Properties of Solids

As you should remember from the kinetic molecular theory, the molecules in solids are not moving in the same manner as those in liquids or gases. Solid molecules
simply vibrate and rotate in place rather than move about. Solids are generally held together by ionic or strong covalent bonding, and the attractive forces between
the atoms, ions, or molecules in solids are very strong. In fact, these forces are so strong that particles in a solid are held in fixed positions and have very little
freedom of movement. Solids have definite shapes and definite volumes and are not compressible to any extent.

There are two main categories of solids—crystalline solids and amorphous solids. Crystalline solids are those in which the atoms, ions, or molecules that make up the
solid exist in a regular, well-defined arrangement. The smallest repeating pattern of crystalline solids is known as the unit cell, and unit cells are like bricks in a wall—
they are all identical and repeating. The other main type of solids are called the amorphous solids. Amorphous solids do not have much order in their structures.
Though their molecules are close together and have little freedom to move, they are not arranged in a regular order as are those in crystalline solids. Common
examples of this type of solid are glass and plastics.

There are four types of crystalline solids:

Ionic solids—Made up of positive and negative ions and held together by electrostatic attractions. They’re characterized by very high melting points and brittleness
and are poor conductors in the solid state. An example of an ionic solid is table salt, NaCl.

Molecular solids—Made up of atoms or molecules held together by London dispersion forces, dipole-dipole forces, or hydrogen bonds. Characterized by low melting
points and flexibility and are poor conductors. An example of a molecular solid is sucrose.

Covalent-network (also called atomic) solids—Made up of atoms connected by covalent bonds; the intermolecular forces are covalent bonds as well. Characterized
as being very hard with very high melting points and being poor conductors. Examples of this type of solid are diamond and graphite, and the fullerenes. As you can
see below, graphite has only 2-D hexagonal structure and therefore is not hard like diamond. The sheets of graphite are held together by only weak London forces!

Metallic solids—Made up of metal atoms that are held together by metallic bonds. Characterized by high melting points, can range from soft and malleable to very
hard, and are good conductors of electricity.

CRYSTAL STRUCTURES WITH CUBIC UNIT CELLS (From https://eee.uci.edu/programs/gchem/RDGcrystalstruct.pdf)

Crystalline solids are a three dimensional collection of individual atoms, ions, or whole molecules organized in repeating patterns. These atoms, ions, or molecules are
called lattice points and are typically visualized as round spheres. The two dimensional layers of a solid are created by packing the lattice point “spheres” into square
or closed packed arrays. (See Below).

Figure 1: Two possible arrangements for identical atoms in a 2-D structure

Stacking the two dimensional layers on top of each other creates a three dimensional lattice point arrangement represented by a unit cell. A unit cell is the smallest
collectionof lattice points that can be repeated to create the crystalline solid. The solid can be envisioned as the result of the stacking a great number of unit cells
together. The unit cell of a solid is determined by the type of layer (square or close packed), the way each successive layer is placed on the layer below, and the
coordination number for each lattice point (the number of “spheres” touching the “sphere” of interest.)

Primitive (Simple) Cubic Structure

Placing a second square array layer directly over a first square array layer forms a "simple cubic" structure. The simple “cube” appearance of the resulting unit cell
(Figure 3a) is the basis for the name of this three dimensional structure. This packing arrangement is often symbolized as "AA...", the letters refer to the repeating
order of the layers, starting with the bottom layer. The coordination number of each lattice point is six. This becomes apparent when inspecting part of an adjacent
unit cell (Figure 3b). The unit cell in Figure 3a appears to contain eight corner spheres, however, the total number of spheres within the unit cell is 1 (only 1/8th of
each sphere is actually inside the unit cell). The remaining 7/8ths of each corner sphere resides in 7 adjacent unit cells.
The considerable space shown between the spheres in Figures 3b is misleading: lattice points in solids touch as shown in Figure 3c. For example, the distance
between the centers of two adjacent metal atoms is equal to the sum of their radii. Refer again to Figure 3b and imagine the adjacent atoms are touching. The edge
of the unit cell is then equal to 2r (where r = radius of the atom or ion) and the value of the face diagonal as a function of r can be found by applying Pythagorean’s
theorem (a2 + b2 = c2) to the right triangle created by two edges and a face diagonal (Figure 4a). Reapplication of the theorem to another right triangle created by an
edge, a face diagonal, and the body diagonal allows for the determination of the body diagonal as a function of r (Figure 4b).

