Summary for the course AE4ASM002

Designing Materials with Aerospace Specific Properties

Y. van Dijk, A. Mitrousias, F.J. van Zanten
October 2015

Thermal properties

There are four thermal properties to be attributed to materials, these are: the specific heat (Cp ), the thermal
expansion coefficient (), the thermal conductivity (), and the thermal diffusivity (D). Of which the thermal
diffusivity can be related to the specific heat and the thermal expansion coefficient in the following manner.

D=

Cp

(1)

The specific heat is defined as the energy required to increase the temperature of 1g of material with 1K.
A quick estimation for the specific heat can be carried out as: Cp = 3 Ravogadro . The contribution of free
electrons and electron spin is small compared to the absorbed energy as the atoms vibrate. The number
of Avogadro can be said to be 6 1034 for ballpark figures, note that this is at 20 C. Counter-intuitive is
the fact that atoms with a high atomic weight have a small specific heat. This can probably be seen by the
fact that they react heavily to phonons. The following relation exists to calculate the required energy for
heating.
Q = m Cp T

(2)

Since the specific heat is an intrinsic material property, it can only be changed by mixing and evaluation on
weight basis. In order to design a material which will help stabilise temperatures at continued heat supply,
it is important to make use of the required energy to undergo a phase transition. A list of selection criteria
can be made for this phase change material, the most important are listed below:
Tmelt must be in the desired temperature range.
Cp , , and must be high, or specific heat, density, and thermal conductivity.
must be low in order to prevent thermal stresses on the structure.
High rate of crystal growth
Chemical stability
Completely reversible freeze/melt cycle
Non-corrosive, non-toxic, non-flammable
Large-scale availabilities
1

Most often paraffins and fatty acids are used; however, they are flammable, have low thermal conductivity in
their solid state and their volumetric latent heat storage capability is low. Eutectic phase change materials
can also be used; they have a sharp melting point similar to pure substances. The disadvantage is the limited
data available.
The coefficient of thermal expansion is defined to be the strain divided by the temperature difference.

L 1

L0 T

(3)

The whole concept of a material expanding when subject to a temperature increase is due to the vibrational
amplitude of the atoms increasing. The atoms exhibit a asymmetric potential well; the inter-atomic distance
increases as the potential energy goes up. A clear relation can be seen between the Youngs modulus and
the linear coefficient of thermal expansion; a high Youngs modulus implies a low coefficient of thermal
expansion.
Possibilities are limited to change the coefficient of thermal expansion for a given material. Exceptions to
this statement is the Nickel-Iron alloy invar (64%F e, 36%N i), which has a uniquely low . Furthermore,
orientated polymers can be created which have a range of 1.5 106 C 1 to 1.0 105 C 1 .
Thermal conductivity is defined as a materials ability to transfer heat through the material. The heat flow,
q, is defined as follows.

q =

T
d

(4)

In the above equation, d stands for the distance over which the heat transfer is considered. As can be seen
from the relation, a larger heat conductivity leads to a larger heat flow across the material. Heat can be
transferred through three different mechanisms; conduction, convection, and radiation.
Conduction occurs in a liquid or gas, it is the movement of heat through transfer of kinetic energy between
atoms or molecules. Convection takes place in a gas or liquid, it is the bulk movement of the fluid caused by
its tendency to rise because of its lower density. Finally, radiation is the dissemination of electromagnetic
energy. It does not require any medium to travel through and is most efficient in a vacuum.
In general, thermal conductivity is highest in metals, followed by the other solids. Moreover, liquids transfer
heat better than gases. All materials transfer heat through molecular collisions; this is most effective in
solids. Heat transfer is possible due to hot areas exchanging more energy to cooler areas. The way the atoms
are bonded plays a large role in a solids ability to conduct heat. The atomic interaction becomes less for
liquids and is least present in gaseous materials; hence they are unable to transfer much heat.
Thermal conductivity for polymers is relatively high if the polymer has a simple, open crystal structure and
consists of atoms of similar weight and size (e.g. polyethylene). When designing a anisotropic material for
heat conductivity, the series and parallel concept can be applied. Consider a composite material stacked
across the horizontal direction. The two heat conductivity constants are as follows, the subscript c and i
denote conductor and isolator, respectively.
v = fc c + (1 f ) i


h = i

c + 2i 2f ()
c + 2i + f ()

(5)


(6)

In order to design a thermal insulator, a poorly conducting material must be chosen and partially replaced by
gas; this will produce a foam. The thermal conduction of a foam is regulated by four processes; conduction
of the solid and gas, convection, and radiative heating of opposing walls. The governing equations for these
processes are given below.

