applied
sciences
Article
Multifunctional MEN-Doped Adhesives: Strengthening, Bond
Quality Evaluation, and Variations in Magnetic Signal with
Environmental Exposure
Juliette Dubon 1 , Gonzalo Seisdedos 1 , Dillon Watring 1 , Mauricio Pajon 1 , Sakhrat Khizroev 2 , Dwayne McDaniel 1
and Benjamin Boesl 1, *
Citation: Dubon, J.; Seisdedos, G.;
Watring, D.; Pajon, M.; Khizroev, S.;
McDaniel, D.; Boesl, B.
Multifunctional MEN-Doped
Adhesives: Strengthening, Bond
Quality Evaluation, and Variations in
Magnetic Signal with Environmental
Exposure. Appl. Sci. 2022, 12, 8238.
https://doi.org/10.3390/
app12168238
Academic Editor: Stefano Invernizzi
Received: 30 June 2022
Accepted: 15 August 2022
Published: 17 August 2022
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Copyright: © 2022 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
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Attribution (CC BY) license (https://
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4.0/).
Appl. Sci. 2022, 12, 8238. https://doi.org/10.3390/app12168238
1 Mechanical and Materials Engineering Department, Florida International University, Miami, FL 33199, USA
2 Department of Electrical and Computer Engineering, University of Miami, Coral Gables, FL 33146, USA
* Correspondence: bboesl@fiu.edu
Featured Application: Non-destructive evaluation of bond quality using magneto-electric nanoparticles.
Abstract: Adhesive bonding of polymer matrix composites offers various advantages over traditional
fasteners, such as a uniform stress state, reduced weight, and delay of composite delamination.
However, adhesive bonding has limited implementation due to challenges in the prediction of
durability. This work introduces a new method to monitor an adhesively bonded composite joint
by dispersing magneto-electric nanoparticles (MENs) into the polymer precursor and monitoring
changes in their surface charge density by evaluating the output magnetic signal under an applied
magnetic field. Real-time monitoring of the curing process of a polymer adhesive was performed and
corroborated via thermal analysis and mechanical testing. Lap shear and end notch flexure testing
showed that adding 1 vol% MENs led to a ~23% increase in shear strength and a ~12% increase in
mode II critical energy release rates compared to the undoped adhesive. Adding 5 vol% MENs also
increased the adhesive’s peak tensile stress by ~8%. Strengthening mechanisms of the doped adhesive
were monitored using in situ electron microscopy. A correlation between water ingression and a
change in the magnetic moment was observed. Results show the MENs’ potential as a structural
health-monitoring tool for a wide range of materials and applications.
Keywords: composites; adhesive bonding; non-destructive testing; magneto-electric nanoparticles
1. Introduction
Polymer matrix composites (PMCs) have shown improved properties over traditional
structural materials, especially weight-normalized properties, such as specific strength and
stiffness [1]. While known for some time, the implementation of PMCs as structural materi-
als is limited by complications in joining complex geometries [2]. Currently, the bonding
of composite panels is completed primarily through the use of mechanical fasteners [3].
However, while their use can create a robust joint with the potential to compartmentalize
crack growth, the process of drilling holes in a laminate remains a consistent challenge. For
example, drilling in a PMC can create edge effects, leading to delamination and interlami-
nar failure, and also create locations of stress concentrations [3]. Furthermore, traditional
mechanical fasteners are mainly manufactured from high-density metals, adding signifi-
cant weight and complexity (possible issues with corrosion, etc.) [4]. Over-design of the
composite panel is often necessary to compensate for these factors, leading to a loss in the
overall efficiency [4].
One solution that could mitigate the issues associated with mechanical fasteners is to
use adhesively bonded composite joints (ABCJs). Adhesive bonds offer the potential to join
complex geometries at a fraction of the weight, simplifying a challenging problem. The
implementation of this type of bond also allows for an improved distribution, eliminates the
https://www.mdpi.com/journal/applsci
 etc.) [4]. Over-design of the composite panel is often necessary to compensate for these
factors, leading to a loss in the overall efficiency [4].
One solution that could mitigate the issues associated with mechanical fasteners is to
Appl. Sci. 2022, 12, 8238 use adhesively bonded composite joints (ABCJs). Adhesive bonds offer the potential to
2 of 11
join complex geometries at a fraction of the weight, simplifying a challenging problem.
The implementation of this type of bond also allows for an improved distribution, elimi-
nates the corrosion occurring in metallic fasteners, and reduces the number of parts of the
corrosion occurring in metallic fasteners, and reduces the number of parts of the structure.
structure. While the potential is vast, the current Federal Aviation Administration certifi-
