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Types of intermetallic phases

1. Describe the difference between daltonids, berthollids, and the

Kurnakov type using schematic phase diagrams!

Daltonides and berthollides: former designation for "stoichiometric" and "non-

stoichiometric" phases. Both can be completely ordered or (more or less) disordered.

Daltonide (after Dalton):

- Compounds composed of elements in fixed proportions ("stoichiometric").
- Composition ABx, usually crystallizes in a different structure than that of the
forming elements (A, B).
- Thermodynamically, a variation of the composition is possible, but this
range of existence is very narrow ("invariant phases")
-= Stroke or line phases
- Only a certain stoichiometric compound is stable (fixed stoichiometry)
- No solubility outside the stoichiometric ratio
- Very strong bond due to ordered structures 🡪 Brittle at low temperatures
- Ordered compound is stable up to the melting point
- Especially for covalent and ionic bonds
- Example: ASr with 1st and 2nd order transformations and independent phases,
stability depending on temperature and concentration, salts (NaCl), molecules
(H2O)
Berthollide (after Berthollet):
- Compounds in which the elements are not all present in constant
proportions
- 🡪 Berthollides have variable compositions ("non-stoichiometric"),
- They may be end-of-life or transitional phases.
- The phases are characterized by finite homogeneity ranges (and solubility
ranges), which in the case of the "final phases" contain the pure components.
As a rule, the phases have a variable, temperature-dependent extension.
- Phases have a (low) variable composition (phase width).
- At least one lattice point in the crystal structure is occupied by two or more
elements or is not fully occupied (degree of occupancy varies).
- Elements are not all present in constant proportions.
- Ordered alloy is stable up to melting point (critical T > Tm)
- Example: Cu-Zn with 1st and 2nd order transformations and independent
phases, stability depending on temperature and concentration; solid solutions,
glasses, alloys, polymers, ceramics (e.g.: lithium graphite C6Lix (x = 0 to 1) or
apatite Ca5(PO4)3X (X = F, Cl, OH)

Kurnakov type:
- (binary) compounds of elements in variable compositions
(stoichiometries)
- Transition between order and disorder is below the melting point
- Formation of the ordered structure at low temperatures from the disordered
solid solution (ordered structure: one type of atom surrounded by as many
atoms of the other type as possible).
- In AB composition (50-50) mostly krz, two krz- grids (partial grids) inserted
into each other.
- In the case of AB3 composition, mostly kfz of four sublattices inserted
into each other (one from A, three from B).
- No strong bonds between the atoms 🡪 Good formability
- Broad minimum of the G curve 🡪 ordered structure stable in
further concentration range
- Examples: Cu3Au, Ti3Al, Fe3Al
24. Describe the difference between daltonides, berthollides and the
Kurnakov type! What role do the chemical properties of the components
play?

Daltonide, Berthollide, Kurnakov phases: see question 1.

Role of chemical properties:

- Mixing enthalpy ΔHmix, critical temperature Tk or congruent melting
temperature Tm, sharpness (curvature) of G-curve ∂ G/∂x22 and
disorder energy increase: a) < b) < c).
- The width of the phase field decreases in the opposite direction.
- Incongruent phases of types b) or c) are caused by the competition of
"stronger" phases.
- The bond character is more often metallic for a) and b) and more often
ionocovalent for c). Van der Waals shares can be found everywhere.
56. What are the so-called Hume-Rothery phases characterized by? What is
the difference between daltonids and bertholids?

Daltonide vs. berthollide: see question 1.

Hume-Rothery Phases:
- Metallic bonds (in contrast to Zintl (ionic) and Grimm-Sommerfeld (covalent))
- Intermetallic phases
- Structures resemble brass
- Example of the influence of the valence electron concentration VEK (=
number of VE/number of atoms) on the structure of an alloy: if VE ratio
increases, higher-lying bands must be occupied 🡪 other structures become
energetically more favorable
- Characteristic: certain phase sequence with the concentration (e.g. kfz, krz,
complex, hdp) 🡪 Depending on the valence of the alloy partner, the valence
shell is filled faster or slower 🡪 determines the position of the solubility limit
in the phase diagram (higher valence 🡪 lower concentration)
- Ex.: Brass forms different structures depending on the ratio of Cu and Zn
VEK Structure Example
3:2 β (krz) CuZn, Cu3Al
21:13 γ (cubic EZ with 52 atoms) Cu5Zn8, Cu9Al4
21:14 ε (hdp) CuZn3, Cu3Sn

Phase diagram of brass.

65.what is the difference between daltonides and berthollides? Give the
definition of valence electron concentration and calculate it using a Hume-
Rothery phase as an example!

Daltonide vs. berthollide: see question 1.

valence electron concentration (see also question 56):

Number of valence electrons
VEK= Number of atoms
The ratios of Hume-Rothery phases are described by the valence electron ratio VEK
(valence electron concentration). As a rule, only s- and p-shells are considered.
Depending on the VEK value of the alloy partner, the valence shell is filled faster or
slower. The VEK value of the alloy partner determines the position of the solubility
limit in the phase diagram (higher value 🡪 lower concentration).

Example:
- Hume Rothery phase in β-brass (CuZn, krz):
VEC = (1-1 + 1-2) / 2 = 1.5
- γ-brass Cu5Zn8 (large EZ with 52 atoms):
VEK = (5-1 + 8-2) / 13 = 21/13 = 1.615.

What are the characteristics of the so-called Hume-Rothery phases? What is

the difference between daltonids and berthollids?

Identical to question 56.

73.describe the difference between daltonides, berthollides and the Kurnakov

type! What role do the chemical properties of the components play?

