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Electrospun Piezoelectric Polymer Nanofiber Layers for Enabling in

Situ Measurement in High-Performance Composite Laminates
Saeid Lotfian,†,‡ Claire Giraudmaillet,† Ata Yoosefinejad,§ Vijay Kumar Thakur,*,†
and Hamed Yazdani Nezhad*,†
†
Enhanced Composites & Structures Centre, School of Aerospace, Transport and Manufacturing, Cranfield University, MK43 0AL
Bedford, U.K.
‡
Materials and Structures, Naval Architecture, Ocean & Marine Engineering, University of Strathclyde, Glasgow G1 1XQ, U.K.
§
Munro Technology Limited, Lufton Height Commerce Park, Yeovil BA22 8UY, U.K.
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ABSTRACT: This article highlights the effects from

composite manufacturing parameters on fiber-reinforced
composite laminates modified with layers of piezoelectric
Downloaded via 95.181.183.54 on September 1, 2018 at 06:33:12 (UTC).

thermoplastic nanofibers and a conductive electrode layer.

Such modifications have been used for enabling in situ
deformation measurement in high-performance aerospace and
renewable energy composites. Procedures for manufacturing
high-performance composites are well-known and stand-
ardized. However, this does not imply that modifications via
addition of functional layers (e.g., piezoelectric nanofibers)
while following the same manufacturing procedures can lead
to a successful multifunctional composite structure (e.g., for
enabling in situ measurement). This article challenges success
of internal embedment of piezoelectric nanofibers in standard manufacturing of high-performance composites via relying on
composite process specifications and parameters only. It highlights that the process parameters must be revised for
manufacturing of multifunctional composites. Several methods have been used to lay up and manufacture composites such as
electrospinning the thermoplastic nanofibers, processing an inter digital electrode (IDE) made by conductive epoxy−graphene
resin, and prepreg autoclave manufacturing aerospace grade laminates. The purpose of fabrication of IDE was to use a resin type
(HexFlow RTM6) for the conductive layer similar to that used for the composite. Thereby, material mismatch is avoided and
the structural integrity is sustained via mitigation of downgrading effects on the interlaminar properties. X-ray diffraction,
Fourier transform infrared spectroscopy, energy dispersive X-ray spectroscopy, and scanning electron microscopy analyses have
been carried out in the material characterization phase. Pulsed thermography and ultrasonic C-scanning were used for the
localization of conductive resin embedded within the composite laminates. This study also provides recommendations for
enabling internally embedded piezoelectricity (and thus health-monitoring capabilities) in high-performance composite
laminates.

1. INTRODUCTION been developed for structural or internal deformation and

Various industries such as aerospace and renewable energy damage measurement in various fields such as optoelec-
sectors intensively use polymer composite materials for their tronics,5−11 pulsed power systems,12−14 temperature and
lightness and tailorable design as well as their outstanding vapor/liquid sensing,15−20 energy harvesting,21−25 and tran-
mechanical properties. However, aviation safety regulations sistors and inverters.20,26−31 In such composites, addition of
and reliability assurance of the structural integrity are crucial electric, dielectric, or other functional materials and fillers
factors in driving the use of such materials in aircraft and enhances the electrical properties32,33 as well as mechanical
turbine blade structures. To satisfy both, nondestructive properties.34
inspection (NDI) of the structure is carried out, which is Piezoelectric sensing has been gaining increased interest for
complicated, costly, and inefficient than that for metallic electric measurement of deformation in structures for years but
structures because of the multiple material structure of the its low durability, low capability for complex parts, and limited
composites. Moreover, existing NDI techniques are unable to strain-to-failure resistivity lessen its possibilities to be
detect zero-thickness interlaminar bond defects (so-called considered for long-term applications.35,36 Fiber optic sensing
kissing and weak bonds) likely to occur in composite
adhesively bonded joints1−3 or composite laminate manufac- Received: May 8, 2018
turing.4 Therefore, development of new in situ health- Accepted: July 27, 2018
monitoring techniques is required. Smart composites have Published: August 9, 2018