While the potential is vast, the current Federal Aviation Administration certification requires
cation requires a demonstration that every bond used on a primary structure maintains
a demonstration that every bond used on a primary structure maintains integrity over
integrity over the expected aircraft life cycle [5]. The motivation behind this restriction is
the expected aircraft life cycle [5]. The motivation behind this restriction is that unlike
that unlike mechanical fasteners, adhesive bonds cannot act to delay damage propagation,
mechanical fasteners, adhesive bonds cannot act to delay damage propagation, potentially
potentially leading to large-scale catastrophic failure [6]. Therefore, to increase the scope
leading to large-scale catastrophic failure [6]. Therefore, to increase the scope of PMC usage,
of PMC usage, a robust and exhaustive structural health-monitoring (SHM) tool must be
a robust and exhaustive structural health-monitoring (SHM) tool must be developed to
developed to evaluate the quality of ABCJs without reliance on the initiation of damage
evaluate the quality of ABCJs without reliance on the initiation of damage in the bond [6].
in the bond [6]. The method should advance beyond the current structural health-moni-
The method should advance beyond the current structural health-monitoring methods
toringasmethods
(such an E/M(such as an E/M
impedance and impedance and wave
wave propagation propagation
approach approach
[7], acoustic and[7], acoustic
ultrasonic
and ultrasonic methods [8], and terrestrial laser scanning [9]) that are
methods [8], and terrestrial laser scanning [9]) that are limited in resolution and scope and limited in resolution
and on
rely scope and rely
damage on damage initiation.
initiation.
In this work, the dispersal and
In this work, the dispersal and integration
integration of of magneto-electric
magneto-electric nanoparticles
nanoparticles (MENs)(MENs)
into an
into an adhesive
adhesive resin resin was
wasused usedtotomonitor
monitorthe thequality
quality of of
a polymer
a polymer adhesive
adhesive whenwhen ex-
posed to an accelerated temperature and a moisture
exposed to an accelerated temperature and a moisture environment. Monitoring wasenvironment. Monitoring was
achieved through
achieved through aa coupling
coupling of of magnetostriction
magnetostriction and and piezoelectricity
piezoelectricity in in the
the MENs
MENs [10].[10].
This consists in having an electric polarization when a magnetic
This consists in having an electric polarization when a magnetic field is applied, while field is applied, while
obtaining magnetic
obtaining magnetic polarization
polarization when when an anelectric
electricfield
fieldisisapplied.
applied.A A schematic
schematic of this
of thisre-
lationship is is
relationship shown
shown in in
Figure
Figure 1. As
1. aAs
result, the dipole
a result, surface
the dipole charge
surface density
charge of theof
density parti-
the
cle induced
particle inducedan electric
an electricfield, which
field, whichcaused
caused a achange
changeininmagnetization
magnetization that that was detected
was detected
using standard
using standard magnetometry
magnetometry techniques
techniques [11].
[11]. The
The variation
variation in in the
the obtained
obtained magnetic
magnetic
moment
moment was associated with the history of the environmental exposure
associated with the history of the environmental exposure of the bond. of the bond. The
integration of MENs also provided a multifunctional effect,
The integration of MENs also provided a multifunctional effect, leading to improved leading to improved shear,
tensile,tensile,
shear, and flexural performance
and flexural over theover
performance unfilled adhesive.
the unfilled Additionally,
adhesive. the strength-
Additionally, the
ening of the adhesive
strengthening of the adhesivedue todue doping was was
to doping investigated
investigated using in situ
using in situmicroscopy
microscopy andanda
ananocomposite
nanocompositetoughening
tougheningmodel. model.The Thechanges
changesin in the
the surface
surface charge density of MENs MENs
were also
were also used
used to tonon-destructively
non-destructively evaluate
evaluate thethe curing
curing process
process of of the
theadhesive.
adhesive. In In the
the
past, MENs
past, MENs have
have been been used
used forfor optical
optical and
and magnetic
magnetic applications
applications [12,13]
[12,13] and and asas materials
materials
for biomedicine
for biomedicine and and drug
drug delivery
delivery [14–16],
[14–16], but
but this
this is
is the
the first
first study
study to to investigate
investigate their
their
potential
potential asas aa multifunctional
multifunctional SHM SHM tool.
tool. Future
Future applications
applications of this this work
work couldcould lead
lead to to
SHM
SHM techniques
techniques that that can
can evaluate
evaluate thethe loading
loading history
history andand damage
damage state state (without
(without reliance
reliance
on
ondamage
damageinitiation)
initiation)for a broad
for a broad range of materials,
range of materials,loading types,
loading geometries,
types, geometries,magnitudes,
magni-
and applications.
tudes, and applications.

