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Materials Today: Proceedings 24 (2020) 453–462 www.materialstoday.com/proceedings

IConAMMA 2018

Comparison of Properties of Carbon Fiber Reinforced

Thermoplastic and Thermosetting Composites for Aerospace
Applications
Sudhin A Ua, Manu Remananb, Ajeesh Gc, Karingamanna Jayanarayanana,b *
a
Center of Excellence in Advanced Materials & Green Technologies (CoE – AMGT), Amrita School of Engineering, Amrita Vishwa
Vidyapeetham, Coimbatore- 641112, India.
b
Department of Chemical Engineering and Materials Science, Amrita School of Engineering, Amrita Vishwa Vidyapeetham, Coimbatore-
641112, India.
c
Advanced Materials Division, Honeywell International Inc., Gurugram- 122002, India

Abstract

In the present study the properties of carbon fiber reinforced poly ether ketone (PEK) is compared with carbon fiber reinforced
epoxy (EP) composite fabricated by compression moulding technique. PEK carbon fiber (PK-CF) composites are prepared by
film stacking method whereas the epoxy carbon fiber (EP-CF) composites are prepared by conventional compression moulding
route maintaining a constant 60wt% carbon fiber. The tensile properties analysis indicated that PK-CF composite possesses a
tensile strength of 425MPa which was much higher than 311MPa recorded by EP-CF. The stress intensity factor (KIC) values of
PK-CF composites are found to be 10% higher than EP-CF counterparts. It is seen that the PK-CF composites possess higher
glass transition temperature enabling them to be used at elevated temperatures. The investigation of flame retardant behaviour of
the composite is conducted by Limiting Oxygen Index (LOI) test, and highest value is obtained for PK-CF composite.
© 2018 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Conference on Advances in Materials and
Manufacturing Applications, IConAMMA 2018.

Keywords: Poly ether ketone; epoxy; tensile properties; fracture toughness; Differential Scanning Caloriemetry; Limiting Oxygen Index

* Corresponding author. Tel.: 91-4222685000; fax: 91-422-2686274

.
E-mail address: kj_narayanan@cb.amrita.edu, kjnarayanan@gmail.com

2214-7853 © 2018 Elsevier Ltd. All rights reserved.

Selection and peer-review under responsibility of the scientific committee of the International Conference on Advances in Materials and
Manufacturing Applications, IConAMMA 2018.
454 Sudhin A.U. et al. / Materials Today: Proceedings 24 (2020) 453–462

1. Introduction

The Composite technology using fiber reinforced polymeric materials is one of the key developments of recent
times. The vast research work carried out in the composites arena for past the few years had a tremendous influence
on the generation and satisfaction of demands raised by the structural engineering community [1]. The development
of polymers which can withstand high service temperature and the production of high performance composites
making use of them meets various challenges raised in aerospace, marine, and nuclear industries. The majority of
engineering composite materials in aerospace applications consists of continuous carbon or glass fiber, reinforcing a
polymeric matrix [2]. Carbon fiber is one of most widely used reinforcement for the preparation of composites in
high end applications [3]. The high strength to weight ratio and the enhancement in mechanical and thermal
properties through the form, orientation and content modification is the uniqueness of carbon fiber reinforced
composites [2-4]. The other important attributes of carbon fibre are high strength, modulus, low thermal expansion,
good creep-resistance, corrosion-resistance etc. [5, 6]. Currently carbon fiber reinforced plastics are used to replace
the metallic components in high temperature and corrosive resistance applications [7].
Among the composites used in aerospace and structural applications, carbon fiber reinforced
epoxies are preferred due to its properties such as failure strength, low creep, high modulus, and relatively low cost.
The main drawbacks of epoxy based composites are their brittle nature, poor resistance to crack initiation and
growth, high moisture absorption, low shelf life [2]. Thermosetting composites have limitations in terms of storage,
hydrothermal aging and insufficient toughness and have processing constraints due to long and strict multi-step
processing [8, 9]. Due to the aforementioned reasons, intense research in the area of replacement of thermoset
composites by high temperature thermoplastic composites is on the rise. The strong and stiff reinforcements like
carbon fiber included in high performance resins such as Poly Aryl Ether Ketone (PAEK), poly ether imide (PEI),
etc are the alternate materials in this context [10]. Aromatic poly ether ketones is a high performance semi-
crystalline thermoplastic polymer which can be used as matrix material due to their unique combination of
properties [11]. The high glass transition temperature (Tg) of approximately 150 ◦C, melting point (370 ◦C),
stiffness, strength, toughness, chemical and solvent resistance, thermo-oxidative stability, flame retardancy, low
dielectric constant, shelf life and recyclability makes them an excellent material to be used as matrix for high
performance composites [12-15].
These composites maintain their physical properties at high temperatures and exhibit thermal stability
even for longer continuous usage period [16, 17]. The multi-directional carbon-fibre reinforced PAEK offers some
significant advantages over similar epoxy carbon fiber composites, and with further development could be a strong
contender as a high performance structural material [17-20]. As we compare with the epoxy carbon fiber composite
the moisture absorption characteristics of CF-PEK composite is much lesser [18]. Investigation of the fracture
surfaces of the carbon fiber-epoxy composites showed that the moisture led to an increase in interface failure [17].
The epoxy matrix became softer with moisture absorption, and the fiber-matrix adhesion decreased. The values for
CF-PEK were not affected by moisture, which can be explained by the low moisture uptake of the PEK matrix [17,
18]. The susceptibility of the epoxy carbon fiber composite to impact loads is another important factor limiting the
design and leads to delamination of the material. It is worth mentioning that PEK CF possesses good impact
resistance and reduced delamination [20].
The aim of this work is to develop carbon fiber reinforced Poly Ether Ketone (PEK) composites for the
applications in aerospace and structural engineering, and to compare it with currently used carbon fiber epoxy
composite. In this work bidirectional carbon fiber fabrics are used as reinforcement and PEK film as the base matrix.
The PEK film and carbon fiber fabrics are stacked one above the other alternatively and made into laminate form in
a hydraulic compression press. The novelty in the manufacturing technique is one of the main highlights of this
study. The tensile strength, hardness, fracture toughness of the PEK CF composites are compared with EP CF ones.
The thermal properties are studied by DSC analysis and the flame retardant behaviour is characterized by
performing limiting oxygen index test.

