CARBON FIBER – POLYMER

MATRIX ADHESION
P PARESH KUMAR :2010B2A1575H

Supervisor : Dr. A. Ramesh Babu

BITS Pilani H.O.D Chemical Engineering
Hyderabad Campus
 AIM OF OUR STUDY

To understand the adhesion between carbon fiber and matrix

(Epoxy) by surface modification of Carbon fibers.
 INTRODUCTION

• Carbon fiber–reinforced polymer, carbon fiber–reinforced

plastic or carbon fiber–reinforced
thermoplastic (CFRP, CRP, CFRTP or often simply carbon fiber,
or even carbon), is an extremely strong and light
fiber-reinforced polymer which contains carbon fibers.
• Polymer can be thermoplastic or thermoset resin
• CFRPs can be expensive to produce but are commonly used wherever high
strength-to-weight ratio and rigidity are required, such as aerospace and automotive
• The binding polymer is often a thermoset resin such as epoxy, but other thermoset
or thermoplastic polymers, such as nylon ,polyesters, vinyl esters , poly propylene
or PEEK are sometimes used.
• Because CFRP consists of two distinct elements (Fibre and Matrix), the material
properties depend on these two elements. So finally it boils down to understanding
the bonding(interactions) between these 2 components in order to produce better
performing composites
 CONTACT ANGLE

• The adhesion(wetting) of resin(matrix) to the CF’s can be

studied by the contact angle that it makes with the CF.
INTERACTIONS BETWEEN LIQUID AND
SOLID MOLECULES
CONTACT ANGLE DEGREE OF SOLID-LIQUID LIQUID-
(IN DEGREES) WETTING INTERACTION LIQUID
INTERACT
ION

θ=0 PERFECT WETTING VERY STRONG VERY

WEAK

0<θ<90 HIGH WETTING STRONG STRONG

WEAK WEAK

90≤θ<180 LOW WETTING WEAK STRONG

θ=180 PERFECTLY NON- VERY WEAK VERY

WETTING STRONG
MATERIALS USED
CARBON FIBERS
a)CF(TAIWAN)-6K tow, (0.5-1.5)%
epoxy sized,density-1.76g/cc

b)CF-DMRL-Silane treated
• Epoxy resin
• For the preparation of epoxy resin DER-332(Sigma Aldrich) and Ethylene diammine (Sigma Aldrich)
was used as hardener.

+
DGEGA/BADGE OR SIMPLY BISPHENOL-A ETHYLENE DI AMINE
 TREATMENT
• 1) ALKYLATION TREATMENT

• All the fibers under consideration (each of the fiber has to be taken strand-wise)
were dipped in 1% solution of NaOH for 10-15 minutes at room temperature and
then washed in very dilute acid(dil. H2SO4) to remove any particles of alkali. Washing
was continued until the fibers were alkali free. The washed fibers were then dried in
a hot air oven at 80°C for about 30 minutes, after which the samples are removed
for further characterization.
• SILANE TREATMENT:

• 3-(Aminopropyl) triethoxy silane [H2N (CH2)3-Si-(OC2H5)3] from Sigma Aldrich was

used as silane. 10% v/v silane solutions were made in aqueous ethanol solution
(90%ethanol + 10% distilled water). Fibers were immersed in this solution for a
period of 15-20 minutes at room temperature and we have to make sure that the
fibers are completely immersed and the wetting has to take place uniformly on all
sides of the fiber. The fibers post the silane treatment are placed in a hot air oven at
80°C for about 30 minutes after which the samples are removed and stored to carry
out characterization .
EXPERIMENTAL PROCEDURE

1.The two samples of carbon fibers were given silane treatment and
alkylation treatment.
 .
2 The fibers are then fixed on a frame made out of thin cardboard .

3. Individual treated fibers are then placed on top of these cardboard frames.

4. Epoxy resin is prepared by mixing epoxy resin DER-332(Sigma Aldrich) and Ethylene diammine (Sigma Aldrich)
and stirred continuously.

5. The resin is then applied to the carbon fibers and the fibers are then cured in an oven at 80 degrees Centigrade
for about 1 hour.
6. The resin is then applied to the carbon fibers and the fibers are then cured in an oven at 80 degrees Centigrade
for about 1 hour.