Figure1.1. Possible
Figure Possiblesample
sample loading
loading history
history influences
influences on theon the output
output magnetic
magnetic signal of signal of MEN-doped
MEN-doped adhesives.
adhesives.
2. Materials and Methods
The carbon fiber composite material selected to manufacture the lap shear and end
notch flexure (ENF) samples was a unidirectional prepreg material (T800H) from Toray.
Following ASTM D5868-01 [17] and ASTM D7905/7905M [18] standards for the manufac-
turing process, the lap shear specimens had a 12-layer layup process and the end notch
flexure specimens had a 10-layer layup process. A polyester peel ply was placed on both
sides of the prepreg layups to prepare the surface for bonding. An autoclave from Amer-
Appl. Sci. 2022, 12, 8238 3 of 11

ican Company Co. was used to cure the prepreg layup at a temperature of 177 ◦ C and
a pressure of 30 psi for 1 hour. The lap shear specimens were cut to a size of 25.4 mm
by 177.8 mm, with a bonded area of 25.4 mm by 25.4 mm, while ENF specimens were
manufactured to be 35 mm by 10 mm. The carbon fiber panels were bonded together
using 3M’s Scotch-Weld two-part epoxy adhesive EC 2615 B/A. A 2:1 resin-to-hardener
ratio was used. For the doped adhesive, MENs, synthesized to consist of a cobalt ferrite
(CoFe2 O4 ) core and barium titanate (BaTiO3 ) shell nanoparticles with a median diameter of
~30 nm [19], were hand-mixed into the hardener component of the epoxy at a 1% volume
concentration prior to curing. The fabrication and characterization of the MENs used in this
study has also been discussed previously [14,15]. Both ENF and lap shear specimens were
placed under vacuum during the adhesive cure in order to minimize void content. Next,
the same epoxy adhesive was used to manufacture the tensile-testing dog-bone samples.
The lap shear specimens were tested using the ASTM D5868-01 standard [17]. A tensile
tester from MTS (Criterion Model 43) was used to test the samples with a loading rate
of 13 mm/min. The dog-bone tensile-testing samples were tested at a rate of 5 mm/min
using the same MTS instrument using ASTM D638-03 [20]. ENF testing was performed
conforming to ASTM D7905/7905M [19] using an MTI Instruments SEM 1000 micro-load
frame in a three-point bend configuration. Testing was performed at a fixed displacement
rate of 0.5 mm/min. The supporting span was 50 mm, while the sample was 120 mm in
length and 3.5 mm in thickness and contained a 25 mm pre-crack. In situ ENF testing was
performed within the chamber of a JEOL JIB-4500 SEM/FIB under vacuum at a pressure of
1.4 × 10−4 Pa or below after Au coating the sample for 30 s. Uncertainty measurements
were obtained using the law of propagation of uncertainty [21]. To obtain the mode II
critical energy release rate, GIIC , in kJ/m2 of the ENF samples, Equation (1) was used as
follows [22]:
9a2 Pδ
GII = (1)
2β(2l 3 + 3a3 )
where a is the pre-crack in meters, P is the load in kN, δ is the displacement of the pre-crack,
β is the width of the ENF samples in meters, and l is the distance between the two bottom
points from the three-point bend test fixture, which is fixed at 0.0165 m.
To study the curing process of the 3M epoxy adhesive, three 8 × 8 × 4 mm samples
were manufactured containing 5 vol% of MENs. This volume percentage was used since
the manufacturing process with the resources available was time-consuming, but a higher
percentage than the previous 1% used for the lap shear and ENF samples was used to
obtain a higher signal using the B–H looper setup. The curing and testing process took
place in a laboratory environment at room temperature (~22 ◦ C). Signal measurements
during the curing process were taken every 2 hours using the B–H looper setup, which is
described later in this section.
Using the same adhesive, samples measuring 5 × 5 × 1 mm and containing 0, 5, 10,
and 15 vol% of MENs were placed in an environmental chamber at 95% relative humidity
and at an elevated temperature of 70 ◦ C. The magnetic signatures were taken prior to
environmental exposure. After a 4-week period, the samples were removed and again
scanned. All magnetic signatures were taken using a vibrating samples magnetometer,
which has a sensitivity of 0.01 µemu [23].
The adhesive’s glass transition temperature was obtained using a Q600 SDT from TA
Instruments to determine its evolution as a function of the curing time during the first
24 hours of curing. The tests were run from room temperature (~22 ◦ C) until 250 ◦ C at a
heating rate of 5 ◦ C/min. Argon gas was used for the testing.
To monitor the local physical properties of adhesives non-destructively and non-
invasively, the magnetic properties of MENs dispersed into these materials were evaluated
using a B–H looper setup. Specifically, this setup was used to characterize the local
properties of adhesive samples, adhesively bonded composite panels, and bonded mini
double-cantilever beam (DCB) samples. The principle of reciprocity states that local val-
Appl. Sci. 2022, 12, 8238 4 of 11

