn 0,87 5,67 6,53 3,34 -2,22 2,99 2,13
Mo 0,80 5,67 6,47 3,35 -9,43 1,80 9,02
Nb 0,80 5,67 6,47 3,35 -6,06 2,29 5,80
Rb 0,80 5,67 6,47 3,24 -42,70 0,17 40,80
Re 0,80 5,67 6,47 3,38 -7,54 2,04 7,21
Se 0,85 5,67 6,51 3,33 -3,18 2,81 3,05
Si 0,84 5,67 6,51 3,32 -1,54 3,17 1,48
Sn 0,81 5,67 6,48 3,34 -4,02 2,65 3,85
Ta 0,81 5,67 6,47 3,37 -5,78 2,32 5,53
V 0,81 5,67 6,47 3,34 -1,79 3,12 1,71
W 0,80 5,67 6,47 3,38 -9,88 1,73 9,45
Zn 0,81 5,67 6,47 3,34 -1,93 3,08 1,85
Zr 0,84 5,67 6,50 3,34 -6,72 2,18 6,43
66
Alloying
J/mol
element (X)
x10-4 x10-3 x10-4 x102 x103
none 3,27 -1,91 -0,75
Al 3,20 0,14 -32,48 -1,57 -0,62
B 3,42 11,18 175,80 -5,42 -2,15
Be 3,29 2,59 1,60 -2,34 -0,93
Bi 2,95 29,36 444,80 -10,63 -4,21
C 3,58 4,32 41,15 -3,16 -1,25
Ca 2,39 105,80 668,30 -25,43 -10,06
Cd 2,94 -3,36 2,35 -1,13 -0,45
Co 3,20 0,34 0,00 -1,89 -0,75
Cr 3,30 2,28 3,04 -2,31 -0,91
Cs 0,50 151,90 1189,00 -36,84 -14,57
Cu 3,07 -4,00 -4,47 -1,03 -0,41
Fe 3,30 1,18 1,63 -2,11 -0,83
Ge 3,17 0,24 -1,39 -1,84 -0,73
Hf 3,16 14,61 179,20 -5,89 -2,33
K 1,55 84,74 611,00 -20,82 -8,23
Li 2,83 -4,45 -4,60 -0,82 -0,32
Mg 2,91 2,60 -17,39 -1,96 -0,78
Mn 3,18 -0,03 5,10 -1,86 -0,74
Mo 3,55 22,08 240,40 -7,94 -3,14
Nb 3,38 12,26 120,70 -5,10 -2,02
Rb 1,13 148,40 1104,00 -35,84 -14,17
Re 3,68 16,51 158,40 -6,34 -2,51
Se 3,29 2,24 46,46 -2,68 -1,06
Si 3,23 -1,42 -36,60 -1,29 -0,51
Sn 3,05 6,09 67,05 -3,38 -1,34
Ta 3,38 11,22 114,20 -4,87 -1,93
V 3,48 -0,48 -48,64 -1,49 -0,59
W 3,55 23,96 247,30 -8,32 -3,29
Zn 3,10 -1,21 6,07 -1,62 -0,64
Zr 3,13 14,30 160,00 -5,66 -2,24
67
Alloying mismatch
Sideal SM (kg,m3)
Element (X) entropy
x10-3 x103 x108 x10-1
none 0,82 5,29 6,04 3,35 -1,51 2,70 1,44
Ag 0,82 5,72 6,54 3,37 -0,36 3,40 0,34
Al 0,82 5,72 6,54 3,34 -1,87 3,08 1,78
B 0,96 5,72 6,68 3,35 -6,43 2,17 6,15
Be 0,87 5,72 6,60 3,35 -2,78 2,86 2,66
Bi 1,02 5,72 6,74 3,37 -12,60 1,37 12,10
C 1,14 5,72 6,86 3,35 -3,74 2,57 3,58
Ca 1,20 5,72 6,92 3,31 -30,20 0,39 28,90
Cd 0,83 5,72 6,55 3,36 -1,34 3,17 1,28
Co 0,84 5,72 6,56 3,36 -2,25 2,97 2,15
Cr 0,84 5,72 6,56 3,36 -2,74 2,87 2,62
Cs 2,96 5,72 8,68 3,24 -43,70 0,12 41,80
Cu 0,83 5,72 6,55 3,36 -1,22 3,20 1,17
Fe 0,84 5,72 6,56 3,36 -2,50 2,92 2,39
Ge 0,84 5,72 6,57 3,35 -2,19 2,99 2,09
Hf 0,86 5,72 6,58 3,38 -6,99 2,09 6,69
K 1,88 5,72 7,60 3,26 -24,70 0,53 23,60
Li 0,83 5,72 6,56 3,33 -0,97 3,29 0,93
Mg 0,86 5,72 6,58 3,33 -2,33 2,97 2,23
Mn 0,88 5,72 6,60 3,36 -2,21 2,96 2,11
Mo 0,82 5,72 6,54 3,37 -9,42 1,78 9,01
Nb 0,82 5,72 6,54 3,36 -6,05 2,27 5,79
Rb 0,82 5,72 6,54 3,25 -42,50 0,17 40,70
Re 0,82 5,72 6,54 3,40 -7,52 2,02 7,19
Se 0,86 5,72 6,59 3,34 -3,18 2,78 3,04
Si 0,86 5,72 6,58 3,34 -1,53 3,14 1,46
Sn 0,83 5,72 6,55 3,36 -4,02 2,62 3,84
Ta 0,82 5,72 6,55 3,38 -5,77 2,30 5,52
V 0,82 5,72 6,55 3,35 -1,77 3,09 1,69
W 0,82 5,72 6,54 3,39 -9,87 1,71 9,44
Zn 0,82 5,72 6,54 3,36 -1,93 3,05 1,84
Zr 0,86 5,72 6,58 3,35 -6,71 2,16 6,42
68
Alloying
J/mol
element (X)
x10-4 x10-3 x10-4 x102 x103
none 0,40 -0,23 -0,09
Al 0,27 0,69 -31,84 0,35 0,14
B 0,59 11,27 174,30 -4,33 -1,71
Be 0,39 2,57 1,51 -0,46 -0,18
Bi -0,03 27,65 426,00 -9,77 -3,87
C 0,81 4,37 44,47 -1,61 -0,64
Ca -0,83 110,00 706,00 -21,20 -8,38
Cd -0,08 -3,41 -0,07 0,34 0,13
Co 0,28 0,05 0,00 -0,16 -0,06
Cr 0,42 1,92 1,00 -0,42 -0,16
Cs -3,36 148,70 1103,00 -29,99 -11,86
Cu 0,08 -4,72 -6,78 0,47 0,19
Fe 0,41 0,98 1,41 -0,34 -0,14
Ge 0,25 0,32 -5,44 -0,07 -0,03
Hf 0,24 14,24 162,40 -4,18 -1,65
K -1,98 84,68 590,60 -16,38 -6,48
Li -0,24 -4,54 -8,15 0,67 0,26
Mg -0,13 3,48 -12,15 -0,01 0,00
Mn 0,24 -0,28 4,90 -0,20 -0,08
Mo 0,79 21,23 210,70 -5,93 -2,35
Nb 0,55 12,85 107,00 -3,27 -1,29
Rb -2,53 145,60 1043,00 -29,14 -11,52
Re 0,99 16,04 130,60 -4,20 -1,66
Se 0,44 1,76 31,70 -0,95 -0,38
Si 0,33 -1,15 -41,24 0,63 0,25
Sn 0,09 6,14 62,58 -1,66 -0,66
Ta 0,55 11,58 98,69 -3,02 -1,19
V 0,69 -0,78 -51,77 0,58 0,23
W 0,79 23,73 225,20 -6,39 -2,53
Zn 0,14 -1,37 5,11 -0,05 -0,02
Zr 0,21 14,58 147,20 -3,93 -1,55
69
Alloying mismatch
Sideal SM (kg,m3)
Element (X) entropy
x10-3 x103 x108 x10-1
none 0,89 5,29 6,18 3,84 -0,18 3,74 0,18
Ag 0,96 5,67 6,62 3,86 0,97 3,22 -0,93
Al 0,95 5,67 6,62 3,84 0,41 3,11 -0,39
B 1,06 5,67 6,72 3,85 -5,14 2,05 4,92
Be 0,98 5,67 6,64 3,85 -0,55 2,89 0,53
Bi 1,24 5,67 6,91 3,86 -11,60 1,25 11,10
C 1,23 5,67 6,90 3,85 -1,91 2,53 1,82
Ca 1,48 5,67 7,15 3,79 -25,10 0,47 24,10
Cd 0,98 5,67 6,64 3,86 0,40 3,08 -0,38
Co 0,95 5,67 6,61 3,86 -0,19 2,97 0,18
Cr 0,95 5,67 6,61 3,85 -0,50 2,91 0,47
Cs 3,62 5,67 9,29 3,69 -35,60 0,17 34,00
Cu 0,94 5,67 6,61 3,86 0,56 3,13 -0,54
Fe 0,95 5,67 6,62 3,86 -0,41 2,92 0,39
Ge 0,95 5,67 6,62 3,84 -0,08 3,00 0,08
Hf 1,02 5,67 6,69 3,88 -4,96 2,07 4,75
K 2,32 5,67 7,99 3,73 -19,40 0,63 18,60
Li 0,98 5,67 6,65 3,82 0,79 3,20 -0,76
Mg 1,03 5,67 6,69 3,82 -0,01 3,00 0,01
Mn 0,98 5,67 6,65 3,85 -0,24 2,95 0,23
Mo 0,94 5,67 6,61 3,86 -7,04 1,82 6,73
Nb 0,95 5,67 6,62 3,86 -3,88 2,28 3,71
Rb 0,95 5,67 6,61 3,71 -34,60 0,26 33,10
Re 0,94 5,67 6,61 3,89 -4,99 2,08 4,77
Se 0,97 5,67 6,63 3,83 -1,13 2,78 1,08
Si 0,96 5,67 6,63 3,83 0,75 3,19 -0,72
Sn 0,98 5,67 6,64 3,85 -1,97 2,61 1,89
Ta 0,96 5,67 6,63 3,88 -3,58 2,31 3,43
V 0,94 5,67 6,61 3,85 0,69 3,17 -0,66
W 0,94 5,67 6,61 3,89 -7,59 1,73 7,26
Zn 0,94 5,67 6,61 3,85 -0,06 3,00 0,06
Zr 1,02 5,67 6,69 3,85 -4,66 2,14 4,46
70
Alloying
J/mol
element (X)
x10-4 x10-3 x10-4 x102 x103
none 0,40 -0,23 -0,09
Ag 0,01 -9,70 4,34 0,77 0,30
Al 0,38 0,67 -31,86 0,27 0,11
B 0,70 11,27 174,40 -4,39 -1,73
Be 0,50 2,57 1,51 -0,54 -0,21
Bi 0,09 27,72 426,80 -9,82 -3,88
C 0,92 4,37 44,36 -1,67 -0,66
Ca -0,71 109,90 705,10 -21,34 -8,44
Cd 0,04 -3,40 0,02 0,28 0,11
Co 0,39 0,06 0,00 -0,23 -0,09
Cr 0,53 1,93 1,08 -0,49 -0,19
Cs -3,22 148,90 1107,00 -30,23 -11,96
Cu 0,20 -4,69 -6,69 0,41 0,16
Fe 0,53 0,99 1,42 -0,42 -0,16
Ge 0,36 0,31 -5,30 -0,14 -0,06
Hf 0,35 14,25 163,00 -4,25 -1,68
K -1,85 84,73 591,60 -16,53 -6,54
Li -0,13 -4,53 -8,02 0,61 0,24
Mg -0,01 3,45 -12,34 -0,08 -0,03
Mn 0,35 -0,27 4,91 -0,26 -0,10
Mo 0,90 21,26 211,80 -6,02 -2,38
Nb 0,66 12,82 107,50 -3,35 -1,33
Rb -2,40 145,70 1046,00 -29,37 -11,62
Re 1,10 16,06 131,70 -4,30 -1,70
Se 0,55 1,78 32,26 -1,03 -0,41
Si 0,44 -1,16 -41,07 0,55 0,22
Sn 0,21 6,14 62,74 -1,73 -0,69
Ta 0,66 11,56 99,24 -3,10 -1,23
V 0,80 -0,77 -51,65 0,50 0,20
W 0,90 23,73 226,00 -6,48 -2,56
Zn 0,25 -1,37 5,14 -0,11 -0,04
Zr 0,32 14,57 147,70 -4,00 -1,58
71
Alloying mismatch
Sideal SM (kg,m3)
Element (X) entropy
x10-3 x103 x108 x10-1
none 0,89 5,29 6,18 3,84 -0,18 3,69 0,18
Ag 0,97 5,72 6,69 3,85 0,91 3,20 -0,87
Al 0,96 5,72 6,69 3,82 0,32 3,09 -0,31
B 1,07 5,72 6,79 3,83 -5,20 2,04 4,98
Be 0,99 5,72 6,71 3,83 -0,64 2,86 0,61
Bi 1,25 5,72 6,97 3,85 -11,70 1,25 11,10
C 1,25 5,72 6,97 3,83 -1,99 2,50 1,90
Ca 1,48 5,72 7,21 3,77 -25,30 0,46 24,20
Cd 0,98 5,72 6,71 3,84 0,33 3,06 -0,31
Co 0,96 5,72 6,68 3,84 -0,27 2,94 0,26
Cr 0,96 5,72 6,68 3,84 -0,58 2,88 0,56
Cs 3,61 5,72 9,34 3,67 -35,90 0,16 34,30
Cu 0,95 5,72 6,68 3,84 0,49 3,11 -0,47
Fe 0,96 5,72 6,68 3,84 -0,49 2,90 0,47
Ge 0,96 5,72 6,69 3,82 -0,17 2,98 0,16
Hf 1,03 5,72 6,75 3,86 -5,05 2,06 4,83
K 2,32 5,72 8,04 3,71 -19,60 0,62 18,80
Li 0,99 5,72 6,72 3,80 0,72 3,18 -0,69
Mg 1,04 5,72 6,76 3,81 -0,10 2,97 0,09
Mn 0,99 5,72 6,72 3,84 -0,31 2,92 0,30
Mo 0,95 5,72 6,68 3,85 -7,14 1,80 6,83
Nb 0,96 5,72 6,69 3,84 -3,97 2,26 3,80
Rb 0,96 5,72 6,68 3,70 -34,80 0,26 33,30
Re 0,95 5,72 6,68 3,88 -5,10 2,06 4,88
Se 0,98 5,72 6,70 3,82 -1,22 2,76 1,16
Si 0,97 5,72 6,70 3,81 0,66 3,16 -0,63
Sn 0,99 5,72 6,71 3,83 -2,06 2,59 1,97
Ta 0,97 5,72 6,70 3,86 -3,67 2,29 3,52
V 0,95 5,72 6,68 3,83 0,59 3,14 -0,57
W 0,95 5,72 6,68 3,88 -7,69 1,71 7,36
Zn 0,95 5,72 6,68 3,84 -0,13 2,98 0,13
Zr 1,03 5,72 6,75 3,83 -4,75 2,12 4,54
72
4.2.2 Interpretation of results
4.2.2.1 Binary Systems
It would be beneficial to discuss the results firstly from the point of view of different
Ti-based binaries. For this purpose, the data corresponding to the binary systems was
summarized in Tables 4.13 and 4.14.
Table 4.13 – Values of various parameters related with GFA for each binary system
Viscosity ∆HM (J) Rc (K/s) ∆η/η0

Binary Mismatch
Sideal SM (kg.m2)
system entropy (Sσ)
x10-3 x103 x108 x10,-1
Ni-Ti2 0,820 5,29 6,10 3,35 -1,51 2,67 1,44
Ni-Ti 1,00 5,76 6,76 3,58 -1,05 2,96 1,01
Ni2-Ti 0,891 5,29 6,18 3,84 -0,183 3,74 0,175
Ti3-Al 0,00666 4,67 4,68 2,81 -3,27 4,28 3,13
Ti-Al 0,00898 5,76 5,77 2,66 -6,58 4,74 6,30
Ti-Al2 0,00119 5,29 5,29 2,56 -7,15 4,33 6,84
Ti2-Fe 0,906 5,29 6,20 3,28 -6,59 2,70 6,726
Ti-Fe 1,11 5,76 6,87 3,46 -7,75 2,20 7,41
Ti-Fe2 1,07 5,29 6,36 3,67 -7,18 3,08 6,87
Ti-Co2 0,820 5,29 6,11 3,35 -1,58 3,58 2,29
Table 4.14 – Ordering and interchange energy and short range order parameter values
for each binary system
Binary ω(AB*) (atu) −ω in Js system (−ω)∗Ζ/2 in Js α1

system x10-3 x102 x103 x10-1
Ni-Ti2 0,3272 -1,905 -0,7533 -0,360
Ni-Ti 0,2031 -1,332 -0,5270 -0,252
Ni2-Ti 0,03983 -0,2319 -0,09170 -0,0438
Ti3-Al 0,8303 -4,086 -1,634 -0,679
Ti-Al 1,254 -8,227 -3,291 -1,13
Ti-Al2 1,535 -8,937 -3,575 -1,32
Ti2-Fe 1,414 -8,233 -3,293 -1,45
Ti-Fe 1,476 -9,681 -3,873 -1,70
Ti-Fe2 1,542 -8,977 -3,591 -1,35
Ti-Co2 0,3294 -1,917 -5,272 -0,240
* A and B are Ti and Ni elements respectively
73
74
Figure 4.1 – GFA parameters vs. Different binary systems
Figure 4.1 represents the GFA parameters for each binary system. The compositional
dependence of Ti-Ni system for GFA parameters are such that the higher Ti
concentration in the binary, the higher the GFA parameters. One exception to this is
viscosity term as the density of Ni is higher than that of Ti, it is clear that higher Ni
concentration will lead to higher viscosity of the system. Other systems seemed to
have similar compositional dependence on GFA parameters. For Ti-Al system,
increasing Al concentration of the system increases the GFA through the parameters
of ordering energy and ∆HM, decrease the GFA through the viscosity parameter. Rc
and mismatch entropy terms reaches maximum in the favor of the GFA at equatomic
concentrations. For Ti-Fe system, both parameters show maximums in the favor of
GFA parameters at equatomic concentrations. Viscosity of the system again increases
at higher concentrations of higher density element, in this case Fe. ∆HM of Ti2Ni was
calculated as -1,51 kJ which shows good relation with the literature data of -4 kJ [40].
In general look, Ti-Ni and Ti-Fe systems seem to have better glass forming
characteristics over Ti-Al and Ti-Co systems. Ti-Ni systems have lower ∆HM values
than Ti-Fe systems and also lower Rc values. Other parameters are very similar for
both systems. In section 3.1, other characteristics of Ti-Ni system was explained and
role of this binary in previous studies on synthesizing Ti-based bulk amorphous alloys
was pointed out. By considering these reasons and the supporting data generated from
theoretical calculations, Ti2Ni binary would be a good candidate for practical study in
this thesis.
4.2.2.1 Alloying additions
The effect of alloying element additions on the GFA of the binary systems should also
be discussed by using the theoretical calculations. It would be focused on Ti-Ni
binary, especially Ti2Ni system as it was chosen to study practically and interpretation
of results for other systems will also be given in Appendix A.
75
Table 4.15 – Elements favoring the glass forming parameters in Ti2-Ni system in
descending order
Ni-Ti(2-) Ni(-)-Ti2
Mismatch Mismatch
ω(AB) Viscosity HM Rc ω(AB) Viscosity HM Rc
entropy entropy
Re Cs Re Cs Cs Re Cs Re Cs Cs
C K W Rb Rb C K W Rb Rb
W Ca Ta Ca Ca Mo* Ca Ta Ca Ca
Mo* C Hf* K K W Bi Hf* K K
V Bi Bi Bi Bi V C Ag Bi Bi
B* B* Ag W W B* B* Bi W W
Ta Mn Mo* Mo* Mo* Nb* Mg Mo* Mo* Mo*
Nb* Be* Cd Re Pb Ta Hf* Cu* B* B*
Fe* Se Nb* Hf* Re Se Zr* Co* Re* Hf*
Cr Mg Cu* Zr* Hf* Cr Li Nb* Hf* Re
Be* Si* Co* B* Zr* Fe* Mn Cd Zr* Zr*
Se Zr* Fe* Nb* B* Sn* Fe* Nb* Nb*
Hf* Mn Ta Nb* Be* Mn Ta Ta
Ge Cr Sn* Ta Cd Cr Sn* C
Fe* Zn C C Se Zn C Sn*
Co* Sn* Se Sn* Ta V Se Se
Cr V Be* Se Si* B* Be* Be*
Li Zr* Cr Be* Ag Sn* Cr Cr
Sn* B* Fe* Cr Ge Be* Fe* Fe*
Cu* Be* Mg Fe* Nb* C Mn Mn
Cd C Co* Mn Al Zr* Co* Co*
Ta Ge Mn Mg Fe* Mg
V Ge Co* Cr Ge
Zn Zn Ge Co* Zn
Ag Al Zn Rb Cd
Al V Al Re
Nb* Si* V Cu*
Mo* Si* W
W Cd Mo*
Re Cu V
Rb Li Zn
* Elements that are used in literature in the production of Ti-based amorphous alloys
As it was decided to concentrate on Ti2Ni system, it would be useful to discuss the

