Unit 1.

Examples of “DO”s for Unit 1. On an exam, these would be examples of either 3 or 5 point problems. The
pasted solutions come from Solution manual, and I have not expressly checked each problem for correctness. If
you see a problem with a solution, please email me.

I am sorry for the formatting of the document. Pasting in the solutions made it have a lot of open spaces around
the pasted solutions that will not close gaps.

Chapter 1.
Examine materials use through history and compare to progress of humankind using the four components of
materials science.
Early humans exhibited traits of materials selection processes, and materials science, in that they tried to select
and improve materials for use as tools, clothing or storage. They understood the property-processing, and
property-performance relationship. As technology progressed, humans were better able to understand the
structure relationship to properties, performance and processing.

List six different property classifications of materials that determine their applicability.
(This is the graphic organizer we did in class for chapter 1)

Cite four components that are involved in the design, production, and utilization of materials, and briefly
describe the interrelationship among their components.
This is the materials tetrahedron we have been working through in class)

Cite three criteria that are important in a materials selection process.

This is any three criteria from (use/purpose, constraints, costs, processing)

List three primary classifications of solid materials, and then cite the distinctive chemical feature of each.
Three main categories are metals, ceramics and polymers (fourth is composites). See section 1.4 in 3rd ED to see
chemical features. (Think Bonding, and electrons)

Note the two types of advanced materials, and cite distinctive features.
See section 1.7 in 3rd ED to learn about semiconductors(electrical properties between metals and ceramics,
electrically sensitive to impurities and doping) and biomaterials (materials that are compatible with human
systems, replace natural body parts, can be metals, ceramics, polymers or composites).

Define a “smart materials” system

A smart materials system responds to some stimulus from its environment. For example, windows which darken
when incident light reaches a certain value. (see section1,5 3rd ED)

Explain the concept of nanotechnology as it relates to materials.

Nanotechnology is materials on the nanoscale, this is focused on the structure-property. Or structure-
performance level.

Assess a material for proposed or actual use in a modern application of materials. (Assignment 1)
This is your assignment one. Know the translation process. Be able to read a materials selection chart for
desired properties.

Chapter 2
Name two atomic models cited in the chapter and note differences between them.
(see section 2.3 3rd ED). Two early models were the Bohr model of the atom, and the quantum mechanical
model. The difference in the model is mainly in the depiction of the electron levels, and electron probability in
the level. Bohr model has the electron pinned to a circular orbital a discrete distance from the nucleus. The QM
model allows for this, but the electron cloud is a probability mapping of where the electron would reside at its
lowest energy state from the nucleus. The cloud is represented as a fuzzy 3-D density of states.
See
http://www.teachersdomain.org/asset/lsps07_int_theatom/

Describe the importance quantum-mechanical principles that relate to electron energies.

See section 2.3 in 3rd ED. Here key concepts include – how the Bohr model described the position and energy
of the electron for hydrogen, and how this helped develop QM with support from the wave-mechanical model,
the Heisenberg Uncertainty Principle. Other key concept includes how Quantum numbers, n, l, m, s describe the
size, shape, and spatial orientation of an electron’s probability density. Each electron has a unique quantum
number that describes it.

Schematically plot attractive, repulsive and net energies versus interatomic separation distances for two atoms
or ions. Be able to note on this plot the equilibrium separation and bonding energy.(Draw the Lennard-Jones
potential for two hydrogen atoms.

From http://www.csb.yale.edu/userguides/datamanip/autodock/html/Using_AutoDock_305.a.html

The pairwise potential energy, V(r) , between two non-bonded atoms can be expressed as a function of
internuclear separation, r , as follows,

Graphically, if reqm is the equilibrium internuclear separation , and e is the well depth at reqm, then:

The exponential, repulsive, exchange energy is often approximated thus,

Hence pairwise-atomic interaction energies can be approximated using the following general equation,

where m and n are integers, and C n and C m are constants whose values depend on the depth of the energy well
and the equilibrium separation of the two atoms' nuclei. Typically the 12-6 Lennard-Jones parameters ( n =12,
m =6) are used to model the Van der Waals' forces 1 experienced between two instantaneous dipoles.

See also http://alcheme.tamu.edu/?page_id=683

Describe ionic, covalent, metallic, hydrogen, and van der Waals bonds. Note which materials exhibit each of
these bonding types.

Material Covalent Metallic Ionic van der Waals dipole

(hydrogen)
Metal X
Ceramic X X X (small extent) X
Polymer X X X (some)
Composite X(some) X(some) X(some) X(some) X (some)

Predict character and properties of atoms and ions, based on periodic table, or by electron configuration.
Calculate bonding forces and energies of two atoms, or ions.
Relate atomic models to current quantum mechanical understanding of atomic structure.