ues of the magnetic fields B and H are reflected by the system’s induced and applied
voltages, respectively.
The application of other techniques, such as vibrating sample magnetometry (VSM),
is limited since the sample needs to be attached to a piezo-actuator, thus requiring a
specific sample preparation. In contrast, the B–H looper setup allows for the evaluation
of the sample’s surface without physically damaging it. This setup takes advantage of
the magneto-electric effect to non-invasively evaluate magnetic signature differences at a
microenvironment level.
Based on the reciprocity principle, the electromotive force (EMF) or measured signal,
ε, in volts is obtained by using Equation (2) as follows:
R
n∆ϕ n∆ Himg M (r )dv
ε= = µ0 (2)
∆t ∆t
where ∆ϕ is the change in the magnetic flux in volt-seconds, ∆t is the change in time
in seconds, n is the number of turns in a coil, M(r) represents how the magnetization is
distributed throughout the sample, and Himg is the normalized reciprocal imaginary field
representing the geometry of the B–H setup.
It can be seen in the B–H looper setup in Figure 2 how it consists of a function generator
equipped in a lock-in amplifier and three different coils. Two detection coils are located
at either side (shown in blue) with the purpose of acquiring a balanced detection. To
amplify the magnetic signal from the sample and to cancel any background noise, these
two detection coils were connected in series. The source coil located in the middle (shown
in orange) was connected to the function generator to generate an AC magnetic field. The
lock-in amplifier connected the detection and source coils and was used to amplify only
the signal at the detection frequency and phase and cancel out all the noise signals at all the
other frequencies. The sensitivity of the setup was reduced down to the microvolt level,
and it was limited by the inductance of the whole setup, which is frequency dependent.
Fortunately, this is not a fundamental limit, and we can further improve it in the future by
Appl. Sci. 2022, 12, 8238 5 of 12
increasing the number of balancing coils and optimizing the geometry of the coils through
numerical simulations.

Figure
Figure2.2.B–H
B–Hlooper
loopersetup
setupdiagram.
diagram.

To
Totest
testthe
thecuring
curingprocess
processusing
usingthetheB–H
B–Hlooper
looperof ofthe
theadhesive
adhesivecontaining
containingMENs,
MENs,an an
input voltage of 4 V and a frequency of 1.3 kHz were used, which is the critical
input voltage of 4 V and a frequency of 1.3 kHz were used, which is the critical frequency. frequency.
To determine
To determine this
this frequency,
frequency,thethefrequency
frequency was
wasswept
sweptfrom 100100
from Hz to
Hz10tokHz, and the
10 kHz, andvalue
the
at which
value the signal
at which due todue
the signal theto
MENs reached
the MENs its maximum
reached was recorded.
its maximum This frequency
was recorded. This fre-
value was
quency characterized
value by the net
was characterized inductance
by the of the whole
net inductance of the system, which is
whole system, influenced
which is in-
fluenced by the sample’s microenvironment [22]. Thus, the inductance is partially deter-
mined by the magnetic dynamics of the MENs dispersed in the sample. The critical fre-
quency value slightly increases when the applied field is further increased via the source
voltage.
When a voltage was applied to the source coil of the B–H looper and the sample was
Appl. Sci. 2022, 12, 8238 5 of 11

by the sample’s microenvironment [22]. Thus, the inductance is partially determined by

the magnetic dynamics of the MENs dispersed in the sample. The critical frequency value
slightly increases when the applied field is further increased via the source voltage.
When a voltage was applied to the source coil of the B–H looper and the sample was
placed next to the coils, the AC magnetic field generated caused a magnetic flux in the
sample containing MENs, due to the surface charge density of the nanoparticles. This mag-
netic flux was perceived by the detection coils, causing a change in signal. The background
signal, which includes the noise factor, prior to putting the sample was subtracted from the
recorded signal for every measurement.

3. Results
3.1. Magnetic Moment on MEN-Doped Adhesive
The influence of surface charge on the magnitude of the magnetic moment generated
during VSM is shown in Figure 3a for MENs with and without a polymer coating. Results
showed a 60% decrease in the magnitude of the magnetic moment when MENs contained
a polymer coating as compared to the free particles. Figure 3b shows the difference in
the VSM signals generated from the undoped and doped (1 vol% MENs) cure polymer
Appl. Sci. 2022, 12, 8238 adhesives (EC 2615 B/A, 3M). The doping of the adhesive resulted in an approximate6 500%
of 12
increase in the magnetic moment from approximately 10 µemu to 50 µemu.

(a) (b)
Figure
Figure 3.
3. (a)
(a)Magnetic
Magneticresponse
responseofof
free MENs
free MENsvs.vs.
polymer-coated MENs;
polymer-coated (b) influence
MENs; of MEN
(b) influence dop-
of MEN
ing on the magnetic signal on a polymer adhesive.
doping on the magnetic signal on a polymer adhesive.

