Problem 6.

1:
In order to determine the coordination number of ZrO2, the ionic radii of zirconium and
oxygen must be found from Table 6-2. In this case, zirconimum is the cation and oxygen is
the anion.

rZr  4  rC  0.087 nm

rO  2  ra  0.132nm

Next, the cation to anion ratio is determined as shown below.

rC 0.087nm
  0.659
ra 0.132nm

Using Table 6-1, it can be determined that the coordination number of ZrO2 is 6, since the
cation to anion ratio is between 0.414 and 0.732.

1
Problem 6.2:

Gypsum is added to Portland cement to react with the calcium aluminate (C3A) and water
to form ettringite. Without the gypsum, the calcium aluminate would react with the water,
causing the cement to set prematurely and negatively impacting the physical properties

2
Problem 6.3:
Network modifiers disrupt the loose networks of SiO44- tetrahedrons in the molten glass,
resulting in lower viscosities.

3
Problem 6.4:

The glass transition temperature of polymers represents the onset of large scale segmental
motion. Below Tg, the polymer is a rigid solid, but above Tg it gradually evolves into a rubbery
solid (like an o-ring). Glasses exist as brittle solids below Tg, but as Tg is passed, the loose
network of tetrahedrons become disrupted and small clusters of these disruptions coalesce into
clusters that allow bulk flow of the material.

4
Problem 6.5:

Much like a galvanic cell, an SOFC uses electrochemistry to convert chemical energy to
electrical energy. In the cell, anodic and cathodic materials are separated by an insulator that
also conducts oxygen atoms from the cathode to the anode. These oxygen atoms react with the
fuel source. SOFCs use nickel oxides as the anodic material and lanthiun-chromate based
materials as interconnectors,

5
Problem 6.6:

Clearly, any list provided here must be representative rather than exhaustive. In general, PAN-
based fibers are used for applications in which the primary role of the fiber is to provide strength,
while mesophase pitch-based fibers are used in applications where thermal conductivity is of
primary importance.

PAN-based fiber applications: Race car bodies

Bicycle frames
Softball bats
Aircraft fuselages
Prosthetic limbs
Marine Applications

Pitch-based fiber applications: Leading-edges of space shuttle nose cone

Battery electrodes
Communication Satellites
Thermal management systems

6
Problem 6.7:

Mesophase pitch is a liquid crystalline region of large carbonaceous molecules formed by

heating materials left from the byproducts of petroleum distillation.

7
Problem 6.8:

In order to determine the coordination number of CaO, the ionic radii of calcium and oxygen
must be found from Table 6-2. In this case, calcium is the cation and oxygen is the anion.

rCa  2  rC  0.106nm

rO  2  ra  0.132nm

Next, the cation to anion ratio is determined as shown below.

rC 0.106nm
  0.803
ra 0.132nm

Using Table 6-1, it can be determined that the coordination number of CaO is 8, since the
cation to anion ratio is between 0.732 and 1.0.

8
Problem 6.9:

Graphite is sometimes considered a polymer and treated like a ceramic because graphite fits
the technical definition of a polymer, but possesses many of the physical properties of
ceramics. A polymer is a molecule constructed of a long chain of repeating monomer units
that are covalently bonded. Graphite fits this description because it is a long chain of six-
member rings that are repeated and are covalently bonded to one another. While fitting the
technical definition of a polymer, graphite behaves far more like a ceramic. It is brittle,
strong, and insulates in the direction perpendicular to the graphene plane. In addition, it has
the highest Young’s Modulus of any material (1,080 GPa).

9
Problem 6.10:

Although diamond and graphite are both allotropes of pure carbon, their crystal structures
result in very different mechanical properties. Diamond forms a clear FCC structure with
carbon atoms also occupying four of the eight tetrahedral sites. The stability of this structure
that gives diamond its extreme hardness, reaching a 10 on the Moh scale. Graphite, on the
other hand, has a layered structure, in which six-member aromatic rings exist in graphene
planes. These rings are connected with strong covalent bonds, but only weak Van der Waals
interactions exist between planes. Thus, the properties of graphite are a strong function of
direction, causing graphite to have a Moh Hardness between 1 and 2.

10
Problem 6.11:

At 1600°C, the phases present are MgO(ss) and MgAl2O4(ss). Using a tie line, it can be
determined that the mass fraction of Al2O3 in the MgO(ss) phase is 2.0%, while the mass
fraction of Al2O3 in MgAl2O4(ss) is approximately 70%. In addition, from the problem
statement, the mass fraction of Al2O3 in the total sample is 60%. In other words:

wMgO  .02
wMgAl2O4  .70
wTotal  .60

Assume that the total mass of the sample is 1 gram. A mass balance is also performed on the
system, and the problem can be solved as shown:

M MgO  M MgAl2O4  M Total  1gram

This can be manipulated to form: M MgO  1gram  M MgAl O 2 4

wMgAl2O4 M MgAl2O4  wMgO M MgO  wTotal M Total

(.70) M MgAl2O4  (.02) M MgO  (.60)(1gram)

(.70)( M MgAl2O4 )  (.02)(1gram  M MgAl2O4 )  (.60)(1gram)

Solving for M MgAl O yields:

2 4
M MgAl2O4 = .85 grams

M MgO  1gram  .85 grams  .15 grams

The first liquid phase begins to form at approximately 2000°C. The temperature at which the
first complete liquid phase forms is approximately 2080°C.