results of ordering energy and Rc calculations and the effect of different alloying
elements on GFA parameters for this system in detail.
76
Table 4.15 indicates in general that the systems consisting of 3 elements mostly have
lower Rc values. This result is not very unexpected as it is known that multi-
component systems have higher glass forming abilities over binary systems or pure
elements. However for the evaluation of glass forming ability of multi-component
systems, one should not take into account only the Rc as this is a theoretically
formulated parameter. The other parameters all contribute in the formulation of the Rc,
however in a realistic model, the contribution of these parameters between themselves
and Rc and other affects would probably be different. All of these parameters have
some empirical or theoretical basis that they affect the glass forming ability of a
system in some manner. So, to end up with a more accurate conclusion, it would be
beneficial to take into account all of the parameters together but not concentrating on
just one.
When the results of theoretical data are compared with the literature data, there seems
to have a good relation between these. Table 4.15 indicates that the most effective
elements that were predicted to increase the glass forming ability are very similar to
that of used in the previous studies in the literature. The studies made up to date on Ti-
based amorphous alloys were summarized in Table 1. From the information of Table
1, it can be concluded that the most used elements with Ti and Ni when synthesizing
amorphous alloys are Zr, Sn, B, Mo, Be, Fe, Hf and Nb. These elements are also
found to increase the glass forming ability in this thesis theoretical studies. Other than
these elements Re, W and C are the new elements that are never used in previous
literature studies. In fact, these three elements are good candidates to increase the
glass forming ability in Ti2-Ni system. Such a result was so encouraging to assume
that the theoretical calculations could be supported by the results in the literature.
As it can be seen from Table 4.15 from a general view, the glass forming ability
parameters of Ti2Ni system tends to increase in favor of enhanced glass forming with
more elements when the alloying element is substituted with the Ti element other than
77
Ni element. So it could be a good starting point in the study of this binary system that
decreasing Ti content could probably be more beneficial. Cs, Rb, Ca, K and Bi
elements seem to increase Rc of the Ti2Ni system and hence the glass forming ability
the most. However, these element’s natures make them unsuitable for preparing a
metal alloy with them. The reactive nature of these elements makes it very hard to
predict the behaviors in the alloy systems so, as a result, using these elements may not
be safe for the purpose of this thesis.
The elements that are intended to be used in synthesizing possible Ti-based alloys are
the transition metals that have the optimum combination of all glass forming
parameters. Hence, the alloying elements that can be used on the basis of theoretical
calculations are W, Mo, Ta, Hf, Nb, Zr, Fe or Cr. Re and Be are also candidate
elements; Re has the most effective one to increase GFA and Be also have a good
effect in favor of GFA and is used in most recent Ti-based bulk amorphous alloys
[40]. However, we can not use these because of the unavailability of these elements.
The alloying elements that favor the GFA are given for other Ti-Ni systems in the
basis of substituted main constituent element in Table 4.16 and Table 4.17. Tables for
other binaries studied will be given in Appendix A.
78
Table 4.16 – Elements favoring the glass forming parameters in Ti-Ni2 and Ti-Ni
system in descending order
Ni-Ti(-) Ni(-)-Ti Ni(2-)-Ti Ni2-Ti(-)
ω(AB) ∆HM Rc ω(AB) ∆HM Rc ω(AB) ∆HM Rc ω(AB) ∆HM Rc
Re Cs Cs Re Ba Ba Re Cs Cs Re Cs Cs
C Rb Rb C Cs Cs C Rb Rb C Rb Rb
W Ca Ca W Rb Rb W Ca Ca W Ca Ca
Mo K K Mo Ca Ca Mo K K Mo K K
V Bi Bi V K K V Bi Bi V Bi Bi
B W W B Bi Bi B W W B W W
Nb Mo Mo Nb W W Nb Mo Mo Nb Mo Mo
Ta Re Pb Ta Mo Mo Ta B Pb Ta B B
Se Hf Re Cr Pb Pb Se Re B Se Re Hf
Cr B Hf Se Re Re Cr Hf Hf Cr Hf Re
Fe Zr B Fe Hf Hf Fe Zr Re Fe Zr Zr
Be Nb Zr Be B B Be Nb Zr Nb Nb
Ta Nb Si Zr Zr Si Ta Nb Ta Ta
Sn Ta Pd Pd Sn Ta Sn C
C C Nb Sb C C C Sn
Se Sn Sb Nb Se Sn Se Se
Be Se Ta Ta Be Se Be Be
Cr Be La La Cr Be Cr Cr
Fe Cr Sn C Fe Cr Fe Fe
Co Fe C Y Mn Fe Mn Mn
Mn Mn Y Sn Co Mn Co Co
Mg Co Se Se Co Mg
Ge Mg Pt Pt Mg Ge
Zn Ge Be Be Ge Zn
Al Zn Cr Cr Zn Cd
Al Fe Fe Cd
V Ti Mn Al
Cd Co Co
Si Mn Ti
Cu Sc Sc
Mg Mg
Ge Ge
Ga Zn
Zn Ga
Al Al
V
Cd
Si
Cu
79
Table 4.17 – Elements favoring the glass forming parameters in Ti-Al and Ti3-Ni
Ti-Al(-) Ti(-)-Al Ti(3-)-Al Ti3-Al(-)
Cs Ba Ba Cs Ba Ba Cs Ba Ba Cs Ba Ba
Rb Rb Rb Rb Cs Cs Rb Rb Cs Rb Rb Cs
K Cs Cs K Rb Rb K Cs Rb K Cs Rb
Ba Ca Ca La Ca Ca Ba Ca Ca Ba Ca Ca
Ca K K Ba K K Ca K K Ca K K
La Bi Bi Ca Bi Bi La Bi Bi La Bi Bi
Y W W Li Mo W Y W W Y W W
Li Mo Mo Y W Mo Li Mo Mo Li Mo Mo
Mg Re Re Mg Re Re Mg Re Re Mg Re Re
Ag Zr Zr Mn Zr Zr Ag Zr Zr Ag Zr Zr
Cd Nb Nb Ag Hf Hf Bi Hf Hf Bi Hf Hf
Bi Hf Hf Cd Nb B Cd Nb Nb Cd Nb Nb
Pb B B Bi B La Pb Ta Ta Pb Ta Ta
Sc Ta Ta Sc Ta Nb Sc Pb Pb Sc Pb Pb
Sn Pb Pb Sn La Ta Sn B B Sn B B
Cu Sb Sb Cu Pb Pb Cu Pd Pd Cu Pd Pd
Sb La La Sb Sb Sb Sb Sb Sb Sb Sb Sb
Zn Y Y Pt Y Y Zn La La Pt La La
Pt Pd Pd Zn Pd Pd Pt Y Y Zn Y Y
Pd Sn Sn Pd Sn Sn Ga Sn Sn Ga Sn Sn
Ga Se Se Ga Se C Pd Mg C Pd Mg C
Zr C C Zr Mg Se Zr Se Mg Zr C Mg
Ge Mg Mg Ge C Mg Ge C Se Ge Se Se
Hf Be Be Hf Be Pt Hf Be Be Hf Be Be
Mn Pt Pt Mo Pt Be Mn Sc Cr Mn Sc Cr
Ge Ge Co Ge Ge Co Cr Ge Cr Ge
Sc Sc Pb Li Ga Ni Ge Pt Ge Sc
Ga Ga Si Ga Li Si Pt Sc Pt Pt
Li Li Be Sc Sc Se Fe Fe Fe Fe
Si Si Si Mn Co Co Co Co
Cr Cr Cr Si Ni Ni Ni Ni
Zn Zn Mn Cr Ga Mn Ga Mn
Fe Fe Zn Zn Si Ga Si Ga
Co Co Fe Fe Zn Si Zn Si
Ni Ni Co Co Mn Zn Mn Zn
Cd Cd Cd Cd Li Li Li Li
Mn Mn Ni Ni Cd Cd Cd Cd
V V V V V V V V
Cu Cu Cu Cu Cu Cu Cu
Ag
80
After completing the theoretical calculations, we have had enough information and
data about the effect of different alloying element additions to the glass forming
ability of selected binary systems. This work provides a narrower range of elements to
study with for obtaining enhanced glass forming in previously selected Ti-based
metallic alloy systems. By choosing the elements predicted to increase glass forming
ability instead of all elements found in the periodic table, it is hoped to save a great
deal of effort and time to develop new bulk metallic glasses.
4.3 Discussion of experimental study
The reasons for choosing Ti2Ni binary system as a starting point for experimental
study was explained in the above sections in detail. For W and Mo are the two metal
elements that increase the glass forming ability of the binary Ti67Ni33 system. Also, Zr
is one of the best candidates to improve glass forming ability and this element is also
known to be a good glass forming alloy base so this three elements are decided to be
used for developing Ti-based bulk amorphous alloy.
4.3.1 Alloy A1, Ti67Ni33
The first alloy prepared is alloy A1 which is the binary Ti67Ni33. It was examined
metallographically and by X-ray diffraction.
SEM photograph of this binary alloy reveals mainly a two phase microstructure with
another black phase homogeneously distributed among the alloy. EDS analysis shows
that dark grey phase composition is close to TiNi intermetallic composition (55% Ti
45% Ni) and dark grey phase composition is close to Ti2Ni intermetallic (65% Ti, 35
% Ni).
81
α-Ti
Ti2Ni
TiNi
Figure 4.2 – SEM photograph (back-scatter image) of alloy A1 (Ti67Ni33)
Figure 4.3 – Ti-Ni phase diagram
82
The X-ray pattern is similar to a crystalline alloy with the greatest peak is at 2θ =
48.5o which corresponds to the intermetallic phase Ti2Ni. Other peaks correspond to
Ti2Ni, TiNi and α-Ti phases.
Figure 4.4 – X-ray scattering diffractogram of alloy A1 (Ti67Ni33)
Although we do not expect α-Ti phase at this composition, the existence of this phase
can be explained by non-equilibrium cooling conditions. As this alloy was copper
mould cast, such a shift in the final microstructure can be understandable.
4.3.2 Alloy A2, Ti60Ni30Mo10
The next step is to modify the binary alloy with alloying elements that have a positive
effect on the glass forming ability of the system. For that purpose Mo was chosen to
be a candidate metallic element and a new alloy (Ti60Ni30Mo10, A2) was prepared. The
alloy was examined metallographically and by X-ray diffraction analysis.
83
Back-scatter Back-scatter
βTi-Mo
phase
Ti2Ni
intermetallic
TiNi
intermetallic
Secondary image
Figure 4.5 – SEM photographs of alloy A2 (Ti60Ni30Mo10)
84
Figure 4.6 – X-ray scattering diffractogram of alloy A2 (Ti60Ni30Mo10)
After analyzing the diffraction pattern of the ternary alloy looks very similar to the
binary alloy except a few new peaks. These peaks arise from the contribution of the
Mo element to the structure of the system. The structure of the A2 alloy also seems so
similar to the binary one at as-polished state. However after etching the specimen, the
structure becomes more distinct with eutectic like region and white flower-like areas.
This implies that the matrix was formed due to the contributions of Ti and Ni atoms
both in the ternary and binary alloys and the white regions in the microstructure of A2
alloy are probably Ti-Mo solid solutions as the EDS analysis reveals this phase as a Ti
and Mo rich one. The difference of the matrix structure of binary Ti67Ni33 and ternary
Ti60Ni30Mo10 is probably because of the shifting of relative composition of Ti and Ni
and the effect of the Mo addition. If the section of the phase diagram analyzed, the
portion around 60 atomic % -70 atomic % Ti there is a peritectic region ending at 67.9
atomic %. At 66.67 atomic % Ti there is Ti2Ni intermetallic and between this
intermetallic and ending point of peritectic region, the peritectic is followed by a
eutectic. This means slight shifts in the composition of the system or in the eutectic
region can change the microstructure from peritectic to eutectic.
85
As a result, the difference in the microstructures of alloys A1 and A2 arises from this
fact where the composition of the system in A2 or the eutectic region of this
composition probably shifts to lead a eutectic microstructure.
Figure 4.7 – Section of Ti-Ni phase diagram
4.3.3 Alloy A3, Ti55Ni30Zr8Mo5W2
4.3.3.1 Copper mould cast
A3 alloy (Ti55Ni30Zr8Mo5W2) is the first multi-component alloy system intended to be

produced in bulk amorphous form. This new multi-component alloy contain Zr and W
additionally which also found the increase the GFA of Ti-Ni based alloys. This system
was produced in a wedge shape to better understanding the GFA of this alloy at
different cooling rates. For this purpose attention is given to examining different
sections of this wedge shaped alloy. The SEM photographs taken at 2000X
magnification are given below:
86
a) b)
c) Schematic view of wedge shaped as-

cast alloy (scale 1:4)
Figure 4.8 – Back-scatter SEM photographs taken form thinnest (a), 0,5 mm from the
thinnest section (b) and thickest (1 mm from thinnest) (c) sections of alloy A3
(Ti55Ni30Zr8Mo5W2).
The photograph taken from the thinnest section of the wedge shaped alloy was shown
in Figure 4.7 (a). As it was seen, there were no sharply distinct phases are found in the
structure; there is a featureless matrix (typical of amorphous alloys) and a few
nebulous bright regions. At intermediate section, the quantity and shape bright regions
87
become more distinct and some dark regions start to appear. At the photograph taken
from the thickest section of A3 (Ti55Ni30Zr8Mo5W2), all the phases in the system
become clearer. There are white irregular shaped regions where these regions were
identified to be a Mo, W and Ti rich phase by EDS analysis. The Ti-Mo phase
diagram indicates that the two elements are completely soluble at these relative
compositions (43,12% Mo, 41,34% Ti) so this is a Mo, β-Ti phase.
The black regions composition was very close to the Ti2Ni intermetallic composition
with nearly 10 atomic % Zr and the grey regions composition was close to TiNi
intermetallic as identified by EDS analysis. Both phases were expected to be in the
structure as the relative composition of Ti and Ni were lead such formations. However
the X-ray analysis reveals that all Ti2Ni peaks shift 5o to lower angles meaning that
this is a new phase containing other elements. Black regions which were thought to be
Ti2Ni intermetallic form EDS analysis but this analysis also showed that 10 atomic %
Zr was found in these regions. As a result these black regions were concluded to be a
Ti-Ni-Zr phase.
88
Figure 4.9 – Ti-Mo phase diagram
Figure 4.10 – X-ray scattering diffractogram of alloy A3 (Ti55Ni30Zr8Mo5W2)
89
The X-ray results do not encourage finding amorphous structure but on the other hand
the featureless matrix at the thin section of the wedge shaped specimen may be a clue
for an amorphous phase or a very small sized crystalline phase; i.e. quasi-crystalline.
Thermal analysis (DSC) was made between the temperature interval 100oC and
1200oC. The pouring temperature of the alloy was 1250o where the elemental mixture
completely melted at 1000oC. The high pouring temperature is used to provide a
higher fluidity hence the problem of material loss due to the solidification of the alloy
in the crucible before pouring was avoided.
The specimens for DSC analysis was taken from the thinnest section of the wedge
shaped alloy as it is expected to have amorphous region especially at this portion of
the alloy because of the higher cooling rate. The DSC traces shown in Figure 4.11
indicate that there were some structural transformations occurring at 717-787 oC.
These can be a kind of structural transformation related to start of a glassy phase or
kind of relaxation due to non-equilibrium cooling.
65
Heat Flow (mW)
55
700oC
615oC
45
985oC
35
550
600
650
700
750
800
850
900
950
1000
1050
1100
1150
1200
Temperature (oC)
Figure 4.11 – DSC trace of alloy A3 (Ti55Ni30Zr8Mo5W2)
90
As it was seen from the DSC traces in Figure 4.11 (a) and (b), the structural
phenomenon occurred could possibly arise because of relatively high cooling rate.
The melting of the alloy occurs in nearly a single stage as there is a big sharp
endothermic peak at 985oC. The temperature of this endothermic event is very much
coinciding with the phase diagram of Ti-Ni binary. At the portion of the phase
diagram corresponds to the initial relative composition of Ti and Ni in the alloy A3
(Ti55Ni30Zr8Mo5W2), there is a peritectic reaction at 985oC, same with the first
endothermic peak of the DSC trace of alloy A3. This means that the thin sections of
alloy A3 has a structure where mostly Ti and Ni elements interact with each other and
the other elements have a modification role. Hence the melting of this specimen taken
from the thinnest section of alloy A3 was occurred at the peritectic reaction and the
second endothermic peak is probably the following liquidus of the system.
The SEM analysis and the DSC traces of alloy A3 shows that this alloy can be a good
candidate for producing a new Ti-based bulk amorphous alloy. By manipulating the
composition of the alloy, the GFA of the system could possibly be increased. The
good glass forming alloys are generally found near deep eutectics and the melting
behavior when analyzed by thermal techniques shows nearly a single distinct
endothermic peak meaning that the multi-component alloy behaves like a eutectic one.
The microstructural and thermal analysis of A3 however showed that the multi-
component alloy is in the peritectic region of Ti-Ni binary phase diagram. However
the relative compositions of Ti and Ni elements in the alloy A3 are so close to the
peritectic + eutectic region of the phase diagram. The DSC traces also confirm this as
the endothermic peak at 985oC exactly coincides with the peritectic reaction
temperature of the Ti-Ni phase diagram and the second less distinct peak is the
liquidus at A3 alloy’s composition. As a result, it would not be a bad idea to modify
the composition of the alloy so as it passes to the eutectic region, more preferably
stays at the region of peritectic + eutectic. This may lead to a high GFA of the alloy.
91
4.3.3.2 Near equilibrium cooled sample
The microstructure of near equilibrium cooled A3 (Ti55Ni30Zr8Mo5W2) was so similar

to that alloy’s copper mould cast one. The amount of grey phase (Ti-Ni-Zr phase) in
the near equilibrium cooled is higher than that of copper mould cast one. Also, the
relative sizes of the phases in both slow cooled and copper mould cast samples are
very close to each other at 150X and 2000X respectively. That implies that the growth
of phases was greatly suppressed in the copper mould cast sample.
a) b)
Ti-Ni-Zr
phase
Ti2Ni
intermetallic
βTi-Mo
phase
c)
Figure 4.12 – Back scatter SEM images of Alloy A3(Ti55Ni30Zr8Mo5W2); (a) and (c)
near equilibrium cooled, (b) copper mould cast one (thickest section) for comparison
92
Figure 4.13 – X-ray scattering diffractogram of near equilibrium cooled sample of
alloy A3 (Ti55Ni30Zr8Mo5W2)
65
60
Heat Flow (mW)
55
50
45
40 985oC
35
550
600
650
700
750
800
850
900
950
1000
1050
1100
1150
1200
Temperature (o C)
Figure 4.14 – DSC trace of near equilibrium cooled alloy A3 (Ti55Ni30Zr8Mo5W2)
Thermal characteristic of near equilibrium cooled alloy A3 is different that there has
no thermal phenomenon such as found in the copper mould cast sample. Equilibrium
cooling conditions set the microstructure of the alloy in a stable condition different
than the copper mould cast one.
93
The alloy A3 was modified to achieve a Ti/Ni ratio more close to the eutectic region.
The new alloy A4 (Ti57Ni28Zr8Mo5W2) was prepared by holding the amounts of
elements other than Ti and Ni constant and changing the Ti percentage form 55 to 57
and Ni percentage from 30 to 28. By doing this it was intended to have an alloy more
closely to the eutectic composition.
The SEM photographs of alloy A4 looks very similar to the previous one A3
(Ti57Ni28Zr8Mo5W2). In the thinnest sections, both alloys have a featureless matrix
typical of amorphous phase. In alloy A4 however, there are a few black spherical
regions identified as a Ti rich (90.14 atomic % Ti) by EDS analysis. The thickest
region of the A4 specimen (1.3 mm from thinnest) is also very similar to the A3
specimen’s intermediate region (0.5 mm from thinnest) with a bit larger phases in
terms of size. Although the microstructures look very similar, in fact there is a great
difference that the bright phases in both microstructures have nearly same sizes at
different distances (means also different cooling rates as a wedge shaped cooper
mould is used) from the thinnest sections. This means that in the latter alloy, the
growth of some phases were inhibited in a longer scale than the former one.
Modifying the composition of Ti and Ni by only 2 atomic % will lead to an increase in
the retardation of the growth of the phases with lower cooling rates.
94
a) thinnest b) thickest (1.3 mm from thinnest)
Schematic view of wedge shaped

as-cast alloy (scale 1:5)
Figure 4.15 – Back-scatter SEM photographs taken form thinnest (a) and thickest (1.3
mm from thinnest) (b) sections of the alloy A4 (Ti57Ni28Zr8Mo5W2).
X-ray analysis of A4 is also very similar to that of alloy A3 so it should not be wrong
to say that the same phases exist in both alloys.
95
Figure 4.16 – X-ray scattering diffractogram of alloy A4 (Ti57Ni28Zr8Mo5W2)
The DSC traces of alloy A4 again has a thermal phenomenon and a single
endothermic event (melting). It was achieved to have a higher level of retardation of
phase growth at lower cooling rates by compositional modification. However the
endothermic peak again corresponds to the peritectic reaction at 985oC on Ti-Ni
binary phase diagram instead of the intended eutectic one. There is a change in the
pattern of the trace at about 593oC, and this looks like a low energy exothermic event.
This may corresponds to the crystallization of glassy phase however there is no such a
distinct glass transition temperature (Tg). If the exothermic peak corresponds to
crystallization, Tg must be in the region of thermal fluctuation caused by the high
temperature accurate thermocouple. As the thermocouple used in the DSC device is
accurate above 500oC, there is a fluctuation below this temperature. Although such an
alloy composition has not been studied previously, the Tg of Ti-based amorphous
alloys are in the range of 450oC-500oC [1-3, 7, 30, 39, and 40] and the crystallization
is about 500oC-550oC [1-3, 7, 30, 39, and 40]. As a result, it is a good probability that
the characteristics of the DSC traces of alloys A3 and A4 is to relate with a glassy
phase when both SEM and thermal analysis are combined with the general data for
amorphous Ti-based alloys. The DSC trace of the alloy remelted and cooled slowly is
given for comparison.
96
70,00
65,00
Heat Flow (mW)
60,00
595oC
55,00
50,00
45,00
985oC
40,00
550 600 650 700 750 800 850 900 950 1000 1050 1100 1150 1200
o
Temperature ( C)
a)
65,00
60,00
Heat Flow (mW)
55,00
50,00
985oC
45,00
600 650 700 750 800 850 900 950 1000 1050 1100 1150 1200
o
Temperature ( C)
b)
Figure 4.17 – DSC trace of alloy A4 (Ti57Ni28Zr8Mo5W2), a) Copper mould cast, b)

Slowly cooled
97
In Figure 4.17 (b) there is not an exothermic peak as in Figure 4.17 (a). As a result, it
is clear that the exothermic event observed in the copper mould cast one is because of
the nonequilibrium cooling conditions and may be an indication of glassy phase.
It is still a question mark that whether being in the region of the peritectic and eutectic
transition would lead to an increase in the GFA of the systems. In the DSC traces of
the previously produced alloys, there is not even a eutectic or peritectic + eutectic or
just a eutectic. So it would be better to try to produce such an alloy falling in that
region and study the structural characteristics.
Alloy A5 is prepared for that purpose with an increased Ti/Ni atomic ratio of 0.702
where the previous alloys A3 and A4 has the Ti/Ni atomic ratios of 0.647 and 0.670
respectively. The new alloy’s composition was Ti59Ni25Zr9Mo5W2.
The SEM photographs of A5 indicates that it has some microstructural features both
thin (relatively fast cooled) and thick sections (relatively slow cooled) unlike in the
previous multi component alloys A3 (Ti55Ni30Zr8Mo5W2) and A4 (Ti57Ni28Zr8Mo5W2)
thin sections. There are dark grey and more bright regions as seen in the back-
scattered SEM image. In Figure 4.18 (a), the dark grey regions are Ti, Ni and Zr rich
regions and in the bright regions Mo and W concentration are just high. Dark spots
consist of nearly pure Ti. These thought to be the titanium particles that did not melt
but, as seen in Figure 4.18 (b), where the thicker section of the specimen was shown,
these darker spots increased in size and number and they have star like shapes. Thick
section of the specimen has again larger and brighter white zones as all observed in
the previous multi-component alloys A3 and A4. Mo concentration is higher than the
bright zones of the same specimen’s thin section (Figure 4.18 (a)). The grey zones are
found to be a Ti, Ni and Zr phase but the structure of the phase is not very clear. By
98
investigating the thermal and X-ray behaviors of this alloy may give more specific
information about the structure of the alloy.
a) thinnest b) thickest (2.0 mm from thinnest)
Schematic view of wedge shaped

as-cast alloy (scale 1:5)
Figure 4.18 – Back-scatter SEM photographs taken form thinnest (a) and thickest (2.0
mm from thinnest) (b) sections of the alloy A4 (Ti59Ni25Zr9Mo5W2).
99
DSC traces of A5 has no sign of any glassy phase or other structural phenomenon that
may occur under a thermal cycle due to non-equilibrium solidification; i.e. Structural
relaxation. However, dissimilar to A3 and A4 alloys thermal behavior, the melting of
alloy A5 is at 945oC instead of 985oC for the previous alloys. At that temperature,
there is the eutectic reaction which corresponds to one found in the Ti-Ni phase
diagram. This implies that the system should have a eutectic type structure. Although
there are no clear eutectic like microstructure seen in the SEM microscopy, the grey
regions (Figure 4.14 (b)) would probably be eutectic type structure.
75,00
70,00
Heat Flow (mW)
65,00
60,00
55,00
945oC
50,00
550 600 650 700 750 800 850 900 950 1000 1050 1100 1150 1200
o
Temperature ( C)
a)
100
65,00
Heat Flow (mW)
55,00
945oC
45,00
550 600 650 700 750 800 850 900 950 1000 1050 1100 1150 1200
o
Temperature ( C)
b)
Figure 4.19 – DSC traces of alloy A5 Ti59Ni25Zr9Mo5W2, a)Copper mould cast alloy
b) Slowly cooled
X-ray analysis is similar to that of alloys A3 (Ti55Ni30Zr8Mo5W2) and A4

(Ti57Ni28Zr8Mo5W2). There are only slight changes in the amount of phases present in
the system. The black flower like regions were identified as a highly Ti-concentrated
phase by EDS analysis previously. This phase should correspond to the α-Ti phase as
there are several peaks form that phase in the X-ray analysis. This can also be
confirmed from the point of view that the eutectic reaction in the Ti-Ni binary is such
that L → α-Ti + δ (Ti2Ni). As it was shown previously by DSC thermal analysis that
the system undergo this eutectic reaction, there must have α-Ti and δ (Ti2Ni) in the
system.
101
Figure 4.20 – X-ray scattering diffractogram of alloy A5 Ti59Ni25Zr9Mo5W2
102
CHAPTER 5
CONCLUSIONS
On the base of theoretical and experimental investigation of GFA parameters and