© 2018 American Chemical Society 8891 DOI: 10.1021/acsomega.8b00940

ACS Omega 2018, 3, 8891−8902
ACS Omega Article

proposes a continuous and real-time health monitoring of treatments has already been reported.43 Therefore, the loss of
composite structures. Its lightness, stability, nonelectromag- performance of the material under temperature treatment has
netic reactivity, robustness, and allowance to be used on large quantitatively been evaluated.
structures make this candidate highly promising in detec- According to a study on stretched PVDF, the transformation
tions.37 Despite the advantages, fibers have relatively low of α phase into β phase seems to be more affected by the
mechanical strength and can irreversibly be damaged and stretching ratio than the stretching temperature.44 Because of
malfunctioned. This may lead to life-span mismatch between the use of aerospace prepregnated thermoset composite pre-
optical fibers and high-performance composite laminates in pregs for manufacturing composite laminates, heat energy at
applications. relatively high temperature (>120 °C) is required for the
For piezoelectric materials, the elastic strain energy of the curing to be effective, for example, approx. 180 °C for carbon
body can be related to their dielectric energy. Thus, a fiber pre-pregs. Reticulation occurs between polymer chains,
proportionality can be established between the mechanical which leads to strongest bonds within the structure and
deformation of the material and an electrical signal change, for solidification of the material. The melting temperature of the
example, change in voltage.38 Categorized as polymers, they PVDF material is 171−175 °C, which means that during
can make ideal candidates to reduce material mismatch in curing, the PVDF fibers will be partially molten. This means
bonding with polymer composites (the foundation of the that the piezoelectric capability of PVDF fibers may still be
current paper). However, because of their particular crystallo- valid after high-temperature exposure. The study in this article
graphic structure, piezoelectric materials are highly anisotropic, aims to present what piezoelectric capabilities can be left at the
which means that the electrical properties vary with the postprocess stage, where the material is solidified for high-
orientation of the crystal.39 Thus, it is necessary to give performance structural applications. The paper is divided to a
orientation to the properties required for directional tailoring. number of sections to address such aim: section 2 presents
The current research work represents a novel, rapid technology data for the materials used in this study and the manufacturing
applicable to large structures that use electrospinning steps to develop an integrated composite laminate-PVDF-inter
technique to produce ultrathin unidirectional polyvinylidene digital electrode (IDE). The section also provides theoretical
fluoride (PVDF) nanofibers and embed such materials onto background for definition of an IDE layout and discusses
the laminates in situ. Introduction of thermoplastic veils and limitations with the manufacturing steps taken. Character-
films has already proven durable and thermally stable ization and microscopy techniques used on the postprocessed
candidates for the purpose of interlaminar toughening in manufactured laminates are also explained. Section 3 presents
composite laminate manufacturing (e.g., see ref 4). However, the results obtained from the techniques described in the latter
their thickness is at the level of ply thickness, for example, 200 section and discusses the possibility of the presence of
μm, and therefore, addition to the overall thickness of the piezoelectric phases pre- and post-manufacturing. Section 4
structure is considerable. Also, such introduction of veils is not presents data from pulsed thermography and ultrasound NDI
fully automated yet and can also have significant increasing techniques and in connection with the results presented in
effect on the overall weight of a laminated structure (if added section 5 discusses the effect of manufacturing steps on the
over each ply). The proposed technology in the current article mechanical performance of such an integrated multimaterial
will have almost zero weight and thickness penalty at its scale- laminate.
up.
PVDF is a fluoropolymer thermoplastic resulting from the 2. MATERIALS AND MANUFACTURING
polymerization of vinylidene difluoride.39 PVDF is chemically The current research addresses aerospace and renewable
stable that prevents from chemical reaction when this material energy applications, which means that the relevant standards
is introduced into a system and shows good resistance to must be followed for the manufacturing choices: type of fibers
oxidation and UV light.40 This polymer is naturally piezo- and resin, stacking sequence, curing cycles, and so forth. To do
electric and belongs to the electroactive polymer family.39 so, the materials (as described below) were processed
PVDF has a semicrystalline polymorphic structure with five according to composite process specifications provided in
phases of α, β, γ, δ, and ε. The first three phases are the most product datasheet.45
commonly used in in situ measurement applications.41 The 2.1. Materials. The following structural grade materials
PVDF polymer chain is composed of two types of groups: CF2 were selected. Table 1 presents the materials and the reason
fluorine group (electrically negative) and CH2 hydrogen group they were chosen. The materials were then processed
(electrically positive). Depending on the localization of these according to the specifications provided by the suppliers, for
groups along the chain, an electrical dipole moment is example, Hexcel. The relevant standards used for such
generated (approximately 5−8 × 10−30 C.m). Thus, its use is processes45 were followed to ensure reliability of processes.
appropriate for sensor and actuator development.42 The composite laminates were manufactured using unidirec-
The electrospinning process is commonly used to produce tional carbon fiber-reinforced thermoset polymer pre-pregs
PVDF nanofibers. The purpose of this study was to rapidly made of high-toughness resin (M21). Each cured ply had the
produce highly oriented PVDF nanofibers and lay up over thickness of approximately 0.125 mm (cured using an
high-performance thermoset composite laminates for enabling autoclave according to the specifications of the supplier).
internal in situ measurement in composite aircraft structures. The plies were stacked to make quasi-isotropic configuration,
During the curing process of the laminates, the PVDF material and the PVDF and conductive layer were added just below the
undergoes high temperature (>Tm) and constant pressure for a upper ply. The laminate was then vacuum-bagged and heated
certain duration depending on the composite process at 180 °C for a duration of 2 h under 7 bar constant pressure.
specifications. As a result, PVDF may undergo a new phase 2.2. Integrated Composite Laminate Definition. The
transformation. The variation of the piezoelectric response of stacking sequence of the composite laminate was chosen to be
the material after PVDF being subjected to temperature symmetric and quasi-isotropic, [−45/+45/90/0]s, which
8892 DOI: 10.1021/acsomega.8b00940
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enables producing composite samples with approximately

similar resin to the one composing the pre-preg. A great

bonding is aimed between the laminate and additional
high performance laminate, easy to deform, shape and
homogenized isotropic properties. Figure 1 schematically

Appropriate for mixing into an epoxy resin for IDE

high quality and conductivity for a very low density.
desirable piezoelectric properties of the nanofibers
reason of their selection

manufacture

fabrication
elements

Figure 1. Quasi-isotropic stacking sequence of integrated composite

laminates.
piezoelectric thermoplastic (PVDF) nanofibers produced by electrospinning and are
structural parts. Thickness of one ply: ∼0.25 mm; curing temperature: 180 °C

All of these materials were chosen for their high quality, innovative, and reliable aspects for the manufacturing steps taken during the project.

shows the main composition of the laminate. The PVDF

high-performance aerospace grade, carbon fiber−epoxy pre-preg, dedicated to

layer was set to be embedded just one layer beneath the upper
ply of the laminate. That would introduce sufficient
justification of internal embedment of an in situ measurement
capability rather than a severe consideration, for example,
description and relevant properties

embedment in the middle layer.