Identical to question 24.

4. what influence does the deviation from the stoichiometric atomic number
ratio have on the lattice site occupation of berthollides? Consider CoAl as an
example!

Berthollides form intermetallic phases with a fixed stoichiometric ratio.

In case of a deviation from the stoichiometric atomic number ratio, the atom of the
component in the superior number must take a place of the other atomic species in
the unit cell.
As a result, the superstructure (order) of the intermetallic phase is destroyed and the
lattice is formed due to the different atomic radii of components
distorted. In the case of a particularly large difference in atomic radii, partially
distorted solid solution phases are formed.
In the example of CoAl: Co atoms are somewhat heavier than Al atoms and therefore
require more space. In the hexagonal EZ of CoAl, the deviation from stoichiometry is
mainly achieved by vacancies. The deflection from the atomic position remains small
(< 0.008 Å).

12. In which alloy systems are Hume-Rothery phases observed? How can
one explain the "magic number ratios"?

See also question 56.

Hume-Rothery phases are observed in systems with metallic bonds whose structures
resemble that of brass. They possess the following properties:
- Alloys of the noble metal subgroup (Cu, Ag, Au), e.g. CuZn, AgZn, AuZn)
- Metallic bonds (dominance of weak covalent and ionic bonds)
- Characteristic phase sequence (kfz, krz, complex, hdp): Marginal solubility of
kfz, then actual phase with concentrations.
- Systematics: Composition - Structure - Group number
- VEK are idealized values
- Mechanically hard and brittle, the disordered phase is deformable
The ratios of Hume-Rothery phases are described by the valence electron ratio VEK
(valence electron concentration). As a rule, only s- and p-shells are considered.
Depending on the VEK value of the alloy partner, the valence shell is filled faster or
slower. The VEK value of the alloy partner determines the position of the solubility
limit in the phase diagram (higher value 🡪 lower concentration).
VEK Structure Example
3:2 β (krz) CuZn, Cu3Al
21:13 γ (cubic EZ with 52 atoms) Cu5Zn8, Cu9Al4
21:14 ε (hdp) CuZn3, Cu3Sn

33. Name the conditions under which intermetallic phases can be observed
with some probability! Compare these conditions with Hume-Rothery's rules
for the existence of solid solution regions!

Hume-Rothery rules for solid solutions:

- The atomic size difference should be < 15%, otherwise the distortion energy
will dominate and segregation will occur.
- The electronegativity difference should be present, but not too large. If it is too
large, ion crystals will form. If it is too small, segregation or topologically close-
packed phases may occur due to the atomic size difference.
- There should be a common predominant bond character, otherwise
segregation will occur. When the bands are full, the phase is changed.
- The lattice structure must be the same to allow complete miscibility.
At least it should be similar (🡪 extended edge solubilities).

Rules for the formation of intermetallic phases (almost identical):

- Formation of a new lattice structure with new lattice parameters (depending
on superstructure), need not be similar for starting materials
- Fixed stoichiometric atomic number ratio required
- External conditions must allow the formation of a superstructure
- concentration should be > 5 at.% (no marginal solubility ranges)
- Atomic size difference < 15
- High symmetry
- Simple stoichiometry
- Small number of elementary cells and grid types
- Similar grid structure
- Bonding character should have similarities (similar electron structure, influence
of band structure).

2. Explain the difference between Zintl phases and Grimm-

Sommerfeld phases and give an example for each!

Zintl phases:
- Intermetallic compounds between strongly electropositive alkali
/alkaline earth metals (left of Zintl line) and moderately electronegative elements
- Formation of polyanionic compounds
- Zintl line lies between main groups III and IV
- Based on differences in electronegativity: heterocoordination (medium to high
space filling), ordering on substitutional and interstitial sites, ionic bonding.
- Electron is attributed to the more electronegative element
- Example: Mg2Si, Ca2Si (structure: A2B)
- Strong ionic compounds (salt-like character)
- Normal valence/valence
- Noble gas configuration due to electron transfer in one or both partners
- High packing density due to stacking ABAB
- Mostly semiconductor or insulator
- Mechanically hard and brittle
- Lattice structure: kfz lattice of anions + cations on tetrahedral gaps

Grimm-Sommerfeld phases:
- Intermetallic phases with covalent character and an average of four
electrons per atom 🡪 tetrahedral coordination of both atoms
- Example: ZnS, SiC, GaAs
- Main group B with each other, Zn group also with S group
- Unfilled outer shells with similar electronegativity: semiconductors with low
space filling, tendency to covalent bonds (octet rule: stability with closed
electron shells).
- Medium strength covalent bonds
- Shared electrons fill the outer shell
- Main groups III + V and II + VI 🡪 average valence of 4
- Noble gas configuration aimed at (octet rule)
- Semiconductors in industrial use
- Mechanically hard and brittle
- Grid structure:
o Zinc blende (ZnS, cubic)
o Wurtzite (β-ZnS, hexagonal) 🡪 Stacking of tetrahedrally
coordinated planes
o kfz/hex lattice of smaller atoms + larger atoms in half of the
tetrahedral gaps
o SiC: polytypism (variable stacking order: cubic and hexagonal)
- Grimm-Sommerfeld rule: Binary compounds of elements of N-k. and N+k.
Main group have properties of the compounds of the N. main group

3. Explain the difference between Zintl phases and Grimm- Sommerfeld

phases and give an example for each! What influence do the dominant
binding ratios in these phases have on coordination and space filling?

Zintl vs. Grimm-Sommerfeld phases: see question 2.

