30/11/2021

AE1108-I: Aerospace Materials

- BSc Aerospace Engineering -

Lecture 11.1: Durability

Environmental degradation in polymers: solvents, UV
(Chapter 14)

Dr. Santiago J. Garcia

Associate Professor Novel Aerospace Materials

Department of Aerospace Structures and Materials
s.j.garciaespallargas@tudelft.nl

Durability and aircraft / spacecraft

Fatigue stress
Degradation of protective coating -> UV, H2O, ∆T
Dissimilar metals (rivet-AA sheet) -> galvanic couple
Accumulation of corrosive solution -> design
Maintenance
Accelerated fatigue corrosion

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(chemical) durability

• It is a function not just of the material but of the environment in which

it operates
• There are many mechanisms, some general, some peculiar to
particular materials and environments
• Material combinations and configurations play a role
• In most cases it is a surface rather than bulk phenomenon’

Durability is a key material attribute, but is one of the more difficult

attributes to characterize, quantify, and use for selection

Factors Affecting Durability

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Flight profile: environment changes

Oliveira et al. Applied Thermal Engineering 98, 2015 Kondyurin et al. 2020, ArXiv, Sydney Epoxy composites in the stratosphere

Degradation / corrosion of materials

Corrosion
(dissolution)
Metals Material loss
Oxidation
(formation of non-metallic film)

Ceramics Resistant, but fail at relatively high temperatures

Swelling & dissolution

Polymers UV
Degradation
Heat
Oxidation

- Loss of aesthetics
- Loss of mechanical properties (e.g. ductility and strength)
- Loss of other physical properties (e.g. thermal isolation)
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Damage in polymers

Weathering/ageing: physical, chemical, and biological processes

leading to the material degradation upon (combined) exposure
to UV, H2O, O2, ∆T, biological factors.

1. Swelling and dissolution

1. Liquid diffuses through paths

2. Swells (separates macromolecules)

Plasticized
Ductile https://www.youtube.com/watch?v=otRU_xkQNJA
Softer Epoxy-based CFRP

3. Dissolves when polymer is completely soluble

Increases: higher chemical structure similarity
between solvent and polymer.
https://www.youtube.com/watch?v=44NC-MOeWk4 T

Decreased: higher MW, degree of crosslinking,

degree of crystallinity, decrease T
Fogaca de Oliveira, et al. Brazilian Journal of B. Hong, et al. Advances in Structural
Chemical Engineering 22(3) (2005) Engineering 21(4):136943321773266 (2017)

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Bond Rupture
1. Radiation (UV, e-beam, x-ray…), Heat, Chemical reaction => provide energy to break bonds

2. Separation of chain segments and reduction of Mw

H2O induced
cleavage

E.g. PET (bottles)

With O2 and high T becomes brittle 10

2. Radiation:
the solar spectrum in wave lengths

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The visible spectrum

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Binding energy in polymers (PE and PP)

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The UV part of the spectrum

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Binding energy in polymers (PE and PP)

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Damage due to UV light

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Effect of UV on epoxy-carbon fibre composites

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Weight loss due to UV radiation

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Effect of UV on stiffness
pristine UV Condens. UV + Condens.
sequential cyclic

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Effect of UV on longitudinal strength

pristine UV Condens. UV + Condens.
sequential cyclic

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Effect of UV on lateral strength

pristine UV Condens. UV + Condens.
sequential cyclic

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3. Oxygen
The free energy of CO2 is lower than that of C, hence given the
right conditions, all polymers will oxidise/burn

A plane on fire due to a cabin fire (4 minutes)

https://www.youtube.com/watch?v=bkOrqj5ubMc
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Resistance to Flammability
• Combustion involves the reaction of free-radicals
• Flame retardants work by either tying up free radicals so they do not react or
by creating a protective layer between the solid polymer and the flammable
gaseous products that enable combustion

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Degradation in Space: e.g. ATOX effect at LEO

Kapton
polyimide

Polymers for space vehicles must resist degradation after prolonged exposure
to cosmic radiation, ATOX impact, etc.

https://www.youtube.com/watch?v=bjyv7bK9X74
Corrosion in space (3 min) 24

SUMMARY: polymers degradation

• Polymers degrade by different mechanisms in a process
known as weathering or ageing that involves one or more
factor: UV radiation, temperature, humidity, solvents, and
oxygen

• Degradation depends on the chemical groups, atoms and

polymeric chains used

• Design with polymers might be based on mechanical

properties but also considering durability

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AE1108-I: Aerospace Materials

- BSc Aerospace Engineering -

Lecture 11.2: Durability

Degradation in metals: oxidation and corrosion
(Chapter 14)

Dr. Santiago J. Garcia

Associate Professor Novel Aerospace Materials

Department of Aerospace Structures and Materials
s.j.garciaespallargas@tudelft.nl

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UV light: no effect on metals

Aluminium

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What is oxidation/corrosion?
The degradation of metal to a more thermodynamically stable form

Metal

Corrosion
Fe
products
Ore

Magnetite (Fe3O4),
Hematite (Fe2O3) Metal oxide
(Fe3O4, Fe2O3,..)
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Oxidation: natural tendency of metals