Ti2Ni system, following conclusions may be drawn.
1. Ordering energy and GFA parameters calculations show that Ti-Ni and Ti-
Fe systems have better bulk glass forming chance among all studied Ti-
based binary systems.
2. In general, Ti2Ni intermetallic composition shows better glass forming

characteristics than TiNi or TiNi2 systems.
3. Substituting alloying elements for Ti instead of Ni in Ti2Ni system will be

more beneficial for enhanced GFA as more elements favor GFA
parameters in that case.
4. Re, C, W, Mo, V, B, Ta, Nb, Fe, Cr, Be, Se are the alloying elements that
increase the ordering energy between Ti and Ni atoms in Ti(2-)Ni system.
5. Cs, Rb, Ca, K, Bi, W, Mo, Pb, Re, Hf, Zr, B, Nb, Ta, C, Sn, Se and Be are
alloying elements that decrease Rc the most.
103
6. The results of theoretical calculations show good agreement with literature
data. Most of the alloying elements that were predicted to increase the
ordering energy and other GFA parameters of Ti2Ni system were
previously used for synthesizing bulk amorphous or amorphous Ti-based
alloys.
7. Alloys A3 (Ti55Ni30Zr8Mo5W2) and A4 (Ti57Ni28Zr8Mo5W2) melt through

a single peritectic reaction at 985oC which corresponds to the peritectic
reaction in Ti-Ni phase diagram.
8. In alloys A3 (Ti55Ni30Zr8Mo5W2) and A4 (Ti57Ni28Zr8Mo5W2), the thinnest

section of the wedge cast samples shows a featureless matrix typical to
glassy alloys.
9. Thermal analysis of these two alloys reveals some thermal phenomenon

occurring at 615oC for alloy A3 and at 700oC and at 595oC for alloys A4
(Ti57Ni28Zr8Mo5W2). These may be concluded as a sign of glassy phase
with the support of metallographic data.
10. The rapidly cooled (copper mould cast) and near equilibrium cooled
samples of alloy A3 (Ti55Ni30Zr8Mo5W2) shows that in the rapid cooled
sample, the growth of the phases were greatly suppressed. At the highest
cooling rate zone (thinnest section of the wedge shaped sample), there are
not any featured microstructure. Some phases found in the near
equilibrium cooled sample (i.e. Ti3Ni4, Figures 4.10 and 4.12) were not
formed in the copper mould cast sample.
11. Alloy A5 Ti59Ni25Zr9Mo5W2 has a featured microstructure in both thinnest

and thickest sections. The thermal analysis of this alloy shows only
melting at 945oC.
104
CHAPTER 6
FUTURE WORKS
By theoretical calculations of ordering energy and Rc, a wide database of different

GFA parameters was established for various Ti containing binaries. This database will
surely provide a framework for the investigation of new Ti-based bulk amorphous
alloys. For the development and efficient use of this database, the following
suggestions will probably be beneficial to utilize:
1. The effect of alloying elements on the ordering energies of Ti containing

binary systems was evaluated for only 1% alloying substitution. For
examining the effects at different percentages, additional calculations
would be done.
2. The compositions in this study were selected arbitrarily. For further

understanding of the effect of alloying elements on GFA and finding the
optimum concentration of an alloying element for the best possible GFA in
practical manner, synthesizing of Ti-based bulk amorphous alloys would
be done in a more systematic manner.
3. Further efforts would be focused on enhancing the GFA of these alloys by

optimizing the processing conditions and/or manipulating the alloy
compositions. As a result, investigation of different processing conditions
would also be conducted.
105
4. The properties, especially mechanical properties as Ti-based bulk
amorphous alloys are good candidates for structural applications, of alloys
synthesized in bulk amorphous structure will be investigated.
106
REFERENCES
[1] D. V. Louzguine, A. Inoue Journal of Materials Science Vol. 35 (2000) p. 4159
[2] D. V. Louzguine, A. Inoue Scripta Mater. Vol. 43 (2000) p. 371
[3] G. He., J. Eckert, W. Lo¨ser Acta Materialia Vol. 51 (2003) pp. 1621–1631
[4] Yu-Chan KIM, Won Tae KIM, Do-Hyang KIM, Ann. Chim. Sci. Mat., 2002, Vol
27 (5), pp. 11-17
[5] A. Inoue, A. Takeuchi, Mat. Trans. Vol 43, No. 8 (2002) pp. 1892-1906
[6] Lement WK, Willens JRH, Duwez P. Nature 1960, p. 187:869
[7] Johnson WL., Materials Science Forum 1996, Vol. 225-227, pp.35-50.
[8] Inoue A. Mater Trans JIM 1995, Vol. 36(7), pp. 866-75.
[9] Wenzhi C., Metallic Functional Materials 1997, Vol. 4, pp. 1-6.
[10] H.W. Kui, A.L. Greer, D. Turnbull, Appl. Phys. Lett. Vol. 45 (1984)
[11] A. Inoue, Acta mater. Vol. 48 (2000), pp. 279-306
[12] A. Inoue, K. Ohtera, K. Kita, T. Masumoto, Jpn. J. Appl. Phys. Vol. 27 (1988)
L2248
107
[13] A. Inoue, T. Zhang, T. Masumoto, Mater. Trans. JIM Vol.30 (1989), p. 965
[14] A. Inoue, T. Zhang, T. Masumoto, Mater. Trans. JIM Vol. 31 (1990), p. 148
[15] A. Inoue, Y. Shinohara, J.S. Gook, Mater. Trans. JIM Vol. 36 (1995), p. 1427
[16] H.M. Wang, I. Yoshii, A. Inoue, Mater. Trans. JIM Vol.40 (10) (1999), p. 1130.
[17] T. Zhang, A. Inoue, Mater. Trans. JIM Vol. 39 (1998), p. 1001
[18] D. Turnbull, Contemp. Phys., Vol. 10, pp. 473-88, 1969
[19] H.A. Davies, B.G. Lewis, Scr. Metall. Mater. Vol. 9 (1975), p. 1109
[20] Giessen, B. C., Hong, J., Kadakoff, L., Polk, D. E., Ray, R. and St. Amand, R.,
‘Proc. 3rd Int. Conf. Rapidly Quenched Metals’, Ed. Cantor, B., Vol 1, p. 249, The
Metals Society, London (1978)
[21] A. Inoue, T. Zhang, T. Masumoto, J. Non-Cryst. Solids pp. 156–158 (1993) 473
[22] Y. Li, H. Jones, H.A. Davies, Scr. Metall. Mater. Vol. 26 (1992), p. 1371.
[23] L.E. Tanner, R. Ray, Scr. Metall. Vol. 11 (1977), p 783.
[24] D.E. Polk, A. Calka, B.C. Giessen, Acta Metall. Vol. 26 (1978)
[25] A. Inoue, T. Masumoto, C. Suryanarayana, A. Hoshi, J. Phys. Vol. 41 (1980) p.

758.
[26] T. Ahang, A. Inoue, T. Masumoto, Mater. Sci. Eng. A181 & A182 (1994), p.
1423
108
[27] K. Amiya, N. Nishiyama, A. Inoue, T. Masumoto, Mater. Sci. Eng. A179 &
A180 (1994) p. 692.
[28] Limin Wang, Liqun Ma and Akihisa Inoue, Mat. Trans. Vol. 42, No:9 (2002) pp.
2346-2349
[29] Limin Wang and Akihisa Inoue, Mat. Trans. Vol 42, No12 (2001) pp. 2637-2640
[30] Tao Zhang, Akihisa Inoue, Materials Science and Engineering A304–306 (2001)
pp. 771–774
[31] Arun Pratap, K.G. Raval, A.M. Awasthi, Materials Science and Engineering
A304–306 (2001) pp. 357–361
[32] M. Calin 1, J. Eckert, L. Schultz, Scripta Materialia Vol. 48 (2003), pp. 653–658
[33] E.S. Park, H.K. Lim, W.T. Kim, D.H. Kim, Journal of Non-Crystalline Solids
Vol. 298 (2002) pp. 15–22
[34] Limin Wang, Chunfei Li, Liqun Ma, Akihisa Inoue, Journal of Alloys and
Compounds Vol. 339 (2002) pp. 216–220
[35] L. Battezati, M. Baricco, P. Fortina, W.-N.Myung, Materials Science and

Engineering A226–228 (1997) pp. 503–506
[36] Chunfei Li, Junji Saida, Masaya Kiminami, Akihisa Inoue, Journal of Non-
Crystalline Solids Vol. 261 (2000) pp. 108-114
[37] Chunfei Lia, Junji Saidaa, Mitsuhide Matsushidaa and Akihisa Inouea, Scripta
Mater., Vol. 42 (2000) pp. 923–927
[38] K.B. Kim, P.J. Warren, B. Cantor, Journal of Non-Crystalline Solids, Vol. 317
(2003), pp. 17–22
109
[39] Yu-Chan Kim, Won Tae Kim and Do-Hyang Kim, Mat. Trans. Vol 43, No5
(2002) pp. 1243-1246
[40] Y.C. Kima, W.T. Kimb, D.H. Kima Materials Science and Engineering Axxx
(2004) xxx–xxx
[41] Liqun Ma, Limin Wang, Tao Zhang and Akihisa Inoue, Mat. Trans. Vol 43, No2
(2002) pp. 277-280
[42] Colligan, G. A. and Bayles, S., Acta Metal., Vol. 10 (1962), p. 895
[43] Turnbull, D. and Chec, R. E., J. Appl. Phys., Vol. 21(1950), p. 805
[44] Waseda, Y and Chen, H. S Sci. Rep. Res. Insts Tohoku Univ., Vol. 28(1980), p.
143
[45] Cargill, G. S. (III), Solid St. Phys., Vol.30(1975), p. 227
[46] Sakata, M., Cowlam, N. and Davies, H.A., (a) J. Phys. Colloque, Vol. 41, C8,
suppl. 8(1980), p.190; (b) J.Phys. F, Vol. 11(1981), L157
[47] Gaskell, P, H., J. Non-cryst. Sloids, Vol. 32(1979), p. 207
[48] H. A. Davies, Phys. Chem. Glasses, Vol. 17 (1976), p. 159
[49] D. R. Uhlmann, in: Materials Science Research, Vol. 4, eds. T. J. Gray, V. D.

Frechette (Plenum, New York, 1969), p. 172
[50] L. Battezzati, C. Antonione and G. Riontino, J. Non-Cryst. Solids Vol.89 (1987)

pp. 114-130.
[51] R N Singh and F Sommer Rep. Prog. Phys., Vol. 60 (1997), pp. 57-150
110
[52] G. Escorial, Phil Mag, Vol. B76 (1997), p. 483
[53] R.N. Singh, F. Sommer, Phys.Chem. Liq. (1997)
[54] R.N. Singh, N.H. March, in: J.H. Westbrook, R. L. Fleischer (Eds), Intermetallic
Compound-Principle and Practice, Ch. 28, Wiley, London, 1994
[55] S.M. Osman, R.N. Singh, Phys. Rev. E51 (1995), p. 332
[56] E.A. Guggenheim, Mixtures, Oxford University Press, Oxford, 1952
[57] F.sommer, R.N. Singh, V.witusiewicz, Journal of Alloys and Compounds, Vol.
325 (2001), pp. 118-128
[58] A. Takeuchi and A. Inoue, Materials Science and Engineering, Elsevier, A304–
306, (2001), pp. 446–451.
[59] F. E. Luborsky, “Amorphous Metallic Alloys”, edited by F. E. Luborsky,

Butterworth and Co., (1983), pp. 1-24.
[60] H. S. Chen, K. A. Jackson, “Metallic Glasses”, editors. J. J. Gilnan and H. J.

Leamy,
[61] American Society for Metals, Metals Park, Ohio, (1978), pp. 74-96.
[62] P. Ramachandrarao, “Metallic glasses”, ed. by. T. R. Anantharaman, Trans Tech

Publications, Switzerland, (1984), pp. 33-34.
[63] METE 540 and 507 Lecture Notes
[64] A.Inoue, Materials Science and Engineering A304–306 (2001), pp. 1–10
111
[65]- A. Inoue, A. Katsuya, Mater. Trans. JIM, Vol. 37 (1996), p. 1332
[66] H.S. Chen, Mater. Sci. Eng., Vol. 23 (1976), p. 151.
[67] A. Peker, W.L. Johnson, Appl. Phys. Lett. Vol. 63 (1993), p. 2342
[68] Xiong Rao *, Qiangfei Xia, Xijiang Li, Pengcheng Si, Intermetallics 8 (2000),
pp. 499-501
[69] Liqun Ma, Limin Wang, Tao Zhang and Akihisa Inoue Mat. Trans., Vol 43, No:2
(2002), pp. 277-280
[70] F. E. Luborsky, Amorphous Metallic Alloys
[71] M. K. Pehlivanoğlu, PhD. Thesis, Production and Development of Bulk Metallic

Glasses, June 2003, METU.
[72] H. M. Türkeş, M. Sc. Thesis, Synthesis and Characterization of Non-Ferrous

Based Bulk Amorphous Alloys, September 2001, METU.
[73] O. Mekhrabov and M. V. Akdeniz, Metallurgical and Materials Transactions A,

Volume 34A, March 2003, pp. 721-734.
[74] O. Mekhrabov and M. V. Akdeniz, Chemical Eng. Comm., Vol. 190, 2003, pp.
898-910.
[75] A. O. Mekhrabov and M. V. Akdeniz, Acta Materialica, vol. 47, no: 7, 1999, pp.
2067-2075.
[76] M. V. Akdeniz and A. O. Mekhrabov, Acta Materialica, vol. 46, no: 4, 1998, pp.
1185-1192.
112
[77] A. O. Mekhrabov, M. V. Akdeniz and M. M. Arer, Acta Materialica, vol. 45, no:
3, 1997, pp. 1077-1083.
[78] Cowley J. M. 1950, Phys. Rev. 77, p. 667
[79] Moelevyn, Hughes, E. A. 1952, Mixtures (Oxford: Oxford University Press)
113
APPENDIX A
Tabulated data of ordering energy, interchange energy, ∆HM, viscosity, mismatch