The
The sensing
sensing capability
capability of
of MENs
MENs predominantly
predominantly comes comes from variations in
from variations in the
the surface
surface
charge density based on the loading history [24]. For the uncoated and coated
charge density based on the loading history [24]. For the uncoated and coated individual individual
particles, Figure
Figure4a 4ashows
showsthe
thepossible
possible mechanism
mechanism forfor a decrease
a decrease in surface
in the the surface
chargecharge
and,
and, as a result,
as a result, the magnetic
the magnetic moment.moment. As a MEN
As a MEN is coated
is coated with polymer
with polymer chains,chains,
free H+free H+
atoms
atoms in the chains
in the chains act to neutralize
act to neutralize the surface
the surface charge
charge [15], [15], increasing
increasing the bondthe bond strength
strength between
between theand
the particle particle and the as
the polymer polymer
well asas well as lowering
lowering the measured
the measured magnetic magnetic
moment, as moment,
shown
as shown 3a.
in Figure in Figure
Figure 3a. Figure how
3b shows 3b shows
addinghowtheadding the nanoparticles
nanoparticles to thecaused
to the adhesive adhesive
the
caused the magnetic properties of the material
magnetic properties of the material to increase. to increase.

3.2. Monitoring of the Curing Process Using the B–H Looper

The B–H looper was used to evaluate the magnetic signal of adhesive samples con-
taining 5% MENs to monitor their curing process. The initial magnetic signal (at curing
hour zero) of the three samples was measured. Subsequent measurements were recorded,
and the percentage increase with respect to the initial signal was obtained. The average
percentage increase of the three samples was calculated and is graphed in red in Figure 5.
It can be observed that there was an increasing trend in the magnetic signal during the first
curing hours, which started converging after approximately 8 h of curing time.

(a) (b)
Figure 4. (a) Charge neutralization of individual MENs as a function of polymer coating; (b) polar-
ization of MENs as a function of water ingression.

Appl. Sci. 2022, 12, 8238
charge density based on the loading history [24]. For the uncoated and coated individual
particles, Figure 4a shows the possible mechanism for a decrease in the surface charge
and, as a result, the magnetic moment. As a MEN is coated with polymer chains, free H+
atoms in the chains act to neutralize the surface charge [15], increasing the bond strength
between the particle and the polymer as well as lowering the measured magnetic moment,
as shown in Figure 3a. Figure 3b shows how adding the nanoparticles to the adhesive 6 of 11

caused the magnetic properties of the material to increase.

Appl. Sci. 2022, 12, 8238 7 of 12

(a) (b)
Figure 4. (a) Charge
4. (a) neutralization of individual
Charge MENs as aasfunction of polymer coating; (b)(b)
polar-
Figure
confirmed by the neutralization
progression of individual MENs
the adhesive’s glassa function of polymer
transition coating;
temperature polar-
(plotted in
ization of MENs as a function of water ingression.
ization
black)ofasMENs as a which
it cured, function of water ingression.
converged at ~137 °C.
3.2. Monitoring of the Curing Process Using the B–H Looper
The B–H looper was used to evaluate the magnetic signal of adhesive samples con-
taining 5% MENs to monitor their curing process. The initial magnetic signal (at curing
hour zero) of the three samples was measured. Subsequent measurements were recorded,
and the percentage increase with respect to the initial signal was obtained. The average
percentage increase of the three samples was calculated and is graphed in red in Figure 5.
It can be observed that there was an increasing trend in the magnetic signal during the
first curing hours, which started converging after approximately 8 h of curing time.
To confirm the magnetic signal results obtained with the B–H looper, tensile testing
was performed on the undoped adhesive to study whether a similar type of convergence
was observed on the adhesive’s mechanical properties. The peak stress with respect to
curing time is plotted in Figure 5 in blue. A similar trend was appreciated, in which there
was a rapid increase in tensile strength during the first curing hours and then it started
converging at around 8 hours of curing time until it reached ~41 MPa. This trend was also
Figure5.
Figure 5. Undoped
Undoped adhesive
adhesivepeak
peakstress
stress(blue), change
(blue), in in
change thethe
magnetic signal
magnetic (red),
signal and and
(red), glassglass
tran-
sition temperature (black) with respect to adhesive curing time.
transition temperature (black) with respect to adhesive curing time.

3.3. Single Lap Shear

To confirm the magnetic signal results obtained with the B–H looper, tensile testing
was performed on the
For the single lapundoped adhesive
shear, Figure to study
6 shows whether a similar
the relationship type
between of convergence
displacement and
was observed on the adhesive’s mechanical properties. The peak stress with
peak stress at failure for each undoped and doped (1 vol% MENs addition) adhesive sam- respect to
curing time is plotted in Figure 5 in blue. A similar trend was appreciated, in
ple. The average shear strength for each condition was 25.01 ± 2.45 MPa and 30.79 ± 2.16which there
was
MPa, a rapid increasesignifying
respectively, in tensilean
strength during
increase of 23%the
forfirst
the curing
doped hours andThis
adhesive. thenincrease
it started
in
converging at around 8 hours of curing time until it reached ~41 MPa. This
the bond strength is significant as the primary application of the addition of MENs trend was is
also
for
confirmed by theand
sensing aspects progression
any gains of
in the
bondadhesive’s
quality areglass transition
secondary. temperature
These (plotted in
samples experienced
black) as itfailure,
cured, and
which ◦
cohesive theconverged
addition ofatthe
~137 C.
nanoparticles did not seem to impact the type of
failure in lap shear testing.
3.3. Single Lap Shear
For the single lap shear, Figure 6 shows the relationship between displacement and
peak stress at failure for each undoped and doped (1 vol% MENs addition) adhesive sample.
The average shear strength for each condition was 25.01 ± 2.45 MPa and 30.79 ± 2.16 MPa,
respectively, signifying an increase of 23% for the doped adhesive. This increase in the bond
strength is significant as the primary application of the addition of MENs is for sensing
aspects and any gains in bond quality are secondary. These samples experienced cohesive
failure, and the addition of the nanoparticles did not seem to impact the type of failure in
lap shear testing.

