Phase transitions in polymeric solids

❑ Amorphous solids are as disordered in the solid phase as they are in

their melts. Vitreously solidified amorphous states are supercooled,
disordered melts or glasses.
❑ They undergo no structural change when heated and transitioning to
the liquid phase. This process is referred to as the glass transition,
and the associated temperature TG as the glass transition
temperature.
❑ No abrupt change of volume occurs at the glass transition. This is
because the structure of the material is identical—i.e., disordered—
above and below TG.

Sketch showing the volume change at a glass Second-order transitions: no transition enthalpy required to break a
transition. TG glass transition temperature crystal lattice. No substantial change in entropy because both states are
approximately equivalent in structure.

No ΔG can be assigned to a second-order transition. But abrupt changes in

other properties such as heat capacity are observed. Because the melt
generally has more translational degrees of freedom above TG, stimulation
requires more enthalpy and the addition of a larger amount of heat is
required to raise the temperature by one degree. Hence, a sharp rise in
heat capacity occurs across a glass transition, Δcp. Page 1
 Phase transitions in polymeric solids

Semicrystalline polymers consist of both crystalline and

amorphous areas.

In principle, polymers are never crystalline to 100 %, so there

is a co-existence of crystalline and amorphous domains.

When heating of a semicrystalline or partially crystalline

polymer, both a glass transition at a temperature TG and a
melting process at a temperature Tm can be observed.

Sketch showing the volume change at the glass TG is always lower than Tm
transition and the melting temperature of partially
crystalline polymers. TG glass transition temperature, Tm
melting temperature

Methods for the Determination of TG and Tm

4.2.1 Static Procedures – 97
4.2.2 Dynamic Procedures – 98 Page 2
 Polymers as materials

Some basic requirements for a suitable material, depending on an actual application:

❑ Mechanical and thermal resilience
❑ Resistance to chemicals, ultraviolet (UV) radiation, and electrical fields
❑ Appearance (inherent color/colorability, transparency, and printability)
❑ Cost of raw materials, production, rework, and assembly
❑ Weight
❑ Dimensional stability, and thus form constancy under different conditions
❑ Resistance to fire

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 Polymers as materials

Fracture Behavior

Tension–elongation curves (σ = f(ε)) of (a) brittle and (b) viscoelastic polymers

❑Stiff materials (with a high Young’s modulus) a relatively minor elongation ε already requires a high stress σ, a
characteristic of polymers below their Tg. The Young’s modulus is given by the initial slope of the curve shown and
the energy needed for fracture by the area under the curve until fracture.

❑The material (such as chewing gum) starts to flow under the external stress at a particular degree of elongation ε
(the yield point). The shape of the curve after exceeding the yield point is relatively poorly defined. The material
eventually fractures whereby the mechanism is referred to as ductile fracture. The energy leading to fracture is again
given by the area under the curve.
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 Polymers as materials
Fracture Behavior ❑ At low temperatures, only limited deformation is possible. The
material is characterized by a high Young’s modulus, i.e., the
material is very stiff and a great deal of force is needed to stretch it.

❑ The material becomes softer with increasing temperature (from T1

to T6), the Young’s modulus sinks. The strength of the material, the
stress at which the material fractures, tends to decrease.

❑ At higher temperatures, the material reaches its yield point. Beyond

the yield point, the form of the curve is no longer well defined. The
material becomes progressively softer, which is reflected in a sinking
Young’s modulus and relatively flatter curves.

❑ The maximum toughness of the material, i.e., the maximum energy

required for fracture, is reached at an average temperature T4. At
Stress–strain curves for a polymer at different temperatures above T4, the curves are flatter, so that the integral
temperatures (increasing from T1 to T6) (the area below the curve ) of the curves are also smaller.

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 Polymers as materials: Tailor-made plastics
Mechanical characteristics

All polymers have approximately the same molecular main

chain stability, no matter what their particular structure,
because they consist of covalent C–C-, C–O-, C–N-, or C–S-
bonds with bond strengths of between 330 and 420
kJ/bond.

Typical examples of intermolecular interactions or cross-

links between polymer chains Page 6
 Polymers as materials: Tailor-made plastics

Schematic depiction of the morphologies of block

Mechanical characteristics polymers having different compositions

(a) Spherical aggregates arise for strongly segregated

block copolymers when the weight fraction of the
one component is less than ca. 15 %.

(b) When the portion is between about 15 % and 35

%, one-dimensional (rod-like) structures are formed.
Polymers have limited solubility in low molecular
solvents. Chemically different polymers are not (c) Between 35 % and 65 %, lamellae can be found
miscible. Solid block copolymers with the two
different polymer blocks usually form separate phases, (d, e) For even higher portions, the corresponding
and the material is heterogeneous at a nanoscale. inverse structures are formed. These percentages
should only be taken as a rough guide.

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 Polymers as materials: Tailor-made plastics
Mechanical characteristics

Electron-microscopies (TEM) of (a) a rod-like and (b) a lamellar

morphology (seen perpendicular to the plane of the page)

If the driving force for the phase separation of the blocks is

relatively low, interpenetrating co-continuous networks can Schematic depiction of a spherical morphology with
form at certain compositions. These are also referred to as a stiff polymer as the continuous phase
gyroid phases and lead to a minimum in the surface area
between the two phases.
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 Polymers as materials: Tailor-made plastics
Mechanical characteristics
❑ A continuous, hard phase makes the material stiff macroscopically.
❑ A soft phase made from a soft, elastic polymer is embedded in such a stiff material, this phase can dissipate energy,
for example, impact energy. Thus, the material becomes substantially less brittle.
❑ This principle is referred to as impact modification. E.g., Styrene copolymers: Non-transparent (opaque), high impact
polystyrene (HIPS) consists of a mixture of neat polystyrene with a graft copolymer having a polybutadiene backbone
and polystyrene side chains.
Thermoplastic elastomers (TPE): A′B′A′-block copolymers where A′ is
a polystyrene segment and B′ a polybutadiene segment.

