UTHSCSA Dental School Reading Assignment:

DRFD 5001, Biomaterials Module Phillip’s Science of Dental Materials, 13th ed., Ch. 2, pp. 34-41
Dr. Kyumin Whang, Rm. 2.569U Updated: August 3, 2023

INTRODUCTION TO POLYMER SCIENCE

LEARNING OBJECTIVES:
To be able to…
1. define all bolded terms in the handout having to do with polymers, their fundamental nature, and
their properties.
2. distinguish the effects of chain length, chain branching and crosslinking on the mechanical
properties of a polymer.
3. distinguish the effects of the three types of polymer tacticity on polymer molecular orientation,
crystallinity, mechanical properties, and optical properties.
4. distinguish the effects of polymer crystallinity on polymer mechanical and optical properties.
5. describe how ‘spherulites’ form when a crystalline polymer forms during polymerization or when a
crystalline polymer cools from a melt.
6. distinguish elastic recovery, plastic deformation, and viscoelastic behavior.
7. relate how the rate (fast or slow) at which a force is applied to a viscoelastic polymeric material
affects its tendency to be deformed or recover.
8. pick out the three factors that affect swelling in polymeric materials.
9. compare material properties of thermoplastics and thermosets.
10. distinguish material properties, such as specific volume and mechanical properties, and molecular
motion above and below the glass transition temperature (Tg).
11. describe the 4 steps of addition polymerization.
12. compare and contrast advantages and disadvantages of addition and condensation polymerization.
13. distinguish the functions of accelerators, initiators, and inhibitors.
Introduction to Polymer Science Dr. Kyumin Whang

Polymers are giant molecules used in many classes of products in dentistry, such as prosthesis (denture
base acrylic), restorations (filled resins), equipment (mixing bowls), impression materials (e.g. silicone
rubber), denture liners, and cements (resin based). Their properties are mainly dependent on their
molecular structure, and are very flexible due to the possibility of all kinds of arrangements; hence their
utility in many different applications. These properties can be explained and predicted in terms of their
chain structure, side-groups, and crosslinking, leading to the possibility of designing polymeric materials
to have specific functions.
KEY TERMS:
Polymer: "Poly" = many, "Mer" = unit or part. A molecule that consists of many repeating units
arranged in long chains. Shorter versions (approximately less than 10 units) are called oligomers.
Monomer: A chemical compound capable of reacting to form a polymer. Monomers generally become
the repeating units (Figure 1).
Polymerization: A chemical reaction in which monomers (low molecular weight) are converted into
polymers (high molecular Polymerization
weight) (Figure 1).
Monomer + Monomer + Monomer + Monomer ® -Mer-Mer-Mer-Mer-
FUNDAMENTAL NATURE
Polymerization
OF POLYMERS
H2C=CH2 + H2C=CH2 + H2C=CH2 + H2C=CH2 ® H3C-(CH2-CH2)n-CH3
Polymers can exist in three
forms: Ethylene Polyethylene
Figure 1: Polymerization of ethylene to polyethylene.
Linear polymers: Polyethylene
is a linear polymer, where the
‘mers’ form a linear chain (Figures 1, 2 and 3).
Branched polymers: Branching is like adding arms to a
polymer chain (Figure 3) and the chance for entanglement
(i.e., temporary connections) increases. The branches may
have already been present in the monomer or the central
monomer may have 2 or more reactive sites allowing the
growth of a side-chain in addition to the main polymer chain.
Crosslinked polymers: Crosslinks are permanent connections
between chains (Figure 3). Theoretically, a highly crosslinked
polymer can be one giant molecule. Crosslinking happens Figure 2: Random coil of polyethylene
either because there was a “crosslinker” that formed bonds (adapted from B.W. Darvell, 1998).

Figure 3: Linear, branched, and cross-linked polymer structures. Light circles = one type of mer unit; dark circles =
another type of mer unit (adapted from R.G. Craig, 1997).

