151 0548 FS2017 K3 Introduction To Polymer Materials

Spring Semester 2017
151-0548-00L Manufacturing of Polymer Composites
Introduction to Polymer Materials

Joanna Wong
23 February 2017
15:00 – 16:00
23.02.2017 1 Manufacturing of Polymer

Table of contents
 General features of polymeric materials
 Thermo-mechanical behaviour
Mr McGuire: I just want to say one word to you.

Just one word.
Benjamin: Yes, sir.
Mr McGuire: Are you listening?
Benjamin: Yes, I am.
Mr McGuire: Plastics.
Career advice to Dustin Hoffman's character in
the movie “The Graduate” (1967)
Thursday, February 23, 2017 Institute of Mechanical Systems - Structure Technology 2
Quelle: Mayorga, G.D.: “Quality Assurance and Quality Control“ in International Encyclopedia of Composites, Ed. S. M. Lee, VCH Publishers, New York 1991
3
World Consumption of Polymers
Year Consumption
(kilotonnes)
2006 240,947
2016 402,022
Accenture, “Trends in manufacturing polymers: Achieving high performance in a multi-polar world” (2008).

Disposable Containers
Clothing
Sealants
Lightweight Insulating
Structures Containers
Sandwich Cores
Acoustic Electrical
Insulation Insulation
Toys Furniture
Decor Filters Thermal Insulation
Floatation
Packaging
Thursday, February
Donnerstag, 23. Februar
23, 2017
2017 Institute of Centre
Mechanical
of Structure
SystemsTechnologies
- Structure Technology 5
Why are polymers interesting materials?
 Source: http://www-materials.eng.cam.ac.uk/mpsite/interactive_charts/stiffness-density/basic.html

But we are here to learn about Composites

So how much carbon is
in my carbon
composite material?
Less than 50%
The
majority is
polymer!
When we speak of polymers, what exactly are we
talking about?
 The word polymer means “many” (poly) “parts” (mer), compare with monomer,
and oligomer
 Polymers consist of several ordered monomer repeat units
 molecules whose molecular weight (or size) is in the range of several thousand or
more.
 Synonyms: Plastic, macromolecules, synthetics
Polypropylene
monomer
polymer

Homopolymers & Copolymers
 When a polymer is made by linking only one type of small molecule, or
monomer, together, it is called a homopolymer.
 When two different types of monomers A and B are joined in the same polymer
chain, the polymer is called a copolymer.
Homopolymer
 Source: http://pslc.ws/mactest/copoly.htm

Small Molecules, eg. water
Oligomers, several repeating unit, eg. Some oils
Polymers, many repeating units, e.g. PET, polycarbonate

Take Away Points
Polymers = plastics
There would be no FRP composites without polymers.
What makes polymers different from small molecules?

 Chain entanglement
 Summation of intermolecular forces
 Time scale of motion
Thermoplastic versus thermosetting polymers.

Why size matters?
• Higher likelihood for entanglement

• Higher intermolecular forces
• Longer time scales for motion

Entanglement

Intermolecular forces

Longer Time Scales

Longer time scales: Pitch drop experiment

Longer time scale: Thermal Motion
Particles – Brownian Motion Polymer – Reptation
Equation for Diffusivity: Time for diffusion:

𝑥2 𝜇𝑅𝑇 𝑅𝑇 6𝜋𝜂𝑟𝑁𝑥 2 𝑙 2 𝑛 3 𝜇𝑓
𝐷= = 𝜇𝑚 𝑘𝑏 T = = 𝑡= 𝑡=
2𝑡 𝑁 6𝜋𝜂𝑟𝑁 2𝑅𝑇 𝑛𝑒 𝑘𝑏 𝑇
D: diffusivity T: temperature
x: displacement N: Avogadro’s number l: Kuhn length
t: time R: Ideal gas constant n: number of Kuhn lengths in chain
μm: mobility η: viscosity μf: coefficient of friction
kb: Boltzmann constant r: particle radius ne: number of lengths in blob model

