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org/IECR Article

Radar Transparent, Impact-Resistant, and High-Temperature

Capable Radome Composites Using Polyetherimide-Toughened
Cyanate Ester Resins for High-Speed Aircrafts through Resin Film
Infusion
Jayalakshmi Cherukattu Gopinathapanicker, Ahmed Inamdar, Anoop Anand,* Makarand Joshi,
and Balasubramanian Kandasubramanian
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ABSTRACT: High-temperature capable (Tg: 280−290 °C), broadband

radar transparent [ε′: 3.3−3.9; ε″: 0.02−0.17; tan δ: 0.01−0.04 and
transmission loss: −0.18 to −1.26 dBl in C, X, and Ku bands (5.4−18 GHz)],
composites were developed using polyetherimide (PEI)-toughened bisphenol
E cyanate ester resin and E glass fabrics through an out-of-autoclave process
called resin film infusion at a range of PEI weight fractions via a solvent-free
method. Their pronounced increase in impact resistance in terms of mode I
interlaminar fracture toughness (GIc; 50−100%), postimpact residual
compressive strength (>85%), and enhanced structural properties such as
tensile strength, compressive strength, in-plane shear strength, and inter-
laminar shear strength compared with control laminates, which later re-
corroborated with a structure−property relationship using surface morphol-
ogy proving that PEI-modified cyanate esters can find extensive applications
in impact-resistant composite radomes for high-speed aircrafts.

1. INTRODUCTION uptake. Cyanate ester (CE) resins are a class of thermoset

Radomes are protective structures of radar or antennae, resins which qualify both high-temperature capabilities, as well
essentially transparent to electromagnetic radiations. Modern as low dielectric properties.5−11 They also offer dimensional
high-speed military aircrafts use polymer matrix composites for stability, resistance to micro-cracks, and low moisture
absorption of (0.5−2.5 wt %), which is considerably low in
radomes because of their high specific strength, specific
comparison to other thermoset resins.12,13 They cure to form
modulus/stiffness, and tailorable electromagnetic proper-
polycyanurates via triazine ring formation.14,15 The excess free
ties.1−3 Because the majority of aviation radars work in the
volume present in triazine rings can take up any excessive stress
broadband microwave frequency region, especially C, X, and
when it undergoes extreme thermal cycling. The absence of
Ku band, 100% transmission without any losses is preferred
hydrogen bonds and presence of C−H linkages, which are
through radomes for effective radar communication.4 These
symmetric, further reduces the polarity and reduces the
radomes also require high impact resistance toward bird hit,
dielectric constant.16,17 Many researchers have explored new
hail stone hits, tool drops, and so forth and high-temperature
applications of CEs in various sectors of research, for example,
capabilities because their operational temperature may exceed
Gu et al., explored high-temperature capability of cyanate ester
more than 200 °C.3 The characteristic of any material to be
resin [bisphenol A dicyanate ester (BADCy)] with polyglycidyl
electromagnetically transparent is its low dielectric constant
methacrylate (PGMA) for the development of self-healing
(permittivity, ε), more specifically, low imaginary permittivity
composites with epoxies (E-51) and Li·et al. have developed a
(ε″), and low loss tangent (tan δ). However, the dielectric
constant increases with increase in temperature beyond glass
transition temperature (Tg) because of increased segmental Received: November 22, 2019
mobility. It also increases with moisture content. Moisture Revised: March 9, 2020
leads to heat buildup in composites, which reduces electro- Accepted: March 19, 2020
magnetic transparency.5 Hence for high-speed aircraft Published: March 19, 2020
radomes, it is mandatory to use high-temperature capable,
highly tough, low loss composite materials with low moisture