Few metals adopt the simple cubic structure because of inefficient use of space. The density of a crystalline solid is related to its "percent packing efficiency". The
packing efficiency of a simple cubic structure is only about 52%. (48% is empty space!)

Body Centered Cubic (bcc) Structure

A more efficiently packed cubic structure is the "body-centered cubic" (bcc). The first layer of a square array is expanded slightly in all directions. Then, the second
layer is shifted so its spheres nestle in the spaces of the first layer (Figures 5a, b). This repeating order of the layers is often symbolized as "ABA...". Like Figure 3b, the
considerable space shown between the spheres in Figure 5b is misleading: spheres are closely packed in bcc solids and touch along the body diagonal. The packing
efficiency of the bcc structure is about 68%. The coordination number for an atom in the bcc structure is eight. How many total atoms are there in the unit cell for a
bcc structure? Draw a diagonal line connecting the three atoms marked with an "x" in Figure 5b. Assuming the atoms marked "x" are the same size, tightly packed
and touching, what is the value of this body diagonal as a function of r, the radius? Find the edge and volume of the cell as a function of r.

Cubic Closest Packed (ccp)

A cubic closest packed (ccp) structure is created by layering close packed arrays. The spheres of the second layer nestle in half of the spaces of the first layer. The
spheres of the third layer directly overlay the other half of the first layer spaces while nestling in half the spaces of the second layer. The repeating order of the layers
is "ABC..." (Figures 6 & 7). The coordination number of an atom in the ccp structure is twelve (six nearest neighbors plus three atoms in layers above and below) and
the packing efficiency is 74%.

Figure 6: Close packed Array Layering. The 1st and 3rd layers are represented by light
spheres; the 2nd layer, dark spheres. The 2nd layer spheres nestle in the spaces of the 1st
layer marked with an “x”. The 3rd layer spheres nestle in the spaces of the 2nd layer that
directly overlay the spaces marked with a “·” in the 1st layer.

Figure 7a & 7b: Two views of the Cubic Close Packed Structure

If the cubic close packed structure is rotated by 45° the face centered cube (fcc) unit cell can be viewed (Figure 8). The fcc unit cell contains 8 corner atoms and an
atom in each face. The face atoms are shared with an adjacent unit cell so each unit cell contains ½ a face atom. Atoms of the face centered cubic (fcc) unit cell touch
across the face diagonal (Figure 9). What is the edge, face diagonal, body diagonal, and volume of a face centered cubic unit cell as a function of the radius?

Figure 8: The face centered cubic unit cell is drawn by cutting a diagonal plane through
an ABCA packing arrangement of the ccp structure. The unit cell has 4 atoms (1/8 of
each corner atom and ½ of each face atom).

Figure 9a:Space filling model of fcc. Figure 9b: The face of fcc. Face diagonal = 4r.

Ionic Solids

In ionic compounds, the larger ions become the lattice point “spheres” that are the framework of the unit cell. The smaller ions nestle into the depressions (the
“holes”) between the larger ions. There are three types of holes: "cubic", "octahedral", and "tetrahedral". Cubic and octahedral holes occur in square array structures;
tetrahedral and octahedral holes appear in close-packed array structures (Figure 10). Which is usually the larger ion – the cation or the anion? How can the periodic
table be used to predict ion size? What is the coordination number of an ion in a tetrahedral hole? an octahedral hole? a cubic hole?

Figure 10. Holes in ionic crystals are more like "dimples" or "depressions" between the
closely packed ions. Small ions can fit into these holes and are surrounded by larger ions
of opposite charge.

The type of hole formed in an ionic solid largely depends on the ratio of the smaller ion’s radius the larger ion’s radius (rsmaller/rlarger). (Table 1).
Empirical Formula of an Ionic Solid

Two ways to determine the empirical formula of an ionic solid are: 1) from the number of each ion contained within 1 unit cell 2) from the ratio of the coordination
numbers of the cations and anions in the solid.

Example: Find the empirical formula for the ionic compound shown in Figures 11 & 12.

First Method: When using the first method, remember most atoms in a unit cell are shared with other cells. Table 2 lists types of atoms and the fraction contained in
the unit cell. The number of each ion in the unit cell is determined: 1/8 of each of the 8 corner X ions and 1/4 of each of the 12 edge Y ions are found within a single
unit cell. Therefore, the cell contains 1 X ion (8/8 = 1) for every 3 Y ions (12/4 = 3) giving an empirical formula of XY3. Which is the cation? anion? When writing the
formula of ionic solids, which comes first?

