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Alloys and
Intermetallic Compounds
From Modeling to Engineering
Alloys and
Intermetallic Compounds
From Modeling to Engineering
Editor
Cristina Artini
Department of Chemistry and Industrial Chemistry
University of Genova
Genova
Italy
p,
A SCIENCE PUBLISHERS BOOK
Cover Acknowledgement
Cover Acknowledgement
·CoverTop-Left
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alloy drop solidified on a ZrB
by kind courtesy of 2M.substrate.
Sullivan Reproduced by kind
·courtesy
Top-right
of Dr. photo of theCNR-ICMATE,
F. Valenza, Galapagos furGenova,
seal: Reproduced by kind
Italy (author courtesy2.1).
of Chapter of J.J. Alava
· Top-right photo of the Galapagos fur seal: Reproduced by kind courtesy of J.J. Alava
· Bottom-left photo of the Juan Fernandez fur seal: Reproduced by kind courtesy of L.P. Osman
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Names:
Names:Alava,
Artini,Juan Joseì, editor.
Cristina, editor.
Title: Tropical pinnipeds : bio-ecology, threats, and conservation / editor,
Names: Alava, Juan Joseì, editor. compounds : from modeling to engineering/editor,
Title: Alloys and intermetallic
Juan JoseìArtini,
Cristina Alava, Department
Faculty of Science, Instituteand
of Chemistry for Industrial
the OceansChemistry,
and
Title: Tropical pinnipeds : bio-ecology, threats, and conservation / editor,
Fisheries,
University The
of University
Genova, of British Columbia, Vancouver, Canada.
Juan Joseì Alava, FacultyGenova,
of Science,Italy.
Institute for the Oceans and
Description:
Description: Boca Raton, FLFL: CRC
: CRCPress, 2017. | “A&science publishers book.”| "A science
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Preface
As I was first contacted by CRC Press with the invitation to propose a

book focused on intermetallic compounds, I immediately came across the
idea of describing the role of modeling in the design of alloys aimed at
specific applications. Experimental difficulties in obtaining the desired
compounds and the desired properties are a common experience among
materials scientists; on the other side, theory is often deemed as a high and
respected knowledge, yet meant to be well separated from experimental
science. In this respect, modeling appears as the perfect bridge between
theoretical and experimental knowledge: it is partly or totally generated
by theory, but it is intended to provide scientists with information useful
to take very practical decisions, such as the choice of the most proper
composition to obtain a certain effect or to investigate a certain property.
The book is divided into two parts: in the first one several ab-initio
and semi-empirical modeling techniques, able to predict thermodynamic
and physical properties, are presented. In the second part some examples
regarding the employment of such methods and of specific mathematical
and engineering simulations for the design of intermetallic compounds
with specific properties, are elucidated and widely discussed. Alloys
aimed at very different applications, such as brazing alloys, biocompatible
materials, metallic glasses, superconductors, thermoelectric compounds,
are among the materials treated. Therefore, my hope is that this collection
of review papers written by distinguished researchers can be of help
for a wide scientific audience: not only for graduate students willing to
approach the topic “modeling” for the first time, but also for scientists
aiming to go in more depth into a particular issue.
Contents
Preface v
Part 1: MODELING tECHNIQUES aND PrEDICtION

OF PrOPErtIES
1.1 Computational thermodynamics: From Experiments 3

to applications
A. Watson, A. Kroupa, A. Dinsdale, J. Vrestal, P. Broz and A. Zemanova
1.2 thermophysical Properties of Metallic alloys from 44
Ab Initio Methods and applications to
thermodynamic Modeling
Mauro Palumbo
1.3 the Formation Volume in rare Earth Intermetallic Systems: 81
a representation by Means of atomic Physical Quantities
M. Pani and F. Merlo
Part 2: rOLE OF MODELING ON tHE DESIGN OF aLLOYS

aND INtErMEtaLLIC COMPOUNDS
2.1 Metal-Ceramic Interactions in Brazing Ultra High 115

temperature Diboride Ceramics
Fabrizio Valenza, Cristina Artini, Sofia Gambaro, Maria Luigia Muolo
and Alberto Passerone
2.2 Metal Surfaces in Medicine: Current Knowledge 147
of Properties, Modeling and Biological response
S. Spriano, S. Ferraris, C. Balagna and M. Cazzola
2.3 Fe-based Superconductors: Crystallochemistry, Band 172
Structure and Phase Diagrams
Alberto Martinelli
2.4 Electronic and Magnetic Properties of Highly Disordered 196
Fe-based Frank Kasper-Phases in View of First Principles
Calculation and Experimental Study
J. Cieslak and J. Tobola
viii Alloys and Intermetallic Compounds: From Modeling to Engineering
2.5 atomistic Modeling to Design Favoured Compositions 228

for the Metallic Glass Formation
J.B. Liu, J.H. Li and B.X. Liu
2.6 Shape Memory alloys: Constitutive Modeling and 259
Engineering Simulations
G. Scalet and F. Auricchio
2.7 Prediction of the thermoelectric Properties of 286
Half-Heusler Phases from the Density Functional theory
V.V. Romaka, P.F. Rogl, R. Carlini and C. Fanciulli
2.8 Skutterudites for thermoelectric applications: 324
Properties, Synthesis and Modeling
R. Carlini, C. Fanciulli, P. Boulet, M.C. Record, V.V. Romaka
and P.F. Rogl
Index 357
About the Editor 359
PART 1
MODELING TECHNIQUES
AND PREDICTION OF PROPERTIES
1.1
Computational Thermodynamics
From Experiments to Applications
A. Watson,1,* A. Kroupa,2 A. Dinsdale,3 J. Vrestal,4 P. Broz 4 and
A. Zemanova 5
INTRODUCTION
The properties of materials, and ultimately their application, are

determined substantially by the composition and quantities of the
different phases present in their microstructure. The nature of the phases
and their relative amounts are determined by the chemical composition of
the material and the processing routes employed. Considering the number
of chemical elements available to the materials scientist, the possible
permutations and the almost infinite variation in processing parameters,
a simple method of trial and error is an impractical route for materials
development. However, the Phase Diagram, and more recently, the advent
of Computational Thermodynamics, have made the process of Materials
Development much easier and more efficient in terms of time and effort.
Phase diagrams show, in a simple visual form, the state of chemical
equilibrium between a number of components as a function of
1
Institute for Materials Research, School of Chemical and Process Engineering, University of
Leeds, Leeds, LS2 9JT.
2
IPM ASCR, Žižkova, 22, Brno, 61662, Czech Republic.
3
Hampton Thermodynamics, Jamnagar Clo. Staines, Middx. UK.
4
Dept. of Chemistry, Masaryk University, Kamenice 753/5, Bohunice, Brno, Czech Republic.
5
IPM ASCR, Žižkova, 22, Brno, 61662, Czech Republic.
* Corresponding author: a.watson@leeds.ac.uk
4 Alloys and Intermetallic Compounds: From Modeling to Engineering
variables such as temperature, pressure or composition. One of the first