2. Materials and methods

The carbon fiber (200 GSM, bi directional 3k weave) was procured from Arrow Technical Textiles Pvt. Ltd., India.
The thermoplastic polymer matrix PEK was purchased from Gharda chemicals Pvt. Ltd. India. The thermosetting
polymer matrix employed was a two component system namely di-glycidal ether of B is phenol A (DGEBA -Ly556
 Sudhin A.U. et al. / Materials Today: Proceedings 24 (2020) 453–462 455

epoxy resin) with tri-ethylene tetra amine (Hy951 epoxy hardener). PEK used was in the form of thin film of
thickness 0.05 mm which was prepared by cast film extrusion from PEK granules of density 1.3 g/cm³. The epoxy
resin had a density of 1.16 g/cm³ and the density of epoxy hardener was 0.95 g/cm³.

2.1 Fabrication method of composites

Carbon fiber reinforced PEK composites was prepared by compression moulding technique in a hydraulic
compression press. The composites preparation started with layer by layer arrangement of PEK and carbon
fiber alternately which is termed as film stacking method as shown in Fig. 1. The composites with 60 wt %
carbon fiber and 40 wt % PEK were used for stacking the laminate. Ten layers of bidirectional carbon fiber
were placed between 11 layers of PEK in an alternative arrangement with bottom and top layers being PEK
films. The stacked PEK/carbon fiber sheets was processed in a compression molding press at 10 bar pressure at
a platen temperature of 410 ◦C for 30 minutes.
Carbon fabric-reinforced epoxy composite was prepared by hand lay-up process, followed by
compression moulding. The bi-directional carbon fabric reinforced with the LY556 Epoxy resin matrix materials,
added with HY951 curing hardener at room temperature were used for laminate fabrication. Ten layers of fabric
were used to obtain approximately 3 mm thick laminates. The epoxy resin was mixed with the hardener in the ratio
100:12 by weight. The carbon fiber reinforcement was maintained at 60 wt %. To ensure uniform thickness of the
sample, a spacer of size 3 mm was used. The mould plates were coated with a release agent for easy removal of the
laminates after curing. The total assembly was kept in a hydraulic press at a pressure of 0.5 MPa and was allowed to
cure for a day at room temperature.

Fig. 1. Layer by layer arrangement of thermoplastic film and reinforced fiber by film stacking method.

3. Characterization techniques

3.1 Mechanical testing

3.1.1 Tensile test

The tensile test was performed in Tinius Olsen H25K-T Universal Testing machine with the load range of
15000N. The testing was carried out according to ASTM D 3039 standards. The test was conducted at room
temperature at a cross head speed of 1.2mm/min with a gauge length of 70mm.Five readings were noted for
both the composites and average value is taken.
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3.1.2 Hardness

Hardness was performed for both the composites using Shore D (Durometer) hardness. The test was carried
out according to ASTM D 2240 standard at five different points for both PK-CF and EP-CF composites and
average value is recorded.

3.1.3 Fracture toughness

The fracture toughness of composite specimens were determined by ASTM D5045-14 using single edge notch bend
(SENB) in UTE-40 capacity 400 kN. The schematic diagram of SENB test is shown in Fig. 2. The stress intensity
factor (KIC) at the crack tip of a single edge notch bending specimen is calculated using the equation (1) for five
different samples for each composite.