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Introduction to Polymer Science Dr. Kyumin Whang

between the chains during

polymerization, or the
monomers had 2 or more
reactive sites allowing the
formation of branches able to
connect with neighboring
chains.
Copolymers: Polymers
formed by using more than
one type of monomer.
Usually the order of the
different monomers is
random (random
Figure 4: Different copolymer structures. Light circles, one type of mer unit; dark
copolymer), but they can be
circles, another type of mer unit (adapted from R.G. Craig, 1997).
formulated where a large
number of one mer type is Brittle
Crosslinked
connected to another mer type
Rigidity
(block copolymer) (Figure 4).
Hard Branched
Chain length, the extent of Strength Straight Chain
chain branching and Soft Hard & Rigid
Melting Gummy Hard
crosslinking, and the Soft Solid
organization of the chains among Solid
themselves are fundamental Liquid
features of polymers that Gas
determine the properties of
polymeric materials. Figure 5 Molecular Weight (Number of Repeat Units, i.e. Chain Length)
illustrates how molecular weight,
Figure 5: Effect of polymer chain length, branching and crosslinking on
branching and crosslinking of mechanical properties.
polymers affect mechanical and
material properties. The longer the polymer chain the greater the number of entanglements (temporary
connections) among chains. Thus, the longer the chains the more difficult it is to distort the polymeric
material; consequently, rigidity, strength and melting temperature increase (there is a strong analogy
with spaghetti). Also, branched and crosslinked polymers have stronger material/mechanical properties
as compared to linear polymers.

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Introduction to Polymer Science Dr. Kyumin Whang

DEMO 1:
Three cylinders of liquid are in the front of the classroom. What are some similarities?

What are some differences?

There are three ball bearings. What might happen when the ball bearings are dropped into the fluids?

What differences do you expect to see? Why?

Using Table 1, what are some similarities Table 1: Chemical formula and molecular weights of methanol,
between the fluids and what are some ethylene glycol and glycerin.
differences?
Methanol Ethylene Glycol Glycerin

CH3OH HOCH2CH2OH HOCH2CH(OH)CH2OH

Mw = 32 62 92

Theorize what will happen when the ball bearing is dropped into the three fluids, and why.

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Introduction to Polymer Science Dr. Kyumin Whang

Tacticity: Tacticity describes the relative

position of the side groups or branches of the
polymer from one unit to the next (Fig. 6),
and it affects material properties. Polymers
can be in one of three different arrangements:
Isotactic polymer: This is when the relative
position of the side groups or branches of the
polymer is always the same.
Syndiotactic polymer: This is when the
sequence of the relative position of the side
groups or branches of the polymer is
alternating.
Atactic polymer: This is when the side
groups are randomly arranged. Figure 6: Possible configurations of polymers with asymmetric
carbons in the chain (adapted from B.W. Darvell, 1998).
Due to the repeating structure of isotactic and
syndiotactic polymers, they can readily form regular arrays and crystallize (described below).
Molecular Organization: Molecular organization can also affect material and mechanical properties
(Figure 7). In some polymers the chains can align themselves to form a highly ordered (i.e., crystalline)
structure. In others the chains are randomly coiled and entangled into an "amorphous" structure
(Figures 2 and 7). Many polymeric materials combine these two forms of organization.

Crystalline Regions Amorphous Regions Combination (Semi-Crystalline)

Highly ordered Random coils
Hard & rigid Soft & flexible or glassy
High melting point Low glass transition temperature
Transparent or translucent Transparent Translucent or opaque
Figure 7: Schematic of different molecular organizations of polymers and their corresponding properties.

Figure 8 is a micrograph of polyethylene oxide spherulites under

cross-polarizers showing the regular crystalline structure. Note that
when a crystalline polymer is polymerized, the crystalline regions
begin forming at the center of the spherulite. This phenomenon can
also be observed when a polymer is cooled from a melt.

Figure 8: Polarized light micrograph

of polyethylene oxide spherulites.

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Introduction to Polymer Science Dr. Kyumin Whang

DEMO 2:
When a strip cut from a sandwich bag is stretched, several things happen. What are some observations
as to the way the strip stretches and feels as it is stretched?

Why does the strip feel different, as it is stretched, especially just before it breaks? Try to explain using
the concepts of crystallinity and amorphousness of the material.

When the stretching is observed under polarized light, what happened?

Why?

Does your initial theory of why the strip feels different, as it is stretched, change in light of what is
observed under polarized light? If so, how?

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Introduction to Polymer Science Dr. Kyumin Whang

POLYMER PROPERTIES:
The combination of polymer chemistry, chain length, branching, crosslinking, and molecular orientation
give rise to different material properties, such as mechanical, dissolution, and thermal properties.
Mechanical Properties:
Elastic Recovery: This is when the material is deformed but rapidly returns to the original shape
(Figure 9) like a rubber ball. It occurs in the amorphous regions of polymers where the randomly coiled
chains straighten and then recoil and return to their original size and location in the material.

Figure 9: Schematic of elastic deformation. Chains uncoil but do not slip past one another (due to amorphous regions,
entanglements or crosslinks).

