Smart Materials and New Technologies

expansion. Thermal conductivity in conductive materials,

such as metals, can be largely explained in terms of the free
electron movements discussed earlier. Thermal energy in the
form of rapid atomic lattice movements is transmitted
through a material via electron movements from the hot to
the cold end. Thermal conductivity in dielectric (insulating)
materials is a more complex action as it occurs through
vibratory phenomena since few or no free electrons exist.
Heat capacity is a measure of the amount of heat needed to
be transferred to a material in order to raise its temperature a
certain amount. Thermal expansion refers to the amount of
dimensional change that occurs in a material as a conse-
quence of a temperature change. Most materials, with the
notable exception of water changing to ice, tend to shrink
with decreasing temperature levels.
Chemical properties of particular interest include a material’s
reactivity, valence and solubility. Reactivity is a measure of
how a material chemically acts with another substance to
produce a chemical change. The term solubility generally
refers to the capability of a material for being dissolved (a
solvent, in turn, is a material, usually liquid, that has the
capability of dissolving another substance). The term valence
generally refers to the capacity of an element to combine with
another to form molecules.
The optical properties of a material, such as its reflectivity,
transmissivity and absorptivity, are complex since they may
depend upon both intrinsic and extrinsic factors. When light is
incident on a material, it is either re-emitted via reflection or
transmission, or it might be converted into heat energy. These
phenomena are closely dependent on the nature of the
material’s electron field at its surface (see Chapter 4).

2.6 General classes of materials

Briefly, there are three primary material classes – metals,
ceramics, polymers – and many related or derivative types fall
into a fourth type known as composites.
Pure metals, including copper, are characterized by their
metallic bonds and regular lattice structures. Many metals
having face-centered cubic organizations are quite ductile
because external forces easily cause slipping among planes
that have preferred directions. Iron and nickel are transitional
metals involving both metallic and covalent bonds, and tend
to be less ductile than other metals. Dislocations and related
phenomena are of extreme importance in understanding how
metals behave.

Fundamental characterizations of materials 41

Smart Materials and New Technologies

Ceramics are characterized by their strong ionic and

covalent bonds. Since there are no free electrons that move
around, these materials have crystal structures that are
electrically neutral and are not good conductors. Dislocation
movements are present in ceramics but are of lesser
importance. In general, ceramics are hard and brittle, and
tend to fail along special cleavage planes. Consequently,
ceramics are normally very hard and brittle. They have high
resistance to heating and are often used as refractory
materials. Glass is an amorphous non-crystalline structure
linked by covalent bonds.
Polymers are composed of long-chain molecular structures.
Individual molecules are covalently bonded. In simple thermo-
plastics, the chains are not directly connected but are bound
together only by weak van der Waals bonds. Hence, they are
quite soft and ductile since external forces can cause chains to
slide by one another relatively easily. These same thermo-
plastics can be easily melted (heat breaks down the van der
Waals bonds) and will then reform into a solid when cooled.
Thus, they can be easily recycled. Thermosets, by contrast,
have additional hardeners added to them that cause the long-
chain molecules to be cross-linked or interconnected.
Common epoxies are thermosets. External forces cannot
cause chains to easily slide by one another. Consequently,
these materials can be quite strong and hard. They cannot,
however, be melted like thermoplastics.
Folded chain polymers have a periodic arrangement of
chains in them that are crystalline in nature, but not cross-
linked, and have multi-layered structures to them. They can
be formed in many ways, including crystallization from dilute
solutions. These semi-crystalline polymers can be quite dense.
They can be made chemically resistant and highly heat
resistant. In Chapter 4 we will see that this class of polymer
is particularly important vis-à-vis smart behaviors since the
semi-crystalline nature of these folded chains allows many
properties to be imparted to them that are not normally
associated with polymers (e.g., conductivity).
Elastomers are polymers that have largely amorphous
structures, but are lightly cross-linked. They can be thought
of as laying between thermoplastics and thermosets. Many
natural materials are elastomeric whereas other elastomers
can be readily synthesized. The Vulcanization process – used
in making common automobile tires – creates cross-links
containing sulfur atoms. The rubber gives the tires elasticity,
s Figure 2-6 General makeup of composite
but the cross-linking makes them sufficiently stiff and hard.
materials intended for high performance Composites are high-performance materials that are made
strength or stiffness applications by combining two or more primary materials. They comprise