2.3. Polymer-Based IDE Layout Definition. The IDE
ultrahigh-quality graphene powder. Density: ∼26.8 g/L
premixed epoxy system. Curing temperature: 180 °C

layer plays a central role in the laminate for a health-

monitoring purpose. The two types of unimorph electrodes
(d33 and d31) were initially considered. However, because of
highly oriented. Fiber diameter: ∼1.5 μm

the porous morphology of the piezoelectric, a reliable electrode

with a d33 configuration appeared to be too risky. FibroTend
layer is ultrathin (∼250 nm to 1 μm) and composed of
numerous fibers, which would easily let a conductive resin flow
through it during the curing cycle, leading to short circuits.
Table 1. Materials Used in the Study: Description and Reason of Their Selectiona

Therefore, the simple d33 configuration was abandoned for a

d31 configuration. The main difficulty was to make sure that
the IDE would be an integrated part of the laminate to serve
structural integrity (i.e., not acting as an external object/
defect) by an effective bonding between the IDE and the pre-
pregs. This aspect is novel and such introduction has rarely
been exercised. The IDE layout was developed using graphene
FGV Cambridge

mixing in a resin (RTM6) similar to that of the composite

Nanosystems
Technology
company

laminate (M21) over the PVDF layer (Figure 1). Therefore,

Limited

curing of the resin from both pre-preg and the IDE was done
Munro
Hexcel

Hexcel

simultaneously to produce strong bonding as the layout was

then an integrated part of the structure. However, a drawback
M21/35%/268/T700 GC

in such an integration technique was that the layout resin was

allowed to flow during autoclave processing and as such, there
commercial name

was no control on its change of geometry. To avoid possible

PVDF FibroTend

CamGraph G1 A
HexFlow RTM6

short circuits during such a flow, the authors took a theoretical

step for design of the IDE layout with the widest possible
spacing according to the recommendations provided in the
HexPly

following section.
2.3.1. Design of the IDE Layout for Composite
Integration. According to studies done on piezoelectric
ceramic materials, the IDE layout strongly influences the
pre-preg unidirectional carbon

performance of a measurement system.46 Referring to the

fiber-reinforced thermoset

definition of the IDE layout in the previous section, it has been

material

shown that the following relationships should be considered

for optimizing the IDE layout performances46
graphene powder

we
PVDF fibers
composite

epoxy resin

= 0.8
hp (1)
where
a

8893 DOI: 10.1021/acsomega.8b00940

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ACS Omega Article

w Accordingly, the conductivity of the resin examined in this

> 6 (closest to 10) and hp > 3.75 μm
s (2) study was increased via high shear mixing of graphene
Another study with a metal IDE on a piezoelectric polymer nanopowders composing of
[poly(3-hexylthiophene-2,5-diyl)] confirms that w must be •40 g of HexFlow RTM6 epoxy resin and
maximized and s must be minimized.47 The piezoelectric •0.8 g of CamGraph G1 A graphene powder,
FibroTend layer provided in this study has a minimum which result in an approximately 2 wt % concentration of
thickness of ∼250 nm, which allowed for calculating the graphene in the epoxy resin. Trials on high shear mixing and
thickness of the electrode fingers ultrasonic exfoliation were carried out to avoid/mitigate the
we presence of high agglomeration. There was no control on
= 0.8 − we = 0.8 × hp reagglomeration during the composite laminate manufacturing
hp (3) process; however, the authors emphasize that the current
Thus: we = 0.8 . 250 = 200 nm. research has mainly been focused on the effect of composite
Moreover, the samples were initially designed following the processing on the presence of piezoelectric phases rather than
ASTM 7264 standard for the four-point bending mechanical reagglomeration.
testing after manufacturing. This led to a sample size of 13 mm 2.4. Laminate Manufacturing. The following steps have
× 90 mm × 2 mm with a potential electrode width of w = 10 been followed to manufacture the modified integrated
mm. Thus, with a least restrictive w/s ratio of 6, the finger composite laminate:
spacing was s = 1.7 mm. (1) Cutting pre-pregs at the neat size of the final sample (30
According to the choice of the resin dispersion method, the mm × 90 mm), with the relevant orientation of 0°, 45°,
nanoscale dispersion appeared difficult to achieve. Therefore, or 90°.
the electrode layout was scaled up to a millimeter scale with (2) Stacking of the pre-preg pieces in the quasi-isotropic
larger electrode fingers (we) and larger finger spacing (s). Also, order (Figure 1).
s should be minimized compared to w which should be (3) Deposition of the conductive resin using jet printing.
maximized. The electrode is placed/printed at the center of the (4) Finishing the laminate with the last eighth ply on which
length of the sample, and the length of the electrode is limited the piezoelectric FibroTend had already been deposited
to fit with the span of the upper clamping fixtures used for via electrospinning, as shown in Figure 3. This ply must
applying the mechanical load. This condition is required to be integrated with the layer of piezoelectric nanofibers
ensure that the electrode is not damaged because of the directly in contact with the electrode to have a close
introduction of localized stress from the fixtures in contact with electrical circuit.
the sample. Therefore, the dimensions of the sample were
reviewed for the specific purpose of integrating with the
composite laminate and recommended as below (shown in
Figure 2).

Figure 3. Eighth ply, Hexply M21 carbon composite (45°) with

PVDF FibroTend nanofibers on top (0°).