(a) (b)
Figure 6. (a) Peak stress of undoped and doped adhesives for single lap shear samples; (b) load–
 peak stress at failure for each undoped and doped (1 vol% MENs addition) adhesive sam-
ple. The average shear strength for each condition was 25.01 ± 2.45 MPa and 30.79 ± 2.16
MPa, respectively, signifying an increase of 23% for the doped adhesive. This increase in
the bond strength is significant as the primary application of the addition of MENs is for
sensing aspects and any gains in bond quality are secondary. These samples experienced
Appl. Sci. 2022, 12, 8238 7 of 11
cohesive failure, and the addition of the nanoparticles did not seem to impact the type of
failure in lap shear testing.

(a) (b)
Figure
Figure 6.
6. (a)
(a) Peak
Peak stress
stress of
of undoped
undoped and
and doped
doped adhesives
adhesives for
for single
single lap
lap shear
shear samples;
samples;(b)
(b)load–
load–
displacement curves for undoped (black) and doped (red) samples.
displacement curves for undoped (black) and doped (red) samples.

3.4.
3.4. End
End Notch
Notch Flexure
Flexure (ENF)
(ENF)
Regarding
Regarding the the ENF
ENF samples,
samples, Figure
Figure 77 shows
shows the the relationship
relationship between
between displacement
displacement
Appl. Sci. 2022, 12, 8238 8 of 12
and
and the
themode
modeII IIcritical
critical energy
energy release
releaseraterate
GIIC G atIIC
failure for each
at failure for sample that was
each sample doped
that was
doped
and and undoped.
undoped. The average The Gaverage
IIC valueG for valuecondition
IIC each for each was condition
503 ± 46 wasJ/m503
2 and ± 564
46 J/m± 372
and2,564
J/m ± 37 J/m2showing
respectively, , respectively, showing
an increase an increase
of 12% of 12%adhesive.
for the doped for the doped adhesive. The
The strengthening
of adhesive bonds
strengthening with the
of adhesive addition
bonds with of thehard ceramic
addition nanoparticles
of hard (such as Al2O
ceramic nanoparticles 3, ZnO,
(such as
and
Al O
2 3
TiO
, 2) is and
ZnO, well documented
TiO 2 ) is well [24–29].
documented These samples
[24–29]. Theseexperienced
samples cohesive
experienced failure,
cohesiveand
the addition
failure, and the ofaddition
the nanoparticles did not seem
of the nanoparticles didto notimpact
seem to theimpact
type of failure
the type of in failure
lap shearin
testing. This study shows how adhesive joints containing MENs
lap shear testing. This study shows how adhesive joints containing MENs show an increase show an increase in me-
chanical
in mechanicalperformance
performance compared
compared to undoped
to undoped joints. TheThe
joints. increase
increasein the critical
in the energy
critical energyre-
lease rate
release ratecan
canbebemodeled
modeledusing using thethe formulation
formulation discussed in in Johnsen
Johnsen et et al.
al.[27],
[27],in inwhich
which
theGGCC of
the ofaaparticle-toughened
particle-toughenedpolymer polymeradhesive
adhesivecan canbe bedetermined
determinedusing usingthe theGGCCof ofthe
the
adhesive(values
adhesive (valuesobtained
obtainedfrom fromENF ENFtesting
testingabove)
above)and andthethechange
changein inenergy
energyrequired
requiredfor for
plasticzone
plastic zonegrowth.
growth. This Thisenergy
energycan canbe beobtained
obtainedfrom fromthe themechanical
mechanicalproperties
propertiesof ofthe
the
ceramic(E
ceramic (EMENs
MENs == 50
50 GPa
GPa [30]),
[30]), the
the volume
volume fraction of the nanoparticles
nanoparticles (1 (1 vol%)
vol%) and and voids,
voids,
and
andthetheplastic
plasticzone
zoneradius
radiusofofthe theunmodified
unmodified polymer.
polymer. Based
Basedonon these inputs,
these inputs,thetherange of
range
the expected
of the expectedcritical energy
critical energyrelease raterate
release as aasfunction
a function of MEN
of MEN addition
additionwaswas calculated
calculated to
be 2 and 2 ,2which slightly under-predicted the experimental G
to between
be between 546546
J/mJ/m 2 and 553 J/m
553 J/m , which slightly under-predicted the experimental G IIC
IIC
values
valuesfound
foundwithwithENFENFtesting
testing(average
(averageofof564 564J/m J/m22).