Coordination and space fulfillment:

Coordination = nearest neighbors of the atom under consideration
Coordination number = number of nearest neighbors of the atom under
consideration.

Zintl phases Grimm-Sommerfeld Phases

Ex: Ba2Si, Ca2Si, Mg2Si Ex: ZnS, SiC, GaAs
- Ionic bonds - Covalent bonds
- Medium to high space filling - Low space filling
- Coordination is determined by - Coordination determined by
size (always heteropolar 🡪 bond number
heterocoordination ABAB). - Smaller atom forms kfz or hex
- Anions form kfz lattices, cations sit lattice, larger atom fills half of
on tetrahedral gaps (except for tetrahedron gaps (zinc-
NaTl structure) aperture, wurtzite)
21. What properties (crystallography, chemistry, mechanics, physics) do
Grimm-Sommerfeld phases possess? Give examples and possible
applications!

Properties of the Grimm-Sommerfeld phases:

- Intermetallic phases with covalent character and an average of four
electrons per atom 🡪 tetrahedral coordination of both atoms
- Main group B with each other, Zn group also with S group
- Unfilled outer shells with similar electronegativity: semiconductors with low
space filling, tendency to covalent bonds (octet rule: stability with closed
electron shells).
- Medium strength covalent bonds
- Shared electrons fill the outer shell
- Main groups III + V and II + VI 🡪 average valence of 4
- Noble gas configuration aimed at (octet rule)
- Semiconductors in industrial use
- Mechanically hard and brittle
- Grid structure:
o Zinc blende (ZnS, cubic)
o Wurtzite (β-ZnS, hexagonal) 🡪 Stacking of tetrahedrally
coordinated planes
o kfz/hex lattice of smaller atoms + larger atoms in half of the
tetrahedral gaps
o SiC: polytypism (variable stacking order: cubic and hexagonal)
- Grimm-Sommerfeld rule: Binary compounds of elements of N-k. and N+k.
Main group have properties of the compounds of the N. main group

Examples: ZnS, GaAs, InP, AlP, CdSe, CdTe, SiC

Applications:
- Semiconductors: LEDs, detectors, transistors
- Insulators
- Silicon carbide SiC: abrasives, heating elements for higher temperatures,
semiconductors (LED), photodiodes, electronics (bipolar transistors,
MISFET, MOSFET), Schottky diodes
- Indium phosphide InP: lasers, data communications, laser diodes,
LEDs, optoelectronics, photonic crystals
- Gallium arsenide GaAs: semiconductors, transistors (RF technology), lasers,
LEDs, laser diodes, solar cells
- Cadmium sulfide CdS, cadmium selenide CdSe: Pigments.
15. sketch the elementary cell of NiAl. What changes occur when the alloy
composition does not correspond to the stoichiometric atomic number ratio
(50:50) (Ni or Al excess) (lattice site occupation)? How can this be determined
experimentally?

See also questions 4, 15, 23, 28, 47, 61, 72, 82.

NiAl crystallizes in the B2 phase with a relatively broad state region (so-called
berthollides). However, the ideal crystal structure can only be formed at the
stoichiometric composition (50:50).

Elementary cell: (prototype CsCl)

- Two cubic primitive space lattices lying inside each other
- Strong order even at high temperatures

Elementary cell NiAl.

Changes in case of deviation of the alloy composition: If additional atoms are added
from one component, they have to sit on lattice sites of the other component. This
destroys the superstructure and distorts the lattice due to the different atomic radii of
the components.
In case of a large deviation of the radii, partially disordered solid solution phases are
formed.
- NiAl is stable for different concentrations (2 to 5 at.%) 🡪 no exact
stoichiometry required
- Deviation from stoichiometry: double occupation of lattice sites, release
of lattice sites or occupation of interstitial sites required
- Change of lattice constants 🡪 Order reduced 🡪 Formation of other phases 🡪
Change of properties (physical properties such as density, melting temperature,
thermal conductivity; mechanical properties such as ductility, yield strength,
creep resistance, ...)
- Strength minimum at 50:50 stoichiometry 🡪 Increase with deviation

Ni surplus:
- Ni atoms (Z = 28, r = 135 pm) are heavier and slightly larger than Al atoms
(Z = 13, r = 135 pm)
- Ni atoms occupy Al lattice sites 🡪 Antistructure atoms
- Yield strength increases (not as much as with Al excess)
- Occurrence of antistructure atoms 🡪 Density increases (ρNi > ρAl)
- Electrical resistance increases (minimum at 50:50 stoichiometry)

Al surplus:
- Al remains in his grid seat
- Structural voids in Ni areas
- Minimum yield strength is at 50:50 stoichiometry (due to solid solution
hardening) 🡪 Yield strength increases most with Al excess
- Formation of structural voids 🡪 Density decreases
- Electrical resistance increases (minimum at 50:50 stoichiometry)

Experimental determination:
- Superstructure visible in TEM
- Study of long-range order with diffraction: Superstructure reflections of NiAl 🡪
Change/distortion when composition is changed

Superstructure reflections of NiAl.

General considerations

26. What structures are observed when a) the octahedron sites and b) the
tetrahedron sites are completely filled with smaller atoms in the face-centered
cubic lattice? How does the space filling depend on the size ratio of the atoms?

In the kfz, there is one octahedral and two tetrahedral sites per lattice atom,
corresponding to four and eight sites per unit cell, respectively 🡪 interstitial
structures. Optimal space filling is achieved when the interstitial atoms touch all
their neighbors without distorting the lattice (no excessive deflection of the
neighboring atoms).
a) All octahedral sites occupied: Formation of B1 structures (NaCl structures) with
an optimal atomic radius ratio of rA/rB ≈ 2.42 and a space filling of 79.3%.
Examples: ArSn, BaTe, TiC, ZrN.
b) All tetrahedral sites occupied: Formation of C1 structures (CaF2 structures)
with an optimal atomic radius ratio of rA/rB ≈ 4.4 and a space filling of 75.7%.
Examples: Al2An, Mg2Si, TiH2.

