ALL-POLYMER COMPOSITES

Presented by:
Mohammad Habibi
Farimah Tikhani
Kiarash Farajzadeh
Milad Irannejad Dr. Hashemi Motlagh
Reinforced Plastices
 PART 1
INTRODUCTION &
PROCESSING
Introduction

■ Recycle
■ Low density
■ Adhesion

3
Process techniques

■ Variety but high accuracy

■ Basic principle
■ Melt spinning, electro spinning, film stacking
■ Hot compaction, cold compaction, over heating
■ Soloutin, partial dissolving,….

4
Electro/melt spinning

■ Elector spraying
■ Infinite length
■ High voltage

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Electro spinning

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Electro spinning

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In situ based techniques

■ Difference in melting temperature

■ Better dispersion
■ Low fiber pullout risk

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Hot compaction

■ Depending on crystallization
■ Processing window
■ Combining with other techniques

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Film stacking

 Simple
 Processing window
 Most used

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Other techniques

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Other techniques

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 PART 2
FIBER/MATRIX INTERFACIAL
ADHESION AND
MORPHOLOGY
Importance of adhesion in All-polymer Composites

 Poor off-axis properties for organic reinforcements like aramid fibers in

comparison to inorganic ones such as glass or carbon fibers
 Improvement of compressive strength by deterring the onset of fiber buckling
 Different failure modes of the composite depending on interfacial adhesion
 The mechanical behavior of composite materials reflects the interactions
between their various constituents; like toughness & mechanical strength

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 Bonding mechanisms of PPCs

Deals with chemistry Relation between molecular structure & adhesion

& physics of the
Enhance or weaken
interphase
any of adhesion
mechanisms
Micro mechanical aspects Macro mechanical aspects
Mechanical interlocking Mechanical interactions
Adsorption interactions wetting
Electrostatic attractions Weak boundary layers
Polymer interdiffusion

Source: J. KALANTAR; The bonding mechanism of aramid fibers to epoxy matrices; Journal of material science, 25; 1990 15
 Improvement of interfacial adhesion

1. Surface treatment: Oxidation, etching, oxygen plasma treatment, ammonia

plasma treatment, chemical treatment, …

Purposes:
 Roughening of the fiber surface in order to enlarge the physical interface with
the matrix resin allowing also for mechanical anchoring
 Chemical activation of the fiber surface
 Creating chemical bonds across the fiber/matrix interface

Sources: -Stoyko Fakirov; Synthetic Polymer-Polymer Composites; Hanser Pub. ; 2012

-P. J. C. Chappell; Surface Modification of Extended Chain Polyethylene Fibres to Improve Adhesion to Epoxy and Unsaturated 16
Polyester Resins; 1991
 Improvement of interfacial adhesion

Change in failure mechanism after plasma treatment

(ECPE/Epoxy)
Source: P. J. C. Chappell; Surface Modification of Extended Chain Polyethylene Fibres to Improve
Adhesion to Epoxy and Unsaturated Polyester Resins; 1991 17
 Improvement of interfacial adhesion

2. Matrix treatment: where fiber

surface is chemically inert

EXP) Addition of HDPE resin to

SEBS matrix to improve its adhesion
to UHMWPE fibers

Source: Z. Zheng; Influence factors of internal structure and interfacial compatibility of UHMWPE fiber/SEBS resin
composites: Processing parameters, structure of fiber and nature of resin; Composites: Part B 43 (2012) 18
 3. Processing parameters: Pressure, Temperature

Source: Z. Zheng; Influence factors of internal structure and interfacial compatibility of UHMWPE fiber/SEBS
resin composites: Processing parameters, structure of fiber and nature of resin; Composites: Part B 43 (2012) 19
 Influence of draw ratio on morphology in MFCs

PET/iPP

Source: Stoyko Fakirov; Synthetic Polymer-Polymer Composites; Hanser Pub. ; 2012 20

 21
Source: Stoyko Fakirov; Synthetic Polymer-Polymer Composites; Hanser Pub. ; 2012
 Influence of viscosity ratio on morphology in MFCs

Source: Stoyko Fakirov; Synthetic Polymer-Polymer Composites; Hanser Pub. ; 2012 22

 Interlaminar shear strength
Measurement of interlaminar shear strength can provide useful information about
interfacial adhesion of composites.