Figure 2. Schematic of the scaled-up IDE electrode layout for

(5) All samples were placed and layed up with the
composite integration. FibroTend layer on top for autoclave processing. In
addition of the required release films for vacuum-
bagging, a metal plate was placed on top of the samples
to ensure uniform pressurization during the curing
The width of the sample was increased to 30 mm with the process. Standard curing cycle as specified in the Hexply
electrode width w of 20 mm. The electrode finger width we was specifications45 (shown in Figure 5) was conducted.
set at 1.5 mm and the spacing between the fingers to 3 mm. Hexcel provides two standard curing cycles for laminates
This scale-up led to the following ratios: we/hp = 12 and w/s =
composed of Hexply M21 T700 CF−epoxy pre-preg
6.67.
having thicknesses of <15 mm: one with a heat-up rate
2.3.2. Conductive Resin. Graphene was supplied in a
powder form by Cambridge Nanosystems (Table 1) for mixing at 1 °C/min and a second at 3 °C/min. The curing cycle
the powder into the epoxy resin. Therefore, the laboratory risk with a heat-up rate of 1 °C/min was selected for this
assessment imposed a use limited to 1 g of powder. It has been study so as to limit the flow of the conductive electrode
shown that the increasing weight percentage of graphene in the resin. Viscosity and the resin flow decrease with the
resin has an increasing effect on the electrical conductivity of duration, whereas temperature constantly increases. The
the resin. Several studies with different polymer and graphene trend in viscosity changes after 100 min according to the
types show a similar specific trend: conductivity increases Hexply specifications, that is, it embarks on a sharp
significantly with graphene content up to reaching a threshold increase with time. A lower heat-up rate enables to
circa 2 wt % graphene filler.48 moderate the viscosity drop until the resin reticulates for
8894 DOI: 10.1021/acsomega.8b00940
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ACS Omega Article

times <100 min and thus significantly reduces the

chance of high resin flow and thus short circuits in the
IDE layout.
To assess the influence of the laminate modification (i.e.,
addition of a FibroTend layer and an electrode), eight
additional samples were also manufactured with no Fibro-
Tend-IDE layer. These samples are referred to as reference
samples in this paper.
2.5. Characterization of PVDF Materials. Scanning
electron microscopy (SEM), energy dispersive X-ray spectros-
copy (EDXS), X-ray diffraction (XRD), and Fourier transform
infrared (FTIR) spectroscopy characterization techniques were
used for analysis of the morphology and crystal phases of five
categories of samples, which are labeled and tabulated in Table
2.

Table 2. Five Categories of PVDFs Used for Morphological

Analysis and Phase Characterization Figure 4. SEM images of (a) PVDF raw powder, (b) Finetex, (c)
FibroTend 1, and (d) FibroTend 2.
# name description
1 FibroTend 1 electrospun oriented PVDF fibers stretched to 100 mm significant variation in the thickness of the fibers can also be
(+25%) and twisted into a bundle observed, as well as no overall trend in orientation as shown in
2 FibroTend 2 electrospun oriented PVDF fibers stretched to 320 mm Figure 4b. The FibroTend 1 bundled fiber sample (stretched
(+300%) and twisted into a bundle
3 FibroTend 3 electrospun oriented PVDF fibers stretched to 320 mm
by 100 mm, 25%) showed different fiber sizes (Figure 4c), with
(+300%) and deposited on an aluminum foil many in excess of 2 μm in diameter (average diameter ≈ 2.3
(highly oriented) 1.2 gsm μm). The FibroTend 2 sample (stretched by 320 mm, 300%)
4 PVDF powder neat PVDF powder Solvay Solef 6020/1001 clearly showed significantly more damaged and broken fibers
5 Finetex unaligned mat of electrospun PVDF fibers, 8.5 gsm (Figure 4d), resulting from those that did not survive the
stretching electrospinning process. At present, there is no
2.6. Postmanufacturing Analysis. The integrated mechanism for removing these fibers, but as can be seen in
laminates were also analyzed after manufacturing using the Figure 4d, they pose a relatively minor surface contamination
characterization techniques described above. The objectives compared to the bulk of the sample. The average fiber
were to understand the IDE pattern localization, the diameter was expectedly lower (<1.5 μm) for the stretched
FibroTend piezoelectric characteristics after curing, the sample FibroTend 2 than for FibroTend 1.
electrical capability of the cured graphene−epoxy resin, and The FibroTend samples were significantly thicker than the
the effects of such multimaterial integration taken in this study fibers observed from the Finetex sample. Also, because of the
on the mechanical properties. Pulsed thermography, ultrasonic bundled nature of the samples supplied by Munro Technology
C-scanning, XRD, FTIR spectroscopy, and electrical resistance Limited, it was not possible to observe the overall trends in
testing were used for post integration stage of the study. fiber alignment.
3.1.2. Energy Dispersive X-ray Spectroscopy. EDXS spectra
3. RESULTS AND DISCUSSION were collected from the PVDF powder, Finetex, and
3.1. Raw Material Characterization. This section FibroTend 1 and 2, and analysis was performed multiple
presents data from the characterization and microscopy times per sample to generate a robust statistical distribution.
techniques described in section 2. Four techniques were used FibroTend 3 was processed precisely identical to FibroTend 2,
for the morphology analysis and crystal-phase characterization. however, on an aluminum substrate and thus was not
FEI/Philips XL30 SEM was used to visually analyze the characterized. Results from the powder indicated a carbon:-
sample quality, homogeneity, and morphology. Estimation of fluorine ratio of between 4:1 and 2:1, indicating significant
the contamination level and composition was also carried out sample contamination, as the expected result was a 1:1 ratio of
using EDXS in the scanning electron microscope. Samples for carbon to fluorine (PVDF unit cell is −C2F2H2−). Finetex
such measurements were vacuumed at 25 °C and gold-coated gave a C/F ratio of 56.5:43.5 based on a relatively large area
on the surface by an approx. 5−10 nm thickness layer. X-ray scan, much closer to the expected values. However, looking at
measurements were carried out using a Siemens D5005 X-ray relatively small areas gave much lower values for fluorine
diffractometer to determine the piezoelectric phases. The content, as low as 15%. That might be explained by a higher
samples for such a measurement were different in size and detection of the carbon tape on which the Finetex is stuck
shape according to Table 2; however, all samples were cleaned depending on the sample regions studied (sign of inhomoge-
off under vacuum for 30 min. FTIR spectroscopy was also neity of the mat porosity). Spectroscopy of the FibroTend
carried out using Jacson FTIR 6200ATR ZnSe, and the fibers (1 and 2) resulted in a wide range of results across the
samples were treated under vacuum for 5 min each. sample, ranging from 10 to 50%, indicating a wide margin of
3.1.1. Scanning Electron Microscopy. Powder sample error, perhaps resulting from thin material samples, or
exhibited a homogeneous sphere size with average diameter contamination resulting from handling of the fibers.
of approximately 100 μm, as shown in Figure 4a. The Finetex The disparity between small-scale and large-area measure-
sample showed an unaligned mat of fibers (Figure 4b), with ments indicated that in certain areas of the fiber, carbon-based
average fiber diameter of ∼150 nm. Some beading and contamination has occurred to increase the apparent
8895 DOI: 10.1021/acsomega.8b00940
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ACS Omega Article