Octahedron and tetrahedron interstitials.

Dependence of the space filling on the size ratio of the atoms: The better the atoms
fit into the gaps, the higher the space filling and packing density. With larger radii,
the lattice is disturbed.

Space filling as a function of atomic size ratio.

38. Assign the appropriate terms and categories to each of the crystal
structures shown:
Prototype: CaF2, Cu3Au, CsCl, NaCl
Example: CuZn, Mg2Si, Ni3Al, TiN
Structural Report: B1, B2, C1, L12
Pearson:cF8, cF12, cP2, cP4.

Structural Report Pearson symbol Prototype Example

B1 cF8 (motor vehicle) NaCl TiN, TiC
B2 cP2 (krz) CsCl CuZn
C1 cF12 (motor CaF2 Mg2Si
vehicle)
L12 cP4 (motor vehicle) Cu3Au Ni3Al

39. What symmetry elements are used to describe crystal structures?

Crystal classes: Summarize the gross aspects of symmetry (Ex: cubic, tetragonal,
orthorhombic, hexagonal, etc.).

Symmetry:
- Elementary cells have symmetry elements for each grid point and for the
arrangement of points in space (🡪 point groups and space groups).
- Symmetry elements: reproduce the atom positions, patterns and other
Symmetry elements to equivalent positions of the unit cell, e.g.: Translation,
rotation, inversion, combinations, ...
- Operators of symmetry elements may only occupy positions that are compatible
with the conditions of the respective mathematical group.
- Symmetry elements of the point groups:
o Rotations around an axis to 1, 2, 3, 4, 6 equivalent positions

o Axes generate entire mesh layers from atomic positions and their
own positions
o Rotational axes with count 5, 7 or higher: not compatible with
translation
o Perpendicular to the image: counts 1, 2, 3, 4, (5,) 6; in the plane: 1 and 2
 o Count 5: needs two motifs (tiles) and becomes aperiodic
(quasicrystals)
o Inversion: at a point, at inversion axes, or at mirror planes (parallel or
perpendicular).

o Point groups:
▪ Herrmann-Mauguin symbols: Description of symmetry from
diffraction images
▪ Schoenflies symbols: Description of the symmetry of the
orbitals (electron states).
o Room groups:
▪ All point symmetries contain
▪ Screw axes
▪ Sliding mirror levels
▪ Totality of all atomic positions and arrangements of the operators
▪ Pearson symbols: Short characterization (simplified) 🡪 Lattice,
centering, atoms per EZ (Ex. system symbol: h = hexagonal, c
= cubic, Ex. lattice symbol: P = primitive, C = side face
centered).
- Nomenclature: many types of sorting possible: Pearson, prototype,
structural report, spatial group.
- Crystal structure:
o Grid built from identical cells with integer translations
o Crystal classes: summarize the gross aspects of symmetry.
Sketch two (different) crystal structures of intermetallic phases of your choice
and explain the ratio of A and B atoms! Give examples for the occurrence of
these phases in each case!

B2 L12

A:B = 1:1 A:B = 1:3

Atomic species A (purple, center): 1 Atomic type A (black, corners): 8 times

times 1 therefore 1 per EZ 1/8 therefore 1 per EZ
Atomic type B (blue, corners): 8 times 1/8 Atomic type B (white, surfaces): 6 times
so 1 per EZ 1/2
so 3 per EZ
Examples: CsCl, NiAl, CuZn Examples: Cu3Au, Ni3Al

57. Define the term intermetallic phases. Sketch two crystal structures of
intermetallic phases and use them to explain the ratio of A and B atoms. Give
examples of the occurrence of these phases in each case.

Sketch crystal structures: see question 20.

Intermetallic phase: In phase diagrams, intermetallic phases are solid states that are
not continuations of elemental states (edge solubilities). They correspond to chemical
compounds, but need not obey fixed valences or special orders. Some intermetallic
phases do not have traditional crystal lattices (quasicrystals, amorphous metals).
The lattice structures of the intermetallic phase differ from those of the components 🡪
superstructures. The lattice bond is a mixed form of predominantly metallic bonds
with covalent or ionic bonds.
As a result, intermetallic phases have special properties (physical and mechanical).
Intermetallic phases can have a stoichiometric composition or form homogeneity
regions in the phase diagram.
Important intermetallic phases are for example: Laves phases, Heusler phases, Zintl
phases, Hume-Rothery phases.
Give a definition for intermetallic phases. Sketch the crystal structure of the L12
phase and use it to show the ratio of A and B atoms. Give at least two
examples of the occurrence of this phase.

Question 66 and 74 are the same question. Question 66 additionally asks for the shortest
complete Burgers vector (see below).

Definition of intermetallic phases: see question 57.

Crystal structure of the L12 phase:

Atomic type A (black, corners): 8 times 1/8 i.e. 1 per EZ
Atomic type B (white, faces): 6 times 1/2 i.e. 3 per EZ
🡺 Ratio A:B = 1:3 Examples:
Cu3Au, Ni3Al.

Crystal structure of the L12 phase.