© XXXX American Chemical Society https://dx.doi.org/10.1021/acs.iecr.9b06439

A Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
wave transparent structural material made with biomolecule
lysozyme/POSS-functionalized PBO fibers in the CE matrix
and evaluated its thermal, mechanical, and dielectric properties
in 107 Hz frequencies.60,61
Notwithstanding, because of the presence of bulky groups,
due to steric effects and high cross-link density, they are
intrinsically brittle 16. Hence, it is inevitable to enhance the
toughness of the CE resin to be used in aircraft radomes
without compromising its intrinsic characteristics such as low
dielectric constant and thermal capabilities. A detailed
literature review has been made in our previous article on
various methods of toughening of CE, its composite fabrication
techniques and properties, and so forth and found that
thermoplastic toughening, specifically, blending with poly-
etherimide (PEI), is a promising method for this application.17
The resultant blend is a type of a semi-interpenetrating
polymer network (semi-IPN). Upon curing the blend, the
morphologies (example: particulate, co-continuous, and phase-
inverted) formed via phase separation, controls their physical
and mechanical properties. Thus, in this regard, researchers
have explored various polymeric materials and their
composites, fabricated via a blending route, for enhancing
the mechanical, thermal, and physical properties of the final
product.18−31,62 Recently, Yang et al. demonstrated an epoxy
nanocomposite with 3D copper nanowires and graphene
aerogel to use as an effective electromagnetic shielding material
with a high thermal conductivity coefficient and electro-
magnetic shielding effectiveness of 47 dB which paved the way
of fabricating lightweight EMI-shielding materials.63
Investigations on thermoplastic toughening of the CE resin
and detailed evaluations on mechanical, thermal, and hot−wet
characteristics were reported mostly on the resin blend and
limited publications are available on composite laminates’
mechanical and electromagnetic properties.32−40 This is
primarily because blending with different modifiers increases
the viscosity of CE, which in turn imposes challenges in
composite fabrication via conventional methods such as resin
transfer molding (RTM), vacuum-assisted RTM, wet layup,
and so forth.35 Rau et al.41 and Hillermeier et al.42,43 have used
a heated pressure injection RTM process and high-pressure-
assisted bleed RTM process, respectively, to use modified CE
resin. These methods are expensive, require special accessories,
time consuming, and not viable processes for high-volume
production. Generally, most of the research on thermoplastic
toughening of CE reportedly used solvents to process blends,
and hence, requires subsequent solvent removal which is not
viable for large-scale production. Excessive solvent usage
deteriorates the quality of the base resin and imposes health
hazards.
In the present investigation, CE was modified with PEI using
a solvent-free method. This method is quick, inexpensive,
environmentally friendly, and feasible for bulk production.
Blend compositions of CE−PEI have been optimized
considering the film formability, tackiness of films, and
appropriate viscosities at different temperatures as required
for the resin film infusion (RFI). RFI is an out-of-autoclave
composite manufacturing method which allows localized a flow
of resin through reinforcements under 1 bar vacuum pressure
resulting in composites with near zero void content.44,45 The
latter is essential for realizing functional composite structures
such as radomes. This manuscript presents electromagnetic,
mechanical, and thermal characteristics of composites realized
with PEI-toughened CE resin as the matrix in comparison to
B https://dx.doi.org/10.1021/acs.iecr.9b06439
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control laminates made with a commercially available CE resin.
Methods of blend preparation, evaluation of rheological,
morphological, and thermal characteristics are also presented.
Standard operating procedure for the fabrication of composite
laminates through RFI is elaborated. In addition to mechanical
properties such as tensile strength, compressive strength,
interlaminar shear strength (ILSS), in-plane shear strength, and
so forth, emphasis has been given on toughness characteristics
such as mode I interlaminar fracture toughness (GIc) and low
velocity impact (LVI) followed by compression after impact
(CAI). All laminates were also evaluated for their electro-
magnetic properties such as real permittivity (ε′), imaginary
permittivity (ε″), loss tangent (tan δ), and transmission loss in
broadband GHz frequency regions such as the C band (5.4−
8.2 GHz), X band (8.2−12.4 GHz), and Ku band (12.4−18
GHz) using a free space measurement system (FSMS).
2. EXPERIMENTAL SECTION
2.1. Materials. The commercially available CE for realizing
control samples, referred to as a pristine resin, used in this
study was Primaset BA 3000 (BADCy) (Figure 1a) from
Figure 1. Molecular structures of (a) CE Primaset BA 3000, (b) CE
Primaset LEcy, (c) PEI, and (d) photograph of E-glass fabric.
Lonza Ltd, Switzerland. Primaset BA 3000 is a semisolid CE
(viscosity: >7000 mPa·s at 80 °C, equivalent weight: 234 g/
equiv, density: 1.19 g/cm3 at 25 °C), with a dielectric constant
of 2.75 and loss factor of 0.003 at 1 MHz, respectively. Glass
transition temperature (Tg) is 310 °C and decomposition
temperature by thermogravimetric analyzer is 420 °C. The
standard cure cycle of the resin is 1 h at 150 °C + 3 h at 200
°C followed by postcuring at 260 °C for 1 h. It is impossible to
further modify this resin for toughness enhancement because
the viscosity is too high which makes the material difficult for
processing. Hence, a low viscosity bisphenol E cyanate ester
called LECy (Figure 1b) was selected for the current
toughening experimentation. “LECy” (4,4′-ethylidene diphenyl
dicyanate) is a liquid CE supplied by Lonza Ltd, Switzerland
(viscosity: 80 mPa·s at 25 °C, equivalent weight: 133 g/equiv,
density: 1.18 g/cm3 at 25 °C), with dielectric constant 2.99,
loss factor 0.005 at 1 MHz, with a Tg more than 300 °C.
The thermoplastic used was PEI (Figure 1c) with trade
name “Ultem” supplied by Sigma-Aldrich, USA (specific
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gravity: 1.27 g/cm3 at 25 °C, MFI: 18 g/10 min (337 °C/6.6