Macromechanical methods

Micromechanical methods
Fragmentation
test

ILSS Pull-out test

Transverse tensile Microindentation

test test

Microbond test

Source: H. D. WAGNER; Study of the interface in Kevlar 49-epoxy composites by means of microbond and
23
fragmentation tests: effects of materials and testing variables; Journal of materials science 28 (1993)
 Interlaminar shear strength

Correlation between the

interface shear strength,
measured by means of (x)
fragmentation and (O)
microbond tests

Source: H. D. WAGNER; Study of the interface in Kevlar 49-epoxy composites by means of microbond and
24
fragmentation tests: effects of materials and testing variables; Journal of materials science 28 (1993)
 Comparative study of the effects of different fibers

Source: Comparative Study of the Effects of Different Fibers on the Processing and Properties of Polypropylene Matrix Composites, MIGUEL
A. LO´ PEZ-MANCHADO, JERICO BIAGIOTTI AND JOSE´ M. KENNY, Journal of THERMOPLASTIC COMPOSITE MATERIALS, Vol. 15—July 2002 25
 Comparative study of the effects of different fibers

Source: Comparative Study of the Effects of Different Fibers on the Processing and Properties of Polypropylene Matrix Composites, MIGUEL
A. LO´ PEZ-MANCHADO, JERICO BIAGIOTTI AND JOSE´ M. KENNY, Journal of THERMOPLASTIC COMPOSITE MATERIALS, Vol. 15—July 2002 26
 Comparative study of the effects of different fibers
Morphological Comparison

Aramid Fiber+ PP Matrix Glass Fiber+ PP Matrix

Good Adhesion
Source: Comparative Study of the Effects of Different Fibers on the Processing and Properties of Polypropylene Matrix Composites, MIGUEL
A. LO´ PEZ-MANCHADO, JERICO BIAGIOTTI AND JOSE´ M. KENNY, Journal of THERMOPLASTIC COMPOSITE MATERIALS, Vol. 15—July 2002 27
 Comparative study of the effects of different fibers
Morphological Comparison

PET Fiber+ PP Matrix Sisal Fiber+ PP Matrix

Poor Adhesion
Source: Comparative Study of the Effects of Different Fibers on the Processing and Properties of Polypropylene Matrix Composites, MIGUEL
A. LO´ PEZ-MANCHADO, JERICO BIAGIOTTI AND JOSE´ M. KENNY, Journal of THERMOPLASTIC COMPOSITE MATERIALS, Vol. 15—July 2002 28
 PART 3
PROPERTIES
Mechanical Properties of MFC (MicroFibril reinforced Composites)

Source: R. J. Shie et al; Fibrillar polymer–polymer composites: morphology, properties and applications; Journal of Materials Science; 2008 30
Mechanical Properties of NFC (NanoFibril reinforced Composites)

According to Bousmina*, only in exceptional circumstances can one observe

improvement greater than 30% in the mechanical performance of nanocomposites.
70/30/0
For MFC

Source*: Bousmina M; Fundamental insight into polymer nanocomposites; p. 219; 2005 31

Mechanical Properties
The influence of Loading

In PE/PET
Various PET concentrations
display completely different
brittle-ductile behaviors

TS and TM ↑
Ductile  brittle behaviors

___ : low-temperature molding

----- : high-temperature molding

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Mechanical Properties
The influence of Loading & Injection mold temperature L ↑ TS and TM ↑ , T ↓ TS and TM ↑

The tensile strength and modulus of PET/PE MRCs injection molded.