11
Problem 6.12:

Ceramics tend to be strong but brittle because of the ionic bonding present between the metal
and non-metal components of the material. Ionic bonds are very and require a relatively
large amount of energy to break. However, once enough energy is applied to break the
bonds, they break completely, making the material brittle. Covelently bonded materials like
polymers are far less brittle because the covalent bonds can “stretch” during plastic
deformation.

12
 Problem 6.13

The stable formation for a coordination number of three would have all four atoms in a plane
with angles of 120 degrees between the anions. The anions, then, become corners of a triangle,
which makes the minimum ratio of radii 0.155.

13
Problem 6.14:

C-S-H plays an important role during the five-stage hydration process of cement. In Stage 1,
calcium and hydroxide ions are released from the C3S. In this stage, CH and C-S-H also
begin to crystallize. These reactions slow after approximately fifteen minutes, and the
cement enters a dormant period, or Stage 2. A coating of C-S-H develops on the surface of
the cement, which creates a diffusion barrier for the water. As the thickness increases, the
reaction rate becomes increasingly controlled by the diffusion. After 2-4 hours, Stage 3
begins as a critical mass of ions is achieved and the reaction rate accelerates. C3S and the
less-reactive C2S hydrate rapidly. Approximately eight hours later, Stage 4 begins as the rate
of reaction decelerates and diffusion completely controls all rates. Stage 5 occurs when
steady-state is achieved, and the hydration is essentially independent of temperature.

The C-S-H in the hardened cement paste provides much of the strength of the cement. As the
C-S-H coatings grow on the C3S and C2S grains, they begin to radiate outward as spikes.
Continued hydration causes the spikes from adjacent particles to interlock, physically
connecting the cement grains together.

14
Problem 6.15:

Terra Cotta makes an ideal choice for many sewer pipe applications. It is light-weight,
inexpensive, has a low coefficient of thermal expansion and is unlikely to be damaged during
freeze-thaw cycles under the ground. It is brittle, but once in place, it is unlikely to
experience fatal blows. The biggest advantage over metal piping is that it is inert and will
not corrode over time, reducing the need for costly repairs and/or replacement.

Problem 6.16:

Capillary pores are the open spaces between grains, while gel pores are spaces within the C-
S-H material in cement. Most of the porosity in cement occurs as gel pores.

15
Problem 6.17:

The difference among armchair, chiral, and zigzag nanotubes relates to the direction of the
graphene plane in which the nanotube is constructed. The nanotubes are classified by a pair
of integers (n,m) that represent a pair of unit vectors what define this direction. In the
armchair configuration, the pair of vectors has m=n, while in the zigzag configuration, the
pair of vectors has m=0. The chiral configuration contains all other vector pairs, with m≠n.

16
Problem 6.18:

Graphite layers are easy to separate because the only forces between layers are weak Van der
Waals interactions. The covalent bonds within each layer are significantly stronger, than the
Van der Waals interactions, however the covalent bonds do not need to be broken to separate
layers.

17
Problem 6.19:

SOFCs are solid oxide fuel cells that use electrochemistry to convert chemical energy to
electrical energy. SOFCs have the potential to provide clean, portable, cost-effective energy
to help alleviate the world’s dependence on the combustion of fossil fuels. The SOFCs can
use existing hydrocarbons to convert chemical energy to electrical energy without the release
of greenhouse gases and using existing hydrocarbon stores.

18
Problem 6.20:

Glazes are applied to whitewares primarily to provide colors upon firing. In most cases, their
function is purely decorative. However, the glazes do provide a water-resistant barrier to the
material.

19
Problem 6.21:

Molten SiO2 forms glass instead of cooling back into a crystalline form because of its high
viscosity. The phase diagram indicates that cristobalite should form upon cooling of the
molten SiO2. Instead, the high viscosity of the SiO2 prevents the tetrahedral molecules from
forming the more thermodynamically stable crystal structure.

20
Problem 6.22:

Although cubic boron nitride possesses exceptional hardness (second only to diamond), it
is extremely difficult to manufacture, especially in large sheets that would be suitable for armor.
Instead, the bulk of its production is used in powders or insulating coatings.

21
Problem 6.23:

A sol-gel is the material formed when a colloidal suspension of metal salts is dried to form a wet,
but solid gel. They are used to deposit ceramic particles are sandpaper backing.

22
Problem 6.24:

The spinel structure pictured above has the Magnesium cations in the tetrahedral sites and the
aluminum ions in the octahedral positions

23
Problem 6.25:

Lapping agents have two primary desirable characteristics:

1. They must have excellent hardness to abrade softer materials
2. They must have sufficient toughness to withstand the process

Diamonds are the hardest known material and have exceptional toughness. Non-gem grade
diamonds (or bort) are found in nature and produced artificially in sufficient quantity to make
their use as a lapping agent financially feasible.