kg), number average molecular weight: 21,000, with dielectric
constant 3.12 at 1 MHz and Tg of 217 °C).
E-glass (8 H satin weave 7781 style; dielectric constant: 6.10
at 1 MHz; areal density: 295 ± 5 g/m2) from Valmiera Glass
UK Ltd., (Figure 1d), fabric with a ply thickness 0.25 mm was
used as the reinforcement for composite fabrication for all
evaluations, except mode I interlaminar fracture toughness
(GIc). Uni-directional E-glass fabric (Chomarat Ruban 8033/
1F) with 500 g/m2 areal density is used as the reinforcement
for fabricating laminates for GIc test.46 All materials of the
subject study were used as received.
2.2. Synthesis of PEI-Toughened CE. Blending of CE
and PEI was carried out using a temperature-assisted solvent-
free technique. Initially, the CE resin was heated over an oil
bath to a temperature range of 110−120 °C. A predetermined
amount of PEI was slowly added to the CE resin, while
continuously stirring at 1000 ± 10 rpm using an overhead
stirrer (IKA make, model: Euro star 20 digital). Film
formability was observed from 15 wt % of PEI concentration
in CE. Weight fraction exceeding 23% of PEI resulted in blends
that are too viscous to process further. Hence, the optimal
concentration of PEI in CE for better film formability suitable
for RFI was found to be in the range of 15−23 wt %. Figure 2. (a) Photograph of the PEI-modified CE resin film. (b)
2.3. Rheological Evaluation. Prior to fabricating Schematic representation of the RFI process.
laminates, pristine, and modified resins were subjected to
rheological evaluation in order to determine the processing
characteristics such as viscosities at different temperature controlled cooling to ambient temperature result in excellent
ranges and infusion temperatures. A modular compact quality composite laminates.
rheometer (Bohlin make, model: Gemini 2) in plate−plate Resin films of the pristine CE resin and PEI-modified CE
mode under a constant shear of 25/s has been used for this at a resins were cast on a siliconized paper using a film casting
temperature range of from 40 to 120 °C. machine. The areal density and thickness of the resin film was
2.4. Morphological and Thermal Characterization. In calculated as follows.
order to characterize morphological features of blends at The areal density and ply thickness of the E glass fabric used
varying PEI concentrations (15−23 wt %), cured samples were was 295 g/m2 and 0.25 mm, respectively. In order to make a
cryogenically fractured and observed under field-emission laminate of dimensions 200 mm (length) × 200 mm (width) ×
scanning electron microscopy (FESEM) (Carl Zeiss AG, 3 mm (thickness), 12 fabric plies were used. Areal density
JSM-6700F). multiplied by the area of the ply will result in the weight of one
Glass transition temperature (Tg) of CE−PEI blends were ply (295 g/m2 × 0.2 m × 0.2 m = 11.8 g). This will result in a
determined using differential scanning calorimetry (DSC total weight of the fabric as 141.6 g (11.8 g × 12 plies). Rule of
Q2000, TA Instruments). A sweep from 20 to 250 °C at 10 mixtures was applied to calculate the individual mass fractions
°C/min ramp rate was given, and further, the samples were of the fabric and resin for a targeted fiber volume fraction (Vf)
heated isothermally at 250 °C for 2 min under a nitrogen of 50%. If volume fraction of the composite is Vf, according to
atmosphere. After cooling at a rate of 25 °C/min to 40 °C, the rule of mixtures
samples were subjected to a second sweep from 40 to 360 °C Vf 50
at 10 °C/min. Tg was noted from the second heat flow curve. = = 0.5
Thermogravimetric analyses (TGAs) were performed using Vc 100 (1)
a thermogravimetric analyzer (Q50, TA Instruments) in an M f /δf
inert atmosphere. A sweep of 30−900 °C at 10 °C/min was 0.5 =
used to find the decomposition temperatures and heat M f /δf + M r /δr (2)
resistance index. where Mf, Mr, δf, and δr are the mass fractions and densities of
2.5. Fabrication of the Composite through RFI. Test the fabric and resin, respectively.
coupons of composites were manufactured through a RFI Considering density of glass fabric, δf = 2.54 g/cm3 and
process.45 This process essentially involves the casting of the density of resin δr = 1.19 g/cm3, eq 2 can be written as Mr =
polymer resin to tacky films. The photograph of the PEI- 0.47Mf. Because Mr + Mf = 1, replace Mr with 0.47Mf. Hence,
toughened CE film is shown in Figure 2a. These films are then Mf = 0.68 and Mr = 0.32. This means that the ratio of the mass
transferred to a fabric. Such a fabric-film layup can be made up of the resin to fabric is 0.32/0.68, for a volume fraction of 50%,
to the required thickness followed by standard vacuum bagging for the given fabric. In addition, the mass of the resin required
molding, which is shown schematically in Figure 2b. Under less
i 0.32 yz
is calculated using eq 3

Mass of the resin required = Mass of the fabric × jjj zz

than 1 bar vacuum pressure, the layup consolidates, subsequent

k 0.68 {
temperature application allows the resin films to melt and
infuse at a predetermined temperature. Further, increasing the
temperature to the desired curing cycle and subsequent (3)