ΔG = - n F ΔE
(Gibbs free energy)
ΔE > 0 =; ΔG < 0; energetically favored
oxidation is spontaneous Energy
minimization!
ΔE < 0 =; ΔG > 0; energetically not favored
oxidation is non spontaneous

Most metals are more stable in coordinate state than in metallic state

This is why most metals are found as compounds in nature

(i.e. oxides, hydroxides, carbonates, sulfates, sulfides and silicates)

1
Mg + H 2 O(l ) + O2 ( g ) → Mg (OH ) 2 ΔG = -596.600 J
2
Exceptions: Gold and Platinum
(stable in most environments because their ΔG increases to go from metal to oxide)
3 3
Au + H 2 O(l ) + O2 ( g ) → Au (OH )3 ΔG = +65.700 J
2 4
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1. Damage due to oxygen: oxidation

(absence of electrolyte)

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Mechanisms of Oxidation
When most metals are exposed to air, an ultra-
thin (nm) surface film of oxide forms

x M (metal) + y O (oxygen) = MxOy (oxide) + energy

- The oxide film separates the metal from the oxygen

- To react farther, either oxygen atoms must diffuse inward through the
film to reach the metal or metal atoms must diffuse outward to reach
the oxygen

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The oxidation reaction of a metal

The oxidation reaction M + O = MO occurs in several steps:
1) The metal forms an ion and releases electrons M = M2+ + 2e-
2) Electrons are captured by oxygen to give an oxygen ion O + 2e- = O2-
3) Oxide formation at surface: M2+ + O2- = MO

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Oxidation Kinetics
mox – mass per unit area of oxide
Am – atomic weight of the metal
Ao – atomic weight of the oxide
Δm – weight gain from oxidation
x – thickness of oxide = mox/ρox
kp – parabolic kinetic constant (kg2/m4s)

∝
 ρox – density of oxide
  t – time
Do – diffusion coefficient of oxygen
∆      
Qd – activation energy
Co – concentration gradient of oxygen

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Oxidation Kinetics
∆   

∆   

• If the oxide adheres to the material, it

gains weight in either a linear (when
cracked or porous) or parabolic (when
dense oxide) way
• If the oxide is volatile, the sample loses
weight in a linear way

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Resistance to Oxidation

• Oxidation rates rise steeply with rising temperatures

– To enable a material to operate at high temperatures, precautions
must be taken to limit the affects of oxidation

• Oxide coatings can be applied to metals like cast irons, steels, or nickel
alloys to prevent material degradation at high temperatures

• Alloying elements such as chromium and silicon form fully dense oxides
that become passive and limit continued oxidation as they are (almost)
impermeable to oxygen

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2. Damage due to corrosion

(in presence of electrolyte)

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Corrosion in aircraft and spacecraft

https://www.youtube.com/watch?v=eKMPojS10DY
Introduction: corrosion in aircraft, FAA (9 min)

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Corrosion elements
SOLUTION
Double layer

• Necessary elements for corrosion:

- Anode
M(OH)2
M → M 2+ + 2e-

M 2+ +2e- - Cathode
- Electrolyte (ion conduction)
2OH-

M
- Electrical contact between anode and
2e- cathode (e- conduction)

Anode Cathode Anode

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Ions in Solution and pH

H2O H+ + OH- [H+] = [OH-]

[H+] · [OH-] = constant at 10-14

= 7 in pure water

• A chemical compound that dissociates in water

increases either the hydrogen ion concentration
or hydroxyl ion concentration

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Half reactions and pH

Oxidation
(increase valence state)
M → M n + + ne −
(anodic half-reaction)
e.g. Fe → Fe 2 + + 2e −

Anode Acid solution

= Overall reaction
2 H + + 2e − → H 2 ( gas ) Total electrochem. reaction

Acid solution with dissolved O2

Reduction O2 + 4 H + + 4e − → 2 H 2O
(decrease valence state)

Basic or neutral solution with dissolved O2

(cathodic half-reaction)
O2 + 2 H 2O + 4e− → 4(OH − )
Cathode Ions in solution
n+
M + ne → M−

e.g. Fe 2+ + 2e − → Fe
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Half reactions and pH

Pourbaix
diagrams

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Metals in (impure) water: ionization

A metal placed in a conducting solution like salt water dissociates into ions and
releases electrons – the anodic reaction

• The electrons accumulate on the iron

giving it a negative charge that grows
until the electrostatic attraction pulls the
metal ions back onto the surface
• Each metal ionizes at a different level
and has different ionization potentials.
Na>> Zn > Fe > Cu > Au > Pt

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Standard electromotive force (emf) series

To measure the emf series: couple metals to the SHE

Standard potential
-V0Fe = 0.44 V

Used to create the

emf series

Callister, materials science & engineering

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The electrochemical potential of metals

Galvanic
couple

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Electrochemistry explained

From batteries to corrosion

https://www.youtube.com/watch?v=teTkvUtW4SA 16 minutes

https://www.youtube.com/watch?v=Rt7-VrmZuds 8 minutes

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The corrosion reaction cell

If a current is allowed, electrons flow from the anode
to the cathode –causing corrosion of the anode