entropy, Rc and ∆H/RT values for Ti-Al, Ti-Fe and Ti-Co systems:
114
Table A.1 – Ti50Al49X1
Alloying ω system in (−ω)∗Ζ/2 in
ω(AB) (atu) ω(AC) (atu) ω(BC) (atu)
element (X) J/mol J/mol
none 1,254E-03 -8,227E+02 -3,291E+03
Ag 1,302E-03 -1,153E-02 -1,320E-02 -5,160E+02 -2,064E+03
B 1,212E-03 1,300E-02 2,271E-02 -1,242E+03 -4,967E+03
Ba 1,480E-03 5,585E-01 4,759E-01 -1,440E+04 -5,760E+04
Be 1,238E-03 3,420E-03 1,620E-03 -8,617E+02 -3,447E+03
Bi 1,296E-03 2,959E-02 3,422E-02 -1,662E+03 -6,646E+03
C 1,182E-03 5,194E-03 6,819E-03 -9,159E+02 -3,663E+03
Ca 1,397E-03 1,231E-01 9,554E-02 -3,742E+03 -1,497E+04
Cd 1,299E-03 -3,455E-03 -2,177E-03 -7,620E+02 -3,048E+03
Co 1,252E-03 1,531E-04 -3,251E-03 -7,652E+02 -3,061E+03
Cr 1,233E-03 1,862E-03 -2,190E-03 -7,892E+02 -3,157E+03
Cs 1,693E-03 1,399E-01 9,925E-02 -4,201E+03 -1,680E+04
Cu 1,278E-03 -5,251E-03 -8,991E-03 -6,369E+02 -2,548E+03
Fe 1,233E-03 8,917E-04 -2,681E-03 -7,702E+02 -3,081E+03
Ga 1,268E-03 -1,824E-03 1,371E-03 -8,087E+02 -3,235E+03
Ge 1,259E-03 4,245E-04 1,307E-03 -8,318E+02 -3,327E+03
Hf 1,259E-03 1,615E-02 1,913E-02 -1,267E+03 -5,069E+03
K 1,536E-03 8,475E-02 5,800E-02 -2,845E+03 -1,138E+04
La 1,348E-03 7,371E-03 9,918E-03 -1,091E+03 -4,364E+03
Li 1,320E-03 -3,576E-03 -3,000E-05 -8,017E+02 -3,207E+03
Mg 1,306E-03 4,771E-03 8,708E-04 -9,134E+02 -3,654E+03
Mn 1,257E-03 -3,786E-04 -3,957E-03 -7,523E+02 -3,009E+03
Mo 1,183E-03 2,582E-02 3,296E-02 -1,524E+03 -6,094E+03
Nb 1,217E-03 1,661E-02 2,122E-02 -1,273E+03 -5,093E+03
Ni 1,251E-03 1,331E-04 -3,273E-03 -7,640E+02 -3,056E+03
Pb 1,294E-03 1,266E-02 1,529E-02 -1,195E+03 -4,779E+03
Rb 1,600E-03 1,428E-01 1,026E-01 -4,222E+03 -1,689E+04
Re 1,157E-03 2,140E-02 2,887E-02 -1,396E+03 -5,583E+03
Sb 1,272E-03 1,212E-02 1,404E-02 -1,158E+03 -4,630E+03
Sc 1,293E-03 8,521E-04 -2,614E-03 -8,088E+02 -3,235E+03
Se 1,235E-03 2,078E-03 8,857E-03 -9,352E+02 -3,741E+03
Si 1,247E-03 -1,021E-03 5,472E-04 -7,954E+02 -3,182E+03
Sn 1,279E-03 6,820E-03 5,986E-03 -9,890E+02 -3,956E+03
Ta 1,217E-03 1,493E-02 1,978E-02 -1,233E+03 -4,930E+03
V 1,198E-03 -9,102E-04 -3,653E-03 -7,114E+02 -2,846E+03
W 1,184E-03 2,890E-02 3,437E-02 -1,583E+03 -6,330E+03
Zn 1,271E-03 -1,192E-03 -1,366E-03 -7,837E+02 -3,135E+03
Zr 1,263E-03 1,731E-02 2,022E-02 -1,299E+03 -5,197E+03
115
Alloying mismatch Viscosity ∆η/η0
Sideal SM ∆HM Rc
Element (X) entropy (kg,m3)
none 8,98E-03 5,76E+00 5,77E+00 2,66E-03 -6,58E+03 4,74E+08 6,30E-01
Ag 8,89E-03 6,17E+00 6,18E+00 2,69E-03 -6,19E+03 4,61E+08 5,92E-01
B 1,69E-01 6,17E+00 6,34E+00 2,67E-03 -1,49E+04 2,90E+08 1,43E+00
Ba 6,07E-01 6,17E+00 6,77E+00 2,65E-03 -1,73E+05 7,77E+04 1,65E+01
Be 7,96E-02 6,17E+00 6,25E+00 2,67E-03 -1,03E+04 3,72E+08 9,89E-01
Bi 1,55E-01 6,17E+00 6,32E+00 2,71E-03 -1,99E+04 2,20E+08 1,91E+00
C 3,45E-01 6,17E+00 6,51E+00 2,67E-03 -1,10E+04 3,46E+08 1,05E+00
Ca 3,07E-01 6,17E+00 6,47E+00 2,64E-03 -4,49E+04 6,08E+07 4,30E+00
Cd 1,21E-02 6,17E+00 6,18E+00 2,69E-03 -9,14E+03 3,96E+08 8,75E-01
Co 3,87E-02 6,17E+00 6,21E+00 2,68E-03 -9,18E+03 3,95E+08 8,78E-01
Cr 3,87E-02 6,17E+00 6,21E+00 2,68E-03 -9,47E+03 3,90E+08 9,06E-01
Cs 1,85E+00 6,17E+00 8,01E+00 2,60E-03 -5,04E+04 3,72E+07 4,82E+00
Cu 3,03E-02 6,17E+00 6,20E+00 2,68E-03 -7,64E+03 4,28E+08 7,31E-01
Fe 4,18E-02 6,17E+00 6,21E+00 2,68E-03 -9,24E+03 3,94E+08 8,84E-01
Ga 1,59E-02 6,17E+00 6,18E+00 2,68E-03 -9,70E+03 3,86E+08 9,28E-01
Ge 4,83E-02 6,17E+00 6,22E+00 2,67E-03 -9,98E+03 3,80E+08 9,55E-01
Hf 3,00E-02 6,17E+00 6,20E+00 2,71E-03 -1,52E+04 2,86E+08 1,45E+00
K 8,90E-01 6,17E+00 7,06E+00 2,61E-03 -3,41E+04 9,87E+07 3,27E+00
La 1,99E-01 6,17E+00 6,37E+00 2,68E-03 -1,31E+04 3,15E+08 1,25E+00
Li 1,47E-02 6,17E+00 6,18E+00 2,65E-03 -9,62E+03 3,92E+08 9,20E-01
Mg 3,30E-02 6,17E+00 6,20E+00 2,66E-03 -1,10E+04 3,64E+08 1,05E+00
Mn 8,86E-02 6,17E+00 6,26E+00 2,68E-03 -9,03E+03 3,96E+08 8,64E-01
Mo 1,44E-02 6,17E+00 6,18E+00 2,69E-03 -1,83E+04 2,47E+08 1,75E+00
Nb 8,98E-03 6,17E+00 6,18E+00 2,69E-03 -1,53E+04 2,89E+08 1,46E+00
Ni 3,87E-02 6,17E+00 6,21E+00 2,68E-03 -9,17E+03 3,95E+08 8,77E-01
Pb 3,87E-02 6,17E+00 6,21E+00 2,71E-03 -1,43E+04 2,99E+08 1,37E+00
Rb 1,11E-02 6,17E+00 6,18E+00 2,61E-03 -5,07E+04 4,77E+07 4,85E+00
Re 1,20E-02 6,17E+00 6,18E+00 2,72E-03 -1,67E+04 2,64E+08 1,60E+00
Sb 1,18E-01 6,17E+00 6,29E+00 2,68E-03 -1,39E+04 3,06E+08 1,33E+00
Sc 3,30E-02 6,17E+00 6,20E+00 2,66E-03 -9,71E+03 3,88E+08 9,28E-01
Se 7,10E-02 6,17E+00 6,24E+00 2,67E-03 -1,12E+04 3,55E+08 1,07E+00
Si 6,30E-02 6,17E+00 6,23E+00 2,66E-03 -9,54E+03 3,89E+08 9,13E-01
Sn 1,33E-02 6,17E+00 6,18E+00 2,68E-03 -1,19E+04 3,45E+08 1,14E+00
Ta 9,69E-03 6,17E+00 6,18E+00 2,71E-03 -1,48E+04 2,93E+08 1,41E+00
V 2,11E-02 6,17E+00 6,19E+00 2,67E-03 -8,54E+03 4,10E+08 8,17E-01
W 1,32E-02 6,17E+00 6,18E+00 2,72E-03 -1,90E+04 2,35E+08 1,82E+00
Zn 1,92E-02 6,17E+00 6,19E+00 2,68E-03 -9,40E+03 3,92E+08 9,00E-01
Zr 3,00E-02 6,17E+00 6,20E+00 2,68E-03 -1,56E+04 2,84E+08 1,49E+00
116
Alloying (−ω)∗Ζ/2 in
ω(AB) (atu) ω(AC) (atu) ω(BC) (atu) ω system in J/mol
element (X) J/mol
none 1,254E-03 -8,227E+02 -3,291E+03
Ag 1,318E-03 -1,158E-02 -1,266E-02 -5,328E+02 -2,131E+03
B 1,229E-03 1,300E-02 2,155E-02 -1,240E+03 -4,960E+03
Ba 1,495E-03 5,572E-01 4,771E-01 -1,439E+04 -5,755E+04
Be 1,255E-03 3,420E-03 1,506E-03 -8,706E+02 -3,483E+03
Bi 1,312E-03 2,953E-02 3,296E-02 -1,656E+03 -6,624E+03
C 1,199E-03 5,197E-03 6,041E-03 -9,168E+02 -3,667E+03
Ca 1,413E-03 1,231E-01 9,278E-02 -3,709E+03 -1,484E+04
Cd 1,316E-03 -3,454E-03 -2,152E-03 -7,734E+02 -3,093E+03
Co 1,269E-03 1,424E-04 -3,211E-03 -7,753E+02 -3,101E+03
Cr 1,251E-03 1,845E-03 -2,149E-03 -7,996E+02 -3,198E+03
Cs 1,708E-03 1,396E-01 1,046E-01 -4,267E+03 -1,707E+04
Cu 1,294E-03 -5,277E-03 -8,687E-03 -6,503E+02 -2,601E+03
Fe 1,250E-03 8,830E-04 -2,683E-03 -7,798E+02 -3,119E+03
Ga 1,284E-03 -1,824E-03 1,324E-03 -8,196E+02 -3,278E+03
Ge 1,276E-03 4,275E-04 1,199E-03 -8,418E+02 -3,367E+03
Hf 1,275E-03 1,614E-02 1,869E-02 -1,273E+03 -5,091E+03
K 1,552E-03 8,465E-02 5,965E-02 -2,869E+03 -1,148E+04
La 1,552E-03 7,345E-03 9,878E-03 -1,222E+03 -4,888E+03
Li 1,365E-03 -3,569E-03 -1,763E-04 -8,293E+02 -3,317E+03
Mg 1,338E-03 4,793E-03 8,169E-04 -9,327E+02 -3,731E+03
Mn 1,323E-03 -3,897E-04 -3,843E-03 -7,953E+02 -3,181E+03
Mo 1,274E-03 2,582E-02 3,181E-02 -1,568E+03 -6,273E+03
Nb 1,201E-03 1,665E-02 2,039E-02 -1,254E+03 -5,015E+03
Ni 1,233E-03 1,224E-04 -3,234E-03 -7,521E+02 -3,008E+03
Pb 1,268E-03 1,262E-02 1,445E-02 -1,167E+03 -4,668E+03
Rb 1,616E-03 1,425E-01 1,060E-01 -4,263E+03 -1,705E+04
Re 1,173E-03 2,142E-02 2,757E-02 -1,392E+03 -5,567E+03
Sb 1,289E-03 1,211E-02 1,348E-02 -1,161E+03 -4,645E+03
Sc 1,309E-03 8,433E-04 -2,609E-03 -8,186E+02 -3,274E+03
Se 1,252E-03 2,062E-03 8,382E-03 -9,412E+02 -3,765E+03
Si 1,264E-03 -1,010E-03 5,294E-04 -8,068E+02 -3,227E+03
Sn 1,296E-03 6,821E-03 5,766E-03 -9,966E+02 -3,986E+03
Ta 1,233E-03 1,496E-02 1,905E-02 -1,235E+03 -4,941E+03
V 1,215E-03 -9,199E-04 -3,811E-03 -7,192E+02 -2,877E+03
W 1,201E-03 2,892E-02 3,227E-02 -1,568E+03 -6,270E+03
Zn 1,287E-03 -1,195E-03 -1,437E-03 -7,934E+02 -3,174E+03
Zr 1,280E-03 1,733E-02 1,964E-02 -1,303E+03 -5,213E+03
117
Sideal SM ∆HM Rc
none 8,98E-03 5,76E+00 5,77E+00 2,66E-03 -6,58E+03 4,74E+08 6,30E-01
Ag 8,89E-03 6,17E+00 6,18E+00 2,69E-03 -6,39E+03 4,57E+08 6,12E-01
B 1,69E-01 6,17E+00 6,34E+00 2,66E-03 -1,49E+04 2,91E+08 1,42E+00
Ba 6,08E-01 6,17E+00 6,78E+00 2,65E-03 -1,73E+05 7,85E+04 1,65E+01
Be 7,95E-02 6,17E+00 6,25E+00 2,66E-03 -1,04E+04 3,71E+08 9,99E-01
Bi 1,56E-01 6,17E+00 6,32E+00 2,70E-03 -1,99E+04 2,22E+08 1,90E+00
C 3,45E-01 6,17E+00 6,51E+00 2,66E-03 -1,10E+04 3,47E+08 1,05E+00
Ca 3,08E-01 6,17E+00 6,48E+00 2,63E-03 -4,45E+04 6,22E+07 4,26E+00
Cd 1,22E-02 6,17E+00 6,18E+00 2,68E-03 -9,28E+03 3,94E+08 8,88E-01
Co 3,86E-02 6,17E+00 6,21E+00 2,67E-03 -9,30E+03 3,93E+08 8,90E-01
Cr 3,86E-02 6,17E+00 6,21E+00 2,67E-03 -9,60E+03 3,88E+08 9,18E-01
Cs 1,85E+00 6,17E+00 8,01E+00 2,59E-03 -5,12E+04 3,58E+07 4,90E+00
Cu 3,03E-02 6,17E+00 6,20E+00 2,68E-03 -7,80E+03 4,26E+08 7,46E-01
Fe 4,17E-02 6,17E+00 6,21E+00 2,67E-03 -9,36E+03 3,92E+08 8,95E-01
Ga 1,59E-02 6,17E+00 6,18E+00 2,67E-03 -9,84E+03 3,85E+08 9,41E-01
Ge 4,83E-02 6,17E+00 6,22E+00 2,67E-03 -1,01E+04 3,78E+08 9,66E-01
Hf 3,00E-02 6,17E+00 6,20E+00 2,70E-03 -1,53E+04 2,86E+08 1,46E+00
K 8,91E-01 6,17E+00 7,06E+00 2,60E-03 -3,44E+04 9,75E+07 3,29E+00
La 2,00E-01 6,17E+00 6,37E+00 2,68E-03 -1,47E+04 2,91E+08 1,40E+00
Li 1,48E-02 6,17E+00 6,18E+00 2,64E-03 -9,95E+03 3,86E+08 9,52E-01
Mg 3,30E-02 6,17E+00 6,20E+00 2,65E-03 -1,12E+04 3,60E+08 1,07E+00
Mn 8,85E-02 6,17E+00 6,26E+00 2,67E-03 -9,54E+03 3,86E+08 9,13E-01
Mo 1,44E-02 6,17E+00 6,18E+00 2,68E-03 -1,88E+04 2,41E+08 1,80E+00
Nb 8,98E-03 6,17E+00 6,18E+00 2,68E-03 -1,50E+04 2,93E+08 1,44E+00
Ni 3,86E-02 6,17E+00 6,21E+00 2,67E-03 -9,03E+03 3,99E+08 8,63E-01
Pb 3,86E-02 6,17E+00 6,21E+00 2,71E-03 -1,40E+04 3,05E+08 1,34E+00
Rb 1,11E-02 6,17E+00 6,18E+00 2,60E-03 -5,12E+04 4,66E+07 4,89E+00
Re 1,20E-02 6,17E+00 6,18E+00 2,72E-03 -1,67E+04 2,65E+08 1,60E+00
Sb 1,18E-01 6,17E+00 6,29E+00 2,68E-03 -1,39E+04 3,06E+08 1,33E+00
Sc 3,30E-02 6,17E+00 6,20E+00 2,65E-03 -9,82E+03 3,86E+08 9,40E-01
Se 7,10E-02 6,17E+00 6,24E+00 2,66E-03 -1,13E+04 3,55E+08 1,08E+00
Si 6,29E-02 6,17E+00 6,23E+00 2,65E-03 -9,68E+03 3,87E+08 9,26E-01
Sn 1,34E-02 6,17E+00 6,18E+00 2,68E-03 -1,20E+04 3,44E+08 1,14E+00
Ta 9,70E-03 6,17E+00 6,18E+00 2,71E-03 -1,48E+04 2,94E+08 1,42E+00
V 2,11E-02 6,17E+00 6,19E+00 2,67E-03 -8,63E+03 4,09E+08 8,26E-01
W 1,31E-02 6,17E+00 6,18E+00 2,71E-03 -1,88E+04 2,38E+08 1,80E+00
Zn 1,92E-02 6,17E+00 6,19E+00 2,67E-03 -9,52E+03 3,90E+08 9,11E-01
Zr 3,00E-02 6,17E+00 6,20E+00 2,67E-03 -1,56E+04 2,84E+08 1,50E+00
118
element (X) J/mol
none 8,303E-04 -4,086E+02 -1,634E+03
Ag 8,955E-04 -1,055E-02 -1,248E-02 -1,480E+02 -5,918E+02
B 8,026E-04 1,291E-02 2,046E-02 -7,746E+02 -3,098E+03
Ba 1,088E-03 5,856E-01 5,125E-01 -1,526E+04 -6,106E+04
Be 8,286E-04 3,412E-03 1,463E-03 -4,782E+02 -1,913E+03
Bi 8,939E-04 3,111E-02 3,322E-02 -1,256E+03 -5,024E+03
C 7,710E-04 5,131E-03 4,686E-03 -5,047E+02 -2,019E+03
Ca 9,980E-04 1,227E-01 9,564E-02 -3,496E+03 -1,398E+04
Cd 8,939E-04 -3,460E-03 -2,317E-03 -3,516E+02 -1,406E+03
Co 8,443E-04 3,913E-04 -3,353E-03 -3,955E+02 -1,582E+03
Cr 8,253E-04 2,224E-03 -2,080E-03 -4,302E+02 -1,721E+03
Cs 1,317E-03 1,449E-01 1,154E-01 -4,210E+03 -1,684E+04
Cu 8,699E-04 -4,680E-03 -8,592E-03 -2,751E+02 -1,100E+03
Fe 8,246E-04 1,091E-03 -2,933E-03 -4,023E+02 -1,609E+03
Ga 8,619E-04 -1,830E-03 1,295E-03 -3,914E+02 -1,566E+03
Ge 8,539E-04 3,610E-04 1,088E-03 -4,287E+02 -1,715E+03
Hf 8,533E-04 1,639E-02 1,986E-02 -8,629E+02 -3,452E+03
K 1,147E-03 8,652E-02 6,433E-02 -2,659E+03 -1,064E+04
La 9,478E-04 7,987E-03 1,106E-02 -6,879E+02 -2,752E+03
Li 9,162E-04 -3,742E-03 -3,869E-04 -3,696E+02 -1,478E+03
Mg 9,015E-04 4,214E-03 8,395E-04 -5,251E+02 -2,100E+03
Mn 8,493E-04 -1,310E-04 -3,909E-03 -3,842E+02 -1,537E+03
Mo 7,754E-04 2,595E-02 3,342E-02 -1,100E+03 -4,399E+03
Nb 8,096E-04 1,573E-02 2,115E-02 -8,374E+02 -3,350E+03
Ni 8,433E-04 3,739E-04 -3,377E-03 -3,945E+02 -1,578E+03
Pb 8,909E-04 1,358E-02 1,347E-02 -7,848E+02 -3,139E+03
Rb 1,216E-03 1,475E-01 1,153E-01 -4,211E+03 -1,684E+04
Re 7,484E-04 2,094E-02 2,876E-02 -9,588E+02 -3,835E+03
Sb 8,689E-04 1,242E-02 1,367E-02 -7,527E+02 -3,011E+03
Sc 8,885E-04 1,049E-03 -2,839E-03 -4,332E+02 -1,733E+03
Se 8,303E-04 2,430E-03 8,497E-03 -5,061E+02 -2,024E+03
Si 8,413E-04 -1,253E-03 5,797E-04 -3,879E+02 -1,552E+03
Sn 8,749E-04 6,811E-03 5,837E-03 -5,954E+02 -2,381E+03
Ta 8,096E-04 1,426E-02 1,992E-02 -8,007E+02 -3,203E+03
V 7,896E-04 -6,862E-04 -4,241E-03 -3,422E+02 -1,369E+03
W 7,760E-04 2,855E-02 3,416E-02 -1,155E+03 -4,622E+03
Zn 8,633E-04 -1,114E-03 -1,730E-03 -3,862E+02 -1,545E+03
Zr 8,579E-04 1,696E-02 2,062E-02 -8,812E+02 -3,525E+03
119
Sideal SM ∆HM Rc
none 6,66E-03 4,67E+00 4,68E+00 2,81E-03 -3,27E+03 4,27E+08 3,13E-01
Ag 6,66E-03 5,11E+00 5,12E+00 2,83E-03 -1,78E+03 4,48E+08 1,70E-01
B 1,69E-01 5,11E+00 5,28E+00 2,81E-03 -9,29E+03 2,76E+08 8,89E-01
Ba 5,92E-01 5,11E+00 5,71E+00 2,79E-03 -1,83E+05 5,02E+03 1,75E+01
Be 7,90E-02 5,11E+00 5,19E+00 2,81E-03 -5,74E+03 3,49E+08 5,49E-01
Bi 1,48E-01 5,11E+00 5,26E+00 2,85E-03 -1,51E+04 1,90E+08 1,44E+00
C 3,44E-01 5,11E+00 5,46E+00 2,81E-03 -6,06E+03 3,29E+08 5,79E-01
Ca 2,97E-01 5,11E+00 5,41E+00 2,78E-03 -4,19E+04 3,55E+07 4,01E+00
Cd 9,37E-03 5,11E+00 5,12E+00 2,83E-03 -4,22E+03 3,85E+08 4,04E-01
Co 3,77E-02 5,11E+00 5,15E+00 2,82E-03 -4,75E+03 3,71E+08 4,54E-01
Cr 3,77E-02 5,11E+00 5,15E+00 2,82E-03 -5,16E+03 3,62E+08 4,94E-01
Cs 1,81E+00 5,11E+00 6,93E+00 2,74E-03 -5,05E+04 1,70E+07 4,83E+00
Cu 2,92E-02 5,11E+00 5,14E+00 2,82E-03 -3,30E+03 4,07E+08 3,16E-01
Fe 4,08E-02 5,11E+00 5,16E+00 2,82E-03 -4,83E+03 3,70E+08 4,62E-01
Ga 1,43E-02 5,11E+00 5,13E+00 2,82E-03 -4,70E+03 3,75E+08 4,49E-01
Ge 4,75E-02 5,11E+00 5,16E+00 2,82E-03 -5,14E+03 3,63E+08 4,92E-01
Hf 2,62E-02 5,11E+00 5,14E+00 2,85E-03 -1,04E+04 2,60E+08 9,91E-01
K 8,70E-01 5,11E+00 5,98E+00 2,75E-03 -3,19E+04 6,20E+07 3,05E+00
La 1,91E-01 5,11E+00 5,31E+00 2,82E-03 -8,25E+03 2,92E+08 7,90E-01
Li 1,17E-02 5,11E+00 5,13E+00 2,80E-03 -4,44E+03 3,84E+08 4,24E-01
Mg 2,91E-02 5,11E+00 5,14E+00 2,80E-03 -6,30E+03 3,40E+08 6,03E-01
Mn 8,81E-02 5,11E+00 5,20E+00 2,82E-03 -4,61E+03 3,72E+08 4,41E-01
Mo 1,28E-02 5,11E+00 5,13E+00 2,83E-03 -1,32E+04 2,19E+08 1,26E+00
Nb 6,84E-03 5,11E+00 5,12E+00 2,83E-03 -1,00E+04 2,68E+08 9,61E-01
Ni 3,77E-02 5,11E+00 5,15E+00 2,82E-03 -4,73E+03 3,72E+08 4,53E-01
Pb 3,77E-02 5,11E+00 5,15E+00 2,85E-03 -9,42E+03 2,75E+08 9,01E-01
Rb 9,26E-03 5,11E+00 5,12E+00 2,75E-03 -5,05E+04 2,20E+07 4,83E+00
Re 1,03E-02 5,11E+00 5,12E+00 2,86E-03 -1,15E+04 2,41E+08 1,10E+00
Sb 1,18E-01 5,11E+00 5,23E+00 2,82E-03 -9,03E+03 2,81E+08 8,64E-01
Sc 2,91E-02 5,11E+00 5,14E+00 2,80E-03 -5,20E+03 3,64E+08 4,97E-01
Se 7,04E-02 5,11E+00 5,18E+00 2,81E-03 -6,07E+03 3,42E+08 5,81E-01
Si 6,23E-02 5,11E+00 5,18E+00 2,80E-03 -4,66E+03 3,75E+08 4,45E-01
Sn 1,05E-02 5,11E+00 5,12E+00 2,83E-03 -7,14E+03 3,21E+08 6,83E-01
Ta 7,20E-03 5,11E+00 5,12E+00 2,85E-03 -9,61E+03 2,73E+08 9,19E-01
V 1,98E-02 5,11E+00 5,13E+00 2,82E-03 -4,11E+03 3,88E+08 3,93E-01
W 1,15E-02 5,11E+00 5,13E+00 2,86E-03 -1,39E+04 2,08E+08 1,33E+00
Zn 1,78E-02 5,11E+00 5,13E+00 2,82E-03 -4,63E+03 3,75E+08 4,43E-01
Zr 2,62E-02 5,11E+00 5,14E+00 2,82E-03 -1,06E+04 2,59E+08 1,01E+00
120
element (X) J/mol
none 8,303E-04 -4,086E+02 -1,634E+03
Ag 8,789E-04 -1,052E-02 -1,247E-02 -1,296E+02 -5,186E+02
B 7,850E-04 1,290E-02 2,041E-02 -7,533E+02 -3,013E+03
Ba 1,071E-03 5,866E-01 5,137E-01 -1,529E+04 -6,115E+04
Be 8,116E-04 3,411E-03 1,462E-03 -4,598E+02 -1,839E+03
Bi 8,769E-04 3,116E-02 3,323E-02 -1,237E+03 -4,948E+03
C 7,544E-04 5,128E-03 4,633E-03 -4,865E+02 -1,946E+03
Ca 9,814E-04 1,227E-01 9,572E-02 -3,481E+03 -1,392E+04
Cd 8,769E-04 -3,461E-03 -2,323E-03 -3,315E+02 -1,326E+03
Co 8,266E-04 4,004E-04 -3,357E-03 -3,772E+02 -1,509E+03
Cr 8,086E-04 2,238E-03 -2,077E-03 -4,130E+02 -1,652E+03
Cs 1,301E-03 1,450E-01 1,157E-01 -4,198E+03 -1,679E+04
Cu 8,523E-04 -4,658E-03 -8,589E-03 -2,568E+02 -1,027E+03
Fe 8,076E-04 1,099E-03 -2,941E-03 -3,846E+02 -1,539E+03
Ga 8,453E-04 -1,830E-03 1,293E-03 -3,714E+02 -1,486E+03
Ge 8,373E-04 3,587E-04 1,083E-03 -4,094E+02 -1,638E+03
Hf 8,363E-04 1,640E-02 1,991E-02 -8,433E+02 -3,373E+03
K 1,131E-03 8,657E-02 6,449E-02 -2,644E+03 -1,058E+04
La 9,312E-04 8,012E-03 1,111E-02 -6,676E+02 -2,670E+03
Li 8,995E-04 -3,748E-03 -3,956E-04 -3,487E+02 -1,395E+03
Mg 8,849E-04 4,190E-03 8,399E-04 -5,058E+02 -2,023E+03
Mn 8,316E-04 -1,213E-04 -3,910E-03 -3,658E+02 -1,463E+03
Mo 7,584E-04 2,596E-02 3,349E-02 -1,080E+03 -4,320E+03
Nb 7,926E-04 1,570E-02 2,118E-02 -8,169E+02 -3,268E+03
Ni 8,256E-04 3,830E-04 -3,382E-03 -3,763E+02 -1,505E+03
Pb 8,739E-04 1,362E-02 1,343E-02 -7,654E+02 -3,062E+03
Rb 1,201E-03 1,476E-01 1,156E-01 -4,201E+03 -1,680E+04
Re 7,314E-04 2,093E-02 2,880E-02 -9,388E+02 -3,755E+03
Sb 8,523E-04 1,243E-02 1,368E-02 -7,334E+02 -2,934E+03
Sc 8,719E-04 1,057E-03 -2,848E-03 -4,148E+02 -1,659E+03
Se 8,136E-04 2,444E-03 8,499E-03 -4,860E+02 -1,944E+03
Si 8,243E-04 -1,262E-03 5,817E-04 -3,682E+02 -1,473E+03
Sn 8,583E-04 6,811E-03 5,840E-03 -5,763E+02 -2,305E+03
Ta 7,926E-04 1,423E-02 1,995E-02 -7,803E+02 -3,121E+03
V 7,730E-04 -6,772E-04 -4,257E-03 -3,250E+02 -1,300E+03
W 7,594E-04 2,854E-02 3,421E-02 -1,136E+03 -4,544E+03
Zn 8,463E-04 -1,111E-03 -1,741E-03 -3,669E+02 -1,468E+03
Zr 8,413E-04 1,695E-02 2,065E-02 -8,611E+02 -3,444E+03
121
Sideal SM ∆HM Rc
none 6,66E-03 4,67E+00 4,68E+00 2,81E-03 -3,27E+03 4,28E+08 3,13E-01
Ag 6,48E-03 5,02E+00 5,03E+00 2,84E-03 -1,56E+03 4,57E+08 1,49E-01
B 1,69E-01 5,02E+00 5,19E+00 2,82E-03 -9,04E+03 2,82E+08 8,65E-01
Ba 5,92E-01 5,02E+00 5,61E+00 2,80E-03 -1,83E+05 4,96E+03 1,75E+01
Be 7,89E-02 5,02E+00 5,10E+00 2,82E-03 -5,52E+03 3,56E+08 5,28E-01
Bi 1,48E-01 5,02E+00 5,17E+00 2,85E-03 -1,48E+04 1,94E+08 1,42E+00
C 3,44E-01 5,02E+00 5,37E+00 2,82E-03 -5,84E+03 3,36E+08 5,58E-01
Ca 2,97E-01 5,02E+00 5,32E+00 2,79E-03 -4,18E+04 3,62E+07 4,00E+00
Cd 9,16E-03 5,02E+00 5,03E+00 2,84E-03 -3,98E+03 3,93E+08 3,81E-01
Co 3,76E-02 5,02E+00 5,06E+00 2,83E-03 -4,53E+03 3,79E+08 4,33E-01
Cr 3,76E-02 5,02E+00 5,06E+00 2,83E-03 -4,96E+03 3,69E+08 4,74E-01
Cs 1,81E+00 5,02E+00 6,83E+00 2,74E-03 -5,04E+04 1,73E+07 4,82E+00
Cu 2,90E-02 5,02E+00 5,05E+00 2,83E-03 -3,08E+03 4,15E+08 2,95E-01
Fe 4,07E-02 5,02E+00 5,06E+00 2,83E-03 -4,62E+03 3,77E+08 4,42E-01
Ga 1,42E-02 5,02E+00 5,04E+00 2,82E-03 -4,46E+03 3,83E+08 4,26E-01
Ge 4,73E-02 5,02E+00 5,07E+00 2,82E-03 -4,91E+03 3,70E+08 4,70E-01
Hf 2,60E-02 5,02E+00 5,05E+00 2,86E-03 -1,01E+04 2,65E+08 9,68E-01
K 8,70E-01 5,02E+00 5,89E+00 2,76E-03 -3,17E+04 6,31E+07 3,04E+00
La 1,91E-01 5,02E+00 5,21E+00 2,83E-03 -8,01E+03 2,98E+08 7,66E-01
Li 1,15E-02 5,02E+00 5,03E+00 2,80E-03 -4,18E+03 3,93E+08 4,00E-01
Mg 2,89E-02 5,02E+00 5,05E+00 2,81E-03 -6,07E+03 3,48E+08 5,81E-01
Mn 8,80E-02 5,02E+00 5,11E+00 2,83E-03 -4,39E+03 3,80E+08 4,20E-01
Mo 1,27E-02 5,02E+00 5,03E+00 2,84E-03 -1,30E+04 2,24E+08 1,24E+00
Nb 6,66E-03 5,02E+00 5,03E+00 2,83E-03 -9,80E+03 2,73E+08 9,38E-01
Ni 3,76E-02 5,02E+00 5,06E+00 2,83E-03 -4,52E+03 3,79E+08 4,32E-01
Pb 3,76E-02 5,02E+00 5,06E+00 2,86E-03 -9,19E+03 2,81E+08 8,79E-01
Rb 9,10E-03 5,02E+00 5,03E+00 2,75E-03 -5,04E+04 2,23E+07 4,82E+00
Re 1,01E-02 5,02E+00 5,03E+00 2,87E-03 -1,13E+04 2,47E+08 1,08E+00
Sb 1,18E-01 5,02E+00 5,14E+00 2,83E-03 -8,80E+03 2,87E+08 8,42E-01
Sc 2,89E-02 5,02E+00 5,05E+00 2,81E-03 -4,98E+03 3,72E+08 4,76E-01
Se 7,03E-02 5,02E+00 5,09E+00 2,82E-03 -5,83E+03 3,49E+08 5,58E-01
Si 6,22E-02 5,02E+00 5,08E+00 2,81E-03 -4,42E+03 3,83E+08 4,23E-01
Sn 1,03E-02 5,02E+00 5,03E+00 2,83E-03 -6,92E+03 3,28E+08 6,62E-01
Ta 7,01E-03 5,02E+00 5,03E+00 2,86E-03 -9,36E+03 2,79E+08 8,96E-01
V 1,96E-02 5,02E+00 5,04E+00 2,82E-03 -3,90E+03 3,96E+08 3,73E-01
W 1,13E-02 5,02E+00 5,03E+00 2,87E-03 -1,36E+04 2,13E+08 1,30E+00
Zn 1,77E-02 5,02E+00 5,04E+00 2,83E-03 -4,40E+03 3,83E+08 4,21E-01
Zr 2,60E-02 5,02E+00 5,05E+00 2,83E-03 -1,03E+04 2,64E+08 9,88E-01
122
element (X) J/mol
none 1,535E-03 -8,937E+02 -3,575E+03
Ag 1,582E-03 -1,227E-02 -1,281E-02 -5,794E+02 -2,318E+03
B 1,495E-03 1,305E-02 2,219E-02 -1,353E+03 -5,413E+03
Ba 1,749E-03 5,340E-01 4,498E-01 -1,341E+04 -5,365E+04
Be 1,521E-03 3,404E-03 1,538E-03 -9,282E+02 -3,713E+03
Bi 1,573E-03 2,839E-02 3,260E-02 -1,711E+03 -6,844E+03
C 1,465E-03 5,246E-03 6,920E-03 -1,005E+03 -4,020E+03
Ca 1,671E-03 1,224E-01 9,018E-02 -3,580E+03 -1,432E+04
Cd 1,579E-03 -3,451E-03 -2,047E-03 -8,397E+02 -3,359E+03
Co 1,534E-03 -3,602E-05 -3,105E-03 -8,256E+02 -3,302E+03
Cr 1,516E-03 1,569E-03 -2,181E-03 -8,452E+02 -3,381E+03
Cs 1,950E-03 1,347E-01 9,590E-02 -3,946E+03 -1,579E+04
Cu 1,559E-03 -5,685E-03 -8,747E-03 -6,936E+02 -2,774E+03
Fe 1,515E-03 7,397E-04 -2,506E-03 -8,320E+02 -3,328E+03
Ga 1,548E-03 -1,815E-03 1,329E-03 -8,946E+02 -3,578E+03
Ge 1,539E-03 4,713E-04 1,261E-03 -9,082E+02 -3,633E+03
Hf 1,538E-03 1,601E-02 1,790E-02 -1,330E+03 -5,321E+03
K 1,802E-03 8,282E-02 5,598E-02 -2,721E+03 -1,088E+04
La 1,624E-03 6,940E-03 9,077E-03 -1,148E+03 -4,593E+03
Li 1,600E-03 -3,453E-03 -4,518E-05 -8,864E+02 -3,545E+03
Mg 1,585E-03 5,130E-03 7,944E-04 -9,674E+02 -3,870E+03
Mn 1,538E-03 -5,732E-04 -3,793E-03 -8,117E+02 -3,247E+03
Mo 1,466E-03 2,580E-02 3,074E-02 -1,595E+03 -6,382E+03
Nb 1,498E-03 1,734E-02 1,992E-02 -1,354E+03 -5,414E+03
Ni 1,533E-03 -5,702E-05 -3,127E-03 -8,248E+02 -3,299E+03
Pb 1,572E-03 1,189E-02 1,493E-02 -1,262E+03 -5,048E+03
Rb 1,863E-03 1,381E-01 9,877E-02 -3,975E+03 -1,590E+04
Re 1,440E-03 2,182E-02 2,680E-02 -1,478E+03 -5,910E+03
Sb 1,550E-03 1,191E-02 1,330E-02 -1,222E+03 -4,887E+03
Sc 1,572E-03 6,997E-04 -2,446E-03 -8,651E+02 -3,460E+03
Se 1,514E-03 1,809E-03 8,235E-03 -1,026E+03 -4,103E+03
Si 1,528E-03 -8,480E-04 4,899E-04 -8,770E+02 -3,508E+03
Sn 1,558E-03 6,827E-03 5,707E-03 -1,051E+03 -4,205E+03
Ta 1,498E-03 1,550E-02 1,850E-02 -1,313E+03 -5,252E+03
V 1,480E-03 -1,070E-03 -3,517E-03 -7,786E+02 -3,114E+03
W 1,466E-03 2,923E-02 3,232E-02 -1,653E+03 -6,610E+03
Zn 1,551E-03 -1,254E-03 -1,244E-03 -8,571E+02 -3,428E+03
Zr 1,542E-03 1,763E-02 1,900E-02 -1,366E+03 -5,462E+03
123
Sideal SM ∆HM Rc
none 1,19E-03 5,29E+00 5,29E+00 2,56E-03 -7,15E+03 4,33E+08 6,84E-01
Ag 1,15E-03 5,72E+00 5,72E+00 2,58E-03 -6,95E+03 4,16E+08 6,65E-01
B 1,60E-01 5,72E+00 5,88E+00 2,56E-03 -1,62E+04 2,45E+08 1,55E+00
Ba 6,09E-01 5,72E+00 6,33E+00 2,55E-03 -1,61E+05 7,07E+04 1,54E+01
Be 7,07E-02 5,72E+00 5,79E+00 2,56E-03 -1,11E+04 3,30E+08 1,07E+00
Bi 1,51E-01 5,72E+00 5,87E+00 2,60E-03 -2,05E+04 1,89E+08 1,96E+00
C 3,36E-01 5,72E+00 6,06E+00 2,56E-03 -1,21E+04 3,01E+08 1,15E+00
Ca 3,05E-01 5,72E+00 6,03E+00 2,53E-03 -4,30E+04 5,43E+07 4,11E+00
Cd 4,79E-03 5,72E+00 5,73E+00 2,58E-03 -1,01E+04 3,50E+08 9,64E-01
Co 3,01E-02 5,72E+00 5,75E+00 2,57E-03 -9,91E+03 3,53E+08 9,48E-01
Cr 3,01E-02 5,72E+00 5,75E+00 2,57E-03 -1,01E+04 3,49E+08 9,70E-01
Cs 1,86E+00 5,72E+00 7,58E+00 2,50E-03 -4,74E+04 3,45E+07 4,53E+00
Cu 2,18E-02 5,72E+00 5,75E+00 2,57E-03 -8,32E+03 3,86E+08 7,96E-01
Fe 3,31E-02 5,72E+00 5,76E+00 2,57E-03 -9,98E+03 3,52E+08 9,55E-01
Ga 7,66E-03 5,72E+00 5,73E+00 2,57E-03 -1,07E+04 3,39E+08 1,03E+00
Ge 3,96E-02 5,72E+00 5,76E+00 2,57E-03 -1,09E+04 3,34E+08 1,04E+00
Hf 2,33E-02 5,72E+00 5,75E+00 2,61E-03 -1,60E+04 2,49E+08 1,53E+00
K 8,94E-01 5,72E+00 6,62E+00 2,50E-03 -3,27E+04 8,99E+07 3,12E+00
La 1,96E-01 5,72E+00 5,92E+00 2,58E-03 -1,38E+04 2,77E+08 1,32E+00
Li 7,52E-03 5,72E+00 5,73E+00 2,54E-03 -1,06E+04 3,44E+08 1,02E+00
Mg 2,64E-02 5,72E+00 5,75E+00 2,55E-03 -1,16E+04 3,24E+08 1,11E+00
Mn 7,96E-02 5,72E+00 5,80E+00 2,57E-03 -9,74E+03 3,54E+08 9,32E-01
Mo 6,26E-03 5,72E+00 5,73E+00 2,58E-03 -1,91E+04 2,11E+08 1,83E+00
Nb 1,19E-03 5,72E+00 5,73E+00 2,58E-03 -1,62E+04 2,48E+08 1,55E+00
Ni 3,01E-02 5,72E+00 5,75E+00 2,57E-03 -9,90E+03 3,53E+08 9,47E-01
Pb 3,01E-02 5,72E+00 5,75E+00 2,61E-03 -1,51E+04 2,60E+08 1,45E+00
Rb 3,07E-03 5,72E+00 5,73E+00 2,50E-03 -4,77E+04 4,41E+07 4,56E+00
Re 3,97E-03 5,72E+00 5,73E+00 2,62E-03 -1,77E+04 2,25E+08 1,70E+00
Sb 1,09E-01 5,72E+00 5,83E+00 2,58E-03 -1,47E+04 2,67E+08 1,40E+00
Sc 2,64E-02 5,72E+00 5,75E+00 2,55E-03 -1,04E+04 3,47E+08 9,93E-01
Se 6,22E-02 5,72E+00 5,79E+00 2,56E-03 -1,23E+04 3,08E+08 1,18E+00
Si 5,41E-02 5,72E+00 5,78E+00 2,55E-03 -1,05E+04 3,43E+08 1,01E+00
Sn 6,06E-03 5,72E+00 5,73E+00 2,58E-03 -1,26E+04 3,04E+08 1,21E+00
Ta 2,14E-03 5,72E+00 5,73E+00 2,61E-03 -1,58E+04 2,52E+08 1,51E+00
V 1,28E-02 5,72E+00 5,74E+00 2,57E-03 -9,34E+03 3,66E+08 8,94E-01
W 5,03E-03 5,72E+00 5,73E+00 2,61E-03 -1,98E+04 2,00E+08 1,90E+00
Zn 1,09E-02 5,72E+00 5,73E+00 2,57E-03 -1,03E+04 3,47E+08 9,84E-01
Zr 2,33E-02 5,72E+00 5,75E+00 2,57E-03 -1,64E+04 2,46E+08 1,57E+00
124
element (X) J/mol
none 1,535E-03 -8,937E+02 -3,575E+03
Ag 1,599E-03 -1,232E-02 -1,282E-02 -5,742E+02 -2,297E+03
B 1,512E-03 1,305E-02 2,223E-02 -1,353E+03 -5,411E+03
Ba 1,765E-03 5,324E-01 4,479E-01 -1,334E+04 -5,336E+04
Be 1,537E-03 3,402E-03 1,541E-03 -9,238E+02 -3,695E+03
Bi 1,589E-03 2,831E-02 3,257E-02 -1,706E+03 -6,826E+03
C 1,483E-03 5,249E-03 6,976E-03 -1,003E+03 -4,014E+03
Ca 1,686E-03 1,224E-01 9,000E-02 -3,562E+03 -1,425E+04
Cd 1,595E-03 -3,451E-03 -2,039E-03 -8,356E+02 -3,342E+03
Co 1,551E-03 -4,776E-05 -3,098E-03 -8,212E+02 -3,285E+03
Cr 1,532E-03 1,550E-03 -2,183E-03 -8,402E+02 -3,361E+03
Cs 1,965E-03 1,344E-01 9,530E-02 -3,914E+03 -1,566E+04
Cu 1,576E-03 -5,712E-03 -8,751E-03 -6,883E+02 -2,753E+03
Fe 1,532E-03 7,304E-04 -2,494E-03 -8,278E+02 -3,311E+03
Ga 1,565E-03 -1,814E-03 1,329E-03 -8,913E+02 -3,565E+03
Ge 1,556E-03 4,743E-04 1,265E-03 -9,045E+02 -3,618E+03
Hf 1,555E-03 1,600E-02 1,785E-02 -1,326E+03 -5,303E+03
K 1,818E-03 8,269E-02 5,573E-02 -2,701E+03 -1,081E+04
La 1,641E-03 6,915E-03 9,024E-03 -1,143E+03 -4,571E+03
Li 1,616E-03 -3,446E-03 -3,707E-05 -8,826E+02 -3,531E+03
Mg 1,602E-03 5,151E-03 7,930E-04 -9,618E+02 -3,847E+03
Mn 1,555E-03 -5,859E-04 -3,789E-03 -8,068E+02 -3,227E+03
Mo 1,483E-03 2,581E-02 3,067E-02 -1,592E+03 -6,369E+03
Nb 1,515E-03 1,738E-02 1,990E-02 -1,350E+03 -5,401E+03
Ni 1,550E-03 -6,913E-05 -3,120E-03 -8,200E+02 -3,280E+03
Pb 1,588E-03 1,184E-02 1,495E-02 -1,259E+03 -5,034E+03
Rb 1,878E-03 1,378E-01 9,826E-02 -3,946E+03 -1,578E+04
Re 1,457E-03 2,185E-02 2,676E-02 -1,475E+03 -5,901E+03
Sb 1,567E-03 1,189E-02 1,329E-02 -1,218E+03 -4,871E+03
Sc 1,588E-03 6,904E-04 -2,435E-03 -8,600E+02 -3,440E+03
Se 1,530E-03 1,793E-03 8,223E-03 -1,023E+03 -4,092E+03
Si 1,544E-03 -8,370E-04 4,871E-04 -8,734E+02 -3,494E+03
Sn 1,575E-03 6,827E-03 5,703E-03 -1,047E+03 -4,187E+03
Ta 1,515E-03 1,554E-02 1,846E-02 -1,310E+03 -5,239E+03
V 1,497E-03 -1,079E-03 -3,497E-03 -7,750E+02 -3,100E+03
W 1,483E-03 2,925E-02 3,227E-02 -1,649E+03 -6,597E+03
Zn 1,568E-03 -1,258E-03 -1,232E-03 -8,529E+02 -3,412E+03
Zr 1,560E-03 1,765E-02 1,896E-02 -1,362E+03 -5,447E+03
125
Sideal SM ∆HM Rc
none 1,19E-03 5,29E+00 5,29E+00 2,56E-03 -7,15E+03 4,33E+08 6,84E-01
Ag 1,04E-03 5,67E+00 5,67E+00 2,58E-03 -6,89E+03 4,21E+08 6,59E-01
B 1,60E-01 5,67E+00 5,83E+00 2,55E-03 -1,62E+04 2,47E+08 1,55E+00
Ba 6,09E-01 5,67E+00 6,27E+00 2,54E-03 -1,60E+05 7,49E+04 1,53E+01
Be 7,05E-02 5,67E+00 5,74E+00 2,55E-03 -1,11E+04 3,33E+08 1,06E+00
Bi 1,51E-01 5,67E+00 5,82E+00 2,60E-03 -2,05E+04 1,91E+08 1,96E+00
C 3,36E-01 5,67E+00 6,00E+00 2,55E-03 -1,20E+04 3,04E+08 1,15E+00
Ca 3,05E-01 5,67E+00 5,97E+00 2,53E-03 -4,27E+04 5,54E+07 4,09E+00
Cd 4,70E-03 5,67E+00 5,67E+00 2,58E-03 -1,00E+04 3,53E+08 9,59E-01
Co 2,99E-02 5,67E+00 5,70E+00 2,57E-03 -9,85E+03 3,57E+08 9,43E-01
Cr 2,99E-02 5,67E+00 5,70E+00 2,56E-03 -1,01E+04 3,53E+08 9,64E-01
Cs 1,86E+00 5,67E+00 7,53E+00 2,49E-03 -4,70E+04 3,55E+07 4,49E+00
Cu 2,16E-02 5,67E+00 5,69E+00 2,57E-03 -8,26E+03 3,90E+08 7,90E-01
Fe 3,29E-02 5,67E+00 5,70E+00 2,56E-03 -9,93E+03 3,55E+08 9,50E-01
Ga 7,51E-03 5,67E+00 5,67E+00 2,56E-03 -1,07E+04 3,42E+08 1,02E+00
Ge 3,94E-02 5,67E+00 5,71E+00 2,56E-03 -1,09E+04 3,38E+08 1,04E+00
Hf 2,33E-02 5,67E+00 5,69E+00 2,60E-03 -1,59E+04 2,51E+08 1,52E+00
K 8,95E-01 5,67E+00 6,56E+00 2,50E-03 -3,24E+04 9,18E+07 3,10E+00
La 1,96E-01 5,67E+00 5,86E+00 2,57E-03 -1,37E+04 2,80E+08 1,31E+00
Li 7,43E-03 5,67E+00 5,67E+00 2,54E-03 -1,06E+04 3,48E+08 1,01E+00
Mg 2,64E-02 5,67E+00 5,69E+00 2,54E-03 -1,15E+04 3,28E+08 1,10E+00
Mn 7,95E-02 5,67E+00 5,75E+00 2,56E-03 -9,68E+03 3,58E+08 9,26E-01
Mo 6,12E-03 5,67E+00 5,67E+00 2,58E-03 -1,91E+04 2,13E+08 1,83E+00
Nb 1,07E-03 5,67E+00 5,67E+00 2,57E-03 -1,62E+04 2,51E+08 1,55E+00
Ni 2,99E-02 5,67E+00 5,70E+00 2,57E-03 -9,84E+03 3,57E+08 9,41E-01
Pb 2,99E-02 5,67E+00 5,70E+00 2,60E-03 -1,51E+04 2,62E+08 1,44E+00
Rb 2,94E-03 5,67E+00 5,67E+00 2,50E-03 -4,73E+04 4,53E+07 4,53E+00
Re 3,83E-03 5,67E+00 5,67E+00 2,61E-03 -1,77E+04 2,27E+08 1,69E+00
Sb 1,09E-01 5,67E+00 5,77E+00 2,57E-03 -1,46E+04 2,70E+08 1,40E+00
Sc 2,64E-02 5,67E+00 5,69E+00 2,55E-03 -1,03E+04 3,50E+08 9,87E-01
Se 6,20E-02 5,67E+00 5,73E+00 2,56E-03 -1,23E+04 3,11E+08 1,17E+00
Si 5,40E-02 5,67E+00 5,72E+00 2,55E-03 -1,05E+04 3,46E+08 1,00E+00
Sn 5,97E-03 5,67E+00 5,67E+00 2,57E-03 -1,26E+04 3,07E+08 1,20E+00
Ta 2,03E-03 5,67E+00 5,67E+00 2,60E-03 -1,57E+04 2,55E+08 1,50E+00
V 1,26E-02 5,67E+00 5,68E+00 2,56E-03 -9,30E+03 3,70E+08 8,90E-01
W 4,89E-03 5,67E+00 5,67E+00 2,61E-03 -1,98E+04 2,02E+08 1,89E+00
Zn 1,08E-02 5,67E+00 5,68E+00 2,56E-03 -1,02E+04 3,51E+08 9,79E-01
Zr 2,33E-02 5,67E+00 5,69E+00 2,57E-03 -1,63E+04 2,49E+08 1,56E+00
126
Table A.13 – Ti50Fe49X1
element (X) J/mol
none 1,476E-03 -9,681E+02 -3,873E+03
Ag 1,451E-03 -7,279E-03 -3,833E-03 -7,879E+02 -3,152E+03
Al 1,465E-03 -5,505E-04 -3,252E-03 -8,933E+02 -3,573E+03
B 1,482E-03 1,118E-02 2,198E-02 -1,382E+03 -5,529E+03
Ba 1,369E-03 5,846E-01 5,062E-01 -1,506E+04 -6,024E+04
Be 1,474E-03 2,526E-03 2,100E-03 -1,008E+03 -4,031E+03
Bi 1,445E-03 3,156E-02 3,670E-02 -1,815E+03 -7,261E+03
C 1,493E-03 4,368E-03 9,311E-03 -1,137E+03 -4,549E+03
Ca 1,407E-03 1,011E-01 6,715E-02 -3,095E+03 -1,238E+04
Cd 1,450E-03 -3,396E-03 -1,338E-03 -8,703E+02 -3,481E+03
Co 1,468E-03 6,538E-04 1,444E-04 -9,545E+02 -3,818E+03
Cr 1,475E-03 2,683E-03 5,412E-04 -9,905E+02 -3,962E+03
Cs 1,264E-03 1,499E-01 1,195E-01 -4,317E+03 -1,727E+04
Cu 1,460E-03 -3,204E-03 -2,574E-03 -8,636E+02 -3,454E+03
Ga 1,460E-03 -1,740E-03 5,504E-04 -9,230E+02 -3,692E+03
Ge 1,462E-03 1,528E-04 -1,210E-04 -9,403E+02 -3,761E+03
Hf 1,463E-03 1,549E-02 1,265E-02 -1,307E+03 -5,228E+03
K 1,343E-03 8,389E-02 6,152E-02 -2,756E+03 -1,102E+04
La 1,427E-03 8,871E-03 8,427E-03 -1,143E+03 -4,571E+03
Li 1,440E-03 -4,667E-03 -5,531E-04 -8,578E+02 -3,431E+03
Mg 1,446E-03 1,580E-03 -2,965E-03 -9,123E+02 -3,649E+03
Mn 1,467E-03 3,096E-04 -6,236E-04 -9,395E+02 -3,758E+03
Mo 1,491E-03 2,321E-02 1,889E-02 -1,507E+03 -6,026E+03
Nb 1,479E-03 1,168E-02 5,979E-03 -1,181E+03 -4,724E+03
Ni 1,469E-03 6,390E-04 1,547E-04 -9,551E+02 -3,820E+03
Pb 1,448E-03 1,449E-02 2,150E-02 -1,398E+03 -5,590E+03
Rb 1,311E-03 1,485E-01 1,159E-01 -4,282E+03 -1,713E+04
Re 1,500E-03 1,714E-02 1,102E-02 -1,331E+03 -5,323E+03
Sb 1,455E-03 1,134E-02 1,116E-02 -1,228E+03 -4,912E+03
Sc 1,450E-03 1,041E-03 -4,000E-06 -9,457E+02 -3,783E+03
Se 1,468E-03 2,075E-03 5,860E-03 -1,047E+03 -4,187E+03
Si 1,466E-03 -1,275E-03 -2,619E-03 -8,924E+02 -3,570E+03
Sn 1,454E-03 6,281E-03 3,759E-03 -1,066E+03 -4,263E+03
Ta 1,479E-03 1,198E-02 5,867E-03 -1,183E+03 -4,733E+03
V 1,486E-03 -6,572E-04 -2,006E-03 -9,210E+02 -3,684E+03
W 1,490E-03 2,479E-02 1,865E-02 -1,523E+03 -6,094E+03
Zn 1,461E-03 -1,267E-03 7,781E-04 -9,328E+02 -3,731E+03
Zr 1,461E-03 1,500E-02 9,796E-03 -1,262E+03 -5,049E+03
127
Sideal SM ∆HM Rc
none 1,11E+00 5,76E+00 6,87E+00 3,46E-03 -7,75E+03 2,20E+08 7,41E-01
Ag 1,10E+00 6,17E+00 7,27E+00 3,47E-03 -9,46E+03 1,89E+08 9,04E-01
Al 1,10E+00 6,17E+00 7,27E+00 3,45E-03 -1,07E+04 1,75E+08 1,03E+00
B 1,23E+00 6,17E+00 7,39E+00 3,46E-03 -1,66E+04 1,16E+08 1,59E+00
Ba 1,95E+00 6,17E+00 8,11E+00 3,41E-03 -1,81E+05 1,96E+03 1,73E+01
Be 1,14E+00 6,17E+00 7,31E+00 3,45E-03 -1,21E+04 1,59E+08 1,16E+00
Bi 1,34E+00 6,17E+00 7,51E+00 3,48E-03 -2,18E+04 8,05E+07 2,08E+00
C 1,40E+00 6,17E+00 7,57E+00 3,45E-03 -1,36E+04 1,38E+08 1,31E+00
Ca 1,55E+00 6,17E+00 7,72E+00 3,41E-03 -3,71E+04 2,87E+07 3,55E+00
Cd 1,12E+00 6,17E+00 7,29E+00 3,47E-03 -1,04E+04 1,77E+08 9,99E-01
Co 1,11E+00 6,17E+00 7,28E+00 3,47E-03 -1,15E+04 1,66E+08 1,10E+00
Cr 1,11E+00 6,17E+00 7,28E+00 3,46E-03 -1,19E+04 1,61E+08 1,14E+00
Cs 3,49E+00 6,17E+00 9,66E+00 3,33E-03 -5,18E+04 8,39E+06 4,96E+00
Cu 1,10E+00 6,17E+00 7,27E+00 3,47E-03 -1,04E+04 1,78E+08 9,91E-01
Ga 1,10E+00 6,17E+00 7,27E+00 3,46E-03 -1,11E+04 1,71E+08 1,06E+00
Ge 1,12E+00 6,17E+00 7,28E+00 3,45E-03 -1,13E+04 1,68E+08 1,08E+00
Hf 1,15E+00 6,17E+00 7,32E+00 3,49E-03 -1,57E+04 1,24E+08 1,50E+00
K 2,31E+00 6,17E+00 8,47E+00 3,36E-03 -3,31E+04 3,42E+07 3,16E+00
La 1,41E+00 6,17E+00 7,57E+00 3,45E-03 -1,37E+04 1,37E+08 1,31E+00
Li 1,12E+00 6,17E+00 7,29E+00 3,43E-03 -1,03E+04 1,81E+08 9,85E-01
Mg 1,16E+00 6,17E+00 7,33E+00 3,44E-03 -1,09E+04 1,72E+08 1,05E+00
Mn 1,15E+00 6,17E+00 7,32E+00 3,46E-03 -1,13E+04 1,67E+08 1,08E+00
Mo 1,10E+00 6,17E+00 7,27E+00 3,47E-03 -1,81E+04 1,07E+08 1,73E+00
Nb 1,10E+00 6,17E+00 7,27E+00 3,47E-03 -1,42E+04 1,39E+08 1,36E+00
Ni 1,11E+00 6,17E+00 7,28E+00 3,47E-03 -1,15E+04 1,66E+08 1,10E+00
Pb 1,11E+00 6,17E+00 7,28E+00 3,48E-03 -1,68E+04 1,16E+08 1,60E+00
Rb 1,10E+00 6,17E+00 7,27E+00 3,35E-03 -5,14E+04 1,21E+07 4,92E+00
Re 1,10E+00 6,17E+00 7,27E+00 3,50E-03 -1,60E+04 1,22E+08 1,53E+00
Sb 1,18E+00 6,17E+00 7,34E+00 3,46E-03 -1,47E+04 1,32E+08 1,41E+00
Sc 1,16E+00 6,17E+00 7,33E+00 3,44E-03 -1,13E+04 1,67E+08 1,09E+00
Se 1,13E+00 6,17E+00 7,30E+00 3,45E-03 -1,26E+04 1,54E+08 1,20E+00
Si 1,13E+00 6,17E+00 7,30E+00 3,44E-03 -1,07E+04 1,75E+08 1,02E+00
Sn 1,12E+00 6,17E+00 7,29E+00 3,46E-03 -1,28E+04 1,52E+08 1,22E+00
Ta 1,11E+00 6,17E+00 7,28E+00 3,49E-03 -1,42E+04 1,37E+08 1,36E+00
V 1,10E+00 6,17E+00 7,27E+00 3,46E-03 -1,11E+04 1,71E+08 1,06E+00
W 1,10E+00 6,17E+00 7,27E+00 3,50E-03 -1,83E+04 1,05E+08 1,75E+00
Zn 1,10E+00 6,17E+00 7,27E+00 3,46E-03 -1,12E+04 1,69E+08 1,07E+00