published phase diagrams was by Heycock and Neville (Heycock and
Neville 1904), who, following earlier work published by Roozeboom
(Roozeboom 1899), combined the cooling curve analysis of liquid
mixtures of Cu and Sn with metallographic study of the solidified alloys.
By plotting the temperatures corresponding to thermal arrests on the
cooling curves at the corresponding alloy compositions, they were able
to produce a simplified version of the Cu-Sn phase diagram, correctly
showing that for all compositions and temperatures above the ‘liquidus
curve’ the alloys are completely liquid, those below the ‘solidus curve’ are
completely solid. In between the two curves, the solid and liquid phases
coexist.
This was essentially the first ‘modeling’ of phase equilibria resulting in
the initiation of large experimental programmes in many countries around
the world, as the importance and applicability of a pictorial representation
of phase equilibrium became fully appreciated. The basic experimental
techniques used by Heycock and Neville soon became standard for the
determination of phase diagrams, particularly for equilibria involving the
liquid phase in higher temperature regimes, and they are still in use today,
albeit in a more refined form. For lower temperature equilibria involving
solid state transformations, other techniques have evolved, generally
relying on electron microscopy or X-ray analysis.
For more than 60 years, phase diagrams were determined by purely
experimental methods. But with the advent of inexpensive but more
powerful computers, it became relatively easy to calculate phase diagrams
using thermodynamic properties; as phase diagrams show the state of
thermodynamic equilibrium. As early as 1908, J.J. Van Laar (van Emmerik
1991) had shown how features of binary phase diagrams can be synthesised
using a simple regular solution model for the thermodynamic properties,
but it was the pioneering work of Larry Kaufman and co-workers (Kaufman
and Bernstein 1970) who took these concepts and began to calculate real
phase diagrams. The Calphad technique (CALculation of Phase Diagrams)
has been under continuous development since the late 1960s and now plays
a prominent role in materials development. Experimental observation
of phase equilibrium is combined with experimental determination of
thermodynamic properties to produce self-consistent thermodynamic
model descriptions of all possible phases in a material system.
By minimisation of the total Gibbs energy for the system as a function of
temperature, pressure and composition, the state of chemical equilibrium
can be calculated, and unlike traditional ‘paper’ phase diagrams, the
calculation can, in principle, be conducted for many components, the
limit being dictated by the array sizes in the software and the availability
of suitable thermodynamic descriptions. But it is important to recognise
Computational Thermodynamics: From Experiments to Applications 5
that, despite recent developments in ab initio methods, the power of the

Calphad technique lies in the fact that it is firmly rooted in experimental
observation, and the accuracy of the calculations relies very much on the
quality of the experimental data that are used in the modeling process.
Experimental Techniques
The experimental techniques that have and continue to be used in the

determination of phase diagrams and thermodynamic properties are
quite varied and need considerable expertise on the part of the user. The
following is not intended to be an exhaustive critique but to just give
an overview of the type of techniques that are available to the materials
scientist. For a more detailed description, the reader should consult
(Kubaschewski et al. 1993; Boettinger et al. 2006).
Phase Diagram Determination

Dynamic methods
It would seem to be a contradiction, but one of the most popular and
successful experimental techniques to determine phase boundaries in an
equilibrium phase diagram, is thermal analysis, which is a dynamic method.
There have been a number of improvements and variations of the method
over the years, but the premise is still the same. Heat flow to or from a
sample is measured with respect to time, and as a phase boundary is
crossed, there is a significant change in the rate of the heat flow owing
to evolution of the enthalpy of transformation on the appearance
(or disappearance) of a phase in the material. As this method is used
mostly for determination of phase boundaries involving the liquid phase,
this heat change is related to the enthalpy of fusion.
At its simplest, thermal analysis can be conducted using a thermocouple
and a stop watch. For example, by measuring and plotting the temperature
of a solidifying alloy with respect to time (Fig. 1), deflections in the cooling
curve give the temperatures of the liquidus, solidus and eutectic reaction.
The main experimental difficulty with this simple set up is that the
heat effects often can be relatively small and thus have only negligible
influence on the cooling curve. A major improvement was the advent of
Differential Thermal Analysis (DTA) which incorporated the measurement
of the temperature of an inert standard in parallel with that of the sample,
and the signal recorded being the difference between the two signals
(Fig. 2). Therefore, if the heat capacity of the sample under study and that
of the reference are very similar, the net output will be zero until a phase
Temperature T1
TE
A Composition B
C
Temperature
T1
TE
Time
Fig. 1: Cooling curve analysis of a simple binary alloy system.
boundary is crossed, giving a well defined peak in the trace from the
detector. Here, instead of plotting temperature versus time, the detector
signal is plotted against sample temperature.
As Thermal Analysis is a dynamic measurement, it has to be said that
equilibrium within the sample is unlikely to be reached. Kinetic constraints
on phase transformation are an issue, but these can be reduced to a large
degree by performing the measurements under slow cooling conditions
(by fixing the cooling rate of the DTA furnace) or by performing the
measurements on sample heating. However, heating/cooling rates need
to be sufficiently fast in order to give a well defined peak; rates between 5
and 20ºC per minute being the norm.
As a refinement of the DTA, the Differential Scanning Calorimeter
measures the heat flow between the sample and the reference as a voltage
Endothermic
ΔT
T1 TE
Temperature
Fig. 2: The DTA Curve.
that is measured with respect to sample temperature. This not only leads to
more accurate determination of transition temperature, but also makes the
determination of the enthalpy change involved relatively straightforward.
Static methods
Dynamic methods of phase diagram determination require that the
phase changes occur within a reasonable time. For high temperature
work, particularly when the liquid phase is involved, these methods
are acceptable and have been the staple techniques for many years, and
continue to be used in the present day. But for lower temperature studies,
particularly for solid state transformations, the times required to reach
equilibrium are far too long for dynamic methods. Static methods involve
preparation of alloys followed by their examination, which could involve
microscopy (electron microscopy with microprobe analysis) or X-ray
diffraction studies.
Typically, samples are prepared at a series of compositions within the
system and then heat treated to equilibrium at a selected temperature. It
is important that the heat treatment takes place in an inert atmosphere,
which can involve sealing in silica ampoules under a reduced pressure of
argon, or in a tube furnace under flowing inert gas. The time required for
the samples to reach equilibrium will depend on the temperature of the
heat treatment; the lower the temperature, the longer the time required.
Samples are then cooled (rapidly quenched if there’s a danger of not
retaining the heat treated structure) for further examination.
For many years, X-ray diffraction has been used for phase analysis.
A simple method of analysis is the disappearing phase technique
(Cullity 1978) (Fig. 3). By comparing diffraction patterns of the samples, it is
possible to detect at which compositions groups of lines that are attributed
to specific phases appear and disappear. Figure 3 shows a schematic binary
phase diagram and a series of hypothetical diffraction patterns resulting
from X-ray analysis of eight different compositions. Composition 1 is the
diffraction pattern for pure component A, whereas that for composition
2 is for the same phase but containing some dissolved component B.
So, the X-ray pattern is essentially the same, but with a shift in the lines
owing to changes in the lattice dimensions owing to the dissolution of
the second component. The diffraction pattern from composition 3 shows
extra lines that come from a second phase in the structure, indicating that
this composition lies in a two-phase field. Of course, the diffraction lines
from the phases in the two phase field will not shift in the same way as
they do in a single phase region, and the compositions of the phases do
not change, only their relative proportions. This is shown in the diagram
of the hypothetical lattice parameters of the α and β phases. The lattice
parameters are constant with respect to total composition within two
phase fields. Composition 5 lies at the composition of the γ intermetallic
compound, and hence the lines associated with the α phase disappear
from the pattern. The patterns resulting from the remaining compositions
show similar behaviour.
Although it is very good as a tool for phase identification, the
drawback in using X-ray analysis is that the resolution of the technique
can be as low as 5% with a corresponding uncertainty in composition of
the location of a phase boundary. Therefore, it is now common practice
to link X-ray studies with electron microscopy and microprobe analysis.
Scanning electron microscopy not only reveals highly magnified detailed
images of multiphase structures, but elemental maps produced by Energy
Dispersive Analysis of X-rays emitted from the surface of the material
reveal compositional variations between the different phases present. A
recent development involves the incorporation of the analytical techniques
into a single instrument. Electron Backscatter Diffraction (EBSD) involves
the use of a special detector within a scanning electron microscope, which
comprises, amongst other things, a phosphor screen and a CCD camera.
The technique employs backscattered electrons that escape the sample,
being diffracted by the crystal lattice of the material under study. The
diffracted backscattered electrons excite the phosphor screen revealing
bands, known as Kikuchi bands, which are then recorded by the CCD
camera. With appropriate analysis, these bands lead to the identification
of the crystal structure of the diffracting lattice.
liquid
Compassionate
x(B)
Lattice parameter
for the y+~
Compassionate
a-phase
a+y Lattice parameter :