42 Fundamental characterizations of materials

 Smart Materials and New Technologies

s Figure 2-7 Two flexible composite sheets

a huge class of materials – there are literally thousands of them

– and are beyond the scope of this treatment to discuss in
detail. Briefly, composite materials are invariably intended for
high-performance applications where their properties are
engineered for specific purposes, and they may be broadly
thought about in terms of their functions. Are they intended
to serve strength or stiffness functions? Are they meant to
reduce thermal conductivity? Are they meant to have special
reflective characteristics? Figure 2–6 shows the general
makeup of composites intended for strength or stiffness
applications. Normally, these composites are made up of
reinforcing materials, resins or matrix materials that the
reinforcing materials are embedded into, and, quite fre-
quently, internal cores are present as well. Different forms of
these kinds of composites can be engineered for specific
strength or stiffness applications, including directions of
stresses and so forth. For other purposes, embedded materials

s Figure 2-8 Typical materials used in composites

Fundamental characterizations of materials 43

Smart Materials and New Technologies

may not serve strength functions at all. Fiber-optic cables, for

example, have been embedded in different materials to serve
as strain or crack detectors in the primary material. Also,
different films or sheet products may be laminated together as
well. The high performance radiant color films with multiple
reflectance qualities, for example, are multi-layered laminates
of different types of films.

2.7 Nanomaterials
The term ‘nanotechnology’ has attracted considerable scien-
tific and public attention over the past few years. The prefix
‘nano’ indicates that the dimensional scale of a thing or a
behavior is on the order of a few billionths of a meter and it
covers a territory as large, if not larger, than that represented
by micro-scale. For comparison, the head of a pin is about one
million nanometers across whereas a DNA molecule is about
2.5 nanometers wide. Given that individual atoms are
nanometer size (for example, 5 silicon atoms is equivalent
to one nanometer), then the ability to build structures one
atom at a time has been a provocative objective for many
materials scientists. In its simplest form, nanotechnology
conceptually offers the potential to build ‘bottom up,’

s Figure 2-9 Relative size comparisons. Nano-scale objects exist at sizes

near the atomic level. Micro-scale objects, such as many MEMs
devices, are much larger (a human hair, for example, is about 50 mm in
diameter) and can be visually seen. Devices at the meso-scale level
(equivalent to millimeter to centimeter scales) are relatively large in
comparison to microscale and nanoscale objects, but still very small
with respect to human dimensions

44 Fundamental characterizations of materials

 Smart Materials and New Technologies

creating materials and structures with no defects and with

novel properties.
As discussed earlier in this chapter, the precise makeup of
different internal structures and the bonding forces between
them largely determine the mechanical, electrical, chemical
and other properties of the solid material. Nanotechnology,
by enabling the complete construction of the molecular
structure, may afford us the possibility to design unprece-
dented and dramatically enhanced properties for the macro-
scale. Indeed, it may even be possible to produce substantially
different properties without even changing the chemical
composition. Already, one nanomaterial – carbon nanotubes
– has been attributed with an electrical conductivity that is 6
orders of magnitude higher than copper, and a strength to
weight ratio that is 500 times greater than that of aluminum.3
Essentially, we will be able to program material properties.
Furthermore, constructing bottom up could also allow for self-
assembly, in which the random (non-continuum) motion of
atoms will result in their combination, or for self-replication, in
which growth occurs through exponential doubling.
Beyond the opportunity to ‘build’ materials from scratch,
nanotechnology also encompasses the development of and
application of nano-sized materials and systems. Nano-
particles are being proposed for inclusion in paints and
abrasives, and nanoprobes are intended to be the basis of in
vivo drug delivery devices. Quantum dots – nanometer-sized
semiconductor crystals capable of confining a single electron
– represent the next generation in luminescent technology as
they essentially are quantum LEDs (light-emitting diodes). The
potential applications for nanotechnology abound, from data
storage to body armor, but this exciting field is still in its
infancy, and many of proposed application domains are, at
best, speculative. Nevertheless, both the technologies and
ideas implicit in thinking about behaviors at the nano-scale
hold great promise for the future.

Notes and references

1 Braddock, S. and Mahoney, M. (1998) Technotextiles.
London: Thames and Hudson.
2 See, for example, Schodek, D. (2003) Structures, 5th edn.
Englewood Cliffs, NJ: Prentice-Hall.
3 These numbers came from a presentation titled ‘An Overview
of Recent Advancements in Nanotechnology’, delivered by
s Figure 2-10 Carbon nanotubes (CNT). A M. Meyyappan of NASA Ames Research Center in October
tubular form of carbon, with a diameter as
small as 1 nm, is produced from sheets rolled
2002. The numbers vary widely from source to source.
into tubes. (NASA Ames)

Fundamental characterizations of materials 45

 3 Energy: behavior, phenomena and environments

Although we often imagine materials as things that can be

weighed, measured and described, and thus as tangible
artifacts, our primary interest as designers is in how materials
behave. A steel column becomes useful when it supports a
load. A pane of glass is meaningful when it transmits light.
When we choose a material, we inherently choose it for its
interaction with some type of energy stimulus, and this is true
even for those materials that we simply wish to view, such as
those in a sculpture. As a result, no discussion of materials can
be complete without an understanding of energy.