Viscoelastic deformation behavior
 For small deformation and at low temperatures mechanical behavior

of polymers can be considered as elastic.
 Depending on the temperature, polymers combine both viscous
liquid and elastic characteristics when undergoing deformation.
dg æ EA ö
– Newton‘s fluid: s = h with h = h0 × exp ç ÷
dt è RT ø
– Hooke‘s law:   G
ETH Zurich, Laboratory of Composite Materials and Adaptive Structures Manufacturing of Polymer Composites - Constitutent Materials | 23.02.2017 | 26
Creep and stress relaxation are well-suited to
investigate the long term material behavior
Creep tests:
 t   t 
0 Creep compliance coefficient J(t)
0

1
 Slope:
h

0 0
Stress relaxation tests:
 t   t 
0
0
Relaxation module G(t)
0

0 0
Maxwell Modell
 Newtonian damper and Relaxation
Hookean elastic spring are d/dt = const. d/dt = 0

connected in series.
 Addition of the deformations:

d  1 d
 
dt  G dt Kriechen
æ tö
s = s 0 exp ç - ÷
è tø
h
with the relaxation time t =  = const. =0
G
Kriech- und Wiederherstellungsverhalten
Voigt-Kelvin-Modell
Relaxation
d/dt = const. d/dt = 0
 Newtonian damper and Hookean

elastic spring are connected in
parallel.
 Addition of the shear stress

components
Kriechen
d
   G
dt
  t 
  1  exp     = const. =0
G   

where  
G
Dynamic Loading
Dynamic loading tests are well suited to
analyze the short time behavior
 Harmonic shear strain
dg
g (t ) = g 0 sin (wt ) and therefore = wg 0 cos (wt )
dt
 The stress and strain are shifted by the phase angle d:

 t    0 sin t 
 (t)   0 sin t  d   GD  0 sin t  d 
 Shear stress can be written as:


Dynamic loading
 Storage Modulus G‘ is in Phase with 

 Loss Modulus G‘‘ is in Phase with d/dt. In purely viscous materials,
strain and stress are shifted by a 90 degree phase lag
G *  G  iG 
GD  G *  G 2  G2
 Mechanical loss factor d:


G
d  tan d 
G
 Komplexer Modul im Zeiger-Diagramm

How do we measure polymer size?

Molecular weight -1-
Molecular weight: mass of a mole of chains.
Low M
High M
• Polymers can have various lengths depending on the number of repeat units.
• During the polymerization process not all chains in a polymer grow to the same
length, so there is a distribution of molecular weights.
• The molecular weight distribution in a polymer describes the relation between the
number of moles of each polymer species and the molar mass of that species.
 Sources: Introduction to polymers, Second Edition, R.J. Young and P.A. Lovell
 www.csun.edu/~bavarian/Courses/MSE%20227/Lectures_Exam1/Ch4-Polymers.ppt
M n  xi M i
M w  wi M i
__
Mn = the number average molecular weight
__
Mw = the weight average molecular weight
Mi = mean (middle) molecular weight of size range i
xi = number fraction of chains in size range i
wi = weight fraction of chains in size range i
 Source: www.csun.edu/~bavarian/Courses/MSE%20227/Lectures_Exam1/Ch4-Polymers.ppt
Molecular weight Example
Imagine a MW distribution as described below:
MW n x MW ni x MW wix MW
(g/mol) n (g/mol) ni (g/mol) wi (g/mol)
10000 1 10000 0.091 909 0.009 94
50000 3 150000 0.273 13636 0.142 7075
100000 5 500000 0.455 45455 0.472 47170
200000 2 400000 0.182 36364 0.377 75472
11 1060000 1.000 96364 1.000 129811

The molecular weight affects the thermo-mechanical properties
of polymers
 Source: http://chem.chem.rochester.edu/~chem421/propsmw.htm
Polymer topology and chain interactions
secondary
bonding
Linear Branched Cross-Linked Network
Kevlar Elastomers Epoxy

The chains attached to
the backbone are
comparable in length
to the backbone itself
 Sources: http://www.chm.bris.ac.uk/webprojects2002/edwards/chemistryc_files/image004.gif
 www.csun.edu/~bavarian/Courses/MSE%20227/Lectures_Exam1/Ch4-Polymers.ppt
 http://pslc.ws/macrog/eposyn.htm
Linear vs cross-linked polymers
Linear Polymer
Stretch
The chains can be stretched, which causes

them to flow past each other. When released,
the polymer will not return to its original form.
Cross-Linked Polymer
Stretch
Relax
The cross-links hold the chains together.
When released, the polymer will return to it's
original form.
 Source: bama.ua.edu/~kshaughn/poly-lecture.ppt