for the
~-phase
Pure A
Cl
2
,,
"'0E 3 a+y
I I 1! li I t
t::
~
c::
.Q
4 a+y ,, I[ II
,,
I 1:
0
~
6
5 y
I
6 y+~
11 II I il . !,
..
7 ~
I l l 1.\
8
Pure B
i I I.
Fig. 3: X-ray analysis using the disappearing phase technique.
Thermodynamic Properties
As indicated earlier, the phase diagram is just one way of describing
thermodynamic equilibrium, and so by knowing the thermodynamic
properties of the phases within a system, it is possible to determine
the nature of equilibrium with respect to the system variables. The
methodology of phase diagram calculation will be described in the
next section. Essentially, the modeling process requires Gibbs energy
descriptions of the phases within a system, which, in principle, can be
derived from enthalpies (of formation, transformation), heat capacities
and component activities.
Enthalpy measurement
Enthalpy as a quantity cannot be measured, but the change in enthalpy
associated with a reaction of some kind can. For the acquisition of these
types of data, calorimetric methods are employed, the exact nature of the
experiment being chosen to suit the materials under investigation and the
thermodynamic quantity that is being determined.
Figure 4 shows a calorimeter in its simplest form. The calorimeter
itself is the vessel in which the reaction under study takes place. This sits
inside a jacket, which represents the ‘surroundings’, which is held at a
constant temperature. The reaction is initiated inside the calorimeter and
the temperature is taken with respect to time. A corrected temperature
rise is measured, and by multiplying this by the ‘Water Equivalent’ of the
calorimeter, a value for the heat effect is calculated. The ‘Water Equivalent’
is essentially the heat capacity of the apparatus and is usually determined
experimentally. This particular technique is known as Isoperibol Calorimetry
where the temperature of the surroundings (Ts) is held constant and the
calorimeter temperature (Tc), which is measured, is a direct function of the
heat effect (Q) from the reaction taking place in the calorimeter.
Outer Jacket (T = const.) Thermometer
CD = corrected temperature rise ΔT

D Baffle
Temperature
Calorimeter
T0
B
A
C
Time QT = WΔT
Fig. 4: Schematic of a simple calorimeter.

Other techniques are available, such as Isothermal Calorimetry, where

Ts = Tc. For example, the Ice Calorimeter devised by Bunsen, captures
the heat produced in the reaction melting a quantity of ice held in the
calorimeter jacket, the weight of which can be measured, leading directly
to the value of the heat effect, knowing the enthalpy of fusion of water.
The Adiabatic Calorimeter uses a completely different approach to the
problem in that it aims to trap all of the heat produced in the reaction
inside the calorimeter (Tc = Ts = f(Q)). The Adiabatic Calorimeter devised
by Dench (Dench 1963) comprises a calorimetric cell suspended within a
furnace. The furnace is maintained at a temperature equal to that inside
the calorimetric cell by using a pair of differential thermocouples. A
central heater supplies heat to the sample material inside the calorimetric
cell. The heat required to form alloys from pressed compacts of the pure
elemental powders can be determined by measuring the heat supplied
directly by the sample heater, to raise the temperature of the material from
a ‘safe’ temperature to a temperature at which alloying is complete (which
is predetermined by a separate experiment). This is compared with the
heat required to raise the temperature of the pure elements over the same
temperature range, the difference between the two quantities being the
enthalpy of formation of the alloy. As the furnace temperature outside the
cell is the same as the temperature inside the cell, there is no net heat
loss from the calorimeter and essentially all of the heat supplied to the
specimen heater is used to raise the temperature of the sample and for the
alloying process. Some minor heat losses can be expected via the heater
leads themselves, but these can be compensated for in the final calculation.
However, the most common type of calorimeter used today is the Heat
Flow calorimeter (Ts – Tc = constant). Typically, a pair of calorimetric cells,
usually positioned side-by-side, are in contact with each other through
many thermocouples which form a thermopile. The reaction under study
takes place in the reaction cell and the heat produced flows through the
thermopile to the reference cell. If the reaction taking place in the reaction
cell is endothermic, then heat flows to the cell from the reference. This
heat effect is realised as a voltage which is then plotted with respect to
time for the duration of the experiment. The integral of this voltage time
curve gives a value of the heat effect when multiplied by an appropriate
calibration constant. Figure 5 shows a schematic of this calorimeter, set up
in its usual configuration as a drop calorimeter.
Here, samples are dropped from a low temperature (typically room
temperature) to a predetermined high temperature, and the heat effect
measured, and with an appropriate calibration constant, a value for the
enthalpy change can be determined. The drop technique can be used for
different types of measurement. For example, by dropping successive
samples of a pure element into a liquid metal held in an appropriate
Sample (T1)
Calorimeter
Block
Reference cell
Reaction cell (T2)
Thermopile
Furnace
Windings
Fig. 5: Heat-flow calorimeter set up as a drop calorimeter.
crucible in the reaction cell, it is possible to determine enthalpies of mixing

of liquid alloys. If alternatively, an appropriate liquid solvent is held in the
crucible, and solid alloys and their component elements are dissolved in
it, it is possible to determine enthalpies of formation of the solid alloys.
The heat effect resulting from the dissolution of an alloy sample will
result in a heat effect that comprises three parts. The enthalpy increment,
namely the heat required to raise the temperature of the sample from
the drop temperature to the calorimeter temperature, the heat effect on
dissolving the sample, and finally, the enthalpy of formation of the alloy,
as the dissolution results in the dispersion of the component elements to,
in principle, infinite dilution; although this is in reality not achieved, but
approached. The enthalpy of formation can be numerically much smaller
than the other two heat effects, and so, if it is chemically possible, a direct
reaction technique should be used to form the alloy within an empty
reaction cell in the calorimeter from the individual components obviating
the need for dissolution (for example (Watson and Hayes 1995)).
The high precision of this instrument, together with the versatility

of the drop technique, has been put to great effect by a number of
laboratories, most notably the group of Kleppa (for example (Meschel
and Kleppa 2004)) and more recently, the group of Ipser in Vienna (for
example (Plevachuk et al. 2014)).
In all types of calorimetric measurement, it is crucial to determine that
the reaction under study goes to completion during the measurement.
It is often better to reproduce the reaction outside the calorimeter, but
replicating the measurement conditions. For example, a direct reaction
measurement takes typically in the region of 20 minutes. Thus a sample
of the same composition and size can be heated quickly to the calorimeter
temperature inside a vertical tube furnace, held for 20 minutes and then
quenched followed by X-ray and EPMA to check that the sample has
been completely alloyed. If alloying is incomplete, a higher temperature
is required for the reaction. This will result in an increase in the enthalpy
increment portion of the heat effect, and hence adversely affect the
uncertainty in the final result. Switching to a lower temperature dissolution
technique may give better results in such a case.
Component activities—vapour pressure measurement

The determination of enthalpy is very useful in that it is relatively easy
to do and it’s an important component of the Gibbs energy. A second
useful quantity that is relatively easy to determine is component activity.
This can be done either as a vapour pressure measurement or via a
galvanic cell.
The activity of a component in a mixture is defined as the ratio of its
fugacity in the mixture to that of the component in the standard state. If
the component is in its gaseous form, then this can be taken to be the ratio
of its equilibrium vapour pressure above the mixture to that above the
pure condensed component, assuming that the gas phase behaves ideally.
Probably the most successful method of activity determination via vapour
pressure measurement is using Knudsen Effusion.
The Knudsen Effusion cell (Fig. 6) is essentially a small container with
a gas-tight lid with a knife-edged orifice, the diameter of which must be
less than one-tenth the mean free path of the vapour inside the cell. The
pressure of the effusing vapour in vacuum is given by:
m 2RT m T
  0.02256
tA M tA M
where m is the mass of the effusing species of molecular weight M,
evaporating through an orifice of cross-sectional area A in time t. R is
the Universal gas constant. Thus, by measuring the weight loss of the
i .
Effusant
lid
""~~l'"li::::Jif
Multiplier
D Faraday Collector
liquid Nitrogen
Magnetic Field
Window for
optical
pyrometer Knudsen
Cell
Thermocouple
To vacuum pump
Fig. 6: Schematic of the Knudsen cell with the mass spectrometer.
cell during effusion it is possible to calculate the pressure of the effusing

species. But by far the most popular and effective use of Knudsen Effusion
is by combining it with mass spectrometry (Fig. 6). The effusing species
are ionised by a beam of monoenergetic electrons. The ionised species are
then subjected to an accelerating potential through a magnetic field that
separates the different species according to charge/mass ratio, and the
intensity of each is recorded. An alternative methodology involves non-
magnetic quadrupole mass spectrometric separation via combination
of direct-current (DC) and radio-frequency (RF) potentials or a pulsed
accelerating potential with ions being separated by ‘Time of Flight’. The
advantage of combining Knudsen Effusion with mass spectrometry is the
ability to identify the effusing species, which is particularly useful if there
is more than one. The intensities of each are recorded, and the activity
is simply the ratio of the ionic intensity of the species effusing from the
mixture to that effusing from the pure component.
Gibbs energies—electrochemical methods