s = K

g =


1

(7)

air

(8)

conv = 0

rad

= 4T te

Ks t

(9)

(10)

An optimal foam density exists for a minimal thermal conductivity. A possible exam question could be to
oam
draw the qualitative thermal conductivity as a function of the specific density; which is defined as fsolid
(see slide 34). Moreover, an optimum pore dimension exists since a gas molecule hitting a solid will not
transfer heat efficiently. A good insulator will minimise gaseous conduction by ensuring a maximum number
of collisions with solid surfaces (instead of gas-gas collisions). The optimum pore diameter equals the mean
free path of a molecule in the gas; similar to the average distance between two collisions (roughly 60nm).
A further reduction in thermal conductivity can be achieved by including thermally stable metal oxide
opacifiers to minimise radiation energy transfer. The particle diameter must be sized to be about the same
wavelength of the incident radiation to produce maximum scatter.
In conclusion, material properties are constrained by their physical limits. They can be tailored by adjusting
the heat processes at the relevant length scale. Correct ability to do so can be extremely rewarding.

Material characterisation

Properties that can be designed for can be categorised; physical, structural and chemical. In which structural
properties are considered to describe the way a material is built. Materials themselves can be characterised
by various inspection techniques; mechanically, thermally, structurally, spectroscopically and electrically. A
selection of the inspection technique is most often based on the required length scale, some processes are
more suited for specific length scales. The selection of probe depends on the desired wavelength of the
inspection. Examples are light microscopy, X-rays, and electrons.
Dynamic mechanical analysis (DMA) is used to determine the mechanical properties of a material. This
can be complex due to the dependence of time and temperature for polymers. X-ray diffraction (XRD) is
based on the way atoms and molecules are arranged with respect to each other. Infrared spectroscopy (IR)
depends on chemical interactions and vibrations.
Important aspects of material characterisation with respect to this course are the ability to explain theoretical
background, analyse experimental data, and correlate this data to the properties of the material.

2.1

Dynamic mechanical analysis

This form of analysis inspects the material response to a dynamic stress. A different reaction is to be
expected based on the mechanical properties of the material. Two distinct responses can be attributed to
an input: an energy loss in internal motion and an elastic response. These two responses together form the
total response of the system.
E = E 0 + iE 00

tan =

E 00
E0

(11)

(12)

(13)

In the above equation, denotes the phase angle of the material response with respect to the applied load
spectrum and denotes the viscosity. The peak of tan does not necessarily indicate the glass transition
point; the Youngs modulus often already decreases at temperatures lower than the peak of tan . The glass
transition point can be observed at the temperature when the loss modulus is highest. It is important to
note that the amorphous parts do not undergo a Tmelt and the crystalline parts do not undergo a Tglass .
The principle of the glass transition temperature is that a gradual motion of main chains starts to become
visible. At the rubbery plateau, this occurs on a large scale. Finally, increasing the temperature to the
melting temperature, will show chain slippage and all structural integrity is lost (e.g. a liquid is formed).
Plasticisers can be added to a polymer to decrease the glass transition temperature. DOP, DEP, and DBP
are examples of PVC plasticisers. Increasing the molecular weight of the polymer only extends the length
of the rubbery plateau; the Tmelt is increased. Regarding thermoset curing, the gelation point is defined
to be the moment in time where E 0 becomes larger than E 00 . During curing, the viscosity of the material
is increasing linearly. Post-curing can be utilised to further increase the stiffness of the polymer and raise
the glass temperature. Post-curing is simply curing at an elevated temperature before the polymer has
fully cured at room temperature, this expedites the cross-linking process and properly aligns the polymers
molecules.
Frequency scans can be used to determine the changes in molecular weight and its distribution. Increasing
the frequency of the applied load spectrum will increase the apparent modulus and decrease the observed
viscosity. It is comparable to changing from a liquid like system to a solid like system.
To conclude, DMA ties together molecular weight and its distribution, chain branching, cross linking, entanglements, crystallinity, localised motion and produces impact properties, dimensional stability, long term
behavior, and temperature performance. This is achieved through application of stress, strain, temperature,
heat history, frequency, and pressure. A practice problem would be the presentation of a DMA image and a
question related to the choice of polymer for various applications.