The reduction potential of each metal dictates which is

the anode and which is the cathode – the metal with
the lower potential acts as the anode

In the figure, the iron corrodes, but the cathodic

reaction is now the hydrolysis reaction

O2 + 2 H 2O + 4e− → 4(OH − )

This reaction allows oxygen to reach the copper, in which iron ions continue to be created
at the anode and hydroxyl ions at the cathode – they react to eventually form rust

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The corrosion reaction cell

• If the environment is changed and copper
sulfate is added to the water, the excess of
copper ions will lead to copper plating on the
cathode
• In the figure, the iron corrodes while copper
ions plate out onto the copper following the
cathodic reaction

This reaction allows oxygen to reach the copper, in which iron ions continue to be created
at the anode and hydroxyl ions at the cathode – they react to eventually form rust

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Concentration cell
e- flow
Same metal in solution

Fe Fe

Fe2+ Fe2+

Fe2+ Fe2+

Fe2+
Fe2+ Fe2+ Fe2+

Low High
concentration Fe2+ concentration Fe2+

Membrane
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Oxygen concentration cell (corrosion

driven by oxygen gradient)
• An oxygen concentration gradient
exists between the metal at the
surface of the water and the metal
further immersed in the water
• The potential difference between the
hydrolysis reaction and the anodic
reaction of iron ions dissociating
drives the corrosion

O2 + 2 H 2O + 4e− → 4(OH − )
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Types of corrosion

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Corrosion forms in metals

Galvanic corrosion – appears between two dissimilar metals make electrical contact in the
presence of an electrolyte. (e.g. rivets joining panels)

body

mandrel

body

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Corrosion forms in metals

Pitting corrosion – appears I alloys with two-phase microstructure in which the two regions lie at
different points on the reduction potential scale and within alloys forming intermetallic precipitates
with different composition to the bulk (e.g. aerospace aluminium alloys)

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Corrosion forms in metals

Intergranular corrosion – occurs because grain boundaries have chemical properties
that differ from those of the grain

Precipitates at GB
grain1
grain2

depletion

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Corrosion forms in metals

Intergranular corrosion – occurs because grain boundaries have chemical properties
that differ from those of the grain

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Corrosion forms in metals

Crevice corrosion - electrolyte is occluded between two metals or a metal and a rubber
ring. This leads to a depletion zone of O2 forcing the localization of the cathode at the O2-
rich zones outside the crevice due to an oxygen concentration cell.

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Corrosion forms in metals

Filiform corrosion - a special form of oxygen concentration cell that occurs on metal
surfaces having an organic coating system. It is recognized by its characteristic worm-like
trace of corrosion products beneath the paint film.

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Corrosion forms in metals

Stress corrosion cracking – accelerated corrosion, localized at cracks in loaded components

Corrosion fatigue – accelerated rate at which fatigue cracks grow in a corrosive environment

Applied
Stress

Air

Corrosive medium

Number of
cycles (N)
1 102 104 106 108

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Fighting Corrosion

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Chose well
the material

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Anti corrosion design rules

• Allow for uniform attack instead of local corrosion

• Avoid fluid trapping
• Suppress galvanic attack
• Avoid crevices
• Consider cathodic protection
• Beware of stress corrosion and corrosion-fatigue
• Design for inspection and maintenance

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Design changes to prevent trapped fluids

reduce the rates of corrosion

Design changes to
minimize
galvanic attack

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Design changes to avoid crevice corrosion

Cathodic protection

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Coatings
• Passive coatings
– Separate the material from the corrosive
environment and are inherently corrosion resistant
• Active coatings
– Have corrosion inhibitors dispersed in the coating
– Sacrificially corrode to protect the metal from
corrosion
• Self-generated coatings
– Rely on alloying in sufficient concentrations so that
a protective film forms spontaneously

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Corrosion Inhibitors in coatings

• Corrosion inhibitors reduce the rate of attack when dissolved or
dispersed in a corrosive medium by moving to the exposed metal
and creating a protective nano-thick layer: they block the anode
or/and the cathode.

• The choice of inhibitor depends on both the material and the

environment, and the coating when embedded in a coating
system

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Ways of Applying Coatings

(a)Paint spraying
(b)Hot dip galvanizing
(c) Electroplating
(d)Metal flame spraying
(e)Polymer powder spraying
(f) Enameling

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Monitoring, Maintenance, and

Replacement

Corrosion inspection, FAA (13 min)

https://www.youtube.com/watch?v=hIcMBENNt6Q

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Summary:
Material gradation can occur due to the presence of oxygen and
electrolyte through electrochemical reactions.

Metal degradation is unavoidable but can be slowed down to

acceptable levels by taking appropriate measures

Corrosion takes place if 4 requirements are being met simultaneously:

- An anode and a cathode material
- An electrolyte, i.e. a liquid into which metals can dissolve and
which is electrically conductive
- A closed electrical circuit

Some of the measures involve adjusting the product geometry

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Recommended exercises:

E14.1, E14.7, E14.13, E14.23, E14.34

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