Gibbs energies of reaction can be determined directly if the reaction
in question can be arranged in the form of an electrochemical cell. For
example, the Gibbs energy of formation of an oxide of metal M, MO, can
be determined electrochemically thus:
Pt < M, MO > | electrolyte | (O2, 1 atm) Pt
A mixture of metal M and its oxide forms one electrode and is
connected to the other electrode (in this case, oxygen gas) by a suitable
electrolyte. Platinum connections complete the electrical circuit to an
appropriate voltage measuring device. With the condition of zero current
flow, the cell is in equilibrium, the reactions taking place at each electrode
being reversible.
M + O2– = MO + 2e– Left-hand side.
½ O2 + 2e– = O2– Right-hand side.
½ O2 + M = MO Overall reaction.
The Gibbs energy for the reaction is given as:
ΔG = –zFE
where z is the number of electrons taking part in the reaction, F is the
Faraday constant (96485.3 C mol–1) and E is the cell voltage.
The nature of the electrolyte depends very much on the current
carrying species. Above, the current carrying species is the electron,
and it’s quite standard for liquid electrolytes to be used for this
purpose. These can be aqueous salts, but often molten salts are used.
Alternatively, positive ions can be the current carrying species.
For example, in solid oxide electrolytes, such as zirconia-based materials,
the current flows as a result of vacancies formed in the crystal lattice as a
result of doping with an aliovalent ion.
Depending on the thermodynamic property required, the cell reaction
can be quite complex. For example, Wierzbicka-Miernik et al. (Wierzbicka-
Miernik et al. 2010) used the following cell to determine the activities of Sn
in ternary Ag-Cu-Sn melts.
(–) Kanthal, Re|Ag-Cu-Sn(liq), SnO2(s)||ZrO2 – Y2O3||Ni(s),
NiO(s)|Pt (+)
Cell reactions:
2NiO + 4e– = 2Ni + 2O2–
Sn + 2O2– = SnO2 + 4e–
Overall:
2NiO + Sn = 2Ni + SnO2
The Gibbs energy of the overall cell reaction is thus a sum of the
chemical potentials of the products minus that of the reactants:
ΔG = –4FE = 2µº(Ni) + µº(SnO2)–2µº(NiO) – (µº(Sn) + RTln(aSn))
and thus knowing the Gibbs energy of the formation of the Ni and Sn
oxides, the activity of Sn in the ternary melt is given by:
–2ΔGOf,NiO + ΔGOf,SnO + 4 FE
2
In(aSn) =
RT
Modeling
Semi-empirical Approach to the Calculation of Phase Diagrams

for Multicomponent Systems
Currently we can hardly imagine any work devoted to the development
of new materials without intensive use of phase diagrams for the class
of materials under study. But it has been the more recent explosion
in phase diagram modeling and the sophisticated application to real
materials problems that has made such an impact on Materials Science
possible. As mentioned in the Introduction, the modern concept of Phase
Diagram Modeling is based on the theoretical work of Gibbs and Van Laar
(Gibbs 1876; van Emmerik 1991) in the late 19th and early 20th century,
setting a clear thermodynamic foundation for the definition of phase
equilibria and established the links between the thermodynamic properties
of any system and the relevant phase diagram.
The thermodynamic properties of all phases potentially stable
in the system under study have to be defined if the phase equilibrium
for a particular set of conditions is to be calculated. The temperature
and pressure are usually defined as independent conditions in the case
of metallic materials and the relevant thermodynamic state function
is the Gibbs energy. The phase equilibrium is then calculated as the
state with the lowest Gibbs energy and by searching for the minima of
this state function with respect to the independent conditions, we can
calculate the whole phase diagram of the system. The phase diagram
2200
1800
FCC_A1
_1400
-
::.::::
~
1000
HCP_A3
600
200
0 10 20 30 40 50
P (MPa)
Fig. 7: The Calculated Phase Diagram for Iron.
for pure iron with respect to temperature and pressure is shown

in Fig. 7.
There is an important difference between the phase diagram and any
type of property diagram. Every point on the phase diagram has a specific
meaning and gives information about the state of the system. In the case of
the property diagram, only the curves on the diagram define any property
of the material. The regions bound by the lines on the phase diagram are
called phase fields and define the conditions under which the materials, in
this case pure iron, exists in the indicated crystallographic structure. The
lines themselves indicate the conditions under which the phases adjacent
to the line coexist in thermodynamic equilibrium. The triple point (see Fig.
7) represents the only temperature and pressure under which the three
phases are in equilibrium in accordance with Gibbs phase rule.
This unary (i.e., one component) phase diagram is the simplest
example that can be used for the prediction of materials chemistry.
The practical importance of these theoretically modelled phase diagrams
increases with the complexity of the system as establishing an
experimental phase diagram for complex systems is very difficult
and only very limited regions can be known by experiment. Phase
diagrams comprising of two components are known as binary phase
diagrams, and they can be reasonably well established by experiment
(see previous section) and consequently can be calculated in the same
way as the unary diagram shown above, using thermodynamic functions,

which are dependent on temperature and also on the composition of the
system. The minimization process with respect to the temperature and
composition (and pressure, if it is not constant) then leads to the binary
phase diagram. The robust, high quality theoretical assessment serves as
basis for further mathematical extrapolation to higher order systems. The
composition of the system, which is an additional independent parameter of
the system, would theoretically lead to a three-dimensional representation
of the phase diagram, but the pressure can be defined as constant for vast
majority of metallic systems and therefore two dimensions are used.
An example is given in Fig. 8.
Figure 8 shows the phase diagrams of the Al-Ni and Al-Fe systems,
both of which exhibit chemically ordered phases, and as such, shows the
difference between the ordering processes in these systems, which are
important for many intermetallics. In the Al-Ni system, there is a first order
phase transformation between γ (FCC_A1) and its ordered modification
γ’ (L12 – Ni3Al), which is crucial for the formation of the two-phase (γ +
γ’) superalloy structure. However, there is no such two-phase field in the
Al-Fe system, and the chemically ordered structure is formed through
a second order phase transformation between BCC_A2 and BCC_B2
phases. This means that the morphology of both alloys will be completely
different, influencing significantly their materials properties. In addition,
the NiAl phase (BCC_B2) is formed at around 50 mol% Al in the Al-Ni
system, exhibiting a very high melting point and the presence of many
defects in the structure leading to wide composition range for the phase.
Robust and precise thermodynamic descriptions of these important binary
systems, together with knowledge of other binary Ni-X (Fe-X) systems (X
being key alloying elements), allows the prediction of the behaviour of
more complex materials.
Computational Thermodynamics, and in particular the Calphad method,
requires a complete description of the thermodynamic state functions of
all phases in the system and their dependence on temperature, pressure
and composition. Ever increasing computer capacity and power has
enabled this method to be applied to the modeling of phase diagrams of
highly complex systems, and its versatility and extreme usefulness was
soon “discovered” not only by those working in basic science but also in
applied science and industrial laboratories.
The Calphad method is based on a sequential (bottom-up approach)
modeling of thermodynamic functions, and in particular the Gibbs energy,
starting from the simplest systems (e.g., unaries), constructing robust and
a 1800
LIQUID
1600
1400
BCC_B2
1200 FCC_A1
T (ºC)
1000
800
600 FCC_A1
+
FCC_L12
400
40 50 60 70 80 90 100
Ni (mol.%)
b 1800
LIQUID
1600
AL5FE4
1400
BCC_A2
1200
T (ºC)
1000
AL2FE
800 FCC_A1
BCC_B2
600
400
30 40 50 60 70 80 90 100
Fe (mol.%)
Fig. 8: Phase Diagram for the Al-Ni (a) and Al-Fe (b) Systems at Atmospheric Pressure.
reliable descriptions of the data for binary and ternary systems, where
the best possible agreement between the modelled phase diagrams and
thermodynamic functions with experimental phase and thermodynamic
data is sought. Such robust descriptions can be used in conjunction with
well tested and reliable models for extrapolating into systems with more
and more components. The combination of powerful computer software
and reliable thermodynamic databases (often available commercially—
see the section “Thermodynamic databases”) give the materials scientist
a powerful tool in alloy design and process engineering, enabling a
limitless number of “virtual experiments” to be conducted, saving time
and the expense associated with huge experimental programmes, making
it possible to obtain detailed descriptions of highly complex materials
systems.
Modeling of the Gibbs Energy of the System