The incompatibility of these polymers also leads to phase

separation. The continuous phase is generally the elastic
polybutadiene.

Because of the hard polystyrene domains that are glassy at room

temperature, the polybutadiene behaves as if it were cross-linked.
However, the physical cross-links are only stable up to the glass
transition temperature of the hard phase. The polystyrene
Phase separation in an A′B′A′-block copolymer transitions into a plastic state when heated above its glass transition,
via physical cross-linking. Example: A′ and the material becomes malleable.
polystyrene segment, B′ polybutadiene segment Page 9
 Polymers as materials: Tailor-made plastics
Mechanical characteristics
Schematic representation of the relationship between melting
temperature Tm and the glass transition temperature TG for
(a) block copolymers, (b) homopolymers, and (c) statistical
copolymers having identical or similar chemical compositions

❑ Because of the phase separation in the solid state, the material has
two melting and two glass transition temperatures at which the
respective, separate polymer blocks undergo the corresponding
phase transitions. These can be observed, for example, by DSC.
❑ However, practically, only two of these four transitions are
important.

❑ The material starts to flow and loses its form only if the
temperature exceeds the highest of the melting temperatures. This
temperature is relevant for processing, and defines the highest
temperature at which the polymer can be used.

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 Polymers as materials: Tailor-made plastics
Mechanical characteristics
❑ The mechanical characteristics of
polymer/GF-compounds can be further
Comparison of the effect of short and long glass fibers (GF) on improved by replacing the fiber by
the tensile strength of polyamide 6 (PA) and polypropylene glass mats and three-dimensional
(PP). (Data provided by G. Heinrich, IPF/Dresden) structures. However, the properties
also depend on the fiber material
(diameter, kind of glass), the kind of
polymer, and the interaction between
the polymer and the fiber.

❑ Other polymers such as polystyrene,

polyoxymethylene, polyester, polyether
ether ketone (PEEK), polycarbonate,
and epoxy and phenolic resins are also
used in such composites. Such
composites are perfectly able to
compete with metals in terms of their
tensile strengths.

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 Polymers as materials: Tailor-made plastics
Optical Characteristics
❑ Amorphous polymers usually appear optically transparent.
Amorphous polymers naturally appear opaque if they contain
chromophores that absorb the incoming light.

❑ Amorphous thermoplastics, such as polystyrene, polymethyl

methacrylate, polyvinyl chloride, or cellulose ester, are thus
transparent, and used for glasses, frostings, photographic materials,
and packaging.

❑ Crystalline polymers are generally opaque. This is because the light

that falls through a crystalline polymer is scattered by the crystal
lamellae; Only a few crystalline polymers, such as polycarbonate
and poly(4-methyl-1-pentene), are transparent because the
crystallites are smaller than the wavelength of visible light.

❑ crystalline polymers, such as polyethylene, polyamides, and

polyacetals, are not suitable for glass production. To make such
polymers transparent the crystallization has to be prevented. This
can be accomplished by, for example, introducing side chains; CH3-
functions are often sufficient

Examples of crystalline and amorphous polymers

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 Polymers as materials: Tailor-made plastics
Materials for lightweight construction
Polymeric foams as lightweight materials
❑ Synthetic materials are usually specifically much lighter than many other materials such as metals and ceramics.
❑ Polymer foams are suitable for sound and heat insulation, and mechanically more demanding foams, such as
furniture cushions.
❑ Polymer foams can be obtained from many polymers, such as polyvinyl chloride, polystyrene, urea-formaldehyde
and phenol-formaldehyde resins, polyurea, polyurethanes, polyvinyl acetal and polyethylene.

Fabrication of polymeric foams

❖ Mixing at high shear and introducing gas by adding low molecular mass additives which are then allowed to
evaporate or chemically.

❑ Foaming a natural rubber is successful if a foaming agent, such as soap, is added to an initial volume of a mixture
of latex rubber, extender, and vulcanization accelerator. The mixture is then vigorously stirred, expanded, and
afterwards solidified using foam stabilizers. In this way, the density of the material can be reduced by up to 90%.

❑ Viscose sponges can emerge when Na-cellulose xanthate is mixed with coarse grained salts, such as Glauber’s
salt, and coagulated in electrolyte solution. The material attains it porous structure because of the multiple salt
inclusions which are later washed out.
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 Polymers as materials: Tailor-made plastics
Materials for lightweight construction
Fabrication of polymeric foams
Chemical agents such as NH4NO2, NH4Cl + NaNO2, azo compounds, sulfohydrazides, or azides that produce
nitrogen when heated are employed as blowing agents

Chemical and physical agents are also used in the production of foams from isocyanates. For instance, the
reaction of a carboxylic acid with an isocyanate to an amide. To enhance foam formation, physical agents, such
as volatile solvents, are frequently added to these systems.

Example of a chemical blowing agent

Reaction of a carboxylic acid with an isocyanate Page 14