Second Method: The second method is less reliable and requires the examination of the crystal structure to determine the number of cations surrounding an anion
and vice versa. The structure must be expanded to include more unit cells. Figure 12 shows the same solid in Figure 11 expanded to four adjacent unit cells.
Examination of the structure shows that there are 2 X ions coordinated to every Y ion and 6 Y ions surrounding every X ion. (An additional unit cell must be projected
in front of the page to see the sixth Y ion ). A 2 to 6 ratio gives the same empirical formula, XY3.

Summary:
 Simple Cubic: 1 total atom Body Centered Cubic: 2 atoms
per cell (1/8 each corner) per cell (1 in center and 1/8
Face Centered Cubic: 4 atoms per cell
for each corner)
(1/2 per face and 1/8 for each corner)

Summary Materials Science and Engineering

1.1 HISTORICAL PERSPECTIVE

(Stone Age, Bronze Age, Iron Age)
The approximate dates for the beginnings of the Stone, Bronze, and Iron Ages were 2.5 million BC, 3500 BC, and 1000 BC, respectively.

Stone Age: 2.5 million years ago

Pottery Age: 4000 B.C.E
Copper Age: 4000 B.C.E – 3000 B.C.E.
Bronze Age: 2000 B.C.E – 1000 B.C.E.  Foundation of metallurgy- Alloys of copper and tin
Iron Age: 1000 B.C.E – 1B.C.E. ◦ Plastics Age: late 20th Century to current time
Semiconductor Age: late 20th Century to current time

1.2 MATERIALS SCIENCE AND ENGINEERING

Materials science involves investigating the relationships that exist between the structures and properties of materials.
Materials engineering is, on the basis of these structure–property correlations, designing or engineering the structure of a material to produce a
predetermined set of properties.

Materials scientist is to develop or synthesize new materials

Materials engineer is called upon to create new products or systems using existing materials, and/or to develop techniques for processing
materials.

Structure of a material usually relates to the arrangement of its internal components.

 Subatomic structure involves electrons within the individual atoms and interactions with their nuclei.
 On an atomic level, structure encompasses the organization of atoms or molecules relative to one another.
 The next larger structural realm, which contains large groups of atoms that are normally agglomerated together, is termed microscopic,
meaning that which is subject to direct observation using some type of microscope.
 Finally, structural elements that may be viewed with the naked eye are termed macroscopic.

Property is a material trait in terms of the kind and magnitude of response to a specific imposed stimulus. Generally, definitions of properties are made
independent of material shape and size.

Virtually all important properties of solid materials may be grouped into six different categories: mechanical, electrical, thermal, magnetic, optical, and
deteriorative. For each there is a characteristic type of stimulus capable of provoking different responses.

 Mechanical properties relate deformation to an applied load or force; examples include elastic modulus (stiffness), strength, and toughness.
 Electrical properties, such as electrical conductivity and dielectric constant, the stimulus is an electric field.
 Thermal behavior of solids can be represented in terms of heat capacity and thermal conductivity.
 Magnetic properties demonstrate the response of a material to the application of a magnetic field.
 Optical properties, the stimulus is electromagnetic or light radiation; index of refraction and reflectivity are representative optical properties.
 Deteriorative characteristics relate to the chemical reactivity of materials.

Processing of materials is the application of heat (heat treatment), mechanical forces, etc. to affect their microstructure and, therefore, their properties.
In addition to structure and properties, two other important components are involved in the science and engineering of materials—namely, processing
and performance. With regard to the relationships of these four components, the structure of a material will depend on how it is processed.
Furthermore, a material’s performance will be a function of its properties.

1.3 WHY STUDY MATERIALS SCIENCE AND ENGINEERING?

 To be able to select a material for a given use based on considerations of cost and performance.
 To understand the limits of materials and the change of their properties with use.
 To be able to create a new material that will have some desirable properties.

Three important criteria in materials selection are in-service conditions to which the material will be subjected, any deterioration of material properties
during operation, and economics or cost of the fabricated piece.

1.4 CLASSIFICATION OF MATERIALS

Solid materials have been conveniently grouped into three basic categories: metals, ceramics, and polymers. This scheme is based primarily on chemical
makeup and atomic structure, and most materials fall into one distinct grouping or another. In addition, there are the composites, which are engineered
combinations of two or more different materials.