Plastic Deformation: This is when the material is deformed and molded into a new, permanent shape
(Figure 10) like stretching silly putty. It occurs because polymer chains slide past one another and
become relocated within the material, resulting in permanent deformation.


Figure 10: Schematic of plastic deformation. Chains slip past one another but don't uncoil.

Viscoelastic Behavior: Plastic "flow" and elastic recovery describe ideal materials. Both occur in real
polymers (Figure 11). Chain length, number of crosslinks, temperature, and rate of force application
(impact vs. squeezing) determine the type of behavior. Elastomers always have a small degree of
permanent deformation, while plastics always show a small degree of elastic recovery after deformation.

Figure 11: Schematic of viscoelastic deformation.

These properties were illustrated in Demo 2, where the

deformation is also called drawing (Figure 12). When a
tensile load is applied, the random coils in the amorphous
regions are straightened and chains become oriented. In
effect, this material becomes more crystalline, making it
stiffer in tension. With further drawing, chain slippage
occurs and the deformation becomes plastic.

Figure 12: Drawing a polymer changes its

structure. Chains become well aligned in the
process (adapted from Darvell, 1998).

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Introduction to Polymer Science Dr. Kyumin Whang

DEMO 3:
This demo illustrates the difference between elastic, plastic and viscoelastic properties through the
curing of polymethyl methacrylate (PMMA). PMMA, or acrylic, is frequently used as denture material
in its crosslinked form and as impression tray materials in its regular form. In orthopedics, it is used as
bone cement in crosslinked form. The polymerization, or curing, of PMMA from its monomer, methyl
methacrylate (MMA) is shown below in the Addition Polymerization section. To cure PMMA, a mixture
of PMMA, MMA and catalyst is made and stirred.
As the polymerization proceeds, how do material properties change?

Based on the principles presented above, hypothesize why.

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Introduction to Polymer Science Dr. Kyumin Whang

Dissolution Properties:
Polymers tend to absorb a solvent, swell and soften rather than dissolve, but as chain length decreases,
they will dissolve. The longer the chains, the slower a polymer dissolves and crosslinking prevents
complete chain separation and inhibits dissolution. Thus, highly crosslinked polymers cannot be
dissolved. Amorphous polymers swell more than crystalline polymers, and elastomers swell more than
plastics. (Find out the definition of elastomer and why it swells more.) Even a small amount of swelling
in dental devices can have undesirable results.
When absorbed molecules (e.g. water) push chains apart and facilitate inter-chain slippage, there is a
lubricating effect called "plasticizing." (Why?)

DEMO 4:
Crystal Soil is a product that is used instead of soil to hydrate plants. They can absorb up to 80-150
times its volume of water and release it slowly! The monomer is acrylamide, and the polymer is
polyacrylamide.

Polymerization

Acrylamide Polyacrylamide
monomer

When Crystal soil is placed in water, what happens?

Based on the principles presented above, hypothesize how this happened.

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Introduction to Polymer Science Dr. Kyumin Whang

Thermal Properties:
Thermoplastics: These are materials that can soften
(flow or melt) when heated and can be molded. The
process is reversible since no new chemical bonds are
formed.
Thermosets: These are materials whereby heat causes
polymerization and crosslinking or just crosslinking to
make new bonds that lock the material into a new
shape. The process is non-reversible (why?). Applying
heat speeds the solidifying reaction but once solidified,
the material will not flow or melt.
Glass Transition Temperature (Tg): When a solid
polymer is cold enough, it is stiff, hard and brittle, and
Figure 13: Specific volume vs. temperature for a
is called glassy. However, when it is heated, it's typical polymer at its Tg (adapted from Darvell,
mechanical behavior changes. At a certain temperature, 1998).
called the glass transition temperature (Tg), there is a
change from being glassy and brittle to ductile or rubbery.
This is not due to the polymer melting. The melting point
of the polymer is much higher.
Tg is an important property used to characterize an
amorphous polymer and is defined in various ways. As
noted above, it is the temperature where the polymer goes
from a glassy to a ductile state. It can also be defined as the
temperature where there is a sudden alteration in the rate of
change of the specific volume; from a low rate of change
below Tg to a high rate of change above Tg (Figure 13).
Tg only marks one of the several stages in the thermo-
mechanical properties of polymers. Figure 14 shows the Figure 14: Correlation of mechanical
correlation of mechanical properties with respect to properties with temperature relative to Tg
temperature relative to the Tg. While there is only one Tg, (adapted from Darvell, 1998).
there are several
smaller changes
in the mechanical
properties as
shown.
Another way to
represent this
relationship is by
plotting the log of
the elastic
modulus against
temperature
(Figure 15). Figure 15: Polymer modulus vs. temperature Figure 16: Polymer modulus vs. temperature
Temperature also correlated with polymer mechanical correlated with dominant molecular processes
corresponds to the properties (adapted from Darvell, 1998). (adapted from Darvell, 1998).
"unfreezing" of a

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Introduction to Polymer Science Dr. Kyumin Whang

particular type of molecular motion (Figure 16). Thus, at low temperatures, the stiffness of primary
valance bonds dominates the behavior, and at high temperatures, chain slippage gives rise to a very low
modulus. Note that these properties are independent of chain length but rather dependent on the ability
of the chain segments to rotate due to thermal energy.