KIC = 1.6 2.6 12.3 21.2 21.8 (1)

P-maximum load (kN)

B-thickness of the sample (m)
W-width of the sample (m)
a -crack length (m)

Fig. 2. Schematic diagram of SENB test

3.2 Thermal properties

3.2.1 Differential scanning calorimetry (DSC)

The thermal properties measurement was carried out using SDT Q6OO V20.9 Build 20 DSC. The characterization
is performed for the virgin PEK and epoxy matrices and composites after reinforcements with carbon fiber. The
melting temperature, crystallisation temperature and glass transition temperature is determined by the curves
obtained from the temperature vs heat flow graphs. During the experiments the sample were heated from room
temperature to 400 ◦C and cooled back to room temperature after 5 minutes at the rate of 10 ◦C/ min.
 Sudhin A.U. et al. / Materials Today: Proceedings 24 (2020) 453–462 457

3.2.2 Limiting oxygen index (LOI)

LOI test is to determine the minimum concentration of oxygen that will support flaming combustion in a glowing
mixture of oxygen and nitrogen. ASTM D2863 is the standard for calculating LOI of polymer composites.
Specimens are tested in the LOI tester (Custom scientific Instruments .Inc & CSI 178). The minimum percentage of
oxygen required for burning the material is calculated for both the PK-CF and EP-CF composites and the values are
compared.

4. Results and discussion

4.1 Tensile property

The tensile strength and modulus of PK-CF and EP-CF composites are compared. The major advantage of using
bidirectional carbon fiber for reinforcement is the uniform distribution of fiber throughout the composite, so that
load can be transferred from one end to other effectively, which will increase the tensile strength of the material [9].
From the experiments the stress-strain graph is plotted, as delineated in Fig. 3. The average tensile strength and
modulus are obtained as 425 MPa and 7.8 GPa for PEK-CF composite and 311 MPa and 5.2 GPa for EP-CF
composite. The elongation at break for PK-CF composite is recorded as 9.43% and that of EP-CF is 11.32%
respectively. The higher values in tensile properties for the thermoplastic composite assigned to the entanglement of
the PEK and carbon fiber material. The addition of high percent of carbon fiber reinforcement is a major factor that
leads to the increase in tensile properties of the samples [7, 10]. For epoxy composites the tensile properties are less
compared to PEK composites, since, as the number of reinforcement layers increase the adhesion of epoxy with
carbon fiber is affected and defects like porosity, voids, etc. increase. These bond line defects ultimately reduces the
strength and tensile properties of the EP-CF composite [3]. All the tensile properties and other mechanical properties
estimated are represented in Table 1.

Fig. 3. Stress-Strain curves of the PK-CF and EP-CF composites.

4.2 Hardness

The shore D hardness increases when the carbon fiber is added to the matrix material showing that the filler material
will enhance the resistance to plastic deformation. The hardness value of PEK is 87 and epoxy is 85 and their
composites exhibits hardness values of 94 and 89 respectively. The resistance to indentation has increased when the
carbon fiber is added to the matrix material. In PK-CF the reinforcement and the matrix has good interaction
generating a strong interface [22]. In the case of EP-CF composite the bonding between the matrix and
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reinforcement is not as efficient leading to decrease in hardness values.

4.3 Fracture toughness

The load taken into consideration while calculating the fracture toughness is the maximum load the material can
bear before fracture in SENB test. The high amount of reinforcement in the matrix material can raise the values of
KIC and there by toughness of the material will increase. Though there is effective transfer of load in the composite,
fracture toughness of the EP-CF composite decreases as the matrix toughness is low due to the brittle nature of
epoxy. On the contrary, the toughness value of the PK-CF composite is high because of the ductile nature of the
matrix. From the results, the average value of KIC for PK-CF composite is found to be 13.71 MPa√m and that for
EP-CF composite is 11.53 MPa√m. The higher value of KIC for the thermoplastic composite is because of the large
area under the stress-strain curve, in comparison with a smaller area for the thermoset composite. [26].

Table 1. Comparison of mechanical properties of the PK-CF and EP-CF composites.

Sample Code Hardness Tensile Tensile Elongation at Stress

strength modulus break intensity
(MPa) (GPa) (%) factor
(MPa √m)

PK-CF 94 425 7.8 11.32 13.71

EP-CF 89 311 5.2 9.43 11.53

4.4 Differential scanning calorimetry

The thermal transitions of the polymer composites are studied by DSC in both heating and cooling range. The
melting temperature and the crystallisation temperature of the matrices are compared in the neat and reinforced
form. The Table 2 shows the melting temperature(Tm), crystallisation temperature (Tc) and glass transition
temperature (Tg) of the matrix phase of the samples.