The shortest complete Burgers vector in L12 is [ 1 1 ̅0 ]. Actually, in kfz crystals the
shortest Burgers vector is ½ [ 1 1 ̅0 ], however, in L12 this shifts an atom to a wrong
position due to the two atom species. In order to shift the atoms to the correct lattice
sites, the "double" Burgers vector is
½ [ 1 1 ̅0 ] is the shortest complete Burgers vector.

Sketch the crystal structure of NiAl and show the ratio of A and B atoms. Draw
the basically possible complete Burgers vectors and give an example of
possible splittings.

Question 53 and 77 are the same question.

Crystal structure of the B2 phase (e.g. NiAl): Atomic

species A (purple, center): 1 times 1 i.e. 1 per EZ
atomic species B (blue, corners): 8 times 1/8
therefore 1 per EZ
🡺 Ratio A:B = 1:1 Examples:
CsCl, NiAl, CuZn
 Crystal structure of the B2 phase.

Burgers vectors: along the most densely packed directions, i.e. in B2 [111]. In normal
krz crystals the Burgers vector is ½ [111], but due to the two atomic species it is [111]
in B2, otherwise the atoms are shifted to inappropriate lattice sites.
Draw in: the directions [111] are the space diagonals (yellow in the figure).

Possible splits of the Burgers vector in B2 are:

[100]+[010]+[001]↔[111]
[110]+[001]↔[111]

Remote Order

25. In superstructure formation, how is the long-range order parameter

defined? How is it related to thermodynamics and kinetics? How can it be
measured?

Superstructure formation when the following rules are satisfied:

- Mean attractive WW with similar atomic size
- Or distortion reduction with slightly different size
- Basically compatibility with host grid required.
Description of the degree of order via "quasichemical models", description of the
superstructure structure in different ways.

Remote order parameters s:

pA-xA pB-xB
s= =
1-xA 1-xB
With xA, xB: mole fractions and pA, pB: probabilities for correct occupation of the
subgrids.
s = 0: statistical distribution
s = 1: perfect order
0 < s < 1: partial order Note: s < 0
for wrong selection
of the subgrids
In the Bragg-Williams model, the internal energy U,
the entropy S, and the free energy F are plotted
versus the long-range order parameter s.

If an alloy with two cubic primitive sublattices a and b

contains N atoms of type A and N atoms of type B, the
long-range order parameter s is defined such that the
number of A atoms in the a lattice is
½(1+s)N and the number of A atoms in the b lattice is
½(1-s)N. Thus, if s = ± 1, the order is perfect and
each sublattice contains only one type of atom
(mixing entropy S = 0). If s = 0, then each sublattice
contains the same number of atoms of types A and B
and no long-range order exists (mixing entropy S =
2NkBln2).

Measurement of the remote order parameter:

- X-ray diffraction: Superstructure peak (see question 13 and 40)
- Calorimetry: specific heat capacity (see question 40)
- Specific resistance (see questions 34 and 40).

13. How to describe the degree of long-range order in the transition from solid
solution to ordered structure in β-brass? How and why does the remote
ordering change the diffraction pattern? What statement does it allow about
the degree of remote order?

The degree of remote order is described by the remote order parameter s:

pA-xA pB-xB
s= =
1-xA 1-xB
With xA, xB: mole fractions and pA, pB: probabilities for correct occupation of the
subgrids.
s = 0: statistical distribution
s = 1: perfect order
0 < s < 1: partial order
Note: s < 0 with wrong choice of subgrids
In principle, the parameter describes how many atoms, viewed globally, are present on the
are in the "right place".
(See also question 25)

The transition from β- to β'-brass is a 2nd order phase transformation (ordered, at TU

= 468°C, β'-brass is krz in CsCl structure).
Thermodynamically, an order temperature is set at which order collapses. The
disruption of order generally occurs through thermal activation.
Diffraction: The superstructure causes additional diffraction reflections
(superstructure reflections), which can be described with atomic form factor and
structure factor.
Superstructure reflex = slight change in scattering density distribution due to n-fold
multiplication of translation periods of the original crystal structure. (hkl)- indices of
superstructure reflexes are n-th fraction of main structure reflexes (depending on
direction). The intensity of the superstructure reflections is given by the deviation from
the averaged scattering density distribution.

Determination of the degree of order:

- 0. approximation: relative peak height of the diffraction reflex
- 1. approximation: relative area under the superstructure peaks
- Better approximation: incorporate order parameters into EZ occupation
scheme and fit to dataset.

34. How does the order setting in the Cu-Au system show up in the course
of the electrical resistance? Give reasons for the behavior!

The electrical resistance scales reciprocally to the mean free path length of the
electrons or their coherence length.
A perfect, very large crystal has a vanishingly small residual resistance at T = 0 K,
even with a superstructure (note: the perfect crystal has band gaps at 0 K (Bragg
reflections at Brillouin zones, but no band gaps) 🡪 the residual resistance at 0 K
stems from the finite defect density, i.e., the deviation from the ideal lattice and from
its superstructure). Scattering occurs due to imperfections:
- Static scattering centers: disordered impurity atoms, vacancies,
ZGA, dislocations, interfaces 🡪 generate residual resistance
- Dynamic defects (T > 0 K): phonons and shielding from other
Electrons 🡪 generate temperature curve. From approx. 20 % of the Debye
temperature, the resistance curve is almost linear and determined by the
lattice vibrations (Note: Normalize to Debye temperature and resistance there,
so that influences of atomic mass, elasticity and electron structure disappear).
- Static and dynamic: localized magnetic moments.
The proportions of defects (residual resistance) and phonons overlap almost without
mutual interference 🡪 Matthiessen's rule. The residual resistance at 4.2 K
characterizes the purity (in the solid solution monotonically with the concentration,
individually for the type of atoms).
Disordered solid solutions have a parabolic shape. The concentrations at which order
exists are at the minima. Coherence distortions around precipitates increase the
resistivity partly above the value of the solid solution.