2.2

X-ray diffraction

The X-ray diffraction pattern of a pure substance can be compared to a fingerprint and is ideally suited for
characterisation and identification of polycrystalline phases. The fundamentals of this technique lie in the
Braggs equation, the relation for constructive interference is displayed below.

n = 2d sin
4

(14)

Crystalline materials are considered to consist of orderly periodic arrangements of atoms. Crystallographic
planes are identified by Miller indices, these indices state the reciprocal of the location of the intercept of the
plane with the x-, y-, and z-axis, respectively. Different crystal systems will display different plane spacing,
d, depending on the Miller indices. For a cubic system, the following is the relation, in which a is the unit
cell length.
1
d2hkl

h2 + k 2 + l2
a2

(15)

Samples with smooth plane surfaces are required for polycrystalline X-ray diffraction. Single crystals display
a perfect repetition of the unit cell. The lattice parameters can be determined from the peak position
through the d-spacing. The peak width provides information on the crystallite size and the presence of
defects. The peak area is the real measure for peak intensity, however, the peak height can be used as
a rough approximation. Note, the X-axis states 2, whereas Braggs equations uses . For simple cubic
systems, all hkl will result in constructive interference, for body-centred cubic, h + k + l must be even, and
for face-centred cubic, h, k, and l, must be all odd or all even. Using this information, the crystal lattice
can be determined from a X-ray diffraction image.

2.3

Fourier transform infrared spectroscopy

Infrared spectroscopy is based on the absorption of infrared radiation which will increase the amplitude
of the atomic vibrations. Covalent bonds are only allowed to stretch at certain frequencies. The position
of absorption bond corresponds to the type of chemical bond; this provides information about the atomic
composition of the tested specimen. There are 6 vibrational modes that an atomic bond can display (see
slide 53).
Characteristic locations of specific bonds for functional groups are tabulated. The fingerprint region lies
between 850cm1 and 1250cm1 and should be avoided when analysing spectra. Analysis should focus on
the strongest absorption peaks and look for characteristic peaks (such as C=O and O-H). As a final remark,
IR spectroscopy can be used to monitor curing reactions. The intensity of peaks for bonds that are visible
in the hardener, but lacking in the final product, provide information on the cure status. Make sure that
you know how to interpret the results of FTIR on how to find the chemical composition of a substance; as
this can be an exam question.

Tuning steel for aerospace engineering

Steel alloys encounter a decreasing usage in aircraft, nonetheless, it still represents 11% of the weight fraction
of a Boeing 777. Designing a new alloy is always carried out based on a set of required properties. These
properties can be roughly listed as: density, stiffness, strength, ductility and corrosion resistance. These
properties are deduced from the microstructure of the alloy which is obtained through the composition and
the processing.

Stiffness
The main alloying atoms determine the stiffness of the alloy. For steels, this is the iron atom, Fe. The
inter-atomic bond strength is dependent on the packing density of the atoms. Intrinsically, steel has a high
stiffness, however, little can be done in order to further increase this property.

Ductility
The ability to deform plastically is called ductility. Plastic deformation occurs through permanent movement
of dislocations through the crystal structure of the metal. A high ductility requires minimal obstruction of
dislocation movement and sources, as well as prevention of dislocation trapping. Grain boundaries act as
an obstruction for dislocation movement, just like precipitations may cancel a dislocation by introducing a
compressive or tensile stress field. For ductility, it is favourable to have a large grain size (tens of microns),
low alloying concentration, and no second phase particles.

Strength
Being the counterpart of ductility, strength is obtained through a small grain size, a high alloying concentration and precipitate density, and exclusion of coarse second phase particles. As can be concluded
from the prerequisites of high strength, the dislocation mobility must be maximally obstructed, just like the
multiplication of dislocations.

Design of a new steel

In order to design for a new steel, the microstructure must be analysed first. A steel consists of various
equilibrium phases, these are presented in the table below.
Phase name

Phase symbol

Crystal structure

Equilibrium

Austenite
Ferrite
Pearlite
Martensite
Bainite

&
0
0

FCC
BCC
FCC & BCC
BCT
BCT

Yes
Yes
Yes
No
No

Table 1: The various phases of steel

To obtain a small grain size, the steel can be rolled when hot and quenched afterwards (rapid cooling).
Larger grain size can be achieved by increased temperature and introducing a holding time, this allows
crystallisation to occur. The precipitates that will form in the steel alloy depend on the composition and
thermodynamic software can be used to predict this behaviour. Sites for nucleation are grain boundaries
and dislocations.
Ductile steels are obtained through a low carbon percentage and coarse grains; a ferritic microstructure
will be generated. The presence of precipitates will decrease the ductility. Application of more carbon will
improve the strength of the steel at a cost of its ductility; a pearlite structure is produced. To reach a certain
balance between ductility and strength, a composite microstructure of pearlite and ferrite will aid.
Moreover, an even improved composite consists of ferrite and martensite; a dual phase steel. This dual
phase steel is obtained through slow cooling followed by rapid cooling. Austenite will first phase change
to ferrite during slow cooling, the remaining austenite is transformed in martensite during the final fast
cooling. Retaining austenite at room temperature can provide the last incremental step in performance: this
can be achieved through addition of silicon (Si), aluminium (Al) or phosphorus (P). The resulting material
is a transformation induced plasticity steel (TRIP). If TRIP is subject to stress the austenite transforms to
martensite.