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Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
i 0.32 zy
=141.6 × jjj zz = 66.6 g
k 0.68 {
Considering four resin films to infuse 12 fabric plies, one
film would weigh 66.6/4 = 16.65 g, which must be of
dimensions 200 × 200 mm. Hence, the areal density of the
resin film required is, ( 16.65200× 1000 × 1000
× 200 ) = 416.47 g/m2. The
casting machine controls the thickness of resin films using a
doctor knife. The machine is set to have precise control of
thickness and, hence, areal densities to result in films of areal
density 416 ± 5 g/m2.
The cast resin film was transferred to a fabric layer (placed
over a mold) ensuring that the film just sticks to the fabric. The
process was repeated to yield sandwiches of resin films and
fabric. This sandwich stack was then vacuum bagged and cured
inside an oven as per the curing cycle. The fiber volume
fraction of all composite laminates of the subject study was
50%.
The curing cycle of laminates with a pristine CE resin was as
follows. The sandwich stack was heated at a rate of 2 °C/min
from ambient to 80 °C and kept for 60 min dwell time, during
which, the resin films melt, drops the viscosity to 8.7 Pa·s and
infuses amid the fabric plies. A range of viscosities of 6−12 Pa·s
has been identified as optimum for infusion. From our previous
experiments, to result in a good quality laminate with pre-
determined fiber volume fraction and near zero void fraction
heating continued from 80 to 150 °C at a rate of 2 °C/min and
held at 150 °C for 60 min as per the technical data sheet. The
curing process takes place with subsequent heating to 200 °C
and holding for 180 min. The cured laminate was then heated
from 200 to 260 °C at a rate of 2 °C/min for postcuring and
held for 60 min to get the desired physical properties.
For the PEI-modified CE resin, viscosity increases with an
increase in PEI content at any given temperature and decreases
exponentially with increase in temperature at all blend ratios.
Temperatures of infusion of each of the blends have been
chosen from rheology data in such a way that the viscosity of
the blend is approximately in the range of 6−12 Pa·s. For all
blend formulations, infusion was carried out for 60 min,
followed by curing at 180 °C for 180 min, and ramp rate was
maintained at 2 °C/min. The cure cycle of pristine CE and
modified CE with 15 wt % PEI is shown in Figure 3a. The
photograph of the E glass laminate realized that using-PEI
modified CE resin is shown in Figure 3b.
The advantages of RFI over other composite fabrication
techniques are many. This process is a cost-effective alternative
for autoclave curing using prepregs. Because resin flow occurs
locally, complete wetting of fibers is ensured and results in
near-zero void fractions. The process also guarantees superior
compaction. The resin film can be stored separately from dry
fabric and hence, cold storage requirements are less when
compared to autoclave curing using prepregs. The resin film
exhibits a light tack at room temperature that allows adhesion
to curved surfaces and, hence, no need of extra tackifiers. High
quality parts can be manufactured using only vacuum; external
application of pressure is not required which avoids the use of
autoclaves. This process also facilitates making of functional
and hybrid composites using fillers with high fiber volume
fractions.45−47
2.6. Evaluation of Electromagnetic Properties. Elec-
tromagnetic properties such as permittivity [real permittivity
(ε′) and imaginary permittivity (ε″)], dissipation factor (loss
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Figure 3. (a) Curing cycle of laminates with pristine CE and 15 wt %
PEI-modified CE (b) PEI-modified CE/E glass laminate.
tangent, tan δ), and transmission loss in dB were measured
using a FSMS from HVS Technologies, Pennsylvania State,
USA along with a Vector Network Analyzer PNA E8364B
from Agilent Technologies, USA in C band, X band, and Ku
bands.48 Measurements were carried out using three different
antennas as the bandwidths are different for different bands
and the dimensions of test laminates were of 150 mm (l) ×
150 mm (w) × 1 mm (t).
2.7. Determination of Mechanical Properties. Compo-
site test specimens for tensile tests were prepared as per ASTM
D3039. The test specimen dimensions were 250 × 25 × 2.5
mm with composite end tabs of 56 mm length and 25 mm
width, to ensure a proper gripping. The gauge length of the
specimen was 138 mm and tests were conducted at a rate of 2
mm/min on a servo hydraulic UTM (BiSS India) of 10 T load
cell capacity. Strain measurements were done using strain
gauges bonded on the specimen and were used for determining
Young’s modulus. Data represented are an average of at least
eight measurements.
Compressive strength of composite specimens were
determined as per ASTM D3410. Specimen dimensions of
142.7 × 25 × 1.5 mm with composite end tabs of 65 mm
length were used. The gauge length of the specimen was 12.7
mm and speed of test was 1 mm/min. In-plane shear strength
of composites were evaluated as per ASTM D3518. Samples of
dimensions 250 × 25 × 3 mm were prepared from ±45°
symmetric and balanced laminates and were subjected to
tensile loading at a cross-head speed of 2 mm/min. ILSS was
evaluated as per ASTM D2344. Specimen dimensions were 36
× 12 × 6 mm and they were loaded under three-point bending
mode, with a rate of testing maintained at 1 mm/min.
2.7.1. Evaluation of Toughness (Impact Resistance)
Characteristics. Double cantilever beam specimens for
evaluation of mode I interlaminar fracture toughness (GIc)
were prepared as per ASTM D5528 with an overall length 125
mm, width 25 mm, thickness 3.24 mm, and an initial
delamination length of 50 mm. Teflon film as specified in
ASTM has been used as an insert to produce the initial
delamination.46 All specimens were tested on UTM under
tension and test speed was maintained at 0.5 mm/min.
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
LVI as per ASTM D7136 followed by CAI was carried out
on laminates with maximum loading of PEI in the CE resin and
compared to that of pristine CE laminates. Specimens were
150 mm in length, 100 mm in width, and 4.2 mm in thickness
and the layup sequence followed was [(45/−45)/(0/90)]4s.
An impactor with a hemispherical striker tip of weight 1.5 kg