Metals-materials in this group are composed of one or more metallic elements (e.g., iron, aluminum, copper, titanium, gold, and nickel), and often also
nonmetallic elements (e.g., carbon, nitrogen, and oxygen) in relatively small amounts.3 Atoms in metals and their alloys are arranged in a very orderly
manner and in comparison to the ceramics and polymers, are relatively dense. With regard to mechanical characteristics, these materials are relatively
stiff and strong, yet are ductile (i.e., capable of large amounts of deformation without fracture), and are resistant to fracture, which accounts for their
widespread use in structural applications. Metallic materials have large numbers of nonlocalized electrons; that is, these electrons are not bound to
particular atoms. Many properties of metals are directly attributable to these electrons. For example, metals are extremely good conductors of electricity
and heat, and are not transparent to visible light; a polished metal surface has a lustrous appearance. In addition, some of the metals (i.e., Fe, Co, and Ni)
have desirable magnetic properties.

The term metal alloy refers to a metallic substance that is composed of two or more elements.

Ceramics-are compounds between metallic and nonmetallic elements; they are most frequently oxides, nitrides, and carbides. For example, common
ceramic materials include aluminum oxide (or alumina, Al2O3), silicon dioxide (or silica, SiO2), silicon carbide (SiC), silicon nitride (Si3N4), and, in
addition, what some refer to as the traditional ceramics—those composed of clay minerals (i.e., porcelain), as well as cement and glass.With regard to
mechanical behavior, ceramic materials are relatively stiff and strong—stiffnesses and strengths are comparable to those of the metals. In addition, they
are typically very hard. Historically, ceramics have exhibited extreme brittleness (lack of ductility) and are highly susceptible to fracture. However, newer
ceramics are being engineered to have improved resistance to fracture; these materials are used for cookware, cutlery, and even automobile engine parts.
Furthermore, ceramic materials are typically insulative to the passage of heat and electricity (i.e., have low electrical conductivities, and are more
resistant to high temperatures and harsh environments than metals and polymers. With regard to optical characteristics, ceramics may be transparent,
translucent, or opaque, and some of the oxide ceramics (e.g., Fe3O4) exhibit magnetic behavior.

Polymers-include the familiar plastic and rubber materials. Many of them are organic compounds that are chemically based on carbon, hydrogen, and
other nonmetallic elements (i.e., O, N, and Si). Furthermore, they have very large molecular structures, often chainlike in nature, that often have a
backbone of carbon atoms. Some of the common and familiar polymers are polyethylene (PE), nylon, poly(vinyl chloride) (PVC), polycarbonate (PC),
polystyrene (PS), and silicone rubber.These materials typically have low densities,whereas their mechanical characteristics are generally dissimilar to the
metallic and ceramic materials—they are not as stiff nor as strong as these other material types. However, on the basis oftheir low densities, many times
their stiffnesses and strengths on a per-mass basis are comparable to the metals and ceramics. In addition, many of the polymers are extremely ductile
and pliable (i.e., plastic), which means they are easily formed into complex shapes. In general, they are relatively inert chemically and unreactive in a
large number of environments. One major drawback to the polymers is their tendency to soften and/or decompose at modest temperatures, which, in
some instances, limits their use. Furthermore, they have low electrical conductivities and are nonmagnetic.

A composite is composed of two (or more) individual materials, which come from the categories previously discussed—metals, ceramics, and polymers.
The design goal of a composite is to achieve a combination of properties that is not displayed by any single material, and also to incorporate the best
characteristics of each of the component materials. A large number of composite types are represented by different combinations of metals, ceramics,
and polymers. Furthermore, some naturally occurring materials are composites—for example, wood and bone. However, most of those we consider in
our discussions are synthetic (or human-made) composites. One of the most common and familiar composites is fiberglass, in which small glass fibers
are embedded within a polymeric material (normally an epoxy or polyester). The glass fibers are relatively strong and stiff (but also brittle), whereas the
polymer is more flexible. Thus, fiberglass is relatively stiff, strong, and flexible. In addition, it has a low density.

Fiberglass is sometimes also termed a “glass fiber–reinforced polymer” composite, abbreviated GFRP.