Corrosion resistance
Addition of chromium (Cr) leads to improved corrosion resistance due to the formation of the chromiumoxide layer (Cr2 O3 ). However, addition of chromium will lead to a ferritic microstructure which is not
of desired strength and stiffness. Introduction of nickel (Ni), manganese (Mn) and copper (Cu) provide
a solution as they help to make the alloy austenitic. Precipitates from molybdenum (Mo) and titanium
(Ti) help to reach the final strength. The latter two precipitates are induced at 450 C - 550 C, which is
important for the production process. The most significant note to remember is that the microstructure is
both a result of the composition and the thermo-mechanical treatment.

Self-healing materials

An engineered system (for example, a CH-47 Chinook) has a limited life time. When the system is new it is at
its highest performance, while in use it accumulates damage and eventually it fails and is replaced. By using
self-healing materials the life of the system can be increased. In current engineering systems and materials
all material processing chains are geared towards putting the atoms and molecules into the right place and to
keep them there(Create a static system). The life is currently increased by preventing and avoiding damage,
once damage occurs the material/part is replaced. Currently we work with damage prevention only.

Figure 1: Material damage types

4.1

Self-healing in engineering

In a nature inspired philosophy the materials are part of a dynamic system, damage is unavoidable and
damage management is used to prevent failure.
A self-healing material is defined as a material that has the built-in ability to partially or fully repair damage
occurring during its service life time. Ideally the performance of the self-healing material will not drop limit
of reliability.
Ideal places for this concept:
Hard to access areas. (off-shore wind mills)
Structures requiring a high reliability. (primary structures in aircraft)
7

 Objects requiring a high surface quality. (exterior of a car)

Applications requiring long life. (tunnels, bridges)
Applications where repairs would cause great inconvenience. (roads)
Applications with specific functions. (phone batteries)

4.2

Design of self-healing materials and systems

The material properties are optimised using the old lessons (structural design and analysis), while taking
in account that healing requires local, temporary, mobility. Design for self-healing taking into account the
specific character of the material. The three distinct self-healing material classes are metals, ceramics, and
polymers.

4.3

Self-healing strategies

The first strategy is extrinsic self healing, which can be done by using spherical capsules, fibres, and
nano/micro containers. This happens in four steps: Cracking, release of capsule content, wetting, and
hardening. The goal is to provide healing over the entirety of the lifetime of the system and to recover 100%
of the mechanical integrity, while being seamlessly integrated in the material structure.
Capsules with monomers are embedded in the polymer matrix. The fragile capsule shell breaks when the
surrounding matrix fails, the monomer reacts with the dispersed catalyst in the matrix to form a cross-linked
polymer network, effectively closing the crack.
Additionally, hollow glass fibres could be used to house the monomer; these would be 55% hollow and are
aligned in the same direction within the same 90 degree parallel. This can be realised in 3 different ways. In
the first option, the fibre carries the healing agent whilst the catalyst is in the matrix. Another option is to
have two, close to each other, fibres carrying either one of the constituents. Lastly, utilising fibres housing
the healing agent which are coated with the catalyst.
A second generation of self-healing fibre composite uses the mechanism of vascular self-healing, inspired by
the human body (only one slide on vascular self-healing). The third generation is a fibre with compartments,
enabling a single fibre to not be depleted after one healing event. These fibres will allow multiple healing
events to take place at different locations.
The second strategy is intrinsic healing. The repair is carried out through thermal repair; also known as
Diels Alder chemistry. Self healing in concrete is done by carbonation of the concrete turning CaO2 into
CaCO3 , filling the crack. The aforementioned method of encapsulation is also used. Additionally, bacteria,
activated when a crack provides them with water, can be used to provide CaCO3 using the following reaction:
2 Ca(CHO2 )2 + 2 O2 2 CaCO3 2 CO2 + 2 H2 O.
Metallic systems can also use self-healing via the usage of a thermal barrier coating system. Where the heat
treatment is interrupted, this causes atoms to remain in solution which can be driven to open volume defects
where they attempt to heal the defect. In ceramics, self-healing is done by adding a component that oxidises
if it meets a crack, for example: MoSi2 (b) + O2 MoSi2 + Mo5 Si3 + SiO2 .
These were all autonomous self healing events, an example of a non-autonomous self healing material could
be asphalt. By locally heating bitumen in recently designed asphalt can be melted and the crack will be
filled.