Table 2. Thermal properties of the samples.

Sample Heating thermogram Cooling thermogram

Code Tm Tg Tm onset Tm endset Tc Tc onset Tc endset

PK 370 155 355 380 327 340 320

PK-CF 375 162 357 386 326 338 322
EP 137 85 121 150 - - -
EP-CF 144 91 128 161 - - -

*. All values of temperature in oC.

The temperature at which the proper melting of PEK starts in the composite is above 355 ◦C (T onset). During the
film stacking process the molten PEK will enter into the layers of carbon fiber mat and a strong bond is formed
between the matrix and the reinforcement. From the DSC analysis it is clear that there is an increase of 5 ◦C in
melting temperature of PEK by the addition of carbon fiber to the matrix. In the case of epoxy, the melting
temperature of is 137 ◦C which is not significantly increased by the addition of the carbon fiber has no significant
change. The heating thermograms of the samples by DSC analysis are delineated in Fig. 4 and Fig. 5. The glass
transition temperature of PEK is 155 ◦C and when carbon fibre is incorporated it rises to 162 ◦C. The increase in Tg
of PEK is suggestive of the better bonding it possesses with carbon fibre fabric. For the epoxy and the EP-CF
composite, the Tg values are found to be 85 ◦C and 91 ◦C respectively.
 Sudhin A.U. et al. / Materials Today: Proceedings 24 (2020) 453–462 459

Fig. 4. Heating thermogram of the PK and PKCF samples

Fig. 5. Heating thermogram of the EP and EPCF samples

At the time of cooling from 400 ◦C to room temperature there is no indication of Tc, since the thermoset material
will not recrystallize once crosslinks are formed they cannot return to the original state [24, 25]. However, in the
case of PK and PK-CF composite while cooling the molecules of PEK are capable of recrystallization which occurs
at 327 ◦C. The cooling thermogram of PK and PK-CF composite is shown in Fig. 6.The crystallization of PEK is
due to the self-nucleating behaviour [11] of the thermoplastic material, whereas in PK-CF material the re-
crystallisation process starts 326 ◦C (Tc onset) until it reaches 320 ◦C (Tc endset) .
460 Sudhin A.U. et al. / Materials Today: Proceedings 24 (2020) 453–462

Fig. 6. Cooling thermogram of PK and PKCF samples

4.5 Limiting oxygen index (LOI)

LOI testing of the samples shows that for both the composites when carbon fiber is added the value increases that is
oxygen percentage rises. The oxygen percentage of the samples under investigation is depicted in Table 3. The
upsurge in LOI is due to the formation of char produced during the combustion of volatiles which will increase of
the amount of oxygen required for sustaining the combustion [27]. The LOI of neat epoxy and PEK are found to be
25 and 35. In the EP-CF and PK-CF composites there is a rise of 28% and above 35% in the LOI values with respect
to the neat matrices. The LOI value of 47 indicated by PK-CF is a testimony of its excellent flame resisting
capability [27]. On comparing the two composites higher thermal stability is recorded by PK-CF samples.

Table 3. Limiting oxygen index of the pristine matrix and the composites.

Sample Code % Oxygen

PK 35
EP 25
PK-CF > 47*
EP-CF 32

* indicates the limiting oxygen index value is exceeding beyond the machine limits.

5. Conclusion

The reinforcement of carbon fiber in PEK and epoxy matrix was successfully carried out by compression moulding
technique. The tensile properties, hardness, fracture toughness and thermal properties of both PK-CF and EP-CF
were compared. From the present work the following conclusions were drawn:
• The tensile strength of PK-CF is found to be more than 100 MPa compared to EP-CF. This indicates the
proper entanglement of carbon fiber with PEK more than that with epoxy resin. The modulus value of PK-
CF is found to be higher than EP-CF.
 Sudhin A.U. et al. / Materials Today: Proceedings 24 (2020) 453–462 461

• The Shore D hardness of PK-CF is 94 which is 5 units higher than that of EP-CF. This indicates that PK-
CF shows higher resistance to indentation.
• KIC value of PK-CF shows 10% increment compared to EP-CF which indicates better fracture toughness
characteristics for PK-CF.
• The DSC analysis alluded the changes in Tg, Tm and Tc of the composites with respect to the base matrix.
The melting point is increased by 5 ◦C for both the composites PK-CF and EP-CF compared to the base
polymers PEK and epoxy resin respectively. Similarly addition of carbon fiber to the base matrix improved
the Tg of the composites.
• Both the composite materials showed a rise in flame retardant behaviour when fillers are added. The LOI
value raised 35% for PK-CF and 28% for EP-CF compared to PEK and epoxy resin respectively.

From the results it is able to conclude that the PK-CF thermoplastic composites is a preferable material for
aerospace industries as it shows superior properties compared to EP-CF thermosetting composites.

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