(see chapter 2)

Explain, using examples, how primary and secondary bonds are present in materials and how they affect
bonding energy. Explain, using examples how valence electrons play a role in bonding. Describe bonding
mechanisms for primary and secondary bonds.
Taking a ceramic primarily ionic material magnesium oxide, MgO, and a polymer precursor ethylene C2H6
The primary bonds are the ionic or covalent single bonds in the material. For MgO, the bond is ionic which
involves a transfer of an electron, and requires a lot of energy to break the bond. In C2H6, the primary bond is a
double bond, in this case, there are secondary bonds involved, hydrogen bonds, as van der Waals forces, and
there is also a slight dipole involved owing to carbon pulling the hydrogen towards its nucleus. These are weak
bonds, compared to the primary double bond between the carbon atoms. Bonding occurs between the valence
electrons in primary bonds, but are due to weak interactions in secondary bonds.

For MgO – Mg has electron configuration 1s22s22p63s2. Its outermost(valence) orbital is 3 which holds two
electrons in the s subshell. The Lewis Dot structure is Mg:
Oxygen has electron configuration 1s22s22p4. Its outermost shell is 2, which holds two electrons in the s and 4
in the p for a total of six electrons in the valence shell. Its Lewis Dot structure is O::: (imagine them on each
side of the O)
Since O has six electrons, it only “needs” two more to form a stable octet (8 electrons). By bonding with Mg, it
gains these two electrons. Because electrons are transferred, the Mg becomes a +2 ion, and O becomes a -2 ion.

Chapter 3
Describe the difference in atomic/molecular structure between crystalline and noncrystalline materials.
In crystalline materials, the atoms are arranged in a regular repeating pattern. In noncrystalline materials, atoms
are arranged in a random arrangement.

Draw unit cells for face centered cubic(FCC), body centered cubic (BCC), and hexagonal close packed(HCP)
structures.

FCC

BCC

HCP
Derive the relationship between unit cell edge length, and atomic radius for face centered cubic, and body
centered cubic crystal structures.
For FCC – See example problem 3.1 in text book 3rd ED
Compute the densities for metals having face centered cubic and body centered cubic crystal structures given
their unit cell dimensions.
Sketch/describe unit cells for sodium chloride, cesium chloride, zinc blende, diamond cubic, fluorite, and
perovskite crystal structures. Do likewise for the atomic structures of graphite and silica glass.
Given the chemical formula for a ceramic compound and the ionic radii of its component ions, predict the
crystal structure.
Given the three direction index integers, sketch the direction corresponding to these indices within a unit cell.
Specify the Miller indices for a plane that has been drawn within a unit cell.
Describe how face centered cubic and hexagonal close packed crystal structures may be generated by stacking
of close planes of atoms. Do the same for the sodium chloride crystal structure in terms of close packed planes
of atoms.
FCC structures can be close packed by packing, see section 3.16 3rd ED, and figures 3.29-3.33.

Distinguish between single crystal and polycrystalline materials.

See section 3.17. Single crystals have a regular repeat pattern that extends to the boundary of the physical
crystal that are in a set crystallographic direction. In poly crystalline, you have a collection of smaller crystals,
all with a direction, but not the same direction.

Define isotropy and anisotropy with respect to material properties.

In isotrophic materials, iso means same, and trop means turning so these materials have same properties no
matter which way you align the crystal directions.
In Anisotropy – there is a variance in some property based on crystallographic direction.

Explain the three most important structures for Metals.

Three most important structures for metals are HCP, FCC and BCC. Some metals change structure in response
to some stimulus like heat, or strain.

Compare and contrast the structures of metal, ceramics and polymer materials
Metals have simple structures that are close packed, like FCC, BCC or HCP. Ceramics can have complex
structures from the seven crystal systems (see table 3.6). Polymers also can adopt a type of unit cell based on
the seven crystal systems.

Calculate the lattice spacing for a crystal given Bragg’s Law, or the interplanar spacing relationship.
Calculate the minimum cation to anion ratio for a ceramic material given the coordination number.
Chapter 4

Describe a typical polymer molecule in terms of its chain structure, and in addition, how the molecule may be
generated from repeat units.
This is what we worked on in class for polymers. See the key for chapter 1-4 quiz.

Draw repeat units for polyethylene, poly(vinyl chloride), polytetrafluoroethylene, polypropylene, and
polystyrene.

Calculate the number-average and weight-average molecular weights, and degree of polymerization for a
specified polymer.
Name and briefly describe the four types of polymer molecular structures, the three types of stereoisomeners,
the two kinds of geometric isomers, the four types of copolymers.

