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Universidad

Carlos III de Madrid MATERIALS SCIENCE AND ENGINEERING


www.uc3m.es

TOPIC 10. COMPOSITE MATERIALS FOR AEROSPACE


INDUSTRY. (Session II)

Polymer matrices in Composite Materials


Thermosetting matrices
Thermoplastic matrices
The interface region
Mean elastic properties of composites
Mechanics of materials approach
g
Elastic deformation of long-fibre composites
p
Elastic deformation in composite with an uniformly dispersed aggregate

Dpt. Materials Sci. and Eng. and Chemical Eng. UC3M Aerospace Materials I
Topic 10: Composite materials. Part II.
POLYMER MATRICES: THERMOSET AND THERMOPLASTIC

PROPERTIES

Thermosetting
gppolymers
y Thermoplastic
p matrices
• Croslinked chains • Semicrystalline. High Tm

• Insoluble
I l bl (swell)
( ll) • C
Consolidation:
lid ti (N chemical
(No h i l
reaction) processing by heat and
pressure
• Amorphous
A h (Tg) • Potentially reprocessed

• Low shelf life • Large shelf life

• Do not flow under stress even at • Potential for fast part fabrication
high T.
• Brittle (low strains at failure) • Very high melt viscosities (high
pressure and high shearing
• Sensitivity to moisture forces during manufacturing
R i f
Reinforcement t damage)
d )

Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Aerospace Materials I
Topic 10: Composite materials. Part II.
POLYMER MATRICES: THERMOSET AND THERMOPLASTIC
THERMOSET THERMOPLATIC
Main Characteristics
• Undergoes chemical change when cured • Non-reacting, no curing required
• low strain to failure • high strain to failure
• low fracture energy • high fracture energy
• processing is irreversible • very high viscosity
• very low viscosity possible • processing is reversible
• absorbs moisture • absorbs little moisture
• highly resistant to solvents • limited resistance to organic solvents, in some case
Advantages
• Relatively low processing temperature • Short processing times possible
• good fiber wetting • reusable scrap
• formable into complex shapes • post-formable can be reprocessed
• liquid-resin manufcturing feasible • rapid processing
• resistant to creep • unlimited shelf life without refrigeration
• high delamination resistance
Disadvantages
• long processing time and long cure (1-2
( h)) • lower resistance to solvents
•restricted storage life • requires high T (300-400 ºC) and P processing

Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M • can be prone to creep Aerospace Materials I
Topic 10: Composite materials. Part II.
POLYMER MATRICES: THERMOSET AND THERMOPLASTIC

Polymer matrix role in composites

•Protects fibres from surface


damage
•Maintains
Maintains fibres in desired
orientations
•Transmits loads between
layers of fibres so that they
resist bending or compression
•Transfers loads to other fibres
when a crack appears

Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Aerospace Materials I
Topic 10: Composite materials. Part II.
Thermosetting Matrix Materials

Thermosetting matrices used in the aerospace industry


• Epoxy
– With elastomeric additives
– With thermopalstic additive
• BMI
• PI (thermoplastic or themostetting)
• Polyester
• Phenolic

Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Aerospace Materials I
Topic 10: Composite materials. Part II.
Thermosetting Matrix Materials
EPOXY
• They are the most used in structural applications.
• Good mechanical properties in general, the temperature can
vary between
b t 60-150
60 150 º C.
C
• They have low shrinkage and good adhesion to most fibers.
• Usually
y cured at 120 ° C and at 180 ° C).
)

Polyimides (PI)
• More expensive and less used that epoxy resins.
• Designed to work with relatively high service temperatures between
130 and 230 ° C
• In g general,, all of these resins have a higher
g water absorption
p and lower
stiffness of epoxy resins

Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Aerospace Materials I
Topic 10: Composite materials. Part II.
Thermosetting Matrix Materials

Bismaleimides (BMI)
• Tg between 275 and 300 ° C. Good performance at high service
t
temperatures
t (250 ° C)
• Can use conventional curing cycles, yielding laminates with low
porosity content.
• Usually a need for post-curing to achieve optimum properties
• Good mechanical properties.
• Present microcracking during prolonged exposure to high
temperatures

Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Aerospace Materials I
Topic 10: Composite materials. Part II.
Thermosetting Matrix Materials
Some Details on Selected Thermosetting Matrix Materias Used in Aerospaced Composites
Matrix Examples Cure Max (wet) Comment on Performance as Matrix
ºC/kPa Capability ºC