“Low” and “High” refer to the injection molding and the processing temperature of PE and PET, respectively
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Mechanical Properties
The influence of Orientation

Stress/strain curves of PP/PET [70:30] MFCs

with various microfibril orientations:

(a) Uniaxial
(b) Crossply
(c) PP neat
(d) Random

Source: Ryan McCardle et al; Effect of Reinforcement Orientation on the Mechanical Properties of Microfibrillar
PP/PET and PET Single-Polymer Composites; Macromolecular Materials and Engineering; 2012 34
Mechanical Properties
a=1
The influence of hot stretch ratio b=3.25
R ↑ TS and TM ↑ & EB ↓ c=6.35
d=11.43
e=19.17
f=25.64
g=47.62

Stress-strain curves & elongation at

break of PET/PE with different hot
stretch ratios. ductile-brittle transition exists between 3.3 and 11.4
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Rheological Properties
L ↑ Vis↑ Pc  PET Vis↑

Log (apparent viscosity) vs. log (shear rate) curves for The apparent viscosity (at shear rate of 12.5 s–1) vs.
pure PE and PET/PE MRCs (hot stretch ratio = 17) at PC and PET concentration. The test temperature is
170’C 170’C for both PC/PE and PET/PE blends
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Epoxy Matrix, PP Fibers

20% carbon fiber and 30% Polypropylene fiber gives the optimum mechanical properties in compression and Impact

Source: Ahmed T. Fadhil et al; Mechanical Properties of Carbon/Polypropylene Fiber

Reinforced Rubber-Modified Epoxy System; Chemistry and Materials Research; 2015 37
 Epoxy Matrix, PVOH Fibers

Tensile strength and Young‘s modulus of CF/EP composite with various content of
nPVA.

Source: Nguyen Tien Phong et al; Improvement in the mechanical performances of carbon
fiber/epoxy composite with addition of nano-(Polyvinyl alcohol) fibers; Composite Structures; 2013 38
 PP Matrix, PET fibers
The influence of Compatibilizer On Properties

WO (without compatibilizer)
WG (with PP-g-GMA:Glycidyl Methacrylate)
WMA (with PP-g-MA:Maleic Anhydride)

Source: Mohammad Asgari et al; Thermal and impact study of PP/PET fibre composites
39
compatibilized with Glycidyl Methacrylate and Maleic Anhydride; Composites; 2011
 EPDM Matrix, PAN fibers

The influence of Fiber content On Mechanical Properties

Source: Shan Jin et al; Effect of polyacrylonitrile (PAN) short fiber on the mechanical properties
of PAN/EPDM thermal insulating composites; Materials Science and Engineering; 2008 40
 NBR Matrix, Nylon fibers

• Addition of nylon fiber to NBR offers good reinforcement, and causes improvement in mechanical properties.
• A fiber length of 6 mm has been found to be optimum for the best balance of properties.
• The cure time and maximum torque is lesser in the sulfur system than in the DCP system.
• Composites vulcanized by the DCP system show better mechanical properties than those by the sulfur system.
• Swelling studies conducted supports the observations of mechanical properties. (solvent uptake behavior)

Source: C. Rajesh et al; Cure Characteristics and Mechanical Properties of Short Nylon
Fiber-Reinforced Nitrile Rubber Composites; Journal of Applied Polymer Science; 2004 41
NBR Matrix, Nylon fibers
The influence of Fiber content
On Cure Properties:

 Max & Min Torque ↑

 Scorch Time ↓

 Cure Time ↓

 Cure Rate ↑

Source: T.D. SREEJA et al; Studies on Acrylonitrile Butadiene Rubber – Short Nylon Fiber Composites; Journal of Elastomers and Plastics; 2002 42
 NBR Matrix, Nylon fibers
The influence of Fiber content On Mechanical Properties C ↑ TS ↑ & EB ↓

Source: T.D. SREEJA et al; Studies on Acrylonitrile Butadiene Rubber – Short Nylon Fiber Composites; Journal of Elastomers and Plastics; 2002 43
 LLDPE Matrix, PET fibers