Zr 1,15E+00 6,17E+00 7,32E+00 3,46E-03 -1,51E+04 1,29E+08 1,45E+00
128
element (X) J/mol
none 1,476E-03 -9,681E+02 -3,873E+03
Ag 1,454E-03 -7,259E-03 -3,821E-03 -7,917E+02 -3,167E+03
Al 1,469E-03 -5,615E-04 -3,255E-03 -8,948E+02 -3,579E+03
B 1,487E-03 1,117E-02 2,198E-02 -1,388E+03 -5,552E+03
Ba 1,372E-03 5,847E-01 5,062E-01 -1,504E+04 -6,018E+04
Be 1,478E-03 2,521E-03 2,098E-03 -1,010E+03 -4,040E+03
Bi 1,450E-03 3,158E-02 3,671E-02 -1,820E+03 -7,279E+03
C 1,497E-03 4,365E-03 9,310E-03 -1,141E+03 -4,563E+03
Ca 1,411E-03 1,010E-01 6,702E-02 -3,085E+03 -1,234E+04
Cd 1,453E-03 -3,397E-03 -1,337E-03 -8,733E+02 -3,493E+03
Co 1,473E-03 6,565E-04 1,426E-04 -9,573E+02 -3,829E+03
Cr 1,479E-03 2,687E-03 5,412E-04 -9,924E+02 -3,969E+03
Cs 1,267E-03 1,499E-01 1,195E-01 -4,311E+03 -1,724E+04
Cu 1,464E-03 -3,193E-03 -2,570E-03 -8,664E+02 -3,466E+03
Ga 1,464E-03 -1,740E-03 5,571E-04 -9,261E+02 -3,704E+03
Ge 1,465E-03 1,516E-04 -1,170E-04 -9,427E+02 -3,771E+03
Hf 1,467E-03 1,550E-02 1,267E-02 -1,309E+03 -5,236E+03
K 1,347E-03 8,386E-02 6,150E-02 -2,752E+03 -1,101E+04
La 1,431E-03 8,885E-03 8,449E-03 -1,145E+03 -4,582E+03
Li 1,444E-03 -4,675E-03 -5,556E-04 -8,611E+02 -3,444E+03
Mg 1,450E-03 1,563E-03 -2,979E-03 -9,131E+02 -3,652E+03
Mn 1,471E-03 3,141E-04 -6,236E-04 -9,417E+02 -3,767E+03
Mo 1,495E-03 2,320E-02 1,891E-02 -1,508E+03 -6,032E+03
Nb 1,482E-03 1,166E-02 5,980E-03 -1,182E+03 -4,726E+03
Ni 1,473E-03 6,418E-04 1,537E-04 -9,574E+02 -3,830E+03
Pb 1,452E-03 1,449E-02 2,149E-02 -1,402E+03 -5,607E+03
Rb 1,315E-03 1,485E-01 1,159E-01 -4,275E+03 -1,710E+04
Re 1,503E-03 1,713E-02 1,102E-02 -1,331E+03 -5,326E+03
Sb 1,459E-03 1,133E-02 1,117E-02 -1,230E+03 -4,921E+03
Sc 1,453E-03 1,035E-03 -4,000E-06 -9,478E+02 -3,791E+03
Se 1,472E-03 2,061E-03 5,876E-03 -1,050E+03 -4,200E+03
Si 1,470E-03 -1,267E-03 -2,614E-03 -8,946E+02 -3,579E+03
Sn 1,458E-03 6,282E-03 3,761E-03 -1,068E+03 -4,270E+03
Ta 1,482E-03 1,199E-02 5,872E-03 -1,184E+03 -4,737E+03
V 1,490E-03 -6,660E-04 -2,002E-03 -9,230E+02 -3,692E+03
W 1,494E-03 2,478E-02 1,865E-02 -1,524E+03 -6,097E+03
Zn 1,465E-03 -1,271E-03 7,781E-04 -9,357E+02 -3,743E+03
Zr 1,465E-03 1,501E-02 9,805E-03 -1,263E+03 -5,054E+03
129
Sideal SM ∆HM Rc
none 1,11E+00 5,76E+00 6,87E+00 3,46E-03 -7,75E+03 2,20E+08 7,41E-01
Ag 1,11E+00 6,17E+00 7,28E+00 3,48E-03 -9,50E+03 1,88E+08 9,09E-01
Al 1,11E+00 6,17E+00 7,28E+00 3,46E-03 -1,07E+04 1,74E+08 1,03E+00
B 1,23E+00 6,17E+00 7,40E+00 3,47E-03 -1,67E+04 1,15E+08 1,59E+00
Ba 1,96E+00 6,17E+00 8,13E+00 3,42E-03 -1,81E+05 1,98E+03 1,73E+01
Be 1,15E+00 6,17E+00 7,31E+00 3,47E-03 -1,21E+04 1,58E+08 1,16E+00
Bi 1,35E+00 6,17E+00 7,52E+00 3,49E-03 -2,18E+04 7,98E+07 2,09E+00
C 1,41E+00 6,17E+00 7,58E+00 3,47E-03 -1,37E+04 1,37E+08 1,31E+00
Ca 1,56E+00 6,17E+00 7,73E+00 3,42E-03 -3,70E+04 2,88E+07 3,54E+00
Cd 1,12E+00 6,17E+00 7,29E+00 3,48E-03 -1,05E+04 1,76E+08 1,00E+00
Co 1,11E+00 6,17E+00 7,28E+00 3,48E-03 -1,15E+04 1,65E+08 1,10E+00
Cr 1,11E+00 6,17E+00 7,28E+00 3,47E-03 -1,19E+04 1,60E+08 1,14E+00
Cs 3,52E+00 6,17E+00 9,68E+00 3,34E-03 -5,17E+04 8,38E+06 4,95E+00
Cu 1,11E+00 6,17E+00 7,28E+00 3,48E-03 -1,04E+04 1,77E+08 9,95E-01
Ga 1,10E+00 6,17E+00 7,27E+00 3,47E-03 -1,11E+04 1,70E+08 1,06E+00
Ge 1,12E+00 6,17E+00 7,29E+00 3,46E-03 -1,13E+04 1,67E+08 1,08E+00
Hf 1,16E+00 6,17E+00 7,33E+00 3,50E-03 -1,57E+04 1,23E+08 1,50E+00
K 2,32E+00 6,17E+00 8,49E+00 3,37E-03 -3,30E+04 3,42E+07 3,16E+00
La 1,42E+00 6,17E+00 7,58E+00 3,46E-03 -1,37E+04 1,36E+08 1,31E+00
Li 1,13E+00 6,17E+00 7,30E+00 3,44E-03 -1,03E+04 1,79E+08 9,88E-01
Mg 1,17E+00 6,17E+00 7,33E+00 3,45E-03 -1,10E+04 1,71E+08 1,05E+00
Mn 1,15E+00 6,17E+00 7,32E+00 3,47E-03 -1,13E+04 1,66E+08 1,08E+00
Mo 1,10E+00 6,17E+00 7,27E+00 3,48E-03 -1,81E+04 1,06E+08 1,73E+00
Nb 1,11E+00 6,17E+00 7,28E+00 3,48E-03 -1,42E+04 1,38E+08 1,36E+00
Ni 1,11E+00 6,17E+00 7,28E+00 3,48E-03 -1,15E+04 1,65E+08 1,10E+00
Pb 1,11E+00 6,17E+00 7,28E+00 3,50E-03 -1,68E+04 1,15E+08 1,61E+00
Rb 1,10E+00 6,17E+00 7,27E+00 3,36E-03 -5,13E+04 1,21E+07 4,91E+00
Re 1,10E+00 6,17E+00 7,27E+00 3,51E-03 -1,60E+04 1,21E+08 1,53E+00
Sb 1,18E+00 6,17E+00 7,35E+00 3,47E-03 -1,48E+04 1,32E+08 1,41E+00
Sc 1,17E+00 6,17E+00 7,33E+00 3,45E-03 -1,14E+04 1,66E+08 1,09E+00
Se 1,14E+00 6,17E+00 7,31E+00 3,46E-03 -1,26E+04 1,53E+08 1,21E+00
Si 1,13E+00 6,17E+00 7,30E+00 3,45E-03 -1,07E+04 1,74E+08 1,03E+00
Sn 1,13E+00 6,17E+00 7,29E+00 3,47E-03 -1,28E+04 1,51E+08 1,23E+00
Ta 1,12E+00 6,17E+00 7,28E+00 3,50E-03 -1,42E+04 1,37E+08 1,36E+00
V 1,10E+00 6,17E+00 7,27E+00 3,47E-03 -1,11E+04 1,70E+08 1,06E+00
W 1,10E+00 6,17E+00 7,27E+00 3,51E-03 -1,83E+04 1,04E+08 1,75E+00
Zn 1,10E+00 6,17E+00 7,27E+00 3,47E-03 -1,12E+04 1,68E+08 1,07E+00
Zr 1,16E+00 6,17E+00 7,33E+00 3,47E-03 -1,52E+04 1,29E+08 1,45E+00
130
element (X) J/mol
none 1,414E-03 -8,233E+02 -3,293E+03
Ag 1,393E-03 -7,584E-03 -4,011E-03 -6,330E+02 -2,532E+03
Al 1,408E-03 -3,930E-04 -3,192E-03 -7,726E+02 -3,091E+03
B 1,425E-03 1,128E-02 2,194E-02 -1,203E+03 -4,811E+03
Ba 1,314E-03 5,834E-01 5,052E-01 -1,521E+04 -6,085E+04
Be 1,415E-03 2,605E-03 2,145E-03 -8,751E+02 -3,500E+03
Bi 1,388E-03 3,133E-02 3,655E-02 -1,655E+03 -6,620E+03
C 1,435E-03 4,399E-03 9,340E-03 -9,801E+02 -3,920E+03
Ca 1,350E-03 1,029E-01 6,897E-02 -3,148E+03 -1,259E+04
Cd 1,392E-03 -3,386E-03 -1,361E-03 -7,280E+02 -2,912E+03
Co 1,411E-03 6,153E-04 1,609E-04 -8,209E+02 -3,284E+03
Cr 1,417E-03 2,623E-03 5,420E-04 -8,624E+02 -3,450E+03
Cs 1,213E-03 1,501E-01 1,196E-01 -4,325E+03 -1,730E+04
Cu 1,402E-03 -3,361E-03 -2,632E-03 -7,231E+02 -2,892E+03
Ga 1,402E-03 -1,741E-03 4,480E-04 -7,779E+02 -3,112E+03
Ge 1,404E-03 1,724E-04 -1,839E-04 -8,065E+02 -3,226E+03
Hf 1,406E-03 1,542E-02 1,240E-02 -1,180E+03 -4,720E+03
K 1,289E-03 8,419E-02 6,182E-02 -2,729E+03 -1,091E+04
La 1,371E-03 8,662E-03 8,092E-03 -1,006E+03 -4,023E+03
Li 1,384E-03 -4,546E-03 -5,191E-04 -7,105E+02 -2,842E+03
Mg 1,388E-03 1,840E-03 -2,754E-03 -8,037E+02 -3,215E+03
Mn 1,409E-03 2,482E-04 -6,266E-04 -8,067E+02 -3,227E+03
Mo 1,433E-03 2,328E-02 1,864E-02 -1,385E+03 -5,542E+03
Nb 1,421E-03 1,198E-02 5,972E-03 -1,073E+03 -4,293E+03
Ni 1,411E-03 6,003E-04 1,720E-04 -8,207E+02 -3,283E+03
Pb 1,391E-03 1,437E-02 2,159E-02 -1,234E+03 -4,934E+03
Rb 1,258E-03 1,486E-01 1,160E-01 -4,294E+03 -1,717E+04
Re 1,442E-03 1,733E-02 1,094E-02 -1,220E+03 -4,882E+03
Sb 1,399E-03 1,152E-02 1,106E-02 -1,097E+03 -4,387E+03
Sc 1,393E-03 1,127E-03 0,000E+00 -8,180E+02 -3,272E+03
Se 1,412E-03 2,277E-03 5,620E-03 -8,976E+02 -3,591E+03
Si 1,409E-03 -1,388E-03 -2,694E-03 -7,603E+02 -3,041E+03
Sn 1,397E-03 6,262E-03 3,727E-03 -9,412E+02 -3,765E+03
Ta 1,421E-03 1,182E-02 5,796E-03 -1,069E+03 -4,275E+03
V 1,429E-03 -5,296E-04 -2,057E-03 -7,919E+02 -3,168E+03
W 1,433E-03 2,488E-02 1,858E-02 -1,412E+03 -5,649E+03
Zn 1,403E-03 -1,199E-03 7,751E-04 -7,907E+02 -3,163E+03
Zr 1,404E-03 1,488E-02 9,674E-03 -1,146E+03 -4,583E+03
131
Sideal SM ∆HM Rc
none 9,06E-01 5,29E+00 6,20E+00 3,28E-03 -6,59E+03 2,70E+08 6,30E-01
Ag 9,05E-01 5,72E+00 6,63E+00 3,30E-03 -7,60E+03 2,42E+08 7,27E-01
Al 9,04E-01 5,72E+00 6,63E+00 3,27E-03 -9,27E+03 2,18E+08 8,87E-01
B 1,04E+00 5,72E+00 6,77E+00 3,28E-03 -1,44E+04 1,51E+08 1,38E+00
Ba 1,64E+00 5,72E+00 7,37E+00 3,24E-03 -1,83E+05 1,99E+03 1,75E+01
Be 9,57E-01 5,72E+00 6,68E+00 3,28E-03 -1,05E+04 1,99E+08 1,00E+00
Bi 1,11E+00 5,72E+00 6,83E+00 3,30E-03 -1,99E+04 1,04E+08 1,90E+00
C 1,22E+00 5,72E+00 6,95E+00 3,28E-03 -1,18E+04 1,76E+08 1,13E+00
Ca 1,29E+00 5,72E+00 7,01E+00 3,24E-03 -3,78E+04 3,13E+07 3,61E+00
Cd 9,14E-01 5,72E+00 6,64E+00 3,29E-03 -8,74E+03 2,24E+08 8,36E-01
Co 9,21E-01 5,72E+00 6,64E+00 3,29E-03 -9,85E+03 2,08E+08 9,42E-01
Cr 9,21E-01 5,72E+00 6,64E+00 3,29E-03 -1,03E+04 2,01E+08 9,90E-01
Cs 3,06E+00 5,72E+00 8,79E+00 3,17E-03 -5,19E+04 9,70E+06 4,96E+00
Cu 9,14E-01 5,72E+00 6,64E+00 3,29E-03 -8,68E+03 2,25E+08 8,30E-01
Ga 9,05E-01 5,72E+00 6,63E+00 3,28E-03 -9,34E+03 2,16E+08 8,93E-01
Ge 9,29E-01 5,72E+00 6,65E+00 3,28E-03 -9,68E+03 2,11E+08 9,26E-01
Hf 9,43E-01 5,72E+00 6,67E+00 3,31E-03 -1,42E+04 1,55E+08 1,35E+00
K 1,97E+00 5,72E+00 7,70E+00 3,20E-03 -3,27E+04 4,02E+07 3,13E+00
La 1,16E+00 5,72E+00 6,88E+00 3,28E-03 -1,21E+04 1,74E+08 1,15E+00
Li 9,19E-01 5,72E+00 6,64E+00 3,26E-03 -8,53E+03 2,29E+08 8,16E-01
Mg 9,47E-01 5,72E+00 6,67E+00 3,26E-03 -9,64E+03 2,12E+08 9,23E-01
Mn 9,66E-01 5,72E+00 6,69E+00 3,29E-03 -9,68E+03 2,09E+08 9,26E-01
Mo 9,04E-01 5,72E+00 6,63E+00 3,30E-03 -1,66E+04 1,33E+08 1,59E+00
Nb 9,04E-01 5,72E+00 6,63E+00 3,29E-03 -1,29E+04 1,70E+08 1,23E+00
Ni 9,21E-01 5,72E+00 6,64E+00 3,29E-03 -9,85E+03 2,08E+08 9,42E-01
Pb 9,21E-01 5,72E+00 6,64E+00 3,31E-03 -1,48E+04 1,49E+08 1,42E+00
Rb 9,03E-01 5,72E+00 6,63E+00 3,19E-03 -5,15E+04 1,35E+07 4,93E+00
Re 9,03E-01 5,72E+00 6,63E+00 3,33E-03 -1,46E+04 1,50E+08 1,40E+00
Sb 9,94E-01 5,72E+00 6,72E+00 3,28E-03 -1,32E+04 1,65E+08 1,26E+00
Sc 9,47E-01 5,72E+00 6,67E+00 3,27E-03 -9,82E+03 2,09E+08 9,39E-01
Se 9,49E-01 5,72E+00 6,67E+00 3,27E-03 -1,08E+04 1,96E+08 1,03E+00
Si 9,42E-01 5,72E+00 6,67E+00 3,27E-03 -9,12E+03 2,19E+08 8,73E-01
Sn 9,17E-01 5,72E+00 6,64E+00 3,29E-03 -1,13E+04 1,89E+08 1,08E+00
Ta 9,09E-01 5,72E+00 6,63E+00 3,31E-03 -1,28E+04 1,70E+08 1,23E+00
V 9,08E-01 5,72E+00 6,63E+00 3,28E-03 -9,50E+03 2,14E+08 9,09E-01
W 9,03E-01 5,72E+00 6,63E+00 3,32E-03 -1,69E+04 1,29E+08 1,62E+00
Zn 9,06E-01 5,72E+00 6,63E+00 3,29E-03 -9,49E+03 2,14E+08 9,08E-01
Zr 9,43E-01 5,72E+00 6,67E+00 3,28E-03 -1,37E+04 1,60E+08 1,32E+00
132
element (X) J/mol
none 1,414E-03 -8,233E+02 -3,293E+03
Ag 1,389E-03 -7,602E-03 -4,023E-03 -6,174E+02 -2,469E+03
Al 1,404E-03 -3,837E-04 -3,188E-03 -7,591E+02 -3,037E+03
B 1,421E-03 1,129E-02 2,194E-02 -1,186E+03 -4,742E+03
Ba 1,311E-03 5,833E-01 5,051E-01 -1,522E+04 -6,087E+04
Be 1,412E-03 2,610E-03 2,147E-03 -8,613E+02 -3,445E+03
Bi 1,385E-03 3,132E-02 3,654E-02 -1,639E+03 -6,557E+03
C 1,431E-03 4,401E-03 9,342E-03 -9,642E+02 -3,857E+03
Ca 1,347E-03 1,030E-01 6,908E-02 -3,146E+03 -1,259E+04
Cd 1,388E-03 -3,385E-03 -1,363E-03 -7,132E+02 -2,853E+03
Co 1,407E-03 6,133E-04 1,619E-04 -8,065E+02 -3,226E+03
Cr 1,413E-03 2,619E-03 5,420E-04 -8,484E+02 -3,393E+03
Cs 1,210E-03 1,501E-01 1,196E-01 -4,321E+03 -1,728E+04
Cu 1,399E-03 -3,370E-03 -2,636E-03 -7,083E+02 -2,833E+03
Ga 1,400E-03 -1,741E-03 4,420E-04 -7,635E+02 -3,054E+03
Ge 1,401E-03 1,741E-04 -1,869E-04 -7,926E+02 -3,171E+03
Hf 1,402E-03 1,541E-02 1,238E-02 -1,166E+03 -4,664E+03
K 1,285E-03 8,420E-02 6,183E-02 -2,722E+03 -1,089E+04
La 1,367E-03 8,649E-03 8,072E-03 -9,913E+02 -3,965E+03
Li 1,380E-03 -4,538E-03 -5,173E-04 -6,954E+02 -2,781E+03
Mg 1,385E-03 1,856E-03 -2,741E-03 -7,910E+02 -3,164E+03
Mn 1,406E-03 2,444E-04 -6,268E-04 -7,928E+02 -3,171E+03
Mo 1,430E-03 2,329E-02 1,862E-02 -1,372E+03 -5,490E+03
Nb 1,418E-03 1,200E-02 5,972E-03 -1,061E+03 -4,244E+03
Ni 1,408E-03 5,978E-04 1,730E-04 -8,068E+02 -3,227E+03
Pb 1,387E-03 1,436E-02 2,159E-02 -1,217E+03 -4,869E+03
Rb 1,255E-03 1,486E-01 1,160E-01 -4,290E+03 -1,716E+04
Re 1,439E-03 1,734E-02 1,094E-02 -1,208E+03 -4,832E+03
Sb 1,395E-03 1,153E-02 1,105E-02 -1,083E+03 -4,331E+03
Sc 1,389E-03 1,131E-03 -4,000E-06 -8,041E+02 -3,216E+03
Se 1,408E-03 2,288E-03 5,605E-03 -8,824E+02 -3,529E+03
Si 1,406E-03 -1,394E-03 -2,699E-03 -7,465E+02 -2,986E+03
Sn 1,394E-03 6,260E-03 3,725E-03 -9,279E+02 -3,712E+03
Ta 1,418E-03 1,181E-02 5,793E-03 -1,056E+03 -4,225E+03
V 1,425E-03 -5,218E-04 -2,060E-03 -7,778E+02 -3,111E+03
W 1,429E-03 2,489E-02 1,857E-02 -1,399E+03 -5,598E+03
Zn 1,401E-03 -1,195E-03 7,749E-04 -7,764E+02 -3,106E+03
Zr 1,401E-03 1,487E-02 9,666E-03 -1,133E+03 -4,530E+03
133
Sideal SM ∆HM Rc
none 9,06E-01 5,29E+00 6,20E+00 3,28E-03 -6,59E+03 2,70E+08 6,726E-01
Ag 8,87E-01 5,67E+00 6,55E+00 3,29E-03 -7,41E+03 2,47E+08 8,210E-01
Al 8,86E-01 5,67E+00 6,55E+00 3,26E-03 -9,11E+03 2,23E+08 1,278E+00
B 1,03E+00 5,67E+00 6,69E+00 3,27E-03 -1,42E+04 1,55E+08 1,616E+01
Ba 1,62E+00 5,67E+00 7,29E+00 3,23E-03 -1,83E+05 2,00E+03 9,299E-01
Be 9,40E-01 5,67E+00 6,61E+00 3,27E-03 -1,03E+04 2,03E+08 1,758E+00
Bi 1,09E+00 5,67E+00 6,75E+00 3,29E-03 -1,97E+04 1,06E+08 1,041E+00
C 1,20E+00 5,67E+00 6,87E+00 3,27E-03 -1,16E+04 1,80E+08 3,345E+00
Ca 1,27E+00 5,67E+00 6,93E+00 3,23E-03 -3,78E+04 3,17E+07 7,736E-01
Cd 8,96E-01 5,67E+00 6,56E+00 3,28E-03 -8,56E+03 2,29E+08 8,723E-01
Co 9,04E-01 5,67E+00 6,57E+00 3,28E-03 -9,68E+03 2,13E+08 9,164E-01
Cr 9,04E-01 5,67E+00 6,57E+00 3,28E-03 -1,02E+04 2,06E+08 4,596E+00
Cs 3,03E+00 5,67E+00 8,70E+00 3,16E-03 -5,19E+04 9,86E+06 7,684E-01
Cu 8,97E-01 5,67E+00 6,56E+00 3,28E-03 -8,50E+03 2,30E+08 8,266E-01
Ga 8,87E-01 5,67E+00 6,55E+00 3,27E-03 -9,16E+03 2,21E+08 8,570E-01
Ge 9,12E-01 5,67E+00 6,58E+00 3,27E-03 -9,51E+03 2,16E+08 1,254E+00
Hf 9,24E-01 5,67E+00 6,59E+00 3,30E-03 -1,40E+04 1,58E+08 2,899E+00
K 1,95E+00 5,67E+00 7,61E+00 3,19E-03 -3,27E+04 4,09E+07 1,069E+00
La 1,14E+00 5,67E+00 6,80E+00 3,27E-03 -1,19E+04 1,78E+08 7,550E-01
Li 9,01E-01 5,67E+00 6,57E+00 3,25E-03 -8,34E+03 2,35E+08 8,539E-01
Mg 9,28E-01 5,67E+00 6,59E+00 3,25E-03 -9,49E+03 2,16E+08 8,571E-01
Mn 9,48E-01 5,67E+00 6,61E+00 3,28E-03 -9,51E+03 2,14E+08 1,472E+00
Mo 8,86E-01 5,67E+00 6,55E+00 3,28E-03 -1,65E+04 1,36E+08 1,140E+00
Nb 8,86E-01 5,67E+00 6,55E+00 3,28E-03 -1,27E+04 1,74E+08 8,721E-01
Ni 9,04E-01 5,67E+00 6,57E+00 3,28E-03 -9,68E+03 2,13E+08 1,311E+00
Pb 9,04E-01 5,67E+00 6,57E+00 3,30E-03 -1,46E+04 1,52E+08 1,285E+00
Rb 8,85E-01 5,67E+00 6,55E+00 3,18E-03 -5,15E+04 1,37E+07 1,297E+00
Re 8,85E-01 5,67E+00 6,55E+00 3,31E-03 -1,45E+04 1,53E+08 1,165E+00
Sb 9,77E-01 5,67E+00 6,64E+00 3,27E-03 -1,30E+04 1,69E+08 8,692E-01
Sc 9,28E-01 5,67E+00 6,59E+00 3,26E-03 -9,65E+03 2,14E+08 9,538E-01
Se 9,32E-01 5,67E+00 6,60E+00 3,26E-03 -1,06E+04 2,00E+08 8,079E-01
Si 9,25E-01 5,67E+00 6,59E+00 3,26E-03 -8,96E+03 2,24E+08 1,000E+00
Sn 8,98E-01 5,67E+00 6,56E+00 3,28E-03 -1,11E+04 1,93E+08 1,136E+00
Ta 8,91E-01 5,67E+00 6,56E+00 3,30E-03 -1,27E+04 1,73E+08 5,832E-01
V 8,90E-01 5,67E+00 6,56E+00 3,27E-03 -9,33E+03 2,18E+08 8,415E-01
W 8,85E-01 5,67E+00 6,55E+00 3,31E-03 -1,68E+04 1,32E+08 1,501E+00
Zn 8,89E-01 5,67E+00 6,55E+00 3,28E-03 -9,32E+03 2,19E+08 8,402E-01
Zr 9,24E-01 5,67E+00 6,59E+00 3,27E-03 -1,36E+04 1,64E+08 1,217E+00
134
element (X) J/mol
none 1,542E-03 -8,977E+02 -3,591E+03
Ag 1,517E-03 -6,917E-03 -3,631E-03 -7,465E+02 -2,986E+03
Al 1,532E-03 -7,440E-04 -3,319E-03 -8,146E+02 -3,259E+03
B 1,549E-03 1,104E-02 2,200E-02 -1,363E+03 -5,452E+03
Ba 1,433E-03 5,847E-01 5,061E-01 -1,464E+04 -5,858E+04
Be 1,540E-03 2,425E-03 2,049E-03 -9,395E+02 -3,758E+03
Bi 1,511E-03 3,179E-02 3,679E-02 -1,777E+03 -7,110E+03
C 1,559E-03 4,330E-03 9,269E-03 -1,091E+03 -4,366E+03
Ca 1,472E-03 9,866E-02 6,468E-02 -2,820E+03 -1,128E+04
Cd 1,516E-03 -3,407E-03 -1,309E-03 -8,165E+02 -3,266E+03
Co 1,535E-03 6,963E-04 1,249E-04 -8,882E+02 -3,553E+03
Cr 1,541E-03 2,742E-03 5,361E-04 -9,168E+02 -3,667E+03
Cs 1,324E-03 1,494E-01 1,191E-01 -4,116E+03 -1,646E+04
Cu 1,527E-03 -3,014E-03 -2,504E-03 -8,058E+02 -3,223E+03
Ga 1,526E-03 -1,737E-03 6,721E-04 -8,715E+02 -3,486E+03
Ge 1,527E-03 1,285E-04 -4,618E-05 -8,760E+02 -3,504E+03
Hf 1,529E-03 1,557E-02 1,294E-02 -1,236E+03 -4,943E+03
K 1,406E-03 8,335E-02 6,103E-02 -2,586E+03 -1,034E+04
La 1,492E-03 9,114E-03 8,818E-03 -1,087E+03 -4,348E+03
Li 1,507E-03 -4,807E-03 -5,899E-04 -8,118E+02 -3,247E+03
Mg 1,512E-03 1,252E-03 -3,220E-03 -8,222E+02 -3,289E+03
Mn 1,534E-03 3,811E-04 -6,194E-04 -8,721E+02 -3,488E+03
Mo 1,557E-03 2,312E-02 1,921E-02 -1,425E+03 -5,701E+03
Nb 1,545E-03 1,133E-02 6,004E-03 -1,088E+03 -4,352E+03
Ni 1,536E-03 6,815E-04 1,352E-04 -8,887E+02 -3,555E+03
Pb 1,514E-03 1,459E-02 2,133E-02 -1,362E+03 -5,450E+03
Rb 1,374E-03 1,480E-01 1,155E-01 -4,070E+03 -1,628E+04
Re 1,565E-03 1,692E-02 1,113E-02 -1,237E+03 -4,947E+03
Sb 1,521E-03 1,111E-02 1,128E-02 -1,163E+03 -4,652E+03
Sc 1,516E-03 9,262E-04 -4,000E-06 -8,773E+02 -3,509E+03
Se 1,534E-03 1,804E-03 6,133E-03 -1,001E+03 -4,003E+03
Si 1,533E-03 -1,128E-03 -2,523E-03 -8,255E+02 -3,302E+03
Sn 1,520E-03 6,304E-03 3,796E-03 -9,919E+02 -3,968E+03
Ta 1,545E-03 1,221E-02 5,967E-03 -1,095E+03 -4,380E+03
V 1,552E-03 -8,209E-04 -1,944E-03 -8,493E+02 -3,397E+03
W 1,556E-03 2,469E-02 1,874E-02 -1,430E+03 -5,721E+03
Zn 1,528E-03 -1,360E-03 7,815E-04 -8,774E+02 -3,509E+03
Zr 1,527E-03 1,518E-02 9,948E-03 -1,180E+03 -4,718E+03
135
Sideal SM ∆HM Rc
none 1,07E+00 5,29E+00 6,36E+00 3,67E-03 -7,18E+03 3,08E+08 6,87E-01
Ag 1,07E+00 5,72E+00 6,80E+00 3,68E-03 -8,96E+03 2,67E+08 8,57E-01
Al 1,07E+00 5,72E+00 6,80E+00 3,65E-03 -9,78E+03 2,57E+08 9,35E-01
B 1,17E+00 5,72E+00 6,90E+00 3,66E-03 -1,64E+04 1,74E+08 1,56E+00
Ba 2,05E+00 5,72E+00 7,78E+00 3,61E-03 -1,76E+05 1,85E+04 1,68E+01
Be 1,09E+00 5,72E+00 6,82E+00 3,66E-03 -1,13E+04 2,34E+08 1,08E+00
Bi 1,37E+00 5,72E+00 7,09E+00 3,68E-03 -2,13E+04 1,27E+08 2,04E+00
C 1,35E+00 5,72E+00 7,08E+00 3,66E-03 -1,31E+04 2,04E+08 1,25E+00
Ca 1,61E+00 5,72E+00 7,33E+00 3,61E-03 -3,38E+04 6,14E+07 3,24E+00
Cd 1,09E+00 5,72E+00 6,82E+00 3,67E-03 -9,80E+03 2,54E+08 9,37E-01
Co 1,07E+00 5,72E+00 6,79E+00 3,67E-03 -1,07E+04 2,43E+08 1,02E+00
Cr 1,07E+00 5,72E+00 6,79E+00 3,67E-03 -1,10E+04 2,39E+08 1,05E+00
Cs 3,77E+00 5,72E+00 9,49E+00 3,52E-03 -4,94E+04 1,91E+07 4,72E+00
Cu 1,06E+00 5,72E+00 6,79E+00 3,68E-03 -9,67E+03 2,57E+08 9,25E-01
Ga 1,06E+00 5,72E+00 6,78E+00 3,66E-03 -1,05E+04 2,47E+08 1,00E+00
Ge 1,07E+00 5,72E+00 6,79E+00 3,66E-03 -1,05E+04 2,46E+08 1,01E+00
Hf 1,14E+00 5,72E+00 6,87E+00 3,70E-03 -1,48E+04 1,89E+08 1,42E+00
K 2,46E+00 5,72E+00 8,18E+00 3,56E-03 -3,10E+04 6,47E+07 2,97E+00
La 1,44E+00 5,72E+00 7,16E+00 3,66E-03 -1,30E+04 2,02E+08 1,25E+00
Li 1,10E+00 5,72E+00 6,83E+00 3,64E-03 -9,74E+03 2,57E+08 9,32E-01
Mg 1,15E+00 5,72E+00 6,87E+00 3,64E-03 -9,87E+03 2,53E+08 9,44E-01
Mn 1,10E+00 5,72E+00 6,82E+00 3,67E-03 -1,05E+04 2,45E+08 1,00E+00
Mo 1,06E+00 5,72E+00 6,79E+00 3,68E-03 -1,71E+04 1,68E+08 1,64E+00
Nb 1,07E+00 5,72E+00 6,80E+00 3,67E-03 -1,31E+04 2,12E+08 1,25E+00
Ni 1,07E+00 5,72E+00 6,79E+00 3,67E-03 -1,07E+04 2,43E+08 1,02E+00
Pb 1,07E+00 5,72E+00 6,79E+00 3,69E-03 -1,63E+04 1,75E+08 1,56E+00
Rb 1,06E+00 5,72E+00 6,79E+00 3,54E-03 -4,88E+04 2,89E+07 4,67E+00
Re 1,06E+00 5,72E+00 6,79E+00 3,71E-03 -1,48E+04 1,90E+08 1,42E+00
Sb 1,13E+00 5,72E+00 6,85E+00 3,66E-03 -1,40E+04 2,00E+08 1,34E+00
Sc 1,15E+00 5,72E+00 6,87E+00 3,65E-03 -1,05E+04 2,44E+08 1,01E+00
Se 1,09E+00 5,72E+00 6,81E+00 3,65E-03 -1,20E+04 2,26E+08 1,15E+00
Si 1,08E+00 5,72E+00 6,80E+00 3,65E-03 -9,91E+03 2,55E+08 9,48E-01
Sn 1,10E+00 5,72E+00 6,82E+00 3,67E-03 -1,19E+04 2,26E+08 1,14E+00
Ta 1,08E+00 5,72E+00 6,81E+00 3,70E-03 -1,31E+04 2,09E+08 1,26E+00
V 1,06E+00 5,72E+00 6,78E+00 3,67E-03 -1,02E+04 2,50E+08 9,75E-01
W 1,06E+00 5,72E+00 6,79E+00 3,71E-03 -1,72E+04 1,67E+08 1,64E+00
Zn 1,06E+00 5,72E+00 6,78E+00 3,67E-03 -1,05E+04 2,45E+08 1,01E+00
Zr 1,14E+00 5,72E+00 6,87E+00 3,66E-03 -1,42E+04 1,98E+08 1,35E+00
136
Alloying
ω(AB) (atu) ω(AC) (atu) ω(BC) (atu) ω system in J/mol (−ω)∗Ζ/2 in J/mol
element (X)
none 1,542E-03 -8,977E+02 -3,591E+03
Ag 1,521E-03 -6,894E-03 -3,618E-03 -7,371E+02 -2,948E+03
Al 1,536E-03 -7,568E-04 -3,323E-03 -8,025E+02 -3,210E+03
B 1,553E-03 1,104E-02 2,200E-02 -1,355E+03 -5,420E+03
Ba 1,437E-03 5,847E-01 5,060E-01 -1,461E+04 -5,845E+04
Be 1,544E-03 2,419E-03 2,046E-03 -9,280E+02 -3,712E+03
Bi 1,515E-03 3,180E-02 3,680E-02 -1,768E+03 -7,073E+03
C 1,563E-03 4,327E-03 9,267E-03 -1,081E+03 -4,325E+03
Ca 1,476E-03 9,849E-02 6,451E-02 -2,796E+03 -1,118E+04
Cd 1,520E-03 -3,408E-03 -1,308E-03 -8,064E+02 -3,226E+03
Co 1,539E-03 6,988E-04 1,239E-04 -8,772E+02 -3,509E+03
Cr 1,545E-03 2,745E-03 5,351E-04 -9,049E+02 -3,620E+03
Cs 1,328E-03 1,493E-01 1,191E-01 -4,098E+03 -1,639E+04
Cu 1,530E-03 -3,002E-03 -2,500E-03 -7,949E+02 -3,179E+03
Ga 1,530E-03 -1,737E-03 6,798E-04 -8,610E+02 -3,444E+03
Ge 1,532E-03 1,273E-04 -4,140E-05 -8,652E+02 -3,461E+03
Hf 1,533E-03 1,558E-02 1,296E-02 -1,224E+03 -4,897E+03
K 1,410E-03 8,331E-02 6,099E-02 -2,569E+03 -1,027E+04
La 1,497E-03 9,129E-03 8,842E-03 -1,077E+03 -4,308E+03
Li 1,511E-03 -4,816E-03 -5,924E-04 -8,019E+02 -3,207E+03
Mg 1,516E-03 1,231E-03 -3,236E-03 -8,095E+02 -3,238E+03
Mn 1,538E-03 3,849E-04 -6,194E-04 -8,606E+02 -3,442E+03
Mo 1,561E-03 2,312E-02 1,923E-02 -1,414E+03 -5,654E+03
Nb 1,549E-03 1,131E-02 6,007E-03 -1,075E+03 -4,301E+03
Ni 1,539E-03 6,843E-04 1,342E-04 -8,773E+02 -3,509E+03
Pb 1,518E-03 1,460E-02 2,131E-02 -1,353E+03 -5,414E+03
Rb 1,378E-03 1,480E-01 1,155E-01 -4,051E+03 -1,620E+04
Re 1,569E-03 1,690E-02 1,114E-02 -1,224E+03 -4,895E+03
Sb 1,525E-03 1,109E-02 1,128E-02 -1,152E+03 -4,608E+03
Sc 1,520E-03 9,184E-04 -4,000E-06 -8,659E+02 -3,464E+03
Se 1,538E-03 1,785E-03 6,151E-03 -9,912E+02 -3,965E+03
Si 1,537E-03 -1,119E-03 -2,517E-03 -8,141E+02 -3,256E+03
Sn 1,524E-03 6,305E-03 3,798E-03 -9,802E+02 -3,921E+03
Ta 1,549E-03 1,223E-02 5,974E-03 -1,082E+03 -4,330E+03
V 1,556E-03 -8,319E-04 -1,940E-03 -8,376E+02 -3,350E+03
W 1,560E-03 2,468E-02 1,874E-02 -1,418E+03 -5,671E+03
Zn 1,532E-03 -1,366E-03 7,823E-04 -8,671E+02 -3,468E+03
Zr 1,531E-03 1,519E-02 9,958E-03 -1,167E+03 -4,669E+03
137
Sideal SM ∆HM Rc
none 1,07E+00 5,29E+00 6,36E+00 3,67E-03 -7,18E+03 3,08E+08 6,87E-01
Ag 1,06E+00 5,67E+00 6,73E+00 3,69E-03 -8,84E+03 2,69E+08 8,46E-01
Al 1,06E+00 5,67E+00 6,73E+00 3,67E-03 -9,63E+03 2,60E+08 9,21E-01
B 1,16E+00 5,67E+00 6,83E+00 3,68E-03 -1,63E+04 1,75E+08 1,56E+00
Ba 2,05E+00 5,67E+00 7,72E+00 3,62E-03 -1,75E+05 1,90E+04 1,68E+01
Be 1,08E+00 5,67E+00 6,75E+00 3,68E-03 -1,11E+04 2,37E+08 1,07E+00
Bi 1,36E+00 5,67E+00 7,03E+00 3,70E-03 -2,12E+04 1,28E+08 2,03E+00
C 1,34E+00 5,67E+00 7,01E+00 3,68E-03 -1,30E+04 2,06E+08 1,24E+00
Ca 1,60E+00 5,67E+00 7,27E+00 3,63E-03 -3,35E+04 6,26E+07 3,21E+00
Cd 1,08E+00 5,67E+00 6,75E+00 3,69E-03 -9,68E+03 2,57E+08 9,26E-01
Co 1,05E+00 5,67E+00 6,72E+00 3,69E-03 -1,05E+04 2,46E+08 1,01E+00
Cr 1,05E+00 5,67E+00 6,72E+00 3,68E-03 -1,09E+04 2,41E+08 1,04E+00
Cs 3,78E+00 5,67E+00 9,45E+00 3,53E-03 -4,92E+04 1,93E+07 4,70E+00
Cu 1,05E+00 5,67E+00 6,72E+00 3,69E-03 -9,54E+03 2,60E+08 9,12E-01
Ga 1,05E+00 5,67E+00 6,72E+00 3,68E-03 -1,03E+04 2,49E+08 9,88E-01
Ge 1,06E+00 5,67E+00 6,73E+00 3,67E-03 -1,04E+04 2,48E+08 9,93E-01
Hf 1,13E+00 5,67E+00 6,80E+00 3,71E-03 -1,47E+04 1,91E+08 1,41E+00
K 2,46E+00 5,67E+00 8,12E+00 3,57E-03 -3,08E+04 6,56E+07 2,95E+00
La 1,43E+00 5,67E+00 7,10E+00 3,67E-03 -1,29E+04 2,04E+08 1,24E+00
Li 1,09E+00 5,67E+00 6,76E+00 3,65E-03 -9,62E+03 2,60E+08 9,20E-01
Mg 1,14E+00 5,67E+00 6,81E+00 3,65E-03 -9,71E+03 2,56E+08 9,29E-01
Mn 1,09E+00 5,67E+00 6,75E+00 3,68E-03 -1,03E+04 2,47E+08 9,88E-01
Mo 1,05E+00 5,67E+00 6,72E+00 3,69E-03 -1,70E+04 1,70E+08 1,62E+00
Nb 1,06E+00 5,67E+00 6,73E+00 3,69E-03 -1,29E+04 2,14E+08 1,23E+00
Ni 1,05E+00 5,67E+00 6,72E+00 3,69E-03 -1,05E+04 2,46E+08 1,01E+00
Pb 1,05E+00 5,67E+00 6,72E+00 3,70E-03 -1,62E+04 1,77E+08 1,55E+00
Rb 1,05E+00 5,67E+00 6,72E+00 3,56E-03 -4,86E+04 2,94E+07 4,65E+00
Re 1,05E+00 5,67E+00 6,72E+00 3,72E-03 -1,47E+04 1,92E+08 1,40E+00
Sb 1,11E+00 5,67E+00 6,78E+00 3,68E-03 -1,38E+04 2,03E+08 1,32E+00
Sc 1,14E+00 5,67E+00 6,81E+00 3,66E-03 -1,04E+04 2,46E+08 9,94E-01
Se 1,08E+00 5,67E+00 6,74E+00 3,67E-03 -1,19E+04 2,28E+08 1,14E+00
Si 1,07E+00 5,67E+00 6,74E+00 3,66E-03 -9,77E+03 2,58E+08 9,35E-01
Sn 1,09E+00 5,67E+00 6,75E+00 3,68E-03 -1,18E+04 2,28E+08 1,13E+00
Ta 1,07E+00 5,67E+00 6,74E+00 3,71E-03 -1,30E+04 2,12E+08 1,24E+00
V 1,05E+00 5,67E+00 6,72E+00 3,68E-03 -1,01E+04 2,53E+08 9,61E-01
W 1,05E+00 5,67E+00 6,72E+00 3,72E-03 -1,70E+04 1,69E+08 1,63E+00
Zn 1,05E+00 5,67E+00 6,72E+00 3,68E-03 -1,04E+04 2,48E+08 9,95E-01
Zr 1,13E+00 5,67E+00 6,80E+00 3,68E-03 -1,40E+04 2,00E+08 1,34E+00
138
Table A.25 – Ti67Co32X1
Alloying
element (X)
none 3,294E-04 -1,917E+02 -5,272E+02
Ag 2,857E-04 -8,074E-03 1,117E-03 -2,967E+01 -8,159E+01
Al 3,101E-04 -1,647E-05 -3,171E-03 -1,479E+02 -4,067E+02
B 3,307E-04 1,075E-02 1,719E-02 -5,203E+02 -1,431E+03
Ba 1,897E-04 5,563E-01 4,662E-01 -1,378E+04 -3,790E+04
Be 3,182E-04 2,382E-03 2,020E-04 -2,230E+02 -6,132E+02
Bi 2,881E-04 2,881E-02 4,294E-02 -1,030E+03 -2,833E+03
C 3,455E-04 4,115E-03 3,948E-03 -3,004E+02 -8,262E+02
Ca 2,362E-04 1,012E-01 6,362E-02 -2,442E+03 -6,716E+03
Cd 2,871E-04 -3,325E-03 2,653E-04 -1,062E+02 -2,921E+02
Cr 3,202E-04 2,263E-03 2,978E-04 -2,228E+02 -6,128E+02
Cs 6,100E-05 1,531E-01 1,207E-01 -3,734E+03 -1,027E+04
Cu 2,986E-04 -3,860E-03 -4,344E-04 -9,743E+01 -2,679E+02
Fe 3,195E-04 1,186E-03 1,183E-04 -2,021E+02 -5,559E+02
Ga 3,033E-04 -1,703E-03 1,299E-03 -1,525E+02 -4,193E+02
Ge 3,077E-04 2,111E-04 -1,393E-04 -1,762E+02 -4,846E+02
Hf 3,067E-04 1,414E-02 1,731E-02 -5,671E+02 -1,560E+03
K 1,580E-04 8,386E-02 6,094E-02 -2,072E+03 -5,697E+03
La 2,612E-04 7,521E-03 1,252E-02 -3,851E+02 -1,059E+03
Li 2,770E-04 -4,589E-03 -3,966E-04 -7,281E+01 -2,002E+02
Mg 2,837E-04 2,207E-03 -1,829E-03 -1,833E+02 -5,040E+02
Mn 3,087E-04 -2,053E-05 4,785E-04 -1,780E+02 -4,894E+02
Mo 3,421E-04 2,115E-02 2,300E-02 -7,579E+02 -2,084E+03
Nb 3,273E-04 1,147E-02 1,133E-02 -4,813E+02 -1,324E+03
Ni 3,114E-04 2,927E-04 0,000E+00 -1,809E+02 -4,976E+02
Pb 2,895E-04 1,343E-02 2,991E-02 -6,517E+02 -1,792E+03
Rb 1,189E-04 1,479E-01 1,109E-01 -3,593E+03 -9,881E+03
Re 3,550E-04 1,550E-02 1,482E-02 -5,971E+02 -1,642E+03
Sb 3,000E-04 1,096E-02 1,406E-02 -4,801E+02 -1,320E+03
Sc 2,905E-04 1,139E-03 2,427E-04 -1,860E+02 -5,114E+02
Se 3,192E-04 2,170E-03 4,477E-03 -2,561E+02 -7,042E+02
Si 3,134E-04 -1,439E-03 -3,493E-03 -1,222E+02 -3,360E+02
Sn 2,966E-04 5,903E-03 6,384E-03 -3,247E+02 -8,931E+02
Ta 3,273E-04 1,053E-02 1,077E-02 -4,600E+02 -1,265E+03
V 3,364E-04 -4,437E-04 -4,816E-03 -1,413E+02 -3,887E+02
W 3,425E-04 2,287E-02 2,354E-02 -7,927E+02 -2,180E+03
Zn 3,020E-04 -1,232E-03 6,136E-04 -1,542E+02 -4,239E+02
Zr 3,047E-04 1,366E-02 1,531E-02 -5,406E+02 -1,487E+03
139
Sideal SM ∆HM Rc
none 8,20E-01 5,29E+00 6,11E+00 3,35E-03 -1,58E+03 3,58E+08 2,29E-01
Ag 8,03E-01 5,67E+00 6,47E+00 3,35E-03 -2,45E+02 3,79E+08 3,54E-02
Al 8,02E-01 5,67E+00 6,47E+00 3,33E-03 -1,22E+03 3,57E+08 1,76E-01
B 9,43E-01 5,67E+00 6,61E+00 3,34E-03 -4,29E+03 2,83E+08 6,20E-01
Ba 1,53E+00 5,67E+00 7,19E+00 3,30E-03 -1,14E+05 1,51E+05 1,64E+01
Be 8,57E-01 5,67E+00 6,52E+00 3,34E-03 -1,84E+03 3,39E+08 2,66E-01
Bi 9,98E-01 5,67E+00 6,66E+00 3,36E-03 -8,50E+03 2,09E+08 1,23E+00
C 1,12E+00 5,67E+00 6,79E+00 3,34E-03 -2,48E+03 3,13E+08 3,58E-01
Ca 1,18E+00 5,67E+00 6,85E+00 3,30E-03 -2,01E+04 9,40E+07 2,91E+00
Cd 8,11E-01 5,67E+00 6,48E+00 3,35E-03 -8,76E+02 3,63E+08 1,27E-01
Cr 8,20E-01 5,67E+00 6,49E+00 3,34E-03 -1,84E+03 3,40E+08 2,66E-01
Cs 2,93E+00 5,67E+00 8,60E+00 3,22E-03 -3,08E+04 3,61E+07 4,45E+00
Cu 8,13E-01 5,67E+00 6,48E+00 3,35E-03 -8,04E+02 3,65E+08 1,16E-01
Fe 8,23E-01 5,67E+00 6,49E+00 3,35E-03 -1,67E+03 3,44E+08 2,41E-01
Ga 8,03E-01 5,67E+00 6,47E+00 3,34E-03 -1,26E+03 3,55E+08 1,82E-01
Ge 8,28E-01 5,67E+00 6,49E+00 3,34E-03 -1,45E+03 3,50E+08 2,10E-01
Hf 8,39E-01 5,67E+00 6,50E+00 3,37E-03 -4,68E+03 2,77E+08 6,76E-01
K 1,85E+00 5,67E+00 7,52E+00 3,25E-03 -1,71E+04 1,06E+08 2,47E+00
La 1,05E+00 5,67E+00 6,72E+00 3,34E-03 -3,18E+03 3,01E+08 4,59E-01
Li 8,16E-01 5,67E+00 6,48E+00 3,32E-03 -6,01E+02 3,73E+08 8,68E-02
Mg 8,43E-01 5,67E+00 6,51E+00 3,32E-03 -1,51E+03 3,49E+08 2,19E-01
Mn 8,65E-01 5,67E+00 6,53E+00 3,34E-03 -1,47E+03 3,46E+08 2,12E-01
Mo 8,02E-01 5,67E+00 6,47E+00 3,35E-03 -6,25E+03 2,52E+08 9,04E-01
Nb 8,02E-01 5,67E+00 6,47E+00 3,35E-03 -3,97E+03 2,94E+08 5,74E-01
Ni 8,20E-01 5,67E+00 6,49E+00 3,35E-03 -1,49E+03 3,48E+08 2,16E-01
Pb 8,20E-01 5,67E+00 6,49E+00 3,37E-03 -5,38E+03 2,65E+08 7,77E-01
Rb 8,01E-01 5,67E+00 6,47E+00 3,24E-03 -2,96E+04 5,28E+07 4,28E+00
Re 8,01E-01 5,67E+00 6,47E+00 3,38E-03 -4,93E+03 2,73E+08 7,12E-01
Sb 8,93E-01 5,67E+00 6,56E+00 3,34E-03 -3,96E+03 2,92E+08 5,72E-01
Sc 8,43E-01 5,67E+00 6,51E+00 3,32E-03 -1,53E+03 3,48E+08 2,22E-01
Se 8,49E-01 5,67E+00 6,51E+00 3,33E-03 -2,11E+03 3,34E+08 3,05E-01
Si 8,41E-01 5,67E+00 6,51E+00 3,32E-03 -1,01E+03 3,61E+08 1,46E-01
Sn 8,14E-01 5,67E+00 6,48E+00 3,34E-03 -2,68E+03 3,22E+08 3,87E-01
Ta 8,06E-01 5,67E+00 6,47E+00 3,37E-03 -3,80E+03 2,96E+08 5,49E-01
V 8,06E-01 5,67E+00 6,47E+00 3,34E-03 -1,17E+03 3,57E+08 1,69E-01
W 8,02E-01 5,67E+00 6,47E+00 3,38E-03 -6,54E+03 2,45E+08 9,45E-01
Zn 8,05E-01 5,67E+00 6,47E+00 3,34E-03 -1,27E+03 3,54E+08 1,84E-01
Zr 8,39E-01 5,67E+00 6,50E+00 3,34E-03 -4,46E+03 2,84E+08 6,45E-01
140
Alloying
element (X)
none 3,294E-04 -1,917E+02 -5,272E+02
Ag 2,943E-04 -8,663E-03 9,180E-04 -2,758E+01 -7,584E+01
Al 3,211E-04 1,983E-04 -3,230E-03 -1,593E+02 -4,381E+02
B 3,440E-04 1,123E-02 1,773E-02 -5,456E+02 -1,500E+03
Ba 1,904E-04 5,653E-01 4,724E-01 -1,397E+04 -3,842E+04
Be 3,304E-04 2,605E-03 2,016E-04 -2,360E+02 -6,490E+02
Bi 2,973E-04 2,933E-02 4,434E-02 -1,063E+03 -2,923E+03
C 3,595E-04 4,342E-03 4,251E-03 -3,180E+02 -8,745E+02
Ca 2,405E-04 1,069E-01 6,773E-02 -2,570E+03 -7,066E+03
Cd 2,957E-04 -3,368E-03 2,035E-04 -1,133E+02 -3,115E+02
Cr 3,320E-04 2,259E-03 2,899E-04 -2,317E+02 -6,373E+02
Cs 5,117E-05 1,519E-01 1,185E-01 -3,681E+03 -1,012E+04
Cu 3,087E-04 -4,066E-03 -5,124E-04 -1,025E+02 -2,819E+02
Fe 3,320E-04 1,170E-03 1,527E-04 -2,118E+02 -5,825E+02
Ga 3,133E-04 -1,739E-03 1,203E-03 -1,602E+02 -4,405E+02
Ge 3,185E-04 2,470E-04 -1,647E-04 -1,854E+02 -5,099E+02
Hf 3,175E-04 1,464E-02 1,776E-02 -5,893E+02 -1,621E+03
K 1,559E-04 8,501E-02 6,115E-02 -2,087E+03 -5,740E+03
La 2,678E-04 7,624E-03 1,265E-02 -3,953E+02 -1,087E+03
Li 2,848E-04 -4,461E-03 -4,657E-04 -8,243E+01 -2,267E+02
Mg 2,927E-04 2,710E-03 -1,676E-03 -1,998E+02 -5,494E+02
Mn 3,195E-04 -4,143E-05 4,886E-04 -1,867E+02 -5,136E+02
Mo 3,569E-04 2,210E-02 2,379E-02 -7,930E+02 -2,181E+03
Nb 3,398E-04 1,237E-02 1,193E-02 -5,120E+02 -1,408E+03
Ni 3,228E-04 3,035E-04 0,000E+00 -1,903E+02 -5,232E+02
Pb 2,983E-04 1,348E-02 3,103E-02 -6,742E+02 -1,854E+03
Rb 1,135E-04 1,486E-01 1,102E-01 -3,586E+03 -9,862E+03
Re 3,709E-04 1,653E-02 1,560E-02 -6,336E+02 -1,742E+03
Sb 3,107E-04 1,127E-02 1,458E-02 -4,996E+02 -1,374E+03
Sc 2,993E-04 1,124E-03 2,777E-04 -1,933E+02 -5,317E+02
Se 3,310E-04 2,208E-03 4,570E-03 -2,677E+02 -7,362E+02
Si 3,248E-04 -1,397E-03 -3,680E-03 -1,300E+02 -3,574E+02
Sn 3,067E-04 6,121E-03 6,649E-03 -3,393E+02 -9,332E+02
Ta 3,398E-04 1,130E-02 1,127E-02 -4,878E+02 -1,342E+03
V 3,496E-04 -5,102E-04 -4,867E-03 -1,491E+02 -4,101E+02
W 3,569E-04 2,404E-02 2,455E-02 -8,330E+02 -2,291E+03
Zn 3,123E-04 -1,223E-03 6,087E-04 -1,633E+02 -4,491E+02
Zr 3,149E-04 1,440E-02 1,587E-02 -5,671E+02 -1,560E+03
141
Sideal SM ∆HM Rc
none 8,20E-01 5,29E+00 6,11E+00 3,35E-03 -1,58E+03 3,58E+08 2,29E-01
Ag 8,19E-01 5,72E+00 6,54E+00 3,37E-03 -2,28E+02 3,75E+08 3,29E-02
Al 8,18E-01 5,72E+00 6,54E+00 3,34E-03 -1,31E+03 3,51E+08 1,90E-01
B 9,58E-01 5,72E+00 6,68E+00 3,35E-03 -4,50E+03 2,76E+08 6,51E-01
Ba 1,55E+00 5,72E+00 7,27E+00 3,31E-03 -1,15E+05 1,34E+05 1,67E+01
Be 8,72E-01 5,72E+00 6,60E+00 3,35E-03 -1,95E+03 3,33E+08 2,81E-01
Bi 1,02E+00 5,72E+00 6,74E+00 3,37E-03 -8,77E+03 2,03E+08 1,27E+00
C 1,14E+00 5,72E+00 6,86E+00 3,35E-03 -2,62E+03 3,06E+08 3,79E-01
Ca 1,20E+00 5,72E+00 6,92E+00 3,31E-03 -2,12E+04 8,64E+07 3,06E+00
Cd 8,28E-01 5,72E+00 6,55E+00 3,36E-03 -9,35E+02 3,57E+08 1,35E-01
Cr 8,36E-01 5,72E+00 6,56E+00 3,36E-03 -1,91E+03 3,35E+08 2,76E-01
Cs 2,96E+00 5,72E+00 8,68E+00 3,24E-03 -3,04E+04 3,66E+07 4,39E+00
Cu 8,29E-01 5,72E+00 6,55E+00 3,36E-03 -8,46E+02 3,60E+08 1,22E-01
Fe 8,38E-01 5,72E+00 6,56E+00 3,36E-03 -1,75E+03 3,38E+08 2,53E-01
Ga 8,19E-01 5,72E+00 6,54E+00 3,35E-03 -1,32E+03 3,50E+08 1,91E-01
Ge 8,44E-01 5,72E+00 6,57E+00 3,35E-03 -1,53E+03 3,44E+08 2,21E-01
Hf 8,56E-01 5,72E+00 6,58E+00 3,38E-03 -4,86E+03 2,71E+08 7,03E-01
K 1,88E+00 5,72E+00 7,60E+00 3,26E-03 -1,72E+04 1,04E+08 2,49E+00
La 1,07E+00 5,72E+00 6,79E+00 3,35E-03 -3,26E+03 2,96E+08 4,71E-01
Li 8,33E-01 5,72E+00 6,56E+00 3,33E-03 -6,80E+02 3,67E+08 9,83E-02
Mg 8,60E-01 5,72E+00 6,58E+00 3,33E-03 -1,65E+03 3,42E+08 2,38E-01
Mn 8,80E-01 5,72E+00 6,60E+00 3,36E-03 -1,54E+03 3,41E+08 2,23E-01
Mo 8,18E-01 5,72E+00 6,54E+00 3,37E-03 -6,54E+03 2,44E+08 9,45E-01
Nb 8,18E-01 5,72E+00 6,54E+00 3,36E-03 -4,22E+03 2,86E+08 6,10E-01
Ni 8,36E-01 5,72E+00 6,56E+00 3,36E-03 -1,57E+03 3,42E+08 2,27E-01
Pb 8,36E-01 5,72E+00 6,56E+00 3,38E-03 -5,56E+03 2,59E+08 8,04E-01
Rb 8,17E-01 5,72E+00 6,54E+00 3,25E-03 -2,96E+04 5,24E+07 4,28E+00
Re 8,17E-01 5,72E+00 6,54E+00 3,40E-03 -5,23E+03 2,64E+08 7,56E-01
Sb 9,09E-01 5,72E+00 6,63E+00 3,35E-03 -4,12E+03 2,85E+08 5,96E-01
Sc 8,60E-01 5,72E+00 6,58E+00 3,34E-03 -1,60E+03 3,43E+08 2,31E-01
Se 8,64E-01 5,72E+00 6,59E+00 3,34E-03 -2,21E+03 3,28E+08 3,19E-01
Si 8,57E-01 5,72E+00 6,58E+00 3,34E-03 -1,07E+03 3,55E+08 1,55E-01
Sn 8,30E-01 5,72E+00 6,55E+00 3,36E-03 -2,80E+03 3,15E+08 4,05E-01
Ta 8,22E-01 5,72E+00 6,55E+00 3,38E-03 -4,02E+03 2,88E+08 5,82E-01
V 8,22E-01 5,72E+00 6,55E+00 3,35E-03 -1,23E+03 3,51E+08 1,78E-01
W 8,17E-01 5,72E+00 6,54E+00 3,39E-03 -6,87E+03 2,37E+08 9,93E-01
Zn 8,21E-01 5,72E+00 6,54E+00 3,36E-03 -1,35E+03 3,48E+08 1,95E-01
Zr 8,56E-01 5,72E+00 6,58E+00 3,35E-03 -4,68E+03 2,77E+08 6,76E-01
142
Table A.29 – Elements favoring the glass forming parameters in Ti-Al2 and Ti-Fe
Ti-Al(2-) Ti(-)-Al2 Ti-Fe(-) Ti(-)-Fe