was impacted from 2 m in height. The impacted samples were
then subjected to compression loading to measure its residual
compressive strength post LVI as per ASTM D7137.
3. RESULTS AND DISCUSSION
3.1. Rheological Characterization. The effect of thermo-
plastic addition on the processing of a blend requires great
attention as rheological properties are highly dependent on the
thermoplastic concentration. The thermoplastic-modified CE
resin usually possesses excellent tackiness and drape.49 The
viscosity−temperature plot shown in Figure 4 shows that, at
Figure 4. Viscosity vs temperature of pristine CE and PEI-modified
CE resins.
any temperature, viscosity of CE−PEI blends increases with an
increase in PEI content, as expected. Also, their viscosities
decrease with increase in temperature. The blend with 15 wt %
PEI content has a viscosity of 88.68 Pa·s at 40 °C and reduces
to 36.81 Pa·s at 50 °C; further heating beyond 90 °C, it drops
to less than 1 Pa·s. The infusion temperature for this resin is
chosen as 70 °C as the viscosity at this temperature is 8.46 Pa·
s. The viscosities of the blends with 18 and 20 wt % PEI show
107.4 and 127.13 Pa·s at 40 °C and 47.98 and 76.9 Pa·s at 50
°C, respectively. The infusion temperatures of blends with 18
and 20 wt % PEI were chosen as 70 and 80 °C, as the
viscosities at these temperatures are 11.18 and 9.38 Pa·s,
respectively. The blend with maximum PEI loading shows a
viscosity of 255 Pa·s at 40 °C, which is higher than all the other
three. The infusion temperature of this blend was chosen as
100 °C as the viscosity is 10.34 Pa·s at 100 °C.
Pristine CE is a semisolid at ambient temperature hence,
viscosity measurements could only be carried out from 50 to
120 °C. The viscosity−temperature plot in Figure 4 depicts
that, at 50 °C, the viscosity is 428 Pa·s and it gradually
decreased to 127 Pa·s at 60 °C and upon further heating
beyond 100 °C, the viscosity reduced to less than 1 Pa·s. The
infusion temperature was chosen as 80 °C because the
viscosity at 80 °C is 8.7 Pa·s which is appropriate for a film
infusion process.
3.2. Morphology of CE−PEI Blends. FESEM of
cryogenically fractured surfaces of blends revealed that the
morphological properties change drastically with respect to
PEI content. The blend which contains 15 wt % of PEI shows
particulate morphology with spherical domains of approx-
imately 600 nm diameter, well dispersed in the CE matrix, as
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shown in Figure 5a. However, in this morphology, particulates
of PEI were observed in larger quantities. This particulate
morphology was the result of nucleation followed by the
growth mechanism, in which, small PEI particles nucleate and
grow with time in the CE matrix.50−52
When the PEI concentration was increased to 18 wt %, the
morphology of blends turned to a co-continuous structure,
where CE and PEI-rich zones were present simultaneously, as
depicted in Figure 5b. Also, it was observed that, small PEI
particles of spherical shape were dispersed in the CE-rich phase
and vice versa. This is because of secondary phase separation
that occurs in earlier phase-separated CE and PEI concentrated
domains.33 However, the particles observed in a CE-rich phase
were relatively small, and very broad particle size distribution
was observed as compared with CE particles dispersed in the
matrix of PEI. Similar co-continuous morphology was observed
for 20 wt % PEI blends, but the size of PEI particles in the CE-
rich phase was larger as compared with 18 wt % PEI blend, as
shown in Figure 5c. The co-continuous morphology at 20 wt %
PEI differs from the 18 wt % PEI in the fact that it has more
PEI-rich areas. This makes it evident that the higher the PEI
content, the higher will be the degree of phase separation in
the blend. Also, it is known that, these co-continuous
morphologies are the result of the spinodal decomposition
mechanism.50,52
Further increase in the PEI concentration to 23 wt % has
resulted in complete phase inversion in which PEI becomes a
matrix and spherical CE particles disperse in it, as shown in
Figure 5d. The average particle size of CE was observed
around 16 μm, which is relatively large as compared with the
particulate morphology observed at 15 wt % PEI and excellent
bonding between the particle and matrix phase seems to exist.
3.3. Thermal Characterization. 3.3.1. Differential Scan-
ning Calorimetry. The DSC thermograms in Figure 6 shows
the glass transition temperature (Tg) values of CE−PEI blends
at various weight fractions of PEI. The blends possess Tg in the
range of 280−290 °C, evident from trimerization exotherm,
which lies in between the Tg values of its constituent polymers,
that is, LEcy (Tg, 303 °C) and PEI (Tg, 217 °C), as expected.
The high Tg of CE is attributed to the formation of a cross-
linked six-member triazine ring, which is thermally stable and
least affected by the dispersed PEI phase.5 The Tg of
commercially available pristine CE is 310 °C. Nonetheless, a
dry Tg of 280−290 °C suffices its intended use for high-speed
aircrafts.
3.3.2. Thermogravimetric Analysis. To study the thermal
stability of blends, TGAs of cured blend samples and PEI were
carried out, the results of which are shown in Figure 7. All
blends represent a similar thermal behavior indicating that PEI
concentration does not really influence the thermal properties
of blends. Initially, up to temperature of 370−380 °C, the
blends remain stable with negligible weight loss. The slight
weight loss might be attributed to the loss of volatile
compounds and loss of uncross-linked monomers.53 Major
weight loss of the blends occurs in zone 2, at a temperature
range of 380−450 °C. This weight loss is due to the
decomposition of CE as the thermal stability of PEI is very
high compared to the former. This is evident from the
thermogram, indicating a weight loss of only <1% at 460 °C,
when tested on a 100% PEI sample (Figure 7).54 The
decomposition starts with the hydrocarbon chain scission,
followed by the cyclization of the triazine ring at approx. 450
°C, that liberates the volatile CE decomposition products.55 At
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Figure 5. Scanning electron micrographs of cryogenically fractured surfaces of CE−PEI blends (a) 15 wt % PEI, (b) 18 wt % PEI, (c) 20 wt % PEI,
and (d) 23 wt % PEI.