7. The samples are then taken out and further measurements can be taken from them.
CONTACT ANGLES AND RESULTS

DMRL-CF -UNTREATED DMRL-CF-ALKYLATED DMRL-CF-SILANE TREATED

CFT-UNTREATED CFT ALKYLATED CFT-SILANE TREATED
RESULTS
GRAPHICAL REPRESENTATION

CONTACT
ANGLE
(DEGREES)
 EXPERIMENT-2

• The process was slightly modified after getting to know that

etching(making the fibers rougher) was critical to enhanced
performance and adhesion of composite(CF-MATRIX).

• This can be achieved by various methods such as Plasma

treatment, wet/chemical treatment, multi-scale carbon nano-
particle coating , CF-MWCNT coating…..etc.
Based on ease to carry out experiment 2 methods(wet-chemical)
were chosen for etching of carbon fiber.
• reaction with (KCLO3 + H2SO4).
• Nitric acid soln(HON3).
 HNO3 TREATMENT

A solution of 30%-wt of HNO3 was prepared and fibers were treated with this solution
for varying amount of time of 30 minutes, 60 minutes 90 minutes and 120 minutes.

After reacting they were washed with deionized water and dried at 50°C for 2 hours.
 CARBON FIBER SURFACE IMAGES

a) Untreated CF

b) 30 min HNO3 Treated

c) 60 min HON3 treated

d) 90 min HNO3 treated

e) 120 min HNO3 treated

 COUPLING
SILANE Treatment: APS aqueous solution was mixed with 1 wt%
concentration. After the silane coupling agent hydrolyzed, the
modified CFF was dipped in the hydrolyzed silane solution for 4 hours

MAH Treatment : For MAH modification fibres were immersed in a

solution of MAH in acetone with a conc. of 2.5 wt% for 4 hours at
room temperature and the solution was mixed continuously, the
fibres were then removed from the solution washed under acetone
and dried in a hot air oven at 80°C. for 1 hour.
 CONTACT ANGLES

N-30-APS N-60-APS
N-90-APS N-120-APS
N-30-MAH N-60-MAH
N-90-MAH N-120-MAH
TREATMENT COUPLING TIME (IN MINS) AVERAGE CONTACT ANGLE(°)’S
HNO3 SILANE-APS 30 38.04
HNO3 SILANE-APS 60 37.95
HNO3 SILANE-APS 90 32.945
HNO3 SILANE-APS 120 32.58
HNO3 MAH 30 38.9
HNO3 MAH 60 35.9
HNO3 MAH 90 34.03
HNO3 MAH 120 31.67
FTIR Spectroscopy
IT CAN BE INFERED THAT
ONLY AFTER TREATING FOR
60 MINUTES THAT THE –OH
BAND IN THE SPECTRUM
APPEARS

IT IMPLIES THAT THE

SAMPLE SHOULD BE
TREATED UPWARDS OF 60
MINS.
 CARBON FIBER THERMOPLATIC COMPSITES
• These composites are being used today in places of thermosetting CFRP, where
weight reduction is of primary concern as compared to strength.
• We tried to make adhesion between cf’s and thermoplastics like nylon-6,
polypropylene etc.
 Bonding with polypropylene

As you can see the bonding of cfrtp composite is not as convincing as cfrts composite.
An alternate process has to be found to study cfrtp composites.
 CONCLUSION
• CARBON-EPOXY bonding was analyzed at micro level. It is
important especially fibers are surface treated.
• since polymer resin can form the spherical droplet based on
wetting and surface tension, contact angle technique was used
for analysis.
• Forming epoxy droplets was easy, but thermoplastics can’t
form droplet so easily. So this technique can’t be used to know
the bonding between Carbon-thermoplastic composites
 REFERENCES
•
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Gindl , Journal of Composite Materials 46(3) 359–367.
• 2. COMPOSITES MANUFACTURING – Material, products, and Process Engineering- Sanjay K. Mazumdar
• 3. S. Hill, New scientist, Feb. 1, 36 (1997).
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14, Marcel Dekker, New York, p. 83.
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640.
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Schlosser "Cellulose" in Ullmann's Encyclopedia of Industrial Chemistry, 2002, Wiley-VCH, Weinheim.
• 7. K. C. Mittal, Silanes and Other Coupling Agents, VSPBV, Netherlands (1992).

• 8. Bascom W. Other continuous fibers, in: Composites, Engineered materials handbook, 1. Materials Park: ASM
International, 1988. P.117–118.d
THANK YOU