percentage of carbon observed. This contamination can come

from the manufacturing process, manipulation, and detection
of the carbon tape on which the sample is stuck for being
analyzed. As no sample exceeded a fluorine ratio of 50%, it can
be assumed that this is an accurate assumption. No peak that
could be attributed to any other atomic element than carbon,
fluorine, or gold (coating) was identified. In particular, no
nitrogen was observed in any of the spectra of the prepared
fibers, indicating that a negligible amount of solvent was
present.
3.1.3. X-ray Diffraction. For determination of the PVDF
phase present in the material, an XRD analysis was carried Figure 6. XRD phase spectrums of three forms of analyzed PVDF,
out.49−52 Figure 5 depicts a typical XRD patterns of the three ranging from 14° to 42°.
α, β, and γ phases in a PVDF material, with both peak angles
and (hkl) planes.52 implies that the level of electrospinning stretching between
+25 and +300% leads to the same crystal composition.
It can be noticed that some peaks are particularly distinct
(high and sharp), whereas others are broader. When a peak is
broad, it is difficult to associate a single value of angle, as in
such cases, the uncertainty of the spectrum reading and the
inaccuracy of the conclusion increases. From these three
graphs, Table 3 can be extracted. It gathers 2θ angles
associated with the peaks observed from each spectrum.
They are sorted by the PVDF phase they represent.

Table 3. Summary of XRD Phase Results for PVDF Powder,

Finetex, and FibroTend
Figure 5. XRD patterns of the three α, β, and γ phases, with both sample angle (2θ, deg) crystal phase associated
peak angles and (hkl) planes.52 powder 17.9, (20.1), 26.5, 26.8, 36, 39.1 Α
Β
18.5, 20.1, 26.8, 38.6 Γ
Finetex Α
Before analyzing the spectrums in details, it is necessary to 20.8, 36.5 Β
highlight a technical limitation of performing XRD on PVDF Γ
FibroTend nanofibers provided. The amount of material FibroTend (20.1) Α
required to produce a valid data is hardly compatible with 20.3 Β
the nanoscale of the fibers. Therefore, the following procedure 20.2 γ
was employed:
• Powder: sufficient amount of the material and reliable Because the reliable quality of the powder spectrum, it can
method. Reliable data were obtained. be concluded that it is composed of α and/or β phases. Some
• Finetex: after several attempts, a full A4 sheet of PVDF characteristic peaks from those two phases (at 20.1° and 26.8°)
has been folded and stuck on a glass holder. The result is are very close to each other, which leads to an ambiguous
acceptable. However, a higher uncertainty of the reading of the spectrum. Regarding Finetex and FibroTend,
measurement should be taken into account because of spectrums are poor; only few peaks on each spectrum can be
the less dense sample (it is difficult to compress the analyzed. In addition, these peaks are really broad, which does
folded sheet). not allow us to conclude with a high certainty that both
• FibroTend 1, 2, and 3: a full A4 amount of PVDF samples made of the stretched fibers are composed of the β
nanofiber has been doubled and folded on a glass holder. crystal phase. In the Finetex spectrum, only β phase
The quality of the measurement is similar to that of the characteristic peaks (20.8° and 36.5°) seem to fit with the
Finetex. peaks obtained. Thus, the PVDF sheet must be mainly
Fibers could have been grinded into powder; however, the composed of β crystal phase. For FibroTend, the result is less
risk of the phase change was likely. Therefore, this option was apparent. The single broad peak obtained can be associated
not considered. For the three types of PVDF samples, the with the three crystal phases (20.1°, 20.3°, and 20.2°). No
spectrum obtained presented a similar structure: significant certain conclusion can be made from this spectrum.
(high intensity) peaks between 17° and 23°, limited (medium The three XRD spectrums are not sufficiently reliable to
intensity) peaks between 24° and 41°, and a flat and status on the crystal phase composition of PVDF powder,
nonsignificant (low intensity) shape elsewhere, as displayed Finetex, and FibroTend. Therefore, further characterization
in Figure 6. The measurement was carried out from 10° to 60°, was carried out. Using a second analytical technique such as
but only a magnified view between 14° and 42° is presented Raman spectroscopy or FTIR spectroscopy technique would
for readability of the report. Note that FibroTend 1 and 2 allow us to remove the doubt on powder (α and/or γ) and
spectrums are not displayed in the figure as no significant FibroTend (β and/or α) phase composition and confirm the β
difference can be identified with the FibroTend 3 spectrum. It phase composition of Finetex. Also, unlikely to XRD phase
8896 DOI: 10.1021/acsomega.8b00940
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ACS Omega Article