Cs Ba Ba Cs Ba Ba Re Ba Ba Re Ba Ba
Rb Rb Cs Rb Rb Cs C Cs Cs C Cs Cs
K Cs Rb K Cs Rb Mo Rb Rb Mo Rb Rb
Ba Ca Ca Ba Ca Ca W Ca Ca W Ca Ca
Ca K K Ca K K V K K V K K
La Bi Bi La Bi Bi B Bi Bi B Bi Bi
Y W W Y W W Ta W W Nb W W
Li Mo Mo Li Mo Mo Nb Mo Mo Ta Mo Mo
Mg Re Re Mg Re Re Pb Pb Cr Pb Pb
Ag Zr B Ag Zr B B B Be B B
Cd Nb Zr Cd B Zr Re Pd Re Pd
Bi B Nb Bi Nb Nb Pd Re Pd Re
Pb Hf Hf Pb Hf Hf Hf Hf Hf Hf
Sc Ta Ta Sc Ta Ta Zr Zr Zr Zr
Cu Pb Pb Cu Pb Pb Sb Sb Sb Sb
Sn Sb Sb Sn Sb Sb Ta Ta Ta La
Zn La La Pt La La Nb La Nb Ta
Pt Y Y Zn Y Y La C La C
Sb Sn C Pd Sn C C Nb C Nb
Pd Se Sn Sb Se Sn Sn Sn Sn Sn
Ga Pd Pd Ga C Se Se Y Se Y
Zr C Se Zr Pd Pd Y Se Y Se
Ge Mg Pt Ge Pt Pt Pt Pt Pt Pt
Hf Pt Mg Hf Mg Mg Be Be Be Be
Mn Be Be Mn Be Be Cr Cr Cr Cr
Ge Ge Co Ge Ge Ni Ni Ni Ni
Ga Ga Ni Ga Ga Co Co Co Co
Li Si Si Li Si Sc Mn Sc Mn
Si Li Be Si Li Ge Sc Ge Sc
Sc Sc Sc Sc Mn Ge Mn Ge
Zn Zn Zn Zn Zn Zn Zn Zn
Cr Cr Cr Cr Ga Ga Ga Ga
Cd Cd Cd Cd V V V V
Fe Fe Fe Fe Mg Mg Mg Mg
Co Co Co Co Al Si Al Si
Ni Ni Ni Ni Si Al Si Al
Mn Mn Mn Mn Cd Cd Cd Cd
V V V V Cu Cu Cu Cu
Cu Cu Cu Cu Li Li Li Li
Ag Ag Ag Ag Ag Ag
143
Table A.30 – Elements favoring the glass forming parameters in Ti2-Fe and Ti-Fe2
Ti(2-)-Fe Ti2-Fe(-) Ti-Fe(2-) Ti(-)-Fe2