The influence of Operation techniques

On Oxygen barrier properties

Oxygen permeability of MFC films

from LLDPE/PET = 70/30 (wt.%).

o U = undrawn
o D8 = draw ratio of 8
o BW = biaxially wrapped
o PT = pelletised
o PR = pressure cooled
o NP = no pressure cooled

Source: R. J. Shie et al; Fibrillar polymer–polymer composites: morphology,

properties and applications; Journal of Materials Science; 2008 44
 Comparative study of the effects of different fibers
The influence of Fiber type on Storage modulus of the Composite

 Aramid fibers are the most

effective reinforcement

Source: Comparative Study of the Effects of Different Fibers on the Processing and Properties of Polypropylene Matrix Composites, MIGUEL
A. LO´ PEZ-MANCHADO, JERICO BIAGIOTTI AND JOSE´ M. KENNY, Journal of THERMOPLASTIC COMPOSITE MATERIALS, Vol. 15—July 2002 45
 Comparative study of the effects of different fibers
The influence of Fiber type on Stress-Strain behavior of the Composite

 Decrease of the elongation at break

 Evident reinforcing effect of Aramid
 More Modulus & Strength

Source: Comparative Study of the Effects of Different Fibers on the Processing and Properties of Polypropylene Matrix Composites, MIGUEL
A. LO´ PEZ-MANCHADO, JERICO BIAGIOTTI AND JOSE´ M. KENNY, Journal of THERMOPLASTIC COMPOSITE MATERIALS, Vol. 15—July 2002 46
 Comparative study of the effects of different fibers
The influence of Fiber type on Impact Strength of the Composite

 Importance of Matrix-Fiber interface

Source: Comparative Study of the Effects of Different Fibers on the Processing and Properties of Polypropylene Matrix Composites, MIGUEL
A. LO´ PEZ-MANCHADO, JERICO BIAGIOTTI AND JOSE´ M. KENNY, Journal of THERMOPLASTIC COMPOSITE MATERIALS, Vol. 15—July 2002 47
 Aspect Ratio (AR)

 comparison between the measured

values of the central diameter and the
Obviously, in addition to the improved calculated values of the effective
adhesion, the essential contribution to the diameter for the cylindrical model
observed mechanical properties profile of
MFCs is related to the very high aspect
ratios (at least 100) of the microfibrils.

the Nano fibrils (NFCs) add the benefit of

having extremely high aspect ratios (often
between 100 and 1000).

Source: Analysis of a retraction mechanism for imbedded polymeric fibers, A. Cohen Et al, Journal of Rheologica Acta, 1989 48
 PART 4
APPLICATION & OUTLOOK
Applications & Outlook

■ Why all polymer composites?

■ Aramid fibers applications
■ Microfibrilar polymer composites(MFCs)
■ Nanofibrilar polymer composites(NFCs)

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Why all polymer composites?

■ Better mechanical property (aramids)

■ Enhancements of other properties like recycling(MFCs).
■ Other application(NFCs)

51
Aramid fibers

■ Abbreviated of ‘aromatic polyamides’

■ combination of: • high strength
and modulus
• low density
• high elongation

nomex

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Aramid fibers

53
Aramid fibers

54
Aramid fibers

55
Aramid fibers

■ Ballistic applications

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Microfibrilar polymer composites(MFCs)

■ Enable to be manufactured in one stage (in situ)

■ An immiscible blend with composite morphology

■ Recyclable as a blend (no minerals)

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MFCs applications
■ MFC application opportunities as packaging with improved barrier
properties (commodity polymers)

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MFCs applications
■ application opportunities as packaging with improved barrier
properties (commodity polymers)

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MFCs applications

■ Application opportunities in vehicle manufacturing

1) Reinforcement of polymer by polymer;
2) – No mineral additives;
3) – Easy processing;
4) – Reduction in weight;
5) – Synergetic effect in mechanical properties;
6) – Applicability for recycling purposes;
7) – Perfect distribution of nanofibrils in nanocomposites (no aggregates);
8) – Opportunities for isolation of micro- or nanofibrils as single material.