Epoxy Hexcel 920 120/700 80+ Best properties all around

Epoxy Hercukes 3501 180/700 100+ Excellent adhesion to fibers


Fiberite 934 Easy to process, wide viscosity range, good wetting
N
Narmco 5208 E
Excellent
ll t water
t andd other
th chemical
h i l resistence
i t
Fairly low toughness, composites sensitive to impact
damage
Sensitive to UV exposure
Epoxy Hercules 3502 180/700 100+ All of the above, plus:
Toughened Fiberite 977-2 Improved tolerance to damage and increased moisture
sensitivity
BMI Hexcel F560 180/700 230 Exceeds epoxy T capability
+ Relatively easy to process
postcure Even less tough than epoxies
200
Undergoes shrinkage during curing
Prone to microcrack with thermal cycling
y g
BMI Cytec 5250-4 80/700 180 All of the characteristics listed for BMI, plus:
Toughned More damage resistant
Lower T capability than untoughned
Polyimide
P l i id PMR 15
PMR-15 300/400 320 Resistant
R i t t to
t oxidation
id ti
Condesation Similar properties to epoxy but overextended T range
Low toughness and difficult to process
Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Aerospace Materials I
Topic 10: Composite materials. Part II.
Thermosetting Matrix Materials

Properties of themosetting resins

Propiedad Polyester Phenolic Epoxy Bismaleimides Polyimida


Density (g/cm3) 1,1-1,5 1,3 1,1-1,4 1,2-1,3 1,2-1,9
Elastic Modulus (GPa) 1,3-4,5 4,4 2,1-6,0 3,4-4,1 3,0-3,1
Tensile Stregnth (MPa) 45-85 50-60 35-90 35-90 80-190
Fratcure toughness (MPa·m-1/2) 0,5 0,6-1,0
Fracture energy(kJ/m2) 0,02 0,3-0,39
Coef.f thermal expansion(10-6 K-1) 100-200 45-110 55-110 60-65 14-90
T (ºC)
Tg 120 190
120-190 275 300
275-300 300 350
300-350
Water Absortio (%) 2-6 4-4,5

Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Aerospace Materials I
Topic 10: Composite materials. Part II.
Thermosetting Matrix Materials
Additi
Additives used
d to
t modify
dif resin
i properties
ti
Solvent are added to reduce the viscosity before curing to aid in handling, wet-
out etc
out, etc.
Plasticizers are added to reduce the elastic modulus and increase the
elongation to failure
Inert fillers, including hollow spheres, are added to alter density, resin flow,
cost, and effective modulus
Toughening agents that precipitate from the reacting matrix during curing as
fine particles, designed to modify the crack propagation properties in a cured
matrix

Toughening mechanisms
• Random dispersion of a thermoplastic second phase in the initial
formulation (polyethersulphone)
• Random dispersion of a rubber second phase in-situ during the
polymerization process (carboxyl or amine terminated poly(butadiene-
co-acrylonitrile:CTBN)
l it il CTBN) rubbers.
bb

Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Aerospace Materials I
Topic 10: Composite materials. Part II.
Thermoplastic Matrix Materials

Currently a considerable effort to try to substitute thermosetting matrices for


thermoplastic matrices.
The main advantages these resins are :
-Materials with unlimited shelf-life
- Storage at room temperature
- Better resistance to impact and moisture
- Toughness (strain at fracture 30% -100%)
100%)
- Good FST behavior (fire, smoke & toxicity)
- Processing speed
- reprocessability, recyclibility

The main disadvantages of these resins are:


- High cost materials
- High processing costs (high temperature and pressure)
- Surface treatment of the carbon fibers
- Special Auxiliary Materials

Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Aerospace Materials I
Topic 10: Composite materials. Part II.
Thermoplastic Matrix Materials
Unlike TS resins
resins, TP are not cross
cross-linked
linked
Broad Classification: Amorphous and Semicrystalline
Amorphous TP Semicrystalline TP
• High concentration of molecular • High degree of molecular order and
entanglements alignment
• Heating leads to disentanglement • May have anisotropic properties
and
d change
h rigid
i id solid
lid →viscous
i liliquid
id (crystalline lamellar units oriented)
• Low resistance to aggressive fluids • Very good resistance to aggressive
• Wide processing window fluids
• Examples: PEI • The processing window can be
critical (especially cooling rate)
• Examples: PEEK, PPS
Thermoplastic processed by injection molding:
Reinforced with carbon fiber or glass:
Examples: PEEK, PA, PTFE

Polyether
y ether ketone ((PEEK)) Poethersulfones PES
Polyphenylene sulfide (PPS) Polyimide PI

Polysulfone PSF Polyethylenimine


y y ((PEI))

Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Aerospace Materials I
Topic 10: Composite materials. Part II.
Thermoplastic Matrix Materials
S
Some D t il on Selected
Details S l t d Thermoplastic
Th l ti Matrix
M t i Materias
M t i used
d in
i Aerospaced
A d Composites
C it

Polymer Example Process Tg ºC Comment on Performance as Matrix


T ºC

PEEK Victrex 400 145 Excellent mechanical properties, including


toughness. For application until 120 ºC. Highly
resistant
i t t to
t damage.
d Excellent
E ll t fire
fi resitance.
it
Most widely used for high-perfomance
composites
PPS Ryton 340 90 Good strength
strength, stiffness and T capability
capability. Some
grade have low viscosity. Resistant to most
PSF Udel 400 190 fluids, but attacked by some solvents. Good fire
resistance. Low impact resistance
PES Vitrex 400 230

PI Kapton 390 320 Selected for highest T applications. Highly


viscous.
i Diffi
Difficultlt tto process. Select
S l t for
f high-T
hi h T
applications.
PEI Ultem 370 215

Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Aerospace Materials I
Topic 10: Composite materials. Part II.
The interface region

INTERFACE: The planar region that separates two components.


Interphase, a new concept, a region of space characterised by a volumen and
property gradients,
gradients that separates two components

The final properties of a composite with a polymeric matrix reinforced with


fibers depends upon the interfacial adherence

Poor adherence matrix‐fibers Good adherence matrix‐fibers
Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Aerospace Materials I
Topic 10: Composite materials. Part II.
The interface region
Bonding mechanism
In most treatment, is assumed than the interfacial bon dis “perfect”. This
means that there is no debonding,
g, cracking g or sliding
g
In practice:
¡¡ manyy important
p phenomena may
p place at the interface !!
y take p

PLASTIC DEFORMATION OF THE MATRIX: CAN INFLUENCE ON FAILURE

A bonding system between the matrix and the fiber is necessary to


consistently achieve the ideal mechanical properties

To Formation of Interfacial bonds:


• Adsorption and wetting
• Interdiffusion and chemical reaction
• Electrostatic attraction
• Mechanical keying

Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Aerospace Materials I
Topic 10: Composite materials. Part II.
The interface region

CONTROL OF BOND STRENGTH: Coupling agents, toughness-reducing coating


and interfacial chemical reaction and diffusion barrier coating

Glass fibres: surface sizing


Strength of glass fibres is determined by: damage during processing, and the
adsorption of water over their surface

• Role of sizings
– binds the filaments (d = 10-20 mm) together for ease
processing,
– lubricates fibres so they can withstand abrasion,
– imparts anti-static properties
– provides some chemical functionalities to the surface
to improve
p interfacial bond strength.
g

• Sizing normally contains a film-forming polymer, such as


polyvinyl acetate
acetate, and a coupling agent (organosilane,
(organosilane
titanate or chromate).
Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Aerospace Materials I
Topic 10: Composite materials. Part II.
Mean elastic properties of composites

Composite material properties: 
mean property of its individual components:

Mean properties depend upon the microstructural
geometry:

Three ideal geometries:
a) Direction parallel to continuous fibers
b) Direction perpendicular to continuous fibers
c)) Direction relative to a composite with a uniformly dispersed 
Di ti l ti t it ith if l di d
reinforcement

Let there be a composite with modulus EC and strength C


The matrix has Em m and y,m and the fiber Ef and f
Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Aerospace Materials I
Topic 10: Composite materials. Part II.
Mean elastic properties of composites
Mi
Micro analyses studies for fiber composites
l di f fib i
MICROMECHANICS : Utilizes microscopic models of composites, in which the fibers and
the matrix are separately modelled.

ASSUMING

FIBERS MATRIX
fibers homogeneous homogeneous
linearly elastic linearly elastic
isotropic isotropic
isotropic,
regularly spaced
perfectly aligned
uniform length

Micromechanics can be approach in three ways:


1. The mechanics of materials: p predict the behaviour of simplified
p models of the
composite material
2. The theory of elasticity: predict upper and lower bound exact analytical or numerical
solutions
3 The
3. Th finite-element:
fi it l t basedon
b d 2-dimensional
2 di i l or 3-dimesional
3 di i l models
d l off varing
i degrees
d
of sophistication
Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Aerospace Materials I
Topic 10: Composite materials. Part II.
Elastic deformation of long-fibre composites
Direction
Di ti parallel
ll l to
t continuous
ti fibers
fib (1-direction):
(1 di ti ) ISOSTRAIN conditions
diti
(Longitudinal Modulus, E1)