analysis, an interest of the FTIR analysis is to be quantitative. It the powder composition (initial raw material) with the highly
enables us to understand better the proportion of each phase stretched, processed fibers (e.g., FibroTend 3). Previously, the
within the material. XRD results in Figure 6 and Table 3 showed that the level of
3.1.4. FTIR Spectroscopy. FTIR wavenumbers (cm−1) electrospinning stretching between +25% (FibroTend 1) and
analyzed in some previous studies for PVDF material are +300% (FibroTend 2, 3) leads to the same crystal
studied.44,50,51,53−55 The absorbance band 840 cm−1 can be composition. This has also been stressed herein by the FTIR
associated to both β and γ phases because of their really close data. Table 4 tabulates each spectrum wavenumbers in
vibrational frequencies. However, a shoulder of the 840 cm−1 association with the peaks observed.
peak at 833 cm−1 can be observed for the γ phase only.50 To
distinguish more clearly those two β and γ phases, further Table 4. Summary of FTIR Results for PVDF Powder,
comparisons should be considered such as peaks at 1275 cm−1 Finetex, and FibroTend 3
(for β) and 1234 cm−1 (for γ), which are specific to each
phase. In Figure 7, the most interesting characteristic peaks for PVDF phase
sample wavenumber (cm−1) associated
distinguishing α, β, and γ crystal phases are displayed.
PVDF powder 613, 760, 855, 975, 1207, 1383 Α
(846), (1275) Β
(846) Γ
Finetex (976), (618) Α
840, 1175, 1275 Β
840, 1175 Γ
FibroTend 3 Α
(747), 838, 1168, 1273, Β
(815), 840, 1175, (1236) Γ

To conclude, the PVDF powder is mainly composed of α

phase, with some potential traces of β and γ phases. This is in
agreement with the XRD results, so the powder crystal
Figure 7. Comparison of FTIR spectrums for α, β, and γ PVDF composition can be considered as confirmed and reliable for
crystal phases.50 further studies. Finetex spectrum displays two peaks (840 and
1175 cm−1), which are common to both β and γ phases.
The five experimental spectrums obtained present similar However, there is a distinct peak at 1275 cm−1 and no peak at
overall spectrums. Figure 8 displays the FTIR attenuated total 1234 cm−1, which are corresponding to the singular peaks
distinguishing the β phase from the γ phase. This leads to the
conclusion in agreement with the XRD results that the Finetex
sample is mainly composed of the β crystal phase. Regarding
the FibroTend, many peaks corresponds to β or γ phases.
However, β peaks are more dominant (higher than the other
representative peaks and more distinct). Therefore, it can be
considered that the FibroTend fibers are mainly composed of β
phase, though some γ phase is remaining. These results from
XRD and FTIR spectroscopy are logical with the manufactur-
ing process that the PVDF powder, Finetex, and FibroTend
undergo and are schematically shown in Figure 9.
FibroTend was stretched up to an average fiber diameter of
∼1.5 μm, whereas Finetex was stretched up to ∼150 nm. The
α phase is the easiest to produce and the most chemically
Figure 8. FTIR spectrums of the five forms of PVDF analyzed,
stable and inert phase, which is a strong interest for
selected range from 550 to 1450 cm−1.

reflectance ZnSe spectrums of the five forms of PVDF

analyzed. Most of the peaks are between 550 and 1450
cm−1. Below 550 cm−1, the quality of the measurement is too
dependent on the device, which makes it unreliable. Above
1450 cm−1, all spectrums are flat with limited peaks.
It can be observed that the trend in the appearance of the
peaks is the same for the five spectrums. However, the powder
spectrum seems slightly different to the other four, with some
peak shifts (around 870, 1070, or 1180 cm−1) and higher
additional peaks at approx. 612, 760, 795, 1207, or 1384 cm−1.
The powder is the raw material and has not been stretched Figure 9. PVDF crystal phases related to electrospinning process; *in
unlike the other samples. To understand better the impact of the case of FibroTend electrospinning PVDF powder was diluted in
electrospinning on the PVDF phase, it is required to compare DMF.

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commercialization purpose of raw PVDF powder. The β phase