Figure7.7.GGIIC
Figure of undoped
IIC of undoped and
and doped
doped adhesives
adhesives with
with 11 vol%
vol% MENs.
MENs.

In addition, a JEOL JIB-4500 Dual Beam FIB-SEM was used to take in situ images and
a video of the failure of one doped ENF sample, which are included as Figure 8 and Video
S1. Imaging shows localized shear loading, plastic zone evolution, and failure of the ABCJ
Appl. Sci. 2022, 12, 8238 8 of 11

Figure 7. GIIC of undoped and doped adhesives with 1 vol% MENs.

In
In addition,
addition,aaJEOL JEOLJIB-4500
JIB-4500DualDualBeam
Beam FIB-SEM
FIB-SEM was used
was to take
used in situ
to take images
in situ and
images
aand
video of theoffailure
a video of oneofdoped
the failure ENF sample,
one doped whichwhich
ENF sample, are included as Figure
are included 8 and Video
as Figure 8 and
S1. Imaging
Video shows localized
S1. Imaging shear loading,
shows localized plastic zone
shear loading, evolution,
plastic and failure
zone evolution, andof the ABCJ
failure of
in
thethe crack
ABCJ tip region.
in the crack tipAsregion.
indicated by the blue
As indicated arrows,
by the blue localized damage damage
arrows, localized was seenwas to
occur
seen tooutside the plastic
occur outside thezone in the
plastic zone form of visible
in the form ofmicrocracking resultingresulting
visible microcracking from thefromdis-
tribution of loading
the distribution away from
of loading away the pre-crack.
from In addition,
the pre-crack. the red arrows
In addition, the red identify the ini-
arrows identify
the initial
tial formation
formation microvoid
microvoid clustercluster
in theinhigh-shear
the high-shear region.
region. The fracture
The fracture surfaces
surfaces of
of the
the failed
failed specimen
specimen showed
showed similar
similar plastic
plastic zonezone development
development in failure
in the the failure
andandcrackcrack tip
tip re-
regions
gions forfor plain
plain samples
samples andand samples
samples containing
containing MENs.MENs. The likely
The most most toughening
likely toughening
mech-
mechanisms,
anisms, in thisincase,
this case, are stress
are stress shielding
shielding of theofcrack
the crack tip localized
tip and and localized stress
stress transfer
transfer to
to the
the stiffer
stiffer nanoparticle
nanoparticle [31].[31].

Figure
Figure 8.
8. In
In situ
situ images
images of
of an
an ENF
ENF specimen
specimen of
of (A)
(A) the
the crack
crack tip
tip region
region prior
prior to
to loading;
loading; (B,C)
(B,C) the
the
deformed crack tip region.
deformed crack tip region.

3.5. Tensile Testing

Table 1 displays the peak tensile stress on undoped and doped samples. It can be ap-
preciated how dispersing 5 vol% MENs into the 3M adhesive increased its maximum tensile
stress compared to the undoped samples, which was 39.5 ± 1.76 MPa and 36.6 ± 1.28 MPa,
respectively. This signifies approximately an 8% increase, confirming that adding MENs to
the epoxy adhesive does not negatively affect its mechanical properties.

Table 1. Maximum tensile stress in undoped and doped adhesives with 5 vol% MENs.

Sample Peak Tensile Stress (MPa) Std. Dev. Avg. Stress

Type/Sample # 1 2 3 4 5 (MPa) (MPa)

Baseline
38.09 36.61 36.10 38.44 35.00 1.28 36.85
(2R:1H ratio)
Doped (5 vol%
38.18 36.32 42.56 40.58 43.84 2.76 40.30
MENs)

3.6. Environmental Exposure

VSM scans were completed in individual cured adhesive resin samples (non-bonded)
with concentrations of 5, 10, and 15 vol% MENs before and after environmental exposure,
with the results shown in Figure 9. Before exposure, the doped adhesive showed an
increasing magnetic moment with increased concentration (3.7 × 10−5 emu for 5 vol%
MENs, 10.2 × 10−5 emu for 10.2 vol% MENs, and 15.5 × 10−5 emu for 15 vol% MENS).
After exposure, the signal saturated and was consistent over varying MEN concentrations
(magnitude approximately 15.0 × 10−5 emu).
 VSM scans were completed in individual cured adhesive resin samples (non-bonded)
with concentrations of 5, 10, and 15 vol% MENs before and after environmental exposure,
with the results shown in Figure 9. Before exposure, the doped adhesive showed an in-
creasing magnetic moment with increased concentration (3.7 × 10−5 emu for 5 vol% MENs,
10.2 × 10−5 emu for 10.2 vol% MENs, and 15.5 × 10−5 emu for 15 vol% MENS). After expo-
Appl. Sci. 2022, 12, 8238 9 of 11
sure, the signal saturated and was consistent over varying MEN concentrations (magni-
tude approximately 15.0 × 10−5 emu).

