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151-0548-00L Manufacturing of Polymer Composites FS 17 Exercise 2

Exercise 2: Solution

MATRIX SYSTEMS

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151-0548-00L Manufacturing of Polymer Composites FS 17 Exercise 2

Task 1: Polymeric materials


a) What part of the composite determines its thermal properties?

The matrix is the component limiting the thermal range where a composite can be used.

b) What is the difference between glass transition temperature and melting temperature?

In polymer science, the melting temperature is the temperature at which the melting of the
crystalline part of a semi-crystalline polymer takes place. The glass transition temperature
is the temperature at which a polymer passes from a glass state (hard and relatively brittle)
into a rubber-like state. While the melting represents an effective phase transition (first or-
der transformation, involving a heat exchange with the external environment to break up
the inter-chains bonds), the glass transition is second order transformation that involves on-
ly the amorphous region of the polymer and entails the passage into a state with higher
(rubber-like) or lower (glass-like) mobility of the polymeric chains (regulated by the avail-
able thermal energy from the environment). The glass transition temperature is always
lower than the possible melting temperature.

c) Draw the qualitative behavior of the stiffness as a function of temperature for the following
classes of polymers and comment on the curves (The glass transition temperature TG is the
same for all three polymers)

Partially crystalline thermoplastic


Amorphous thermoplastic
Thermoset

Range I: It is found bellow Tg, and is also known as glass state. The polymer chains re-
main frozen in space, as they have not enough energy to undergo any type of motion.

Range II: It is found between Tg and Tm, and can also be called rubber-elastic state.
Thermal energy activates additional molecular degrees of freedom. The polymer chains are
now free to rotate, inducing a loss of stiffness in the polymer. This effect is less pro-
nounced for semicrystalline thermoplastics: only the amorphous regions soften at TG. The
crystalline regions still contribute substantially to the overall stiffness of a component.

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151-0548-00L Manufacturing of Polymer Composites FS 17 Exercise 2

Range II: Shortly ahead of the melting temperature stiffness begins to drop drastically. The
polymer is in the melting range, where the first crystallites start to melt.

Interesting remark: in contrast to metals, which exhibit an almost fixed defined melting
point, semicrystalline thermoplastics do not feature a unique melting point, but an interval
or a range of melting,

d) What is the degree of polymerization and what influence has on the final properties of the
resin?

The degree of polymerization is the number of times a monomer is repeated on a polymer


chain. It is defined as the ratio between the number-average molecular weight (Mn) and the
molecular weight of the monomer unit (Mo).


=
0

The higher the degree of polymerization is the better thermal and chemical resistance of
the polymer as we have more intermolecular bonds. However, very high viscosities (almost
solid state) are also obtained at room temperature, which make the processability of the
material more difficult. High temperatures (above the melting points) or solvents are in this
case needed.

e) Discuss also the influence of the crosslink density on the material properties.

Following the same reasoning, the higher the crosslink density is the higher the number of
intramolecular bonds on a polymer. The chains cannot slide or rotate because they are
fixed into position. There are less available degrees of freedom and hence higher Tg.

f) How does the branching of the molecules affect the glass transition temperature?

The free volume of a molecule is the space between this molecule and the ones sur-
rounding it. Branching increases the distance between molecules, resulting in a reduction
of the intermolecular forces. Therefore, less energy is necessary to release some degrees of
freedom, so the Tg reduces.

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151-0548-00L Manufacturing of Polymer Composites FS 17 Exercise 2

Consider the reaction, taking place in alkaline medium, between bisphenol-A and epichlo-
rohydrin.

g) If the resin has a degree of polymerization of 0 (1 bisphenol-A + 2 epichlorohydrin) and is


cured with a diamine hardener, with a molecular weight of 82g/mol and 4 reactive hydro-
gens. What is the mass of hardener necessary to cure 450g of resin?

82
= = = 20.5/
. 4

= 21 12 + 24 1 + 4 16 = 340/

. 100 2 100
= = = 0.588
340

= 4.5 = 0.588 20.5 4.5 = 54.2

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151-0548-00L Manufacturing of Polymer Composites FS 17 Exercise 2

Task 2: Thermomechanical properties


a) A table with polymer material data is given to you at the end of this exercise. Why for
some polymers the maximum service temperature is above its glass transition? Why this is
not the case for amorphous polymers?
Using semicrystalline polymers above their glass transition temperature permits to improve
their ductility without a critical impact on their thermomechanical properties (stiffness for
example), as the glass transition takes place only in their amorphous regions. However,
amorphous polymers cannot be used above their glass transition temperature as this criti-
cally lowers their thermomechanical properties.

b) Two well-established techniques in thermomechanical analysis are DSC and TGA. What
are the parameters that can be obtain through each of these analyses?
DSC: Tg, Tm, enthalpy, degree of crystallinity and heat capacity.
TGA: fiber volume content and type of fibers.

c) You are given a unidirectional composite having an unknown composition with the follow-
ing information:

1. A DSC curve of the unknown material;


2. Two TGA curves obtained at different operating conditions:
O2 atmosphere (A complete combustion of the material is observed.)
Ar atmosphere (Ar is a noble gas and the atmosphere is considered to be inert.)
3. The properties of the most common composite materials.