Figure 6. DSC curves of CE−PEI blends at various weight fractions Figure 7. TGA plots of PEI and CE−PEI blends at various PEI
of PEI. weight fractions.

Table 1. Comparison of Heat Resistance Index of Pristine

around 500 °C, the second weight loss signal was observed. PEI and PEI-Modified CE Resins
The loss in weight is attributed to the of PEI decomposition materials T5 (°C) T30 (°C) heat resistance index (°C)
present in the blend, as shown in zone 3. 100% PEI 530 570 271.46
The heat resistance index for all the samples64,65 were 15 wt % PEI in CE 417.23 467.66 219.26
calculated using the formula 18 wt % PEI in CE 414.79 461.46 216.96
Theat ‐ resistance index = 0.49 × [T5 + 0.6 × (T30 − T5)] 20 wt % PEI in CE 415.84 466.19 218.56
23 wt % PEI in CE 414.59 463.99 217.67
where, T5 and T30 represent the decomposition temperatures
of 5 and 30% weight losses, which are given in the Table 1.
The heat resistance index for pristine PEI is 271.46 °C and for 3.4. Measurement of Electromagnetic Properties.
PEI-modified blends it is in the range of 216−219 °C, shows Radome material should possess very low loss tangent and
high thermal stability of PEI. negligible transmission loss (ideally < −1 dB) over wide
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Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
bandwidths. The inter relation between the intrinsic electro-
magnetic properties (permittivity εr) are given in the following
equations
εr = (ε′ − jε″) (4)
where (ε′), (ε″) represents the real and imaginary permittivity
of the material through which the electromagnetic waves are
getting transmitted. Loss tangent (tan δ) is defined as the ratio
of imaginary permittivity (ε″) and real permittivity (ε′).
ε″
tan δ =
ε′ (5)
When electromagnetic waves travel from one medium to
another, the intrinsic impedance “Z” encountered by the
electromagnetic waves is related to the material properties, as
given in the eq 6 as
ij μ yz
Z = jjj r zzz
jε z
1/2
k r{ (6)
where μr is the relative permeability of the material, for
nonmagnetic composite materials it is unity. The transmission
coefficient (T) as defined in eq 7 shows, to get full
transmission (very low transmission loss) through one medium
to another, their intrinsic impedances must be similar or in
another words its intrinsic loss properties such tan δ and ε″
would be as less as possible.3 Detailed relationships of these
parameters more specifically for composites have been
reported by many researchers.4,66,67
2Z 2
Transmission coefficient, T =
|Z1 + Z 2| (7)
and the transmission loss in dB would be represented as
Transmission loss (dB) = −20 log|T | (8)
where, Z1 and Z2 are the intrinsic impedances of medium 1 and
medium 2, respectively.
Calculation of dielectric properties of composites based on
the rule of mixtures are widely studied and reported by many
researchers and found that the effective permittivity of
composites depend on the dielectric properties of its matrix
and reinforcements with respect to its volume fractions and
type of constituents.56−58 This statement is well proven by the
electromagnetic results such as ε′, ε″, tan δ, and transmission
loss of composites realized with PEI-modified CE and pristine
CE resins in Figure 8a−d. The data in Figure 8c,d provide
important parameters for a radome design viz. the low loss
tangent (tan δ) and low transmission loss clearly depict that
both are increasing with increasing concentration of PEI
ranging from (tan δ, 0.017−0.008 for 15%), (tan δ, 0.04−0.010
for 23%) and transmission loss (T.L) (−0.18 to −1.18 for
15%), (−0.19 to −1.194 for 23%), through C, X, and Ku
bands, respectively. This is because the intrinsic electro-
magnetic properties of PEI and E-glass fabrics are higher than
that of LEcy; which are (ε′, 2.99 at 1 MHz) for LEcy, (ε′, 3.12