Piezoelectric materials

The piezoelectric effect is the conversion of mechanical energy to electrical energy (direct) and vice versa
(inverse). Examples of the piezoelectric effect used in daily life, knocking sensor and spark generation are
examples of the direct effect. Examples of the inverse effect are buzzers (operate at resonance frequency)
and ultrasonic transducer. As the frequency of the electric field increases the impedance decreases until it
reaches a minimum. This is the minimum impedance frequency and it approximates the series resonance
frequency, this is the frequency at which the oscillation is most efficient (resonance frequency). Increasing
the frequency even more causes the impedance to rapidly rise to a maximum which is known as the parallel
resonance frequency (anti-resonance frequency).
Inverse piezo-effect is used for the creation of actuators, these actuators are a factor 1000 faster and can
generate tremendous forces (3 kg/mm2 vs 30 kg), however the have a very low displacement range (0.1 mm
vs 1 m) and their accuracy is relatively low w.r.t. step motor actuators (0.1 mm / 0.01 m vs 1000 mm / 10
m). In diesel injection systems, piezo-actuators are used because they are very fast and create a very stiff
actuation train, the actuators also can be located very close to the jet-needle. Vibrations can be turned into
electrical current and manipulated after which it can be transformed into a vibration again. This sequence of
transformations is used to create noise reduction/cancelling. The first application of the piezoelectric effect
was a phonograph pickup based on a single crystal Rochelle salt.

5.1

Piezoelectric ceramics

Piezoelectric ceramics are made by heating fine PZT (Pb[Zr(x)Ti(1-x)]O3 ) powders to create a uniform
powder, which is mixed with an organic binder and formed into structural elements [source], then the
element is sintered at about 1200 degrees Celsius, to create a shape with a dense crystalline structure.
Permittivity of the material can be described by the Curie-Weiss law, which is stated below. In which C is
the Curie-Weiss constant [] and T0 is the Curie-Weiss temperature [K].
=

C
T T0

(16)

Ferroelectric materials have a transition temperature, referred to as the Curie temperature. Below this
temperature the symmetry of the cube is lost and the material becomes an electric dipole. When the crystal
goes below the Curie temperature. Multiple regions (Weiss domains) with different polarization directions
are formed, which are separated by domain walls. These materials can be poled by using a strong, direct
current electric field at a temperature slightly below the Curie temperature Ps (saturation polarization) after
the electric field is removed the material has a remnant polerization Pr and the element is permanently
elongated (STRAIN). The original polerization curve is called the virginal curve. A poled ferroelectric
material exhibits hysteresis. The hysteresis curve is given by plotting the polarization and reversing the
electric field as shown below. The electric field required to change the polarization is called the coercive field
Ec .
Polarization causes strain, caused by the force induced by the electric field, which can be shown in the
so-called butterfly loop. The strain during poling is called the poling strain, which causes a stress in the
material. If the coercive field is applied the polarization will be reversed and the the butterfly loop is made
as shown in the figure below.

Figure 2: Typical hysteresis loop, taken from reading material Chapter 3 Piezoelectric Materials figure
3.10

Figure 3: Typical loop, taken from reading material Chapter 3 Piezoelectric Materials figure 3.13
Hard and soft piezoceramics
Hard piezoceramics (PCs) have pinned omain walls whereas soft PCs have easy to move domain walls, and
a high piezoelectric constant. The piezoelectric constant for hard PCs is moderate but it has low losses
whereas the soft PCs have high losses. The soft PCs are used in generators, actuators and senosrs while the
hard PCs are used in transducers motors actuators and transformers.

5.2

Piezoelectric polymers

The piezoproperties of polymers like PVDF are several times larger than the piezoproperties of quartz. In
polymers the intertwined long-chain modules attract each other and repel each other when an electric field
is applied.

10

5.3

Dopants

Dopants (alloys): Isovalent dopants: Directly influence the Curie temperature. Compensating dopants:
make the properties of the material along the morphotropic phase boundary better. Donor doping: lead is
replace with a large three valent ion. Causing the material to become a soft piezoelectric material, making
the poling process easier. Acceptor doping: replacing titanium ions with lower valent ions, like nickle or
iron. Oxygen vacancies are formed causing the material to become a hard piezoelectric material, usefull for
high driving voltages and frequencies (over 10 kHz)
Source, https://www.americanpiezo.com/piezo-theory/whats-a-transducer.html 31-10-2015, by APC International, Ltd.

Polymer properties

There are many different parameters which influence the mechanical properties of polymers. A short summation is given: chemical composition and its distribution, the polymer topology and morphology, the molecular
weight and its distribution, and, finally, additives. Keep in mind that all these parameters also influence the
cost to produce polymers.