Thermosetting polymers
 Thermosetting polymers are provided as uncured resins, or monomers
(oligomers) that undergo a chemical reaction to form a polymer network
 Thermosetting plastics when heated, will chemically decompose, so they can
not be recycled. Yet, once a thermoset is cured it tends to be stronger than a
thermoplastic.
 The networked structures are thermosets.
Thermosets Elastomer
 Menges, G.: Werkstoffkunde der Kunststoffe, 2. Auflage; Carl Hanser Verlag, München, Wien 1984
 Domininghaus, H.: Die Kunststoffe und ihre Eigenschaften; 4. Auflage, VDI-Verlag, Düsseldorf 1992
Thermoplastics polymers
 A thermoplastic is a polymer that turns to a liquid when heated above Tm and
freezes to a very glassy state when cooled below Tg.
 Most thermoplastics are high-molecular-weight polymers whose chains

associate through weak Van der Waals forces (polyethylene); stronger
dipole-dipole interactions and hydrogen bonding (nylon).
 Typically, linear polymers with minor branched structures (and flexible

chains) are thermoplastics.
Thermoplastics
amorphous Semicrystalline
 Principali classi di materiali polimerici, Universita’ di Salerno.
Polymer crystallinity
crystalline
region
Polymers are rarely 100% crystalline
 Difficult for all regions of all chains to
become aligned;
 A crystalline polymer has two components:
the crystalline and the amorphous portion.
amorphous
region
Thermosets versus Thermoplastics
Spaghetti
Fishing net

Glass transition and melting
 Glass Transition Temperature (Tg): The temperature (actually a range of

temperatures) at which chains in amorphous (i.e., disordered) regions of the
polymer gain enough thermal energy to begin sliding past one another at a
noticeable rate. Polymers with no order are hard and brittle below a certain
temperature and soft and pliable above it.
 Melting Temperature (Tm): The temperature (actually a range of temperatures)

at which the ordered regions of a crystalline polymer melt, similar to a small
molecule. Crystallization is essential for many high-performance polymers
because it greatly increases the strength of the material.
 Melting is something that happens to a crystalline polymer, while the glass

transition happens only to polymers in the amorphous state.
 Source: http://chem.chem.rochester.edu/~chem421/propsmw.htm

Glass transition and melting
This is another big difference between melting and glass transition.
Heat capacity: The amount of heat required to raise the temperature of one
degree Celsius of one gram of the polymer.
 Source: http://pslc.ws/mactest/tg.htm

Wrap-up thermomechanical behaviour
Me is a critical molecular weight.

Below this value, the molecules are
too short for interacting among them.
 Source: Polymere Werkstoffe & Werkstoffcharakterisierung, composite technologien 2008

Thermomechanical behaviour of different polymers
Thermosets
Dynamic Module
Loss factor
Temperature
Semi-crystalline Thermoplastics Amorphous Thermoplastics

Dynamic Module
Dynamic Module
Loss factor
Loss factor
Temperature Temperature
Domininghaus, H.: Die Kunststoffe und ihre Eigenschaften; 4. Auflage, VDI-Verlag, Düsseldorf 1992
Behaviour in Hot/Wet Environments
 Water absorption is descirbed by

the Fick's first law:
c
  D
x
 F is the diffusion flux [mol/m2.s]
– D [m2/s] is the diffusion
coefficient, which depends on the
temperature
– c is the concentration
Arendts, F.J., Aktuelle Entwicklungen in der Strukturtechnik, Z. Flugwiss.