DEMO 5:
What did you just observe in the video clip? Was it freezing?

Describe in your own words, what happened as related to Tg.

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Introduction to Polymer Science Dr. Kyumin Whang

CHEMISTRY OF POLYMERIZATION:
Curing: This is the chemical reaction in which low molecular weight materials (monomers or small
polymers) are converted into higher molecule weight materials (polymers) in order to attain desired
properties. It is also called polymerization. This process may involve crosslinking.
Setting: This is the extent to which curing has progressed.
Initial Set: This is when the material has undergone sufficient polymerization to hold its shape
temporarily.
Final set: This is when the reaction (polymerization) is complete.
Monomers may be joined together via two main types of chemical reactions: addition polymerization or
condensation polymerization.
Addition Polymerization:
This is when monomers are added sequentially to another in a chain-growth reaction. Polymers
produced by this method are simple multiples of the monomer.
There are 4 steps in this process. The example used to demonstrate addition reaction is the curing of
PMMA.

Step 1: Activation - Application of energy (heat or light) to cause an initiator ("catalyst") to chemically
decompose and form free radicals (very reactive molecular fragments).
Heat alone, or room temp. + accelerator, or light (UV or visible)

INITIATOR FREE RADICALS

BENZOYL PEROXIDE R•

Step 2: Initiation - Breaking of monomer double bonds causing them to begin reacting with other
monomers.
FREE RADICAL + MONOMER ACTIVATED MONOMER
R• + METHYL METHACRYLATE R-MMA•

Step 3: Propagation - Continuation of the addition of monomer to the activated, growing chain.
ACTIVATED MONOMER + MONOMER GROWING CHAIN
R-MMA• + MMA R-[MMA]2• … + nMMA R-[MMA]n+1•
(n » 50,000)

Step 4: Termination - Two free radicals react, a stable molecule then forms, and the reaction stops.
R-[MMA]n+1• + •MMA-R R-[MMA]n+1-MMA-R

Accelerator: This is a catalyst that makes the initiator unstable at ambient (i.e., normal) temperatures.
Therefore, additional heat is not needed. In dental materials, they are usually aromatic amines. They are

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Introduction to Polymer Science Dr. Kyumin Whang

always found in "self"-curing (also called "cold"-curing or “chemical” curing) polymer resin systems.
They must be mixed with the initiator before polymerization will begin. Thus, two-part systems are
used. One part has the initiator, the other the accelerator.
Inhibitor: This is an additive that reacts with free radicals faster than do monomers. They are also
called free radical "scavengers." They delay initiation and allow for sufficient working time, and act as
a preservative to extend storage life/"shelf life." They are typically a hydroquinone similar to food
preservatives such as BHA (Butylated hydroxyanisole) & BHT (butylated hydroxytoluene).
Condensation Polymerization:
This is also called step growth polymerization, where all monomers react simultaneously. A catalyst is
used to activate the monomer and small molecules (e.g. water and HCl) are usually eliminated from the
polymer chain ("condensed out"). Thus, the unit parts of the polymer have a slightly different chemical
formula than the original monomer. Examples include some elastomeric impression materials.
These "condensed" byproducts (such as H2O and HCl) can degrade properties. If these byproducts
evaporate, it can lead to porosity & shrinkage. If they are retained, it can lead to plasticity (softening).

DEMO 6:
Nylon is made via a condensation polymerization reaction. In the case of the
nylon rope trick, describe what is happening initially at the interface of the two
immiscible layers of a diamine dissolved in an aqueous solution of sodium
hydroxide and a diacyl chloride in an organic solvent.

Now describe what is happening when the polymerized layer from the middle is
lifted out.

n ClCO-[CH2]n-COCl + n NH2-[CH2]m-NH2
diacyl chloride diamine

-[CO-(CH2)n-CO-NH-(CH2)m-NH]-n + 2n HCl
polyamide
What do you think happens to the HCl?

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