Thermoplastics
The chains of thermoplastics can be individually recognised, they exhibit a molecular weight distribution
which will yield a number average and a weight average molecular weight. Its structure is linear, branched,
star-shaped, dendritic or hyperbranched. Amorphous parts of a polymer only possess a glass temperature
(Tglass ), whilst crystalline parts only display a melting temperature (Tmelt ). This means that semi-crystalline
structures, which are made out of both amorphous and crystalline parts, show both transition temperatures.
Therefore, polystyrene (PS), which is fully amorphous, does not have a Tmelt . Polyethylene terephthalate
(PET), however, is semi-crystalline and shows both temperatures. From a recycling perspective, only polymers which display a Tmelt can be recycled. The viscosity is roughly equal to the molecular weight to the
power 3.4; = M n3.4
w .
The weight average (Mw) is defined as the average of the sum of all molecular weights present in the entire
material, the number average (Mn) is equal to the molecular weight which is most common in the material.
The molecular weight distribution (MWD) can either be narrow or broad, depending on the polymerisation
method, and is defined as follows.

MWD =

Mw
Mn

(17)

Mono disperse polymers have a MWD equal to 1, polydisperse polymers usually show a MWD between 1
and 2. Important to note is that polymerising above the molecular weight of entanglement is not useful as
the viscosity increases and the mechanical properties do not improve significantly.
Block copolymers are built of two or more monomers. The sequence of monomers can be chosen to be at
random, alternating, or in blocks. Names for these polymers are poly(A-co-B), poly(A-alt-B), and polyAblock-polyB, respectively. Blending of the monomers will not result in a coherent material, they must be
covalently bonded to form a copolymer.

11

To further tailor the properties of the polymer, additives can be taken into consideration. Various functions
exist for additives, for example, fillers such as carbon black increase the Youngs modulus, improve UV
stability, and lower the price for the base resin. Other fillers are carbon, glass, various polymers, and
ceramic fibres. Stabilisers will prevent degradation during melt processing, anti-oxidants are added to bond
to deteriorating elements such as oxygen, and flame retardants can be considered for high temperature usage.
Finally, plasticisers can be added to decrease the glass temperature; this will soften the polymer.

Thermosets
In these polymers, all chains are connected and no MWD exists; they can be densely- or slightly cross-linked
(which influences the Youngs modulus). Thermosets are always amorphous and therefore do not show a
melting temperature. Recycling is only possible through reshaping above the glass transition temperature.

The transition temperatures

From a structural point of view, the glass and melting transition points are extremely important. What is
the temperature range a specific polymer can be used? The exact positions of these transition temperatures
do not exist as they depend on the molecular weight of the polymer, the thermal history and the heating
rate. An estimation of Tglass is that it represents 0.5-0.8 times the value of Tmelt in Kelvin. Note that
Tglass and Tmelt are not the only transition temperatures. The temperatures denoted by T and T generally
indicate a large transition in fracture toughness and ductility, respectively. The specific heat and volume
thermal expansion coefficient are defined to be as follows.
H
T p

(18)

1 V
V T p

(19)

Cp =

For measuring Tglass three methods are provided; differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DTMA), and heat deflection temperature (HDT). DSC measures the heat flow between
a reference sample and an actual sample. Distinct peaks are visible for both the Tglass and Tmelt . DMTA
applies a small dynamic strain and measures the mechanical properties such as the Youngs modulus and
the loss modulus. A peak in the loss modulus represents the Tglass and the Tmelt can be found by the final
drop of the Youngs modulus. Please refer back to material characterisation for an extensive description.
Generally, DMTA values, measured at 1Hz, for Tglass are higher than DSC values. The exam will most
definitely include a question about the choice of polymer to use for a specific product based on the values of
Tglass and Tmelt .

Selection criteria for aerospace polymers

The most important properties of a polymer enabling it to be used for aerospace applications are highstrength and stiffness, thermal stability, low coefficient of thermal expansion, non-flammability, easy processing, a high Tglass and low elongation at break. Examples are epoxies (thermoset) and PEEK and PEKK
(thermoplastics).
Thermosets can be created when a monomer with functionality larger than 2 is introduced. This will cause
branching to take place and leads to the creation of networks. The control of the cross-linking is critical for
12