Re Ba Ba Re Ba Ba Re Ba Ba Re Ba Ba
C Cs Cs C Cs Cs C Cs Cs C Cs Cs
Mo Rb Rb Mo Rb Rb Mo Rb Rb Mo Rb Rb
W Ca Ca W Ca Ca W Ca Ca W Ca Ca
V K K V K K V K K V K K
B Bi Bi B Bi Bi B Bi Bi B Bi Bi
Ta W W Nb W W Ta W W Nb W W
Nb Mo Mo Ta Mo Mo Nb Mo Mo Ta Mo Mo
Cr Pb Pb Pb Pb B B Cr B B
Be Re Pd Re Pd Pb Pb Be Pb Pb
Pd Re Pd Re Re Pd Pd Pd
B B B B Hf Hf Hf Hf
Hf Hf Hf Hf Pd Re Re Re
Zr Zr Zr Zr Zr Zr Zr Zr
Sb Sb Sb Sb Sb Sb Sb Sb
Nb Ta Nb Ta Ta La La La
Ta Nb Ta Nb C C C C
La La La La Nb Ta Ta Ta
C C C C La Nb Nb Nb
Sn Sn Sn Sn Se Pt Pt Pt
Y Y Y Y Pt Y Y Y
Se Se Se Se Sn Se Se Se
Be Be Be Be Y Sn Sn Sn
Cr Cr Cr Cr Be Be Be Be
Pt Pt Pt Pt Cr Cr Cr Cr
Co Co Ni Ni Ni Ni Ni Ni
Ni Ni Co Co Co Co Co Co
Sc Sc Sc Mn Zn Sc Sc Sc
Mn Mn Mn Sc Sc Mn Mn Mn
Ge Ge Ge Ge Ge Zn Zn Zn
Mg Mg Mg Mg Mn Ge Ge Ge
V V V V Ga Ga Ga Ga
Zn Zn Zn Zn V V V V
Ga Ga Ga Ga Si Mg Mg Mg
Al Al Al Al Mg Cd Cd Cd
Si Si Si Si Cd Si Si Si
Cd Cd Cd Cd Al Al Al Al
Cu Cu Cu Cu Li Cu Li Li
Li Li Li Li Cu Li Cu Cu
Ag Ag Ag Ag Ag Ag Ag Ag
144
Table A.31 – Elements favoring the glass forming parameters in Ti-Co2 system in
descending order
Ti-Co(2-) Ti(-)-Co2
ω(AB) ∆HM Rc ω(AB) ∆HM Rc
Re Ba Ba Re Ba Ba
C Cs Cs C Cs Cs
W Rb Rb W Rb Rb
Mo Ca Ca Mo Ca Ca
V K K V K K
B Bi Bi B Bi Bi
Nb W W W W
Ta Mo Mo Mo Mo
Cr Pb Pb Pb Pb
Fe Re Re Re Re
Se Hf Hf Hf Hf
Be Zr Pd Pd Pd
Pd B Zr B
B Zr B Zr
Nb Sb Nb Sb
Sb Nb Sb Nb
Ta Ta Ta Ta
La La La La
Sn C Sn C
C Y C Y
Y Sn Y Sn
Se Se Se Se
Be Be Be Be
Cr Pt Cr Pt
Pt Cr Pt Cr
Fe Fe Fe Fe
Mg Mn Mn
Sc Mg Ni
Ni Sc
Sc Mg
Ge Ge
Zn Zn
Ga Ga
Al V
V Al
Si
Cd
145