Matthiessen's rule is valid for Au in Cu as well as for Cu in Au. Provided there is no

close order with distortions, the parabola is symmetrical (parabola x(1-x)
🡪 Description of the resistance of binary systems according to Nordheim). At
Quenching superimposes the parabola with the Cu-Au interpolation (T-
dependence). The slope at the edge and the vertex height of the parabola depend
on the atomic species.
If the order is (partially) set), minima occur when the coherence length of the order
domains is larger than the thermal scattering length. For the composition Au3Cu, an
increase of the curve occurs: the order setting starts, the domains are small and
many antiphase boundaries are present. Due to the coherent interfaces and
deviations of the lattice constants (lattice misfit) distortions occur.

General temperature effect for Cu-Au alloys: The slope of the temperature curve of
the resistance is approximately the same for the perfect order and for the statistical
solid solution. The ordinate shift corresponds to the residual resistance (difference
between Nordheim and linear interpolation).
When the disordered solid solution cools below T0, the resistance initially follows the
order setting (order is established 🡪 electrons are scattered less frequently 🡪 greater
mean free path length 🡪 resistance decreases). With decreasing temperature,
however, it deviates from this. Since the order setting takes a lot of time, it freezes
during a continuous measurement as soon as the cooling becomes faster than the
mobility of the atoms. In the case of ideal cooling (very slow, unrealistic for
measurement), the ideal R(s) curve overlaps additively with the temperature curve
for s = 1.
In addition to individual diffusion jumps, long-range transport must be considered
when breaking down segregations or antiphase boundaries. Diffusion (freezing)
depends on the cooling rate dT/dt. If this is slower, the temperature is lower.
According to Matthiessen, the temperature coefficient is almost independent of the
temperature.
Plastic deformation destroys the order and new nuclei are formed (here: AuCu3,
relative resistivity at RT). The "quenched" curve represents the disordered crystal,
the
"tempered" the ordered. With plastic deformation,
there is a reduction in long-range order due to
antiphase boundaries. With moderate deformation
(after quenching), the resistance increases due to the
near order and distortions. At large deformation, a
solid solution is present. At extreme deformation,
dynamic deformation occurs and both order and
distortion occur (depends on history and exact path).

40. How does the phase transformation from the ordered L12 structure to
the disordered solid solution in Cu75 Au25 make itself felt when calorimetry,
X-ray diffraction, and electrical resistivity are used to investigate it?

X-ray diffraction (see question 13): The superstructure causes additional diffraction
reflections (superstructure reflections), which can be described with atomic shape
factor and structure factor.
Superstructure reflex = slight change in scattering density distribution due to n-fold
multiplication of translation periods of the original crystal structure. (hkl)- indices of
superstructure reflexes are n-th fraction of main structure reflexes (depending on
direction). The intensity of the superstructure reflections is given by the deviation from
the averaged scattering density distribution.
Determination of the degree of order:
- 0. approximation: relative peak height of the diffraction reflex
- 1. approximation: relative area under the superstructure peaks
- Better approximation: incorporate order parameters into EZ occupation
scheme and fit to dataset.

Electrical resistivity (see question 34): The electrical resistivity scales reciprocally with
the mean free path length of the electrons. Disordered solid solutions exhibit a
parabolic shape (x(1-x)), minima occur at concentrations where the solid solution is
ordered. Coherence distortions around precipitates increase the value of the
resistance so that it is partially above the value for the solid solution.

Calorimetry: The heat flow is measured when the temperature changes (change in
heat content). Either ΔQ/ΔT is scanned or cP is measured stepwise.
The curve has a continuous lambda shape,
the degree of order decreases steadily. The
base line corresponds to the specific heat of
the disordered solid solution. Above the base
at T > T0 the effect of the near order occurs.
The peak occurs at the phase transition (e.g.
2nd order transition for β-brass).
The energy required to destroy the order
corresponds in amount and course to the
energy gain when the order is set.

Cu75Zn25 (corresponding to β-brass) has a 2nd order phase transition. Above T0 there is
no long-range order. Below T0, s increases continuously from 0 (at T0) to 1 (at T = 0).
The destruction of the order costs energy (order energy). A lambda-shaped
component from dUconfig/dT is superimposed on the specific heat.

81: How do you describe the degree of long-range order in the transition from
solid solution to ordered structure? Use the example of Cu-Zn in the mixing
ratio 50:50!

The degree of remote order is described by the remote order parameter s:

pA-xA pB-xB
s= =
1-xA 1-xB
With xA, xB: mole fractions and pA, pB: probabilities for correct occupation of the
subgrids.
s = 0: statistical distribution
s = 1: perfect order
0 < s < 1: partial order
Note: s < 0 with wrong choice of subgrids
In principle, the parameter describes how many atoms, viewed globally, are present on the
are in the "right place".
(See also question 25)

In the case of β-brass, there is a 2nd order phase transition. Above T0 there is no
long-range order. Below T0, s increases continuously from 0 (at T0) to 1 (at T = 0).
The destruction of the order costs
energy (order energy). A lambda-shaped
component from dUconfig/dT is
superimposed on the specific heat.

The remote order parameter can be

determined by X-ray diffraction,
calorimetry or by electrical resistance
(see question 40).
Topologically close-packed phases, Laves phases, quasicrystals

27. What are "topologically close-packed phases," what properties do

they possess, and what causes them?