The axial strain


1f 1m
1C|  f  m 
Ef Em

For a composite in which the fibres are much stiffer than the matrix (Ef>>Em), the
reinforcement is subject to much higher stresses (1f>>1m) than the matrix and there is a
redistribution of the load

The overall stress  1C  1  V f  1m  V f  1 f


 1C 1  V f  1m  V f  1 f   1  V f  1m 
The Young’s modulus of the composite E1C    Vf 
 1C  1 f E f    1 f 
Using the ratio between the stresses in the componts: 

E1C  1  V f Em  V f E f eq 1


Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M ”rule of mixtures” Aerospace Materials I
Topic 10: Composite materials. Part II.
Elastic deformation of long-fibre composites
Direction
Di ti perpendicular
di l tot continuous
ti fib
fibers (2 di ti ) ISOSTRESS conditions
(2-direction): diti
(Transverse Modulus, E2)

2C = f =m and assuming that the area  stress does not change 


after the stress is applied 

Also, the length of each component:
Lm=AmLC
Lf=AfLC LC Am Lm A f L f
andd LC=Lm+Lf  
LC Lm Lf

When a stress applied in the 2-direction  2C   2 f   2 f E f   2 m   2 m Em


 the overall net strain is
 2C  V f  2 f  1  V f  2 m
and the transverse strains for the fiber, matrix, and composite are:

2 2 2
f  , m  , 2 
E' f Em E2
Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Aerospace Materials I
Topic 10: Composite materials. Part II.
Elastic deformation of long-fibre composites

 and the composite modulus:

2 2f E f Em
  
 2 V f  2 f  1 V f  2 m  EmV f  E f (1  V f )
E2 C

Vf V
1
 '  m eq 2
E2 C E f Em

E’f: is the effective transverse modulus of the fiber

Normaly Ef>>Em and for typical fiber comosites with Vf=50‐60%, the matrix has only a small effect upon E1 
Em
E1  E f V f and E2 
Vm

Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Aerospace Materials I
Topic 10: Composite materials. Part II.
Elastic deformation of long-fibre composites

Example: fiberglass reinforced epoxy resin

Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Aerospace Materials I
Topic 10: Composite materials. Part II.
Elastic deformation of long-fibre composites

Let there be a composite with modulus EC and strength C


The matrix has Em m and y,m and the fiber Ef and f
Strength
For similar reasons as those explained before, the
strength C of an unidirectional composite follows the
same rule of mixtures

 C   f V f   y ,m (1  V f )
Fibers break before the matrix because they are more
brittle. When this happens, the equation transforms to:

 C   m (1  V f )

A minimum Vf (critical) is required. If Vf is lower than


the critical value, the strength of the materials is
reduced.

Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Aerospace Materials26I
Topic 10: Composite materials. Part II.
Elastic deformation of long-fibre composites

Major Poisson’s Ratio 12


2
 12   Where the only applied stress is 1
1
The transverse deformation is W=Wf +Wm or     2C W=f (VfW)+m(VmW) and

12= ratio of contraction in the transverse direction


 12   f V f  mVm consequent of an extension in the fiber direction

Prediction of E1 and E2 for triaxal stress condiction


Equiations 1 and 2 a do not allow for the triaxials tress contition in the matrix rsulting
from the contraint cuased by the fibers. Two modified versions for  E (1 and 2‐
direction) considering triaxial stress conditions :
direction) considering triaxial stress conditions :
1-direction: E1 2-direction: E2

E1  E f V f  Em' Vm h
where
  

1 V f V m V f E f m E m   f 2

E 'm 
Em

E2 E f Em E f V f E f Vm Em   1 

1  2m2 
m and f are Poisson’s ratio for the matrix material and fiber respectively
Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Aerospace Materials I
Topic 10: Composite materials. Part II.
Elastic deformation in composite with an uniformly dispersed aggregate

Rule of mixtures: The properties of a composite material depend upon the relative
quantities and properties of its constituents
A thorough treatment of this system is complex and depends on the nature of the dispersed
phase and the matrix. An approximation is given by the equation:

E  vl E  vh E
n
C l
n n
h
l= lower modulus phase
h= higher modulus phase

Upper bound: n=1


Lower bound: n=-1
n 1

Particle-reinforced composite  Isotropic properties


Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Aerospace Materials I
Topic 10: Composite materials. Part II.
Improvement of mechanical properties

Increase of toughness to fracture of some  Increase of strength of epoxy resin with 
ceramic matrix composites
ceramic matrix composites different reinforcements
different reinforcements

Dpt. Materials Sci. and Eng. and Chem. Eng. UC3M Aerospace Materials I

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