can be achieved after mechanical stretching, such as electro-
spinning. This process stretches and aligns polymer fibers and
leads to a reorganization of the polymer chain. Both Finetex
and FibroTend are mainly composed of this process. The γ
phase remains from the dissolution of the raw PVDF powder
into dimethylformamide (DMF), preliminary of the electro-
spinning. The efficiency of the process is not 100%, which
justifies why not all of the material is made of β phase and
explains the lower traces of γ phase remaining in Finetex.
3.2. Postprocessed Material Characterization. Once
composite pre-pregs, PVDF, and the conductive IDE layer
were layed up, the laminate was cured to integrate the layers. A Figure 11. FTIR spectrums of both modified and reference composite
new set of XRD and FTIR analysis was then carried out to laminates.
understand the impact of the curing parameters (temperature,
duration, and pressure) on the PVDF crystal phase and to
identify any piezoelectric remnant phases as curing-linked PVDF FibroTend crystal phase. A new set of experimentations
modification of the phases may lead to reduction of will be highly valuable to understand better the impact of the
piezoelectricity capability. curing features on the PVDF piezoelectric crystal phase, and
3.2.1. X-ray Diffraction. XRD phase analysis on the also, samples with a thicker FibroTend layer may provide a
integrated composite laminates was carried out. However, for clearer spectrum.
this study, the FibroTend layer embedded between composite 3.2.3. Electrical Resistance Characterization. Even though
plies (having had ∼200 μm thickness) was too thin (∼250 the conductive resin from the IDE layout has flown during the
nm) and the amount of material was not sufficient for processing, an electrical resistance was able to be measured,
determining the crystal phase. As seen in Figure 10, no peak using a coarse range of 1−100 MΩ. The resistivity was
approximately 2.5−35 MΩ comparable to that of the layer
cured for initial trials outside the laminate. This clearly shows
that there is either no or slight short circuit because of resin
flow or contact with carbon fibers during laminate embedment
and curing. The IDE design recommendations in section 2.3
were then able to efficiently enable internal conductive layer
embedment. As aforementioned, such an embedment technol-
ogy is highly advantageous and superior to current state-of-the-
arts as the conductive nanoparticles have been distributed
inside a thermoset polymer resin which is identical to the
polymer matrix of the composite. Such a similarity should
provide enhanced structural integrity via avoiding bond
degradation due to material mismatch. NDI and mechanical
testing have followed the manufacturing step to investigate the
enhancements. The following sections presents their results.
Figure 10. XRD spectrums of both modified and reference composite
laminates. 4. NDI DATA
The NDI data are presented in this section only for the
previously observed with the raw PVDF material (Figure 6) composite laminates post cure, the two types of integrated
was detected. Figure 10 shows that the integrated and the laminate (internally embedded with PVDF-conductive layers)
reference (with no PVDF-IDE layers) samples have similar and the reference laminate (only carbon composite pre-pregs).
spectrums. This confirms that only the main laminate structure NDI was carried out on the samples prior to mechanical
(carbon fiber and epoxy resin) contributes to the detections. A testing.
slight increase (∼3%) of the main peak (around 25.5°) was 4.1. Pulsed Thermography. Two types of comparisons
observed for the integrated sample. This is due to the detection were achieved with the two samples:
of graphene present in the conductive resin forming the
conductive layer.56,57 1. On the integrated sample, comparison of a region with
3.2.2. FTIR Spectroscopy. FTIR spectroscopy was per- the central conductive resin and a region without it (at
formed on the integrated and reference samples. Similar to samples runways/corners) and
XRD results, no characteristic peak previously seen with the 2. comparison between samples with and without
PVDF raw material (Figure 8) can be observed on the FibroTend-conductive layers.
integrated sample spectrum, displayed in Figure 11. Also, no The pulsed thermography examinations showed that the
significant difference can be observed between the integrated thermal diffusivity behavior is different in regions containing or
and reference sample spectrums, except a lower intensity of the not containing the conductive resin, within a sample
integrated sample spectrum. This attributes to the presence of containing the FibroTend layer (Figure 12). This is due to a
additional conductive resin absorbing energy provided for the difference in thermal conductivity of the two samples linked to
analysis, which lessen the output energy detected. the presence of graphene nanomaterials, which in this case is
To conclude, postmanufacturing material characterization enhanced by the conductive resin (Figure 13). The difference
with XRD and FTIR techniques did not allow us to identify the can be distinguished clearly in figures showing the 1st and 2nd
8898 DOI: 10.1021/acsomega.8b00940
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Figure 14. Image of transmission contrast of the reference sample.

Figure 12. Thermal decay contours at 2 seconds post flashing of the

samples: (a) reference sample and (b) integrated laminate sample
(with FibroTend-conductive layer) (dimensions of the sample: 30 ×
90 mm). Figure 15. Image of transmission contrast of the integrated sample
(width of samples: 30 mm).
derivatives of the thermal decay behavior (Figures 13c,d and
14), respectively, representing the rate and acceleration of the element composing the sample, for example, carbon and
decay with respect to time. This qualitative analysis is to graphene.58 This comparison highlights a difference in the
highlight that flash thermography may be interesting to assess composition between the two samples, that is, depending on
the quality of the manufacturing (e.g., curing state) based on the composition of the laminate, the intensity of the image can
the NDI response of the rein-based electrode layout. vary.
4.2. Ultrasonic C-Scanning. Figures 14 and 15 show
ultrasound C-scanning images of the reference and integrated 5. EFFECT ON THE MECHANICAL PROPERTIES
samples, respectively. Results for all samples per each type The samples were tested mechanically post NDI using
were consistent. Therefore, one representative sample per each standard four-point bend testing.59 The integrated samples
type only is shown below. were not symmetric because of the presence of eccentric
The contrast in Figure 14 is not as high as that in Figure 15, PVDF-conductive layers (Figure 1). Therefore, two sets of
where the conductive layer is present in the integrated experiments were carried out considering the two dissimilar
laminate. The right edge in both samples and two left corners sides of the sample:
in the integrated laminate show high contrast which attributes
to the carbon composite pre-preg been bent damaged during • Five integrated samples were tested with the FibroTend
manufacturing. Transmission in Figure 14 is within a 40−85% facing up (maximum strain on FibroTend).
range, whereas in Figure 15, the transmission rises up to 100%, • Five integrated samples were tested with the FibroTend
especially in the central region encompassing the conductive facing down (minimum strain on FibroTend).
layer. According to the literature, epoxy resin has a high For the reference samples, even though the composition was
transmission coefficient (0.955) compared to any other symmetric, the manufacturing-induced defects can be consid-

Figure 13. Evolution of thermal decay with time at center and corner of the samples for (a) reference sample, (b) integrated laminate sample (with
FibroTend-conductive layer), (c) 1st derivative of thermal decay for both samples, and (d) 2nd derivative of thermal decay for both samples.