Topologically close-packed phases (= Frank-Kasper phases): intermetallic

compounds with complex crystallographic structure and special mechanical
properties. Some TCP phases are quasicrystals because their structure is a
combination of periodic and aperiodic. The structure of TCPP is often not
stoichiometric.

Features:
- Crystallographically densely packed planes: Consequence of symmetry
and coordination number 🡪 the higher the packing density the more stable
the crystal
- Atomic positions between the crystallographic planes
- Complex crystal structure: combination of primitive partial lattices (octahedron
+ tetrahedron), e.g. kfz and hdp have one octahedron and two tetrahedron
sites per lattice site, krz has three octahedron and six tetrahedron sites
- High symmetry properties:
o one lattice site: up to 48 equivalent atomic positions
o Configuration entropy increases with symmetry
o High symmetry stable at high temperatures
- High coordination numbers:
o Metal bond unsaturated
o Binding strength grows with number of neighbors
o dominated by atoms with high coordination ("thick" atoms with
influence of VEZ)
- Very large elementary cells
- Metallic bond character
- High mass density: local packing density up to 80 %, density correlates with
heat of formation and phase stability
- Problem of different atomic size: solid solutions destabilized by
dislocation energy, difference of electronegativity often missing for
superstructures 🡪 distorted tetrahedra allow optimal bond lengths without
gaps (tetrahedra around ZGP are well-suited).

Examples:
- A15 phases, e.g. Nb3Sn: polarizable with reversed spin 🡪 Superconductor
- Laves phases
- σ-, µ- M-, P- and R-phases

Applications: High temperature structure, superconductivity

41. What are Laves phases? Give the atomic radius ratio and the
proportion of A and B atoms. Which structural variants occur?

Questions 41, 60 and 80 are the same question.

Laves phases: topologically close-packed intermetallic phases with defined composition.

Structure: hexagonal C14 or C36, cubic C15 (depending on metals and temperature).
Cause: optimal packing of spheres of different sizes.
Composition: AB2 (atomic number ratio 1:2) with radius ratio ideally rA/rB = 1.225 (there
are also deviations, e.g. KNa2 with ratio 1.25), on the A- sites (CN = 16) diamond type
(cubic or hex like wurtzite), on the B- sites (CN = 12) tetrahedral assemblies on the
tetrahedral sites unoccupied in diamond. Properties:
- hard and brittle
- not plastically deformable at RT
- Almost perfect electrical conductivity
- purely metallic bond
Examples:
- MgZn2 (C14, hex)
- MgCu2 (C15, cub)
- MgNi2 (C36, double hex)

- Main directions with CN = 16 form skeletons in <111>-direction (C15) and in

<0001>-direction (C14, C36) by stacking layer packages as (111) or (0001)
planes.
- Tetrahedron networks stacked in equal directions with interpenetration (main
directions reach through hexagonal gaps of Kagomé networks of
tetrahedra).
48.what is special about quasicrystals? How can quasicrystalline structures be
described? If possible, show this using the example of a one-dimensional
quasiperiodic structure.

Quasicrystals: topologically densely packed phases with an ordered but aperiodic

structure. The atoms (or molecules) have a locally regular structure, but globally this
is aperiodic, because each cell is surrounded by a different pattern. Incompatible
symmetries are integrated by adapted assembly.
The coordination polyhedra resemble those of crystals, but there is only a deterministic long-
range order. The diffraction reflections are sharp.

Description: The aperiodic pattern cannot be reproduced by parallel displacement

(thus different from the crystal). It can be generated by projecting the points in the
six-dimensional space onto the three-dimensional subspace. The unit cell is an
icosahedron.
Compared to the crystal, "forbidden" counts appear (5, 8, 10 or 12). The reciprocal
space is densely occupied with reflections. By "zooming in", more and more fainter
points appear (inflation symmetry), which are self-similar by a factor of τ3.

Example: A quasicrystal which can be described on the basis of an icosahedron

vector basis is overdetermined in 3D, but cubically primitive in 6D. The geometry
(angles and projections) can be represented by the equilateral pentagon.
A quasiperiodic pattern arises when any point of the 6D space that is within a
certain distance of the 3D subspace is projected onto the subspace and the angle
represents an irrational number τ , such as the golden ratio, then a quasiperiodic
pattern arises. This means that the locations of the centers of symmetry have
irrational coordinates.
The 3D projection of the 6D periodicity is an aperiodic Fibonacci sequence.

The quasiperiodic pattern can be seen in the scanning tunneling

microscope. A quasicrystal always has a cut surface that shows the
pattern of Penrose parquetization.

From left to right: icosahedron, projection (pentagon),

aperiodic Fibonacci series, Penrose pattern.
92. Describe at least three engineering applications of topologically close-
packed phases.

Topologically close-packed phases exhibit high crystal symmetry and a high

coordination number. It follows that the packing density is high.
They are mainly used for high temperature applications and as superconductors.
- A15 phases have the chemical formula A3B (A: transition metal, B: any) and the
structure type Cr3Si. They are mostly superconducting up to about 20 K and
several 10 T, they are classical type II superconductors. Example: Niobium
germanium Nb3 Ge is superconducting up to 23.2 K and is used in
superconducting
Quantum interference units used.
- Laves phases (see question 41) exhibit high high-temperature strength and
have a purely metallic bond, resulting in almost perfect electrical conductivity.
Examples are Terfenol (TbFe2 ), which is used as a sensor or actuator in
magnetostriction, MoFe2 for precipitation hardening
or MgNi2 as hydride storage. CeFe2 , SmCo2 and other compounds are used
as hard magnetic materials (permanent magnets).
- σ-phases are usually undesirable due to their high brittleness.
Anisotropy, lattice error, Burgers vector

14. What are antiphase boundaries? Where do they occur and how can
they arise? Describe the difference to the other areal defects!