3.1 Fundamentals of energy

What is energy? This is a difficult question, as energy is not
a material thing at all, even though it is the fundamental
determinant of all processes that take place among and
between all entities. Whenever an entity – from an atom to an
ecosystem – undergoes any kind of change, energy must
transfer from one place to another and/or change form. For
example, heat must be transferred – added or removed – for
the temperature of an object to change, and the form of
energy must change from kinetic to electrical when a turbine
rotates a shaft in a generator. Conceptually, all forms of
energy can be divided into two generic classes:
* Potential energy: stored energy that can flow. The energy
that is stored by virtue of position, bending, stretching,
compression, chemical combination. Examples include
water behind a dam, boulder on top of a hill, a coiled
spring, gasoline.
* Kinetic energy: energy that is flowing. The energy of motion
that moves from high potential entities to low potential
entities. Examples include water falling over a dam, a
boulder rolling down a hill, the combustion of gasoline in
an engine.

Within these two classes, energy takes many different forms,

and each form is characterized by a fundamental variable that
becomes useful as energy only when difference comes into
play. Without a difference between one state and another,
energy cannot flow. As a result, energy can only be quantified
and measured as it moves or by its potential to move.

46 Energy: behavior, phenomena and environments

 Smart Materials and New Technologies

HEAT driven by temperature difference

WORK driven by pressure difference
POTENTIAL: driven by height difference
ELECTRICAL: driven by charge difference
KINETIC: driven by momentum difference
ELASTIC: driven by deflection difference
CHEMICAL: driven by atomic attraction differences
NUCLEAR: driven by quanta differences
MAGNETIC: driven by moving charge differences

What, then, governs this movement? Although the flow of

energy determines the behavior and state of all things – living
and inanimate – scientists did not develop an understanding
of it until 1850, two centuries after the establishment of
Newtonian physics. The 19th century developments in steam
engine technology finally led to the discovery of an important
principle: the conservation of energy. This principle is perhaps
the most fundamental building block of physics, and it is also
the foundation for the branch of physics known as thermo-
dynamics – the science of energy.

3.2 Laws of thermodynamics

Derived from the Greek words thermé (heat) and dynamis
(force), thermodynamics describes the branch of physics
concerned with the conditions of material systems and the
causes of any changes in those conditions. A material system
may be comprised of anything from a solid to a liquid to a gas
as well as a mixture thereof, but it is distinguishable as an
identifiable quantity of matter that can be separated from
everything else – the surroundings – by a well-defined
boundary. The conditions of a system at any given moment
are known as its state, which basically encompasses all that
can be measured – temperature, pressure and density – as
well as its internal energy.
The nature of the relationship between a system and its
surroundings is governed by the Laws of Thermodynamics.
There are four laws, of which the first three are most relevant
for our discussions. Even though each law makes a reference
to heat (hence thermo-dynamics), together they govern the
dynamics of all forms of energy.

ZEROTH LAW OF THERMODYNAMICS (ALSO

KNOWN AS ‘THE LAW OF THE THERMOMETER’)
If two entities are in thermal equilibrium with a third entity
(such as a thermometer), then they are in thermal equilibrium

Energy: behavior, phenomena and environments 47

Smart Materials and New Technologies

with each other. Essentially, this law tells us that equilibrium is

a condition without difference, and thus without further
energy exchange.

FIRST LAW OF THERMODYNAMICS (ALSO KNOWN

AS ‘THE LAW OF CONSERVATION OF ENERGY’)
While energy assumes many forms, the total quantity of
energy cannot change. As energy disappears in one form, it
must appear simultaneously in other forms – energy is thus
indestructible and uncreatable (in the Newtonian world-
view). More formally, the rate of energy transfer into a system
is equal to the rate of energy transfer out of a system plus any
change of energy inside the system. The First Law can be
conceptually represented by the following expression:

(energy of system) þ
(energy of surroundings) ¼ 0

If energy is convertible and indestructible, then it must be

possible to measure all forms of it in the same units.
Regardless of whether the energy is electrical, or thermal, or
kinetic, we can measure it in kilowatt-hours, and convert it
into calories, BTUs, foot-pounds, joules, electron volts and so
on. While it may be difficult to imagine that one could talk
about foot-pounds of heat, or calories of electric current, the
First Law establishes their equivalence.
The generation of electricity in a power plant is an excellent
example of the First Law, as energy must go through many
transformations before it can become directly useful at a
human scale. The combustion of coal (chemical energy)
produces the heat that converts water into steam (thermal
energy) that is used to drive a turbine (mechanical energy)
that is used to rotate a shaft in a generator thereby producing
electrical energy. These are just the energy exchanges within
a power plant, we could also extend the transformations in
both directions: the chemical energy in the coal results from
the decay of plant materials (more chemical energy) which
originally received their energy from the sun (radiant energy)
where the energy is produced by fusion (nuclear energy), and
so on. In the other direction, electricity produced by the
power plant might be used to run the compressor (kinetic
energy) of a chiller that provides chilled water (thermal
energy) for cooling a building.
This tidy accounting of energy might lead one to conclude
that there cannot be a global energy problem, as energy is
never destroyed. This, however, is where the Second Law
comes into play.

48 Energy: behavior, phenomena and environments

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SECOND LAW OF THERMODYNAMICS (ALSO

KNOWN AS ‘THE LAW OF ENTROPY’ OR ‘THE
CLAUSIUS INEQUALITY’
Entropy is an extensive property of a system that describes
the microscopic disorder of that system. Whenever a process
occurs, the entropy of all systems must either increase or, if
the process is reversible, remain constant. In 1850, Rudolf
Clausius stated this in terms of directionality: ‘It is impossible
to construct a machine operating in a cyclic manner which is
able to convey heat from one reservoir at a lower
temperature to one at a higher temperature and produce
no other effect on any part of the environment.’1 In other
words, there is a natural direction to processes in the
universe, resulting in an energy penalty to move in the
opposite direction. Water above a waterfall will naturally flow
to a lower level, but it must be pumped up from that level to
return to its starting point.
Although the second law is often rhetorically interpreted
as ‘increasing randomness’, entropy is neither random nor
chaotic. The concept of ‘exergy’ explains just what the
penalty is when we attempt to reverse a process.

EXERGY (ALSO KNOWN AS AVAILABILITY)

The exergy of a thermodynamic system is a measure of the
useful work that can be produced in a process. Work is any
interaction between a system and its surroundings that can be
used to lift a weight, and as such, work is harnessable. Lost
work is the difference between the ideal work and the work
actually done by the process. Basically, even though the laws
of thermodynamics state that energy can never be destroyed,
lost work is that which has been wasted, in the sense that it
can become unavailable for further transformation, and thus
unavailable for human use. Wasted work turns up as heat. So,
for example, if a generator converts kinetic energy into
electrical energy at an efficiency of 90%, then 90% of the
initial energy produces work, and the remaining 10%
produces heat. Referring back to the Second Law, we begin
to recognize that, on a universal level, every single process
is reducing the amount of concentrated energy available
while increasing the amount of distributed (and therefore,
unharnessable) heat.
With this understanding of the rules by which energy is
converted from one form to another, we can now express the
First Law more formally:

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Smart Materials and New Technologies

Q (heat)

W (work) ¼ U (internal energy) þ Ek

(kinetic energy) þ Ep (potential energy)

Both heat and work are transient phenomena; systems do

not possess heat or work as they might possess internal or
potential energy. Instead, heat and work are only manifested
by the transfer of energy across the boundary between a
system and its surroundings. As such, a thermodynamic
boundary is a region of change, rather than a discontinuity.
Why is the study of thermodynamics important for under-
standing the behavior of materials and, more importantly,
that of smart materials? For architects, the most typical
interaction for a material is the load produced by gravitational
forces. As a result, properties represented by Young’s modulus
or the yield point are the most familiar. Classical discussions
of mechanics would suffice. But, as mentioned earlier, the
behavior of a material is dependent upon its interaction with
an energy stimulus. All energy interactions are governed by
the laws of thermodynamics, whether it is the appearance of
an object in light or the expansion of a material with heat.
Material properties determine many aspects of these interac-
tions. For example, one material property may determine
the rate at which energy transfers; another property may
determine the final state of the object. A general thermo-
dynamic relationship between a material system and its
energy stimulus can be conceptualized by the following:

state of the object or material system
property

¼ function of energy transfer

As an example, if we look at Fourier’s Law, which calculates

the rate of heat transfer through a material, we can begin to
see how the material property of conductance determines the
state of the object.

T (U  A) ¼ Q
T ¼ temperature, Q ¼ heat transfer rate,
U ¼ conductance, A ¼ area

The state of the object (or material system) is denoted by the

state variable of temperature, whereas the heat transfer rate
represents the amount of energy exchanged or transformed
by the object. The area is an indication of how much material
is being affected, and the property of conductance ultimately
determines either what the temperature of the object will be
or how much heat must transfer in order for the object to
reach a particular temperature.

50 Energy: behavior, phenomena and environments