Weltraumforschung, 16 (1992) 231-246
 The variation of the water
concentration is described by the
Fick's second law:
c 2 c
D 2
t x
Water absorbtion in the matrix is

affecting mechanical properties
 Reduction of matrix stiffness and
strength
 accentuate viscoelastic
deformation
 Reduction of the glass transition
temperature Tg
 Reduction of the interlaminar shear
stiffness
Deutsche Zentrum für Luft- und Raumfahrt
P. Ermanni, Die kombinierte Nasswickel- und Prepregbauweise: Ein Verfahren zur wirtschaftlichen Herstellung von CFK-
Flugzeugrumpfstrukturen, Dissertation ETH Nr. 9339, Zürich 1990.

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Spring Semester 2017

151-0548-00L Manufacturing of Polymer Composites

Introduction to Polymer Materials

23.02.2017 1 Manufacturing of Polymer

 General features of polymeric materials

Mr McGuire: I just want to say one word to you.

Thursday, February 23, 2017 Institute of Mechanical Systems - Structure Technology 4

Decor Filters Thermal Insulation

Thursday, February 23, 2017 Institute of Mechanical Systems - Structure Technology 6

Thursday, February 23, 2017 Institute of Mechanical Systems - Structure Technology 7

Less than 50%

Thursday, February 23, 2017 Institute of Mechanical Systems - Structure Technology 10

Thursday, February 23, 2017 Institute of Mechanical Systems - Structure Technology 11

Oligomers, several repeating unit, eg. Some oils

Polymers, many repeating units, e.g. PET, polycarbonate

Thursday, February 23, 2017 Institute of Mechanical Systems - Structure Technology 12

There would be no FRP composites without polymers.

What makes polymers different from small molecules?

Thermoplastic versus thermosetting polymers.

Thursday, February 23, 2017 Institute of Mechanical Systems - Structure Technology 13

• Higher likelihood for entanglement

Thursday, February 23, 2017 Institute of Mechanical Systems - Structure Technology 16

Thursday, February 23, 2017 Institute of Mechanical Systems - Structure Technology 17

Thursday, February 23, 2017 Institute of Mechanical Systems - Structure Technology 19

Thursday, February 23, 2017 Institute of Mechanical Systems - Structure Technology 21

Thursday, February 23, 2017 Institute of Mechanical Systems - Structure Technology 22

Equation for Diffusivity: Time for diffusion:

Thursday, February 23, 2017 Institute of Mechanical Systems - Structure Technology 23

 For small deformation and at low temperatures mechanical behavior

 Newtonian damper and Relaxation

Hookean elastic spring are d/dt = const. d/dt = 0

 Addition of the deformations:

d/dt = const. d/dt = 0

 Newtonian damper and Hookean

 Addition of the shear stress

 The stress and strain are shifted by the phase angle d:

 Shear stress can be written as:

 Storage Modulus G‘ is in Phase with 

 Mechanical loss factor d:

 Komplexer Modul im Zeiger-Diagramm

Thursday, February 23, 2017 Institute of Mechanical Systems - Structure Technology 33

Imagine a MW distribution as described below:

10000 1 10000 0.091 909 0.009 94

50000 3 150000 0.273 13636 0.142 7075

100000 5 500000 0.455 45455 0.472 47170

200000 2 400000 0.182 36364 0.377 75472

11 1060000 1.000 96364 1.000 129811

Thursday, February 23, 2017 Institute of Mechanical Systems - Structure Technology 36

Linear Branched Cross-Linked Network

Kevlar Elastomers Epoxy

The chains can be stretched, which causes

Thursday, February 23, 2017 Institute of Mechanical Systems - Structure Technology 39

 Most thermoplastics are high-molecular-weight polymers whose chains

 Typically, linear polymers with minor branched structures (and flexible

Thursday, February 23, 2017 Institute of Mechanical Systems - Structure Technology 43

 Glass Transition Temperature (Tg): The temperature (actually a range of

 Melting Temperature (Tm): The temperature (actually a range of temperatures)

 Melting is something that happens to a crystalline polymer, while the glass

Thursday, February 23, 2017 Institute of Mechanical Systems - Structure Technology 44

Thursday, February 23, 2017 Institute of Mechanical Systems - Structure Technology 45

Me is a critical molecular weight.

 Source: Polymere Werkstoffe & Werkstoffcharakterisierung, composite technologien 2008

Thursday, February 23, 2017 Institute of Mechanical Systems - Structure Technology 46