at 1 MHz) for PEI, and (ε′, 6.1 at 1 MHz) for E glass fabrics,
respectively. The dielectric constant (ε′) of the pristine CE
resin is 2.75 at 1 MHz. Hence, its loss tangent and transmission
loss are also slightly less compared to that of composites with
the modified CE resin.
However, on a broader perspective, these differences are
negligible when we design impact-resistant radomes for
G https://dx.doi.org/10.1021/acs.iecr.9b06439
pubs.acs.org/IECR Article
Figure 8. (a) Real permittivity (ε′), (b) imaginary permittivity (ε″),
(c) loss tangent (tan δ), and (d) transmission loss of composites with
PEI-modified CE and pristine CE in C, X, and Ku bands.
broadband frequencies. Negligible transmission loss is found
in C and X bands which is in the range of −0.18 to −0.70 dB
indicating characteristics for low loss radomes. In the Ku band,
the transmission loss (Figure 8d) lies in the range of −0.7 to
−1.26 dB for all laminates. The other properties such as ε′ and
ε″ from Figure 8a,b are in the range of 3.3−3.9, 0.02−0.24,
respectively, for all laminates with modified CE, which are
either equal or comparable with that of pristine laminates in
5.4−18 GHz. 0Mzabi et al. have reported the effect of heating
(below glass transition temperature) on the dielectric proper-
ties in pristine PEI materials. The dielectric properties of PEI
were studied by a dielectric spectroscopy method in the 5 Hz
to 12.5 MHz frequency region. They reported that dipolar
relaxations are getting affected with respect to increase in
temperature and frequencies. This results in reduction of real
permittivity (ε′) as the material is not able to change its dipole
orientations as quickly as with the increase in frequency and
temperature, resulting in the decrease of formation of relaxing
dipoles.68
The transparency can be further improved by replacing the
E-glass fabric with highly pure quartz fabric (SiO2 content
>99.9%) reinforcement because the dielectric constant of
quartz fabric is 3.74 at 10 GHz.59 Quartz fabrics, though
expensive in comparison to E-glass fabrics, can be used for
realizing advanced composite radomes with CE resins, where
transmission loss of less than −0.5 to −1 dB is required.
3.5. Mechanical Properties of Composites. Tensile
strength, tensile modulus, compression strength, in-plane shear
strength, ILSS, and toughness characteristic mode I inter-
laminar fracture toughness (GIc) were evaluated, compared
with those of pristine composite laminates and the results are
shown in Table 2. Effect of PEI loading on tensile properties of
composites as per Table 2 shows that, tensile strength of
laminates with 15 wt % PEI loading is comparable to that of
pristine composites. When PEI concentration was increased to
18 and 20 wt %, it resulted in maximum tensile strength, which
was more than 20% higher as compared to pristine CE.
However, a further increase in the PEI concentration to 23 wt
% resulted in degradation in tensile strength of composites.
Similarly, tensile modulus was higher for 18 and 20 wt % with
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

Table 2. Comparison of Mechanical Properties of Glass-Reinforced Laminates of Pristine CE and PEI-Modified CE Resins
PEI-modified CE resins
properties of E-glass reinforced composites with different resin matrices pristine CE
(fiber vol. fraction: 50%) resin 15 wt % 18 wt % 20 wt % 23 wt %
tensile strength, MPa 293 ± 5 305 ± 8 372 ± 21 376 ± 6 327 ± 2
tensile modulus, GPa 15.3 ± 1 15.6 ± 1 18.3 ± 1 17.6 ± 1 15.9 ± 1
compressive strength, MPa 298 ± 16 371 ± 10 406 ± 5 389 ± 8 361 ± 22
in plane shear strength, MPa 81.0 ± 3 75.5 ± 5 79.3 ± 2 76.6 ± 4 157.1 ± 2
ILSS, MPa 35 ± 5 35.5 ± 2 41.6 ± 1 43.6 ± 1 38.3 ± 2
fracture toughness, GIc (kJ/m2) 0.403 ± 0.05 0.455 ± 0.04 0.625 ± 0.01 0.640 ± 0.05 0.824 ± 0.03