- What material is the matrix composed of?


According to the DSC, TG is 190C. This is most likely true for PSU.

- What material is the fibre?


From the TGA we know on the one hand that the fibres can be burnt in oxygen, on the
other hand that they stay stable up to 2500C under inert conditions (Argon atmosphere).
This condition can only apply for carbon fibres.

- What is the fibre volume content?

Composite mass = 10 g, Fibres mass = 7g and Matrix mass = 3g


mf 7g
=
V = = 4.02 cm3
f
f 1.74 g cm 3

mm 3g
=
V = = 2.45 cm3
m
m 1.24 g cm 3

Vf 4.02 cm3
V= = = 0.621
= 62 %
V f + Vm 4.02 cm3 + 2.45 cm3
f .cont

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151-0548-00L Manufacturing of Polymer Composites FS 17 Exercise 2

DSC
TGA (O2)
TGA (Ar)

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151-0548-00L Manufacturing of Polymer Composites FS 17 Exercise 2

1) Fibres
Carbon Glass
3
Density [g/cm ] 1.74 2.55
E-Modulus [GPa] 240 73
Elongation at break [%] 1.5 4.5
Tensile strength [GPa] 3.6 3.5

2) Thermoplastic polymers
PP PET PBT PA 6 PA 66
Structure Semicryst. Semicryst. Semicryst. Semicryst. Semicryst.
3
Density [g/cm ] 0.94 1.32 1.31 1.12 1.12
E-Modulus [GPa] 1.9 2.7 2.5 1.9 2.1
Elongation at break [%] 120 130 120 94 83
Tensile strength [MPa] 36 55 56 73 73
Gass transition temperature [C] -18 77 60 50-60 50-60
Max. Service temperature [C] 85 74 70 100 100
Impact strength (IZOD, unnotched) No break No break No break No break No break
[J/m]
-1 -6 -6 -6 -6 -6
Coefficient of thermal expansion [K ] 15010 7010 13010 7010 7010
Chemical resistance Good High High Good Good
Fire behaviour Flammable at Flammable Flammable Flammable Flammable
345C without additives without additives without additives without additives

PES PSU PEI PPS PEEK


Structure Amorphous Amorphous Amorphous Semicryst. Semicryst.
3
Density [g/cm ] 1.4 1.24 1.35 1.43 1.33
E-Modulus [GPa] 3.7 2.5 3.7 3.6 4.5
Elongation at break [%] 30 10-75 42 4 37
Tensile strength [MPa] 99 75 100 87 110
Glass transition temperature [C] 230 190 220 88 140
Max. Service temperature [C] 200 170 200 160 260
Impact strength (IZOD, unnotched) No break No break 1300 900 No break
[J/m]
-1 -6 -6 -6 -6 -6
Coefficient of thermal expansion [K ] 5510 5410 6210 4910 4710
Chemical resistance High Good High High High
Fire behaviour Barely flamma- Barely flamma- Barely flamma- Barely flamma-
Flame retardant
ble ble ble ble

3) Thermosetting polymers
Epoxy Polyester Vinyl ester BMI
Structure Amorphous Amorphous Amorphous Amorphous
3
Density [g/cm ] 1.2 1.2 1.1 1.3
E-Modulus [GPa] 3.2 3.9 3.2 4.1
Elongation at break [%] 1.5-8.0 1.0-6.5 2.0-8.0 1.5-3.3
Tensile strength [MPa] 73 63 76 79
Glass transition temperature [C] 65-175 70-120 70 230-345
Max. Service temperature [C] 130 150 100 190
2
Fracture toughness [J/m ] 5-15 10-20 - 24-33
-1 -6 -6 -6
Coefficient of thermal expansion [K ] 4510 5410 - 3110
Chemical resistance Good Limited Good High
Fire behaviour Flammable Fire retardant Barely flamma-
without additives - ble

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151-0548-00L Manufacturing of Polymer Composites FS 17 Exercise 2

Task 3: Composition of the fibres


Discuss which type of fibres would be more convenient for each case.

1- Bulletproof vest
A Bulletproof vest requires high impact strength, because it must transfer the kinetic energy
of the projectile to the vest without failure at the impact point.
The suitable material is Kevlar: It is a long molecule. The summation of all Van der Walls
forces gives a high material strength. Carbon would be in this case too brittle for impact re-
sistance. Another good point is the protection from high temperatures as it is not thermal con-
ductive.

2- Nose of an airplane.
The airplane nose is usually accommodates communication and navigation instruments.
Glass fibres: they are radiolucent, which means they permit the radiations to pass through
them.

3- Aerospace structures.
Two important parameters on aerospace are stiffness and lightweight design.
Carbon fibres: they offer the best specific stiffness and strengths, so they are ideal for high
performance lightweight design in an industry that is willing to pay a premium price for a
small increase in performance.

Sources: (1) and (3) Airbus, (2) Dupont.

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