Ti-Based Bulk Amorphous Alloy Thesis

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Ti-Based Bulk Amorphous Alloy Thesis

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SYNTHESIS AND CHARACTERIZATION OF

TI-BASED BULK AMORPHOUS/NANOCRYSTALLINE ALLOYS FOR

IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE

SYNTHESIS AND CHARACTERIZATION OF TI-BASED BULK

January 2004, 145 pages

MÜHENDİSLİK UYGULAMALARI İÇİN Tİ-ESASLI İRİ VE

Ocak 2004, 145 sayfa

Amorf ve iri ve hacimli amorf metal alaşımlar teorik mukavemetleri, yüksek

Bu tez çalışmasında, Ti-esaslı iri ve hacimli amorf alaşımların modellenmesi ve

Teorik hesaplamalardan çıkan sonuçların literatürdeki verilerle uyum içinde olduğu

Tezin ikinci kısmında, teorik sonuçlardan yararlanarak yüksek cam oluşturma

I am truly grateful to my family for their never-ending support and encouragement,

ABSTRACT .................................................................................................................. iii

ACKNOWLEDGEMENT .......................................................................................... viii

TABLE OF CONTENTS ...............................................................................................ix

LIST OF SYMBOLS ................................................................................................. xiii

1.1 General Remarks ........................................................................................1

1.2 Scope of this thesis.....................................................................................3

1.3 Historical Background................................................................................4

1.3 Parameters for defining glass forming alloys.............................................7

1.3.1 Glass transition temperature (Tg) ....................................................8

1.3.2 Reduced glass transition temperature (Trg) ...................................10

1.3.3 Supercooled liquid region (∆Tx) ...................................................10

1.3.4 Maximum attainable thickness in amorphous form (tmax).............10

1.3.5 Critical cooling rate (Rc) ...............................................................11

1.4 Properties of Ti-based amorphous alloys .................................................11

2.1 Theory of glass forming alloys ................................................................14

2.1.1 Semi-empirical Approach .............................................................16

2.1.2 Thermodynamic and Kinetic Approach ........................................19

2.1.2.1 Ordered liquid alloys.........................................................20

2.1.2.3 Short range order...............................................................31

2.2 Electronic Theory of Alloys.....................................................................33

2.2.1 Principles of One-electron Theory ................................................33

2.2.2 Nearly-free Electron Model (NFE) ...............................................34

2.2.3 The Pseudopotential Theory of Interatomic Interactions..............38

2.2.4 Application of Pseudopotential Theory to Ti-based Binary

2.3 Theoretical modeling of Ti-based bulk glass forming systems................39

2.3.1 Selection of candidate Ti-based bulk glass forming system .........39

2.3.2 Evaluation of glass forming parameters........................................41

2.3.3 Fundamental equation of critical cooling rate..............................42

2.3.4 Gibbs free energy for the multicomponent system ......................43

2.3.4.1 Regular solution model ..................................................43

2.3.4.2 Mismatch term in entropy of mixing.............................44

2.3.5 Viscosity at melting temperature for glass-forming alloys ..........45

2.3.6 Modified equation of critical cooling rate....................................46

2.3.7 Ordering energy calculations .......................................................47

3.1 Ti-Ni binary system..................................................................................50

3.1.1 Development of candidate bulk amorphous forming alloys ........59

3.1.2 Alloy preparation .........................................................................52

3.2 Crucible Production...............................................................................55

3.3 Structural characterization.....................................................................56

4. RESULTS AND DISCUSSIONS ..........................................................................59

4.1 Discussion of ordering energy and other GFA parameters ...................59

4.1.1 Data Tables................................................................................60

4.1.2 Interpretation of results .............................................................73

4.1.2.1 Alloying additions .......................................................75

4.2 Discussion of experimental study .........................................................81

4.2.1 Alloy A1, Ti67Ni33 .......................................................................81

4.2.2 Alloy A2, Ti60Ni30Mo10 ................................................................83

4.2.3 Alloy A3, Ti55Ni30Zr8Mo5W2 .........................................................86

4.2.3.1 Copper mould cast.......................................................86

4.2.3.2 Near equilibrium cooled sample .................................92

4.2.4 Alloy A4, Ti57Ni28Zr8Mo5W2 .........................................................94