In order to produce high-quality, accurate predictions of phase equilibria
using the Calphad method, it is crucial to have an accurate description of
the Gibbs energy of each phase that may potentially exist in the system
under study. Such Gibbs energy functions are stored in thermodynamic
databases in the form of polynomial expressions, the coefficients of which
are obtained by experiment and/or from theoretical evaluations.
The temperature dependence of the Gibbs energy (G) of a component
(element or any pure species) is often expressed as:
G = a + bT + cTln(T) + Σ d iT n
where a, b, c & di are adjustable coefficients.
With appropriate differentiation, it is possible to derive expressions for
Enthalpy, Entropy and Heat Capacity (Cp). It’s possible to add additional
terms to cater for pressure dependence or magnetic contributions (Lukas
et al. 2007).
This treatment is adequate to model unary (one component) systems,
but in dealing with binary, ternary and multicomponent systems, it is
necessary to consider phases that contain more than one component,
such as solutions or compounds. This requires consideration of the
combination of the Gibbs energies for the components plus a contribution
from the composition dependence. Thus, the molar Gibbs energy of
a substitutional solution phase Φ can be considered to be the sum of a
number of contributions:
GΦm = GΦref + GΦid + GΦe + GΦmag + GΦp + … (1)
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erection, with a copious description, as also, plans, elevations,
sections, and details of the most prominent features of the building
or structure, illustrated, and the work, from its great utility, will take a
place amongst the magazines of the present day, second only to the
great magazine of the north.[1]
“A large and beautiful field lies open before you, and by bringing
before the public some of the noble metropolitan structures, the
beautiful street architecture, and suburban villas, you will create a
love for reading and study amongst a most important class, that will
force The Builder on, till it has attained the ‘Corinthian order’ as a
magazine, and the companion of every artizan.
“A magazine has always occurred to me as the best mode to bring
the architecture of this country in its best form before the public,
always acknowledging the name of the professional gentlemen
employed in the erection illustrated; so much so, that I have often
been tempted to suggest the idea to some of the London publishers,
as there the erections are as a source inexhaustible.
“Though The Builder may be an instrument of much good, if
correctness of plans and details are guaranteed, its fall will be as
certain, if it should be a medium of ‘book-making,’ so often seen
thrown before the public.
“It will likewise add to the value of The Builder, by continuing the
portraitures of men so eminent in architectural skill as the noble-
minded William of Wykeham, already illustrated in the Precursor
number.
“I would respectfully suggest the propriety of detaching the
advertisements from The Builder, so far as to allow a separate
binding of the work.
“Reviews of architectural works are also highly commendable in
The Builder, as they increase in quantity of late years; and a
guidance to purchasers therefore is valuable.
“With best wishes for the prosperity of the undertaking, in a
continual increasing circulation, I must beg the forwarding to your
correspondent here, such of the numbers as have been issued.
“I remain, most respectfully,
“Joseph J. Roebuck, Joiner.”
“Manchester-Road, Huddersfield, Feb. 13, 1843.”
[1] Chambers’s.
“Sir,
“Judging from a perusal of The Builder that it is your intention to
give to the building world the first information upon all matters
connected with its interests, I beg therefore to apprize you that at this
moment, a bill is preparing very secretly (at least the ground-work for
one) for Parliament, upon which it is presumed, as secretly will be
obtained, a New Building Act.
“Whatever objections there may be (and I readily admit there are
many) to our present Building Act, yet I do not think it requires
altogether to be superseded.
“From private information I learn, that the majority of clauses in the
intended new bill, are exceedingly arbitrary, and calculated only to
oppress the Builders without the least additional benefit to the public,
and indeed, I am of opinion that if adopted, it will prove a source of
great inconvenience and expense to all parties in any way connected
with building. I should, therefore, recommend a Meeting of
speculative Builders immediately, to take into consideration the best
means to oppose the bill in Parliament.
“I shall be most happy to give my best assistance in this matter, as
also to forward the views of the proprietor of The Builder.
“I am, Sir, your obedient servant,
“John Reid, Surveyor.”
“90, Canterbury-buildings, Lambeth,
“February 14th, 1843.”
The foregoing letter came to hand as we were going to press. We
have only time to assure our correspondent that we will pay
immediate attention to the subject it refers to, and we invite further
information from all those who may be in the way of procuring it. At
the same time we would urge a calm and steady purpose in the
pursuit of this or any similar object of our vigilance.
Legislation on matters affecting building interests, above all things,
should be deliberate and not capricious. Much mischief may be done
by over anxious meddlings, indeed, we may say in this respect with
Shakspeare in Hamlet,
“Better bear the ills we have than fly to others that we know not
of,”
or run the risk of so doing.
ON METAL WORKS.
(From Pugin’s principles of Pointed Architecture.)
We now come to the consideration of works in metal; and I shall
be able to shew that the same principles of suiting the design to the
material and decorating construction, were strictly adhered to by the
artists of the middle ages, in all their productions in metal, whether
precious or common.
In the first place, hinges, locks, bolts, nails, &c., which are always
concealed in modern designs, were rendered in Pointed
Architecture, rich and beautiful decorations; and this, not only in the
doors and fittings of buildings, but in cabinet and small articles of
furniture. The early hinges covered the whole face of the door with
varied and flowing scroll-work. Of this description are those of Notre
Dame at Paris, St. Elizabeth’s church at Marburg, the western doors
of Litchfield cathedral, the Chapter House at York, and hundreds of
other churches, both in England and on the Continent.
Hinges of this kind are not only beautiful in design, but they are
practically good. We all know that on the principle of a lever, a door
may be easily torn off its modern hinges, by a strain applied at its
outward edge. This could not be the case with the ancient hinges,
which extended the whole width of the door, and were bolted through
in various places. In barn doors and gates these hinges are still
used, although devoid of any elegance of form; but they have been
most religiously banished from all public edifices as unsightly, merely
on account of our present race of artists not exercising the same
ingenuity as those of ancient times, in rendering the useful a vehicle
for the beautiful. The same remarks will apply to locks which are now
concealed, and let into the styles of doors, which are often more than
half cut away to receive them.
A lock was a subject on which the ancient smiths delighted to
exercise the utmost resources of their art. The locks of chests were
generally of a most elaborate and beautiful description. A splendid
example of an old lock still remains at Beddington Manor House,
Surrey, and is engraved in my father’s work of examples. In
churches we not unfrequently find locks with sacred subjects chased
upon them, with the most ingenious mechanical contrivances to
conceal the keyhole. Keys were also highly ornamented with
appropriate decorations referring to the locks to which they
belonged; and even the wards turned into beautiful devices and
initial letters. Railings were not casts of meagre stone tracery, but
elegant combinations of metal bars, adjusted with a due regard to
strength and resistance.
There were many fine specimens of this style of railing round
tombs, and Westminster Abbey was rich in such examples, but they
were actually pulled down and sold for old iron by the order of the
then dean, and even the exquisite scroll-work belonging to the tomb
of Queen Eleanor was not respected. The iron screen of King
Edward the Fourth’s tomb, at St. George’s Chapel, Windsor, is a
splendid example of ancient iron-work. The fire-dogs or Andirons, as
they were called, which supported either the fuel-logs where wood
was burnt, or grates for coal, were frequently of splendid design. The
ornaments were generally heraldic, and it was not unusual to work
the finer parts in brass, for relief of colour and richness of effect.
These form a striking contrast with the inconsistencies of modern
grates, which are not unfrequently made to represent diminutive
fronts of castellated or ecclesiastical buildings with turrets, loopholes,
windows, and doorways, all in the space of forty inches. The fender
is a sort of embattled parapet, with a lodge-gate at each end; the end
of the poker is a sharp pointed finial; and at the summit of the tongs
is a saint. It is impossible to enumerate half the absurdities of
modern metal-workers; but all these proceed from the false notion of
disguising instead of beautifying articles of utility. How many objects
of ordinary use are rendered monstrous and ridiculous because the
artist, instead of seeking the most convenient form and then
decorating it, has embodied some extravagancies to conceal the real
purpose for which the article was made! If a clock is required it is not
unusual to cast a Roman warrior in a flying chariot, round one of the
wheels of which, on close inspection, the hours may be descried; or
the whole of a cathedral church reduced to a few inches in height,
with the clock-face occupying the position of a magnificent rose
window. Surely the inventor of this patent clock-case could never
have reflected that according to the scale on which the edifice was
reduced, his clock would be about 200 feet in circumference, and
that such a monster of a dial would crush the proportions of any
building that could be raised. But this is nothing when compared to
what we see continually produced from those inexhaustible mines of
bad taste, Birmingham and Sheffield; staircase turrets for inkstands,
monumental crosses for light shades, gable ends hung on handles
for door porters, and four doorways and a cluster of pillars to support
a French lamp; while a pair of pinnacles supporting an arch is called
a Gothic-pattern scraper, and a wiry compound of quatrefoils and fan
tracery an abbey garden seat. Neither relative scale, form, purpose,
nor unity of style, is ever considered by those who design these
abominations; if they only introduce a quatrefoil or an acute arch, be
the outline and style of the article ever so modern and debased, it is
at once denominated and sold as Gothic.
SUSPENSION ROOF.
TO THE EDITOR OF THE BUILDER.
Sir—I have introduced the suspension principle in two or three
instances with great success, where nothing else could have
answered the purpose; and as it was through you that the first
impression was made upon my mind of its practicability for building
purposes, I at once send you a rude sketch of the last one I have
used. It is to carry a roof, lead-flat, and ceiling; it is in connection with
the old mansion, an enlargement of the cooking kitchen, taking out
the whole of the end wall, 16 feet wide, and making or adding to the
same a large bow, which is covered with lead. I have marked the
different parts as follows:
A. Suspension-rods secured to walls, 1 inch round, iron, flat in the
walls.
B. Screw bolts, 1 inch round, iron.
C. Nuts at bottom of bolts, and brace.
D. Brace, ½ inch round, iron.
E. Head to brace.
F. Iron plate under wood plate, 3 inches by ½ inch, flat.
G. Wood plate, 3 inches thick.
H. Lead-flat.
I. Joists to ditto.
J. Ceiling-joists.
K. Principal beam of roof.
I must give you to understand the bow, lead-flats, &c., were done
before I came here, and supported in a manner that gave offence to
every one; you will now perceive there is a straight ceiling and no
obstruction to light or any thing else.
The suspension-rods are fixed to the bolts as the link of a chain,
the brace screws them tight together, and the bottom nuts screw up
and camber the plate, which renders the whole complete and very
strong. I had it put together and fixed in about two hours, so that you
will perceive it can be applied in any situation without doing any
damage, by merely boring the holes and making good the joint round
the bolts on either a floor, roof, or flat.
I have applied others in different places, and have made them as
circumstances required, to carry scores of tons weight. They have
given the greatest satisfaction possible to all concerned.
I am happy to inform you that our architect and the master-builder
will both be subscribers to your valuable work. I think from this
neighbourhood you will have a dozen names.
Yours most obediently,
T. P. Hope,
Clerk of Works, Richmond.
THE ENTHUSIAST.
We beg to introduce the Enthusiast to our readers, for such the
world is pleased now and then to call him; his real character,
however, shall be judged of by the reflecting and considerate; the
name may stick to him as a matter of small account, for a wiser man
than ourselves has said “there’s nothing in a name.”
When we speak of the reflecting and considerate, it is not to be
implied that all persons do not at times and in their way reflect and
consider; but it is hard to do so while we are involved in the business
of ordinary life; like players at cards, we are absorbed in the
calculations that affect them, and in the consideration of the “hand”
we hold. We find even the most skilful, straining to recollect himself
of the past progress, and speculating on the future chances of the
game—so it is with the mass of human beings. Could we look but on
as cool spectators of the games, and shifts, and moves of general
life, we should pity, smile, expostulate, reprove, where now at best
we give a vacant look, an unmeaning sigh, rage and burn, as in turns
we feel the instinct of weakness or passion, and are driven to act
under their impulses—but we are drawing the portrait of the
multitude, and losing sight of the Enthusiast.
How shall we catch his likeness and how present it to our readers?
It must be drawn with many lines and a patient hand. We are not
limners, or choose not to be, who cut out profiles in black, with a pair
of scissors; nor can we daguerrotype him at a glance. No! The
Enthusiast must be the subject of many sittings, though we may give
a complete feature or, sketch at each of his aspect for the day; and
in doing so, we promise ourselves what we hope will be largely
shared in by our readers, a fair amount of interest and gratification.
Enthusiast has some eccentricities, or to speak more plainly, has
his oddities. Tell him so however, tell him as a friend, and he is
enthusiastic to rid himself of his oddities. He has friends who now