8899 DOI: 10.1021/acsomega.8b00940

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ered that may induce slight unsymmetrical properties, for integrated samples with FibroTend and the conductive layer
example, the downside of the laminate is not directly exposed show advantageous bending properties in terms of failure load
to heat during curing as it is laid on the table/fixture of the when facing down and disadvantageous ones when facing up,
oven, and heat is mainly reached via conductivity from the compared to their respective reference samples. However,
exposed faces of the sample. Thus, on the same principle, whatever the side of testing (either facing up or down), the
samples were tested faced up and samples faced down to integrated samples fail at a lower deflection than that for the
provide a comparative study. For all samples, the load- reference samples. Also, it can be seen that the difference of
deflection curves were extracted. Figure 16 shows typical maximal deflection is more important between the integrated
and reference samples when samples are facing down than
when they are facing up. This attributes to the maximal strain
occurring in the sample at the outer surface undergoing tensile
stresses, opposite to the loading pin surface, as epoxies are
more susceptible to tensile damage than compressive.
However, it has been shown in the literature that sudden
drop points in lateral loading (such as that in four-point bend
tests) corresponds to extensive interlaminar delamination
occurring between internal layers (herein composite plies).60
When the FibroTend layer was on the outer side (facing
floor), this additional polymer layer associated with conductive
resin played a more important role. It confirms that the
FibroTend and/or the graphene−epoxy resin are a disadvant-
age for the laminate properties in terms of maximal deflection.
Figure 16. Typical four-point bending load-deflection curve for This observation is supported by the visual assessment of the
reference samples. samples after failure. The modified samples facing floor always
delaminate and break at the FibroTend layer interface.
results for the reference samples. The tests were proven Thus, it can be concluded that the FibroTend layer and, in
consistent via providing repeatable data. For each sample, a particular, the conductive resin addition
maximal load followed by a sudden drop corresponding to the • decreases the maximal deflection achievable,
occurrence of macroscopic interlaminar delamination damage • increases the failure load when located at the outer face
was observed (highlighted within a red circle in the figure).
(facing floor), and
Data at such point are presented in Figure 17 for the integrated
• decreases the failure load when located at the inner face
(facing ceiling).
It can be assumed that the conductive resin plays a larger
role than the FibroTend layer for decreasing the mechanical
properties of the laminate. The conductive epoxy has minor
mechanical strength compared to the PVDF nanofibers and its
volume fraction is more important than the 0.2 gsm of
FibroTend embedded. Thus, a reduction of the conductive
resin quantity used for the IDE would be of interest in terms of
both the IDE manufacturing as detailed in Design of the IDE
Layout for Composite Integration section as well in ensuring
satisfying mechanical properties. Nevertheless, because of the
significant standard deviation of the results, a larger campaign
of mechanical testing would be of interest to confirm these
observations.
Figure 17. Average load vs deflection values obtained with four-point This first mechanical testing in this study allows us to raise a
bending test. crucial topic: to what extend the FibroTend layer and the
conductive resin play a mechanical role in the flexural
and referenced samples faced up and down. Facing up and toughness of the laminate: delamination, bonding, interlaminar
down did not give any definite conclusions for the load- shear, and failure propagation mode are as many points of
carrying capacity in bending as the load was higher for the interest for a further work. Independent of the electrical aspect
faced-down integrated samples and vice versa for the reference of the targeted health monitoring in this study, the additional
ones. However, faced-down samples exhibited higher de- elements within the laminate must not reduce significantly the
flection. mechanical performances. If due to health monitoring, the
Even if the standard deviations are not negligible, a general mechanical performances of the laminates are less advanta-
tendency can be observed. The orientation of the sample geous, their use might be questioned at the material selection
seemed to significantly influence the flexural behavior. Samples step of the structure design.
facing down reached a maximal deflection around 8−9 mm,
whereas samples facing up (as depicted in Figure 1) reached a 6. CONCLUSIONS
higher range around 11−12 mm. This difference may be This research highlights the importance of requiring new
explained by the manufacturing parameters such as the process cycles for addition of internal piezoelectric capability
aforementioned nonsymmetric curing. The unsymmetrical and conductive layers. It proposes to use a polymer system for
8900 DOI: 10.1021/acsomega.8b00940
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nanotubes/poly(ε-caprolactone) composite vapour sensors. Carbon
AUTHOR INFORMATION 2009, 47, 1930−1942.
(16) Castro, M.; Kumar, B.; Feller, J. F.; Haddi, Z.; Amari, A.;
Corresponding Authors Bouchikhi, B. Novel e-nose for the discrimination of volatile organic
*E-mail: Vijay.Kumar@cranfield.ac.uk (V.K.T.). biomarkers with an array of carbon nanotubes (CNT) conductive
*E-mail: h.yazdani-nezhad@cranfield.ac.uk (H.Y.N.). polymer nanocomposites (CPC) sensors. Sens. Actuators, B 2011, 159,
ORCID 213−219.
Vijay Kumar Thakur: 0000-0002-0790-2264 (17) Zhang, Y.-C.; Dai, K.; Pang, H.; Luo, Q.-J.; Li, Z.-M.; Zhang,
W.-Q. Temperature and time dependence of electrical resistivity in an
Notes anisotropically conductive polymer composite with in situ conductive
The authors declare no competing financial interest.

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microfibrils. J. Appl. Polym. Sci. 2012, 124, 1808−1814.
(18) Rybak, A.; Boiteux, G.; Melis, F.; Seytre, G. Conductive
ACKNOWLEDGMENTS polymer composites based on metallic nanofiller as smart materials for
The authors would like to acknowledge the UK EPSRC funded current limiting devices. Compos. Sci. Technol. 2010, 70, 410−416.
projects, STRAINcomp (ref. no. EP/R016828/1) and (19) Patel, I.; Siores, E.; Shah, T. Utilisation of smart polymers and
CAMREG (ref. no. EP/P007805/1). The authors would also ceramic based piezoelectric materials for scavenging wasted energy.
Sens. Actuators, A 2010, 159, 213−218.
like to thank supports from FGV Cambridge Nanosystems Ltd. (20) Zhou, Y.; Han, S.-T.; Roy, V. Nanocomposite Dielectric
and Munro Technology Ltd.

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8902 DOI: 10.1021/acsomega.8b00940

ACS Omega 2018, 3, 8891−8902