Questions 14, 51 and 78 are the same question.

Antiphase boundaries (planar crystal structure defects): Boundaries where two

differently ordered domains meet (both domains are perfectly but differently ordered
in terms of partial lattice). Then the long-range order is destroyed (nonsensical result
for the long-range order parameter s), although the environment is ordered and the
different sublattices are occupied by the same atomic species. The two crystal
regions are shifted against each other by half a lattice translation if the order is the
same.

This can occur, for example, when nucleation

begins in different regions during the transition
from the disordered to the ordered state, with the
choice of sublattices being random and therefore
different. If these differently ordered regions grow
together, the partial lattice occupation changes
abruptly at the interfaces. These interfaces are
called antiphase boundaries, and the perfectly but
sublattice differently ordered crystal regions are
called domains. They can be visualized in the
TEM. [Gottstein]
Antiphase boundaries exist in different planes in the superstructure crystal. They
are also formed during plastic deformation (dislocation slip). The antiphase domain
corresponds to the coherence length in scattering phenomena.
Differences from other areal defects:
- APBs appear only in ordered structures (heterocoordinated)
- Energy: SISF < APB < CSF
- Differences to grain boundaries: Grain boundaries separate two grains of a
crystal, i.e. two regions with different spatial orientation of the lattice and
possibly also different chemical composition (in APB, however, only the long-
range order parameter differs).
- Difference from twin boundaries: Twin boundaries separate the two parts of
a crystal twin that have the same crystal structure and chemical
composition.
- Difference from SISF: SISF largely preserve the near order,
transform the fundamental lattice (e.g., fcc 🡪 hcp), and do not
generate antistructure atoms.
- Difference from CSF: CSF correspond to "ordinary" stacking faults, they
transform the basic lattice and generate antistructure atoms.

22.How do antiphase boundaries, complex stacking faults and structurally

intrinsic stacking faults (e.g. in AuCu3 ) differ?

Antiphase limits Complex stacking errors Structural intrinsic

stacking fault
- appear only in - "common" - equivalent close order
ordered structures stacking errors largely preserved
- same crystal lattice - destroy the - Transformation of the
on both sides symmetry of the grid base grid (fcc 🡪 hdp)
- Remote order destroyed - transform base grid - no antistructure atoms
- Displacement by ½ (fcc 🡪 hdp) generates
lattice site: on both - generate - produce energetically
sides the atoms have Antistructure atoms more favorable twins
an "unsuitable" - create twins with - Cause: Super
neighbor disturbed superstructure Shockleys
- Periodicity is present (energetically
- Cause: coalescence unfavorable)
of partial areas or - Cause: Complex
plastic deformation Shockleys
42. Explain the various types of complete and partial dislocations that can
occur in Ni3Al! Which surface defects are caused by the incomplete
dislocations?

Question 42 and 83 are the same question.

Ni3Al has the structure L12. The following dislocation types (complete and partial) can
occur:
- Complete dislocation: lattice invariant; connect equivalent points; leave
base lattice and superstructure intact; translation period.
- Partial dislocations: are incomplete, thus lattice-variant either for basic
lattice or for superstructure or for both
- Super substitutions: are complete in the ordered crystal
- Superpartials: were complete in disordered solid solution, are incomplete
(too short) in ordered state.
- Complex Shockley: in disordered solid solution, normal Shockley partial
dislocations; convert kfz and hdp into each other; in superstructure, they
also disrupt the superstructure itself
- Super-Shockley: special combination of two Shockley partial dislocations that
still convert kfz and hdp into each other, but now also produce two
equivalent superstructure regions (e.g. Ni3Al (cubic) and Ni3Sn (hex)).

Surface defects due to incomplete dislocations:

- Partial dislocations can create surface defects due to sliding
- Incomplete dislocations can create antiphase boundaries
- Two incomplete Shockley dislocations can cause stacking faults (SISF or
CSF), transforming both the lattice from kfz to hdp and creating
superstructures
- Partial dislocation networks can also form twins and martensitic
cause phase transformations.
35. Using a small section of a plane square lattice occupied in
heterocoordination in composition AB, show how two step dislocations create
an antiphase boundary! What determines the distance between the
dislocations?

Antiphase boundaries can be generated by superpartial dislocations. These are

complete in the disordered solid solution, but incomplete in the ordered one, because
they are too short.
Ordered particles (e.g. from the phase Ni3Al) can be cut by dislocation lines. This
destroys the order and creates an antiphase boundary.

The spacing of the dislocations is determined by the energy γ of the surface defect. If
it is very large (energetically "expensive" dislocation splitting), only narrow antiphase
boundaries form (narrow bands in the TEM). Energetically more favorable dislocation
splittings appear as broad bands in the TEM.
The balance of forces results in:
μ ∙ b2
γ=
2π∙r
The total energy decreases due to the splitting.

In classical kfz crystals, dislocations have Burgers vector ½ [ 1 1 ̅0 ] and the

displacement of an atom by this Burgers vector results in its return to a lattice site
where it belongs. However, in phase L12, for example, an atom would be shifted to an
inappropriate lattice site. This would increase the potential energy of the system.
The crystal counteracts the shift in the form of an antiphase boundary.

5. show on the elementary cell of Ni3 Al the conventional slip plane and the
splitting possibilities of a super dislocation!

Question 5 and 16 are the same question.

Ni3Al is
kfz, the slip (at moderate temperatures) there is practically only in the plane
(111). The Burgers vector is movable only in the direction [111].