respect to other composites. Compression strength was also 4. CONCLUSIONS

found to be higher for 18 and 20 wt % PEI, approximately 40%
in comparison to control values. Higher loading of 23 wt % of
PEI in CE resulted in the degradation of compressive strength
of composites. Thus, from tensile and compression properties,
it can be concluded that a co-continuous morphology is
effective in resulting the highest tensile as well as compression
properties of the composite, which was fabricated with 18 to
20 wt % of PEI in CE. A similar observation was reported by
Tao et al. 34 and Chang et al. 39 that co-continuous
morphologies are effective in enhancing the tensile as well as
compressive properties. However, their studies were mainly
focused on the evaluation of blends only. These improved
properties associated with a co-continuous morphology can
also be attributed by the crack path deflection by dispersed PEI
particles and excessive plastic deformation of the PEI-rich
phase.35 Evaluation of in-plane shear strength shows that
properties of 15, 18, and 20 wt % are in a similar range to
pristine laminates but the 23 wt % PEI loading enhanced the
resistance toward shear forces. Evaluation of ILSS shows that
for all combinations, the values are mostly comparable to that
of composites with pristine CE.
Fracture toughness GIc was found to be higher for the 23 wt
% PEI blend, revealing a phase-inverted morphology. This
improvement is mainly because of the formation of tough
thermoplastic domains as the major component compared to
CEs which help in excessive plastic deformation for yielding.
Because the enhancement of toughness characteristic GIc is
higher for 23 wt % PEI-loaded composites, further evaluation
for finding toughness in terms of residual compressive strength
after impact loading (LVI followed by CAI) was done only on
laminates with 23 wt % PEI and pristine CE. The results
represented in Figure 9 shows an improvement of more than
85%, clearly indicating that PEI-toughened CE laminates have
PEI-toughened CE resins were prepared through a solvent-free
temperature-assisted method and its process parameters were
optimized to realize composites through RFI. A range of
concentration of PEI in CE was found suitable for RFI.
Morphological features of blends were studied and observed
that, morphology changes with increasing PEI concentration
from particulate in 15 wt %, via co-continuous in 18−20 wt %,
to phase inverted in 23 wt %. Thermal analysis using DSC and
TGA shows that all the four blends possesses high Tg in the
range of 280 °C−290 °C and are thermally stable up to 350 °C
without any signs of decomposition. Electromagnetic evalua-
tion for finding real permittivity (ε′), imaginary permittivity
(ε″), and loss tangent (tan δ) shows that the values range from
3.3 to 3.9, 0.02 to 0.17 and 0.01 to 0.04, respectively, in C, X,
and Ku bands, respectively, which are well comparable with
that of pristine laminates. The low transmission loss of −0.18
to −0.70 dB in the C band and X band of PEI-modified CE
laminates clearly indicate their possible use in low loss aircraft
radomes. In the Ku band, the transmission losses are in the
range of −0.7 0to −1.26 dB which are negligible for an impact-
resistant radome operating over broadband frequencies, when
compared with pristine composites. Detailed mechanical
characterization of laminates shows that, tensile strength,
tensile modulus, and compressive strength are higher for 18
and 20 wt % PEI-loaded laminates, attributed by co-continuous
morphologies. Toughness characteristics such as mode I
interlaminar fracture toughness (GIc) and post-LVI compres-
sive studies shows that a composite with 23 wt % PEI (phase-
inverted morphology) has highest toughness. Considering the
higher thermal stability, good electromagnetic transparency,
excellent toughness characteristics, and enhanced mechanical
properties, it can be concluded that CE−PEI formulations
could be an innovative advanced matrix material that can be
used for realizing impact-resistant high-temperature capable
aircraft radomes.

■
higher toughness when compared to pristine laminates.
AUTHOR INFORMATION
Corresponding Author
Anoop Anand − Composites Research Centre, Research and
Development Establishment (Engineers), DRDO, Ministry of
Defence, Pune 411015, India; orcid.org/0000-0002-9064-
6803; Phone: 91-20-27044866; Email: aanand@rde.drdo.in;
Fax: +91-20-27044009
Authors
Jayalakshmi Cherukattu Gopinathapanicker − Composites
Research Centre, Research and Development Establishment
(Engineers), DRDO and Department of Metallurgical and
Figure 9. Residual compressive strength (CAI after LVI) of pristine Materials Engineering, Defence Institute of Advanced
CE/E-glass and CE with PEI (23 wt %)/E-glass laminates. Technology, Ministry of Defence, Pune 411015, India
H https://dx.doi.org/10.1021/acs.iecr.9b06439
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
Ahmed Inamdar − Department of Metallurgical and Materials
Engineering, Defence Institute of Advanced Technology, Ministry
of Defence, Pune 411025, India
Makarand Joshi − Composites Research Centre, Research and
Development Establishment (Engineers), DRDO, Ministry of
Defence, Pune 411015, India
Balasubramanian Kandasubramanian − Department of
Metallurgical and Materials Engineering, Defence Institute of
Advanced Technology, Ministry of Defence, Pune 411025,
India; orcid.org/0000-0003-4257-8807
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.iecr.9b06439
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The first author is thankful to V. Murkute, V. Gavande, and S.
Tandon for their support.
■
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