See section 4.8 3rd Edition – See class slidedeck for images and examples of these.
Four types of polymer structures:
1. Linear
2. Branched
3. Crosslinked
4. Network
Three types of stereoisomers
1. Isotactic
2. Atatic
3. Syndiotatic

Four types of copolymers 1. Random

2. alternating
3. block
4. graft
Cite the differences in behavior, and molecular structure for thermoplastic, and thermosetting polymers.
Briefly describe the crystalline state in polymeric materials.
The crystalline state in polymeric materials is dependent on the packing of molecular chains to produce an
ordered array. The degree of crystallinity may range from completely amorphous to totally crystalline. The
density measurements tell you something about the crystallinity, and there is a formula you can use to calculate
degree of cyrstallinity from the density.

Briefly describe/diagram the sperulitic structure for a semicrystalline polymer.

Calculate the average repeat unit molecular weight for a copolymer.

Calculate percent crystallinity for a given polymer.
Compare the crystalline state in metals, semiconductors, and polymers.
Crystalline state Metals Semiconductors Polymers
Some amorphous, most All crystalline, some Some polycrystalline,
crystalline, some mixed, polycrystalline some amorphous, some
some polycrystalline crystal, some mixed

Explain why spherulites are considered to be the polymer analogue to grains in polycrystalline metals and
ceramics.
Spherulites are analog to grains in that they have boundaries, they are a mix of crystalline and amorphous, and
they give properties to the materials based on size and structure of spherulite.

Compare and contrast elevated temperature response of polymers to metals and ceramic materials.

Crystalline state Metals Semiconductors Polymers

Melt, gain disorder up to Melt, gain disorder up to Depends on polymer type
melting point, regain melting point. Not always crystalline – melt
order when cooled reversible when cooled. Amorphous – glass
transition temp – get
rubbery
Some crystals decompose
when heated to elevated
temps.
Chapter 5
Describe both vacancy and self-interstitial crystalline defects.
Vacancy is a missing atom in a structure, found in all categories of materials
Self-interstitial is when an atom of the same type as the lattice moves into an interstitial site.

Calculate the equilibrium number of vacancies in a material at some specified temperature, given the relevant
constants.
Name the two types of solid solutions and provide a brief written definition, and/or schematic sketch of each.
The two types of defects found in solid solutions are substitutional, and interstitial. In substitutional, an atom of
the same size or large (solute) goes in place of an atom of the lattice (solvent). In interstitial, a smaller atom
(solute) goes in between atoms to an interstitial site in the atomic lattice (solvent).
Name and describe different ionic point defects that are found in certain ceramic materials.
For an ionic material – See section 5.4 – vacancy(anion, cation), interstitial, self-interstitial, Frenkel, Schottky,
F-centers

Given the masses and atomic weights of two or more elements in a metal alloy, calculate the weight percent and
atom percent for each element.
For each of the edge, screw, and mixed dislocations: describe and make a drawing of the dislocation, note the
location of the dislocation line, and indicate the direction along which the dislocation line extends.
Describe the atomic structure within the vicinity of a grain boundary, and a twin boundary.
Twinning has a clean mirror image boundary with no disorder, the direction of the crystal growth changes

For grain boundaries, the edges are disordered owing to the way the crystal grows up to another grain.
Calculate the Schottky defects possible in a given crystal.
List factors that determine the degree to which a solute dissolves in a solvent to form a solid solution, and
explain the effect on formation of a solid solution.

Factors affecting the extent of solid solution:

1. Atomic/ionic size: If the atoms or ions in a solid solution have similar ionic radii, then the solid solution
is often very extensive or complete. Generally, if the size difference .is less than about 15%, then
extensive solid solution is possible. For example, Mg2+ and Fe2+ have a size mismatch of only about 7%,
and complete solid solution between these two elements is observed in a wide range of minerals.
However, there is a 32% size difference between Ca2+ and Mg2+, and we expect very little substitution of
Mg for Ca to occur in minerals.
2. Temperature: High temperatures favour the formation of solid solutions, so that endmembers which are
immiscible at low temperature may form complete or more extensive solid solutions with each other at
high temperature. High temperatures promote greater atomic vibration and open structures, which are
easier to distort locally to accommodate differently-sized cations. Most importantly, solid solutions have
a higher entropy than the endmembers, due to the increased disorder associated with the randomly
distributed cations, and at high temperatures, the -TS term in the Gibb's free energy stabilises the solid
solution.
3. Structural flexibility: Although cation size is a useful indicator of the extent of solid solution between
two endmembers, much depends on the ability of the rest of the structure to bend bonds (rather than
stretch or compress them) to accommodate local strains.
4. Cation charge: Heterovalent substitutions (i.e. those involving cations with different charges) rarely lead
to complete solid solutions at low temperatures, since they undergo complex cation ordering phase
transitions and/or phase separation at intermediate compositions. These processes are driven by the need
to maintain local charge balance in the solid solution as well as to accommodate local strain.