the production of thermosets, both prior to the gel point and after gelation. Two different methods exist for
the processing of thermosets into structural elements. The monomers can be mixed on location and then
processed into final shape. The other option is to use a pre-polymer; either a A-, B-, or C-stage polymer.
The stage refers to the solubility and fusibility of the oligomer.
Epoxy resins are used as bonding material, adhesive, and coating. They can also be found in structural
applications through the form of reinforced composites. Finally, electrical insulation and chip packaging are
another way they are utilised. They are strong, stiff, and have good impact toughness. However, they are
sensitive to moisture and solvents, and show creep. The curing takes places due to the addition of a hardener
(often an anhydride or diamine). It is important to keep in mind that the Tglass and mechanical properties
are a function of the degree of cross-linking; more cross-linking will lead to a higher Youngs modulus.
Epoxies are typically only cured to 80% in order to prevent brittle failure. A possible exam problem would
be to indicate the change in Youngs modulus versus temperature when a polymer is changed in composition
or thermal history.
The harsh operating conditions for aerospace polymers dictate the ability to resist long-term exposure to
a combination of the following: flowing or static air, hot, wet, and cold conditions, chemical and electrical
actions, and radiation. A list of the most important attributes which contribute to the high performance is
displayed below. A typical exam question would be to rank various polymers on the strength; keep in mind
secondary bonding forces.
Primary bond strength
Resonance stabilisation
Secondary bonding forces
Molecular weight and MWD
Molecular symmetry
Rigid intra-chain structure
Cross-linking
Additives and reinforcements
Thermal stability can be assessed through thermogravimetric analysis (TGA), which monitors the residual
weight during the addition of heat. Isothermogravimetric analysis (ITGA) is comparable to TGA, however,
the temperature is kept constant and time is the running variable. Mechanical properties of carbon reinforced
polymers show a different response to aging for different resins; they can either improve or degrade. This
is an important aspect to take into account. Polymers must also be evaluated for their behaviour under
complex thermo-mechanical loading to ensure structural integrity throughout the structures lifetime.

Corrosion

Corrosion is defined as the disintegration of material into its constituent atoms, this happens due to
(electro)chemical reactions with the environment. This results in loss of mechanical properties (ductility, strength), other physical properties (absorption, degradation) and loss of appearance. There is a direct
correlation between the corrosion rate and magnitude of a N aCl concentration. The elements needed for
aqueous corrosion are: an anode (oxidation reaction), a cathode (reduction reaction), electrolyte (ion conduction), electrical contact between anode and cathode (e- conduction) and corrodants (CO2 , O2 , bacteria,
algae, H2 , S- , H+ /OH- ). An example for both an oxidation process and a reduction process are in Equations
20 and 21.
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M e M en+ + ne

(20)

2H + + 2e H2

(21)

Materials with a high potential are cathodic; lower potential makes the materials behave anodic. Materials
in the galvanic series can change from anodic to cathodic; depending on neighbouring elements. Pitting
corrosion occurs in alloys only. Passivation means no current potential with variation. The corrosion penetration rate (CPR) is equal to the thickness loss over unit time period. The equation for the corrosion
penetration rate is displayed below, in which W is the weight loss after time t and k is a constant.

CP R =

KW
At

(22)

The corrosion rate can be be defined to be the following, where r represents the corrosion rate in mol/m2 ,
i denotes the current density in A/m2 , n stands for the number of electrons, and F is a constant equal to
96.500. Furthermore, this equation can be rewritten to obtain the result displayed in Equation 24, in which
A is the area in m2 and M is the atomic mass of the metal in g/mol.

r=

i
nF

iAM
W
=
t
nF

(23)

(24)

As can be seen from both equations, the corrosion rate depends on current density. The so called Vickers
hardness (HV) and corrosion rate have a linear relation; a higher HV leads to higher corrosion rate. Corrosion
can be divided in three major categories: pitting corrosion, intergranular corrosion and exfoliation.

Pitting corrosion
Attack in impurities, precipitates, intermetallics (IMs) and weak spots in general. Pitting corrosion is difficult
to detect and causes extreme damage when compared to the total corrosion volume. Direct consequences
are serious degradation of structural capability, especially for structures with a single load path which are
highly loaded. It creates local stresses that accelerate crack formation and growth. Pitting corrosion can
take place in all aerospace alloys. Pitting corrosion can nullify the normally high resistance of high strength
materials. Keep in mind that fatigue cracks nucleate form corrosion pits.

Intergranular and exfoliation corrosion

Especially affects the high strength aluminium-alloys (7xxx, high tensile yield strength and low weight). They
have decreased ductility and increased notch sensitivity and are well susceptible to corrosion. The increased
corrosion susceptibility is due to the Cu and Zn (alloying) elements which create IMs and precipitates when
given a heat treatment. These two than create strong galvanic couples.