24
Problem 6.26:

The sintering process uses heating to cause the coalescences of adjacent particles. The
intergranular spaces shrink and eventually become incorporated into the final structure as small,
spherical pores. Vitrification is the process by which regions of coalesced tetrahedrons form into
rigid solid structures, but there is no formalized grain structure in the precursor material, just a
loose network of tetrahedrons.

25
Problem: 6.27

Silica Glass is a transparent ceramic material with a density of 2.5 g/cm3. It is an

amorphous solid that is strong, but quite brittle. It has a Young’s modulus of 72 GPA and is
generally transparent.
Portland cement is an opaque material whose properties vary greatly with setting time
and conditions. However, it tends to be denser than glass (2.7 – 3.2 g/cm3) with better
compressive strength but less tensile. Portland Cement usually is mixed with aggregate to form
concrete.

26
27
Problem 6.28:
Small amounts of fly ash have essentially no measurable effect on the properties of
Portland cement. Fly ash is a waste product of coal combustion processes. The material is
comprised primarily of oxides (SiO2, Fe2O3, Al2O3 and CaO) and their relative distributions
depend on the type of coal that is burned. With over 71 million tons of fly ash generated in the
United states each year, disposal is a costly issue. Adding the fly ash to the cement finds a
sustainable reuse for the waste material and serves as a filler, lowering the cost of the cement.

28
Problem 6.29:

The list provided here must be representative, not exhaustive. In addition to silica-based
nanoparticles in cancer treatments, BaTiO3 nanoparticles in multilayer capacitors, and SiC
nanoparticles in armor, other uses would include:

 Silica, hydroxyapatite, and zirconia nanoparticles serve as gene delivery vehicles that
import DNA into a cell;
 Thermal pastes that prevent short circuits in electrical applications;
 Anti-graffiti coating for walls;
 Improved tire adhesion;
 Scratch-resistant eyewear;
 Delivery mechanisms for anti-microbial materials in food packaging;
 DNA Probes;
 Steel strengthening;
 Sunscreens (though the FDA has recommended limiting their use);
 Drug delivery.

29
Problem 6.30:

At 2400C, the mixture is an equilibrium blend of MgO and liquid. Extending a tie line shows
that the solid phase contains approximately 8% Al2O3, while the liquid phase contains
approximately 37% Al2O3. A mass balance on Al2O3 provides:

(0.37)ML + (0.08)MS = (0.20)MT and

ML + MS = MT If we assume a basis of 1g (MT =1g) then

(0.37)ML + (0.08)(1- ML) = (0.20)(1) and

ML = .414

So the mass fraction of liquid in 41.4%

30
Problem 6.31:

The most significant properties for refractory materials include high-melting point, cost, and low
coefficient of thermal expansion.

31
Problem 6.32:

In traditional powder pressing, the powdered material is compressed only from the top and
bottom. Isotactic powder pressing involves an expandable balloon that applies essentially
uniform pressure from all directions at once.

32
Problem 6.33:

The balance of charges in ceramics makes them very strong, highly inert, and brittle. The
ionic bonds that form between the ions provide great strength and are difficult to break, but they
are highly inflexible. With no opportunity for plastic deformation, the material will break in
brittle failure. The presence of equal numbers of positive and negative ions also makes that
material resistant to corrosion, because it has, in effect, already corroded.

33
Problem 6.34:

a.) Carbon fibers have higher strength-to-weight ratios than high-performance polymers and
tend to lead to better mechanical properties in the composites. They also can be
fashioned with anisotropic thermal conductivities so that they can be used to conduct heat
away from leading edges and are better able to withstand compressive loads. The
primary downside to their use is cost.
b.) Racing car frames fit the argument above as well.
c.) In addition to all of the reasons above, carbon fibers have significantly higher modulus
which adds to the stiffness. Overall, it is unlikely that the use of carbon fibers instead of
high-performance polymers like Kevlar will have enough difference in properties to
impact anyone’s game, but carbon fibers make a nice marketing angle for high-end clubs.

34
Problem 6.35:

Ceramics are essentially immune to corrosion, because the balance of positive and negative ions
means that they have essentially already corroded. There is no way to oxidize the metallic ions
when they are already bonded to a negative ion (often oxygen).

35
Problem 6.36:

Stage 1 occurs during the first minutes after water is mixed with the cement. Calcium

and hydroxide ions are released from the C3S, resulting in heat generation and a rapid rise in pH.

CH and C-S-H also begin to crystallize in Stage 1. After approximately 15 minutes, the cement

enters a dormant period (Stage 2) during which the reaction slows. A coating of C-S-H develops

on the surface of the cement, which creates a diffusion barrier for the water. As the thickness

increases, the reaction rate becomes increasingly controlled by the diffusion. After 2-4 hours, a

critical mass of ions is achieved and the reaction rate (Stage 3) accelerates. During Stage 3, both

C3S and the less-reactive C2S hydrate rapidly. After about 8 hours, the rate of reaction

decelerates and diffusion completely controls all rates (Stage 4). Finally, a steady-state (Stage 5)

occurs in which the hydration is essentially independent of temperature.

, Calcination, Clinkering, and Cooling

36