Explain the mechanism involved in a substitutional impurity replacing a host atom in a ceramic material.
Since there are both anions and cations, a substitutional impurity will substitute for the host ion to which it is
most similar in electrical charge.

Explain how crystals compensate for a charge difference between a host atom and an impurity atom which
substitutes it.
For an impurity atom having a charge different from the host ion for which it substitutes, the crystal must
compensate for the charge imbalance so that electroneutrality is maintained within the entire system. To do this
the crystal may have to create lattice defects including vacancies, interstitials or both to compensate charge.
Compare the point defect process in polymers to that of ceramics and metals.
Polymers have defects, but since they are not rigid 3-D crystals, the defects are different. See section 5.5 The
main type of defects are point defects (vacancies and interstitials), chains ending where they shouldn’t, or
branches misplaced are also defects, as are chains extending beyond the crystal structure. See Figure 5.7

Analyze drawings or micrographs to identify and justify defects in a material.

Most defects in the above micrograph are line defects, since they are two dimensional. You cann’t tell mich
more from image.
In the STM image above left , there is a vacancy in the center of the circle. Same to the right, but the lattice
looks like it has compensated for the defect through stain in the lattice.

And that's what it looks like in an STM image: A step begins at the dislocation core.

Explain how interfacial defects differ from other types of defects.

Interfacial defects are boundaries that have 2Dimensions and generally separate regions of the material with
different crystal structures, and/or crystallographic orientations. These differ because they are 2 D defects, but
are not line defects or 1D point defects.

Defend the premise that lattice vibrations are a type of defect.

At any temperature above absolute zero, the atoms in a crystal are not still. They vibrate around their
equilibrium positions in a complex manner that is determined by the overall structure of the crystal. The
amplitude of the vibration is determined by the temperature, while the frequency of the vibration ( is
primarily determined by the crystal structure. The lattice vibrations are actually elastic waves whose modes of
vibration are determined by the crystal structure. The lattice vibrations can be quantized, by which we mean
that one lattice vibration is made up of many particles, called phonons. Each “unit” of lattice vibration can be
thought of as a phonon. Thus we think of the crystal as containing many phonons, more at high temperature (as
vibration increases), and fewer at low temperature. A phonon has an energy and a momentum, just as any other
particle does. In this way, it is like a defect. These phonons can interact with other particles (such as electrons)
in the solid, thus allowing the exchange of energy and momentum within the crystal or with energy sources
outside the crystal. For example, when a piece of matter radiates heat, we can think of it as giving up phonons
to the environment. When the same body absorbs heat from the environment, we can think of it as absorbing
phonons from the energy source.

Chapter 6
Name and describe the two atomic mechanisms of diffusion.
Jumping – atoms stepwise move from one lattice site to another by:
1. Jumping from vacancy to vacancy
2. Moving from one interstitial site to another

Distinguish between steady-state and non-steady-state diffusion.

Steady state has constant flux, or flow of particles (by diffusion), across some described area in a certain
amount of time. To solve problems like this, you use Fick’s First Law.
Non- Steady State has non-constant flux, and uses Fick’s Second Law.

Draw/Illustrate an example of steady and non-steady state diffusion.

Here you would have an image of a constant flux or flow of particles over time. See Figure and graph 6.4. For
non steady state diffusion you should have a graph like 6.5

6.4 Briefly explain the concept of steady state as it applies to diffusion.

Solution
Steady-state diffusion is the situation wherein the rate of diffusion into a given system is just equal to the
rate of diffusion out, such that there is no net accumulation or depletion of diffusing species—i.e., the diffusion flux
is independent of time.
6.5 (a) Briefly explain the concept of a driving force.
(b) What is the driving force for steady-state diffusion?
Solution
(a) The driving force is that which compels a reaction to occur.
(b) The driving force for steady-state diffusion is the concentration gradient.

Write Fick’s first and second laws in equation form, and define all parameters. Note the kind of diffusion for
which each of these equations is normally applied.
Discuss with justification, conditions and application of Fick’s first and second law to differing cases for
diffusion.
Calculate the diffusion coefficient for some material at a specified temperature, given the appropriate diffusion
constants.
Note one difference in diffusion mechanisms for metals and ionic solids.
In metals the diffusion mechanism is for one type of ion only, but in ionic solids you have to consider you could
have anions and cations diffusing. Ionic materials usually diffuse by vacancy rather than interstitials. (see
section 6.7)

Create a schematic graph of lnD versus 1/T, for two hypothetical materials given activation energy and
diffusion coefficient. Be able to discuss the implications for materials design and performance.