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7.1

Corrosion behaviour of aerospace aluminium alloys

2xxx series
Main alloying elements are Cu, M g and M n. The main precipitate is an s-phase (Al-Cu-M g) and accounts
for 60% of the total amount of precipitates. This series is most susceptible to pitting corrosion and general
attack. Temper affects highly the susceptibility to intergranular corrosion (IGC) and stress corrosion cracking
(SCC). The copper content has a deteriorating influence on ICC and pitting and to some extent on IGC.

6xxx series
Main alloying elements are M g, Si and sometimes Cu and/or M g. The main precipitate is M g2 Si. Susceptibility to corrosion varies with composition and strengthening treatment. However, in general the corrosion
resistance is good, especially to pitting corrosion. They do have worse properties than 2xxx and 7xxx, unless
Cu is added. If Cu is added, however, the resistance to IGC drastically reduces, unless they are over-aged
beyond the peak strength.

7xxx series
Alloying elements are Zn, M g and only sometimes Cu. However, the ones with Cu are used in aerospace.
They have low corrosion resistance; equivalent to 2xxx, but more complex mechanisms are involved.

Microstructural feature relation to corrosion

At a large scale, corrosion occurs around clusters of the constituent and impurity particles lead to severe
pitting. On a smaller scale, attacks take place around isolated IM; dispersoids and precipitates lead to micro
galvanic corrosion. Isolated IM attacks happen if the IM acts as a cathode and the anode is formed by the
aluminium matrix. Filiform corrosion happens underneath a film.
During intergranular corrosion, the grain boundary is preferentially attacked which is anodic to the bulk
material. Initiation occurs at IMs in the surface (from pits and grain boundaries (GB) at the surface).
This happens due to precipitation free zones (PFZ) as a result of precipitation at the grain boundary and
due to the anodic second phase at grain boundary (e.g. Al2Cu), just like segregated alloying elements and
imperfections. IGC penetrates more rapidly than pitting corrosion due to sharper tips. Corrosion rings
indicate serious IGC and so called plumes indicate H2 evolving sites and pitting.
Corrosion fatigue decreases the maximum number of fatigue cycles and allowable stresses. Corrosion fatigue
can be identified by three different mechanisms. The corrosion is accelerated by the fatigue crack, or the
propagating crack is influenced by a prior corroded region, or the corrosion causes the load path to change
direction.
Stress corrosion cracking leads to the most common cracking problems. For stress corrosion to take place,
a susceptible material (2xxx, 7xxx) must be present. Furthermore, a corrosive environment and a sustained
tensile stress as driving force are required. Note that the orientation of the material grain with respect to the
tensile stress can influence the crack growth. IGC is the main precursor of SCC. The main ways to combat
SCC are heat treatments, e.g. over-aging for a 7xxx alloy.
Hydrogen embrittlement of an aluminium alloy is introduced as the hydrogen produced during corrosion
diffuses into the material in vulnerable areas. This leads to metastable aluminum hydride and causes brittle
IG fracture. Also, it results in decohesion of the GB containing segregated (separate) Mg. Hydrogen
embrittlement is still an unclear topic, though.

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Protection
A coating can be applied to protect the metal from corrosion to take place. Such a coating systems includes
the following layers: a topcoat (Solid color, P U ), a primer (Cr+ or Cr free, Epoxy amine), and a pretreatment (Anodized/pickled/conversion coating, oxide/sol-gel/wash primer).
To apply the coating system, the following steps must be taken.
Selective oxidation (IM removal and surface etching)
Deposition or growth of manufactured oxide via electrochemical (anodizing) or chemical (conversion
coating) means
Use of an organic coating for specific applications (e.g. primer and topcoat).
The purpose of the steps that must be taken are to make sure correct adhesion of the coating system, to
provide a sacrifice material, it acts as a barrier to corrosion attacks and it will release corrosion inhibitors.
The solubility, inhibitive power and transport of inhibitors are within the primer. The usage of chromium
VI in a coating systems hinders the local anodes and cathodes which effectively reduces the corrosion rate.

Miscellaneous
Crevice corrodant can go in but not out (too narrow)
Corrosion front @ one grain (IGC)
Particle can go from anodic to cathodic due to atom loss (s-phase)
Hydrogen infuses metal and properties drop even after polishing of oxide
Removal of IMs is favourable
Crevice corrosion can happen even without 2 metals, cathodic reaction in air
Recycling creates impurities
M g and F e together reduce chemical action and thus corrosion.
Aging occurs in the solute elements
Quenching of the alloy leads to a supersaturated solid solution
Moderate heat forms finely dispersed precipitates
Non-equilibrium microstructures exist which make Al properties highly temperature dependent.
Pitting corrosion is related to IMs
Cu high rate of oxigen reduction
7xxx strength form -phase M gZn and precursors
Addition of Cu works well against SCC

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