1.5 ADVANCED MATERIALS

Materials that are utilized in high-technology (or high-tech) applications are sometimes termed advanced materials. By high technology we mean a
device or product that operates or functions using relatively intricate and sophisticated principles

These advanced materials are typically traditional materials whose properties have been enhanced, and also newly developed, high-performance
materials. Furthermore, they may be of all material types (e.g., metals, ceramics, polymers), and are normally expensive. Advanced materials include
semiconductors, biomaterials, and what we may term “materials of the future” (that is, smart materials and nanoengineered materials).

Semiconductors have electrical properties that are intermediate between the electrical conductors (i.e., metals and metal alloys) and insulators (i.e.,
ceramics and polymers). Furthermore, the electrical characteristics of these materials are extremely sensitive to the presence of minute concentrations of
impurity atoms, for which the concentrations may be controlled over very small spatial regions.

Biomaterials are employed in components implanted into the human body to replace diseased or damaged body parts. These materials must not produce
toxic substances and must be compatible with body tissues (i.e., must not cause adverse biological reactions). All of the preceding materials—metals,
ceramics, polymers, composites, and semiconductors—may be used as biomaterials.

Smart (or intelligent) materials are a group of new and state-of-the-art materials now being developed that will have a significant influence on many of
our technologies. The adjective smart implies that these materials are able to sense changes in their environment and then respond to these changes in
predetermined manners—traits that are also found in living organisms.

Components of a smart material (or system) include some type of sensor (that detects an input signal), and an actuator (that performs a responsive and
adaptivefunction). Actuators may be called upon to change shape, position, natural frequency, or mechanical characteristics in response to changes in
temperature, electric fields, and/or magnetic fields.

Four types of materials are commonly used for actuators: shape-memory alloys, piezoelectric ceramics, magnetostrictive materials, and
electrorheological/magnetorheological fluids. Shape-memory alloys are metals that, after having been deformed, revert back to their original shape
when temperature is changed. Piezoelectric ceramics expand and contract in response to an applied electric field (or voltage); conversely, they also
generate an electric field when their dimensions are altered. The behavior of magnetostrictive materials is analogous to that of the piezoelectrics, except
that they are responsive to magnetic fields.Also, electrorheological and magnetorheological fluids are liquids that experience dramatic changes in
viscosity upon the application of electric and magnetic fields, respectively.

One new material class that has fascinating properties and tremendous technological promise is the nanomaterials. Nanomaterials may be any one of
the four basic types—metals, ceramics, polymers, and composites. However, unlike these other materials, they are not distinguished on the basis of their
chemistry, but rather, size; the nano-prefix denotes that the dimensions of these structural entities are on the order of a nanometer (10–9 m)—as a rule,
less than 100 nanometers (equivalent to approximately 500 atom diameters).

The “bottom-up” approach, and the study of the properties of these materials is termed nanotechnology

One legendary and prophetic suggestion as to the possibility of nanoengineered materials was offered by Richard Feynman in his 1959 American
Physical Society lecture titled “There’s Plenty of Room at the Bottom.”

Chapter 2 Atomic Structure and Interatomic Bonding

Atomic Structure

-Each atom consists of a very small nucleus composed of protons and neutrons, which is encircled by moving electrons. Both electrons and protons
are electrically charged, the charge magnitude being 1.602X10^-19 C, which is negative in sign for electrons and positive for protons; neutrons are
electrically neutral. Masses for these subatomic particles are infinitesimally small; protons and neutrons have approximatelythe same mass, 1.67x10^-
27 kg, which is significantly larger than that of an electron, 9.11x10^-31 kg.

-Each chemical element is characterized by the number of protons in the nucleus, or the atomic number (Z). For an electrically neutral or complete
atom, the atomic number also equals the number of electrons.

-The atomic mass (A) of a specific atom may be expressed as the sum of the masses of protons and neutrons within the nucleus

-Thus atoms of some elements have two or more different atomic masses, which are called isotopes

-The atomic weight of an element corresponds to the weighted average of the atomic masses of the atom’s naturally occurring isotopes.2 The atomic
mass unit (amu) may be used to compute atomic weight.

-The atomic weight of an element or the molecular weight of a compound may be specified on the basis of amu per atom (molecule) or mass per
mole of material. In one mole of a substance there are 6.022 1023 (Avogadro’s number) atoms or molecules. These two atomic weight schemes are
related through the following equation: amu/atom 1 or (molecule) = 1 g/mol