and then tell him so; he has enemies who also take the same liberty;
but it is ten to one, if you examine it, that both friends and enemies,
in specifying some particular oddity, confront and contradict each
other, and leave the poor Enthusiast not wiser, but more perplexed,
between them. Indeed, so much do they themselves blunder, and so
much of guess-work is there in their opinions, that to give things their
right names, judging from effects, we should call the friend an
enemy, and the enemy a friend. The only conclusion we can come to
is by canvassing the motives of each, to decide that the well-
meaning and evil-doing are ranged on the one side, and the evil-
meaning and well-doing on the other. So odd are many things and
many persons besides Enthusiast; but we are again sketching from
the crowd, and Enthusiast sits impatient, or rather his friends are
impatient, which with them is much the same thing.
Enthusiast is an architect! Upon my word, some one will exclaim,
what is coming to us now-a-days?—architects and architecture are
obtruded upon us at every turn; and a certain lady of a certain age
(which means, as everybody knows, no very large portion of a
century) indignantly expostulates against this attempt to engross the
public mind and attention with these “new fanglements” of a
profession and an art which her father and grandfather’s days could
very well do without. “Formerly,” she says (which means about the
ancient period of her youth), “we hardly heard the mention of such
things. Architects, indeed! formerly the word even was scarcely so
much as known among us. I recollect,” says she, “having my
attention forced upon it somewhere in my school readings, in some
out of the way chapter or exercise, which poor Mrs. Cross-stitch
imposed on me at the ‘finishing’ of my education. I recollect reading
something about architecture, and how I mispronounced the word,
and how Mrs. Letterhead, our class mistress, told me to pronounce
the ch like k; and how she gave us a spelling task with that and
several other hard words to learn at home in the evening, and how
my poor father, when he heard me my task at my bed-time, had a
dispute with our neighbour, Percy Fullpurse, as to which was the
greater personage, the archdeacon or the architect; for they both
insisted that Miss Letterhead was wrong in her pronounciation, as
Percy had it; and how Percy, who was a great authority with us, for
we thought riches and wisdom went very much together, decided
that the archdeacon and the architect had nothing to do with each
other, but that the architect was something he could not exactly tell
what or how, but he believed had something to do with the quarter of
the Archipelago, with which also he had nothing to do. All this I
recollect, and certainly, though I may now smile at the ignorance of
my poor father and neighbour Percy, yet I am not bound to hold with
all that we are hearing and having dinned into our ears every day.
Almost every third person I meet with has some friend or friend’s
friend who is an architect, or is acquainted with an architect—and I
meet with them at parties; and there is Cousin Symmetry has placed
his son by his first wife as pupil to an architect; but what call can
there be, or what to do for so many architects? Architects, like
Proctors, should keep their places, and some two or three of them
inhabit a cathedral town, to take care of those fine old buildings and
the churches, for the churchwardens, they say, do not look to those
things properly; but, Lord bless us, do not let us be bored with
architecture at every turn. Let them have a bookseller specially to
themselves, if they will—and now I think of it, I recollect something of
an old established shop in that way somewhere in Holborn; but here
I see Messrs. Longman are publishing works on architecture, and
Mr. Tilt pushing them before one’s noses, and Bell & Wood, and
others, as the advertisements tell us. Nay, to crown all! there is that
very Boz, in his new work, Martin Chuzzlewit, beginning with an
architect, which, by the way, proves what I have always said, that he
is wearing out his subjects—and mind what I say again, it will break
down! He should take popular characters and popular subjects; but
an architect! Why, not one in a thousand knows or cares any thing
about architects. Trash! and now just do look at this—a weekly
paper, called The Builder! and another character to be drawn out—
an Enthusiast, who is also an architect! Well, upon my word, that is
good! We have heard of castles in the air; I suppose we are going to
have a builder of them, and that this Enthusiast is to be the architect.
Well, that is as it should be—the clouds for the architects, and the
architects for the clouds.”
But when shall we sit down to our business?—Miss Fatima Five-
and-forty has had the turn of our pencil, and Enthusiast still awaits its
return.
Enthusiast is an architect; that is, he is so for this limning; for
Enthusiast enters into most things, and is the life and soul of them.
We cannot go into his parentage, to shew how he is allied to, or of
the family of, the Geniuses; but really it is a difficult task this
sketching that we have undertaken, and reminds us of one of
George Cruikshank’s humours, under the head of “Ugly Customers;”
not that we are so much out of love with our subject as with the task
we have undertaken.
Do excuse us, good readers, for a while longer, and we will tell you
a story about this same Enthusiast. It is a trick of some of our
contemporary painters, to beguile the sitter by a conversation on
some topic which throws him from the restraint of posture-making;
perhaps if we try it, Enthusiast may be caught in a more favourable
attitude, and we may close the day with some success for our
hitherto failing and disappointed pencil.
Enthusiast was one day engaged in a discussion with a lady
friend, and had, in the usual warmth of his manner, been descanting
on the beauties and properties of Church Architecture in connection
with the proposed erection of a suitable structure of this class in a
wealthy manufacturing town. “It should be a cathedral,” said he, “at
least in dimension, in aspect, in decorations and appointments.” He
had dwelt on the peculiar features it should possess, on the facilities
that could be commanded, on the energies that ought to be exerted,
and so on, when he was cut short in his rhapsody by the cruel
observation of the lady,—and a common one it is,—“There is no
money for such things now-a-days.”
Casting his eyes around, as if in a reverie of thought, he scanned
the character of the various luxuries of the well-appointed drawing-
room in which they sat. Glancing from the broad mirror boldly
superposed on the massive carved chimney-piece of Carrara
marble, which in its turn enclosed the highly-polished steel and
burnishings of a costly Sheffield grate and its furniture, to the rich silk
hangings of the windows—their gilded cornices and single sheets of
plate-glass—thence to the chairs of rosewood and ivory inlaid, the
seats of silken suit—the companion couch and ottoman of most
ample dress—the curious and costly cabinet, the screens, the gold-
mounted harp, the “grand piano.”—Pacing once the length of the
room on the gay velvet of the carpet, he turned again and rested his
view on the table, choicely decked with books, most expensive in all
the appliances of paper, type, illustration, and binding—having done
all this, with breath suppressed and stiflings of emotion, which fain
had broken out with a scornful repetition of the lady’s words, “there is
no money for such things now-a-days,” he quietly disengaged
himself of his passion, and by an apparently easy transition ran on
thus:
“I have been calling to mind some of my early readings, and most
prominent just now is the recollection of the observations of Hope
when treating the subject of Egyptian Architecture and commenting
on the vastness of the Pyramids; he enters into a speculation as to
the means by which the people of that country under the Pharaohs
were enabled to find the leisure, or the time necessary for the
construction of such stupendous works, and he ventures to ascribe it
to the natural fertility of the soil caused by the annual over-flowings
of the Nile, thus demanding less from the Egyptians of the labour
and care of agriculture; and hence the drift of their exertions in the
direction of architecture. True, the bounty of nature would go a long
way in supplying to the cravings of art the leisure and opportunity for
gratification. True, those pyramids are evidence of the direction of
great means and great powers to an end which astounds more than
it edifies us, but what were the bounties of Egypt’s irrigating water,
what the greatness of their pyramids compared with that bounty
which Providence has given us in the mineral and the out-growing
mechanical characteristics of this favoured country, and the
pyramids which we erect as if in emulation of Egyptian vanity and
inutility?” “Pyramids!” interrupted the lady, “Ah, it is always so with
you, to propound to us first some extravagant project, and when
driven from your ground by a common sense and practical answer,
to take shelter in some ambiguity or paradox. Pyramids, Sir,—what is
your meaning?” “Here,” said the Enthusiast, “here, madam, are
stones from some of the English pyramids, of which your Scotts, and
Byrons, and Bulwers, and Marryatts have been the architects.
Compare the labours, and the end of the labours of these ingenious
minds with those of the architects of the Egyptian pyramids, and tell
me then the difference in amount. See the glories and untiring
industry of him of Abbotsford, devoted to an incessant wearing out of
the energies of his mind in designing pyramids of fiction—look on the
ant-like bustle and activity of the thousands whom he brought into
requisition to be engaged in the building—look at the millions of
devotees who have prostrated and continue to prostrate themselves
at these great entombments of his genius.—The paper-makers—the
printers—the artists employed in illustration—the binders—the
booksellers—the advertizing—the correspondence—the carrying—
volumes, pyramids of volumes to advertize alone—an endless train
of carriages and lines of road for the conveyance—the Builders and
makers employed on all these—and on the establishments of
printers, booksellers, &c.—and then the excited million of
expectants, the absorbed and half-entranced readers—the hours,
days, weeks, months, and years of reading—the impatience of
interruption till the whole delusion is swallowed—the readings again
and again—the contagion from the elders to the younger—children
even bewildered with the passion to peep into, to pore over, and last,
to read as rote-books these little better than idle fables—bootless in
their aim and object, and pointless in all but their rival obtuseness of
the mountain-mocking pyramids. The fertility, the leisure, and the
vanities of Egypt!—oh, madam, their country was sterility—their
leisure, incessant bustle compared with what we enjoy; and their
vain direction of labour and thought not to be named after this
enumeration of vanities. Pyramids!—where they had one we have
ten. Where ages were required by the Egyptians, we in as many
years outvie them, and yet your answer to my aspirations is, “We
have no money for such things as these!”
Reader, we have beguiled ourselves and you, and not the
Enthusiast, into a sitting; and one feature is sketched of his likeness
and his character.
STREET SWEEPING MACHINE.
We give the following notice in connexion with the subject of Wood
Pavements, believing, as we do, that the efficiency of that mode of
paving greatly depends upon its being kept clean; an object which
this invention will materially facilitate.
Patent Self-Loading Cart, or Street-Sweeping Machine.
The Self-loading Cart has been lately brought into operation in the
town of Manchester, where it has excited a considerable degree of
public attention. It is the invention of Mr. Whitworth, of the firm of
Messrs. Joseph Whitworth & Co., engineers, by whom it has been
patented, and is now in process of manufacture. The principle of the
invention consists in employing the rotatory motion of locomotive
wheels, moved by horse or other power, to raise the loose soil from
the surface of the ground, and deposit it in a vehicle attached.
It will be evident that the self-loading principle is applicable to a
variety of purposes. Its most important application, however, is to the
cleaning of streets and roads. The apparatus for this purpose
consists of a series of brooms suspended from a light frame of
wrought iron, hung behind a common cart, the body of which is
placed as near the ground as possible, for the greater facility of
loading. As the cart-wheels revolve, the brooms successively sweep
the surface of the ground, and carry the soil up an inclined plane, at
the top of which it falls into the body of the cart.
The apparatus is extremely simple in construction, and will have
no tendency to get out of order, nor will it be liable to material injury
from accident. The draught is not severe on the horse. Throughout
the process of filling, a larger amount of force is not required that
would be necessary to draw the full cart an equal distance.
The success of the operation is no less remarkable than its
novelty. Proceeding at a moderate speed through the public streets,
the cart leaves behind it a well-swept track, which forms a striking
contrast with the adjacent ground. Though of the full size of a
common cart, it has repeatedly filled itself in the space of six minutes
from the principal thoroughfares of the town before mentioned.
The state of the streets in our large towns, and particularly in the
metropolis, it must be admitted, is far from satisfactory. It is
productive of serious hindrance to traffic, and a vast amount of public
inconvenience. The evil does not arise from the want of a liberal
expenditure on the part of the local authorities. In the township of
Manchester, the annual outlay for scavenging is upwards of 5,000l.
This amount is expended in the township alone. In the remaining
districts of the town, the expense is considerable. Other towns are
burdened in an equal or still greater proportion. Yet, notwithstanding
the amount of outlay, the effective work done is barely one-sixth part
of what would be necessary to keep the public streets in proper
order. In the district before referred to, they were a short time ago
distributed into the following classes, according to the frequency of
cleaning them:—Class A,—once a week; B,—once a fortnight; C,—
once a month. It may be safely asserted, that all these streets should
be swept, at least, six times oftener. The main thoroughfares, as well
as the back streets and confined courts, crowded with the poorer
part of the population, absolutely require cleaning out daily. But the
expense already incurred effectually prevents a more frequent
repetition of the process. The expensiveness of the present system,
in fact, renders it altogether inefficient; nor is there any chance of
material improvement in this important department of public police,
unaccompanied by a corresponding reduction in the rate of
expenditure.
According to the Kunctsblatt, a German painter, Edward Hansen,