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Single polymer composites

61
MFCs applications

Applications for biomedical purposes

– scaffold materials suitable for tissue engineering

62
Nanofibrilar polymer composites(NFCs)

■ Electrospinning is an efficient technique for the fabrication of polymer nanofibers

– Composite application
– Other applications

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NFCs applications

64
NFCs applications

■ Composite application

65
NFCs applications

■ Filtering applications

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NFCs applications

■ Biomedical application
– Medical prostheses

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NFCs applications

■ Biomedical application
– Tissue template

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NFCs applications

■ Biomedical application
– Cosmetics

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NFCs applications
■ Biomedical application
– Drug delivery

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NFCs applications

■ Protective clothing application

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NFCs applications

■ Electrical and optical application

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NFCs applications
■ Other functional application

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CONCLUSION &
OUTLOOK
 References

● Stoyko Fakirov; Synthetic Polymer-Polymer Composites; Hanser Pub. ; 2012

● J. Kalantar; The bonding mechanism of aramid fibers to epoxy matrices; Journal of material science, 25; 1990
●P. J. C. Chappell; Surface Modification of Extended Chain Polyethylene Fibres to Improve Adhesion to
Epoxy and Unsaturated Polyester Resins; 1991
● Z. Zheng; Influence factors of internal structure and interfacial compatibility of UHMWPE fiber/SEBS resin
composites: Processing parameters, structure of fiber and nature of resin; Composites: Part B 43 (2012)
● H. D. Wagner; Study of the interface in Kevlar 49-epoxy composites by means of microbond and
fragmentation tests: effects of materials and testing variables; Journal of materials science 28 (1993)
● R. J. Shie et al; Fibrillar polymer–polymer composites: morphology, properties and applications;
Journal of Materials Science; 2008
● Bousmina M; Fundamental insight into polymer nanocomposites; p. 219; 2005
75
 References
● Ryan McCardle et al; Effect of Reinforcement Orientation on the Mechanical Properties of Microfibrillar
PP/PET and PET Single-Polymer Composites; Macromolecular Materials and Engineering; 2012
● Stoyko Fakirov; Nano- and Microfibrillar Single-Polymer Composites: A Review; Macromolecular Materials
and Engineering; ; 2012
● Ahmed T. Fadhil et al; Mechanical Properties of Carbon/Polypropylene Fiber Reinforced Rubber-
Modified Epoxy System; Chemistry and Materials Research; 2015
● Mohammad Asgari et al; Thermal and impact study of PP/PET fibre composites compatibilized with
Glycidyl Methacrylate and Maleic Anhydride; Composites; 2011
● Mala Pinyo et al; Thermal and mechanical properties of high density polyethylene with
polypropylene fiber composites. ; Proceedings of The 2nd Polymer Graduate Conference; 2009
● A. Cohen Et al; Analysis of a retraction mechanism for imbedded polymeric fibers; Journal of
Rheologica Acta, 1989
76
 References
● Shan Jin et al; Effect of polyacrylonitrile (PAN) short fiber on the mechanical properties of
PAN/EPDM thermal insulating composites; Materials Science and Engineering; 2008
● C. Rajesh et al; Cure Characteristics and Mechanical Properties of Short Nylon Fiber-Reinforced
Nitrile Rubber Composites; Journal of Applied Polymer Science; 2004
● T.D. SREEJA et al; Studies on Acrylonitrile Butadiene Rubber – Short Nylon Fiber Composites;
Journal of Elastomers and Plastics; 2002
● R. J. Shie et al; Fibrillar polymer–polymer composites: morphology, properties and applications;
Journal of Materials Science; 2008
● Z. Huang; A review on polymer nanofibers by electrospinning and their applications in
nanocomposites; Composites Science and Technology; 2003
● Miguel lopez-manchado et al; Comparative Study of the Effects of Different Fibers on the Processing and
Properties of Polypropylene Matrix Composites; Journal of thermoplastic composite materials, 2002
77
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