(a) (b)

(c) (d)
Figure
Figure 9.
9. Magnetic
Magnetic signatures
signatures before
before and
and after
after environmental
environmental exposure
exposure of
of (a)
(a) 00 vol%
vol% concentration,
concentration,
(b) 5 vol% concentration, (c) 10 vol% concentration, and (d) 15 vol% concentration.
(b) 5 vol% concentration, (c) 10 vol% concentration, and (d) 15 vol% concentration.

As
As illustrated
illustrated in
in Figure
Figure 4b,
4b, water
water ingression had the
ingression had the opposite
opposite effect on the
effect on the magnetic
magnetic
moment. Thiscan
moment. This can occur
occur since
since the polarization
the polarization of the of the surface
surface charge ofcharge of MENs
MENs can can
experience
an increase due to the ingression of polar H2 O molecules. As the concentration of MENs
increases, the magnetic moment can result from both the increased amount of magnetic
material and the agglomeration of MENs, resulting in a higher percentage of MENs with
uncoated free surfaces. After exposure, the saturation point of the magnetic moment was
most likely the result of water ingression being a surface-area-dominated phenomenon.

4. Discussion
Using MENs to non-destructively evaluate adhesives using a magnetic signal can
aid with the widespread implementation of adhesive bonding. It has been shown how
this method detects magnetic changes that are affected by variations in the sample’s
microenvironment, which allows one to measure changes in the material at a localized
level. Correlating the curing process of the doped polymer adhesive with the strength
of the output magnetic signal, and corroborating it with thermal analysis and tensile
testing, shows the potential of this method to non-destructively evaluate materials not
only during their lifetime but also during their manufacturing process. In addition, being
able to measure changes in the surface charge density of MENs allows for the analysis of
materials that undergo harsh environmental conditions, which causes the ingression of
water molecules that polarize the surface of MENs.
Ideally, for each specific material, a baseline calibration curve needs to be obtained.
Knowing how MENs behave in each material and how the magnetic signal evolves during
the curing process will help to know when a specific sample is not curing ideally. This
would help to observe whether a sample is incorrectly manufactured or whether the curing
Appl. Sci. 2022, 12, 8238 10 of 11

parameters are not correct. Future studies will focus on obtaining calibration curves for
common adhesives used in the aerospace industry and then determining when specific
samples undergo a curing process deviated from the baseline.
It is important to highlight that the tensile, lap shear, and end notch flexure testing
shows enhancement in the mechanical properties of the adhesive bond when dispersing
MENs into the adhesive. This means that the addition of these nanoparticles to the adhesive
does not negatively influence the integrity of the adhesive bond when a low volume
percentage is added. This is necessary so that MENs can successfully be used in industries,
such as aerospace and automotive, where the integrity of bonds is of primary importance.

5. Conclusions
VSM and the B–H looper setup were used to non-destructively evaluate an adhesive
resin doped with magneto-electric nanoparticles. These setups were used to obtain changes
in the surface charge density in the nanoparticles of ABCJs with respect to curing time
and varying history of environmental exposure. There was a strong correlation between
the magnetic signal obtained during the curing process of the doped adhesive and its
mechanical and thermal properties. There was also a relationship between the increased
levels of exposure and an increase in the measured magnetic moment (up to a saturation
point). In addition, mechanical property evaluation revealed an increase in the shear
strength, mode II critical energy release rate (GIIC ), and tensile strength of MEN-doped
adhesives. With further refinement and development, this technique has the potential to
become a non-destructive evaluation tool for damage and quality inspection in both in-field
and manufacturing settings.

Supplementary Materials: The following supporting information can be downloaded at: https://www.
mdpi.com/article/10.3390/app12168238/s1, Video S1: In situ video of the failure of one doped ENF
sample inside the SEM chamber.
Author Contributions: Methodology, S.K. and B.B.; validation, J.D.; investigation, D.W. and M.P.;
writing—original draft preparation, G.S.; writing—review and editing, B.B. and D.M.; project admin-
istration, D.M. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by the Office of Naval Research (ONR; grant number N00014-
18-1-2028) managed by Mr. Bill Nickerson. It was also partially funded by NSF PREM IMPAQT by
providing student support (grant number 2122078).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: Special thanks to 3M for contributing the two-part epoxy adhesive for the project.
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design
of the study; in the collection, analysis, or interpretation of data; in the writing of the manuscript; or
in the decision to publish the results.

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