of Basle, has been commissioned to prepare cartoons for the oil
paintings intended to decorate the church at Oscott, which Mr. Pugin
is about to build at the Earl of Shrewsbury’s expense. One of the
designs, “The Last Judgment,” is spoken of as exceedingly beautiful.
On the same authority, we learn that Thorwalsden has sustained a
loss by the wreck of a ship, bound from Leghorn to Hamburg. On
board were several of his works, most of which were saved, but were
completely spoiled by the sea-water; from which we infer that they
were plaster casts.
Gothic Architecture.
Westminster Hall Roof.

CHAPTER I.
We now beg to draw attention to what we consider will be found
the most important feature in this number, inasmuch as it is the
commencement of the task with which we have charged ourselves to
enter upon the investigation and elucidation of the character and
principles of Gothic Architecture.
We use this unhappy term, Gothic, for no other reason than that
as we address ourselves mainly to the workmen, and as the style of
architecture so designated (originally in opprobrium) has now and for
long obtained the appellation in a popular sense, we feel unwilling to
depart from it until a thoroughly correct epithet shall have been
devised and accepted amongst us; that we are justified in this
decision, or rather indecision, we think may be shewn by the various
opinions of parties who may be said to rank as the authorities on
such points. Mr. Pugin is anxious that it should be called “Pointed, or
Christian Architecture.” Mr. Whewell and others have lately been
pleading for a title which the prevalence of vertical lines and
principles of construction, as in contradistinction to the horizontal
character of Greek architecture, appear to them to justify; others
again have contended for the term “English Architecture.” Now,
without committing ourselves to an opinion of our own, we think
there is sufficient ground for hesitating as to the adoption of this or
that novelty, notwithstanding our strong objection to the inapt and
absurd term “Gothic.”
Our task will be formidable, as to the length of time it will occupy,
the pains-taking it will require, the expense it will entail upon us, and,
above all, the system with which it must be conducted. But what
good thing is to be accomplished without some one or more of all
these? We only hope to be cheered on by the approving smiles and
the patient co-operation of those for whom we undertake it.
And how do we commence this task, so as to give promise that a
system may be observed, without which the best efforts in other
respects are likely to fail? It will not do to enter upon it at random, or
without due preparation, both on our own part and that of our
readers. We shall, therefore, proceed to state our object in selecting
the illustration we have done as the heading of this paper.
Let the carpenters look to it, and let them look on it with pride—
nay, let them look on it as we have done, with reverence. Let them
remember that this was the work of great spirits of their department.
It is a master-piece, and we have chosen it on this account, as we
shall continue, for some weeks to come, to make choice of similar
master-pieces, in the masons’ department. Oh! we have such
glorious examples at our hands. And then, again, as to ornamental
brickwork, and brass and latten work, and that gorgeous coloured
glazing, and such mastery in the carvers’ and sculptors’ art; these
we choose, to fire the breasts of our readers. We would excite them
by such glowing description of the land of promise into which we
propose to lead them, that the future steps, however irksome or
laborious, may be trodden with a light and gladsome foot. For the
present, then, and as we have said, for weeks to come, we shall
select the instances of varied excellence in roofs, vaults, arching, in
traceried windows, doorways, screens, in elaborate specimens of
“bench carpentry,” such as stalls, pulpits, railings, tabernacle and
screen work, in monumental brasses and other memorials of
sepulture, in moulded and enriched brickwork; the encaustic and
coloured pavements, the staining in glass, and generally all such
matter in the province of the artificer as may be regarded with the
admiring eye of the discerning practitioner.
Borrowing a similitude from what we are otherwise bound to
deprecate, we would speak of these as the trophies of our
predecessors in campaigns of glory, bidding every good soldier in
this day of later, though of similar service, to burn with ardour until he
may have successfully emulated the doings of his ancestry.
Yes, every carpenter should feel proud of a calling which enrols
him in the ranks of a craft whose arms are emblazoned and charged
with insignia such as these; but we promise the same evidences of
distinction to every department of the building fraternity.
This Westminster-Hall roof, spanning over an area of 74 feet wide
and 270 feet in length, rearing its ridge to the height of 90 feet,

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Alloys and intermetallic compounds :

from modeling to engineering 1st

Coulson and Richardson’s Chemical Engineering, Fourth

Foundations in Biomaterials Engineering 1st Edition

Multiphysics Modeling with Application to Biomedical

Introduction to control engineering modeling analysis

Utilisation of Bioactive Compounds from Agricultural

Transportation Engineering Theory Practice and Modeling

Disease Mapping From Foundations to Multidimensional

Bioactive Compounds from Plant Origin Extraction

As I was first contacted by CRC Press with the invitation to propose a

Part 1: MODELING tECHNIQUES aND PrEDICtION

1.1 Computational thermodynamics: From Experiments 3

Part 2: rOLE OF MODELING ON tHE DESIGN OF aLLOYS

2.1 Metal-Ceramic Interactions in Brazing Ultra High 115

2.5 atomistic Modeling to Design Favoured Compositions 228

The properties of materials, and ultimately their application, are

variables such as temperature, pressure or composition. One of the first

that, despite recent developments in ab initio methods, the power of the

The experimental techniques that have and continue to be used in the

Phase Diagram Determination

Fig. 1: Cooling curve analysis of a simple binary alloy system.

Fig. 2: The DTA Curve.

a+y Lattice parameter :

Outer Jacket (T = const.) Thermometer

CD = corrected temperature rise ΔT

Fig. 4: Schematic of a simple calorimeter.

Other techniques are available, such as Isothermal Calorimetry, where

Reaction cell (T2)

Fig. 5: Heat-flow calorimeter set up as a drop calorimeter.

crucible in the reaction cell, it is possible to determine enthalpies of mixing

The high precision of this instrument, together with the versatility

Component activities—vapour pressure measurement

Fig. 6: Schematic of the Knudsen cell with the mass spectrometer.

cell during effusion it is possible to calculate the pressure of the effusing

Gibbs energies—electrochemical methods

Semi-empirical Approach to the Calculation of Phase Diagrams

for pure iron with respect to temperature and pressure is shown

way as the unary diagram shown above, using thermodynamic functions,

Modeling of the Gibbs Energy of the System

According to the Kunctsblatt, a German painter, Edward Hansen,

Westminster Hall Roof.

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